JPH10193379A - Polyethylene injection molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture an ethylene polymer composition injection molded body of a superior mechanical strength. SOLUTION: An injection molded body is an ethylene homopolymer prepared by using a metallocene catalyst or a copolymer of ethylene with 3-20 α-olefin having the density in the range of 0.940-0.970g/cm<3> and the melt flow rate at 190 deg.C and 2.16kg load in the range of 0.05-100g/10 minutes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an injection molded article made of polyethylene, and more particularly, to a polyethylene having excellent mechanical strength as compared with a conventionally known injection molded article of an ethylene polymer or an ethylene polymer composition. The present invention relates to an injection molded article, for example, a beer container, a pallet, and the like.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene homopolymer, ethylene
Polyethylene such as α-olefin copolymer has excellent properties such as excellent mechanical strength, and is therefore used as a raw material for various molded articles. For example, by injection molding, small container caps, beer containers,
It is molded on pallets. As a raw material of such an injection molded article, generally, polyethylene polymerized by a Ziegler type catalyst is used.

In recent years, there has been a tendency to reduce the thickness of these compacts for cost reduction. In order to reduce the thickness of the molded body, it is necessary to increase the rigidity of the raw material resin. However, if the rigidity of the resin increases, the impact strength of the molded body decreases.

[0004] Ethylene polymers produced by a Ziegler-Natta type catalyst typified by a magnesium chloride-supported titanium type catalyst have almost no long-chain branching and excellent impact strength. Although it is used as a body, further improvement in rigidity and impact strength is desired. On the other hand, the ethylene copolymer produced by the high-pressure method and the ethylene copolymer produced by the Cr-Philips catalyst have a longer chain branch than the ethylene copolymer produced by the Ziegler-Natta catalyst. Poor impact strength due to presence.

[0005] For this reason, if an injection molded article made of an ethylene polymer having a better balance of rigidity and mechanical strength than that of a conventional injection molded article made of an ethylene polymer appears, its industrial value will be extremely large.

The present inventors have studied ethylene polymers in view of such prior art, and found that ethylene polymers produced using a specific metallocene catalyst are:
It has excellent moldability, and the mechanical strength and rigidity are the same as those of the Ziegler type, and it has been found that an injection molded article obtained from this polymer has excellent mechanical strength.

A blend of a high-density ethylene polymer and a low-density ethylene polymer, wherein at least one of the ethylene polymers is produced using a metallocene catalyst The polymer composition is particularly excellent in moldability, mechanical strength, rigidity and the like, and the injection molded article obtained from this composition was found to be excellent in mechanical strength, and completed the present invention.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyethylene injection-molded article having excellent mechanical strength, such as a beer container and a pallet. .

[0009]

SUMMARY OF THE INVENTION A polyethylene injection molded article according to the present invention is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms produced using a metallocene catalyst. , (1) Density is 0.940 ~
In the range of 0.970g / cm ^3, (2) a melt flow rate (190 ° C., under a 2.16kg load measurement) 0.0
Ethylene polymer (A) in the range of 5 to 10 g / 10 minutes
It is characterized by consisting of.

[0010] The ethylene polymer (A) as described above is
For example, it can be produced using the following metallocene catalyst. [I] a transition metal compound represented by the following general formula (i),
[II] a compound capable of activating the transition metal compound [I], and (II-1) an organoaluminum compound;
2) a carrier-supported metallocene comprising: aluminoxane; and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair, and [III] a fine particle carrier. catalyst.

[0011]

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(Wherein, M represents a transition metal atom belonging to Groups 4 to 6 of the periodic table, and R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other; A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. And a part of groups adjacent to each other may be bonded to form at least one ring together with the carbon atom to which those groups are bonded, and X ¹ and X ² may be the same or different from each other A hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a nitrogen-containing group, and Y is A divalent hydrocarbon group, a divalent silicon-containing group or Indicating the valency of germanium-containing group.) Further, the above-mentioned ethylene polymer (A) can also be prepared using the following metallocene catalyst. [I] a transition metal compound represented by the following general formula (ii) or a transition metal compound represented by the following general formula (iii), and [II] a compound capable of activating the transition metal compound [I]. And (II-1) an organoaluminum compound, (II-
2) a carrier-supported metallocene comprising: aluminoxane; and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair, and [III] a fine particle carrier. catalyst.

[0013]

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(Wherein M, X ¹ and X ² are the same as those in the general formula (i), and R ^{5 to} R ⁹ may be the same or different from each other, and at least two or more thereof are methyl Or ethyl, the other being a hydrogen atom, and R ^10-
R ¹⁴ may be the same or different, and at least two of them are methyl or ethyl, and the others are hydrogen atoms. )

[0015]

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(Wherein, M, X ¹ and X ² are the same as those in the general formula (i), and R ^{15 to} R ¹⁹ may be the same or different, and four of them are methyl or Ethyl and the others are hydrogen atoms, or 5 are methyl or ethyl, and R ²⁰ and R ²¹ may be the same or different from each other, and have an alkyl group having 1 to 5 carbon atoms or (A hydrogen atom.) Other embodiments of the polyethylene injection molded article according to the present invention include (B) an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. And (B
-1) a density in the range of 0.950 to 0.980 g / cm ³ , and (B-2) a melt flow rate (190 ° C., 2.16
(based on kg load): 0.01 to 1000 g / 10 min .: ethylene polymer: 20 to 90% by weight; and (C) ethylene and an α-olefin having 3 to 20 carbon atoms. Are coalesced and have a (C-1) density of 0.910
0.965 g / cm ³ , and (C-2) melt flow rate (measured at 190 ° C. under a load of 2.16 kg) of 0.
Ethylene polymer in the range of 0003 to 35 g / 10 min: 80 to 10% by weight, wherein the ethylene polymer (B) and the ethylene polymer (C)
Is a polymer produced using a metallocene catalyst, and (1) the density (d _B ) of the ethylene polymer ( _B ) and the density (d _C ) of the ethylene polymer ( _C ) (D _B / d _C ) is greater than 1 and (2)
Density is in the range of 0.940~0.970g / cm ^{3, (3)} a melt flow rate (190 ° C., 2.16 kg
(Measured under load) in the range of 0.05 to 10 g / 10 min.

The above-mentioned ethylene polymer (B) and / or ethylene polymer (C) can be produced, for example, using the following metallocene catalyst. [I] a transition metal compound represented by the general formula (i), [II] a compound capable of activating the transition metal compound [I], and (II-1) an organoaluminum compound; -
2) a carrier-supported metallocene comprising: aluminoxane; and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair, and [III] a fine particle carrier. catalyst.

The above-mentioned ethylene polymer (B) and / or ethylene polymer (C) can be produced, for example, using the following metallocene catalyst. [I] a transition metal compound represented by the general formula (ii) or a transition metal compound represented by the general formula (iii), and [II] a compound capable of activating the transition metal compound [I]. And (II-1) an organoaluminum compound, (II-
2) a carrier-supported metallocene comprising: aluminoxane; and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair, and [III] a fine particle carrier. catalyst.

Such an injection molded article made of polyethylene is
Excellent mechanical strength.

[0020]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the polyethylene injection molded article according to the present invention will be specifically described. The polyethylene injection molded article according to the present invention is an ethylene homopolymer or an ethylene polymer (A), which is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, produced using a metallocene catalyst. ) Is obtained by injection molding.

Here, the α-olefin having 3 to 20 carbon atoms includes propylene, 1-butene, 1-pentene,
1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,
Examples thereof include 1-octadecene and 1-eicosene.

In the ethylene polymer (A), the constituent units derived from ethylene are present in a proportion of 55 to 100% by weight, preferably 65 to 100% by weight, more preferably 70 to 100% by weight, and contain carbon atoms. The constituent unit derived from the α-olefin having a number of 3 to 20 is desirably present in a proportion of 0 to 45% by weight, preferably 0 to 35% by weight, more preferably 0 to 30% by weight.

In the present invention, the composition of the ethylene polymer is ¹³
Determined by C-NMR spectrum. The ¹³ C-NMR spectrum of an ethylene polymer is usually determined by dissolving approximately 200 mg of a sample uniformly in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube, at a measurement temperature of 120 ° C., a measurement frequency of 25.05 MHz, a spectrum width of 1500 Hz, and a pulse. It is measured under the conditions of a repetition time of 4.2 sec. And a pulse width of 6 μsec.

Such an ethylene polymer (A) has a density of 0.940 to 0.970 g / cm ³ , preferably 0.945 to 0.970 g / cm ³ , more preferably 0.950 to 0.5 g / cm ³ . 965 g / cm ³ , and the melt flow rate is 0.05 to 100 g / 10 min, preferably 0.1 to 50 g / 10 min, and more preferably 0.5 to 2 g.
It is desirable to be in the range of 0 g / 10 minutes.

In the present invention, the density of the ethylene polymer is determined by measuring the melt flow rate measured at 190 ° C. under a load of 2.16 kg at a melt flow rate of 120 ° C. for 1 hour, and gradually cooling to room temperature over 1 hour. , Measured with a density gradient tube.

The ethylene polymer has a melt flow rate of 190 according to ASTM D1238-65T.
It is measured at 2.degree. C. under a load of 2.16 kg. The ethylene-based polymer (A) having the above-mentioned properties is, for example, in the presence of a metallocene catalyst as described below, so that the density of the polymer from which ethylene can be obtained is 0.940 to 0.970 g / cm ^3. Or homopolymerized, or the density of the copolymer to obtain ethylene and α-olefin 0.940 ~
It can be manufactured by copolymerizing to 0.970 g / cm ³ .

The polyethylene forming the polyethylene injection-molded article according to the present invention has a density of 0.940 to 0.97.
0 g / cm ³ and the melt flow rate is
It is sufficient that the polyethylene is in the range of 0.05 to 100 g / 10 minutes. Examples of such polyethylene include the following ethylene polymer (B) and the following ethylene polymer (C).
And an ethylene polymer composition comprising:

The ethylene polymer (B) is an ethylene homopolymer or a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. 3 carbon atoms
Examples of the α-olefin of Nos. 20 to 20 include the same α-olefins as described above.

In the ethylene polymer (B), the constituent units derived from ethylene are present in a proportion of 55 to 100% by weight, preferably 65 to 100% by weight, more preferably 70 to 100% by weight, and contain carbon atoms. The constituent unit derived from the α-olefin having a number of 3 to 20 is desirably present in a proportion of 0 to 45% by weight, preferably 0 to 35% by weight, more preferably 0 to 30% by weight.

The density of the ethylene polymer (B) is 0.9
50 to 0.980 g / cm ³ , preferably 0.955 to
0.980 g / cm ³ , more preferably 0.960 to
It is in the range of 0.980 g / cm ³ and the melt flow rate is 0.01 to 1000 g / 10 min, preferably 0.0
2 to 500 g / 10 min, more preferably 0.03 to 300
g / 10 minutes.

The ethylene polymer (C) is a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the α-olefin having 3 to 20 carbon atoms include the same α-olefins as described above.

In the ethylene polymer (C), the constituent units derived from ethylene are present in a proportion of 55 to 99% by weight, preferably 65 to 98% by weight, more preferably 70 to 96% by weight, and contain carbon atoms. The constituent unit derived from the α-olefin having 3 to 20 is 1 to 45% by weight, preferably 2 to 45% by weight.
It is desirably present at a rate of about 35% by weight, more preferably 4% to 30% by weight.

The density of the ethylene polymer (C) is 0.9
10 to 0.965 g / cm ³ , 0.915 to 0.960
g / cm ^3, in the range of 0.920~0.955g / cm ^3, melt flow rate, 0.0003～35G
/ 10 min, 0.0004-10 g / 10 min, 0.0005-
It is desirable to be in the range of 1.0 g / 10 minutes.

The ethylene-based polymer composition for forming the polyethylene injection-molded article according to the present invention comprises the ethylene-based polymer (B) and the ethylene-based polymer (C). B) is 20 to 90% by weight, preferably 30 to 80% by weight, more preferably 40 to 75% by weight.
% By weight, and the ethylene-based polymer (C) contained 1% by weight.
It is desirably contained in an amount of 0 to 80% by weight, preferably 20 to 70% by weight, more preferably 25 to 60% by weight.

The ethylene-based polymer (B) and the ethylene-based polymer (C) have a difference between the density (d _B ) of the ethylene-based polymer ( _B ) and the density (d _C ) of the ethylene-based polymer (C). The ratio (d _B / d _C ) is greater than 1, preferably 1.
005 to 1.08 are used in combination.

The ethylene polymer composition has a density of 0.9.
40 to 0.970 g / cm ³ , preferably 0.945 to 0.945 g / cm ³
0.970 g / cm ³ , more preferably 0.950 to
0.965 g / cm ³ , and the melt flow rate is 0.05 to 100 g / 10 min, preferably 0.1 to 100 g / 10 min.
It is desirable to be in the range of 50 g / 10 min, more preferably 0.5 to 20 g / 10 min.

In the ethylene polymer composition, the ethylene polymer (B) and the ethylene polymer (C) are selected so as to satisfy the above-mentioned properties, and are blended by a known method or by polymerization. Can be manufactured directly.

The blending method is as follows: (1) Ethylene polymer (B), ethylene polymer (C) and other components to be added as required
A method of blending using a kneader or the like.

(2) Ethylene polymer (B), ethylene polymer (C) and other optional components
A suitable good solvent (eg; hexane, heptane, decane,
A solvent such as cyclohexane, benzene, toluene and xylene) and then removing the solvent.

(3) A solution is prepared by separately dissolving the ethylene polymer (B), the ethylene polymer (C) and other components to be added, if necessary, in a suitable good solvent, and then mixing. How to remove.

(4) A method of combining the above methods (1) to (3), and the like. As a method for directly producing an ethylene-based polymer composition composed of an ethylene-based polymer (B) and an ethylene-based polymer (C) by polymerization, for example, by a two-stage polymerization process, the ethylene-based polymer (B) And polymerizing the ethylene-based polymer (C) in the subsequent stage, or polymerizing the ethylene-based polymer (C) in the preceding stage and polymerizing the ethylene-based polymer (B) in the subsequent stage. it can.

Further, using a plurality of polymerizers, the ethylene polymer (B) is polymerized in one of the polymerizers, and then the ethylene polymer (B) is polymerized in the other polymerizer in the presence of the ethylene polymer (B). The polymer (C) is polymerized, or the ethylene polymer (C) is polymerized in one polymerization vessel, and then the ethylene polymer (C) is polymerized in the other polymerization vessel in the presence of the ethylene polymer (C). It can also be produced by polymerizing B).

Preparation of Ethylene Polymer Ethylene polymer (A), Ethylene polymer (B)
And the ethylene-based polymer (C) are produced using a metallocene catalyst. In the present invention, [I] a transition metal compound having a specific structure, [II] the transition metal compound [I] (II-1) an organoaluminum compound, (II-
2) a carrier-supported metallocene comprising: aluminoxane; and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair, and [III] a fine particle carrier. A catalyst can be used.

Each component forming such a catalyst will be described. As the transition metal compound [I], for example, a bridged metallocene compound represented by the following general formula (i) can be used.

[0045]

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In the formula, M represents a transition metal atom belonging to Groups 4 to 6 of the periodic table, and specifically, titanium, zirconium,
Hafnium, vanadium, niobium, tantalum, chromium,
Molybdenum or tungsten, preferably titanium, zirconium or hafnium, particularly preferably zirconium.

R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other and include a hydrogen atom, a halogen atom,
1-20 carbon atoms which may be substituted by halogen
A hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and a part of adjacent groups is bonded to form a ring together with a carbon atom to which those groups are bonded. It may be formed. Note that R ^{1 to} R ⁴ represented by two each indicate that when they are combined to form a ring, they are preferably combined with each other by a combination of the same symbols, for example, R ¹ and R ¹ Indicate that it is preferable to combine with and to form a ring.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl , Octyl, nonyl, dodecyl,
Alkyl groups such as eicosyl, norbornyl, adamantyl, vinyl, propenyl, alkenyl groups such as cyclohexenyl, benzyl, phenylethyl, arylalkyl groups such as phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, And aryl groups such as biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like.

Further, these hydrocarbon groups may be substituted with halogen. The ring formed by combining R ^{1 to} R ⁴ includes a benzene ring, a naphthalene ring, an acenaphthene ring,
Fused rings such as indene rings, benzene rings, naphthalene rings,
Examples include an alkyl group such as methyl, ethyl, propyl, and butyl, and a group in which a hydrogen atom on a condensed ring group such as an acenaphthene ring and an indene ring is substituted with halogen.

Examples of the silicon-containing group include monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl and triphenylsilyl. Trialkyl-substituted silyls such as dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; hydrocarbon-substituted silyl silyl ethers such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon such as trimethylphenyl And a substituted aryl group.

Examples of the oxygen-containing group include a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy and butoxy, an alloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, and an arylalkoxy group such as phenylmethoxy and phenylethoxy. No.

Examples of the sulfur-containing group include a substituent in which the oxygen of the oxygen-containing compound has been replaced by sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate. , Sulfonate groups such as trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p -Sulfinate groups such as toluenesulfinate, trimethylbenzenesulfinate and pentafluorobenzenesulfinate.

Examples of the nitrogen-containing group include an amino group, methylamino, dimethylamino, diethylamino, an alkylamino group such as dipropylamino, dibutylamino and dicyclohexylamino, phenylamino, diphenylamino, ditolylamino, dinaphthylamino and methylphenylamino. And an arylamino group or an alkylarylamino group.

Examples of the phosphorus-containing group include dimethylphosphino, diphenylphosphino and the like. X ¹ and X ² may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with halogen, an oxygen-containing group, a sulfur-containing group or It is a nitrogen-containing group. Specific examples of these atoms or groups include the same atoms and groups as those described for R ^{1 to} R ⁴ .

Y is a divalent hydrocarbon group, a divalent silicon-containing group or a divalent germanium-containing group. Specifically, as the divalent hydrocarbon group, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-
Alkylene groups such as trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene; and arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene.

Examples of the divalent silicon-containing group include methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, Alkylsilylenes such as di (p-tolyl) silylene and di (p-chlorophenyl) silylene, alkylarylsilylenes, arylsilylene groups, and alkyldisilylenes such as tetramethyl-1,2-disilylene and tetraphenyl-1,2-disilylene , An alkylaryldisilylene group, an aryldisilylene group, and the like.

Examples of the divalent germanium-containing group include compounds in which silicon of the above-mentioned divalent silicon-containing group is substituted with germanium. Such a transition metal compound [I]
Examples thereof include dimethylsilylene-bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis ( Trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene- (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene-bis (1
-n-butyl-3-methylcyclopentadienyl) zirconium dichloride, ethylene- (pentamethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, etc. No.

In the above examples, disubstituted cyclopentadienyl rings include 1,2- and 1,3-substituted. In addition, a transition metal compound in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten in the above zirconium compound can also be used.

Among the transition metal compounds represented by the general formula (i), a transition metal compound represented by the following general formula (ia) is preferable.

[0060]

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Wherein M, R ¹ , R ³ , X ¹ , X ² and Y are the same as in the formula (i), and R ^{22 to} R ²⁵ and R ⁴¹
To R ⁴⁴ may be the same or different from each other, a hydrogen atom, a halogen atom, an alkyl group or an aryl group, the alkyl group or aryl group may be substituted by halogen or an organic silyl group. As the compound represented by the formula (ia), more specifically, dimethylsilylene-bis (indenyl) zirconium dichloride, dimethylsilylene-bis (indenyl) zirconium dibromide, dimethylsilylene-
Bis (indenyl) dimethylzirconium, dimethylsilylene-bis (indenyl) diphenylzirconium,
Dimethylsilylene-bis (indenyl) methylzirconium monochloride, dimethylsilylene-bis (indenyl) zirconium bis (methanesulfonate), dimethylsilylene-bis (indenyl) zirconium bis (p
-Toluenesulfonate), dimethylsilylene-bis (indenyl) zirconiumbis (p-toluenesulfonate), dimethylsilylene-bis (indenyl) zirconiumbis (trifluoromethanesulfonate),
Dimethylsilylene-bis (indenyl) zirconium trifluoromethanesulfonate, dimethylsilylene-
Bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene-bis (2-methylindenyl) zirconium dichloride, dimethylsilylene-bis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethyl Silylene- (indenyl) (fluorenyl) zirconium dichloride, dimethylsilylene-
Bis (fluorenyl) zirconium dichloride, diphenylsilylene-bis (indenyl) zirconium dichloride, methylphenylsilylene-bis (indenyl) zirconium dichloride, ethylene-bis (indenyl)
Dimethyl zirconium, ethylene-bis (indenyl)
Zirconium dichloride, ethylene-bis (indenyl) zirconium bis (trifluoromethanesulfonate), ethylene-bis (indenyl) zirconium bis (methanesulfonate), ethylene-bis (indenyl) zirconium bis (p-toluenesulfonate) , Ethylene-bis (indenyl) zirconium bis (p-chlorobenzenesulfonate), ethylene-bis (2-methylindenyl) zirconium dichloride, isopropylidene-bis (indenyl) zirconium dichloride, isopropylidene-bis (2-methyl Indenyl)
Zirconium dichloride, dimethylsilylene-bis (4,5
-Benzoindenyl) zirconium dichloride, dimethylsilylene-bis (2-methyl-4,5-benzoindenyl) zirconium dichloride, dimethylsilylene- (2-methyl-
4,5-benzoindenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, ethylene-bis (2-methyl-4,5-benzoindenyl) zirconium dichloride, methylene-bis (2- Methyl-4-phenylindenyl)
Zirconium dichloride, ethylene-bis (2-methyl-4-
Phenylindenyl) zirconium dichloride, dimethylsilylene-bis (2-ethyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene-bis (2-ethyl-4- (α-naphthyl) indenyl) zirconium dichloride, ethylene-bis ( 2-ethyl-4-phenylindenyl) zirconium dichloride, ethylene-bis (2-ethyl-4- (α-naphthyl) indenyl) zirconium dichloride, ethylene-bis (2-n-propyl-4- (α-naphthyl) Indenyl) zirconium dichloride, ethylene-
Bis (2,4,7-trimethylindenyl) zirconium dichloride, isopropylidene-bis (2,4,7-trimethylindenyl) zirconium dichloride and the like can be mentioned.

Further, in the above-mentioned zirconium compounds, transition metal compounds in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten can also be mentioned.

In the present invention, a non-bridged metallocene compound represented by the following general formula (ii) or (iii) can also be used as the transition metal compound [I].

[0064]

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In the formula, M, X ¹ and X ² are the same as those in the general formula (i). R ^{5 to} R ⁹ may be the same or different, and at least two of them are methyl or ethyl, and the others are hydrogen atoms.

R ^{10 to} R ¹⁴ may be the same or different, and at least two of them are methyl or ethyl, and the others are hydrogen atoms. Specific examples of the compound represented by the general formula (ii) include bis (1,3-
Dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-diethylcyclopentadienyl) zirconium dichloride, bis (1-ethyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1,2,3-
Trimethylcyclopentadienyl) zirconium dichloride, bis (1,2,4-trimethylcyclopentadienyl)
Zirconium dichloride, (1,3-dimethylcyclopentadienyl) (1,3-diethylcyclopentadienyl) zirconium dichloride and the like can be mentioned.

Further, in the above-mentioned zirconium compounds, transition metal compounds in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten can also be mentioned.

[0068]

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In the formula, M, X ¹ and X ² are the same as those in the general formula (i). R ^{15 to} R ¹⁹ may be the same or different, and four of them are methyl or ethyl, and the other is a hydrogen atom, or five are methyl or ethyl.

R ²⁰ and R ²¹ may be the same or different and are an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-
Butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl and the like.

Specific examples of the compound represented by the general formula (iii) include (pentamethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride and (pentaethylcyclopentadienyl) (cyclopentadienyl). (Dienyl) zirconium dichloride, (pentamethylcyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (pentamethylcyclopentadienyl) (butylcyclopentadienyl) zirconium dichloride, (pentamethylcyclopentadienyl) (1,3-dimethylcyclopentadienyl) zirconium dichloride, (pentamethylcyclopentadienyl)
(1-butyl-3-methylcyclopentadienyl) zirconium dichloride and the like.

Further, a transition metal compound in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten in the above-mentioned zirconium compound can also be used.

Among these, those having a 5-substituted cyclopentadienyl ring and an unsubstituted cyclopentadienyl ring are particularly preferred. Compound [II] capable of activating the above transition metal compound [I] (hereinafter also referred to as “component [II]”)
(II-1) organoaluminum compound, (II-2)
Aluminoxane and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair are used.

The organoaluminum compound (II-1) (hereinafter also referred to as “component (II-1)”) is represented by, for example, the following general formula (iv). During ^{_{R a n AlX 3-n ...}} (iv) ( wherein, R ^a represents a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, n represents 1
3. ) In formula (iv), R ^a is the number of carbon atoms 1 to 1
2 hydrocarbon groups such as an alkyl group, a cycloalkyl group or an aryl group, specifically, methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl, tolyl And so on.

Such an organoaluminum compound (II-
1) is, specifically, trimethylaluminum,
Triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, trialkylaluminum such as tri-2-ethylhexylaluminum, alkenylaluminum such as isoprenylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, Dialkylaluminum halides such as dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, alkylaluminum sesquichlorides such as ethylaluminum sesquibromide, methylaluminum dichloride Ethylaluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide,
Examples thereof include alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum compound (II-1), a compound represented by the following general formula (v) can also be used. ^{_{R a n AlY 3-n ...}} (v) ( wherein, R ^a is as defined above, Y is -OR ^b group, -
OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -S
iR ^f ₃ or —N (R ^g ) AlR ^h ₂ ; n is 1 to 2; R ^b , R ^c , R ^d and R ^h are methyl,
Ethyl, isopropyl, isobutyl, cyclohexyl,
Phenyl and the like, ^Re is a hydrogen atom, methyl, ethyl, isopropyl, phenyl, trimethylsilyl and the like, and ^Rf and ^Rg are methyl, ethyl and the like. Specific examples include the following compounds. (1) Compounds represented by R ^a _n Al (OR ^b ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, and (2) R ^a _n Al (OSiR ^c ₃ ) _{3 -n} , for example, Et ₂ Al (OSiMe ₃ ), (iso-
(Bu) ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (O
SiEt ₃₎ such _{^{as, (3) R a n Al}} (OAlR d 2) 3-n
For example, Et ₂ AlOAAlE
t ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) _2, etc.
_{^{(4) R a n Al (}} NR e 2) a compound represented by _{3-n, e.g., Me 2 AlNEt 2, Et 2} AlNHMe, M
e ₂ AlNHEt, Et ₂ AlN (SiMe ₃ ) ₂ , (i
so-Bu) ₂ AlN (such as _{SiMe 3) 2, (5)} R a n
A compound represented by Al (SiR ^f ₃ ) _3-n , for example,
(6) R ^a _n Al such as (iso-Bu) ₂ AlSi Me ₃
^{(N (R g) AlR h} 2) a compound represented by _{3-n, e.g., Et 2 AlN (Me) AlEt} 2, (iso-Bu) 2
AlN (Et) Al (iso-Bu) ₂ etc.

Of these, the general formulas ^Ra ₃ Al, ^{Ra
_{n Al (OR b) 3-}} n, R a n Al (OAlR d 2) 3-n
The compound represented by is particularly preferable, and a compound in which ^Ra is an isoalkyl group and n = 2 is particularly preferable.

The organoaluminum compound (II-1) can be used alone or in combination of two or more.
The aluminoxane (II-2) (hereinafter also referred to as “component (II-2)”) may be a conventionally known benzene-soluble aluminoxane, or a benzene as disclosed in JP-A-2-276807. It may be an insoluble organic aluminum oxy compound.

The aluminoxane as described above can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, for example, magnesium chloride hydrate, copper sulfate hydrate,
An organic aluminum compound such as trialkylaluminum is added to a suspension of a hydrocarbon medium such as aluminum sulfate hydrate, nickel sulfate hydrate, or cerous chloride hydrate, and the adsorbed water or water of crystallization is added to the suspension. A method of reacting with an aluminum compound. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used for producing the aluminoxane include the same compounds as those described above as the organoaluminum compound (II-1).

Of these, trialkyl aluminum and tricycloalkyl aluminum are particularly preferred. Organoaluminum compounds can be used in combination.

Solvents used in the production of aluminoxane include benzene, toluene, xylene, cumene,
Aromatic hydrocarbons such as cymene, pentane, hexane, heptane, octane, decane, dodecane, hexadecane,
Aliphatic hydrocarbons such as octadecane, cyclopentane,
Alicyclic hydrocarbons such as cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil; and halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially chlorinated compounds And hydrocarbon solvents such as bromides. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

In the benzene-insoluble organic aluminum oxy compound, the Al component soluble in benzene at 60 ° C. is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. Insoluble or poorly soluble.

The solubility of such an organoaluminum oxy compound in benzene is determined by comparing the solubility of the organoaluminum oxy compound with 100 milligram atoms of Al to 10 mg.
After suspending in 0 ml of benzene and mixing at 60 ° C. for 6 hours with stirring, the mixture was filtered while hot at 60 ° C. using a G-5 glass filter equipped with a jacket, and the solid part separated on the filter was removed by 60 ° C. After washing four times with 50 ml of benzene at 50 ° C., the amount of Al atoms present in the total filtrate (x
Mmol) (x%).

The aluminoxane (II-2) can be used alone or in combination of two or more. The compound (II-3) (hereinafter also referred to as “component (II-3)”) which forms an ion pair by reacting with the transition metal compound [I] includes:
JP-A-1-501950, JP-A-1-50203
No. 6, JP-A-3-179005, JP-A-3-179005
JP 179006, JP-A-3-207703,
JP-A-3-207704, USP-532110
The Lewis acids, ionic compounds and carborane compounds described in the specification of No. 6, etc. can be exemplified.

As the Lewis acid, triphenylboron,
Tris (4-fluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-
Dimethylphenyl) boron, tris (pentafluorophenyl) boron, MgCl ₂ , Al ₂ O ₃ , SiO ₂ -A
l ₂ O _{3 and the} like.

Examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, and ferrocarbon. Cenium tetra (pentafluorophenyl) borate and the like can be mentioned.

Examples of the carborane compound include dodecaborane, 1-carboundecaborane, bis-n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarboundeca) borate, and tri-n-butylammonium (Trideca hydride-7-carboundeca) borate and the like.

These components (II-3) can be used alone or in combination of two or more. As the compound [II] capable of activating the transition metal compound [I], the components (II-1), (II-2) and (II-
Two or more compounds selected from 3) can be used in combination.

[III] The carrier has a particle size of 10 to 300.
μm, preferably 20 to 200 μm
Particulate solids are used. As this carrier, there is no porous material.
Organic oxides are preferably used, specifically, SiO 2 _Two, A
l_TwoO_Three, MgO, ZrO_Two, TiO_Two, B_TwoO_Three, Ca
O, ZnO, BaO, ThO_TwoEtc or a mixture of these
Object, eg SiO_Two-MgO, SiO_Two-Al _TwoO_Three, Si
O_Two-TiO_Two, SiO_Two-V_TwoO_Five, SiO_Two-Cr_TwoO_Three,
SiO_Two-TiO_Two-MgO or the like is used. Among these
Then, SiO_TwoAnd / or Al _TwoO_ThreeThe main component
Are preferred.

The above inorganic oxide contains a small amount of Na ₂ CO.
₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ S
O ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg
(NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li
Carbonates such as ₂ O, sulfates, nitrates and oxide components may be contained.

The properties of the carrier [III] vary depending on the kind and the production method, but the specific surface area is 50 to 1000 m.
² / g, more preferably 100 to 700 m ² / g, and those having a pore volume of 0.3 to 2.5 cm ³ / g are preferably used.

Such an inorganic carrier may be used, if necessary,
It can be used after firing at 0 to 1000 ° C, preferably 150 to 700 ° C. The amount of water adsorbed on the carrier [III] is
It is preferably less than 1.0% by weight, more preferably 0.1% by weight.
More preferably, it is less than 5% by weight. Further, the surface hydroxyl group is preferably at least 1.0% by weight, more preferably 1.5 to 4.0% by weight, and particularly preferably 2.0 to 3.5% by weight.

Here, the amount of water adsorbed on the carrier (% by weight) is 2
The weight loss when dried at a temperature of 00 ° C. for 4 hours under a normal pressure and a nitrogen flow is determined as the amount of adsorbed water. The amount of surface hydroxyl groups (% by weight) of the carrier is 200 ° C. at normal pressure,
The weight of the carrier obtained by drying under nitrogen flow for 4 hours is X
(G), and the weight of the calcined product obtained by calcining the carrier at 1000 ° C. for 20 hours and having no surface hydroxyl groups obtained is represented by Y
(G) can be calculated by the following equation.

Surface hydroxyl group content (% by weight) = {(XY) / X} × 100 An organic compound can also be used as the carrier [III]. For example, ethylene, propylene, 1-butene, 4-methyl Use of (co) polymers mainly composed of α-olefins having 2 to 14 carbon atoms such as -1-pentene or polymers or copolymers mainly composed of vinylcyclohexane and styrene Can be.

The catalyst preferably used for producing the ethylene-based polymer (A), the ethylene-based polymer (B) and the ethylene-based polymer (C) includes the above-mentioned carrier [III] and a transition metal compound [I ] And the component [II] are supported on a carrier-supported metallocene catalyst (solid catalyst).

[0098] This solid catalyst comprises the components [I] and [II]
And the carrier [III] can be prepared by bringing the component [II] into contact with the carrier [III] in any order.
And then mixed contact with the transition metal compound [I].

Each of these components can be brought into contact in an inert hydrocarbon solvent. Examples of the solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and hexadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and cyclooctane;
Aromatic hydrocarbons such as benzene, toluene and xylene,
Halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, petroleum fractions such as gasoline, kerosene and light oil, and mixtures thereof can be used.

In preparing a catalyst from each of these components, the transition metal compound [I] is used in an amount of usually 5 × 10 ^{-6 to} 5 × 10 ^-4 mol, preferably 10 ^-5 to 2 mol per 1 g of the carrier [III].
× 10 ^- used ⁴ molar quantities. In the component [II], the atomic ratio (Al or B / transition metal) of the transition metal compound [I] to aluminum or boron of the component [II] to the transition metal is usually 10 to 500, preferably 20 to 200. Used in quantity. When organoaluminum compound (II-1) and aluminoxane (II-2) are used as component [II], aluminum atom (Al-1) in component (II-1) and aluminum atom (Al-2) in component (II-2) Aluminum atom (Al-
It is desirable that the compound be used in such an amount that the atomic ratio (Al-1 / Al-2) of 2) becomes 0.02 to 3, more preferably 0.05 to 1.5.

These components are usually used at -50 to 150 ° C.
Preferably at a temperature of -20 to 120 ° C, usually for 1 minute to 50
The contact is carried out for a time, preferably 10 minutes to 25 hours. The solid catalyst prepared as described above has a transition metal compound [I] of 5 × 1 as a transition metal atom per 1 g of the support [III].
It is preferably carried in an amount of 0 ^{-6 to} 5 × 10 ^-4 gram atoms, and more preferably in an amount of 10 ^-5 to 2 × 10 ^-4 gram atoms. The component [I
I] is preferably carried in an amount of 10 ^{−3 to} 5 × 10 ⁻² gram atoms as aluminum or boron atoms per 1 g of the support [III], and more preferably 2 × 10 ⁻³ to 2 × 10 ^−2.
It is preferably carried in an amount of × 10 ^-2 gram atoms.

For the production of the ethylene-based polymer (A), the ethylene-based polymer (B) and the ethylene-based polymer (C), the above-mentioned solid catalyst can be used as it is. Can be used after preliminarily polymerizing to form a prepolymerized catalyst.

The prepolymerized catalyst is composed of the above components [I] to [II]
In the presence of [I], it can be usually prepared by prepolymerizing an olefin in an inert hydrocarbon solvent.
Preferably, a solid catalyst is formed from each of the components [I] to [III]. In addition to this solid catalyst, component [II] may be further added.

In the prepolymerization, the transition metal compound [I]
Is usually 5 × 10 ^{−6 to} 5 × 10 ⁶ per 1 g of the carrier [III].
^-4 mol, preferably 10 ^-5 to 2 × 10 ^-4 mol. The component [II] is an atomic ratio of aluminum or boron in the component [II] to the transition metal in the transition metal compound [I] (Al or B / transition metal) and is usually 10 to 5%.
00, preferably from 20 to 200. When the organoaluminum compound (II-1) and the aluminoxane (II-2) are used as the component [II], the aluminum atom (Al-1) in (II-1) and the aluminum atom in (II-2) The atomic ratio (Al-1 / Al-2) of (Al-2) is 0.0
It is preferably used in an amount of 2 to 3, more preferably 0.05 to 1.5.

The concentration of the transition metal compound [I] or the solid catalyst formed from each component in the prepolymerization system is usually 10 ^-6 in terms of transition metal per liter of polymerization volume.
It is desirable that the amount be from ² to ^10-2 mol, more preferably from 5 x ^10-5 to ^10-2 mol.

The prepolymerization is carried out at a temperature of usually -20 to 60 ° C, preferably 0 to 50 ° C, for 0.5 to 100 hours, preferably for about 1 to 50 hours. As the prepolymerized olefin, ethylene and an α-olefin having 3 to 20 carbon atoms as described above can be used, and these may be copolymerized.

As the prepolymerization catalyst, an olefin may be introduced into a solid catalyst suspension prepared using an inert hydrocarbon solvent, or the solid catalyst formed in the inert hydrocarbon solvent may be converted from the suspension. After separation, the suspension may be suspended again in an inert hydrocarbon and the olefin may be introduced into the resulting suspension.

Preliminary polymerization produces an olefin polymer (prepolymer) in an amount of 0.1 to 500 g, preferably 0.2 to 300 g, more preferably 0.5 to 200 g per 1 g of the carrier [III]. Is desirable.

In the prepolymerized catalyst thus obtained, the transition metal compound [I] is about 5 × 10 ^{-6 to} 5 × 10 ^-4 gram atom, preferably 10 ^-5 gram atom as the transition metal per 1 g of the support [III]. In an amount of ~ 2 x 10 ^-4 gram atoms, the component [I
I] is the molar ratio of aluminum or boron in component [II] to transition metal (Al or B / transition metal), 5
It is desirable that the catalyst is carried in an amount of from 200 to 200, and more preferably from 10 to 150.

The prepolymerization can be carried out either batchwise or continuously, and can be carried out under reduced pressure, normal pressure or increased pressure. In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of 0.2 to 7 dl / g, preferably 0.1 μm, in the presence of hydrogen.
It is desirable to produce a prepolymer of about 5 to 5 dl / g.

In the production of the ethylene polymer (A) and the ethylene polymer (B), ethylene is homopolymerized in the presence of the solid catalyst or the prepolymerization catalyst as described above, or ethylene and another α- Copolymerize with olefin.
In the production of the ethylene-based polymer (C), ethylene and another α-polymer are added in the presence of a solid catalyst or a prepolymerization catalyst as described above.
-Copolymerize with the olefin.

This (main) polymerization is carried out in a slurry liquid phase or gas phase. In slurry polymerization, an inert hydrocarbon may be used as a solvent, or an olefin itself may be used as a solvent. Specific examples of the inert hydrocarbon solvent used in slurry polymerization include the same as described above. Among these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferred.

The polymerization can be carried out in any of a batch system, a semi-continuous system and a continuous system.
In the (main) polymerization, the solid catalyst or the prepolymerized catalyst is usually a transition metal / liter (polymerization volume) of 10 ^-8 to 10 ^-3 gram atom / liter, and more preferably 10 ^-7 to 10 ^-4 gram atom / liter. It is desirable to use it in such an amount that

In the main polymerization carried out using a prepolymerization catalyst, component [II] not supported on a carrier may be added. Component [II] is based on the atomic ratio of aluminum or boron in component [II] to transition metal (Al or B /
Transition metal), 5 to 300, preferably 10 to 200,
More preferably, it can be used in an amount of 15 to 150.

The (main) polymerization can be carried out usually at a temperature of -50 to 200 ° C, preferably 0 to 100 ° C.
In particular, when the ethylene polymer (A) is produced by a slurry polymerization method, it is usually 0 to 200 ° C, preferably 20 to 200 ° C.
It is desirable to carry out the polymerization at a temperature of 150 ° C, and when producing by a gas phase polymerization method, it is desirable to carry out the polymerization at a temperature of usually 50 to 120 ° C, preferably 60 to 110 ° C.

When the ethylene polymer (B) is produced by the slurry polymerization method, it is desired that the polymerization is usually carried out at a temperature of 0 to 200 ° C., preferably 20 to 150 ° C. It is desirable that the polymerization is carried out at a temperature of usually 50 to 120 ° C, preferably 60 to 110 ° C.

When the ethylene-based polymer (C) is produced by the slurry polymerization method, it is usually in the range of 0 to 200 ° C., preferably 20 to 150 ° C .; 50 to 120 ° C, preferably 60 to 11
It is desirable to polymerize at a temperature of 0 ° C.

The polymerization pressure is usually from normal pressure to 100 kg / cm.
² , preferably under normal pressure to 50 kg / cm ² . The density and melt flow rate (molecular weight) of each obtained ethylene-based polymer can be adjusted by a conventionally known method such as adjusting the amount of comonomer, making hydrogen exist in the polymerization system, or changing the polymerization temperature and polymerization pressure. can do.

The polyethylene injection-molded article of the present invention can be obtained by injection-molding the above-mentioned ethylene polymer (A) or ethylene polymer composition. The polyethylene injection molded article of the present invention can be manufactured by a conventionally known injection molding apparatus. As the molding conditions, conventionally known conditions can be adopted.

The polyethylene injection-molded article of the present invention may contain a weather-resistant stabilizer, a heat-resistant stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, an anti-fog agent, a lubricant, Additives such as pigments, dyes, nucleating agents, plasticizers, antioxidants, hydrochloric acid absorbents, antioxidants and the like may be added as necessary.

The polyethylene injection-molded product thus obtained, for example, a container, a pallet or the like has excellent rigidity and mechanical strength.

[0122]

The injection molded article made of polyethylene according to the present invention comprises:
The polymer is polymerized by the metallocene catalyst, has a narrow molecular weight distribution, and is injection-molded with an ethylene polymer having specific physical properties, and therefore has excellent mechanical strength.

[0123]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

In the present invention, an ethylene polymer,
Evaluation of the physical properties of the ethylene-based polymer or the ethylene-based polymer composition is performed as follows. [IZ impact test]
The test was performed according to JIS K7110.

[0125]

[Catalyst Preparation Example 1] Preparation of a solid catalyst component 3.0 g of silica dried at 250 ° C for 10 hours was 50 ml.
And then cooled to 0 ° C. Thereafter, a toluene solution of methylaluminoxane (Al = 1.
17.8 ml were added dropwise over 30 minutes. At this time, the temperature in the system was kept at 0 ° C. Continue 0
C. for 30 minutes, then heated to 95.degree. C. over 30 minutes and reacted at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method.

The solid component thus obtained was washed twice with toluene and then resuspended in 50 ml of toluene. 22.2 m of a toluene solution of bis (1,3-methyl, p-tolyl-cyclopentadienyl) zirconium dichloride (Zr = 0.00517 mmol / ml) was introduced into the system.
1 was added dropwise at 20 ° C. over 30 minutes. Next, the temperature was raised to 80 ° C., and the reaction was performed at that temperature for 2 hours. Then, the supernatant was removed and washed twice with hexane to obtain 1 g.
A solid catalyst containing 2.3 mg per zirconium was obtained.

Preparation of Prepolymerized Catalyst (a-1) 4 g of the solid catalyst obtained above was resuspended in 200 ml of hexane. 5.0 ml of a decane solution of triisobutylaluminum (1 mmol / ml) was added to the system, and 35
Preliminary polymerization of ethylene at 2 ° C. for 2 hours gave a prepolymerized catalyst (a-1) containing 2.2 mg of zirconium per gram of solid catalyst and prepolymerized with 3 g of polyethylene.

[0128]

[Catalyst Preparation Example 2] Preparation of Prepolymerized Catalyst (a-2) In Preparation Example 1, bis (indenyl) zirconium dichloride was used in place of bis (1,3-methyl, p-tolyl-cyclopentadienyl) zirconium dichloride. A solid catalyst and then a prepolymerized catalyst (a-2) were prepared in the same manner as in Preparation Example 1 except for using.

[0129]

[Catalyst Preparation Example 3] Preparation of Prepolymerized Catalyst (a-3) Preparation Example 1 was the same as Preparation Example 1, except that bis (2-methylindenyl) zirconium dichloride was used in place of bis (indenyl) zirconium dichloride. A solid catalyst and then a prepolymerized catalyst (a-3) were prepared in the same manner as described above.

[0130]

Example 1 Production of Ethylene Polymer (A-1) [Polymerization] Into a 2-liter stainless steel autoclave sufficiently purged with nitrogen, 1 liter of dehydrated and purified hexane was charged. ° C and replaced with a mixed gas of ethylene and hydrogen (hydrogen content: 0.05 mol%).

Next, 1.5 ml of a decane solution of triisobutylaluminum (1 mmol / ml) and the prepolymerized catalyst (a-1) prepared as described above were added to the system in an amount of 0.45 mg in terms of zirconium atoms. Was added.

Thereafter, a mixed gas of ethylene and hydrogen having the same composition as described above was introduced, and polymerization was started at a total pressure of 8 kg / cm ² -G. After that, replenish only the mixed gas,
While maintaining the total pressure at 8 kg / cm ² -G, polymerization was carried out at 80 ° C. for 1.5 hours.

After completion of the polymerization, the polymer was filtered and dried at 80 ° C. overnight. As a result, the melt flow rate (MFR) measured at 190 ° C. under a load of 2.16 kg was 0.028.
g / 10 minutes, and 115.5 g of an ethylene polymer (A-1) having a density of 0.953 g / cm ³ was obtained.

[0134]

Example 2 Production of ethylene polymer (A-2) Example 1 was repeated except that the prepolymerized catalyst (a-2) was used in place of the prepolymerized catalyst (a-1). Similarly, ethylene was polymerized.

As a result, 241.0 g of an ethylene polymer (A-2) having an MFR of 1.3 g / 10 min and a density of 0.955 g / cm ³ was obtained.

[0136]

Example 3 Production of Ethylene Polymer (A-3) In Example 1, instead of using a mixed gas of ethylene and hydrogen having a hydrogen content of 0.05 mol%, a mixed gas of ethylene and hydrogen having a hydrogen content was used. Ethylene was polymerized in the same manner as in Example 1 except that 0.07 mol% was used.

As a result, 250.5 g of an ethylene polymer having an MFR of 4.7 g / 10 min and a density of 0.961 g / cm ³ was obtained.

[0138]

Example 4 Production of Ethylene Polymer (A-4) Example 3 was repeated except that the prepolymerized catalyst (a-3) was used in place of the prepolymerized catalyst (a-2). Similarly, ethylene was polymerized.

As a result, 65.8 g of an ethylene polymer having an MFR of 0.15 g / 10 min and a density of 0.963 g / cm ³ was obtained. The above ethylene polymer (A-1 to
Table 1 shows the mechanical properties of 4). It can be seen that the ethylene polymer compositions obtained in Examples 1 to 4 are excellent in moldability, mechanical strength and rigidity.

[0140]

[Table 1]

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Claims (6)

[Claims] 1. An ethylene homopolymer prepared by using a metallocene catalyst or ethylene having 3 to 20 carbon atoms.
(1) a density in a range of 0.940 to 0.970 g / cm ³ , and (2) a melt flow rate (measured at 190 ° C. under a load of 2.16 kg). Is an ethylene-based polymer (A) having a range of 0.05 to 100 g / 10 minutes. 2. The ethylene-based polymer (A) is produced using the following metallocene catalyst.
[I] a transition metal compound represented by the following general formula (i): [II] a compound capable of activating the transition metal compound [I], and [II] -1) an organoaluminum compound, (II-
2) a carrier-supported metallocene comprising: aluminoxane; and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair; and [III] a fine particle carrier. Catalyst; (Wherein, M represents a transition metal atom belonging to Groups 4 to 6 of the periodic table, and R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other, and include a hydrogen atom, a halogen atom, A hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group; X ¹ and X ² may be the same or different from each other, and a part of a hydrogen atom may be bonded to a part of adjacent groups to form at least one ring together with the carbon atom to which those groups are bonded. Represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a nitrogen-containing group; Hydrocarbon group, divalent silicon-containing group or 2
Shows a monovalent germanium containing group. ) 3. The ethylene polymer (A) is produced using the following metallocene catalyst.
[I] a transition metal compound represented by the following general formula (ii) or a transition metal compound represented by the following general formula (iii): [II] the transition metal compound [I] ] (II-1) an organoaluminum compound, (II-
2) a carrier-supported metallocene comprising: aluminoxane; and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair, and [III] a fine particle carrier. Catalyst; (Wherein, M, X ¹ and X ² are the same as those in the general formula (i), and R ^{5 to} R ⁹ may be the same or different from each other, and at least two or more thereof are methyl or ethyl. And other are hydrogen atoms, and R ^{10 to} R ¹⁴ may be the same or different from each other, and at least two or more of them are methyl or ethyl and the others are hydrogen atoms. (Wherein, M, X ¹ and X ² are the same as those in the general formula (i), and R ^{15 to} R ¹⁹ may be the same or different, and four of them are methyl or ethyl. And the others are hydrogen atoms, or 5 are methyl or ethyl, and R ²⁰ and R ²¹ may be the same or different from each other, and may be an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. is there.) (B) an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, wherein the (B-1) density is 0.950 to 0.980 g / in the range of cm ^3, (B-2) melt flow rate (190 ° C., 2.1
(Based on 6 kg load) in the range of 0.01 to 1000 g / 10 min: 20 to 90% by weight; and (C) copolymer weight of ethylene and an α-olefin having 3 to 20 carbon atoms. Are coalesced and have a (C-1) density of 0.910
0.965 g / cm ³ , and (C-2) melt flow rate (measured at 190 ° C. under a load of 2.16 kg) of 0.
Ethylene polymer in the range of 0003 to 35 g / 10 min: 80 to 10% by weight, wherein at least one of the ethylene polymer (B) and the ethylene polymer (C) is produced using a metallocene catalyst. a polymerisation body, (1) the ethylene polymer (B) density (d _B) of the ratio (d _B between the density (d _C) of the ethylene polymer (C)
/ D _C ) is greater than 1 and (2) the density is 0.940 to
In the range of 0.970 g / cm ^3, in that it consists of (3) a melt flow rate (190 ° C., under a 2.16kg load measurement) is in the range of 0.05 to 10 g / 10 min ethylene polymer composition Characteristic injection molded product made of polyethylene. 5. The polyethylene injection-molded article according to claim 4, wherein the ethylene polymer (B) and / or the ethylene polymer (C) are produced using the following metallocene catalyst; [I] a transition metal compound represented by the general formula (i), [II] a compound capable of activating the transition metal compound [I], and (II-1) an organoaluminum compound; -
2) a carrier-supported metallocene comprising: aluminoxane; and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair, and [III] a fine particle carrier. catalyst. 6. The polyethylene injection-molded product according to claim 4, wherein the ethylene-based polymer (B) and / or the ethylene-based polymer (C) is produced using the following metallocene catalyst; [I] a transition metal compound represented by the general formula (ii) or a transition metal compound represented by the general formula (iii), and [II] a compound capable of activating the transition metal compound [I]. And (II-1) an organoaluminum compound, (II-
2) a carrier-supported metallocene comprising: aluminoxane; and (II-3) at least one compound selected from compounds which react with the transition metal compound [I] to form an ion pair, and [III] a fine particle carrier. catalyst.