WO2016060445A1

WO2016060445A1 - Ethylene/1-hexene or ethylene/1-butene copolymer having outstanding working properties and environmental stress cracking resistance

Info

Publication number: WO2016060445A1
Application number: PCT/KR2015/010788
Authority: WO
Inventors: 김중수; 권혁주; 최이영; 이기수; 송은경; 송낙규; 홍대식; 김우리; 김시용
Original assignee: 주식회사 엘지화학
Priority date: 2014-10-13
Filing date: 2015-10-13
Publication date: 2016-04-21

Abstract

The present invention relates to an ethylene/1-hexene or ethylene/1-butene copolymer having outstanding working properties. The ethylene/1-hexene or ethylene/1-butene copolymer according to the present invention has a high molecular weight and a wide molecular weight distribution and has outstanding working properties and has outstanding environmental stress cracking resistance and hence can be used in high-pressure heating piping, mining pipes or large-diameter pipes and the like.

Description

【Specification】

[Name of invention]

^'' Ethylene / 1-Nexene or Ethylene / 1-Butene Copolymer with Excellent Processability and Environmental Impact Crack Resistance

[Cross Citation with Related Application (s)]

This application is filed with Korean Patent Application No. 10-2014-0137867 filed October 13, 2014, Korean Patent Application No. 10-2014-0137868 filed October 13, 2014, and Korean Patent Application No. 10-2015 filed October 13, 2015 Claiming the benefit of priority based on -0142491, all contents disclosed in the literature of the relevant Korean patent application are incorporated as part of this specification.

Technical Field

The present invention relates to an ethylene / 1—nuxene or ethylene / 1-butene copolymer having excellent processability and environmental impact crack resistance.

Background Art

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed for their respective characteristics. Ziegler-Natta catalysts have been widely applied to existing commercial processes since the invention in the 50s, but are characterized by a wide molecular weight distribution of polymers because they are multi-multi-site catalysts with multiple active sites. There is a problem that there is a limit in securing the desired physical properties because the composition distribution of the monomer is not uniform. Meanwhile, the metallocene catalyst is composed of a combination of a main catalyst composed mainly of transition metal compounds and a cocatalyst composed of an organometallic compound composed mainly of aluminum, and such a catalyst is a homogeneous complex catalyst. catalyst), the molecular weight distribution is narrow according to the characteristics of the single active site, the homogeneous composition of the comonomer is obtained, the stereoregularity of the polymer according to the ligand structure modification and the polymerization conditions of the catalyst, copolymerization characteristics, It has the characteristic to change molecular weight, crystallinity, etc. U.S. Patent No. 5,914,289 describes a method for controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount of solvent used to prepare a supported catalyst and It takes a lot of time to prepare, and it was cumbersome to support each of the metallocene catalyst used. Korean Patent Application No. 2003-12308 discloses a method of controlling the molecular weight distribution by supporting a double-nucleated metallocene catalyst and a mononuclear metallocene catalyst on a carrier together with an activator to polymerize by changing the combination of catalysts in the reactor. Doing. However, this method has a limitation in realizing the characteristics of each catalyst at the same time, and also has the disadvantage that the metallocene catalyst portion is liberated in the carrier component of the finished catalyst to cause fouling during the reaction. . Therefore, in order to solve the above disadvantages, there is a continuous need for a method of preparing an olefin polymer having a desired physical property by preparing a common supported metallocene catalyst having excellent activity. On the other hand, linear low density polyethylene is prepared by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst, and has a narrow molecular weight distribution, a short chain branch of a constant length, and a long chain branch. The linear low density polyethylene film has the characteristics of general polyethylene, and has high breaking strength and elongation, and excellent tearing strength and fall stratification strength, so that the use of stretch film or overlap film, which is difficult to apply to the existing low density polyethylene or high density polyethylene, increases. Doing. By the way, linear low density polyethylene using 1-butene or 1-nuxene as comonomers is mostly manufactured in a single gas phase reactor or a single loop slurry reaction vessel, and is more productive than a process using 1-octene comonomers, but these products are also Due to the limitation of catalyst technology and process technology, physical properties are inferior to that of 1-octene comonomer, and molecular weight distribution is narrow, resulting in poor processability. have. Many efforts have been made to improve this problem and US Patent No. 4 935,474 describes two methods for producing polyethylene having a wide molecular weight distribution using two or more metallocene compounds. U.S. Patent No. 6,828,394 describes a process for producing polyethylene, which has good processability and is particularly suitable for films, using a combination of good comonomer bonds and good non-commonomers. In addition, US Patent Nos. 6, 841, 631, and US Patent Nos. 6, 894, and 128 are used as metallocene catalysts using at least two metal compounds, and polyethylene having bimodal or polycrystalline molecular weight distribution is used. It is described that it can be applied to the use of film, blow molding, pipe and the like. However, these products have improved processability, but there is a problem in that the extrusion appearance is rough and the physical properties are not stable even under relatively good extrusion conditions because the dispersion state by molecular weight in unit particles is not uniform. Against this background, there is a constant demand for manufacturing a better product having a balance between physical properties and processability, and in particular, an improvement in environmental stress cracking resistance is required.

[Content of invention]

[Problem to solve]

In order to solve the problems of the prior art, the present invention is to provide an ethylene / 1-nuxene or ethylene / 1-butene copolymer excellent in workability and excellent in environmental impact crack resistance.

[Solution of problem]

In order to solve the above problems, the present invention provides a cetylene / 1-nuxene or ethylene / 1-butene copolymer satisfying the following conditions:

The weight average molecular weight (g / mol) is 10, 000 to 400, 000,

Molecular weight distribution (Mw / Mn, PDI) is 2 to 30,

Environmental stress crack resi st ance instantiated by full notch creep test (FNCT) according to ISO 16770 at 4.0 MPa and 80 ^° C; ESCR) is 400 hours to 20,000 hours,

Ethylene / 1-nuxene or ethylene / 1-butene copolymers. Hereinafter, the present invention will be described in detail. Ethylene / 1-Nexene Copolymer

Preferably, the ethylene 八 -nuxene copolymer according to the present invention,

Density (g / cirf) is from 0.930 to 0.950,

MFR ₂ .i ₆ (g / 10 min, measured by ASTM 1238 at 190 ^° C) is 0.1 to 5,

A melt flow rate ratio _{_{_{(MFR 21. 6 / MFR 2}}} . 16, measured by ASTM 1238 eseo 190 ^° C) is 10 to 200. Also preferably, the weight average molecular weight (Mw, g / mol) of the ethylene / 1-nuxene copolymer is 10,000 to 400,000. More preferably, the weight average molecular weight is 50,000 or more, 60,000 or more, 70,000 or more, 80,000 or more, 90,000 or more, 100,000 or more, 110,000 or more, or 120,000 or more, 350,000 or less, 300,000 or less, 250,000 or less, 200,000 or less, or 150,000 It is as follows. Also preferably, the molecular weight distribution (Mw / Mn, PDI) of the ethylene / 1-nuxene copolymer is 2 to 30. According to the broad molecular weight distribution as described above, the ethylene / 1-nuxene copolymer may exhibit excellent processability. More preferably, the molecular weight distribution is 3 or more, 25 or less, 20 or less, 15 or less, 14 or less, 13 or less, 12 or less, 11 or less, or 10 or less. The ethylene / 1-nuxene copolymer of the present invention has a high molecular weight and a wide molecular weight distribution and has excellent physical properties and processability. In addition, the ethylene / 1-nuxene copolymer of the present invention, known ethylene / 1-nuxene Compared with the copolymer, it has a wider molecular weight distribution and a melt flow rate ratio (MFRR), so that the fluidity is remarkably improved, thereby showing better processability. Preferably, the ethylene / 1-haeksen copolymer, a melt flow rate ratio _{_{(MFRR, MFR 21. 6 /}} MFR 2. 16) is 10 to 200. By having the melt flow rate ratio in the above range, the flowability at each load can be appropriately adjusted, and workability and mechanical properties can be improved at the same time. More preferably, the melt flow rate ratio is 15 or more, 20 or more, 25 or more, or 30 or more, 190 or less, 180 or less, 170 or less, 160 or less, 150 or less, 140 or less, 130 or less, or 120 or less. Also preferably, MF¾. ₁₆ (melt flow index, measured at 190 ^° C., 2.16 kg load according to ASTM D1238) is 0.1 to 5 g / 10 min, more preferably 0.1 to 3 g / 10 min. Also preferably, the density of the ethylene / 1 'nucleene copolymer is 0.930 to 0.950 g / cirf, preferably 0.935 to 0.950 g / cuf. Also preferably, the ethylene / 1-nuxene copolymer has an environmental stress crack resistance (ESCR) of 400 MPa measured by full notch creep test (FNCT) according to ISO 16770 at 4.0 MPa and 80 ^° C. 1 hour to 20,000 hours. More preferably, the environmental stress crack resistance is 600 hours or more, 800 hours or more, 1,000 hours or more, 1,200 hours or more, 1,400 hours or more, 1,600 hours or more, 1,800 hours or more, or 2,000 hours or more. In addition, the larger the value of the environmental stress crack resistance is the better the physical properties, so there is no practical limit to the upper limit, for example, 8,760 hours or less, 8,000 hours or less, its 000 hours or less, 6,000 hours or less, 5,000 hours or less, 4,000 hours or less ， Or 3,000 hours or less. In the ethylene / 1 'nucleene copolymer, the content of the 1-nucleene comonomer may be about 0.5 to about 10 weight%, preferably about 1 to about 5 weight). However, it is not limited thereto. Ethylene / 1-Butene Copolymer

Preferably, the ethylene / 1-butene copolymer according to the present invention is

Density (g / cu) is 0.930 to 0.950,

MFR ₅ (g / 10 min, measured by ASTM 1238 at 190 ^° C) is 0.1 to

5

The melt flow rate ratio (MFR ₂₁ _.6 / MF¾, measured by ASTM 1238 at 190 ^° C.) is 10 to 200. Also preferably, the weight average molecular weight (Mw, g / mol) of the ethylene / 1-butene copolymer is 10,000 to 400, 000. More preferably, the weight average molecular weight is 50,000 or more, 100,000 or more, 150,000 or more, 200,000 or more, 210,000 or more, 220,000 or more, or, 230,000 or more, 350,000 or less, 300,000 or less, 290,000 or less, 280,000 or less, 270,000 or less, 260,000 Or 250,000 or less. Also preferably, the molecular weight distribution (Mw / Mn, PDI) of the ethylene / 1-butene copolymer is 2 to 30. According to the broad molecular weight distribution as described above, the ethylene / 1-butene copolymer may exhibit excellent processability. More preferably, the molecular weight distribution is 5 or more, 7 or more, 10 or more, 15 or more, 16 or more, 17 or more, 18 or more, or 19 or more, 28 or less, 27 or less, 26 or less, 25 or less, 24 or less. 23 or less, or 12 or less. The ethylene / 1-butene copolymer of the present invention has a high molecular weight and a wide molecular weight distribution, and has excellent effects on physical properties and processability. In addition, the ethylene / 1'butene copolymer of the present invention has a wider molecular weight distribution and a melt flow rate ratio (MFRR) than the known ethylene / 1-butene copolymer, and thus the fluidity is remarkably improved, and thus it is possible to exhibit more excellent processability. Preferably, the ethylene / 1-butene copolymer has a melt flow rate ratio (MFRR, MFR _21.6 / MFR ₅ ) of 10 to 200. By having the melt flow rate ratio in the above range, the flowability at each load can be appropriately adjusted, thereby improving workability and mechanical properties at the same time. More preferably, the melt flow rate ratio is 15 or more, 20 or more, 25 or more, or 30 or more, 180 or less, 150 or less, 100 or less, 50 or less, 40 or less, 35 or less, 34 or less, or 33 or less. _. Also preferably, MFR ₅ (melt flow index measured at 190 ^° C., 5 kg load based on ASTM D1238) of the ethylene / 1-butene copolymer is 0.1 to 5 g / 10 min, more preferably 0.1 To 3 g / 10 min. Also preferably, the density of the ethylene / 1-butene copolymer is 0.930 to 0.950 g / cuf, preferably 0.935 to 0.950 g / cirf. Also preferably, the ethylene / 1 \ butene copolymer has an environmental stress ^' encracking resistance (ESCR) measured by full notch creep test (FNCT) according to ISO 16770 at 4.0 MPa and 80 ^° C. 400 hours to 20,000 hours. More preferably, the X-ray environmental stress crack resistance is at least 600 hours, at least 800 hours, at least 1,000 hours, at least 1,200 hours, at least 1,400 hours, at least 1,600 hours, at least 1,800 hours, or at least 2,000 hours. to be. In addition, the larger the value of the environmental stress cracking resistance is the better the physical properties, so there is no practical limit to the upper limit, for example, 8,760 hours or less, 8,000 hours or less, 7,000 hours or less, 6,000 hours or less, 5,000 hours or less, 4,000 hours or less, or It can be up to 3,000 hours. In the ethylene / 1-butene copolymer, the content of the 1-butene comonomer may be about 0.5 to about 10% by weight, preferably about 1 to about 5% by weight, but is not limited thereto. Catalyst for preparing copolymer

The ethylene / 1-nuxene or ethylene / 1-butene copolymer as described above can be prepared using a metallocene catalyst. The metallocene catalyst that can be used includes at least one first metallocene compound represented by Formula 1 below; And at least one mixture of the second metallocene compound selected from compound compounds represented by the following Chemical Formulas 3 to 5.

[Formula 1]

In Chemical Formula l,

A is hydrogen halogen, Cwo alkyl, C ₂ - ₂₀ alkenyl, C ₆ - ₂₀ aryl, C ₇ - ₂₀ alkylaryl, C ₇ - ₂₀ arylalkyl, CHO alkoxy, C2-20 alkoxyalkyl, C ₃ - ₂₀ heterocycloalkyl alkyl, or C ₅ - ₂₀ membered heteroaryl;

D is -E, -S-, -N (R)-or -Si (RR ')-, wherein R and R' are the same as or different from each other, and are each independently hydrogen, halogen, d-20 alkyl, C ₂ - ₂₀ alkenyl, or C ₆ - ₂₀ aryl;

L is d- ₁₀ straight or branched chain alkylene;

. B is carbon, silicon, or germanium;

Q is hydrogen, halogen, alkyl, C ₂ - ₂₀ alkenyl Al, C ₆ - ₂₀ aryl, C ₇ - ₂₀ alkylaryl, or C ₇ - ₂₀ aryl-alkyl;

M is a Group 4 transition metal;

X ¹ and X ² are the same or different and are each independently halogen, Cwo alkyl, C ₂ - ₂₀ alkenyl, C ₆ - ₂₀ aryl, nitro, amido, d- ₂₀ alkylsilyl, ₂₀ alkoxy, or sulfone carbonate Cwo ego;

C ¹ and C ² are the same as or different from each other, and are each independently represented by one of the following Chemical Formula 2a, Chemical Formula 2b, or Chemical Formula 2c, except that C ¹ and C ² are both Chemical Formula 2c;

[Formula 2a]

In the general formula 2a, 2b and 2c, to R ₁₇ and "to" are the same or different and are each independently hydrogen, halogen, ₍₂₀ alkyl, C ₂ - ₂₀ alkenyl, ₂₀ alkylsilyl, silyl, alkoxy silyl , d- ₂₀ alkoxy, C ₆ eu ₂₀ aryl, C ₇ - ₂₀ alkylaryl, or C ₇ -. ₂₀ and arylalkyl, wherein R ₁₀ to R ₁₇ is of the two or more adjacent to each other are connected to each other substituted or unsubstituted Aliphatic or Can form an aromatic ring;

[Formula 3] In Formula 3,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals One, they may be substituted with a hydrocarbon of 1 to 20 carbon atoms;

R ^a and ^ are the same or different, each independently represent hydrogen, alkyl, and ₍₁₀ alkoxy, C ₂ of each other - ₂₀ alkoxyalkyl, C ₆ - ₂₀ aryl, C ₆ - ₁₀ aryloxy, C ₂ - ₂₀ alkenyl, C _{_7-40} alkylaryl, C _{_7-40} arylalkyl, C ₈ - ₄₀ arylalkenyl, or C ₂ - ₁₀ alkynyl;

Z ¹ is a halogen atom, d- ₂₀ alkyl, C ₂ - ₁₀ alkenyl, C ₇ - ₄₀ alkylaryl, C ₇ - ₄₀ arylalkyl, C ₆ - ₂₀ aryl, optionally substituted d-20 alkylidene, substituted unsubstituted amino, C ₂ - ₂₀ alkyl, an alkoxy, or a C ₇ - ₄₀ aryl-alkoxy;

n is 1 or 0;

[Formula 4] In Formula 4,

M ² is a Group 4 transition metal;

Cp ³ and Cp ⁴ are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals They may be substituted with a hydrocarbon having 1 to 20 carbon atoms;

R ^c and R ^d are the same or different and each is independently hydrogen, alkyl, each ₍₁₀ alkoxy, C ₂ - ₂₀ alkoxyalkyl, C ₆ - ₂₀ aryl, C ₆ - ₁₀ aryloxy, C ₂ - ₂₀ alkenyl, C ₇ -4o alkylaryl, C ₇ - ₄₀ arylalkyl, C ₈ - ₄₀ arylalkenyl, or C ₂ - ₁₀ alkynyl;

Z ² is a halogen atom, d- ₂₀ alkyl, C ₂ - ₁₀ alkenyl, C ₇ - ₄₀ alkylaryl, C ₇ - ₄₀ Arylalkyl, C ₆ - ₂₀ aryl, optionally substituted d- ₂₀ alkylidene, substituted or unsubstituted amino, C ₂ - ₂₀ alkyl, an alkoxy, or a C ₇ - ₄₀ aryl-alkoxy;

B ¹ is one or more of a carbon, germanium, silicon, phosphorus or nitrogen atom containing radical which crosslinks the Cp¾ ^c ring and the Cp ⁴ R ^d ring or crosslinks one Cp ⁴ R ^d ring to M ² or Is a combination of;

m is 1 or 0;

[Formula 5]

In Chemical Formula 5,

M ³ is a Group 4 transition metal;

Cp ⁵ is any one selected from the group consisting of cyclopentadienyl, indenyl, 4, 5, 6, gtetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms And;

R ^e is hydrogen, alkyl, d- ₁₀ alkoxy, C ₂ - ₂₀ alkoxyalkyl, C ₆ - ₂₀ aryl, C ₆ - 10 aryloxy, C ₂ - ₂₀ alkenyl, C ₇ - ₄₀ alkylaryl, C ₇ - ₄₀ Arylalkyl, C ₈ ᅳ ₄₀ arylalkenyl, or C ₂ — ₁₀ alkynyl;

Z ³ is a halogen atom, alkyl, C ₂ - ₁₀ alkenyl, C ₇ - ₄₀ alkylaryl, C ₇ - ₄₀ arylalkyl, C ₆ _ ₂₀ aryl, substituted or unsubstituted ₍₂₀ alkylidene, substituted or unsubstituted amino, C ₂ - ₂₀ alkyl, an alkoxy, or a C ₇ - ₄₀ aryl-alkoxy;

B ² is at least one or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp¾ ^e ring and J;

J is any one selected from the group consisting of NR ^f , 0, PR ^f and S, wherein R ^f is alkyl, aryl, substituted alkyl, or substituted aryl. Hereinafter, the substituents of Chemical Formulas 1, 3, 4, and 5 will be described in more detail. The CHO alkyl includes straight chain or branched alkyl, and specifically methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, nuclear chamber, heptyl, octyl, etc., but only It is not limited. The C ₂ - to ₂₀ alkenyl, including alkenylene of straight or branched chain and, specifically allyl, ethenyl, propenyl, butenyl, pentenyl, but may include a circle, and thus are not limited thereto. The C _S - ₂₀ aryl includes monocyclic or condensed aryl, and specifically includes phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, and the like, but is not limited thereto. The C ₅ - ₂₀ heteroaryl group include a monocyclic or condensed ring includes heteroaryl, carbazolyl, pyridyl, quinoline, isoquinoline, thiophenyl, furanyl, imidazole, oxazolyl, thiazolyl, triazine, tetrahydro Hydropyranyl, tetrahydrofuranyl, and the like, but is not limited thereto. Examples of the C alkoxy include mesooxy, ethoxy, phenyloxy, cyclonuxyloxy, and the like, but are not limited thereto. To the Group 4 transition metal it may include titanium, zirconium, hafnium, etc., but not limited only thereto _i. R ₁₇ and to 'in Formulas 2a, 2b, and 2c are each independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl tert-butyl, pentyl, nucleus, heptyl, octyl, phenyl, halogen, trimethylsilyl And triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, methoxy, or ethoxy, but are not limited thereto. L of the general formula (1) is C ₄ - ₈ straight or branched chain alkylene of one to more preferred, but is not limited thereto only. Further, the alkylene group alkyl, C ₂ - ₂₀ alkenyl, or C ₆ - can be unsubstituted or substituted with ₂₀ aryl. In addition, A in Formula 1 is hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, mesooxymethyl, tert-butoxymethyl, 1-ethoxyethyl, 1-methyl- 1-meth It is preferably oxyethyl, tetrahydropyranyl, or tetrahydrofuranyl, but is not limited thereto. In addition, B of Formula 1 is preferably silicon, but is not limited thereto. The first metallocene compound of Chemical Formula 1 may form a structure in which an indeno indol derivative and / or a fluorene derivative are crosslinked by a bridge, and may act as a Lewis base to the ligand structure. By having a non-covalent electron pair, it is supported on the surface having the Lewis acid characteristic of the carrier and shows high polymerization activity even when supported. It is also highly active as it contains an electronically rich indeno indole group and / or fluorene group, and due to proper steric hindrance and electronic effects of lagande, not only has low hydrogen reaction but also maintains high activity even in the presence of hydrogen. do. In addition, the beta-hydrogen of the polymer chain in which the nitrogen atom of the indeno indole derivative is grown is stabilized by hydrogen bonding to inhibit beta-hydrogen eliminat ion, thereby polymerizing an ultra-high molecular weight olefin polymer. According to an embodiment of the present invention, specific examples of the compound represented by Chemical Formula 2a may include a compound represented by one of the following structural formulas, but the present invention

According to an embodiment of the present invention, specific examples of the compound represented by Chemical Formula 2b may include a compound represented by one of the following structural formulas, but the present invention is limited thereto.

According to an embodiment of the present invention, specific examples of the compound represented by Formula 2c may include a compound represented by one of the following structural formulas, but the present invention

According to one embodiment of the present invention, a specific example of the metallocene compound represented by Chemical Formula 1 may be represented by one of the following structural formulas, but is not limited thereto.

LI

88.OTO / SlOZaM / X3d S »090 / 9I0Z OAV

The Crabium 1 metallocene compound of Chemical Formula 1 has excellent activity and may be a high molecular weight ethylene / 1-nuxene or ethylene / 1-butene copolymer. In particular, it exhibits high polymerization activity even when used on a carrier. Ultra high molecular weight ethylene / 1-nuxene or ethylene / 1'butene copolymers can be prepared. In addition, the first metal of the general formula (1) according to the present invention in the case of the polymerization reaction including hydrogen in order to produce an ethylene / 1- nucene or ethylene / 1- butene copolymer having a high molecular weight and a wide molecular weight distribution The Rosene compound exhibits low hydrogen reaction properties and is still capable of polymerizing ultra high molecular weight ethylene / 1-nuxene or ethylene / 1-butene copolymers. Therefore, even when used in a mixture with a catalyst having other properties, an ethylene / 1'nucleene or ethylene / 1'butene copolymer can be produced that satisfies the high molecular weight properties without degrading the activity. Ethylene / 1'nucleene or ethylene / 1-butene copolymer having a wide molecular weight distribution while including a hexane or ethylene / 1'butene copolymer can be easily produced. The first metallocene compound of Chemical Formula 1 is prepared as a ligand compound by connecting an indenoindole derivative and / or fluorene derivative with a bridge compound, and then a metal precursor compound is added to perform metallization (retal iat ion). Can be obtained. The manufacturing method of the said 1st metallocene compound is concretely demonstrated to the Example mentioned later. The compound represented by Chemical Formula 3 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.

In Formula 4, when m is 1, it means that Cp¾ ^c ring and Cp ⁴ R ^d ring or Cp ^{4 d} ring and M ² is a bridge compound structure cross-linked by B ¹ , when m is 0 It means a non-crosslinked compound structure. The compound represented by Chemical Formula 4 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.

88.OTO / SlOZaM / X3d S »090 / 9I0Z OAV

In addition, the compound represented by Formula 5 may be, for example, a compound represented by the following structural formula. It is not limited only to this.

A metal used in the present invention, the metallocene catalyst is one of the metallocene compound to the second metal is selected from compounds represented by at least one of the metallocene compound to the first metal of the formula (1), and the formula (3) to ^"general formula (5) At least one species may be supported on a carrier together with a promoter compound. In addition, the supported metallocene catalyst may induce the production of a long chain branch (LCB) in the ethylene / 1-nuxene or ethylene / 1-butene copolymer prepared. In the supported metallocene catalyst according to the present invention, the cocatalyst supported on the carrier for activating the metallocene compound is an organometallic compound containing a Group 13 metal, and polymerizes the olefin under a general metallocene catalyst. If it can be used when it is not particularly limited. Specifically, the promoter compound contains aluminum of the following formula (6) It may include one or more of the first cocatalyst, and the borate-based second cocatalyst of the formula (7).

[Formula 6]

In Formula 6, R ₁₈ are each independently a halogen, halogen substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more, [Formula 7]

T ⁺ [BG ₄ ] ^to

In formula (7), T ⁺ is a + monovalent polyatomic ion, Β is boron in +3 oxidation state, G is independently hydride, dialkylamido, halide, alkoxide, aryloxide hydrocarbyl, halocarbyl and Selected from the group consisting of halo-substituted hydrocarbyls, wherein G has up to 20 carbons, but at up to one position G is a halide. By using these first and second cocatalysts, the molecular weight distribution of the finally produced polyolefin can be made more uniform, and the polymerization activity can be improved. The U cocatalyst of Chemical Formula 6 may be an alkylaluminoxane compound having a repeating unit-linked linear, circular or reticular type. Specific examples of the first cocatalyst include methylaluminoxane (MA0) and ethyl. Aluminoxane, isobutyl aluminoxane, butyl aluminoxane, etc. are mentioned. In addition, the second cocatalyst of Formula 7 may be a borate-based compound in the form of a trisubstituted ammonium salt, or a dialkyl ammonium salt, a trisubstituted phosphonium salt. Specific examples of such a second cocatalyst include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate and tripropylammonium tetraphenylborate _: tri (η-butyl) ammonium tetraphenylborate , Methyltetracyclooctadecylammonium tetraphenylborate, Ν, Ν- dimethylaninium tetraphenylborate, Ν, Ν-diethylaninium tetraphenylborate, N, N-dimethyl (2, 4, 6-trimethylaninium) tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyldioctadecylammonium Tetrakis (pentafluorophenyl) borate, triethylammonium, tetrakis (pentafluorophenyl) borate,

Tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) borate ， Ν , Ν-dimethylaninium tetrakis (pentafluorophenyl) borate, Ν, Ν-diethylaninium tetrakis (pentafluorophenyl) borate, ^-dimethyl (2,4,6-trimethylaninynium) tetrakis (Pentafluorophenyl) borate ，

Trimethylammonium tetrakis (2, 3, 4, 6-tetrafluorophenyl) borate,

Triethylammonium tetrakis (2,3,4,6—tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri (η-butyl) ammonium tetra Kis (2,3,4,6-, tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, Ν, Ν-dimethylaninynium Tetrakis (2,3,4,6-tetrafluorophenyl) borate, Ν, Ν-diethylaninynium tetrakis (2,3,4,6-tetrafluorophenyl) borate or Ν, Ν-dimethyl- (2,4,6-trimethylaninynium) tetrakis—borate compounds in the form of trisubstituted ammonium salts such as (2,3,4,6-tetrafluorophenyl) borate; Borate type in the form of dialkylammonium salt, such as dioctadecyl ammonium tetrakis (pentafluorophenyl) borate, ditetradecyl ammonium tetrakis (pentafluorophenyl) borate, or dicyclonucleosilammonium tetrakis (pentafluorophenyl) borate compound; Or triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate or tri (2,6-, dimethylphenyl) phosphonium tetrakis (pentafluorophenyl Borate compounds of the trisubstituted phosphonium salt form, such as a) borate, etc. are mentioned. In the supported metallocene catalyst according to the present invention, represented by the formula (1) The mass ratio of the total transition metal to the carrier contained in the first metallocene compound or the second metallocene compound represented by Formulas 3 to 5 may be 1:10 to 1: 1. When the carrier comprises the carrier and the metallocene compound in the above mass ratio, the optimum shape can be exhibited. In addition, the mass ratio of the promoter compound to the carrier can be 1: 1 to 1: 100. In the supported metallocene catalyst according to the present invention, a carrier containing a hydroxy group on the surface may be used, and preferably, a semi-ungsung hydroxyl group and a siloxane group are dried to remove moisture on the surface. The carrier which has is used. For example, silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, and these are typically oxides, carbonates, such as Na ₂ O, K ₂ C0 ₃ , BaS0 _4> and Mg (N0 ₃ ) ₂ , Sulfate, and nitrate components. The drying temperature of the carrier is preferably 200 to 80 CTC, more preferably 300 to 60 C C, and most preferably 300 to 400 ^° C. When the drying temperature of the carrier is less than 200 ^° C., the moisture is too much and the promoter on the surface is reacted. If the drying temperature is higher than 800 ^° C, the surface area decreases as the pores on the surface of the carrier are combined. It is not preferable because there are not many groups and only siloxane groups are left to decrease the reaction site with the promoter. The amount of hydroxy groups on the surface of the carrier is preferably from 0.1 to 10 mmol / g, more preferably from 0.5 to 5 dl ol / g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions for preparing the carrier or by drying conditions such as temperature, time, vacuum or spray drying. When the amount of the hydroxy group is less than 0.01 mmol / g, the reaction space with the promoter is small, and when the amount of the hydroxyl group is greater than 10 μL ol / g, It is not preferable because it may be due to moisture other than the hydroxyl group. On the other hand, the ethylene / 1-hexene or ethylene / 1-butene co-polymer according to the present invention can be produced by polymerizing ethylene and 1-hexene or 1-butene in the presence of the supported metallocene catalyst described above. The polymerization reaction may be performed by copolymerizing ethylene and 1-nuxene or 1-butene using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor. . And, the polymerization temperature may be about 25 to about 500 ^° C, preferably about 25 to about 200 ^° C, more preferably about 50 to about 15 C C. In addition, the polymerization pressure may be about 1 to about 100 Kgf / cui ² , preferably about 1 to about 50 Kgf / crf, more preferably about 5 to about 30 Kgf / ciif. The supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane nucleic acid, heptane, nonane, decane, and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, such as dichloromethane and chlorobenzene. The solution may be dissolved or diluted in a hydrocarbon solvent substituted with a chlorine atom. The solvent used herein is preferably used by removing a small amount of water, air, or the like acting as a catalyst poison by treating a small amount of alkyl aluminum, and may be carried out by further using a promoter. Ethylene / 1-nuxene or ethylene / 1-butene copolymer according to the present invention is a combination of the catalyst of formula 3 to 5 mainly to polymerize low-molecular weight polymer chain, and the catalyst of formula 1 mainly to polymerize high-molecular weight polymer chain Are prepared by copolymerizing ethylene and 1-nuxene or 1-butene monomers. Due to the interaction of these two or more catalysts, the polymer has a broad molecular weight distribution and a high molecular weight region, particularly a log M in the region of 5.5-6.0. A polymer can be obtained in which the chains are contained in a higher content. As a result, the ethylene / 1-nuxene or ethylene / 1-butene copolymer, for example, can exhibit a molecular weight distribution curve as shown in Figures 1 and 2, excellent processability by a wide molecular weight distribution, The log M may exhibit excellent FNCT characteristics according to the high content of the polymer chains in the region of 5.5 to 6.0. Due to the above-described physical layer, the ethylene / 1-nuxene or ethylene / 1-butene copolymer according to the present invention is excellent in workability and formability, excellent environmental resistance crack resistance high pressure heating tube, mining pipe or large diameter pipe It can be preferably applied to the back.

[Effect of the Invention] ^"ethylene / 1 haeksen or ethylene / 1-butene copolymer according to the present invention, the high molecular weight and having a broad molecular weight distribution, the stress cracking resistance is excellent and a high voltage heating pipes, large diameter pipes or mining Applicable to pipes and the like.

[Brief Description of Drawings]

1 shows a GPC curve of a polymer prepared in Comparative Examples and Examples of the present invention.

2 shows the GPC curves of the polymers prepared in Comparative Examples and Examples of the present invention.

[Specific contents to carry out invention]

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

[First Metallocene Compound]

Preparation Example 1

1-1) Preparation of Ligand Compound

2 g of f luorene was dissolved in 5 mL MTBE and 100 mL of hexane, 5.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath [7]. 3.6 g of (6- (tert-butoxy) hexyl) dichloro (methyI) silane was dissolved in 50 mL of nucleic acid (hexane) and transferred to a slurry of f luorene ^~ Li for 30 minutes in a dry ice / acetone bath and stirred at room temperature overnight. At the same time, 5,8-dimethyl-5,10-di hydr oi ndeno [1, 2-b] i ndo 1 e (12 mmol, 2.8 g) was also dissolved in 60 mL of THF and 5.5 mL of 2.5 M n1 BuLi hexane solution was added. It was added dropwise in a dry ice / acetone bath and stirred overnight at silver. NMR sampling the reaction solution between fluorene and (6- (tert_butoxy) hexyl) dichloro (methyl) silane to confirm the completion of the reaction, 5,8-dimethy 卜 5, l ()-dihydroindeno [l, 2-b] The indole-Li solution was transferred under dry ice / acetone bath. Stir overnight at room temperature. After the reaction was extracted with ether / water (extraction) to remove the residual moisture of the organic layer with MgS0 ₄ to obtain a ligand compound (Mw 597.90, 12 mmol), it was confirmed in 1H- 匪 R that two isomers were formed.

¾ NMR (500 MHz, d6 ^to benzene): -0.30 to -0.18 (3H, d), 0.40 (2H, m), 0.65 to 1.45 (8H, m), 1.12 (9H, d), 2.36 to 2.40 (3H , d), 3.17 (2H, m), 3.41-3.43 (3H, d), 4.17-4.21 (1H, d), 4.34-4.38 (1H, d), 6.90-7.80 (15H, m)

1-2) Preparation of Metallocene Compound

7.2 g (12 mmol) of the ligand compound synthesized in 1-1 was dissolved in 50 mL of diethylether, and 11.5 mL of 2.5 M n-BuL i hexane solution was added dropwise in a dry ice / acetone bath, followed by stirring at room temperature overnight. Vacuum drying brown color sticky oil. It was dissolved in toluene to obtain a slurry. ZrCl ₄ (THF) ₂ was prepared, and 50 mL of toluene was added to prepare a slurry. 50 mL of ZrCl ₄ (THF) ₂ was transferred to a luene slurry in a dry ice / acetone bath. The solution was changed to violet color at room temperature overnight. The reaction solution was filtered to remove LiCl. The toluene of the filtrate was removed by vacuum drying, and the nucleic acid was added and sonicated for 1 hour. The slurry was filtered to obtain 6 g (Mw 758.02, 7.92 隱 ol, yield 66 mol%) of a dark violet metallocene compound as a filtered solid. Two isomers were observed on 1 H-NMR.

¾ NMR (500 顧 z, CDC1 ₃ ): 1.19 (9H, d), 1.71 (3H, d), 1.50 to

1.70 (4H, m), 1.79 (2H, m), 1.98-2.19 (4H, m), 2.58 (3Η, s), 3.38 (2Η, m), 3.91 (3Η, d), 6.66-7.88 (15H, m)

[Second metallocene compound]

Preparation Example 2 Preparation of [tBiHHC¾) ₆ "C5H4] ₂ ZrCl ₂ ]

6-chlorohexanol was used to prepare -81 ^ 7 ⁽ ( ⁽ : ¾) _6- (1 by the method presented in Tetrahedron Lett. 2951 (1988)), where NaCp was prepared. The reaction yielded 卜 ^ 1-0-((¾) ₆ ᅳ (： ₅ ¾ (yield 60%, bp 80 ^° C / 0.1 醒 Hg) .T-Butyl-0- (C¾) at -78 ^° C. _6- C ₅ H ₅ was dissolved in THF, normal butyllithium (n-BuLi) was slowly added, and then heated to room temperature and reacted for 8 hours, and the solution was again reacted with ZrCl ₄ (THF) at -78 ^° C. _A pre-synthesized lithium salt solution was slowly added to a suspension solution of ₂ (1.70 g, 4.50 μl) / THF (30 mL) and reacted further for 6 hours at room temperature. The resultant was dried in vacuo and filtered by adding a hexane solvent to the obtained oily liquid material, and the filtered solution was dried in vacuo and then the nucleic acid was added to induce a precipitate ^at low temperature (_20 ^° C.). Filtered out at low silver to give the [tBu-0- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ compound as a white solid (yield 92%).

¾ NMR (300 Hz z, CDC1 ₃ ): 6.28 (t, J = 2.6 Hz, 2H), 6.19 (t, J = 2.6 Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 2.62 (t, J = 8 Hz), 1.7-1.3 (m, 8H), 1.17 (s, 9H)

¹³ C NMR (CDC1 ₃ ): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00 Preparation Example 3 ((tBiH) ᅳ ¾) ₆ ) ¾) 3ί: ₅ (α¾) ₄ ) Preparation of (ίΒιι-Ν) Τί (: 1 ₂ ; Ι) At room temperature, 50 g of Mg (s) was added to a 10 L reaction vessel and 300 mL of THF was added. The temperature was maintained at 50 ^° C. After the reactor temperature had stabilized, 250 g of 6-t-buthoxyhexyl chloride was added at 5 mL / min using a feeding pump. The reactor temperature was increased by about 4 to 5 ^° C. with the addition of 6-t-subsilicate nucleus chloride, 12 hours under continuous addition of 6-t-butoxynucle chloride. After 12 hours of reaction, a black reaction solution was obtained, and 2 mL of the resulting black solution was taken, and water was added thereto to obtain an organic layer, and then purified by 6 H-NMR (6-t-buthoxyhexan). e) It was confirmed that the Gringanrd reaction proceeded well from the 6-t-butoxynucleic acid, thereby synthesizing 6-t-butoxynuxyl magnesium chloride. .

500 g of MeSiCls and 1 L of THF were added to the reactor, and the reaction temperature was reduced to -20 ^° C. 560 g of the synthesized 6-t'butoxynucleated magnesium chloride was added to the reaction vessel at a rate of 5 mL / min using a feeding pump. After feeding the Grignard reagent, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours, it was confirmed that a white MgCl ₂ salt was produced. 4 L of nucleic acid was added to remove the salt through a labdori to obtain a filter solution. After adding the obtained filter solution to the reaction, the nucleic acid was removed at 70 ^° C to obtain a pale yellow liquid. Obtained liquid 1H- Through NMR, it was confirmed that the desired methyl (6-t-buthoxy hexyDdichlorosilane} compound.

C (CDC1 ₃ ): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7 (s, 3H) tetramethyl After adding 1.2 mo 1 (150 g) of cyclopentadiene and 2.4 L of THF to the reaction vessel, the reaction temperature was changed to -20 ^° C. The reactor was added at a rate of 5 mL / min using an n-BuLi 480 mL feeding pump. After adding n 一 BuLi, the reaction was stirred for 12 hours while slowly bringing the reaction temperature to room temperature. After 12 hours of reaction, an equivalent amount of methyl (6-t-buthoxy hexyDdichlorosilane) (326 g, 350 mL) was added quickly to the reaction vessel. After stirring for 12 hours, the reaction mixture was cooled to 0 ^° C., and then 2 equivalents of t-BuN¾ were added.The reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. 4 L of nucleic acid was added to obtain a filter section with salts removed from the labyrinth, and the filter solution was added to the reactor again, and the nucleic acid was removed at 70 ^° C to obtain a yellow solution. NMR confirmed that it was a methyl (6-t- butyloxysilane) (tetramethyl CpH) t-butylaminosilane (Methyl (6-t-buthoxyhexyl) (tetramethylCi) H) t- Butylaminosilane) compound. n-BuLi and ligand dimethyl (tetramethyl CpH) t-butylaminesilane

TiCl ₃ (THF) ₃ (10 μl) was rapidly added to the dilithium salt of a -78 ^° C ligand synthesized in THF solution from (Dimethyl (tetramethylCpH) t-Butylaminosi lane). The reaction solution was stirred for 12 hours while slowly releasing to room temperature at -78 ^° C. After stirring for 12 hours, an equivalent amount of PbCl ₂ (10 隱 ol) was added to the semi-aqueous solution in silver, followed by stirring for 12 hours. After stirring for 12 hours, the blue vagina obtained a black solution. After removing THF from the resulting semi-aqueous solution, nucleic acid was added to filter the product. After removing the nucleic acid from the filter solution to obtain, the desired ([methyl (6-t -but hoxyhexy 1) si lyl (ri 5-tetramethylCp) (t ^~ Butylamido)] TiCl ₂ ) (tBu-0- (CH ₂ ) ₆ ) (C¾) Si (C ₅ (C¾) ₄ ) (tBu-N) TiCl ₂ was confirmed.

-證 (CDC1 ₃ ): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 to 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H), 0.7 (s, 3H)

[Supported Catalyst]

Comparative Examples 1-1 and 1-2

5.0 kg of toluene solution was added to a 20 L sus high-pressure reactor, and the reaction temperature was maintained at 40 ^° C. 1,000 g of dehydrated silica (SYLOPOL 948, manufactured by Grace Davison, Inc.) was applied to the reactor at a temperature of 600 ^° C. for 12 hours, and after the silica was sufficiently dispersed, 80 g of the metallocene compound of Preparation Example 2 was added. in it is dissolved in toluene and allowed to banung and stirred for 2 hours at 200 rpm at 40 ^° C. After the stirring was stopped and settling for 30 minutes, the reaction solution was decant at k> n. Into the reaction, 2.5 kg of toluene was added, and 9.4 kg of 10 wt% methylaluminoxane (MAO) / luene solution was added thereto, followed by stirring at 40 ^° C. at 200 rpm for 12 hours. After the reaction, the stirring was stopped and settling for 30 minutes, followed by decantation of the reaction solution. 3.0 kg of toluene was added and stirred for 10 minutes, and then stirring was stopped, settling for 30 minutes, and decantation of the toluene solution. In the half unggi toluene 3.0 kg of a, which was in the manufacture of a 29.2 wt% Example 3 Metal In the metallocene compound / a 236 mL toluene solution to anti-unggi, stirred for two hours at 200 rpm at 40 ^° C to banung . After lowering the reaction temperature to room temperature, the stirring was stopped and settling for 30 minutes, followed by decantation of the reaction solution. 2.0 kg of toluene was added to the reaction vessel, stirred for 10 minutes, the stirring was stopped, settling for 30 minutes, and the reaction solution was decantation. 3.0 kg of nucleic acid was added to the reactor, the nucleic acid slurry was transferred to a fil ter dryer, and the hexane solution was filtered. Drying under reduced pressure at 40 ^° C. for 4 hours to prepare a 910g-Si0 ₂ common supported catalyst. Examples 1-1 and 1-2

The supported catalyst was prepared in the same manner as in Comparative Examples 1-1 and 1-2, except that 314 mL of the metallocene compound / luluene solution of Preparation Example 3 was added in Comparative Examples 1-1 and 1-2. Prepared. Example 1-3

6.0 kg of toluene solution was added to a 20 L sus high pressure reaction vessel, and the reaction temperature was maintained at 40 ^° C. 1 000 g of dehydrated silica (Grace Davi son, SYL0P0L 948) was subjected to vacuum at 12 ^° C. for 12 hours at a temperature of 600 ^° C., and the silica was evenly dispersed to prepare metallocene of Preparation Example 2. 80 g of the compound was dissolved in toluene, and then reacted by stirring at 40 ^° C for 2 hours. After the stirring was stopped and set tling for 30 minutes, the reaction solution was dec ant at i on. 2.5 kg of * luene was added to the reaction vessel, 9.4 kg of 10 wt% methylaluminoxane (MAO) / luene solution was added thereto, followed by stirring at 40 ^° C. at 200 rpm for 12 hours. After the reaction, the stirring was stopped, sett ling for 30 minutes, and the reaction solution was decanta on. 3.0 kg of toluene was added thereto, stirred for 10 minutes, the stirring was stopped, settling for 30 minutes, and the toluene solution was decant at ion. 3.0 kg of toluene was added to the reaction vessel, 314 mL of the 29.2% metallocene compound of Preparation Example 3 / luene solution was added to the reactor, followed by stirring at 40 ^° C. at 200 rpm for 12 hours. 80 g of the metallocene compound of Preparation Example 1 and 1,000 mL of ^' luluene were put in a flask to prepare a solution, and soni cat ion was performed for 30 minutes. In this way the metallocene compound / the metallocene prepared in Example 1, a toluene solution prepared in the reactor and allowed to banung and stirred for 2 hours at 200 rpm at 40 ^° C. After the reaction temperature was lowered to room temperature, stirring was stopped, sett ling for 30 minutes, and the reaction solution was decant at ion. 2.0 kg of toluene was added to the reactor, the mixture was stirred for 10 minutes, the stirring was stopped, settling for 30 minutes, and the toluene solution was decant at ion. 3.0 kg of nucleic acid was added to the reactor, the nucleic acid slurry was transferred to a fil ter dryer, and the nucleic acid solution was filtered. Drying under reduced pressure at 40 ^° C. for 4 hours to prepare a 890g-Si0 ₂ common supported catalyst. Comparative Example 2-1

3.0 kg of toluene solution was added to a 20 L sus high pressure reactor and the reactor temperature was maintained at 40 ^° C. 500 g of silica (Grace Davi son, SP2212) was added to the reaction vessel, and the silica was sufficiently dispersed. After addition of 3.00 kg of 10 wt methaluluminoxane (MA0) / luene solution, the temperature was raised to 80 ^° C. Stirred at rpm for at least 15 hours. After the reaction temperature was lowered to 40 ^° C. again, 144 g of 7.5 wt catalyst Preparation Example 2 / luene solution was added to the reaction vessel, and the mixture was stirred at 200 rpm for 1 hour. 240 g of 8.8 wt% catalyst Preparation Example 1 / luene solution was charged to a reactor and stirred at 200 rpm for 1 hour. Catalyst Preparation Example 3 (18 g) was dissolved in toluene, added to a reaction vessel, and stirred at 200 rpm for 2 hours. 70 g of a co-catalyst (ani inium tetraki s (pentaf luorophenyl) borate) was diluted in toluene and added to the reaction vessel, followed by stirring at 200 rpm for 15 hours or more. After lowering the reactor temperature to room temperature, the stirring was stopped, sett ling for 30 minutes, and the reaction solution was decantat ion. The toluene slurry was transferred to a fil ter dryer and filtered. 3.0 kg of toluene was added and stirred for 10 minutes, and then stirring was stopped and filtered. Into the reaction, add 3.0 kg of nucleic acid for 10 minutes After stirring, stirring was stopped and filtered. Drying under reduced pressure at 50 ^° C. for 4 hours to prepare a 500g-Si0 ₂ supported catalyst. Examples 2-1 to 2-3

Put 3.0 kg of toluene solution into 20L sus high pressure reactor and adjust the reactor temperature.

Kept ^at 40 ^° C. 500 g of silica (Grace Davi son, SP2212) was added to the reactor, and the silica was dispersed well. Then, 2.78 kg of 10 wt methylaluminoxane (MAO) / luluene solution was added and the temperature was reduced to 80 ^° C and 200 rpm. The mixture was stirred for 15 hours or more. After the reaction temperature was lowered to 4 again (C, 300 g of 7.5 wt% Catalyst Preparation Example 2 / luene solution was added to the reaction vessel and stirred at 200 rpm for 1 hour. 8.8 wt% Catalyst Preparation Example 1 / luene 250 g of the solution was added to the reaction vessel and stirred at 200 rpm for 1 hour, Catalyst Preparation Example 3 (20 g) was dissolved in toluene, charged into a reactor, and stirred at 200 rpm for 2 hours. 70 g of tetraki s (pentaf luorophenyl) borate) was diluted in toluene and added to the reaction vessel, and stirred at 200 rpm for more than 15 hours, after the reaction temperature was lowered to room temperature, the stirring was carried out, and the set tling was performed for 30 minutes. The reaction solution was decantat ion, the toluene slurry was transferred to a fil ter dryer and filtered, 3.0 kg of toluene was added and stirred for 10 minutes, the stirring was stopped and filtered. Stir for 10 minutes, then stir and And it was in. 50 ^° C and dried under reduced pressure for 4 hours to prepare a 500g-Si0 ₂ catalyst.

[Ethylene / 1-Nexene Copolymer]

Each of the common supported metallocene catalysts prepared in Examples 1-1 to 1-3 and Comparative Examples 1-1 and 1-2 was subjected to i sobutene slurry loop process continuous polymerization reactor (reaction volume of 140 L, reaction flow rate 7 m / s) to prepare an olefin polymer. As the comonomer, 1-nuxene was used, and the reactor pressure was maintained at 40 bar and the polymerization temperature was 9 (TC. In Examples 1-1 to 1-3 and Comparative Examples 1-1 and 1-2, respectively, Common support The polymerization conditions using the metallocene catalyst are summarized in Table 1 below. Table 1

[Ethylene / 1-butene copolymer]

Each of the common supported metallocene catalysts prepared in Examples 2-1 to 2-3 and Comparative Example 2-1 was subjected to bimodal operation to two reactors using a hexane s lurry st ired tank process integrator. Fin polymer was prepared. 1-butene was used as comonomer. In Examples 2-1 to 2-3 and Comparative Examples 2-1, polymerization conditions using the respective common dam metallocene catalysts are summarized in Table 2 below. Table 2

[Physical Property Evaluation of Polymer]

Physical properties of the polymers prepared in Examples and Comparative Examples were evaluated by the following methods. 1) Density: ASTM 1505

2) Melt Index (MFR, 2.16 kg / 21.6 kg): Measured temperature 190 ^° C, ASTM 1238

3) MFR (MFR ₂₁ _.6 / MFR ₂ .i6): MFR ₂₁ . ₆ Melt index (MI, 21.6kg load) divided by the rate MFR ₂ .i ₆ (MI, 2.16kg load).

4) Mn, Mw, PDI, GPC curve: Pre-treat the sample by dissolving at 160 ^° C for 10 hours in l, 2,4-Trichlorobenzene containing 0.0125% of BHT using PL-SP260,

Using PL-GPC220, the number average molecular weight and the weight average molecular weight were measured at a measurement temperature of 160 ^° C. The molecular weight distribution was expressed as the ratio of weight average molecular weight and number average molecular weight.

5) Full Notch Creep Test (FNCT): M. Flissner in Kunststoffe 77 (1987), pp. 45 et seq.] And the ISO currently in force

It was measured according to 16770. Breakage time due to shortening of stress initiation time by notch (1.5 画 / safety razor blade) at 10% concentration of IGEPAL C0-630 (Etoxilated Nonyl phenol, Branched), a male crack facilitating medium using a tension of 4.0 MPa at 80 ^° C This has been shortened. Specimens were fabricated by robing three specimens of 10 가로, 10 腿, and 100 길이 length from a compressed plate of 10 두께 thickness. The notch element specifically manufactured for this purpose uses a safety razor blade to provide a central notch to the specimen. Notch depth is 1.5 mm. Measured until the time the specimen is broken. The results are shown in Tables 3 and 4 below. In addition, the GPC curve of each polymer is shown in FIG. 1 and FIG.

[Table 3]

MFRR 21.6 / 2.16-33 34 32 33 120

Mn-40,000 36,300 36,100 31,600 14,200

Mw-150,000 137,000 145,000 132,000 128,000 Li D-3.74 3.77 4.02 4.18 9.05

FNCT Hours300 400 2,000 2,000 3,000

GPC Curve Figure 1

First, as shown in Figures 1 and 2, it can be seen that the polymer portion (log M = 5 ~ 6) content of the Example was increased compared to the respective comparative examples. In particular, when the GPC curves were similar, it was confirmed that even a small change in the content of the polymer portion (log M-5-6) had a great influence on the FNCT (Table 3 and Table 4).

Claims

[Patent Claims]

[Claim 1]

The weight average molecular weight (g / mol) is 10,000 to 400, 000,

Molecular weight distribution (Mw / Mn, PDI) is 2 to 30,

With an environmental stress crack resistance (ESCR) of 400 to 20,000 hours, instantaneous with full notch creep test (FNCT) according to ISO 16770 at 4.0 MPa and 80 ^° C.

Ethylene / 1-hexene or ethylene / 1-butene copolymers.

[Claim 2]

The method of claim 1,

With 600 to 8760 hours of envin mental stress crack resistance (ESCR) measured by full notch creep test (FNCT) according to ISO 16770 at 4.0 MPa and 80 ^° C.

Copolymer.

[Claim 3]

The method according to claim 1, wherein the ethylene / 1 'nucleene copolymer is

Density (g / cuf) is 0.930 to 0.950,

MFR ₂ .i ₆ (g / 10 min, measured by ASTM 1238 at 190 ^° C.) from 0.1 to

5

Melt flow rate ratio _{_{_{(MFR 21. 6 / MFR 2}}} . 16, measured by ASTM 1238 eseo 190 ^° C) of 10 to 200 people,

Copolymer.

[Claim 4]

According to claim 13,

The weight average molecular weight is 50,000 to 350,000 g / m,

Copolymer.

[Claim 5]

The method of claim 3,

The molecular weight distribution is 3 to 25,

Copolymer.

[Claim 6]

The method of claim 3,

¾0 ₂ . ₁₆ is 0.1 to 3 g / 10 min,

Copolymer.

[Claim 7]

According to claim 3,

The melt flow rate ratio is 15 to 180,

Copolyester.

[Claim 8]

According to claim U, wherein the ethylene / 1-butene copolymer,

Density (g / cirf) is from 0.930 to 0.950,

MFR ₅ (g / 10 min, measured by ASTM 1238 at 19 CTC) is 0.1 to 5,

Melt flow rate ratio (MFR ₂₁ _.6 / MFR ₅ , measured by ASTM 1238 at 190 ^° C) is 10 to 200,

Copolymer ᅳ

[Claim 9]

The method of claim 8,

The weight average molecular weight is 50,000 to 350,000 g / mol,

Copolymer.

[Claim 10] The method of claim 8,

The molecular weight distribution is 7 to 28,

Copolyester.

[Claim 11]

According to claim 8,

MFR ₅ is 0.1 to 3

Copolymer

[Claim 12]

According to claim 18,

The melt flow rate ratio is 15 to 180,

Co-polymer

[Claim 13]

In U,

The ethylene / 1 'nucleene or ethylene / 1' butene copolymer is at least one first metallocene compound represented by the formula (1); And it is prepared by polymerizing ethylene and 1-nuxene or 1-butene in the presence of at least one 2 metallocene compound selected from compounds represented by the following formulas (3) to (5),

Notarized coalescence ：

[Formula 1]

In Chemical Formula 1,

A is hydrogen, halogen, alkyl, C ₂ - ₂₀ alkenyl Al, C ₆ - ₂₀ aryl, C ₇ - ₂₀ alkylaryl, C ₇ - ₂₀ arylalkyl, d- ₂₀ alkoxy, C ₂ - ₂₀ alkoxyalkyl, C ₃ - ₂₀ heterocycloalkyl or C ₅ - ₂₀ membered heteroaryl;

D is -0- -S-, -N (R)-or -Si (R) (R ')-, where R and R' are The same or different and each is independently hydrogen, halogen, d-20 alkyl, C ₂ - ₂₀ alkenyl, or C ₆ - ₂₀ aryl;

L is straight or branched chain alkylene;

B is carbon, silicon or germanium;

Q is hydrogen, halogen, d-20 alkyl, C ₂ - ₂₀ alkenyl, C ₆ - ₂₀ aryl, C ₇ - ₂₀ alkylaryl, or C ₇ - ₂₀ aryl-alkyl;

M is a Group 4 transition metal;

X ¹ and X ² are the same or different and each is independently halogen, alkyl, ₍₂₀ alkenyl, C ₆ - ₂₀ aryl, nitro, amido, d-20 alkyl silyl, d-20-alkoxy or CO sulfone carbonate, and ;

C ¹ and C ² are the same as or different from each other, and each independently

2a, Formula 2b or Formula 2c, except that C ¹ and C ² are both Formula 2c;

2a]

[Formula 2b]

In the general formula 2a, 2b and 2c, R to Ri ₇ and "to" are the same or different and each is independently hydrogen, halogen, C o alkyl, C ₂ of each other - ₂₀ alkenyl, Cwo alkylsilyl, Cwo silyl alkyl, ₂₀ alkoxysilyl, d- ₂₀ alkoxy, C ₆ - ₂₀ aryl, C ₇ - ₂₀ alkylaryl, or C ₇ - ₂₀ alkyl and aryl, wherein R ₁₀ to R ₁₇ is of the two or more adjacent to each other are connected to each other substituted or May form an unsubstituted aliphatic or aromatic ring;

[Formula 3]

In Chemical Formula 3,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4, 5, 6, gtetrahydro ᅳ 1-indenyl, and fluorenyl radicals And these May be substituted with a hydrocarbon having 1 to 20 carbon atoms;

R ^a and R ^b are the same or hydrogen with different and are each independently of one another, Cwo alkyl, alkoxy, C _₂ - ₂ ᄋ alkoxyalkyl, C ₆ - ₂₀ aryl, C ₆ - ₁₀ aryloxy, C ₂ - ₂₀ Al kedil , C ₇ - ₄₀ alkylaryl, C ₇ - ₄₀ arylalkyl, C ₈ - ₄₀ arylalkenyl, or C ₂ - ₁₀ alkynyl;

Z ¹ is a halogen atom, ₂₀ alkyl, C ₂ - ₁₀ alkenyl, C ₇ - ₄₀ alkylaryl, C ₇ - ₄₀ arylalkyl, C ₆ -. ₂₀ aryl, substituted or unsubstituted d- value does not ₂₀ alkylidene, substituted unsubstituted amino, C ₂ - ₂₀ alkyl, an alkoxy, or a C ₇ - ₄₀ aryl-alkoxy;

n is 1 or 0;

[Formula 4]

(Cp¾ ^c ) _m B Cp ⁴ R ^d ) M ² Z ² ₃ - _m

In Chemical Formula 4,

M ² is a Group 4 transition metal;

Cp ³ and Cp ⁴ are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4, 5, 6, tetrahydrobrom 1-indenyl and fluorenyl radicals; They may be substituted with a hydrocarbon having 1 to 20 carbon atoms;

R ^C and R ^d are the same or different and each is independently hydrogen, CHO, alkoxy, C ₂ of each other - ₂₀ alkoxyalkyl, C ₆ - ₂₀ aryl, C ₆ - ₁₀ aryloxy, C ₂ - ₂₀ alkenyl, C _{_7-40} alkylaryl, C _{_7-40} arylalkyl, C ₈ - ₄₀ arylalkenyl, or C ₂ - ₁₀ alkynyl;

Z ² is a halogen atom, d u ₂₀ alkyl, C ₂ - ₁₀ alkenyl, C ₇ - ₄₀ alkylaryl, C ₇ - ₄₀ arylalkyl, C ₆ - ₂₀ aryl, substituted or not alkylidene eu optionally substituted non-substituted are amino, C ₂ - ₂₀ alkyl, an alkoxy, or a C ₇ - ₄₀ aryl-alkoxy;

B ¹ is one or more or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom-containing radicals which crosslinks the Cp¾ ^c ring and the Cp ⁴ R ^d ring or crosslinks one Cp ^d ring with M ² ego;

m is 1 or 0;

[Formula 5]

In Chemical Formula 5,

M ³ is a Group 4 transition metal;

Cp ⁵ is any one selected from the group consisting of cyclopentadienyl, indenyl, 4, ^{5, 6} , 7-tetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms Can be;

R ^e is hydrogen, alkyl, alkoxy, C ₂ - ₂₀ alkoxyalkyl, C ₆ - ₂₀ aryl, C ₆ -

10 aryloxy, C ₂ - ₂₀ alkenyl, C ₇ - ₄₀ alkylaryl, C ₇ - ₄₀ arylalkyl, C ₈ - ₄₀ arylalkenyl, or c ₂ - ₁₀ alkynyl;

Z ³ is a halogen atom, d- ₂₀ alkyl, C ₂ - ₁₀ alkenyl, C ₇ - ₄₀ alkylaryl, C ₇ - ₄₀ arylalkyl, C ₆ - ₂₀ aryl, alkylidene, substituted or unsubstituted substituted or unsubstituted are amino, C ₂ - ₂₀ alkyl, alkoxy, or c ₇ - ₄₀ aryl-alkoxy;

J is any one selected from the group consisting of NR ^f , 0, PR ^f and S, wherein R ^F is alkyl, aryl, substituted alkyl or substituted aryl of CO.