KR101904496B1 - Multimodal polyolefin resin and article prepared with the same - Google Patents

Abstract

여기서, id는 inner diameter(파이프 내경), od는 outside diameter(파이프 외경), en는 wall thickness(파이프 두께)이다.A multimodal polyolefin resin having high melt strength, excellent moldability, mechanical strength, processability and appearance, and a molded article produced therefrom. The multimodal polyolefin resin provides a polyolefin resin which satisfies the following requirements (1) to (7) or satisfies the requirements (1), (2), (8) and (9) below. (1) Density (d): 0.930 to 0.960 g / cm < 3 >; (2) Melt flow index (MIP, 190 캜, 5.0 kg load condition): 0.01 to 10.0 g / 10 min; (3) a ratio (Mw / Mn, Molecular weight distribution (MWD)) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) measured by gel permeation chromatography (GPC): 10 to 60; (4) When the molecular weight is measured by gel permeation chromatography (GPC), two or more peaks appear; (5) the weight average molecular weight (Mw) of the polymer taken at position B of Definition 1 below in a shaped pipe exceeds 0.1% of the weight average molecular weight (Mw) of the polymer taken at position A; (6) In a molded pipe, the polymer taken at position A in the following definition 1 has a weight average molecular weight (Mw) of not more than 10,000 and a polymer taken at position B has a weight average molecular weight (Mw) Exceeds 0.1%; (7) In a molded pipe, the content of a polymer having a weight average molecular weight (Mw) of 1,000,000 or more and a polymer taken at a position B of the following definition 1 in a polymer having a weight average molecular weight (Mw) Content exceeds 0.1%. (8) The Z-average molecular weight (Mz) measured by gel permeation chromatography (GPC) of the polymer taken at the position B in the following definition 1 in the shaped pipe is smaller than the Z-average molecular weight (Mz) of the polymer collected at the position A Exceeding 0.1%; And (9) the Z + 1 average molecular weight (Mz + 1) measured by gel permeation chromatography (GPC) of the polymer taken at position B of Definition 1 below in the shaped pipe is greater than the Z + 1 It exceeds 1% of average molecular weight (Mz + 1).
[Definition 1]
In a pipe having a standard value ratio SDR = od / en (Standard Dimension Ratio) value of 2 to 20,

Where id is the inner diameter, od is the outside diameter, and en is the wall thickness.

Description

TECHNICAL FIELD [0001] The present invention relates to a multimodal polyolefin resin and a molded article produced from the same,

More particularly, the present invention relates to a multimodal polyolefin resin having high melt strength, excellent moldability, mechanical strength, processability and appearance, and a molded article produced therefrom .

In order to use a polyolefin resin for a specific use, the toughness, strength, environmental stress, and crack resistance of the polyolefin resin should be excellent. When the molecular weight of the polyolefin resin (polymer) is increased, these properties are easily improved, but when the molecular weight of the polymer is increased, the moldability of the resin is deteriorated. Because of the disadvantage of such polyolefin resins, it is preferable to use the polyolefin resin having a single physical property singly, but to appropriately adjust the structure of the polymer or to use an appropriate processing aid, rather than using polyolefin resins having different physical properties in combination. However, in general, the polyethylene resin made of a Ziegler-Natta and metallocene catalyst has a narrow molecular weight distribution, and when used alone, causes various problems. Therefore, when a polymer having a broad molecular weight distribution or a multimodal molecular weight distribution is used, moldability is improved while characteristics such as toughness, strength, environmental stress and crack resistance are maintained and the disadvantages of a polyolefin resin having a narrow molecular weight distribution are solved can do.

A polyolefin having a multimodal molecular weight distribution is a polyolefin containing two or more components having different molecular weights, for example, a relatively high-molecular-weight component and a low-molecular-weight component in a relatively balanced manner. A great deal of research has been conducted to produce polyolefins having a broad molecular weight distribution or a multimodal molecular weight distribution. One method is a post-reactor or melt blending method in which polyolefins having two or more different molecular weights are blended together before or during processing. For example, U.S. Pat. No. 4,461,873 discloses a method for physically blending polymers of two different physical properties to produce this point polymeric blend. However, when such a physical blend is used, a molded article having a high gel content tends to be produced, and due to a defective product appearance due to a gel component, it can not be used for a film or the like. In addition, the physical blending method requires a complete uniformity, which leads to an increase in manufacturing cost.

Another method of producing a polyolefin having a multimodal molecular weight distribution, for example, a polyolefin having a bimodal molecular weight distribution, is to use a multistage reactor. The method comprises using two or more reactors wherein a first polymer component having one of two different molecular weight distributions of the bimodal polymer in a first reactor is produced under certain conditions, 2 reactor and a second polymer component having a molecular weight distribution different from the first polymer component in the second reactor is prepared under conditions different from the reaction conditions of the first reactor. Although the above method can solve the problems associated with the gel, the use of multiple reactors may result in reduced efficiency or increased manufacturing costs, and when high molecular weight components are produced in the first reactor, Components are not produced, and the polyolefin particles finally produced can be composed only of high molecular weight components.

Another method of producing polyolefins having a broad molecular weight distribution or a multimodal molecular weight distribution is to polymerize polyolefins using a catalyst mixture in a single reactor. Recently, in the art, various attempts have been made to produce polyolefins having a broad molecular weight distribution or a multimodal molecular weight distribution, in a single reactor, using two or more different catalysts. With this method, the resin particles are uniformly mixed at the subparticle level, and resin components having different molecular weight distributions are present in the same phase. For example, U.S. Patent Nos. 4,530,914 and 4,935,474 disclose the use of ethylene or higher alpha-olefins in the presence of a catalyst system comprising two or more metallocenes and aluminoxanes having different reaction evolution and termination rate constants, Discloses a method for producing a polyolefin having a broad molecular weight distribution by polymerizing an olefin. In addition, U.S. Patent Nos. 6,841,631 and 6,894,128 disclose a process for producing a polyethylene having a bimodal or multimodal molecular weight distribution using a metallocene catalyst comprising at least two metal compounds, , Pipes, hollow molded articles, and the like. Although the polyethylene produced in this way has good processability, the dispersion state of the polyethylene component by the molecular weight in the unit particle is not uniform, and the appearance is coarse and the physical properties are not stable even under comparatively good processing conditions.

U.S. Patent No. 4,937,299 discloses the preparation of polyolefins using a catalyst system comprising two or more metallocenes with different reaction ratios for the monomers to be polymerized. In addition, U.S. Patent No. 4,808,561 discloses that a metallocene is reacted with aluminoxane in the presence of a support to produce a supported catalyst. The metallocene is supported on a support to form a solid powder catalyst. As the support, inorganic materials such as silica, alumina, silica-alumina, magnesia, titania, zirconia and mixtures thereof and inorganic materials such as polyolefins (for example, finely divided polyethylene) have been used. The aluminoxane was deposited on the dehydrated support material.

Typically, polymers made with a Ziegler-Natta catalyst alone or with a metallocene catalyst system have narrow molecular weight distributions, so that satisfactory polyolefins with a multimodal molecular weight distribution or a broad molecular weight distribution can not be produced. Accordingly, in the art, a method for producing a bimodal resin using a mixed catalyst system containing a Ziegler-Natta catalyst and a metallocene catalyst component is known. The mixed catalyst system or mixed catalyst system typically comprises a combination of a heterogeneous Ziegler-Natta catalyst and a homogeneous metallocene catalyst. The mixed catalyst system is used for producing a polyolefin having a broad molecular weight distribution or a bimodal molecular weight distribution, and is a means for controlling the molecular weight distribution and polydispersity of the polyolefin.

U. S. Patent No. 5,539, 076 discloses a metallocene / non-metallocene mixed catalyst system for making specific point density high density copolymers. The catalyst system is supported on the inorganic carrier. The problem with the supported Ziegler-Natta and metallocene catalyst systems is that the supported hybrid catalysts are less active than homogeneous single catalysts, making it difficult to produce polyolefins with tailor-made properties. In addition, since a polyolefin is produced in a single reactor, there is a fear that a gel generated in the blending method may be generated, insertion of a comonomer into a high molecular weight portion is difficult, and the shape of the resulting polymer may be poor. The two polymer components are not uniformly mixed, and quality control may become difficult.

Korean Patent No. 1437509 discloses a catalyst composition and a polymerization method for producing a multimodal polyolefin resin having a small extrusion load during molding and an excellent extrusion amount because of a large amount of extrusion. It is disclosed that the resin is a mixture of two or more different kinds of polymers, and exhibits excellent workability in spite of a high molecular weight and a low melt flow index. However, such a resin has a disadvantageous roughness on the surface when processing a large diameter pipe. When the molten resin is subjected to high stress during extrusion molding, there is a difference in elastic energy depending on the position inside the extruder, and the polymer chains are moved to be energy equilibrium. . In bimodal or multimodal polyolefin, the difference in molecular weight of each polymer chain is larger than that of general monododal polyolefin, so that the difference in elastic energy is large and the movement of polymer chains is easier. For this reason, it is difficult to evenly distribute the molecules, which can cause problems such as surface roughness.

In addition, conventional bimodal products have a great difference in elastic energy between polymer chains, and when the polymers are subjected to high stress at the time of processing, the polymer chains having relatively low molecular weight and low elastic energy move toward the stressed extruder wall surface, Polymer chains with a high molecular weight and a high elastic energy travel in a direction with low stress. As a result, the polymer chains having low molecular weight are distributed in the outer surface direction of a molded product (for example, a pipe) to be produced, and surface roughening and melt fracture (phenomenon that the surface is not smooth and ruggedly broken during polymer processing) Is issued.

Accordingly, it is an object of the present invention to provide a method for producing a multi-modal polyolefin resin composition which suppresses the outward migration of polymer chains having relatively low molecular weight generated by energy difference in extrusion molding by increasing the melt strength, . Another object of the present invention is to provide a far-modal polyolefin resin having a molecular weight, a molecular weight distribution and a melt flow index ratio (Shear Response, SR) having an appropriate range for molding under high stress extrusion conditions such as pipes and films. Still another object of the present invention is to provide a multimodal polyolefin resin having a low extrusion load during molding and a low stress applied to the molten resin, minimizing a difference in elastic energy between polymer chains, and exhibiting excellent productivity. It is still another object of the present invention to provide a polyolefin resin molded article excellent in appearance characteristics and mechanical strength.

In order to achieve the above object, the present invention provides a polyolefin resin satisfying the following requirements (1) to (7). The present invention also provides a polyolefin resin which satisfies the following requirements (1), (2), (8) and (9) (1) Density (d): 0.930 to 0.960 g / cm < 3 >; (2) Melt flow index (MIP, 190 캜, 5.0 kg load condition): 0.01 to 10.0 g / 10 min; (3) a ratio (Mw / Mn, Molecular weight distribution (MWD)) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) measured by gel permeation chromatography (GPC): 10 to 60; (4) When the molecular weight is measured by gel permeation chromatography (GPC), two or more peaks appear; (5) the weight average molecular weight (Mw) of the polymer taken at position B of Definition 1 below in a shaped pipe exceeds 0.1% of the weight average molecular weight (Mw) of the polymer taken at position A; (6) In a molded pipe, the polymer taken at position A in the following definition 1 has a weight average molecular weight (Mw) of not more than 10,000 and a polymer taken at position B has a weight average molecular weight (Mw) Exceeds 0.1%; (7) In a molded pipe, the content of a polymer having a weight average molecular weight (Mw) of 1,000,000 or more and a polymer taken at a position B of the following definition 1 in a polymer having a weight average molecular weight (Mw) Content exceeds 0.1%. (8) The Z-average molecular weight (Mz) measured by gel permeation chromatography (GPC) of the polymer taken at the position B in the following definition 1 in the shaped pipe is smaller than the Z-average molecular weight (Mz) of the polymer collected at the position A Exceeding 0.1%; And (9) the Z + 1 average molecular weight (Mz + 1) measured by gel permeation chromatography (GPC) of the polymer taken at position B of Definition 1 below in the shaped pipe is greater than the Z + 1 It exceeds 1% of average molecular weight (Mz + 1).

[Definition 1]

In a pipe having a standard value ratio SDR = od / en (Standard Dimension Ratio) value of 2 to 20,

Where id is the inner diameter, od is the outside diameter, and en is the wall thickness.

The multimodal polyolefin resin according to the present invention has a high melt strength so that the distribution of polymer chains throughout the formed article is uniform, the extrusion load during molding is small, the difference in elastic energy between the polymer chains is minimized, and the productivity is excellent. In addition, the multimodal polyolefin resin molded article according to the present invention is excellent in appearance characteristics and mechanical strength.

1 is GPC data of the polyethylene obtained in Examples 1 to 3 and Comparative Examples 1 to 4 of the present invention.
2 is a graph showing the molecular weight and the melt strength of the polyethylene obtained in Examples 1 to 3 and Comparative Examples 1 to 4 of the present invention.
3 is a graph showing the relationship between the pulling speed and the melt strength of the polyethylene obtained in Examples 1 to 3 and Comparative Examples 1 to 4 of the present invention.
4 is a view showing a sampling position of a pipe formed of polyethylene obtained in Example 2, Comparative Example 1 and Comparative Example 4. Fig.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings. In the following description, the polyolefin resin may be simply referred to as a polymer or a polyolefin, or may be referred to as an ethylene-based polymer, a polymer, a polymer, an olefin polymer or the like, if necessary.

The multimodal polyolefin resin according to the present invention is a polyolefin resin having a broad molecular weight distribution, for example, a bimodal or multimodal molecular weight distribution, and is particularly suitable for blow molding, extrusion molding and film molding, The molded body has excellent mechanical strength and appearance. The polyolefin resin according to the present invention is produced so as to satisfy the following requirements (1) to (7) or to satisfy the requirements of (1), (2), (8) .

(1) The density (d) is 0.930 to 0.960, preferably 0.934 to 0.954, more preferably 0.940 to 0.954 g / cm3.

(2) The melt flow index (MIP, 190 캜, 5.0 kg load condition) is 0.01 to 10.0, preferably 0.1 to 1, more preferably 0.2 to 0.5 g / 10 min.

(3) The ratio (Mw / Mn, Molecular weight distribution (MWD)) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 10 to 60, 50, and more preferably 12 to 40. [ The weight average molecular weight is preferably 100,000 to 400,000, more preferably 120,000 to 300,000.

(4) When the molecular weight is measured by gel permeation chromatography (GPC), two or more peaks appear. Here, the polyolefin forming the peak (M _Hp ) having the largest molecular weight improves the mechanical properties and the melt strength of the polymer resin, and the polyolefin forming the peak (M _Lp ) having the smallest molecular weight improves the moldability of the polymer resin Function.

(5) In a molded pipe, the weight average molecular weight (Mw) of the polymer taken at position B of Definition 1 below is 0.1, preferably 1, more preferably 1 Exceeds 2%.

(6) In a molded pipe, the polymer taken at position A in the following definition 1 has a weight average molecular weight (Mw) of not more than 10,000 and a polymer taken at position B has a weight average molecular weight (Mw) , Preferably more than 1, more preferably more than 2%.

(7) In a molded pipe, the content of a polymer having a weight average molecular weight (Mw) of 1,000,000 or more and a polymer taken at a position B of the following definition 1 in a polymer having a weight average molecular weight (Mw) Is more than 0.1, preferably 1, more preferably more than 2%.

(8) The Z-average molecular weight (Mz) measured by gel permeation chromatography (GPC) of the polymer taken at the position B in the following definition 1 in the shaped pipe is smaller than the Z-average molecular weight (Mz) of the polymer collected at the position A 0.1%, preferably more than 1%. The Z average molecular weight is preferably 100,000 to 10,000,000, more preferably 200,000 to 5,000,000, and most preferably 500,000 to 3,000,000.

(9) The Z + 1 average molecular weight (Mz + 1) measured by gel permeation chromatography (GPC) of the polymer taken at position B in the following definition 1 in the shaped pipe is the Z + 1 Exceeds 1%, preferably 5%, of the average molecular weight (Mz + 1). The Z + 1 average molecular weight is preferably 1,000,000 to 10,000,000, more preferably 500,000 to 5,000,000, and most preferably 1,000,000 to 3,000,000.

 [Definition 1]

In a pipe having a standard value ratio SDR = od / en (Standard Dimension Ratio) value of 2 to 20,

Where id is the inner diameter, od is the outside diameter, and en is the wall thickness.

In order to prevent deformation of the outer surface at high stress during pipe processing, the weight average molecular weight (Mw) of the polymer located on the outer surface of the finished pipe is preferably at least 150,000, more preferably 200,000 or more. In Rheology analysis, the ratio of the energy storage modulus (G ') at a shear rate of 100 rad / s and 0.1 rad / s should be 200 or less, more preferably 150 or less. Therefore, if the molecular weight of the polyolefin resin is out of the above range, the moldability of the polyolefin resin is lowered, and the physical properties of the molded article may be deteriorated.

The polyolefin resin according to the present invention has a melt flow index ratio (SR: high load melt flow index / melt flow index) value of 10 to 300, preferably 10 to 100, more preferably 20 to 50, A melt tension of 3.0 to 10, preferably 4 to 8 gf, and a melt strength of at least 1 cN, preferably 2 to 10, more preferably 3 to 8, 8 cN and the Relaxation Time value is 400 seconds or less, preferably 0.1 to 200 seconds or less.

Also, the modulus ratio index (MRI) is 20 to 200, preferably 50 to 180, and the long chain branch / 1,000C is 1 / 1,000C or less, preferably 0.05 to 0.5 / 1,000 C or less, and the shear thinning index (STI) is 20 to 100, preferably 20 to 80, more preferably 20 to 50. If the condition of the polyolefin resin according to the present invention is out of the above ranges, there may be problems such as sagging phenomenon or surface roughness during the molding of the pipe.

The olefin monomers for forming the polyolefin resin according to the present invention include linear aliphatic olefins of 2 to 12 carbon atoms, preferably 2 to 10 carbon atoms, cyclic olefins of 3 to 24 carbon atoms, preferably 3 to 18 carbon atoms, dienes , Trienes, styrenes, and the like can be used. Examples of the linear aliphatic olefin include ethylene, propylene, butene-1, pentene-1, 3-methylbutene-1, hexene-1, 4-methylpentene- , Decene-1, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, 3,4-dimethyl-1-hexene and mixtures thereof . Examples of the cyclic olefin include cyclopentene, cyclobutene, cyclohexene, 3-methylcyclohexene, cyclooctene, tetracyclodecene, octacyclodecene, dicyclopentadiene, norbornene, 5-methyl- Norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5,5,6-trimethyl- , Ethylene norbornene, and mixtures thereof. As the dienes and trienes, polyenes having 4 to 26 carbon atoms and having 2 or 3 double bonds are preferable. Specific examples thereof include 1,3-butadiene, 1,4-pentadiene, 1,4-hexa Diene, 1,5-hexadiene, 1,9-decadiene, 2-methyl-1,3-butadiene, and mixtures thereof. Examples of the styrenes include styrene and styrene substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen group, an amine group, a silyl group, a halogenated alkyl group, or a mixture thereof. The olefin monomers may be homopolymerized or alternating, random, or block copolymerized.

Preferably, the polyolefin resin according to the present invention is at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl- Dodecene, 1-hexadecene, 1-octadecene, norbornene, norbornene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, Butadiene, 1,5-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene and mixtures thereof Homopolymers or copolymers of olefin monomers. Further, the polyolefin resin according to the present invention is characterized in that the main component is selected from the group consisting of ethylene, propylene and mixtures thereof, and the remaining auxiliary component is a polyolefin resin derived from an? -Olefin having 4 to 10 carbon atoms, such as 6 to 8 carbon atoms It is preferable that the content of the constituent unit is 0.01 to 3.0% by weight. Here, the content of the comonomer (-olefin) can be measured by 13C-NMR.

The polyolefin resin according to the present invention can be suitably used in the form of a blow molded article, an injection molded article, a sheet, a film, an extrusion molded article such as a blow molded article, an inflation molded article, a cast molded article, an extrusion laminated molded article, But also for the production of fibers, monofilaments, nonwoven fabrics and the like. Particularly, the polyolefin resin of the present invention is useful for the production of an extrusion molded article such as a blow molded article, a pipe or a die, or a film formed article. The polyolefin resin according to the present invention can be crosslinked in a molding process, and the molded article includes a composite molded article (such as a laminate) comprising a portion made of a polyolefin resin and a portion made of another resin according to the present invention. The shaped body may further contain additives, modifiers and the like in order to improve physical properties.

In the case of molding a pipe using the polyolefin resin according to the present invention, it is preferable that the molded pipe further satisfies the following conditions (10) and (11).

(10) According to KS M 3408, in a pipe water pressure test in which a stress corresponding to a pressure of 5.4 MPa is applied to water at 80 ° C. to measure the time at which the pipe is broken, the pipe breaking time exceeds 165, preferably over 200 hours do.

(11) According to KS M 3408, in a pipe water pressure test in which a stress corresponding to a pressure of 12.4 MPa is applied to water at 20 ° C to measure the time at which the pipe is broken, the pipe breaking time exceeds 100, preferably over 200 hours do..

The polyolefin resin according to the present invention is excellent in the outer surface of the molded article because the molecular weight of the polymer located on the outer surface of the processed molded article (e.g., pipe) is higher than the molecular weight of the polymer located in the central portion. The polyolefin resin according to the present invention contains a relatively high molecular weight polymer relative to a low molecular weight polymer and a relatively low molecular weight polymer relative to the polymer having a high molecular weight. Therefore, when the polyolefin resin is molded, a chain transfer phenomenon The outer surface of the molded article can be excellently manufactured. That is, in the chain transfer phenomenon, the medium-length chain serves to inhibit the polymer having a long chain from moving to the inside (center).

The polyolefin resin according to the present invention is a catalyst system for expressing a polymer having a relatively low molecular weight, at least one first organic transition metal compound represented by the following formula (1), a catalyst system for expressing a relatively intermediate molecular weight polymer, And at least one second organic transition metal compound, at least one third organic transition metal compound represented by the following formula (3), which is a catalyst system for expressing a relatively high molecular weight polymer, and aluminoxane, .

[Chemical Formula 1]

(L ¹ ) (L ² ) (X ¹ ) (X ² ) M ¹

(2)

(L ³ -Q ¹ _n -L ⁴ ) (X ³ ) (X ⁴ ) M ²

(3)

_{^{(L 5 -Q 2 n -L 6}} ) (X 5) (X 6) M 3

M ¹ , M ² and M ³ are independently titanium, zirconium (Zr) or hafnium (Hf), and L ¹ , L ² , L ³ , L ⁴ and L ⁵ and L ⁶ are each independently a cyclic hydrocarbon group having 5 to 30 carbon atoms and having at least two conjugated double bonds and X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently halogen Atom or hydrocarbon group. Q ¹ and Q ² are each independently a silane group or a hydrocarbon group containing a substituent, and n is an integer of 1 to 5.

First, the organometallic compound represented by Formula 1 will be described in detail. M ¹ in Formula 1 is titanium (Ti), zirconium (Zr), or hafnium (Hf), and L ¹ and L ² each independently represent a substituted or unsubstituted C 5 -C 30 The number of carbon atoms of the cyclic hydrocarbon group is preferably from 5 to 15, more preferably from 5 to 13, and more preferably from 2 to 5. The number of carbon atoms of the cyclic hydrocarbon group is preferably from 5 to 15, Is more preferable. Examples of L ¹ and L ² include a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group, a pentylene group, a substituted pentylene group and the like . L ¹ and L ² may be partially substituted with 1 to 6 substituents selected from the group consisting of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, An aryl group having 4 to 20 carbon atoms, an alkylaryl group having 6 to 20 carbon atoms, a substituted or unsubstituted cyclopentadienyl group having 5 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, 20 haloaryl groups and mixtures thereof. X ¹ and X ² are each independently a halogen atom or a hydrocarbon group. Examples of the halogen atom include chlorine (Cl), fluoro (F), bromine (Br) and iodo The hydrocarbon group is an alkyl group, a cycloalkyl group or an aryl group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms. Specific examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl and isobutyl, cycloalkyl groups such as cyclopentyl and cyclohexyl , An aryl group such as a phenyl group.

Non-limiting examples of the first organic transition metal compound represented by Formula 1 include bis (cyclopentadienyl) zirconium difluoride, bis (methylcyclopentadienyl) zirconium difluoride, bis (n-propylcyclo Zirconium dichloride, bis (cyclopentylcyclopentadienyl) zirconium difluoride, bis (cyclopentadienyl chloropentadienyl) zirconium dipyrite, bis (cyclopentylcyclopentadienyl) Bis (indenyl) zirconium difluoride, bis (fluorenyl) zirconium dichloride, bis (isobutylcyclopentadienyl) zirconium difluoride, bis (diphenylcyclopentadienyl) zirconium difluoride, bis Zirconium dichloride, zirconium difluoride, bis (4,5,6,7-tetrahydro-1-indenyl) zirconium difluoride, bis (cyclopentadienyl) zirconium dichloride, Zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (normal-propylcyclopentadienyl) zirconium dichloride, bis (normal-butylcyclopentadienyl) zirconium dichloride, Bis (cyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (isobutylcyclopentadienyl) zirconium dichloride, bis ) Zirconium dichloride, bis (fluorenyl) zirconium dichloride, bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis Zirconium dibromide, bis (normal-propylcyclopentadienyl) zirconium dibromide, bis (normal-butylcyclopentadienyl) zirconium dibromide, Zirconium dibromide, bis (cyclopentylcyclopentadienyl) zirconium dibromide, bis (cyclopentylcyclopentadienyl) zirconium dibromide, bis (1,3-dimethylcyclopentadienyl) zirconium dibromide, bis Bis (cyclopentadienyl) zirconium dibromide, bis (indenyl) zirconium dibromide, bis (fluorenyl) zirconium dibromide, bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dibromide , Cyclopentadienyl zirconium trifluoride, cyclopentadienyl zirconium trichloride, cyclopentadienyl zirconium tribromide, cyclopentadienyl zirconium triiodide, methylcyclopentadienyl zirconium trifluoride, methylcyclopentadiene Nylzirconium trichloride, methylcyclopentadienyl zirconium tribromide, methylcyclopene Butylcyclopentadienyl zirconium tribromide, butylcyclopentadienyl zirconium triiodide, pentamethyl zirconium tri-iodide, butyl cyclopentadienyl zirconium tri-fluoride, butyl cyclopentadienyl zirconium trichloride, butyl cyclopentadienyl zirconium tribromide, butyl cyclopentadienyl zirconium tri- Pentamethylcyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium tribromide, pentamethyl cyclopentadienyl zirconium tri iodide, indenyl zirconium trifluoride, indenyl Zirconium trichloride, indenyl zirconium tribromide, indenyl zirconium triiodide, 4,5,6,7-tetrahydroindenyl zirconium trifluoride, 4,5,6,7-tetrahydroindenyl zirconium trichloride , 4,5,6,7-tetrahydroindenylzircon Methyl indenyl zirconium tribromide, methyl indenyl zirconium tri-iodide, methyl indenyl zirconium tri-fluoride, methyl indenyl zirconium trichloride, methyl indenyl zirconium tribromide, There may be mentioned a zirconium compound such as zirconium compound, zirconium compound, zirconium compound, zirconium compound, zirconium compound, zirconium compound, zirconium compound, zirconium compound, zirconium compound, zirconium compound, zirconium compound, zirconium compound, Oleylzirconium tribromide, fluorenylzirconium triiodide, and the like.

Next, the second and third organic transition metal compounds represented by Chemical Formulas 2 and 3 will be described. M ² and M ³ in the general formulas (2) and ( ³⁾ are each independently the same as the definition of M ¹ in the general formula (1), and L ³ , L ⁴ , L ⁵ and L ⁶ each independently represent L ¹ and L ² And X ³ , X ⁴ , X ⁵ and X ⁶ are each independently the same as defined for X ¹ and X ² . Each of Q ¹ and Q ² is a group of linking L ³ and L ⁴ and L ⁵ and L ⁶ , and each independently a silane group and a hydrocarbon group, preferably an alkenyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms A silyl group, an arylsilyl group having 6 to 20 carbon atoms, an arylalkenyl group having 6 to 20 carbon atoms, an alkane having 1 to 20 carbon atoms, and a mixture thereof. Specific examples thereof include alkenyl groups such as methylidene, ethylene and isopropylidene, An alkylsilane group such as dimethylsilane, an arylsilane group such as diphenylsilane, an arylalkenyl group such as diphenylmethylidene, an arylsilyl group such as diphenylsilyl, and an alkane such as ethane.

The second organic transition metal compound represented by Formula 2 is a catalyst component capable of forming a polymer having a relatively intermediate molecular weight (for example, a weight average molecular weight of 50,000 to 200,000), and the third organic transition metal compound represented by Formula 3 The metal compound is a catalyst component capable of producing a polymer having a high molecular weight (for example, a weight average molecular weight of 200,000 to 1,000,000). Both of these compounds can stably and relatively exhibit polymerization even at a high temperature (about 80 ° C or higher) (comonomer) insertion ability is superior to the catalyst component (first organic transition metal compound) that expresses a low molecular weight polymer. The second organic transition metal compound and the third organic transition metal compound may be combined with one or two aryl groups bonded to the bridging atoms of the bridged ligand of the cyclopentadienyl- type portion of the rigidly- bridged ligand Bridged ansa-metallocene, preferably comprising one or both phenyl groups. The term " ansa-metallocene "

Non-limiting examples of the second organic transition metal compound represented by Formula 2 and the third organic transition metal compound represented by Formula 3 include rac-ethylene bis (1-indenyl) zirconium dichloride, rac-ethylene bis Dimethyl-silanediylbis (2-methyl-tetrahydrobenzenylidene) zirconium dichloride, rac-dimethylsilanediylbis (2-methyl- (2-methyl-5,6-cyclopentadienylindenyl) zirconium dichloride, rac-dimethylsilylbis (2-methyl-4-phenylindene) zirconium dichloride, rac-diphenylsilanediylbis Zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenyl (diphenylsilyl) zirconium dichloride, Silyl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride (Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (3-tert-butylcyclopentadienyl) (2 Di-tert-butylfluorene-9-yl) zirconium dichloride, diphenylmethylidene (3-tert- butyl-5-methylcyclopentadienyl) (2,7- (9-fluorenyl) -1-phenyl- ethane] zirconium dichloride, 1,2-bis (9-fluorenyl) zirconium dichloride, (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2-phenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2-phenyl-cyclopentadienyl) (2-phenyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (2-phenyl-cyclopentadienyl) (2,7-di-tert-butylfluoro 9-yl) zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (p- tolyl) -tetrahydropentrene] zirconium dichloride, [isopropylidene- Cyclopentadienyl) - (9-fluorenyl)] zirconium dichloride, [isopropylidene (2- (m-tolyl) -cyclopentadienyl) - (9- [(M-tolyl) -cyclopentadienyl] - (9-fluorenyl)] zirconium dichloride, [isopropylidene (2- ) - cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, [diphenylmethylidene (2- (m- tolyl) -cyclopentadienyl) Zirconium dichloride, [isopropylidene (2- (o-tolyl) -cyclopentadienyl) (9-fluorenyl)] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (2,4-dimethylphenyl) -tetrahydropentrene] zirconium Diisopropylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl)] zirconium dichloride, [isopropylidene (2- ) -Cyclopentadienyl) (9-fluorenyl)] zirconium dichloride, [diphenylmethylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, [isopropylidene (2- (2,3-dimethyl-3-methylphenyl) Phenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, [isopropylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, [diphenylmethylidene (2- (2,3- dimethylphenyl) cyclopentadienyl) Di-tert-butylfluorene-9-yl)] zirconium dichloride, diphenylmethylidene (2- (2,4-di (Methylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, [4- (fluorenyl) -4,6,6- (2-tetramethylphenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (2,6-difluorophenyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (3,5-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium di Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (chlorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (pentafluorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (biphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, Zirconium dichloride, isopropylidene (2- (3,5-diphenyl-phenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2-naphthyl-cyclopentadienyl Zirconium dichloride, diphenylmethylidene (2-tetramethylphenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (2,6- (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (2,4-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (fluorophenyl) -cyclopentadienyl) zirconium dichloride, diphenylmethylidene Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (pentafluorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (3,5-di-tert-butylphenyl) -cyclopentadienyl) Zirconium dichloride, diphenylmethylidene (2- (biphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, and the second organic transition metal compound and the third organic transition metal compound may be used independently or in combination of two or more of the above compounds .

The aluminoxane is used for the removal of an activator function and impurities. For example, aluminoxane represented by the following formula (4) can be used. The aluminoxane may have a linear, cyclic or network structure. For example, the linear aluminoxane may be represented by the following formula (5), and the cyclic aluminoxane may be represented by the following formula (6).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the general formulas (4), (5) and (6), R 'is a hydrocarbon group and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and most preferably R' Preferably an integer of 1 to 50, more preferably an integer of 10 to 40, and y is an integer of 3 to 50, preferably an integer of 10 to 40.

In the present invention, commercially available alkylaluminoxanes may be used, and as the non-limiting examples of the alkylaluminoxanes, there may be mentioned methylaluminoxane, ethylaluminoxane, butylaluminoxane, isobutylaluminoxane, hexylaluminoxane, , Decylaluminoxane, and the like. The aluminoxane is commercially available in the form of various types of hydrocarbon solutions. Of these, aliphatic acid solution of aromatic hydrocarbon is preferably used, and aluminoxane solution dissolved in toluene is more preferably used. The aluminoxane used in the present invention may be used alone or in combination of two or more. The alkylaluminoxane may be prepared by various methods such as adding an appropriate amount of water to trialkylaluminum or reacting a hydrocarbon compound or an inorganic hydrate including water with trialkylaluminum, And aluminoxane are mixed together.

In the catalyst for olefin polymerization to be used in the present invention, the amount of the second organic transition metal compound represented by Formula 2 is 0.01 to 100 moles per mole of the first organic transition metal compound represented by Formula 1, Preferably 0.1 to 20 moles, more preferably 0.5 to 10 moles. The amount of the third organic transition metal compound represented by Formula 3 is 0.01 to 100 moles, preferably 0.1 to 20 moles, and more preferably 0.5 to 10 moles per mole of the first organic transition metal compound . If the amount of the first organic transition metal compound represented by the formula (1) is too small, a polymer having a high molecular weight may be produced. If the amount is too large, a polymer having a low molecular weight may be produced.

The aluminoxane is used in an amount of 1 mole in total of the first organic transition metal compound represented by Formula 1, the second organic transition metal compound represented by Formula 2, and the third organic transition metal compound represented by Formula 3, The aluminum of aluminoxane may be used in an amount of 1 to 100,000 moles, preferably 1 to 5,000 moles, and more preferably 1 to 2,500 moles. For example, the first and second organic transition metal compounds and the aluminoxane are mixed so that 1 to 100,000 moles, preferably 1 to 5,000 moles, of aluminum is used per mole of the total organic transition metal compound The catalyst for olefin polymerization according to the present invention can be produced.

The mixing of the catalyst components can be optionally carried out without particular limitation. For example, the organometallic compound, the first, second and third organic transition metal compounds and aluminoxane can be mixed simultaneously for 5 minutes to 24 hours, preferably 15 minutes to 16 hours. The mixing may also be performed by first mixing the organometallic compound and the aluminoxane for 5 minutes to 10 hours, preferably 15 minutes to 4 hours, and then adding the mixture to the mixture of the first organic transition metal compound and the aluminoxane, A solution prepared by mixing the second organometal compound and aluminoxane for 5 minutes to 10 hours, preferably 15 minutes to 4 hours, is added to a solution mixed for 5 minutes to 24 hours, preferably 15 minutes to 16 hours And mixing for 5 minutes to 24 hours, preferably 15 minutes to 16 hours. The mixing can be carried out in an inert atmosphere of nitrogen or argon without using a solvent or in the presence of an inert hydrocarbon solvent such as heptane, hexane, benzene, toluene, xylene or the like, or a mixture thereof, The temperature is 0 to 150 캜, preferably 10 to 100 캜. The catalyst in a solution state, which is uniformly dissolved in the hydrocarbon solvent or the like, can be used as it is or in the form of a solid powder from which the solvent has been removed. In the solid powder catalyst, , And the like.

The catalyst to be used in the present invention may be a mixture of the organometallic compound, the first to third organic transition metal compounds and aluminoxane supported on an organic or inorganic carrier. Therefore, the catalyst used in the present invention can be used in the form of a solid powder or a catalyst in a homogeneous solution state, as well as an organic or inorganic porous carrier (silica, alumina, silica-alumina mixture or the like) Catalyst. The method of contacting (supporting) the catalyst in a solution state with the porous carrier is as follows, but is not limited to the following method. The supporting method may be carried out by mixing a catalyst in a solution state prepared by mixing the organometallic compound, the first to third organic transition metal compounds and aluminoxane with the porous carrier (for example, a pore size of 50 to 500 Å and a pore size of 0.1 to 5.0 Lt; 3 > / g / cm < 3 > / g) to form a slurry state; To the slurry mixture is added an acoustic wave or a vibration wave in the frequency range of 1 to 10,000 kHz, preferably 20 to 500 kHz, at 0 to 120 캜, preferably 0 to 80 캜 for 0.1 to 6 hours, For 3 hours to uniformly penetrate the catalyst components deep into the fine pores of the porous carrier; And drying the catalyst components permeated into the micropores of the porous carrier by a vacuum treatment or a nitrogen flow, and a catalyst in the form of a solid powder can be produced through the above steps. The acoustic wave or vibration wave is preferably ultrasonic waves. The method of contacting (supporting) the catalyst with the carrier is carried out by adding the acoustic wave or vibration wave and then using the hydrocarbon selected from the group consisting of pentane, hexane, heptane, isoparaffin, toluene, xylene, And then washing it.

As the porous carrier, porous inorganic materials, inorganic salts or organic compounds having fine pores and large surface area may be used without limitation. The form of the inorganic (inorganic salt or inorganic) carrier in the porous carrier may be any form as long as it can obtain a predetermined form in the process for producing the supported catalyst, and may be in the form of powders, particles, flakes, foils, Can be exemplified. Regardless of the form of the inorganic carrier, the maximum length of the inorganic carrier is 5 to 200 μm, preferably 10 to 100 μm, the surface area of the inorganic carrier is 50 to 1,000 m 2 / g, the pore volume is 0.05 to 5 cm 3 / g. In general, the inorganic carrier must be subjected to a water or hydroxy group removal process before use. The process may be performed by baking the carrier at a temperature of 200 to 900 ° C in an inert gas atmosphere such as air, nitrogen or argon. Non-limiting examples of the inorganic salt or inorganic material include silica, alumina, Bauxite, zeolite, MgCl ₂ , CaCl ₂ , MgO, ZrO ₂ , (TiO ₂ ), boron oxide (B ₂ O ₃ ), calcium oxide (CaO), zinc oxide (ZnO), barium oxide (BaO), thorium oxide (ThO ₂ ) SiO ₂ -MgO), silica-alumina (SiO ₂ -Al ₂ O ₃ ), silica-titanium oxide (SiO ₂ -TiO ₂ ), silica-vanadium pentoxide (SiO ₂ -V ₂ O ₅ ) SiO ₂ -CrO ₃ ), silica-titanium oxide-magnesium oxide (SiO ₂ -TiO ₂ -MgO), or a compound containing a small amount of carbonate, sulphate or nitrate in these compounds And examples of the organic compound include starch, cyclodextrin, synthetic polymer, and the like. The solvent used when contacting the catalyst in the solution state with the porous carrier may be an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc .; aliphatic hydrocarbon solvents such as benzene, monochlorobenzene, Aromatic hydrocarbon solvents such as trichlorobenzene and toluene, and halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane, dichloroethane and trichloroethane. When the catalyst for olefin polymerization to be used in the present invention is supported on a carrier, the composition of each component of the catalyst is the same as that of the solution or solid state catalyst, and the loading amount of the aluminum component in the catalyst for olefin polymerization is 100 wt% 5 to 30 parts by weight, preferably 7 to 20 parts by weight, per 100 parts by weight of the catalyst, and the amount of the transition metal component supported on the catalyst is 0.01 to 2 parts by weight, preferably 0.05 to 1.5 parts by weight.

Next, the polymerization method of the polyolefin according to the present invention will be described. Since the catalyst composition exists not only in a homogeneous solution state but also in a form supported on an organic or inorganic porous carrier or in the form of an insoluble particle of a carrier, the polyolefin according to the present invention can be used in a liquid phase, a slurry phase, Can be polymerized. In addition, each polymerization reaction condition may be appropriately modified depending on the state of the catalyst used (homogeneous or heterogeneous phase (supported type)), polymerization method (solution polymerization, slurry polymerization, gas phase polymerization) . If the polymerization is carried out in liquid phase or slurry, the solvent or olefin itself may be used as the medium. As the solvent, propane, butane, pentane, hexane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, benzene, toluene, xylene, dichloromethane, chloroethane, 1,2-dichloroethane, Benzene, etc. These solvents may be mixed in a certain ratio. In the polymerization or copolymerization of the olefin of the present invention, the amount of the first to third organic transition metal compounds is not particularly limited, but the center metal concentration of the first to third organic transition metal compounds in the reaction system used for polymerization is preferably 10 ^-8 to 10 mol / l, more preferably 10 ^-7 to 10 ^-2 mol / l.

In the polymerization or copolymerization of olefins according to the present invention, the polymerization temperature is not particularly limited, since it may vary depending on the reactants, the reaction conditions, etc., but is usually 70 to 110 ° C. Specifically, the polymerization temperature is 0 to 250 ° C, preferably 10 to 200 ° C when solution polymerization is carried out, and 0 to 120 ° C, preferably 20 to 110 ° C when slurry or gas phase polymerization is carried out . Further, the polymerization pressure is from atmospheric pressure to 500 kgf / cm 2, preferably from atmospheric pressure to 60 kgf / cm 2, more preferably from 10 to 60 kgf / cm 2, and the polymerization can be carried out batchwise, semi-continuously or continuously . The polymerization can also be carried out in two or more stages with different reaction conditions, and the molecular weight and molecular weight distribution of the final polymer produced using the catalyst according to the invention can be varied by varying the polymerization temperature or by injecting hydrogen in the reactor . The polymerization of the polyolefin resin according to the present invention can be carried out in a conventional single loop reactor, a gas phase reactor, an internally circulating fluidized bed (ICFB) reactor (see Korean Patent No. 981612, No. 999543, No. 999551, etc.) ≪ / RTI >

The polyolefin according to the present invention can be polymerized through a prepolymerization and a prepolymerization step. In the prepolymerization step, it is preferable that the olefin polymer or copolymer is produced at 0.05 to 500 g, preferably 0.1 to 300 g, more preferably 0.2 to 100 g per 1 g of the olefin catalyst. Examples of the olefins usable in the prepolymerization process include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, And? -Olefins having 2 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, .

Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples illustrate the present invention and are not intended to limit the scope of the present invention. In the following examples, the catalyst was prepared by the Schlenk technique in which air and moisture were completely blocked, and purified dry nitrogen was used as an inert gas. Further, the solvent was dried with sodium metal in an inert nitrogen atmosphere. In the present specification and examples, the measurement method of each property is as follows.

(1) Density: Measured according to ASTM 1505 and ASTM D 1928.

(2) Melt flow index (MIP, 5.0 kg / 10 min): Measured according to ASTM D1238 at 190 占 폚.

(3) High-load Melt Flow Index (MIF, 21.6 kg / 10 min): Measured according to ASTM D1238 at 190 ° C.

(4) Melt Flow Index Ratio (SR): The high load Melt Flow Index (MIF) / melt flow index (MIP)

(5) GPC molecular weight and molecular weight distribution (Mw, Mz, Mz + 1, MWD): Measured as follows using gel permeation chromatography (GPC, 220 products of Polymer Laboratory Inc.). Two separation columns, Olexis and one guard, were used and the column temperature was maintained at 160 ° C. Calibration was performed using a standard polystyrene set manufactured by Polymer Laboratory, and trichlorobenzene containing 0.0125% by weight of dibutyl hydroxyl toluene (BHT) as an antioxidant was used as an eluent. The sample was prepared at a ratio of 0.1 to 1 mg / ml, the injection amount was 0.2 ml, the injection time was 30 minutes, and the pump flow rate was 1.0 ml / min for 30 to 60 minutes. (Mn), weight average molecular weight (Mw) and z average molecular weight (Mz) were measured in terms of polyethylene after the universal calibration using Polystyrene standards Easical A and Easical B (Agilent). As the detector, a refractive index (RI) detector was used. The molecular weight distribution (Mw / Mn) represents the ratio of the weight average molecular weight to the number average molecular weight.

(6) Low molecular weight content (LMW%): The low molecular weight content was extracted using GPC data and Gaussian law analyzed in (5) above using the program (Origin Pro 8.6) Respectively.

(7) Cross-fractionation chromatography (CFC): Cross-fractionation chromatography (CFC, PolymerChar Inc.) was measured as follows. Two separation columns, Olexis and one guard, were used and the column temperature was maintained at 150 ° C. Calibration was performed using a standard polystyrene set from Polymer Laboratory. Trichlorobenzene was used as the eluent. The concentration of the sample was 70 ~ 80 mg / ml, the injection volume was 0.5 ml, and the pump flow rate was 1.0 ml / min. After the injection of the sample, the temperature of the oven was raised to 40 ° C / minute and the temperature was raised to 150 ° C. After holding at 150 캜 for 60 minutes, the temperature was lowered at 40 캜 / min to lower the temperature of the sample to 95 캜. Maintained at 95 캜 for 45 minutes, lowered to 30 캜 at 0.5 캜 / minute, and then kept for 30 minutes. Thereafter, the temperature of the sample was raised from 35 ° C to 120 ° C, and the temperature-divided fractions were divided into 22 fractions at intervals of 4 ° C and 0.5 ml of each sample was injected. The eluted fractions were collected on a TREF column and an Olexis column, The TREF value and the molecular weight were measured. Next, a calibration curve using a standard polystyrene set was used to calculate the PE-converted molecular weight. Data processing was performed using "CFC calibration", which is a device part analysis program. It took about 600 minutes to complete the analysis and an infrared spectrometer was used as the detector.

(8) Melt Tension: A copy graph (Capirograph 1B, manufactured by Toyoseiki) was used to measure the following. Using a capillary having a length of 10 mm and a diameter of 1.0 mm, 5 to 10 g of a pellet sample was measured at a measurement temperature of 230 ° C., a velocity of 10 mm / min, and a draw of 30 m / min And the average value was obtained by measuring three times per one sample.

(9) Tensile Strength at Yield: Measured according to ASTM D638. The test speed was 50 mm / min, and the average value was obtained by measuring 5 times per one specimen.

(10) Elongation: Measured according to ASTM D638. The test speed was 50 mm / min, and the average value was obtained by measuring 5 times per one specimen.

(11) Flexural Modulus: Measured according to ASTM D790. 5% deformation, and 5 measurements per specimen.

(12) Izod impact strength: Measured according to ASTM D256. The width and thickness of the test piece were measured, a V-notch was formed, and the impact strength value was measured by applying a shock to the test piece. The average value was obtained by measuring at least five times.

 (13) Pipe water pressure test: Measured according to KS M ISO 1167. A pipe having an outer diameter of 34 mm and a thickness of 3.5 mm was placed in water at 20 ° C and a circumferential stress corresponding to a pressure of 12.4 MPa was applied to the inside of the pipe to measure the time at which the pipe was broken. A pipe having an outer diameter of 34 mm and a thickness of 3.5 mm was inserted and a circumferential stress corresponding to a pressure of 5.4 MPa was applied to the inside of the pipe to measure the time at which the pipe was broken.

(14) Pipe Appearance: Judged as good, normal, or bad by visual observation.

(15) Evaluation of Product Formability: The extruded product was extruded at an extrusion temperature (die temperature) of 200 mm × 34 mm and a thickness of 3.5 mm using a pipe extruder (Wonil ENG, 16 ㅨ Die Dia., 41 ㅨ Screw Dia. mm were extruded.

(15a) Resin melt pressure (bar): Under the above processing conditions, when the pipe was extruded, the resin melt pressure generated at the extruded site was measured.

(15b) Extrusion amount (g / min): Under the above processing conditions, when the film and the pipe were extruded, the weight of the resin extruded per minute was measured.

(16) Shear Thinning Index (STI): Measured using the following equation (1). A Rhometrics Mechanical Spectrometer (RMS-800) instrument was used, and the method was a parallel plate, measured at a diameter of 25 mm and a temperature of 190 ° C.

[Formula 1]

STI =? _0.1 /? ₁₀₀

Here, η is _0.1 The strain is a viscosity at a rate of 0.1 rad / s, and the value of η ₁₀₀ is a viscosity at a strain rate of 100 rad / s.

       (17) Modulus Ratio Index (MRI): Measured using the following equation (2). A Rhometrics Mechanical Spectrometer (RMS-800) instrument was used. The method was a parallel plate, and was measured at a diameter of 25 mm and a temperature of 190 ° C.

[Formula 2]

MRI = G ' ₁₀₀ / G' _0.1

Where G 'is the storage modulus _0.1 (Storage Modulus) at strain rate 0.1 rad / s, G' ₁₀₀ is It is the storage modulus at a strain rate of 100 rad / s.

       (18) Long Chain Branch / 1,000C: Measured using the following formula 3 (Macromolecules 1999, 32, 8454-8464).

[Formula 3]

LCBI =? ₀ ^0.196 / [?] X1 / 4.7-1

Where η ₀ is the zero shear viscosity at 190 ° C. and [η] is the intrinsic viscosity at 150 ° C.

(19) relaxation time, s (relaxation time, τ ₀ ) was measured using the following equation (4).

 [Formula 4]

η = η ₀ / (1 + (γτ ₀ ) ⁿ )

 Where n is the power law index of the material, η is the measured complex viscosity, and γ is the strain rate, shear rate (x-axis value in the RMS frequency sweep according to the Cox-Mertz rule).

[Preparation Example 1] Preparation of catalyst

(Isobutylcyclopentadienyl) zirconium dichloride ((iBuCp) ₂ ZrCl ₂ ) as a first organic transition metal compound and diphenylmethylidene (normal) as a second organic transition metal compound in a 150 L reactor in a nitrogen atmosphere, Zirconium dichloride (Ph ₂ C (2,7-t-BuFlu)) (nBu-Cp) ZrCl ₂ ) and methyl (methylcyclopentadienyl) (2,7- Alumoxane (MAO, 10% toluene solution, manufactured by Albemarle) was mixed and stirred at 60 DEG C for 60 minutes to prepare a solution. The fired silica (SiO ₂ ) was added to the solution at a temperature of 250 ° C and sonicated for 1 hour, and then the supernatant was removed. Next, the remaining solid particles were washed twice with hexane, and then dried in vacuum to prepare a supported catalyst of a solid powder flowing freely.

[Preparation Example 2] Preparation of catalyst

(Isobutylcyclopentadienyl) zirconium dichloride ((iBuCp) ₂ ZrCl ₂ ) as a first organic transition metal compound and ethylene (bisindenyl) zirconium dichloride as a second organic transition metal compound in a 150 L reactor in a nitrogen atmosphere, Zirconium dichloride (rac-Et (Ind) ₂ ZrCl ₂ ), diphenylmethylidene (n-butylcyclopentadienyl) (2,7-di-tert-butylfluoren- ) Zirconium dichloride (Ph ₂ C (2,7-t-BuFlu)) (nBu-Cp) ZrCl ₂ and methylaluminoxane (MAO, manufactured by Albemarle, 10% toluene solution) ≪ / RTI > to prepare a solution. Silica (SiO ₂ ) calcined at 250 ° C was added to the solution, and ultrasonic waves were applied for 1 hour, and then the supernatant was removed. Next, the remaining solid particles were washed twice with hexane, and then dried in vacuum to prepare a supported catalyst of a solid powder flowing freely.

[Manufacturing Example 3] Pipe molding

A pipe having a nominal diameter of 50 mm, an outer diameter of 60 mm, a thickness of 5.5 mm and an approximate inner diameter of 49 mm was formed by using the polymer of Example 2 and Comparative Examples 1 and 4 through a pipe extruder.

[Examples 1 to 3, Comparative Example 1] Ethylene / 1-hexene copolymerization and physical properties evaluation of the copolymer

The copolymerization method was carried out in accordance with a polymerization method of a continuous single loop method well known to a person skilled in the art, and the mixed supported metallocene catalyst obtained from Preparation Example 1 was continuously fed into a single loop slurry polymerization step at a rate of 1.5 g / h, Polyethylene was prepared by using 1-hexene as a monomer. The polymerization conditions of the polyethylene were described in detail. First, a 53 L single-loop reactor was filled with isobutane, ethylene, hexene-1 and the catalyst were continuously injected to continuously obtain polyethylene. .

Example 1 Example 2 Example 3 Comparative Example 1 Catalyst preparation method Production Example 2 Production Example 2 Production Example 2 Production Example 1 Polymerization temperature (캜) 89 89 89 89 Ethylene mol% 12 12 12 12 1-hexene (wt%) 1.2 1.2 1.2 1.2 Hydrogen (mg / kgC2) 200 150 100 200 Catalytic activity (gPE / gCat-hr) 3,500 3,400 3,200 3,500

[Comparative Examples 2 to 4] Property evaluation of commercial copolymers

The physical properties and formability of three types of commercially available polyethylene products (Comparative Examples 2 to 4) were compared under the same conditions as those of the polyethylene of Examples 1 to 3 and Comparative Example 1. Comparative Example 2 is a product of 8,000 M high density polyethylene produced by Lotte Chemical Co., Comparative Example 3 is a product of HIDEN ^ㄾ P600 high density polyethylene produced by Korea ^Emulsifier , Comparative Example 4 is Yuzex ^ㄾ 6100 high density polyethylene produced by SK Chemical ^Co., Products. The raw materials of Comparative Examples 2 to 4, which are commercially available, were compared with the raw material properties of Examples 1 to 3 and Comparative Example 1, and the results are shown in Table 2 below. The polymer of Examples 1 to 3 and Comparative Example 1 And Comparative Examples 2 to 4 Sheet properties, pipe properties and extrusion moldability of the polyethylene product are shown in Tables 3, 4 and 5.

division Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Number
G
water
castle














MIP (5 Kg), g / 10 min 0.38 0.23 0.19 0.38 0.27 0.21 0.25 SR (F / P) 24.7 25.6 25.1 25.3 22.8 33.2 42.9 Density, g / ㎤ 0.9493 0.9486 0.9491 0.9499 0.9467 0.949 0.9483 Molecular weight distribution Bimodal Bimodal Bimodal Bimodal Bimodal Bimodal Bimodal LMW (%) 55.5 56.4 56.9 58.0 - 54.5 59.7 Mw (g / mol) 157,968 187,076 199,521 179,659 261,642 234,315 263,537 Mz (g / mol) 763,876 864,153 941,756 759,359 1,801,018 1,702,804 2,161,748 Mw > 1,000,000 (%) 4.0 5.5 6.6 6.4 9.6 9.0 10.6 Mw > 5,000,000 (%) 0.01 0.02 0.03 0.06 0.62 0.48 0.86 MWD (Mw / Mn) 13.92 11.90 13.52 15.16 16.98 22.63 25.03 Melt Strength (cN) 3.79 3.73 3.22 2.80 0.20 0.76 0.50 Melt Tension
(gf, @ 230 [deg.] C) 6.01 ND ND 4.43 5.01 4.22 4.5 Shear Thining Index (STI) 21.3 30.5 32 18.7 37.9 44.2 50.7 Modulus Ratio Index (MRI) 167.0 100.4 97.9 164.2 44.2 40.8 30.3 Relaxation Time, τ ₀ (s) 1.85 1.97 1.90 1.66 243.14 65.88 447.05 LCBI 0.07 0.07 0.06 0.11 0.46 0.28 0.65

division Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Sheet properties



Yield point tensile strength, kg / ㎠ 265 255 270 277 248 265 253 Elongation,% 776 753 766 770 804 784 754 Flexural modulus, kg / ㎠ 11651 11439 11537 12169 10213 11281 11296 Izod impact strength,
(Notch, room temperature), kg cm / cm 18.8 33.3 32.7 22.0 28.7 23.3 16.9 Izod impact strength, (Notch, -20 ° C), kg cm / cm 10.3 16.8 19.6 13.6 17.8 12.4 8.8

division Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Pipe properties
HS (20 DEG C @ 12.4 MPa)
→ ISO standard more than 100hr 209.9 > 332 401 > 255 > 215 > 110 217 HS (80 DEG C@5.4 MPa)
→ ISO standard 165hr or more 213 > 1370 > 313 > 215 > 200 > 200 > 200

division Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Pipe formability (200 ° C)

Resin melt pressure (Bar) 96.7 107.5 106.5 114.6 116.8 114.2 99.7 Ampere (A) 61.7 to 64.4 64.4 to 68.0 64.6 to 68.8 66.5 to 69.4 67.7 to 71.5 66.8 ~ 70.1 62.1 to 65.4 Screw revolution
(rpm) 64 64 64 64 64 64 64 Motor rpm (rpm) 970 970 970 970 970 970 970 Extrusion amount
(g / min) 740.0 766.7 776.7 678.3 748 773 767.7 Extrusion amount / resin melt pressure 7.7 7.1 7.3 5.9 6.4 6.8 7.7 Pipe surface Good Good Good Bad Good Good Good

Analysis of the weight average molecular weight, Z average molecular weight, Z + 1 average molecular weight, low molecular weight content, and solubilization temperature in the molded pipe of Examples 1 to 3 and Comparative Example 1 and Comparative Examples 2 to 4 of the polyethylene product The results are shown in Table 6 below.

division Pipe Collection Location Example 2 Comparative Example 1 Comparative Example 4 Mw The center (A) 204,966 175,441 244,754 Outside (B) 209,657 174,158 225,700 Mz A 1,061,098 913,630 2,358,007 B 1,123,767 908,164 2,036,455 Mz + 1 A 2,065,774 1,733,105 5,729,000 B 2,503,773 1,724,060 4,639,116 LMW% A 58.3 58.7 63.8 B 57.5 60.2 67.0 Mw < 10,000,% A 15.5 18.7 23.9 B 14.7 19.5 24.5 Mw > 1,000,000,% A 7.5 5.8 9.7 B 7.7 5.6 8.9 Tm A 130.0 128.0 129.4 B 129.3 128.4 129.7

Classification (Center A → External B) Example 2 Comparative Example 1 Comparative Example 4 ? Mw (%) 2.24 -0.74 -8.44 △ Mz (%) 5.58 -0.60 -15.79 ? Mz + 1 (%) 17.49 -0.52 -23.49 LMW (%) -1.39 2.49 4.78 ? Mw < 10,000 (%) -5.44 4.10 2.45 △ Mw> 1,000,000 (%) 2.60 -3.57 -8.99 Tm (%) -0.54 0.31 0.23

1 is GPC data of the polyethylene obtained in Examples 1 to 3 and Comparative Examples 1 to 4 of the present invention. As shown in FIG. 1, the results of GPC analysis of the polyethylene obtained in Examples 1 to 3 and Comparative Example 1 all show a bimodal form, and the results of GPC analysis of polyethylene of Comparative Example 2, which is commercially available, And the GPC of the polyethylene of Comparative Examples 3 to 4 shows a bimodal form.

As shown in Table 2 and FIG. 1, the weight average molecular weights (Mw) of Examples 1 to 3 and Comparative Example 1 are much lower than the weight average molecular weights of commercially available Comparative Examples 2 to 4. Generally, polyethylene having a high weight average molecular weight is known to have excellent impact strength and long-term properties in terms of physical properties as compared to polyethylene having a relatively low weight average molecular weight. For this reason, in order to increase the physical properties of the product, the weight average molecular weight is increased to the extent that the processability of the product is not reduced. However, as shown in Tables 3 and 4, the polyethylene of Examples 1 to 3 of the present invention exhibits a relatively low weight average molecular weight, but exhibits superior impact strength and long-term properties.

From the viewpoint of moldability, as shown in Table 2, the melt index and the melt index ratio of Example 3 show a very low value as compared with Comparative Examples 1 to 4. This means that the viscosity in the molten state during molding is high and the viscosity is high even under the processing conditions of high strain. However, as shown in Table 5, it exhibits a lower melt pressure and motor ampere during pipe forming in an extruder. This is because the weight average molecular weight of Comparative Examples 2 to 4 is relatively low and thus the viscosity is lower in the high strain region.

It is also important to prevent sagging during pipe forming. In order to increase the dimensional stability, it is important to increase the melt tension and the melt strength. To this end, it is generally intended to increase the polymer content of a weight average molecular weight of 1,000,000 g / mol or more. More preferably, the more the ultrahigh molecular weight polymer having a weight average molecular weight of 10,000,000 g / mol or more, the more the sagging phenomenon is reduced. However, as shown in Table 2 and FIG. 1, the contents of Examples 1 to 3 and Comparative Example 1 are very low in comparison with the contents of Comparative Examples 2 to 4 in comparison with the contents of weight average molecular weight of 1,000,000 g / mol or more. On the other hand, as shown in Figs. 2 and 3, the polymers of Examples 1 to 3 exhibit a very high melt tension and melt strength as compared to Comparative Examples 2 to 4. Fig.

In order to produce a polymer exhibiting a high melt tension and a melt strength, there is a method of increasing the polymer content of a weight average molecular weight of 1,000,000 g / mol or more as mentioned in the above description, and another method is a long chain branch, The number of which is increased. However, in order to produce a product having long-term properties such as pipe, it is necessary to minimize the long-chain branching which reduces the long-term properties. The long chain branch index (LCBI) values defined in the literature Macromolecules 1999, 32, 8454-8464 were analyzed and shown in Table 2. Comparing the LCBI values of Examples 1 to 3 with the LCBI values of Comparative Examples 1 to 4, it shows very low values. As a result, the long-chain branching group for reducing long-term properties is small, and the combination of polymer chains is different from that of the polymer chains of Comparative Examples 1 to 4 in terms of the composition, so that it can be expected to have a high melt tension and melt strength.

It is also important to prevent surface roughness (Melt Fracture) during pipe forming. Polymers used in pipes generally exhibit high weight average molecular weights in order to increase long term properties, and such high molecular weight and high melt viscosity may cause surface roughness during molding. POL YMER ENGINEERING AND SCIENCE, JULY 2004, Vol. 44, No. 7, it is a phenomenon that occurs due to the fact that polymers having relatively low molecular weight in the extruder during molding move toward the pipe outer surface due to chain migration. Here, the inside means, in the case of a pipe, a central portion of the thickness of the pipe, for example, the pipe. Since polymers having relatively low molecular weight located on the outer surface have low modulus of elasticity, it is difficult to retain the frictional energy generated in the extruder wall, and when the extruder is discharged from the extruder, energy is released. Here, the outer surface means a surface abutting with an empty space in the case of a pipe and a surface exposed to the outside. To prevent this, it is necessary to suppress the movement of the polymer chains having a relatively low molecular weight in the extruder in the outer direction. For this purpose, in the present invention, the introduction of a third polymer having a relatively high molecular weight as compared to the low molecular weight polymer and a relatively low molecular weight as compared with the high molecular weight polymer was carried out in the bimodal polymer prepared in Comparative Example 1. This was achieved through the third organic transition metal compound described in Production Example 2. In order to demonstrate the chain movement inhibition effect of the third polymer claimed in the present invention, the pipe was molded as in Production Example 3, and after collecting the sample at the position described in FIG. 4, the weight average molecular weight And gel permeation chromatography (GPC) and DSC to determine the melting temperature (Tm).

As shown in Table 6, the sample taken at the external position (B) of Comparative Example 1 having the bimodal form without the third polymer and the commercially sold Comparative Example 4 had a weight relative to the sample taken at the center position (A) Average molecular weight, Z average molecular weight, and Z + 1 average molecular weight are low.

In addition, bimodal products have higher density of polymer with relatively low molecular weight than polymer with high molecular weight due to processing characteristics and polymer properties. The melting temperatures of the samples taken at the outer (B) position of Comparative Examples 1 and 4 are higher than those of the samples taken at the center (A) position.

The difference in molecular weight and melting temperature depending on each sampling position means that the polymer chains having relatively short length move in the direction of the wall with relatively high stress (friction energy) in the extruder, , Which means that the polymer chains of relatively long length and high modulus of elasticity (G ') move in the direction of center with relatively little energy in the extruder for energy equilibrium.

As shown in Tables 6 and 7, the sample 2 obtained in the present invention has a weight average molecular weight of 2% or more and a Z average molecular weight of 5% or more, as compared with the sample taken at the center position (A) And the average molecular weight of Z + 1 increased by 15% or more. This is because chains having a relatively high molecular weight and a high modulus of elasticity are present on the outer surface so that a high friction energy generated from the wall surface of the extruder can be retained without being released when the extruder is discharged. Through these evaluations, it has been proved that the third polymer inhibits the chain movement of the first polymer and the second polymer so that the surface roughness (Melt Fracture) does not occur.

Overall, in comparison of sheet properties in Table 3, Example 3 of the present invention showed the best results at low temperature and room temperature Izod impact strength.

Although the polymer of Example 3 of the present invention has the lowest melt flow index in Table 5 comparing the pipe formability, even though the resin melt pressure and motor ampere relative to Comparative Examples 1 to 3 polymer are lower than 10% , Showing the highest amount of extrusion, indicating excellent moldability. This resulted in high molding results using low energy. As a result of the water resistance test of the pipe in spite of this high formability, the results of Examples 1 to 3 were equal to or better than those of Comparative Examples 1 to 4. Therefore, the polyethylene of the present invention is superior in moldability and appearance while realizing equivalent physical properties as compared with conventional polyethylene, and has the advantage of increasing the productivity of a molded article with the same energy consumption.

In addition, the molecular weight distributions obtained from gel permeation chromatography (GPC) for the respective polyethylene in Examples 1 to 3 and Comparative Examples 1 to 4 are shown in FIG. Fig. 2 is a graph showing the molecular weight and melt strength of the polyethylene obtained in Examples 1 to 3 and Comparative Examples 1 to 4 of the present invention. Fig. 3 is a graph showing the relationship between the molecular weight and the melt strength of the polyethylene obtained in Examples 1 to 3 and Comparative Examples 1 to 4 A graph showing the relationship between the pulling speed and the melt strength of polyethylene. As shown in Figs. 2 and 3, the polyethylene obtained in Examples 1 to 3 exhibited a relatively excellent fusion strength as compared with the polyethylene obtained in Comparative Examples 1 to 4, and showed similar melt strength when the pulling rate was low, As the pulling speed increases, the required force increases and exhibits excellent melt strength.

Fig. 4 is a view showing sampling positions of pipes made of polyethylene obtained in Example 2, Comparative Example 1 and Comparative Example 4. Fig. As shown in Fig. 4, a sample was taken according to Fig. 4 and the following definition 1 for molecular weight analysis according to the position of the formed pipe.

[Definition 1]

In a pipe having a standard value ratio SDR = od / en (Standard Dimension Ratio) value of 2 to 20,

Where id is the inner diameter, od is the outside diameter, and en is the wall thickness.

Claims (18)

(1), wherein the polymer has a melt strength of 1 cN or more as measured by a capillary rheometer and is characterized by comprising at least one first organic transition metal compound represented by the following formula (1), one represented by the following formula And a catalyst composition comprising at least one second organic transition metal compound, at least one third organic transition metal compound represented by the following general formula (3), and aluminoxane.
(1) Density (d): 0.934 to 0.954 g / cm &lt; 3 &gt;;
(2) Melt flow index (MIP, 190 캜, 5.0 kg load condition): 0.1 to 10.0 g / 10 min;
(3) a ratio (Mw / Mn, Molecular weight distribution (MWD)) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) measured by gel permeation chromatography (GPC): 10 to 60;
(4) When the molecular weight is measured by gel permeation chromatography (GPC), two or more peaks appear;
(5) the weight average molecular weight (Mw) of the polymer taken at position B of Definition 1 below in a shaped pipe exceeds 0.1% of the weight average molecular weight (Mw) of the polymer taken at position A;
(6) In a molded pipe, the polymer taken at position A in the following definition 1 has a weight average molecular weight (Mw) of not more than 10,000 and a polymer taken at position B has a weight average molecular weight (Mw) By weight, more than 0.1% by weight; And
(7) In a molded pipe, the content of a polymer having a weight average molecular weight (Mw) of 1,000,000 or more and a polymer taken at a position B of the following definition 1 in a polymer having a weight average molecular weight (Mw) It is more than 0.1 wt% than the content.
[Definition 1]
In a pipe having a standard value ratio SDR = od / en (Standard Dimension Ratio) value of 2 to 20,

Where id is the inner diameter, od is the outside diameter, and en is the wall thickness.

(L ¹ ) (L ² ) (X ¹ ) (X ² ) M ¹
???????? (L ³ -Q ¹ _n -L ⁴ ) (X ³ ) ????? (X ⁴ ) M ²
(L ⁵ -Q ² _n -L ⁶ ) (X ⁵ ) (X ⁶ ) M ³
M ¹ , M ² and M ³ are independently titanium, zirconium (Zr) or hafnium (Hf), and L ¹ , L ² , L ³ , L ⁴ and L ⁵ and L ⁶ are each independently a cyclic hydrocarbon group having 5 to 30 carbon atoms and having at least two conjugated double bonds and X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently halogen And Q ¹ and Q ² are each independently a silane group or a hydrocarbon group containing a substituent and n is an integer of 1 to 5. The method according to claim 1, wherein the melt flow index (MIP, 190 캜, 5.0 kg load condition) is 0.1 to 1 g / 10 min, the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) (Mw / Mn) of the average molecular weight (Mn) is 12 to 50, and the weight average molecular weight (Mw) of the polymer collected at the position B of the above definition 1 is (Mw) of the polymer taken at position B is greater than 1% of the weight average molecular weight (Mw) of the polymer taken at position A, and the polymer taken at position A has a weight average molecular weight (Mw) of at least 1,000,000 is greater than 1% by weight of the polymer taken at position B and having a weight average molecular weight (Mw) of at least 1,000,000, wherein the polymer has a weight average molecular weight By weight of the polyolefin resin The pipe. The pipe according to claim 1, wherein the polyolefin resin has a weight average molecular weight (Mw, measured by gel permeation chromatography) of 100,000 to 400,000. The pipe according to claim 1, wherein the polyolefin resin has a melt index flow ratio (SR) value of 10 to 300. The pipe according to claim 1, wherein the polyolefin resin has a Relaxation Time value of 400 seconds or less. The pipe according to claim 1, wherein the polyolefin resin has a viscosity ratio (STI) value of 20 to 100. The pipe according to claim 1, wherein the polyolefin resin has an elastic ratio (MRI) value of 20 to 200. The pipe according to claim 1, wherein the long-chain branch (LCBI) value of the polyolefin resin is 1 / 1,000C or less. The pipe according to claim 1, further comprising a polyolefin resin satisfying the following conditions (10) and (11).
(10) According to KS M 3408, the pipe breakdown time shall exceed 165 hours in the pipe water pressure test to measure the time at which the pipe is broken by applying a stress corresponding to a pressure of 5.4 MPa at 80 ° C water.
(11) According to KS M 3408, the pipe breaking time exceeds 100 hours in the pipe water pressure test, which measures the time at which the pipe is broken by applying a stress corresponding to a pressure of 12.4 MPa at 20 ° C water. (1), wherein the composition has a melt strength of 1 cN or more as measured by a capillary rheometer and satisfies the following requirements (1), (2), (8) , At least one second organic transition metal compound represented by the following formula (2), at least one third organic transition metal compound represented by the following formula (3), and aluminoxane.
(1) Density (d): 0.934 to 0.954 g / cm &lt; 3 &
(2) Melt flow index (MIP, 190 캜, 5.0 kg load condition): 0.1 to 10.0 g / 10 min,
(8) The Z-average molecular weight (Mz) measured by gel permeation chromatography (GPC) of the polymer taken at the position B in the following definition 1 in the shaped pipe is smaller than the Z-average molecular weight (Mz) of the polymer collected at the position A Exceeding 0.1%,
(9) The Z + 1 average molecular weight (Mz + 1) measured by gel permeation chromatography (GPC) of the polymer taken at position B in the following definition 1 in the shaped pipe is the Z + 1 It exceeds 1% of average molecular weight (Mz + 1).
[Definition 1]
In a pipe having a standard value ratio SDR = od / en (Standard Dimension Ratio) value of 2 to 20,

Where id is the inner diameter, od is the outside diameter, and en is the wall thickness.

(L ¹ ) (L ² ) (X ¹ ) (X ² ) M ¹
???????? (L ³ -Q ¹ _n -L ⁴ ) (X ³ ) ????? (X ⁴ ) M ²
(L ⁵ -Q ² _n -L ⁶ ) (X ⁵ ) (X ⁶ ) M ³
M ¹ , M ² and M ³ are independently titanium, zirconium (Zr) or hafnium (Hf), and L ¹ , L ² , L ³ , L ⁴ and L ⁵ and L ⁶ are each independently a cyclic hydrocarbon group having 5 to 30 carbon atoms and having at least two conjugated double bonds and X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently halogen And Q ¹ and Q ² are each independently a silane group or a hydrocarbon group containing a substituent and n is an integer of 1 to 5. The process according to claim 10, wherein the melt flow index (MIP, 190 ° C, 5.0 kg load condition) is 0.1 to 1 g / 10 min. Measured by gel permeation chromatography (GPC) of the polymer taken at position B, and the Z average molecular weight (Mz) measured by GPC is more than 1% of the Z average molecular weight (Mz) of the polymer collected at position A Wherein the Z + 1 average molecular weight (Mz + 1) is greater than 5% of the Z + 1 average molecular weight (Mz + 1) of the polymer taken at position A; 11. The polyolefin resin according to claim 10, wherein the polyolefin resin has a Z average molecular weight (Mz, measured by a gel permeation chromatography) of 100,000 to 10,000,000 and a Z + 1 average molecular weight (Mz + Measured) is from 1,000,000 to 10,000,000. The pipe according to claim 10, wherein the polyolefin resin has a melt index flow ratio (SR) value of 10 to 300. The pipe according to claim 10, wherein the polyolefin resin has a Relaxation Time value of not more than 400 seconds. The pipe according to claim 10, wherein the polyolefin resin has a viscosity ratio (STI) value of 20 to 100. The pipe according to claim 10, wherein the polyolefin resin has an elastic ratio (MRI) value of 20 to 200. The pipe according to claim 10, wherein the long-chain branch (LCBI) value of the polyolefin resin is 1 / 1,000C or less. delete

Images