JPS6036546A - Polyethylene resin composition - Google Patents

Abstract

PURPOSE:To provide a composition exhibiting excellent moldability by blow molding, extrusion molding, etc., and having high impact resistance and environmental stress cracking resistance, by compounding two kinds of specific polyethylenes composed of an ethylene homopolymer and an ethylene/alpha-olefin copolymer. CONSTITUTION:The objective polyethylene resin composition is produced by compounding (A) 90-35wt% polyethylene selected from an ethylene homopolymer and an ethylene/alpha-olefin copolymer polymerized by a magnesium compound- based Ziegler catalyst, and composed of a low molecular weight part (A-L) having a molecular weight of 9,000-90,000 and a high molecular weight part (A-H) having a molecular weight of 100,000-1,500,000 wherein the molecular weight ratio of (A-H)/(A-L) is 4-200 and the weight ratio of (A-L)/(A-H) is 70:30-30:70 and (B) 10-65wt% polyethylene having a molecular weight of 50,000-500,000 and selected from an ethylene homopolymer and an ethylene/alpha- olefin copolymer polymerized by a supported chromium compound catalyst combined with an organometallic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyethylene composition having excellent physical and chemical properties and molding processability, and which has excellent molding properties in hollow, extrusion, injection-blow molding applications, etc. ]
properties, excellent impact resistance and environmental stress cracking resistance (hereinafter referred to as E
It relates to a polyethylene composition having good physical properties such as scR.

Polymers with a relatively high molecular weight and a relatively wide molecular weight distribution are suitable for use in polyethylene hollow, single-sided (υ), injection molding and blow molding applications.

Several methods have been proposed for producing polyethylene with a wide molecular 9'' distribution.

As one method, a method of mixing high molecular weight polyethylene and low molecular weight polyethylene has been proposed (Tokuden IJ, No. 15-3215, Japanese Patent Publication No. 45-2200).
Publication No. 7, Japanese Unexamined Patent Publication No. 1983-. 100444, JP 54-100445, JP 54-1 (IL, 6
No. 57, JP 55-6 (1542, JP 55-60543) iJi, 4> Uil DB
56-:: Publication No. 7841, JP-A-4i7-13
3] Publication No. 36).

In addition, as another method, a multi-stage polymerization method of two or more stages has been attempted (Japanese Patent Publication No. 11349/1983, Japanese Patent Publication No. 11349/1983).
-42775, JP-A-51-47 (JP-A-179, JP-A-5219788).

Polymers produced by these methods have a wide molecular weight distribution and good E S CR.

The inventors of the present application investigated the example of the shell shown above using a magnesium compound-based Ziegler type catalyst, and found that the molecular weight distribution was widened and the E S CR was improved, but -force, Those polyethylenes have low impact strength,
Furthermore, there are many disadvantages in terms of practical properties, such as poor melt viscoelastic properties during molding (thickness of 4" - easy to occur in molded products, and the inability to mold molded products with complex shapes. I understand.

The present invention improves these drawbacks of polyethylene composed of a low molecular weight part and a high molecular weight part polymerized by a magnesium compound-based Ziegler type catalyst, and provides a polyethylene composition that is comprehensively excellent in both processability and physical properties. It is something.

7Z That is, the present invention consists of a polyethylene (m) and IB) selected from a homopolymer of ethylene and a copolymer of ethylene and α-olefin, and (It polyethylene (A) is a magnesium compound (11) Polyethylene+A+ is polymerized using a Ziegler type catalyst, and polyethylene (Bl is a monomer polymerized using a chromium compound-supported catalyst combined with an organometallic compound. Low molecular weight (A, -L) and molecular weight of 10 to 150
The molecular weight of A-H/the molecular weight of A-L is 4 to 200, and the amount of IN of A-L to A-Il is the weight of 70:30 ratio
The molecular weight of (#l) polyethylene [J3) is 50,000 to 500,000 to 500,000, and the amount of (Bl) in the composition is 10 to 65% by weight. It is.

According to the present invention, it has both physical properties such as excellent impact resistance and ESCR1 rigidity, which have a wide range of industrial applications, and excellent molding processability, and has applications such as hollow, extrusion and injection blow molding. A suitable polyethylene composition is given.

The present invention will be explained in detail below.

The polyethylenes (AI and IB) which are the constituent components of the present invention are selected from the group consisting of ethylene homopolymers and copolymers of upper nalene and α-olefins.

The α-olenylene used in the copolymerization has a carbon number of j to 14, and includes, for example, propylene, butene, pentene, hexene, 4-methylbenzone, decene, and the like.

Polyethylene (A) consists of a low molecular weight part (A J, ) and a high molecular weight part (A - H). L) is 0.
50,000 to 90,000, and 1 L of molecules of A-Il (M W A-
)1) is 10 to 150. MWA-L is 0.5
If the amount is less than 10,000, the uniform dispersion and physical properties of each component will decrease.
-If the force exceeds 9 forces, the molecular weight of the composition will be within an appropriate range-
J-amount)lii becomes wider (and the workability decreases.The tlJ"-t ratio is 10,000 to 70,000. On the other hand, MwA
-,, is less than 10,000, the molecular weight of the composition decreases, and E
SCR also decreased by 1-1.

If it exceeds 1.5 million, fish eyes may occur and the uniform dispersibility of each component in the composition may decrease, resulting in poor balance in both processability and physical properties.More preferably 20 to 1
It is 0,000,000.

In addition, the ratio between MWA-11 and MWA-L (MWA-
H/MWA-L) is 4 to 200; if it is less than 4, the molecular weight distribution is narrow and processability is low, making it impossible to obtain the excellent physical properties of the present invention. On the other hand, even if it exceeds 200, there is no advantage in improving moldability and physical properties (and there are also disadvantages in terms of manufacturing).More preferred is 7 to 150.

Also, the density of A-L is 0.91-0.98'I/d, and the density of A-H is 091-0.97'jlcrr? It is. The density of A-1t is lower than that of A-L and polyethylene [B].
Trimming of the layers is preferred because it improves both processability such as extrudability and physical properties such as impact resistance and ESCR.

The molecular weight (MWs) of polyethylene FBI is 5 to 50
10,000, preferably 80,000 to 400,000, density 0.91 to 0
．． 98 W/ar? , preferably 0.94-097g
−□.

In addition, in order to improve the balance between moldability and physical properties of the composition, a particularly desirable embodiment is M W s/MWA-
When L is 12 or more, M W +), / M 1νA-H
is 09 or less, and furthermore, the MWB is lower than the molecular edge of polyethylene (A), (bλll, ).

The ratio of A-L silk to A-11 silk in polyethylene (Al) ranges from 70:30 to 30:7 (), preferably from 60:40 to 40:60.

When the amount of A-L or A-IIO exceeds 7()%,
The molecular weight distribution becomes narrow, resulting in poor balance between processability and physical properties.

Also, the amount of polyethylene tut in the composition is 1 by weight.
It ranges from 0 to 65% by weight, preferably from 15 to 55% by weight. When the amount of (11) is less than 10%,
Processability and impact strength are not improved; on the other hand, if it exceeds 65%, the molecular weight distribution becomes narrow, processability deteriorates, and ESC
[If ζ is bad, the characteristics of the polyethylene composition of the claimed invention will be impaired.

Next, a catalyst for producing polyethylene (Al) and (A)
The manufacturing method will be explained.

As the magnesium compound-based Ziegler type catalyst referred to in the present invention, any system capable of producing organic magnesium or inorganic magnesium can be used.

Examples include magnesium chloride, hydroxymagnesium chloride, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium alkoxide, -7g
Organic acid salts of sium, complexes of these with electron-donating compounds such as alkyl, organic acid esters, or mixtures thereof, organomagnesium compounds having a carbon-magnesium bond, such as dialkylmagnesium, alkyl red sea bream /um chloride, argylmagnesium-J-rukoxide, alkylmagnesium silogide, or these ゛f (complex of a foam magosium compound and an electron donor of ether ζ9), components and halides, for example,
A reaction product of hydrochloric acid, chlorinated hydrocarbon, silicon tetrachloride, and tin tetrachloride is used as a magnesium component at °C, and this is reacted with titanium and/or a vanadium adduct to form a metallized component. A catalyst consisting of a figurine is used.

Particularly preferred catalysts in the present invention include (1) general formula M, IMgpR'p R"qXrYll
(In the formula, α is 0 or a number larger than 0, p10q0r +
S has the relationship of 71α+2β, M is a metal element belonging to Group 1 to Group II of the periodic table, R1 and Bt are hydrocarbon groups having the same or different number of carbon atoms, X and Y are Identical groups are different groups, halogen + OR”
, 08iR'R5R', NR'R'.

Represents a group SR', R3, R4, R5, Re,
R? , R8 represents a hydrogen atom or a hydrocarbon group, and R9 represents a hydrocarbon group; (11) a titanium or vanadium compound containing at least one halogen atom; IA/,
B, Si, Ge.

Sn r Te + S b halide compound (Il
~il+00) Among them, it consists of (a solid catalyst component [A] formed by reacting 11 and (11) or (1) and (11) with flil and an organometallic compound Ln].As an organometallic compound CDI , compounds of groups 1 to m of the periodic table, and particularly preferred are complexes containing organoaluminum compounds and organomagnesium.

The reaction between the catalyst component CAI and the organic bidder compound CB) 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 1 to 300 f) component CBI to 11 components f) mmo
It is preferable to carry out within the range of /.

Instead of the catalyst component [A], a Ti compound supported on an inorganic carbon compound may be used.

Among these catalyst systems, JP-B No. 52-3 is the most desirable system because it can omit the decatalyst step industrially.
6788 Publication, Japanese Patent Publication No. 52-36790, Japanese Patent Publication No. 52-36791, Japanese Patent Publication No. 52-36792, Japanese Patent Publication No. 52-50070, Japanese Patent Publication No. 52-3
6794 Publication, Special Publication No. 52-36795, Special Publication No. 52-36796, Special Publication No. 52-36915, Special Publication No. 52-36917, Special Telephone F@53
-(i019, JP 50-21876, JP 50-31835, JP 50-720
．． 44, JP-A-50-78619, and JP-A-53-40696.

The polyethylene is produced by suspension polymerization, solution polymerization, gas phase polymerization, or the like.

It is industrially desirable to produce the polyethylene body by two-stage polymerization, and several two-stage polymerization methods have already been proposed. A particularly preferred method for the present application will be described below.

The polymerization is carried out in a saturated hydrocarbon having 4 to 10 carbon atoms. The order of polymerization may be (A-L)-(A-H) or (A-H)-(A-L).

For simplicity, the (A-L)-(A-II) pattern will be explained with reference to the drawings.

The low molecular weight part (A-L) has a polymerization pressure of 1 to 30 kI7'a
1G, preferably 3 to 25 kl/'dG, and the polymerization temperature is 60 to 100°C, preferably 70 to 90°C.

The high molecular weight part (A −) 1) has a polymerization pressure of 05 to 3 o
kttlc3fG, preferably 0.5-20 kg, /
crrr? The polymerization temperature is 40 to 110°C, preferably 60 to 90°C.

In polymerization reactor 1, polymer, hexane, hydrogen,
Catalyst components etc. are supplied, and low molecular weight polyethylene (A-
L) is polymerized. The σ slurry in the mixer 1 is led to a flash drum 3, where unreacted ethylene and hydrogen are removed. The removed ethylene and hydrogen are pressurized by the compressor 4 and returned to the polymerizer IK. On the other hand, the slurry in the seven lash drums 3 is introduced into the second stage polymerization vessel 6 by the pump 5. In the polymerization vessel 6, ethylene, comonomer, hexane, catalyst components, etc. are supplied from the line 7, and polymerization of high molecular weight polyethylene ('A-)1) is carried out, and the polymer in the polymerization vessel 6 undergoes a post-treatment process as a product. It is then taken out.

The flow explained above is one of the typical examples of the present invention, and in some cases, the high molecular weight part (A - H,
) may be polymerized, and then the low molecular weight portion (A-L) may be polymerized in the polymerization vessel 6. In that case, it is possible to omit the flash drum 3. Furthermore, the contents of the polymerization vessel may be circulated from the rear stage 11+ and the bundle 6 to the front stage polymerization vessel 1.

Polyethylene (polyethylene) can be continuously polymerized using such a flow sheet.

In this way, the polyethylene body) is produced by two-stage polymerization, but it is also possible to separately prepare a low molecular weight part and a high molecular weight part and then combine them.

The polyethylene body produced in this way has a wide molecular weight distribution, and the amount of double bonds is 0 per i, ooo carbon number.
．． The number of F; S CIζ is good, but on the other hand, the impact resistance is low and the balancing effect during melting is low.

Next, a catalyst and a manufacturing method for producing polyethylene (Bl) will be explained.

The chromium compound-supported catalyst combined with an organometallic compound referred to in the present invention includes, for example, a combination of a solid component in which a chromium compound is supported on an inorganic oxide carrier and an organic gold halide.

A more specific explanation will be given below.

As the inorganic oxide carrier used in the present invention, silica, alumina, silica-alumina, zirconia, thoria, etc. can be used, but silica and silica-alumina are preferable. High porosity volumes are particularly preferred.

The supported chromium compounds include chromium oxides, or compounds which at least partially form chromium oxide upon calcination, such as chromium/chloride, mexinochloride, nitrate, acetate, sulfate, Examples include oxalate, alcolade, etc., specifically chromium trioxide, chromyl chloride, potassium dichromate, ammonium chromate), chromium nitrate, chromium acetate, chromium acetate, acetonate, dikusha butyl chloride, etc. Examples include romate.

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

The chromium compound can be supported on the press 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. In this case, a non-aqueous solvent such as toluene may be used.The amount of chromium to be supported is determined by the x
i] 0.05 to 5%, preferably 0.1 to 5%
Friend within the range of 3%).

Firing 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 water 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 of controlling molecular weight, etc. by adding ticnates, fluorine-containing salts, etc. during loading or baking.

In addition, silylchromate, amine and trioxide (bu)
A catalyst obtained by supporting a compound such as zP-u-Cr-0-P(OR)2 on the above-mentioned carrier may also be used as the solid component (n). .

Organozinc compounds used in combination include the following:

(al General formula AIJLnX3-(1 (wherein, R is a hydrocarbon group, X is a halogen, OR' or 03iIζ2rc
represents a group RR4, R', R2, It3. R
' is a hydrocarbon, and n is a number of 14 n, 43'.

(+1) Organozinc compound represented by the general formula ZnRmX2-yrl (wherein R is a hydrocarbon group, X is a group 01L', R1 is a hydrocarbon group, and m is a number 14 m42) .

(c) An organolithium compound represented by the general formula LiR (wherein R represents a hydrocarbon group).

(d+ General K BRIIXs -4 (wherein, R is a hydrocarbon group, X is a halogen, OR' or 08iR2R"R
R', R3, R' are hydrocarbon groups, R2 is a hydrogen atom or a hydrocarbon group, l is 14
An organic boron compound represented by the number 143.

Polyethylene (3) is produced by suspension polymerization, solution polymerization, gas phase polymerization, etc. using a chromium compound-supported catalyst containing K and metal compounds. ) has a moderately wide molecular weight (i), that is, when the melt index (RII) is 1 to 11
R (under Ml measurement conditions, load 21. (a+ in ikf)
The quotient obtained by dividing the +1 constant value by MI) is 50 to 120, the amount of 2Jl bonds is 03 to 2 per 1,000 carbons, and the magnesium compound Ziegler type contactor is more than 6 polyethylene. , exhibiting high badis effect.

The reason why the polyethylene 47rj resin composition of the present invention exhibits excellent moldability and physical properties is that the molecular weight The polyethylene CB+ has a relatively wide distribution and a suitable bathyssis effect, and the polyethylene CB+ is connected and the molecules are well matched, and the optimum molecular weight distribution or distribution ff5 takes the form P1. Conceivable.

For mixing polyethylene (AI) and (81), common methods such as powder state, slurry state, pellet state, etc. are used. 2. Do this using a kneading machine, an ig kneading machine, etc.

AI of the polyethylene composition thus produced
I&i0.001~l Oi/710m1n, density is 0.91~097 d preferable, or 0.935
~0.9657/a! Out. The molecular weight distribution is M I
R is 60 or more, preferably 75 or more. In addition, when using 1' for injection-blown molding, M,
I is preferably 05 to 35'710 min, hollow,
O, OO5-17 for extrusion molding. /10 m1n is preferable, and 001 to 0.59710 m1n is particularly preferable.

The polyethylene composition contains substances that can be added or blended with polyolefins, such as heat stabilizers, antioxidants, ultraviolet absorbers, pigments, antistatic agents, lubricants, fillers, other polyolefins, thermoplastic resins, rubbers, etc. , can be used as needed. It is also possible to mix a foaming agent and carry out foam molding.

As described in detail below, the polyconaref composition obtained by the present invention has the following characteristics.

(1) θII during melting; dynamic 1\t'7, lh'jsu1
11.・11 rows 1-1 backing has a good balance and has excellent moldability. Especially for hollow molding, pipes, etc.
1" for extrusion molding of hats, injection blow molding, etc.: Good soil filling properties and small unevenness in the thickness of the molded product.

(2) Ir1llfJ,,,il+1 (3j
m< f4 :L; YopiEscit is high (all these characteristics are well balanced for practical use.

(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, stretching, 11'lJ rolling, and foaming 7".

Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited to these Examples in any way.

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

(1) Iν1: represents melt index, AST
, MD123H, temperature 190℃, city 2-16
6111 determined under the exemption of kf.

(Ill l+l r IL; M 1 measurement strip 1'F, 16, load 21.6 / AI The thicker δ is, the broader the molecular weight distribution.

(+in molecular weight (btw); using decalin@liquid, 1
Hardness viscosity (η) measured at 35°C and Journal of Polymer Science, Vol. 36, p. 01 (1957) g(
2) i~, 71 = 6.8 X 10-' M W
The MW was determined from "o". All molecular weights in the present invention are based on this method.

((V) dense f31; ASTIVID-15(15(
c I, Takatte measurement f-0 (vl S% strength;
Izot shock with knob by ASTM I)-25G.

('/ll E S CR; Indicates stress fracture resistance at random. 200 oml capacity handle molded using a blow molding machine equipped with 5011 Staryu, cylinder temperature Hy 1 OC, mold 4 molds -10'C) A bottle (mi95St) is filled with 200 ml of an aqueous solution of 33% nonionic surfactant, sealed tightly, and placed in an oven at 60° C., and the time until a crank occurs in the bottle is measured.

(vl9 Shock resistance of bottle; Cold water (1
3°C), tightly capped, and repeatedly dropped from a height of 1.9 m onto a concrete surface to measure the number of times it takes for the bottle to break.

(vIil) Extrusion processability; using the above blow molding (2), cylinder temperature 190°C, screw rotation speed 46 rpm
Measure the amount of extrusion when extruding.

(Ixl die swell; outer diameter 16?, inner diameter 1F11
It is expressed as the weight of the balance of 20crIL length when extruded using a No. 1171 blow molding die under the above conditions (Vtll).

B) Thickness irregularities on the bottle: For the bottle made in (■1) above, the thickness of the pinch-off welded part of the nondle part, which tends to become thinner, was visually observed and found to be in very good condition. Good condition! February is represented by ○, -=J, bad condition is represented by △, and very bad condition is represented by X.

Examples] -1 (l) Synthesis of catalyst for polyethylene (A) Trichlorosilane (1-(S i C1, J 1 mol/l hexane solution 21 was placed in a 81 autoclave and kept at 50°C. composition A/1Mgo-o (CtHi)t,
o (n-C4H9)[1-5(UO3)+9) s-
1 mole of organoaluminium-magnesium complex of i/
1 of hexane solution 21 was lowered under stirring for 2 hours,
The pillow will react at this temperature for another 2 hours. The solid component produced was washed twice with 2 portions of hexane by the precipitation method. After 2 hours of titanium tetrachloride was added to the slurry containing this solid component and reacted at 130° C. for 2 hours, the solid catalyst was immediately released and washed with hexane until free halogen was no longer detected. This solid catalyst contained 21% titanium.

(2) Production of polyethylene particles by two-stage polymerization First, in order to produce a low molecular weight part, a reaction volume of 30,010 mm as shown in the drawing was prepared.
Polymerization was carried out in polymerization vessel 1. Polymerization temperature was 83℃, polymerization pressure was 1
1 EI/dG. Into this polymerization vessel 1, the above solid catalyst was added at a continuous rate of 1.3 mmo/(based on Ti atoms)/Hr.
Triethylfluminiuno at a rate of 40p/Hr
Hexane was supplied at a rate of 100%, and ethylene was added to 7% NA4Hr and hydrogen was added as a quantity regulator.
7. Gas phase hydrogen production is approximately 90 mol%. ) and carry out polymerization. The liquid content of the polymer slurry in the polymerization vessel was led to a flash drum 3 at a pressure of 1 k11/crfG and a temperature of 75°C, and after separating unreacted ethylene and hydrogen, the pressure was increased to the M upper vessel 6 with a slurry pump 5. Introduction-1-Z
,. In the polymerization vessel 6, the temperature is 80°C, I = 1 - force 8), y/c
Polymerization is carried out with rrF G. I'm going to take care of the equipment 6
The size is 250p.

7.5 ryy of trienal aluminum was added to the polymerization vessel 6.
Purified hexane at a rate of no l (based on metal atoms) / Hr, 40-e/13r, etele7';:y7.
2 NV/1it-, and hydrogen and budene-1 were each supplied at a gas phase concentration of about 2 mol.
It was introduced at a concentration of about 25 mol %, and the polymerization was unsuccessful.

After completing the two-stage polymerization in this way, the Ml of the powder (including polyethylene) obtained from the polymerizer 6 was 0.17'.
J/l 0rnin,, density is 0.956 W7'ct
It was i.

In addition, from the results of a separate one-stage polymerization experiment conducted under similar conditions, it was found that the polymerization rate in the first-stage polymerization vessel 1 was
The low molecular weight part (A-L) of A+ has a molecular weight of about 13.0 (
10, density approximately 0.974 i/ct, second stage polymerizer 6
High molecular weight part (A-H) of polyethylene (A) polymerized with
) is estimated to have a molecular weight of about 540,000 and a density of about 0939y/crIt, respectively.

(3) Synthesis of catalyst solid component (al) for polyethylene (B) Dissolve chromium trioxide 107- in distilled water 2.0001 RA, and add silica (Gra
de 952) 500 f 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 8°C for 5 hours under dry air circulation to obtain a solid component ta+.The obtained solid component (al) contained 13% chromium and was stored at room temperature under a nitrogen atmosphere. Shi1ko.

(4) Method for producing polyethylene (+3) Polyethylene (13) was produced by a polymerization reaction using a polymerization vessel with a reaction volume of 2F104. Polymerization temperature is 83
℃, the polymerization pressure was 'l k&:/(iG, and the amount of combined product was 10.5 Kp/Hr. The polymerization was controlled so that the amount produced was 7'j, f
i5] Body components (+il at a concentration of 77 m9/J+, di-actyl aluminum ethoxide (component (b)) at 0.0
75 mmol l/l O) (X# I'(, 40
．． e/I-1, was carried out together with purified hexane of r. Using hydrogen as a molecular weight regulator, the concentration of hydrogen is about 30 mol%, butene-1 is added to make the gas phase concentration about ().1 mol%, the molecular weight is about 110,000, the density is 0.96677 (G Polyethylene (131) was produced.

(5) Production of polyethylene resin composition The polyethylene (A+ and (Bl) powders produced as described above were mixed in a weight ratio of 75 yen 125, and then this mixture was heated and treated with anti-oxidation shavings. Tetrakis[methylene-5-(,3',5'-di-t-]-f-#-4'
-hydrogysifoniraflobione-1-) methane 3
00 ppm, and 3o of dilauryl-3,3'-teodibrobimenic acid nisder.

P Pm was added and thoroughly stirred and mixed in a Hen 7 El mixer. This mixture was manufactured by Farrell JIJ F CRi.
At a temperature of 220℃, crosstalk (7, then this
The polyethylene resin composition was extruded and pelletized at a temperature of 25℃ (1℃) using a Tfill extruder to produce a polyethylene resin composition.As shown in Table 1, the performance of this polyethylene resin composition was as follows: It shows very excellent performance in both properties and physical properties.

Example]-2 Except that the polyethylene powders (A+ and (1)) produced in Example 1-1 were mixed in the amounts shown in Table 1, additives, mixing, kneading, extrusion conditions, etc. A composition of polyethylene 81 fat A was produced in the same manner as in Example 1.1. Table 1 shows the results of evaluating the performance.

Comparative Examples] -1 to 1-4 'If = Mu polyethylene powder produced in Example 1-1) and (Bl) were mixed in the amounts shown in Table 1. The kneading and extrusion conditions were the same as in Example 1-1, and the performance of the polyethylene resin composition was evaluated. Table 1 shows the results.

Example 2-1 (]) Synthesis of catalyst of polyethylene 81 fat di-herbal magnesium 138t triethylaluminum 1
9S/- with 24 volumes of rhoheptane (4-eo)
The composition "Mga (C21■s)s(n -CJ
lo) +t organoaluminium-magnesium complex was synthesized. 800 mff of n-heptane solution containing 400 mmo/(547) of this complex and 400 mmo/(547) of titanium tetrachloride
8 fl of n-heptane solution containing mmo# (O
After removing moisture and oxygen by purging with dry nitrogen, the mixture was reacted at -20°C for 4 hours with stirring. The resulting hydrocarbon-insoluble solid was isolated and washed with n-hebutane.
A solid of I was obtained.

(2) Production of polyethylene (N) Using the above catalyst, low molecular weight polyethylene (A-
L) and polymer (1) polyethylene (A-11) were each produced by the method and conditions described below and used as raw materials for a polyethylene composition.

In Example 1-1, polyethylene (1j) was combined using a dowel divider, the polymerization temperature was 86°C, and the polymerization pressure was 11k4I/cw?G.Catalyst Triethylaluminum was introduced at a concentration of 0.5 mmovJ, and the solid catalyst was introduced together with 301/Hr of hexanoate so that the amount of TJL synthesis was 8'j'/11.r. The comonomer was butene-
1 was used. Low molecular weight polyethylene (A, -L) has a sono molecular weight of 30,000 and a density [0,967V10r? The gas phase composition was adjusted so that The hydrogen concentration is about 65%,
The butene-J concentration was about 1%, and the catalyst efficiency was about 140,000 tons of polymer/7 Tl. Polyethylene 7 (A -) J) with a molecular weight of Karasu has a molecular i of 300,000 and a density of 0.935.
The gas phase composition was adjusted to be 't/L00:IrL'.The hydrogen concentration was about 9% and the butene-1 concentration was about 6%.
The catalyst efficiency was approximately 400,000 topolymer/iTi.

(3) Synthesis of catalyst solid component (&) for polyethylene tBl Instead of using chromium trioxide 105', chromium acetate (m
Solid component (a) was synthesized and stored in the same manner as in Example 1-1, except that monohydrate 25!7- was used and the calcination temperature was 600°C. (4
Production example of polyethylene fB] In -1, the solid component ta+ synthesized in (3) was prepared by using the same 1f fractionator, polymerization temperature, and pressure as the catalyst used to polymerize polyethylene (Bl). Diethylzinc at a concentration of 0.075 +nmo e/l at a concentration of 73 m9/l
introduced with hexanoyl of 40/, /Ilr at a concentration of
-It is. Hydrogen concentration approximately 20 mol%, butene-1 concentration approximately 27A
・%, molecular weight 120,000, density 0.9 s sy7 crr
Polyethylene +81 of r was produced.

(5) Manufacture of the polyethylene resin composition as described above.
and (13-1;) powder with a nail ratio of 31.5
38.5 to 300, and then this compound a was heated and treated with an antioxidant, n-)phthadecyl-β-(4'
-Hydroxy-3F, s/-di-t-butylphenyl)propionate 500 ppm.

Tetrakis (2,4-ditertibutylphenyl)
, i, 200 ppm of 4F-biphenylene difluoride, and calcium stearate, 5
A polyethylene composition was produced by adding 00 ppm and using the same conditions as in Example 1 for mixing, mixing, extrusion, etc. Its performance is shown in Table 2.

Example 2-2 () Production of polyethylene (Bl Example) The same polymerization vessel used to polymerize polyethylene (II) in 1. Solid component synthesized in 2-1 (al 62
At a concentration of 1n9/1, butyllithium 0. O65mm
It was introduced at a concentration of ol/l with 401/■ir of hexane. Hydrogen a degree approximately 25 mol%, butene-1 concentration approximately 1
5mol 9b, molecular weight 16ka, density 0958 Y/cr
Polyethylene (13) of d was produced.

Example 2- except that ethylene (B-=-4) was used.
A polyethylene composite was produced in the same manner as in Example 1.

The performance is shown in Table 2.1-0 Comparative Example 2-1 Constant polyethylene (A-L) and (A
-II) as shown in Table 2, and
The mixing and kneading conditions were the same as in Example 2-1, and the polyethylene composition was crushed to 6 m. Its performance is shown in Table 2.

Comparative Example 2-2 The catalyst used in polyethylene (A+) in Example 2-1 was used, and the polymerization vessel, polymerization temperature, and pressure were the same as in the case of polyethylene (13+) in Example 1-1. , polyethylene (B-3) was made of !P![7].The hydrogen concentration was about 3
A polyethylene composition was produced in the same manner as in Example 2-1 except that 5% and the concentration of butene-1 was approximately 0.5 mol 3). Its performance is shown in Table 2.

(Used to make polyethylene in Example 1-1 for production of polyethylene (A)) 17
Polyethylene was produced by two-stage polymerization using a catalyst and one reactor. The polymerization conditions for the first stage (low molecular weight part) were as follows: ethylene at a rate of 8.5 NM-Hr, hydrogen at about 42 mol%, and butene-1 at about 7 mol%. , Example 1-] Polymerization was carried out in the same manner as in 7. c.

Next, unreacted ethylene and hydrogen were separated in a flash drum in the same manner as in Example]-], and in the second stage (for the polymerization of the high molecular weight part, the polymerization temperature was set at 70°C, the pressure was set at 5'V, /cI
r? Polymerization was carried out in the same manner as in Example 1-1, except that ethylene was used at a rate of 6 nm Hr, hydrogen was added at about 5 mol %, and octene-1 was added at about 5 mol %. (Produced AJ. This polyethylene (
Ml of Al powder is 006, density +1.941!
lr/Crn”.

In addition, from a separate experiment conducted under similar conditions,
Polyethylene (low molecular weight part (A-) of Shu) 1 m has a molecular weight of approximately 41,000.The density is approximately (1945'!/cIL"
, the island molecular location (A-117) has a molecular weight of about -10,000 and a density of about 0.93577 cm'', respectively.

(2) Production of polyethylene tn+ In Example 1-1, the catalyst and polymerization vessel used to produce polyethylene (Bl) were used except that butene-1 was reduced to about 2 mol % and hydrogen to 0 mol '3'O. , Example 1-1
Polynye'7-Ren (13) was prepared under the same polymerization conditions. This polyethylene (Bl) has a molecular weight of 250,000 and a density of 0.954j/-/σ3.

A polyethylene composition was produced in the same manner as in Example 9111 except for mixing. Its performance is shown in Table 31
-0 Comparative Example 3-1 Polyethylene (added AJ, σ 1, ill
The performance of polyethylene was evaluated in the same manner as in Example 1-1 for Rikokan No. 1. Write it in Table 3.
j-6

[Brief explanation of drawings]

Figure σ" eye j1, 2BM which is part of the embodiment of the invention J
FIG. In the figure; 1 is a polymerization vessel;
2 is a line, 3 is a 7-layer drum, 4 is a compressor, 5 is a pump, 6 is a polymerization vessel, and '7 is a diine. Special contract amount Mft person Asahi Kasei Industries Co., Ltd. drawing

Claims (1)

[Scope of Claims] 1 Polyethylene selected from the group consisting of an ethylene homopolymer and a copolymer of ethylene and α-olefin] and (Bl), (11 polyethylene (A+
is polymerized using a magnesium compound-based Ziegler type catalyst, and polyethylene CB+ is polymerized using a chromium compound-supported catalyst combined with an organometallic compound. It consists of a low molecular weight part (A-L) with a molecular weight of 90,000 and a high molecular weight part (A-H) with a molecular weight of 100,000 to 1.5 million, and the molecular weight of (A-H) / (A
-L) has a molecular weight of 4 to 200, and (A, -
The amount of L) to the amount of (A-H) ranges from 70:30 to 30:70 by weight, and the amount of polyethylene tA in the composition ranges from 70:30 to 30:70.
The amount of (11υ) polyethylene (the molecular weight of II is 50,000 to 500,000, and the amount of tB in the composition is in the range of 10-65% by weight). Polyethylene resin composition 2
The polyethylene resin composition 3 according to claim 1, in which the polyethylene resin is formed by two-stage polymerization, wherein the molecular weight of the polyethylene (13) is from 80,000 to 400,000, and the molecular weight of the polyethylene (the molecular weight of BJ/ (〕～-L)
The polyethylene resin composition 4 according to claim 1 or 2, wherein the molecular weight of polyethylene (BJ molecular weight/(bar H) is 09 or less and the molecular weight of polyethylene (BJ) is 09 or less, tB) density of 0.94 to 0.9
Polyethylene resin composition 5 according to claim 1, 2, or 3, wherein the density of the composition is 0.935 to 0.9655'7'
7. The polyethylene composition according to claim 1.2.3 or 4, which is