WO2016167548A1 - Ethylene/α-olefin copolymer having excellent processability and surface characteristics - Google Patents

Ethylene/α-olefin copolymer having excellent processability and surface characteristics Download PDF

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Publication number
WO2016167548A1
WO2016167548A1 PCT/KR2016/003848 KR2016003848W WO2016167548A1 WO 2016167548 A1 WO2016167548 A1 WO 2016167548A1 KR 2016003848 W KR2016003848 W KR 2016003848W WO 2016167548 A1 WO2016167548 A1 WO 2016167548A1
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Prior art keywords
alkyl
aryl
ethylene
alpha
alkenyl
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PCT/KR2016/003848
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French (fr)
Korean (ko)
Inventor
승유택
선순호
조솔
최이영
이기수
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주식회사 엘지화학
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Priority claimed from KR1020160038476A external-priority patent/KR101831418B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2017533912A priority Critical patent/JP6788590B2/en
Priority to CN201680007527.4A priority patent/CN107207661B/en
Priority to EP16780271.9A priority patent/EP3225638B1/en
Priority to US15/549,103 priority patent/US10266626B2/en
Publication of WO2016167548A1 publication Critical patent/WO2016167548A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene

Definitions

  • the present invention relates to an ethylene / alpha-olefin co-polymer having excellent processability and surface properties.
  • Ellefin 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.
  • the Ziegler-Natta catalyst has been widely applied to the existing commercial processes since the invention in the 50s, but has a wide molecular weight distribution of the polymer because it is a multi-site catalyst with multiple active sites. , There is a problem in that the composition distribution of the comonomer is not uniform and there is a limit in securing desired physical properties.
  • 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 modification of the ligand structure of the catalyst and the change of polymerization conditions, copolymerization characteristics, It has the characteristic to change molecular weight, crystallinity, etc.
  • linear low density polyethylene is prepared by copolymerizing ethylene and alpha olepin 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.
  • linear low density polyethylene films have high breaking strength and elongation, and excellent tear strength and fall stratification strength, so that the use of stretch films and overlap films, which are difficult to apply to existing low density polyethylene or high density polyethylene, has increased. Doing.
  • linear low density polyethylene using 1-butene or 1-nuxene as comonomers is mostly produced 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 the catalyst technology and the process technology used, there is a problem that the physical properties are inferior to that of using the 1-octene comonomer, and the processability is poor because the molecular weight distribution is narrow. Many efforts are being made to improve these problems.
  • U.S. Pat.No. 4,935,474 reports on the preparation of polyethylene having a wide molecular weight distribution using two or more metallocene compounds. US Pat. No.
  • the present invention is to provide an ethylene / alpha-lepin copolymer excellent in environmental impact crack resistance.
  • the present invention provides an ethylene / alpha -olefin copolymer satisfying the following conditions:
  • the weight average molecular weight (g / mol) is 50,000 to 150,000
  • Density (g / cuf) is 0.940 to 0.970
  • Spherulite has a diameter of 20 m or less
  • Ethylene / alpha-lepine copolymer having a half crystallization time of 6 minutes or less at 123 ° C.
  • Ethylene / alpha-copolymers are semi-crystal line polymers whose surface properties are mainly influenced by the crystal structure.
  • Most of the polymer chains exist in the form of being folded at a short distance without being stretched in a straight line.
  • the folded chains form a bundle of lamellar, and spherulite is formed by the three-dimensional growth of the lamellae. .
  • this sphere has a lot of influence on the surface properties of the polymer, the smaller the size of the sphere can be improved the surface characteristics of the polymer.
  • the structure of the sphere is influenced by various factors such as the molecular weight of the polymer, the molecular weight distribution, the amount of comonomers, and the distribution of comonomers.
  • the size of the spherical structure decreases as the molecular weight of the polymer increases and the amount of the comonomer increases.
  • a melt index, a density, etc. become large, and the polymer which has a desired characteristic cannot be manufactured.
  • the crystallization rate of the polymer is related to the processability of the polymer, the faster the crystallization rate is advantageous to the processing of the polymer.
  • the present invention is characterized by inducing LCB (Long Chain Branch) to the ethylene / alpha-lepine copolymer using a catalyst to be described later, to reduce the size of the spherical crystals and to increase the crystallization rate.
  • LCB Long Chain Branch
  • the ethylene / alpha-olefin copolymer according to the present invention has a diameter of spherulite of 20 ⁇ or less, a half crystallization time of 6 minutes or less, preferably 5 minutes or less at 123 ° C. There is a feature called.
  • the diameter of the spherical crystal may be measured by observing the surface of the ethylene / alpha-olefin copolymer with a microscope or the like. Specifically, the diameter of the sphere is ethylene / alpha -olefin copolymer at 190 ° C. After the complete melting, the crystallization temperature was reached after reaching the crystallization temperature at the rate of KTC / min, and the diameter of the well was taken as the size of each well overlapping as the well grew.
  • the half crystallization time is measured using a differential calorimeter analysis (DSC), and after the ethylene / alpha-olefin copolymer is completely melted at 190 ° C, the crystallization temperature (123 °) It is time when it is half of calorie peak which appears after sharpening up to C) (80 ° C / min) and holding for 1 hour.
  • DSC differential calorimeter analysis
  • the size of the spherical crystal is significantly smaller than that of the other case, and semicrystallization is also achieved.
  • MFR 2 . 16 (melt flow index, measured at 190 ° C., 2.16 kg load based on ASTM D1238) is from 0.5 to 10, more preferably from 4 to 8.
  • the MFRR 5 /2.i 6 of the ethylene / alpha-olefin copolymer (melt flow index measured at 190 ° C, 5 kg load based on ASTM D1238, measured at 190 ° C, 2.16 kg load The value divided by the melt flow index) is 3 to 8, more preferably 3 to 4.
  • alpha-olefin monomer examples include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene, 1— Octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-nucleadecene, 1-aitocene and the like, and two or more kinds thereof may be used.
  • 1-butene may be used as the alpha-olefin monomer.
  • the content of the alpha-olefin which is the comonomer in the ethylene / alpha-olefin copolymer is not particularly limited and may be appropriately selected according to the use, purpose, etc. of the copolymer. More specifically, it may be more than 0 and 99 mol% or less.
  • the ethylene / alpha-olefin copolymer as described above may 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 it may be a mixture of one or more second metallocene compound selected from the compound represented by the formula (3 to 5).
  • A is hydrogen, halogen, alkyl, CHO, C 2 - 20 alkenyl, Cg-20 aryl C7-20 alkyl, aryl, C 20 arylalkyl group, d- 20 alkoxy, C 2 - 20 alkoxyalkyl, C3-20 heterocycloalkyl, or C 5 - 20 membered heteroaryl;
  • D is — 0-, —S—, —N (R) — or Si (RR ′) —, where R and R ′ are the same 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, 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 are each independently an alkyl with a halogen, and C 2 of each other - 20 alkenyl, C 6 - to 20 aryl, nitro, amido, d-20 alkyl, d- 20 alkoxy, or silyl Sulfonate;
  • c 1 and c 2 are the same as or different from each other, and are each independently represented by one of Formula 2a, 2b or 2c below, except that C 1 and C 2 are both Formula 2c;
  • R 17 and "to" are the same or different and each is independently selected from the group consisting of hydrogen halogen, d-20 alkyl, C 2 of each other - 20 alkenyl, alkylsilyl, d- 20 alkyl silyl, d-20 alkoxysilyl, d-20 alkoxy, C 6 - 20 aryl, C 7 - 20 alkylaryl, or C 7 - 20 aryl-alkyl, substituted are the 0 to R 17 of the two or more adjacent to each other are connected to each other Or may form an unsubstituted aliphatic or aromatic ring;
  • 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, tetrahydro-1-indenyl, and fluorenyl radicals One, they may be substituted with a hydrocarbon of 1 to 20 carbon atoms;
  • R a and R b are the same or different and each is independently hydrogen, Cwo alkyl, 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,. 20 alkyl, C 2 - 10 alkenyl, C 7 - 40 alkylaryl, C 7 - 40 arylalkyl, C 6 - 20 aryl, optionally substituted d-20 alkylidene, amino which is optionally substituted, C 2 - 20 alkyl, an alkoxy, or a C 7 - 40 aryl-alkoxy;
  • n 1 or 0;
  • 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, 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 - 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 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 Cp3 ⁇ 4 c ring with the Cp 4 R d ring or crosslinks one Cp 4 R d ring with M 2 or Is a combination of;
  • n 1 or 0;
  • 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;
  • R e is hydrogen, alkyl, d- 10 alkoxy, C 2 - 20 alkoxyalkyl, C 6 - 20 aryl, C 6 -
  • 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, optionally substituted d-20 alkylidene, substituted 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 Cp3 ⁇ 4 e ring and J;
  • R F is CHO alkyl, aryl, substituted alkyl or substituted aryl.
  • R F is CHO alkyl, aryl, substituted alkyl or substituted aryl.
  • 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 it includes a linear or branched alkenyl, Specifically, allyl, ethenyl, propenyl, butenyl, pentenyl, etc. may be mentioned, but is not limited thereto.
  • the C 6 - 20 aryl include, includes a monocyclic or condensed ring aryl group. Specifically, phenyl, biphenyl, naphthyl, and the like, but phenanthrenyl, fluorenyl day, and thus are 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 Pyranyl, tetrahydrofuranyl and the like, but are not limited thereto.
  • Examples of the Cuo alkoxy include methioxy, etoxy, phenyloxy, cyclohexyloxy and the like, but are not limited thereto.
  • Examples of the Group 4 transition metal include titanium, zirconium, hafnium, and the like, but are not limited thereto.
  • Formulas 2a, 2b, and 2c to R 17 and I to ' are each independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, nucleus, heptyl, octyl, phenyl, halogen, Trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, methoxy, or more particularly, but is 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.
  • alkylene group is C o alkyl, C 2 - may be substituted or unsubstituted aryl as 20 - 20 alkenyl, or C 6.
  • a of Formula 1 is hydrogen, methyl, ethyl, propyl, isopropyl n-butyl, tert-butyl, mesoxymethyl, tert-butoxymethyl, 1-ethoxyethyl, 1-methyl- 1-methoxyethyl, tetrahydropyranyl, or tetrahydrofuranyl, preferably It is not limited only.
  • the crab 1 metallocene compound of Formula 1 is a non-covalently formed structure in which an indeno indole derivative and / or a fluorene derivative are crosslinked by a bridge, and may act as a Lewis base to the ligand structure. By having an electron pair, it is supported on the surface having the Lewis acid characteristic of the carrier, and shows high polymerization activity even when supported. In addition, due to the electronically rich indeno indole and / or fluorene group, the activity is high, and due to the proper steric hindrance and the electronic effect of the ligand, the reaction is not only low but also maintains high activity even in the presence of hydrogen. .
  • 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.
  • specific examples of the compound represented by Formula 2a may include a compound represented by one of the following structural formulas, but the present invention
  • specific examples of the first metallocene compound represented by Chemical Formula 1 may include compounds represented by the following structural formulas, but are not limited thereto.
  • the first metallocene compound of Chemical Formula 1 has excellent activity and may polymerize a high molecular weight ethylene / alpha-lepine co-polymer. In particular, even when used on a carrier, it shows high polymerization activity, and thus an ultra high molecular weight ethylene / alpha-olefin copolymer can be prepared. In addition, in order to prepare an ethylene / alpha-olefin copolymer having a high molecular weight and a wide molecular weight distribution, a polymerization reaction including hydrogen is carried out.
  • the first metallocene compound of formula 1 according to the present invention exhibits low hydrogen reaction properties and is still capable of polymerizing an ultra high molecular weight ethylene / alpha-olefin copolymer with high activity. Therefore, an ethylene / alpha-olefin copolymer that satisfies high molecular weight characteristics can be produced even when used in combination with a catalyst having different properties without degrading the activity, while including the polymer ethylene / alpha-olefin co-polymer. Ethylene / alpha-olefin copolymers having a wide molecular weight distribution can be readily prepared.
  • the C1 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 metal lat i on. It can be obtained by the method of manufacturing the first metallocene compound described in detail in Examples to be described later.
  • Examples of the compound represented by Formula 3 include one of the following structural formulas
  • the metallocene catalyst used in the present invention may be at least one of the U metallocene compounds represented by Formula 1, and one of the second metallocene compounds selected from the compounds represented by Formulas 3 to 5.
  • the above may be supported on the carrier together with the cocatalyst compound.
  • the supported metallocene catalyst may induce the production of a long chain branch (LCB) in the ethylene / alpha olefin copolymer prepared.
  • the cocatalyst supported on the carrier for activating the metallocene compound is an organometallic compound containing a Group 13 metal. It will not be specifically limited if it can be used at the time of superposition
  • the cocatalyst compound may include at least one of an aluminum-containing first cocatalyst of Formula 6, and a borate-based second cocatalyst of Formula 7 below.
  • R 18 is each independently a halogen, halogen substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more, 7]
  • T + is a + monovalent polyatomic ion
  • B is a boron in +3 oxidation state
  • G is independently a hydride, dialkylamido, halide, alkoxide, Aryloxide, hydrocarbyl, halocarbyl and halo-substituted hydrocarbyl, wherein G has up to 20 carbons, but at less than one position G is a halide.
  • the C 1 cocatalyst of Chemical Formula 6 is linear, circular, or reticular alkyl having a repeating unit bonded thereto. It may be an aluminoxane-based compound, and specific examples of the first cocatalyst include methyl aluminoxane (MA0), ethyl aluminoxane, isobutyl aluminoxane or butyl aluminoxane.
  • the C2 cocatalyst of Formula 7 may be a borate-based compound in the form of a trisubstituted ammonium salt, a dialkyl ammonium salt, or a trisubstituted phosphonium salt.
  • the mass ratio of the total transition metal to the carrier contained in the near U metallocene compound represented by Formula 1 or the second metallocene compound represented by Formulas 3 to 5 is 1 : May be from 1 to 1,000.
  • the carrier and the metallocene compound are included in the mass ratio, an optimal shape can be exhibited.
  • the mass ratio of the promoter compound to the carrier may be from 1: 1 to 1: 100.
  • the carrier may be a carrier containing a hydroxy group on the surface, and preferably has a highly reactive hydroxyl group and a siloxane group which are dried to remove moisture on the surface. Carriers can be used.
  • silica, silica-alumina, and silica ⁇ magnesia dried at high temperature may be used, and these are usually 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 800 ° C., more preferably 300 to 600 ° C., most preferably 300 to 400 ° C. When the drying temperature of the carrier is less than 200 ° C, the water content is too much and the cocatalyst reacts, and when it exceeds 800 ° C, the surface area decreases as the pores on the surface of the carrier are combined, and the surface is hydroxy on the surface.
  • 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 mmol / 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. If the amount of the hydroxy group is less than 0.01 mmol / g, the reaction space with the promoter is small. If the amount of the hydroxy group is more than 10 mmol / g, it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle.
  • the ethylene / alpha-lepine copolymer according to the present invention can be produced by polymerizing ethylene and alpha-olefin in the presence of the supported metallocene catalyst described above.
  • the polymerization reaction may be performed by copolymerizing ethylene and alpha-lephine using one continuous slurry polymerization reaction vessel, a loop slurry reaction vessel, a gas phase reactor, or a solution reactor.
  • the polymerization temperature may be about 25 to about 500 ° C, preferably about 25 to about 200 ° C, more preferably about 50 to about 150 ° C.
  • the polymerization pressure may be about 1 to about 100 Kgf / crf, preferably about 1 to about 50 Kgf / cirf, more preferably about 5 to about 30 Kgf / cuf.
  • the supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, nucleic acid, heptane, nonane, decane, isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane, chlorobenzene and the like.
  • the solution may be dissolved or diluted in a hydrocarbon solvent substituted with the same chlorine atom.
  • Ethylene / alpha-olefin copolymer according to the present invention is a combination of a catalyst of the general formula (3) to 5 to mainly polymerize the low molecular weight polymer chain, and a catalyst of the formula (1) mainly to polymerize the high molecular weight polymer chain, ethylene and alpha It is prepared by copolymerizing an -olefin monomer.
  • the ethylene / alpha-olefin copolymer according to the present invention has excellent processability and surface properties, and can be usefully applied to manufacture various products.
  • 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 thereto and sonicated for 1 hour.
  • the slurry was filtered to give 6 g (Mw 758.02, 7.92 mmol, yield 66 mol%) of a dark violet metallocene compound as a filtered solid. Two isomers were observed on -NMR.
  • 50 mg of the supported catalyst prepared in Preparation Example 3 was quantified in a dry box, and each was placed in a 50 mL glass bottle, sealed with a rubber diaphragm, and taken out of the dry box to prepare a catalyst to be injected.
  • the polymerization was carried out in a 2 L metal alloy reaction vessel, which was equipped with a mechanical stirrer and temperature controlled and used at high pressure. Inject 1 L of nucleic acid containing 1.0 mmol triethyl aluminum and 5 mL of 1—nuxene into the reactor, add the prepared supported catalyst to the reactor without air contact, and then gas at 80 ° C.
  • the ethylene monomer was polymerized for 1 hour with continuous addition of pressure at 9 kgf / cm 2 .
  • MFR 5 melt index (MI, 5kg load) is set to MFR 2 .
  • the ratio is divided by 16 (MI, 2.16kg load).
  • the PL-GPC220 was used to measure the number average molecular weight weight average molecular weight 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.

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Abstract

The present invention relates to an ethylene/α-olefin copolymer. The ethylene/α-olefin copolymer according to the present invention has excellent processability and surface characteristics, and thus can be usefully applied to the manufacturing of various products.

Description

【명세서】  【Specification】
【발명의 명칭】  [Name of invention]
가공성 및 표면 특성이 우수한 에틸렌 /알파-올레핀 공중합체 【기술분야】  Ethylene / alpha-olefin copolymer with excellent processability and surface properties [Technical Field]
관련 출원 (들)과의 상호 인용  Cross Citation with Related Application (s)
본 출원은 2015년 4월 13일자 한국특허 출원번호 제 10-2015- 0051831호 및 2016년 3월 30일자 한국특허 출원번호 제 10-2016-0038476호에 기초한 우선권의 이익을 주장하며， 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다. 본 발명은 가공성 및 표면 특성이 우수한 에틸렌 /알파-올레핀 공증합체에 관한 것이다.  This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0051831 dated April 13, 2015 and Korean Patent Application No. 10-2016-0038476 dated March 30, 2016, and the corresponding Korean patent All content disclosed in the literature of the applications is included as part of this specification. The present invention relates to an ethylene / alpha-olefin co-polymer having excellent processability and surface properties.
[배경기술]  [Background]
을레핀 중합 촉매계는 지글러 나타 및 메탈로센 촉매계로 분류할 수 있으며， 이 두 가지의 고활성 촉매계는 각각의 특징에 맞게 발전되어 왔다. 지글러 나타 촉매는 50년대 발명된 이래 기존의 상업 프로세스에 널리 적용되어 왔으나， 활성점이 여러 개 흔재하는 다활성점 촉매 (mul t i-s i te catalyst )이기 때문에， 증합체의 분자량 분포가 넓은 것이 특징이며， 공단량체의 조성 분포가 균일하지 않아 원하는 물성 확보에 한계가 있다는 문제점이 있다. 한편， 메탈로센 촉매는 전이금속 화합물이 주성분인 주촉매와 알루미늄이 주성분인 유기 금속 화합물인 조촉매의 조합으로 이루어지며， 이와 같은 촉매는 균일계 착체 촉매로 단일 활성점 촉매 (s ingle si te catalyst )이며， 단일 활성점 특성에 따라 분자량 분포가 좁으며, 공단량체의 조성 분포가 균일한 고분자가 얻어지며， 촉매의 리간드 구조 변형 및 중합 조건의 변경에 따라 고분자의 입체 규칙도， 공중합 특성， 분자량， 결정화도 등을 변화시킬 수 있는 특성을 가지고 있다. 미국특허 등록번호 게 5 , 914， 289호에는 각각의 담체에 담지된 메탈로센 촉매를 이용하여 고분자의 분자량 및 분자량 분포를 제어하는 방법이 기재되어 있으나， 담지촉매 제조시 사용된 용매의 양 및 제조시간이 많이 소요되고， 사용되는 메탈로센 촉매를 담체에 각각 담지시켜야 하는 번거로움이 따랐다. 대한민국특허 출원번호 제 10-2003-0012308호에는 담체에 이중핵 메탈로센 촉매와 단일핵 메탈로센 촉매를 활성화제와 함께 담지하여 반웅기 내 촉매의 조합을 변화시키며 중합함으로써 분자량 분포를 제어하는 방안을 개시하고 있다. 그러나, 이러한 방법은 각각의 촉매의 특성을 동시에 구현하기에 한계가 있으며， 또한 완성된 촉매의 담체 성분에서 메탈로센 촉매 부분이 유리되어 반웅기에 파을링 ( foul ing)을 유발하는 단점이 있다. 따라서， 상기한 단점들을 해결하기 위해서 간편하게 활성이 우수한 흔성 담지 메탈로센 촉매를 제조하여 원하는 물성의 을레핀계 중합체를 제조하는 방법에 대한 요구가 계속되고 있다. 한편， 선형 저밀도 폴리에틸렌은 중합촉매를 사용하여 저압에서 에틸렌과 알파 을레핀을 공중합하여 제조되어， 분자량 분포가 좁고 일정한 길이의 단쇄분지를 가지며， 장쇄분지가 없는 수지이다. 선형 저밀도 폴리에틸렌 필름은 일반 폴리에틸렌의 특성과 더불어 파단강도와 신율이 높고， 인열강도， 낙추층격강도 등이 우수하여 기존의 저밀도 폴리에틸렌이나 고밀도 폴리에틸렌의 적용이 어려운 스트레치 필름， 오버랩 필름 등에의 사용이 증가하고 있다. 그런데, 1-부텐 또는 1-핵센을 공단량체로 사용하는 선형 저밀도 폴리에틸렌은 대부분 단일 기상반응기 또는 단일 루프 슬러리 반웅기에서 제조되며, 1-옥텐 공단량체를 사용하는 공정 대비 생산성은 높으나， 이러한 제품 역시 사용 촉매기술 및 공정기술의 한계로 물성이 1-옥텐 공단량체 사용시보다 크게 열세하고， 분자량 분포가 좁아 가공성이 불량한 문제가 있다. 이러한 문제의 개선을 위해 많은 노력이 진행되고 있으며， 미국특허 등록번호 게 4 ,935 ,474호에는 2종 또는 그 이상의 메탈로센 화합물이 사용되어 넓은 분자량 분포를 갖는 폴리에틸렌 제조법에 대해 보고되어 있다. 미국특허 등록번호 계 6,828,394호에는 공단량체 결합성이 좋은 것과 그렇지 않은 것을 혼합사용해 가공성이 우수하고 특히 필름용에 적합한 폴리에틸렌 제조방법에 대해 보고되어 있다. 또한, 미국특허 등록번호 제 6, 841,631호， 미국특허 등록번호 게 6,894,128호에는 적어도 2종의 메탈 컴파운드가 사용된 메탈로센계 촉매로 이정 또는 다정 분자량분포를 갖는 폴리에틸렌을 제조하여， 필름， 블로우몰딩， 파이프 등의 용도에 적용이 가능하다고 보고되어 있다. 하지만 이러한 제품들은 가공성은 개선되었으나 단위 입자 내의 분자량별 분산상태가 균일하지 못해 비교적 양호한 압출조건에서도 압출외관이 거칠고 물성이 안정적이자 못한 문제가 있다. 이러한 배경에서 물성과 가공성 간의 균형이 이루어진 보다 우수한 제품의 제조가 끊임없이 요구되고 있으며， 특히 가공성 및 표면 특성이 우수한 폴리에틸렌 공중합체의 필요성이 더욱 요구된다. Ellefin 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. The Ziegler-Natta catalyst has been widely applied to the existing commercial processes since the invention in the 50s, but has a wide molecular weight distribution of the polymer because it is a multi-site catalyst with multiple active sites. ， There is a problem in that the composition distribution of the comonomer is not uniform and there is a limit in securing desired physical properties. 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 modification of the ligand structure of the catalyst and the change of polymerization conditions, copolymerization characteristics, It has the characteristic to change molecular weight, crystallinity, etc. U.S. Pat.Nos. 5,914, and 289 described on the respective carriers Although a method of controlling the molecular weight and molecular weight distribution of a polymer by using a metallocene catalyst has been described, the amount of solvent used in preparing the supported catalyst and the preparation time are high, and the metallocene catalyst used is supported on the carrier, respectively. Hassle to do. Korean Patent Application No. 10-2003-0012308 discloses a method in which a molecular weight distribution is controlled by supporting a double-nucleated metallocene catalyst and a mononuclear metallocene catalyst on a carrier together with an activator to polymerize by changing a combination of catalysts in a reaction vessel. Disclosing the plan. 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 released from the carrier component of the finished catalyst, causing fouling. . Therefore, in order to solve the above disadvantages, there is a continuous need for a method for preparing a common supported metallocene catalyst having excellent activity and preparing a olefinic polymer of desired physical properties. On the other hand, linear low density polyethylene is prepared by copolymerizing ethylene and alpha olepin 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. In addition to the properties of general polyethylene, linear low density polyethylene films have high breaking strength and elongation, and excellent tear strength and fall stratification strength, so that the use of stretch films and overlap films, which are difficult to apply to existing low density polyethylene or high density polyethylene, has increased. Doing. By the way, linear low density polyethylene using 1-butene or 1-nuxene as comonomers is mostly produced 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 the catalyst technology and the process technology used, there is a problem that the physical properties are inferior to that of using the 1-octene comonomer, and the processability is poor because the molecular weight distribution is narrow. Many efforts are being made to improve these problems. U.S. Pat.No. 4,935,474 reports on the preparation of polyethylene having a wide molecular weight distribution using two or more metallocene compounds. US Pat. No. 6,828,394 reports a method for producing polyethylene that has good comonomer binding properties and those which do not have good processability and is particularly suitable for films. Further, US Patent No. 6, 841,631 and US Patent No. 6,894,128 prepare polyethylene having bimodal or polycrystalline molecular weight distribution with a metallocene catalyst using at least two metal compounds, and film, blow molding. It is reported that it can be applied to the use of pipes and the like. However, these products have improved processability, but there is a problem in that the extrusion appearance is coarse 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 producing a better product having a balance between physical properties and processability, and in particular, a need for a polyethylene copolymer having excellent processability and surface properties is further required.
[발명의 내용]  [Content of invention]
【해결하려는 과제】  [Problem to solve]
상기 종래기술의 문제점을 해결하기 위하여， 본 발명은 내환경 웅력 균열성이 우수한 에틸렌 /알파-을레핀 공중합체를 제공하고자 한다.  In order to solve the problems of the prior art, the present invention is to provide an ethylene / alpha-lepin copolymer excellent in environmental impact crack resistance.
【과제의 해결 수단】  [Measures of problem]
상기 과제를 해결하기 위하여, 본 발명은 하기의 조건을 만족하는 에틸렌 /알파-올레핀 공중합체를 제공한다:  In order to solve the above problems, the present invention provides an ethylene / alpha -olefin copolymer satisfying the following conditions:
중량 평균 분자량 (g/mol)이 50,000 내지 150 ,000이고，  The weight average molecular weight (g / mol) is 50,000 to 150,000,
분자량 분포 (Mw/Mn)가 3 내지 8이고，  Molecular weight distribution (Mw / Mn) is 3 to 8,
밀도 (g/cuf)가 0.940 내지 0.970이고，  Density (g / cuf) is 0.940 to 0.970,
구정 (spherulite)의 직경이 20 m 이하이고， 및  Spherulite has a diameter of 20 m or less, and
123°C에서 반결정화 시간 (half crystallization time)이 6분 이하인， 에틸렌 /알파-을레핀 공중합체. 에틸렌 /알파 -공중합체는 반결정 (semi-crystal line) 고분자로서， 이러한 고분자의 표면 특성은 결정 구조에 주로 영향을 받는다. 대부분의 고분자 사슬은 직선으로 펼쳐지지 않고 짧은 거리에서 접혀지는 형태로 존재하게 되는데, 접혀진 사슬은 다발을 이루어 라멜라 (lamellar)를 형성하고， 이러한 라멜라의 3차원 성장에 의해 구정 (spherulite)이 형성된다. 특히, 이러한 구정이 고분자의 표면 특성에 많은 영향올 주게 되며， 이러한 구정의 크기가 작을수록 고분자의 표면 특성이 향상될 수 있다. 구정의 구조는 고분자의 분자량， 분자량 분포， 공단량체의 양， 공단량체의 분포 등 다양한 요인에 영향올 받는다. 일반적으로 고분자의 분자량이 커지고， 공단량체의 양이 증가하면 구정의 크기가 감소하는 것으로 알려져 있다. 그러나, 이 경우 용융 지수나 밀도 등이 커져 원하는 특성을 가지는 고분자를 제조할 수 없다. 한편， 고분자의 결정화 속도는 고분자의 가공성과 관련이 있으며, 결정화 속도가 빠를수록 고분자의 가공에 유리하다. 또한, 결정화 속도가 빠르면 결정의 크기가 미세화되고 따라서 구정의 크기 또한 작아질 수 있다. 이에， 본 발명에서는 후술할 촉매를 사용하여 에틸렌 /알파-을레핀 공중합체에 LCB(Long Chain Branch)를 유도하여， 구정의 크기를 작게 하고 또한 결정화 속도를 높이는 특징이 있다. 구체적으로， 본 발명에 따른 에틸렌 /알파-올레핀 공중합체는 구정 (spherulite)의 직경이 20 μνι 이하이고, 123°C에서 반결정화 시간 (half crystallization time)이 6분 이하， 바람직하게는 5분 이하라는 특징이 있다. 후술할 본 발명의 일실시예와 같이， 구정의 직경은 에틸렌 /알파- 올레핀 공중합체의 표면을 현미경 등으로 관찰하여 측정할 수 있다. 구체적으로， 상기 구정의 직경은 에틸렌 /알파-올레핀 공중합체를 190°C에서 완전히 용융시킨 후， KTC/분 속도로 결정화 온도까지 도달시킨 후 측정하며， 이때 구정의 직경은 구정이 성장함에 따라 각각의 구정이 겹쳐질 때의 크기로 한다. 또한， 상기 반결정화 시간 (half crystallization time)은 시차 주사 열량계 (Differential Calorimeter Analysis; DSC)를 이용하여 측정하며， 에틸렌 /알파-올레핀 공중합체를 190°C에서 완전히 용융시킨 후， 결정화 온도 (123°C)까지 급넁 (80°C/분)하여 1시간 동안 유지한 후 나타나는 열량 피크의 절반일 때의 시간으로 한다. 본 발명의 실시예에 따르면， 후술할 촉매를 사용하여 에틸렌 /알파- 을레핀 공중합체에 LCB(Long Chain Branch)를 유도한 경우， 그렇지 않은 경우에 비하여 구정의 크기가 현저히 작았으며， 또한 반결정화 속도 또한 동일한 분자량을 가지는 에틸렌 /알파—올레핀 공중합체에 비하여 현저히 빨랐다. 또한 바람직하게는， 상기 에틸렌 /알파-을레핀 공중합체의 MFR 2.16(ASTM D1238에 의거하여 190 °C, 2.16kg 하중에서 측정한 용융 유동 지수)이 0.5 내지 10, 보다 바람직하게는 4 내지 8이다. 또한 바람직하게는， 상기 에틸렌 /알파-올레핀 공중합체의 MFRR5/2.i6(ASTM D1238에 의거하여 190°C， 5kg 하중에서 측정한 용융 유동 지수를 190 °C, 2.16 kg 하중에서 측정한 용융 유동 지수로 나눈 값)이 3 내지 8, 보다 바람직하게는 3 내지 4이다. 본 발명에 따른 에틸렌 /알파-올레핀 공중합체에서, 상기 알파-올레핀 단량체의 구체적인 예로는 프로필렌， 1-부텐, 1-펜텐, 4-메틸 -1-펜텐, 1- 핵센， 1-헵텐， 1—옥텐， 1-데센， 1-운데센, 1—도데센， 1-테트라데센， 1- 핵사데센， 1-아이토센 등이 있으며, 이들을 2종 이상 사용할 수도 있다. 바람직하게는， 상기 알파-올레핀 단량체로 1-부텐을 사용할 수 있다. 상기 에틸렌 /알파—올레핀 공중합체에세 상기 공단량체인 알파- 올레핀의 함량은 특별히 제한되는 것은 아니며， 공중합체의 용도, 목적 등에 따라 적절하게 선택할 수 있다. 보다 구체적으로는 0 초과 99 몰% 이하일 수 있다. 상기와 같은 에틸렌 /알파-올레핀 공중합체는 메탈로센 촉매를 이용하여 제조할 수 있다. 상기 사용할 수 있는 메탈로센 촉매는 하기 화학식 1로 표시되는 제 1 메탈로센 화합물 1종 이상; 및 하기 화학식 3 내지 5로 표시되는 화합물 중에서 선택되 제 2 메탈로센 화합물 1종 이상의 혼합물일 수 있다. Ethylene / alpha-lepine copolymer having a half crystallization time of 6 minutes or less at 123 ° C. Ethylene / alpha-copolymers are semi-crystal line polymers whose surface properties are mainly influenced by the crystal structure. Most of the polymer chains exist in the form of being folded at a short distance without being stretched in a straight line. The folded chains form a bundle of lamellar, and spherulite is formed by the three-dimensional growth of the lamellae. . In particular, this sphere has a lot of influence on the surface properties of the polymer, the smaller the size of the sphere can be improved the surface characteristics of the polymer. The structure of the sphere is influenced by various factors such as the molecular weight of the polymer, the molecular weight distribution, the amount of comonomers, and the distribution of comonomers. In general, it is known that the size of the spherical structure decreases as the molecular weight of the polymer increases and the amount of the comonomer increases. However, in this case, a melt index, a density, etc. become large, and the polymer which has a desired characteristic cannot be manufactured. On the other hand, the crystallization rate of the polymer is related to the processability of the polymer, the faster the crystallization rate is advantageous to the processing of the polymer. In addition, the higher the crystallization rate, the smaller the size of the crystals and thus the smaller the size of the spherical crystal. Accordingly, the present invention is characterized by inducing LCB (Long Chain Branch) to the ethylene / alpha-lepine copolymer using a catalyst to be described later, to reduce the size of the spherical crystals and to increase the crystallization rate. Specifically, the ethylene / alpha-olefin copolymer according to the present invention has a diameter of spherulite of 20 μνι or less, a half crystallization time of 6 minutes or less, preferably 5 minutes or less at 123 ° C. There is a feature called. As in the embodiment of the present invention to be described later, the diameter of the spherical crystal may be measured by observing the surface of the ethylene / alpha-olefin copolymer with a microscope or the like. Specifically, the diameter of the sphere is ethylene / alpha -olefin copolymer at 190 ° C. After the complete melting, the crystallization temperature was reached after reaching the crystallization temperature at the rate of KTC / min, and the diameter of the well was taken as the size of each well overlapping as the well grew. In addition, the half crystallization time is measured using a differential calorimeter analysis (DSC), and after the ethylene / alpha-olefin copolymer is completely melted at 190 ° C, the crystallization temperature (123 °) It is time when it is half of calorie peak which appears after sharpening up to C) (80 ° C / min) and holding for 1 hour. According to an embodiment of the present invention, when a long chain branch (LCB) is induced to an ethylene / alpha-lepine copolymer using a catalyst described below, the size of the spherical crystal is significantly smaller than that of the other case, and semicrystallization is also achieved. The rate was also significantly faster compared to ethylene / alpha-olefin copolymers having the same molecular weight. Also preferably, MFR 2 . 16 (melt flow index, measured at 190 ° C., 2.16 kg load based on ASTM D1238) is from 0.5 to 10, more preferably from 4 to 8. Also preferably, the MFRR 5 /2.i 6 of the ethylene / alpha-olefin copolymer (melt flow index measured at 190 ° C, 5 kg load based on ASTM D1238, measured at 190 ° C, 2.16 kg load The value divided by the melt flow index) is 3 to 8, more preferably 3 to 4. In the ethylene / alpha-olefin copolymer according to the present invention, specific examples of the alpha-olefin monomer are propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene, 1— Octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-nucleadecene, 1-aitocene and the like, and two or more kinds thereof may be used. Preferably, 1-butene may be used as the alpha-olefin monomer. The content of the alpha-olefin which is the comonomer in the ethylene / alpha-olefin copolymer is not particularly limited and may be appropriately selected according to the use, purpose, etc. of the copolymer. More specifically, it may be more than 0 and 99 mol% or less. The ethylene / alpha-olefin copolymer as described above may 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 it may be a mixture of one or more second metallocene compound selected from the compound represented by the formula (3 to 5).
Figure imgf000008_0001
Figure imgf000008_0001
상기 화학식 1에서，  In Chemical Formula 1,
A는 수소， 할로겐， CHO 알킬， C2-20 알케닐 Cg-20 아릴 C7-20 알킬아릴, C기 20 아릴알킬, d-20 알콕시， C2-20 알콕시알킬， C3-20 헤테로시클로알킬， 또는 C5-20 헤테로아릴이고; A is hydrogen, halogen, alkyl, CHO, C 2 - 20 alkenyl, Cg-20 aryl C7-20 alkyl, aryl, C 20 arylalkyl group, d- 20 alkoxy, C 2 - 20 alkoxyalkyl, C3-20 heterocycloalkyl, or C 5 - 20 membered heteroaryl;
D는 — 0-， -S- , -N(R)- 또는 Si (R R ' )-이고, 여기서 R 및 R '은 서로 동일하거나 상이하고， 각각 독립적으로 수소， 할로겐， d-20 알킬, C2-20 알케닐， 또는 C6-20 아릴이고; D is — 0-, —S—, —N (R) — or Si (RR ′) —, where R and R ′ are the same or different from each other, and are each independently hydrogen, halogen, d-20 alkyl, C 2 - 20 alkenyl, or C 6 - 20 aryl;
L은 d-10 직쇄 또는 분지쇄 알킬렌이고; L is d- 10 straight or branched chain alkylene;
B는 탄소， 실리콘 또는 게르마늄이고; .  B is carbon, silicon or germanium; .
Q는 수소， 할로겐， 20 알킬, C2-20 알케닐， C6-20 아릴, C7-20 알킬아릴， 또는 C7-20 아릴알킬이고; Q is hydrogen, halogen, 20 alkyl, C 2 - 20 alkenyl, C 6 - 20 aryl, C 7 - 20 alkylaryl, or C 7 - 20 aryl-alkyl;
M은 4족 전이금속이며;  M is a Group 4 transition metal;
X1 및 X2는 서로 동일하거나 상이하고， 각각 독립적으로 할로겐， 에 알킬， C2-20 알케닐， C6-20 아릴， 니트로， 아미도， d-20 알킬실릴， d-20 알콕시 또는 에 술폰네이트이고; c1 및 c2는 서로 동일하거나 상이하고， 각각 독립적으로 하기 화학식 2a , 화학식 2b 또는 하기 화학식 2c 증 하나로 표시되고， 단, C1 및 C2가 모두 화학식 2c인 경우는 제외하며 ; X 1 and X 2 are the same or different and are each independently an alkyl with a halogen, and C 2 of each other - 20 alkenyl, C 6 - to 20 aryl, nitro, amido, d-20 alkyl, d- 20 alkoxy, or silyl Sulfonate; c 1 and c 2 are the same as or different from each other, and are each independently represented by one of Formula 2a, 2b or 2c below, except that C 1 and C 2 are both Formula 2c;
Figure imgf000009_0001
Figure imgf000009_0001
상기 화학식 2a， 2b 및 2c에서， 내지 R17 및 ' 내지 '는 서로 동일하거나 상이하고， 각각 독립적으로 수소 할로겐， d-20 알킬， C2-20 알케닐， 알킬실릴， d-20 실릴알킬， d-20 알콕시실릴， d-20 알콕시， C6-20 아릴， C7-20 알킬아릴， 또는 C7-20 아릴알킬이며， 상기 0 내지 R17 중 서로 인접하는 2개 이상이 서로 연결되어 치환 또는 비치환된 지방족 또는 방향족 고리를 형성할 수 있고; In the general formula 2a, 2b and 2c, to R 17 and "to" are the same or different and each is independently selected from the group consisting of hydrogen halogen, d-20 alkyl, C 2 of each other - 20 alkenyl, alkylsilyl, d- 20 alkyl silyl, d-20 alkoxysilyl, d-20 alkoxy, C 6 - 20 aryl, C 7 - 20 alkylaryl, or C 7 - 20 aryl-alkyl, substituted are the 0 to R 17 of the two or more adjacent to each other are connected to each other Or may form an unsubstituted aliphatic or aromatic ring;
[화학식 3] 상기 화학식 3에서， [Formula 3] In Chemical Formula 3,
M1은 4족 전이금속이고; · Cp1 및 Cp2는 서로 동일하거나 상이하고， 각각 독립적으로 시클로펜타디엔닐， 인데닐， 4，5，6，그테트라하이드로 -1-인데닐， 및 플루오레닐 라디칼로 이루어진 군으로부터 선택된 어느 하나이고， 이들은 탄소수 1 내지 20의 탄화수소로 치환될 수 있으며; 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, tetrahydro-1-indenyl, and fluorenyl radicals One, they may be substituted with a hydrocarbon of 1 to 20 carbon atoms;
Ra 및 Rb는 서로 동일하거나 상이하고， 각각 독립적으로 수소， Cwo 알킬, 알콕시， C2-20 알콕시알킬， C6-20 아릴， C6-10 아릴옥시， C2-20 알케닐， C7-40 알킬아릴， C7-40 아릴알킬， C8-40 아릴알케닐， 또는 C2-10 알키닐이고; R a and R b are the same or different and each is independently hydrogen, Cwo alkyl, 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;
Z1은 할로겐 원자， .20 알킬， C2-10 알케닐， C7-40 알킬아릴, C7-40 아릴알킬， C6-20 아릴， 치환되거나 치환되지 않은 d-20 알킬리덴， 치환되거나 치환되지 않은 아미노, C2— 20 알킬알콕시， 또는 C7-40 아릴알콕시이고; Z 1 is a halogen atom,. 20 alkyl, C 2 - 10 alkenyl, C 7 - 40 alkylaryl, C 7 - 40 arylalkyl, C 6 - 20 aryl, optionally substituted d-20 alkylidene, amino which is optionally substituted, C 2 - 20 alkyl, an alkoxy, or a C 7 - 40 aryl-alkoxy;
n은 1 또는 0이고;  n is 1 or 0;
[화학식 4] - [Formula 4]-
(Cp3Rc)mB1(Cp4Rd)M2Z2 3-m (Cp 3 R c ) m B 1 (Cp 4 R d ) M 2 Z 2 3 - m
상기 화학식 4에서，  In Chemical Formula 4,
M2는 4족 전이 금속이고; M 2 is a Group 4 transition metal;
Cp3 및 Cp4는 서로 동일하거나 상이하고， 각각 독립적으로 시클로펜타디에닐， 인데닐， 4， 5，6， 7-테트라하이드로 -1-인데닐 및 플루오레닐 라디칼로 이루어진 군으로부터 선택된 어느 하나이고， 이들은 탄소수 1 내지 20의 탄화수소로 치환될 수 있으며; 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;
Rc 및 Rd는 서로 동일하거나 상이하고， 각각 독립적으로 수소， 알킬， d-10 알콕시 , C2— 20 알콕시알킬， C6-20 아릴， C6-10 아릴옥시， C2-20 알케닐， C7-40 알킬아릴， C7-40 아릴알킬， C8-40 아릴알케닐， 또는 c2— 10 알키닐이고; R c and R d are the same or different and each is independently 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 - 40 arylalkenyl, or c 2 - 10 alkynyl;
Z2는 할로겐 원자， d-20 알킬， C2-10 알케닐， C7-40 알킬아릴， C7-40 아릴알킬， C6-20 아릴， 치환되거나 치환되지 않은 d-20 알킬리덴， 치환되거나 치환되지 않은 아미노， C2-20 알킬알콕시 , 또는 C7-40 아릴알콕시이고; B1은 Cp¾c 고리와 Cp4Rd 고리를 가교 결합시키거나， 하나의 Cp4Rd 고리를 M2에 가교 결합시키는， 탄소， 게르마늄， 규소， 인 또는 질소 원자 함유 라디칼 중 하나 이상 또는 이들의 조합이고; 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 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 with the Cp 4 R d ring or crosslinks one Cp 4 R d ring with M 2 or Is a combination of;
m은 1 또는 0이고;  m is 1 or 0;
[화학삭 5]  [Chemical Machining 5]
(Cp¾e)B2(J)M3Z3 2 (Cp¾ e ) B 2 (J) M 3 Z 3 2
상기 화학식 5에서,  In Chemical Formula 5,
M3은 4족 전이 금속이고; M 3 is a Group 4 transition metal;
Cp5는 시클로펜타디에닐， 인데닐， 4，5，6，7-테트라하이드로 -1-인데닐 및 플루오레닐 라디칼로 이루어진 군으로부터 선택된 어느 하나이고, 이들은 탄소수 1 내지 20의 탄화수소로 치환될 수 있으며 ; 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;
Re는 수소， 알킬， d-10 알콕시 , C2-20 알콕시알킬， C6-20 아릴， C6-R e is hydrogen, alkyl, d- 10 alkoxy, C 2 - 20 alkoxyalkyl, C 6 - 20 aryl, C 6 -
10 아릴옥시， C2-20 알케닐， C7-40 알킬아릴， C7-40 아릴알킬， C8-40 아릴알케닐， 또는 C2-10 알키닐이고; 10 aryloxy, C 2 - 20 alkenyl, C 7 - 40 alkylaryl, C 7 - 40 arylalkyl, C 8 - 40 arylalkenyl, or C 2 - 10 alkynyl;
Z3은 할로겐 원자， d-20 알킬， C2— 10 알케닐, C7-40 알킬아릴， C7-40 아릴알킬， C6-20 아릴， 치환되거나 치환되지 않은 d-20 알킬리덴， 치환되거나 치환되지 않은 아미노, C2-20 알킬알콕시， 또는 C7-40 아릴알콕시이고; 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, optionally substituted d-20 alkylidene, substituted unsubstituted amino, C 2 - 20 alkyl, an alkoxy, or a C 7 - 40 aryl-alkoxy;
B2는 Cp¾e 고리와 J를 가교 결합시키는 탄소， 게르마늄， 규소， 인 또는 질소 원자 함유 라디칼중 하나 이상 또는 이들의 조합이고; 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;
J는 NRf , 0, PRf 및 S로 이루어진 군에서 선택된 어느 하나이고， 상기 RF는 CHO 알킬, 아릴， 치환된 알킬 또는 치환된 아릴이다. 상기 화학식 1 , 3， 4 및 5의 치환기들을 보다 구체적으로 설명하면 하기와 같다. 상기 CHO 알킬로는， 직쇄 또는 분지쇄의 알킬을 포함하고， 구체적으로 메틸, 에틸， 프로필， 이소프로필， n-부틸, tert-부틸, 펜틸, 핵실， 헵틸， 옥틸 등을 들 수 있으나， 이에만 한정되는 것은 아니다. 상기 C2— 20 알케닐로는， 직쇄 또는 분지쇄의 알케닐을 포함하고， 구체적으로 알릴， 에테닐， 프로페닐， 부테닐， 펜테닐 등을 들 수 있으나， 이에만 한정되는 것은 아니다. 상기 C6-20 아릴로는, 단환 또는 축합환의 아릴을 포함하고， 구체적으로 페닐， 비페닐， 나프틸， 페난트레닐， 플루오레날 등을 들 수 있으나， 이에만 한정되는 것은 아니다. 상기 C5-20 헤테로아릴로는， 단환 또는 축합환의 헤테로아릴을 포함하고, 카바졸릴， 피리딜， 퀴놀린， 이소퀴놀린 티오페닐， 퓨라닐， 이미다졸， 옥사졸릴, 티아졸릴， 트리아진, 테트라하이드로피라닐， 테트라하이드로퓨라닐 등을 들 수 있으나, 이에만 한정되는 것은 아니다. 상기 Cuo 알콕시로는, 메특시， 에특시, 페닐옥시， 시클로헥실옥시 등을 들 수 있으나， 이에만 한정되는 것은 아니다. 상기 4족 전이금속으로는 티타늄， 지르코늄， 하프늄 등을 들 수 있으나, 이에만 한정되는 것은 아니다. 상기 화학식 2a , 2b 및 2c의 내지 R17 및 I 내지 '는 각각 독립적으로 수소， 메틸， 에틸， 프로필， 이소프로필， n-부틸， tert-부틸， 펜틸， 핵실， 헵틸, 옥틸, 페닐， 할로겐， 트리메틸실릴， 트리에틸실릴， 트리프로필실릴， 트리부틸실릴， 트리이소프로필실릴， 트리메틸실릴메틸， 메톡시, 또는 에특시인 것이 더욱 바람직하나， 이에만 한정되는 것은 아니다. 상기 화학식 1의 L은 C4-8 직쇄 또는 분지쇄 알킬렌인 것이 더욱 바람직하나， 이에만 한정되는 것은 아니다. 또한， 상기 알킬렌기는 C o 알킬， C2-20 알케닐， 또는 C6-20 아릴로 치환 또는 비치환될 수 있다. 또한， 상기 화학식 1의 A는 수소， 메틸， 에틸, 프로필， 이소프로필 n-부틸， tert-부틸， 메특시메틸, tert-부톡시메틸， 1-에록시에틸， 1-메틸- 1-메톡시에틸, 테트라하이드로피라닐， 또는 테트라하이드로퓨라닐인 것이 바람직하나， 이에만 한정되는 것은 아니다. J is any one selected from the group consisting of NR f , 0, PR f and S, wherein R F is CHO 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, it includes a linear or branched alkenyl, Specifically, allyl, ethenyl, propenyl, butenyl, pentenyl, etc. may be mentioned, but is not limited thereto. The C 6 - 20 aryl include, includes a monocyclic or condensed ring aryl group. Specifically, phenyl, biphenyl, naphthyl, and the like, but phenanthrenyl, fluorenyl day, and thus are 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 Pyranyl, tetrahydrofuranyl and the like, but are not limited thereto. Examples of the Cuo alkoxy include methioxy, etoxy, phenyloxy, cyclohexyloxy and the like, but are not limited thereto. Examples of the Group 4 transition metal include titanium, zirconium, hafnium, and the like, but are not limited thereto. In Formulas 2a, 2b, and 2c to R 17 and I to 'are each independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, nucleus, heptyl, octyl, phenyl, halogen, Trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, methoxy, or more particularly, but is 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 is C o alkyl, C 2 - may be substituted or unsubstituted aryl as 20 - 20 alkenyl, or C 6. In addition, A of Formula 1 is hydrogen, methyl, ethyl, propyl, isopropyl n-butyl, tert-butyl, mesoxymethyl, tert-butoxymethyl, 1-ethoxyethyl, 1-methyl- 1-methoxyethyl, tetrahydropyranyl, or tetrahydrofuranyl, preferably It is not limited only.
또한, 상기 화학식 실리콘인 것이 바람직하나， 이에만 한정되는 것은 아니다. 상기 화학식 1의 게 1 메탈로센 화합물은 인데노 인돌 ( indeno indole) 유도체 및 /또는 플루오렌 ( f luorene) 유도체가 브릿지에 의해 가교된 구조를 형성하며， 리간드 구조에 루이스 염기로 작용할 수 있는 비공유 전자쌍을 가짐으로써 담체의 루이스 산 특성을 지니는 표면에 담지되어 담지 시에도 높은 증합 활성을 나타낸다. 또한 전자적으로 풍부한 인데노 인돌기 및 /또는 플루오렌기를 포함함에 따라 활성이 높고， 적절한 입체 장애와 리간드의 전자적인 효과로 인해 수소 반웅성이 낮을 뿐 아니라 수소가 존재하는 상황에서도 높은 활성이 유지된다. 또한 인데노 인돌 유도체의 질소 원자가 자라나는 고분자 사슬의 beta-hydrogen을 수소결합에 의해 안정화시켜 beta-hydrogen el iminat ion을 억제하여 초고분자량의 올레핀계 중합체를 중합할 수 있다. 본 발명의 일 실시예에 따르면， 상기 화학식 2a로 표시되는 화합물의 구체적인 예로는 하기 구조식들 중 하나로 표시되는 화합물을 들 수 있으나 본 발 In addition, it is preferable that the above formula silicon, but is not limited thereto. The crab 1 metallocene compound of Formula 1 is a non-covalently formed structure in which an indeno indole derivative and / or a fluorene derivative are crosslinked by a bridge, and may act as a Lewis base to the ligand structure. By having an electron pair, it is supported on the surface having the Lewis acid characteristic of the carrier, and shows high polymerization activity even when supported. In addition, due to the electronically rich indeno indole and / or fluorene group, the activity is high, and due to the proper steric hindrance and the electronic effect of the ligand, the reaction is not only low but also maintains high activity even in the presence of hydrogen. . 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 Formula 2a may include a compound represented by one of the following structural formulas, but the present invention
Figure imgf000013_0001
Figure imgf000013_0001
Figure imgf000014_0001
본 발명의 일 실시예에 따르면， 상기 화학식 2t)로 표시되는 화합물의 구체적인 예로는 하기 구조식 들 중 하나로 표시되는 화합물을 들 수 있으나， 본 발명이 이에
Figure imgf000014_0001
According to one embodiment of the present invention, specific examples of the compound represented by Chemical Formula 2t) include a compound represented by one of the following structural formulas, but the present invention is
Figure imgf000014_0002
Figure imgf000014_0002
Figure imgf000015_0001
본 발명의 일 실시예에 따르면， 상기 화학식 2c로 표시되는 화합물의 구체적인. 예로는 하기 구조식 들 중 하나로 표시되는 화합물을 들 수 있으나，
Figure imgf000015_0001
According to an embodiment of the present invention, specific compounds of Formula 2c. Examples include compounds represented by one of the following structural formulas,
Figure imgf000015_0002
본 발명의 일 실시예에 따르면, 상기 화학식 1로 표시되는 제 1 메탈로센 화합물의 구체적인 예로는 하기 구조식들 증 하나로 표시되는 화합물 들 수 있으나， 이에만 한정되는 것은 아니다.
Figure imgf000015_0002
According to one embodiment of the present invention, specific examples of the first metallocene compound represented by Chemical Formula 1 may include compounds represented by the following structural formulas, but are not limited thereto.
Figure imgf000015_0003
Figure imgf000016_0001
Figure imgf000015_0003
Figure imgf000016_0001
Figure imgf000017_0001
상기 화학식 1의 제 1 메탈로센 화합물은 활성이 우수하고 고분자량의 에틸렌 /알파-을레핀 공증합체를 중합할 수 있다. 특히， 담체에 담지하여 사용할 경우에도 높은 중합 활성을 나타내어， 초고분자량의 에틸렌 /알파- 을레핀 공중합체를 제조할 수 있다. 또한， 고분자량과 동시에 넓은 분자량 분포를 갖는 에틸렌 /알파- 올레핀 공중합체를 제조하기 위해 수소를 포함하여 중합 반웅을 진행하는 경우에도 본 발명에 따른 화학식 1의 제 1 메탈로센 화합물은 낮은 수소 반웅성을 나타내어 여전히 높은 활성으로 초고분자량의 에틸렌 /알파-올레핀 공중합체의 중합이 가능하다. 따라서， 다른 특성을 갖는 촉매와 흔성으로 사용하는 경우에도 활성의 저하 없이 고분자량의 특성을 만족시키는 에틸렌 /알파-올레핀 공중합체를 제조할 수 있어， 고분자의 에틸렌 /알파- 올레핀 공증합체를 포함하면서 넓은 분자량 분포를 갖는 에틸렌 /알파- 올레핀 공증합체를 용이하게 제조할 수 있다. 상기 화학식 1의 게 1 메탈로센 화합물은 인데노인돌 유도체 및 /또는 플루오렌 유도체를 브릿지 화합물로 연결하여 리간드 화합물로 제조한 다음， 금속 전구체 화합물을 투입하여 메탈레이션 (metal lat i on)을 수행함으로써 수득될 수 있다.、 상기제 1 메탈로센 화합물의 쩨조방법은 후술하는 실시예에 구체화하여 설명한다. 상기 화학식 3으로 표시되는 화합물로는 예를 들어 하기 구조식들 중 하나로
Figure imgf000017_0001
The first metallocene compound of Chemical Formula 1 has excellent activity and may polymerize a high molecular weight ethylene / alpha-lepine co-polymer. In particular, even when used on a carrier, it shows high polymerization activity, and thus an ultra high molecular weight ethylene / alpha-olefin copolymer can be prepared. In addition, in order to prepare an ethylene / alpha-olefin copolymer having a high molecular weight and a wide molecular weight distribution, a polymerization reaction including hydrogen is carried out. Even in this case, the first metallocene compound of formula 1 according to the present invention exhibits low hydrogen reaction properties and is still capable of polymerizing an ultra high molecular weight ethylene / alpha-olefin copolymer with high activity. Therefore, an ethylene / alpha-olefin copolymer that satisfies high molecular weight characteristics can be produced even when used in combination with a catalyst having different properties without degrading the activity, while including the polymer ethylene / alpha-olefin co-polymer. Ethylene / alpha-olefin copolymers having a wide molecular weight distribution can be readily prepared. The C1 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 metal lat i on. It can be obtained by the method of manufacturing the first metallocene compound described in detail in Examples to be described later. Examples of the compound represented by Formula 3 include one of the following structural formulas
Figure imgf000018_0001
Figure imgf000018_0001
Figure imgf000019_0001
상기 화학식 4에서， m이 1인 경우는 Cp¾c 고리와 Cp d 고리 또는 Cp4Rd 고리와 M2가 B1에 의해 가교 결합된 브릿지 화합물 구조인 것을 의미하며 , m이 0인 경우는 비가교 화합물 구조를 의미한다. 상기 화학식 4로 표시되는 화합물로는 예를 들어 하기 구조식들 중 하나로 니다.
Figure imgf000019_0001
In Formula 4, when m is 1, it means that a Cp¾ c ring and a Cp d ring or a Cp 4 R d ring and M 2 is a bridge compound structure cross-linked by B 1 , and when m is 0, the ratio Means a compound compound. Examples of the compound represented by Formula 4 include one of the following structural formulas.
Figure imgf000019_0002
Figure imgf000019_0002
Figure imgf000020_0001
Figure imgf000020_0001
 
Figure imgf000021_0001
본 발명에서 사용되는 메탈로센 촉매는 상기 화학식 1로 표시되는 거 U 메탈로센 화합물의 1종 이상， 및 상기 화학식 3 내지 화학식 5로 표시되는 화합물 중 선택되는 제 2 메탈로센 화합물의 1종 이상을 조촉매 화합물과 함께 담체에 담지한 것일 수 있다. 또한， 상기 담지 메탈로센 촉매는 제조되는 에틸렌 /알파ᅳ올레핀 공중합체에서 LCB(Long Chain Branch)의 생성을 유도할 수 있다. 본 발명에 따른 담지 메탈로센 촉매에 있어서， 상기 메탈로센 화합물을 활성화하기 위하여 담체에 함께 담지되는 조촉매로는 13족 금속을 포함하는 유기 금속 화합물로서， 일반적인 메탈로센 촉매 하에 을레핀을 중합할 때 사용될 수 있는 것이라면 특별히 한정되는 것은 아니다. 구체적으로， 상기 조촉매 화합물은 하기 화학식 6의 알루미늄 함유 제 1 조촉매， 및 하기 화학식 7의 보레이트계 제 2 조촉매 중 하나 이상을 포함할 수 있다.
Figure imgf000021_0001
The metallocene catalyst used in the present invention may be at least one of the U metallocene compounds represented by Formula 1, and one of the second metallocene compounds selected from the compounds represented by Formulas 3 to 5. The above may be supported on the carrier together with the cocatalyst compound. In addition, the supported metallocene catalyst may induce the production of a long chain branch (LCB) in the ethylene / alpha olefin 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. It will not be specifically limited if it can be used at the time of superposition | polymerization. Specifically, the cocatalyst compound may include at least one of an aluminum-containing first cocatalyst of Formula 6, and a borate-based second cocatalyst of Formula 7 below.
[화학식 6]  [Formula 6]
-[Al (R18)-0-]k- 화학식 6에서， R18은 각각 독립적으로 할로겐， 할로겐 치환 또는 비치환된 탄소수 1 내지 20의 하이드로카빌기이고， k는 2 이상의 정수이고， [화학식 7] -[Al (R 18 ) -0-] k -In formula 6, R 18 is each independently a halogen, halogen substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more, 7]
T+(BG4]" - 화학식 7에서， T+은 +1가의 다원자 이온이고， B는 +3 산화 상태의 붕소이고， G는 각각 독립적으로 하이드라이드， 디알킬아미도， 할라이드， 알콕사이드， 아릴옥사이드， 하이드로카빌， 할로카빌 및 할로-치환된 하이드로카빌로 이루어진 군에서 선택되고, 상기 G는 20개 이하의 탄소를 가지나， 단 하나 이하의 위치에서 G는 할라이드이다. 이러한 게 1 및 제 2 조촉매의 사용에 의해， 최종 제조된 폴리올레핀의 분자량 분포가 보다 균일하게 되면서， 중합 활성이 향상될 수 있다. 상기 화학식 6의 게 1 조촉매는 선형， 원형 또는 망상형으로 반복단위가 결합된 알킬알루미녹산계 화합물로 될 수 있고， 이러한 제 1 조촉매의 구체적인 예로는, 메틸알루미녹산 (MA0) , 에틸알루미녹산， 이소부틸알루미녹산 또는 부틸알루미녹산 등을 들 수 있다. 또한， 상기 화학식 7의 게 2 조촉매는 삼치환된 암모늄염， 또는 디알킬 암모늄염， 삼치환된 포스포늄염 형태의 보레이트계 화합물로 될 수 있다. 이러한 게 2 조촉매의 구체적인 예로는, 트리메탈암모늄 테트라페닐보레이트, 메틸디옥타데실암모늄 테트라페닐보레이트， 트리에틸암모늄 테트라페닐보레이트， 트리프로필암모늄 테트라페닐보레이트 '트리 (n-부틸)암모늄 테트라페닐보레이트， 메틸테트라데사이클로옥타데실암모늄 테트라페닐보레이트， Ν,Ν- 디메틸아닐늄 테트라페닐보레이트， Ν,Ν-디에틸아닐늄 테트라페닐보레이트， Ν， Ν-디메틸 ( 2 , 4， 6-트리메틸아닐늄)테트라페닐보레이트， 트리메틸암모늄 테트라키스 (펜타플로오로페닐 )보레이트， 메틸디테트라데실암모늄 테트라키스 (펜타페닐)보레이트， 메틸디옥타데실암모늄 테트라키스 (펜타플루오로페닐)보레이트， 트리에틸암모늄， 테트라키스 (펜타플루오로페닐)보레이트， T + (BG 4 ] " -In formula 7, T + is a + monovalent polyatomic ion, B is a boron in +3 oxidation state, G is independently a hydride, dialkylamido, halide, alkoxide, Aryloxide, hydrocarbyl, halocarbyl and halo-substituted hydrocarbyl, wherein G has up to 20 carbons, but at less than one position G is a halide. By the use of a promoter, the molecular weight distribution of the finally produced polyolefin may be more uniform, and the polymerization activity may be improved.The C 1 cocatalyst of Chemical Formula 6 is linear, circular, or reticular alkyl having a repeating unit bonded thereto. It may be an aluminoxane-based compound, and specific examples of the first cocatalyst include methyl aluminoxane (MA0), ethyl aluminoxane, isobutyl aluminoxane or butyl aluminoxane. In addition, the C2 cocatalyst of Formula 7 may be a borate-based compound in the form of a trisubstituted ammonium salt, a dialkyl ammonium salt, or a trisubstituted phosphonium salt. Trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate ' tri (n-butyl) ammonium tetraphenylborate ， Methyl tetradecyclooctadecyl ammonium tetraphenylborate, Ν, Ν- dimethylaninium tetraphenylborate, Ν, Ν-diethylaninium tetraphenylborate, Ν, Ν-dimethyl (2, 4, 6-trimethylaninium) Tetraphenylborate, Trimethylammonium Tetrakis (pentafluorophenyl) borate, Methylditetradecylammonium Tetrakis (pentaphenyl) borate, Methyldioctadecylammonium Tetrakis (pentafluorophenyl) borate, Triethylammonium, Tetrakis (Pentafluorophenyl) borate ，
트리프로필암모늄테트라키스 (펜타프루오로페닐)보레이트， 트리 (η- 부틸)암모늄 테트라키스 (펜타플루오로페닐)보레이트， 트리 (2급- 부틸)암모늄테트라키스 (펜타플루오로페닐)보레이트, Ν,Ν-디메틸아닐늄 테트라키스 (펜타플루오로페닐)보레이트， Ν,Ν- 디에틸아닐늄테트라키스 (펜타플루오로페닐)보레이트， Ν,Ν—디메틸 (2,4,6- 트리메틸아닐늄)테트라키스 (펜타플루오로페닐)보레이트， Tripropylammonium tetrakis (pentafluorophenyl) borate, tri (η-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) borate, N , Ν-dimethylaninium tetrakis (pentafluorophenyl) borate, Ν, Ν-diethylaninium tetrakis (pentafluorophenyl) borate, Ν, Ν-dimethyl (2,4,6-trimethylaninynium) Tetrakis (pentafluorophenyl) borate ，
트리메틸암모늄테트라키스 (2， 3,4, 6—테트라폴루오로페닐)보레이트， Trimethylammonium tetrakis (2, 3,4, 6—tetrafluorofluoro) borate,
트리에틸암모늄 테트라키스 (2,3,4,6-테트라플루오로페닐)보레이트, 트리프로필암모늄 테트라키스 ( 2， 3 , 4 , 6-테트라플루오로페닐)보레이트， 트리 (η-부틸)암모늄 테트라키스 ( 2， 3， 4， 6-，테트라플루오로페닐)보레이트， 디메틸 (t-부틸)암모늄 테트라키스 (2, 3ᅳ 4, 6-테트라플루오로페닐)보레이트， Ν,Ν—디메틸아닐늄 테트라키스 (2，3，4，6-테트라플루오로페닐)보레이트， Ν,Ν- 디에틸아닐늄 테트라키스 (2,3,4,6-테트라플루오로페닐)보레이트 또는 Ν,Ν- 디메틸 -(2，4,6-트리메틸아닐늄)테트라키스 -(2，3，4，6- 테트라플루오로페닐)보레이트 등의 삼치환된 암모늄염 형태의 보레이트계 화합물; 디옥타데실암모늄 테트라키스 (펜타플루오로페닐)보레이트， 디테트라데실암모늄 테트라키스 (펜타플루오로페닐)보레이트 또는 디사이클로핵실암모늄 테트라키스 (펜타플루오로페닐)보레이트 등의 디알킬암모늄염 형태의 보레이트계 화합물; 또는 트리페닐포스포늄 테트라키스 (펜타플루오로페닐)보레이트， 메틸디옥타데실포스포늄 테트라키스 (펜타플루오로페닐)보레이트 또는 트리 (2,6-디메틸페닐)포스포늄 테트라키스 (펜타플루오로페닐)보레이트 등의 삼치환된 포스포늄염 형태의 보레이트계 화합물 등을 들 수 있다. 본 발명에 따른 담지 메탈로센 촉매에 있어서， 화학식 1로 표시되는 거 U 메탈로센 화합물, 또는 화학식 3 내지 5로 표시되는 제 2 메탈로센 화합물에 포함되는 전체 전이금속 대 담체의 질량비는 1 ： 10 내지 1 ： 1 , 000 일 수 있다. 상기 질량비로 담체 및 메탈로센 화합물을 포함할 때, 최적의 형상을 나타낼 수 있다. 또한， 조촉매 화합물 대 담체의 질량비는 1 ： 1 내지 1 ： 100 일 수 있다. 본 발명에 따른 담지 메탈로센 촉매에 있어서， 상기 담체로는 표면에 하이드록시기를 함유하는 담체를 사용할 수 있으며， 바람직하게는 건조되어 표면에 수분이 제거된， 반응성이 큰 하이드록시기와 실록산기를 가지고 있는 담체를 사용할 수 있다. 예컨대， 고온에서 건조된 실리카， 실리카 -알루미나, 및 실리카ᅳ 마그네시아 등이 사용될 수 있고， 이들은 통상적으로 Na20, K2C03 ) BaS04 , 및 Mg(N03)2 등의 산화물, 탄산염 , 황산염， 및 질산염 성분을 함유할 수 있다. 상기 담체의 건조 온도는 200 내지 800°C가 바람직하고， 300 내지 600 °C가 더욱 바람직하며 , 300 내자 400°C가 가장 바람직하다. 상기 담체의 건조 온도가 200°C 미만인 경우 수분이 너무 많아서 표면의 수분과 조촉매가 반웅하게 되고, 800°C를 초과하는 경우에는 담체 표면의 기공들이 합쳐지면서 표면적이 줄어들며 , 또한 표면에 하이드록시기가 많이 없어지고 실록산기만 남게 되어 조촉매와의 반응자리가 감소하기 때문에 바람직하지 않다. 상기 담체 표면의 하이드록시기 양은 0. 1 내지 10 mmol /g이 바람직하며， 0.5 내지 5 mmol /g일 때 더욱 바람직하다. 상기 담체 표면에 있는 하이드록시기의 양은 담체의 제조방법 및 조건 또는 건조 조건， 예컨대 온도， 시간， 진공 또는 스프레이 건조 등에 의해 조절할 수 있다. 상기 하이드록시기의 양이 0. 1 mmol/g 미만이면 조촉매와의 반웅자리가 적고， 10 mmol /g을 초과하면 담체 입자 표면에 존재하는 하이드록시기 이외에 수분에서 기인한 것일 가능성이 있기 때문에 바람직하지 않다. 한편， 본 발명에 따른 에틸렌 /알파-을레핀 공중합체는， 상술한 담지 메탈로센 촉매의 존재 하에서， 에틸렌 및 알파-올레핀을 중합시킴으로써 제조할 수 있다. 상기 증합 반웅은 하나의 연속식 슬러리 중합 반웅기， 루프 슬러리 반웅기， 기상 반응기 또는 용액 반응기를 이용하여 에틸렌 및 알파- 을레핀을 공중합하여 진행할 수 있다. 그리고， 상기 중합 온도는 약 25 내지 약 500°C , 바람직하게는 약 25 내지 약 200°C , 보다 바람직하게는 약 50 내지 약 150°C일 수 있다. 또한, 중합 압력은 약 1 내지 약 100 Kgf/crf , 바람직하게는 약 1 내지 약 50 Kgf/cirf , 보다 바람직하게는 약 5 내지 약 30 Kgf/cuf일 수 있다. 상기 담지 메탈로센 촉매는 탄소수 5 내지 12의 지방족 탄화수소 용매， 예를 들면 펜탄, 핵산, 헵탄， 노난， 데칸， 및 이들의 이성질체와 를루엔， 벤젠과 같은 방향족 탄화수소 용매， 디클로로메탄, 클로로벤젠과 같은 염소원자로 치환된 탄화수소 용매 등에 용해하거나 희석하여 주입할 수 있다. 여기에 사용되는 용매는 소량의 알킬 알루미늄 처리함으로써 촉매 독으로 작용하는 소량의 물 또는 공기 등을 제거하여 사용하는 것이 바람직하며, 조촉매를 더 사용하여 실시하는 것도 가능하다. 본 발명에 따른 에틸렌 /알파-올레핀 공중합체는 저분자량의 고분자 쇄를 주로 중합하는 화학식 3 내지 5의 촉매와， 고분자량의 고분자 쇄를 주로 중합하는 화학식 1의 촉매를 함께 사용하여， 에틸렌 및 알파-올레핀 단량체를 공중합하여 제조된다. 이러한 2종 이상의 촉매의 상호 작용으로 인하여, 전체적으로 분자량 분포가 넓으면서도， 고분자량 명역에 있는 고분자 쇄들이 보다 높은 함량으로 포함된 중합체가 얻어질 수 있다. Triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri (η-butyl) ammonium tetra Keith (2, 3, 4, 6-, tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2, 3 ᅳ 4, 6-tetrafluorophenyl) borate, Ν, Ν—dimethylaninium Tetrakis (2,3,4,6-tetrafluorophenyl) borate, Ν, Ν-diethylaninynium tetrakis (2,3,4,6-tetrafluorophenyl) borate or Ν, Ν-dimethyl- Borate compounds in the form of trisubstituted ammonium salts such as (2,4,6-trimethylaninynium) tetrakis- (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 dicyclonuclear ammonium tetrakis (pentafluorophenyl) borate compound; Or triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate or tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) Borate compounds in the form of trisubstituted phosphonium salts, such as a borate, etc. are mentioned. In the supported metallocene catalyst according to the present invention, the mass ratio of the total transition metal to the carrier contained in the near U metallocene compound represented by Formula 1 or the second metallocene compound represented by Formulas 3 to 5 is 1 : May be from 1 to 1,000. When the carrier and the metallocene compound are included in the mass ratio, an optimal shape can be exhibited. In addition, the mass ratio of the promoter compound to the carrier may be from 1: 1 to 1: 100. In the supported metallocene catalyst according to the present invention, the carrier may be a carrier containing a hydroxy group on the surface, and preferably has a highly reactive hydroxyl group and a siloxane group which are dried to remove moisture on the surface. Carriers can be used. For example, silica, silica-alumina, and silica ᅳ magnesia dried at high temperature may be used, and these are usually 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 800 ° C., more preferably 300 to 600 ° C., most preferably 300 to 400 ° C. When the drying temperature of the carrier is less than 200 ° C, the water content is too much and the cocatalyst reacts, and when it exceeds 800 ° C, the surface area decreases as the pores on the surface of the carrier are combined, and the surface is hydroxy on the surface. 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 mmol / 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. If the amount of the hydroxy group is less than 0.01 mmol / g, the reaction space with the promoter is small. If the amount of the hydroxy group is more than 10 mmol / g, it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle. Not desirable On the other hand, the ethylene / alpha-lepine copolymer according to the present invention can be produced by polymerizing ethylene and alpha-olefin in the presence of the supported metallocene catalyst described above. The polymerization reaction may be performed by copolymerizing ethylene and alpha-lephine using one continuous slurry polymerization reaction vessel, a loop slurry reaction vessel, 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 150 ° C. In addition, the polymerization pressure may be about 1 to about 100 Kgf / crf, preferably about 1 to about 50 Kgf / cirf, more preferably about 5 to about 30 Kgf / cuf. The supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, nucleic acid, heptane, nonane, decane, isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane, chlorobenzene and the like. The solution may be dissolved or diluted in a hydrocarbon solvent substituted with the same chlorine atom. The solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkyl aluminum, and may be carried out by further using a promoter. Ethylene / alpha-olefin copolymer according to the present invention is a combination of a catalyst of the general formula (3) to 5 to mainly polymerize the low molecular weight polymer chain, and a catalyst of the formula (1) mainly to polymerize the high molecular weight polymer chain, ethylene and alpha It is prepared by copolymerizing an -olefin monomer. By the interaction of these two or more catalysts Due to this, a polymer having a wide molecular weight distribution as a whole and having a higher content of the polymer chains in the high molecular weight region can be obtained.
【발명의 효과】  【Effects of the Invention】
본 발명에 따른 에틸렌 /알파-올레핀 공증합체는， 우수한 가공성 및 표면 특성을 가져 여러 제품을 제조하는데 유용하게 적용할 수 있다.  The ethylene / alpha-olefin copolymer according to the present invention has excellent processability and surface properties, and can be usefully applied to manufacture various products.
【도면의 간단한 설명】  [Brief Description of Drawings]
도 1은， 본 발명의 일실시예에서 제조한 중합체의 구정을 관찰한 것이다.  1 is to observe the spherical shape of the polymer prepared in one embodiment of the present invention.
도 2 및 3은， 본 발명의 비교예에서 제조한 중합체의 구정을 관찰한 것이다.  2 and 3 observe the spherical shape of the polymer produced in the comparative example of the present invention.
【발명을 실시하기 위한 구체적인 내용】  [Specific contents to carry out invention]
이하， 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐， 이에 의해 본 발명의 내용이 한정되는 것은 아니다. 제조예 1  Hereinafter, preferred embodiments of the present invention 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. Preparation Example 1
단계 1) 리간드 화합물의 제조  Step 1) Preparation of Ligand Compound
Fluorene 2 g을 5 mL MTBE, hexane 100 mL에 녹여 2·5 Μ n-BuLi hexane so hit km 5.5 mL를 dry ice/acetone bath에서 적가하여 상온에서 밤새 교반하였다. (6-(tert-butoxy.)hexyl)dichloro(methyl)silane 3.6 g을 핵산 (hexane) 50 mL에 녹여 dry ice/acetone bath하에서 fluorene一 Li 슬러리를 30분 동안 transfer하여 상온에서 밤새 교반하였다. 이와 동시에 5 , 8-d i me thy 1 -5 , 10-d i hydr o i ndeno [ 1 , 2-b ] i ndo 1 e (12 mmol, 2.8 g) 또한 THF 60 mL에 녹여 2.5M n— BuLi hexane solution 5.5 mL를 dry ice/acetone bath에서 적가하여 상온에서 밤새 교반하였다. fluorene과 (6-(tert_ butoxy)hexyl )di chloro(methyl )si lane 과의 반웅 용액을 NMR 샘플링하여 반응 완료를 확인한 후 5,8-dimethy卜 5,10-dihydroindeno[l,2-b]indole-Li solution을 dry ice/acetone bath하에서 transfer하였다. 상온에서 밤새 교반하였다. 반웅 후 ether /water로 추출 (extract ion)하여 유기층의 잔류수분을 MgS04로 제거 후 리간드 화합물 (Mw 597.90, 12隱 ol)을 얻었으며 이성질체 (isomer) 두 개가 생성되었음을 -NMR에서 확인할 수 있었다. 2 g of fluorene was dissolved in 5 mL MTBE and 100 mL of hexane, and 5.5 mL of 2 · 5 Μ n-BuLi hexane so hit km was added dropwise in a dry ice / acetone bath, followed by stirring at room temperature overnight. 3.6 g of (6- (tert-butoxy.) Hexyl) dichloro (methyl) silane was dissolved in 50 mL of nucleic acid (hexane), and then transferred to a fluorene one Li slurry for 30 minutes in a dry ice / acetone bath and stirred at room temperature overnight. At the same time 5, 8-di me thy 1 -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 2.5M n— BuLi hexane solution 5.5 mL was added dropwise in a dry ice / acetone bath and stirred overnight at room temperature. NMR sampling the reaction solution of fluorene with (6- (tert_butoxy) hexyl) dichlorochloro (methyl) si lane to confirm the reaction was completed, and then 5,8-dimethy 卜 5,10-dihydroindeno [l, 2-b] indole Li solution was transferred under dry ice / acetone bath. Stir overnight at room temperature. After reaction, extraction was performed with ether / water (extract ion) to remove the residual moisture of the organic layer with MgS0 4 to obtain a ligand compound (Mw 597.90, 12 隱 ol). Two isomers were generated in -NMR.
¾ NMR (500 MHz, d6-benzene): -0.30 ~ -0.18 (3H, d)， 0.40 (2H, m), 0.65 ~ 1.45 (8H, m)， 1.12 (9H, d), 2.36 - 2.40 (3H, d), 3.17 (2H, m), 3.41 ~ 3.43 (3H, d) , 4.17 ~ 4.21 (1Η, d), 4.34 ~ 4.38 (1Η, d), 6.90 ~ 7.80 (15H, m) 단계 2) 메탈로센 화합물의 제조 ¾ NMR (500 MHz, d 6 -benzene): -0.30 to -0.18 (3H, d), 0.40 (2H, m), 0.65 to 1.45 (8H, m), 1.12 (9H, d), 2.36-2.40 ( 3H, d), 3.17 (2H, m), 3.41-3.43 (3H, d), 4.17-4.21 (1Η, d), 4.34-4.38 (1Η, d), 6.90-7.80 (15H, m) Step 2) Preparation of Metallocene Compounds
상기 단계 1에서 합성한 리간드 화합물 7.2 g (12 隱 ol)을 diethylether 50 mL에 녹여 2.5 M n-BuLi hexane solution 11.5 mL를 dry ice/acetone bath에서 적가하여 상온에서 밤새 교반하였다. 진공 건조하여 갈색 (brown color)의 sticky oil을 얻었다. 를루엔에 녹여 슬러리를 얻었다. ZrCl4(THF)2를 준비하고 를루엔 50 mL를 넣어 슬러리로 준비하였다. ZrCl4(THF)2의 50 mL 를루엔 슬러리를 dry ice/acetone bath에서 transfer하였다. 상온에서 밤새 교반함에 따라 보라색 (violet color)으로 변화하였다. 반웅 용액을 필터하여 LiCl을 제거하였다. 여과액 (filtrate)의 틀루엔을 진공 건조하여 제거한 후 핵산을 넣고 1시간 동안 sonication하였다. 슬러리를 필터하여 여과된 고체 (filtered solid)인 짙은 보라색 (dark violet)의 메탈로센 화합물 6 g (Mw 758.02, 7.92 mmol, yield 66 mol%)을 얻었다. -NMR상에서 두 개의 isomer가 관찰되었다. 7.2 g (12 μL) of the ligand compound synthesized in Step 1 was dissolved in 50 mL of diethylether, and 11.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath, followed by stirring at room temperature overnight. Drying in vacuo gave a brown colored 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 thereto and sonicated for 1 hour. The slurry was filtered to give 6 g (Mw 758.02, 7.92 mmol, yield 66 mol%) of a dark violet metallocene compound as a filtered solid. Two isomers were observed on -NMR.
¾ 證 (500 丽 z, CDC13): 1.19 (9H, d)， 1.71 (3H, d) , 1.50 ~¾ (500 ley 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(3H, s), 3.38 (2H, m), 3.91 (3H, d)， 6.66 ~ 7.88 (15H, m) 제조예 2 1.70 (4H, m), 1.79 (2H, m), 1.98-2.19 (4H, m), 2.58 (3H, s), 3.38 (2H, m), 3.91 (3H, d), 6.66-7.88 (15H, m) Preparation Example 2
6-클로로핵사놀 (6-chlorohexanol)을 사용하여 문헌 (Tetrahedron Lett. Using 6-chlorohexanol, Tetrahedron Lett.
2951 (1988))에 제시된 방법으로 t-Butyl-0-(CH2)6-Cl을 제조하고， 여기에 NaCp를 반웅시켜 t-Butyl-0-(C¾)6-C5H5를 얻었다 (수율 60%, b.p. 80 °C I 0.1 mmHg) . 2951 (1988)) to prepare t-Butyl-0- (CH 2 ) 6 -Cl, which was reacted with NaCp to give t-Butyl-0- (C¾) 6 -C 5 H 5 ( Yield 60%, bp 80 ° C 0.1 mmHg).
또한， -78°C에서 t-Butyl-0-(CH2)6-C5H5를 THF에 녹이고， 노르말 부틸리륨 (n-BuLi)을 천천히 가한 후， 실온으로 승온시킨 후， 8시간 반웅시켰다. 그 용액을 다시 _78°C에서 ZrCl4(THF)2(1.70 g, 4.50 mmol)/THF(30 mL)의 서스펜젼 (suspension) 용액에 기 합성된 리튬염 (lithium salt) 용액을 천천히 가하고 실온에서 6시간 동안 더 반응시켰다. Also, dissolve t-Butyl-0- (CH 2 ) 6 -C 5 H 5 in THF at -78 ° C, slowly add normal butylium (n-BuLi), and then warm to room temperature, 8 hours I responded. The solution was slowly added to a solution of pre-synthesized lithium salt in a suspension solution of ZrCl 4 (THF) 2 (1.70 g, 4.50 mmol) / THF (30 mL) at _78 ° C. The reaction was further performed for 6 hours.
모든 휘발성 물질올 진공 건조하고, 얻어진 오일성 액체 물질에 핵산 (hexane) 용매를 가하여 걸러내었다. 걸러낸 용액을 진공 건조한 후， 핵산을 가해 저온 (-2CTC)에서 침전물을 유도하였다. 얻어진 침전물을 저온에서 걸러내어 흰색 고체 형태의 [tBu-0-(C¾)6-C5H4]2ZrCl2 화합물을 얻었다 (수율 92%). All volatiles were dried in vacuo and the resulting oily liquid material was filtered off by addition of a hexane solvent. The filtered solution was vacuum dried and nucleic acid was added to induce precipitate at low temperature (-2CTC). The obtained precipitate was filtered at low temperature to give a [tBu-0- (C¾) 6 -C 5 H 4 ] 2 ZrCl 2 compound as a white solid (yield 92%).
- ¾ NMR (300匪 z, CDC13): 6.28 (t, J - 2.6 Hz, 2 H), 6.19 (t, J = 2.6 Hz, 2 H), 3.31 (t, 6.6 Hz, 2 H), 2.62 (t, J = 8 Hz), 1.7 - 1.3 (m, 8 H), 1.17 (s, 9 H). 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, 8 H), 1.17 (s, 9 H).
13C NMR (CDCls): 135.09, 116.66， 112.28, 72.42， 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00. 제조예 3 13 C NMR (CDCls): 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
단계 1) 담지체 건조  Step 1) Carrier Drying
실리카 (Grace Davison사 제조 SYL0P0L 948)를 400°C의 온도에서 15시간 동안 진공을 가한 상태에서 탈수하였다. 단계 2) 담지 촉매 제조 Silica (SYL0P0L 948, manufactured by Grace Davison) was dehydrated under vacuum at a temperature of 400 ° C. for 15 hours. Step 2) preparing supported catalyst
상기 단계 1의 건조된 실리카 10 g를 유리 반웅기에 넣고， 를루엔 100 mL을 추가로 넣고 교반하였다. 10 wt% 메틸알루미녹산 (MAO)/를루엔 용액을 50 mL를 가하여 40°C에서 교반하며 천천히 반응시켰다. 이후 충분한 양의 를루엔으로 세척하여 반웅하지 않은 알루미늄 화합물을 제거하고， 감압하여 남아 있는 를루엔을 제거하였다. 다시 를루엔 100 mL를 투입한 후， 상기 제조예 1에서 제조된 메탈로센 촉매 0.25 隱 을 를루엔에 녹여 같이 투입하여 1시간 동안 반웅을 시켰다. 반응이 끝난 후， 상기 제조예 2에서 제조된 메탈로센 촉매 0.25 隱 을 를루엔에 녹여 투입한 후， 1시간 동안 반웅을 추가로 시켰다. 반웅이 끝난 후， 교반을 멈추고 를루엔층을 분리제거 후， 아닐리늄 보레이트 (Ν, Ν-dimethyl ani l inium tetraki s(pentaf luorophenyDborate , AB) 1.0 mmol을 투입하고 1시간 동안 교반을 시킨 후， 50t에서 감압하여 를루엔을 제거하여， 담지 촉매를 제조하였다. 실시예 1 : 에틸렌 /알파-올레핀 공중합체 10 g of the dried silica of step 1 was placed in a glass reactor, and 100 mL of toluene was further added and stirred. 50 mL of 10 wt% methylaluminoxane (MAO) / luene solution was added thereto, followed by slow reaction at 40 ° C. with stirring. After washing with a sufficient amount of toluene to remove the unreacted aluminum compound, and to remove the remaining toluene under reduced pressure. Again 100 mL of toluene was added, and 0.25 隱 of the metallocene catalyst prepared in Preparation Example 1 was dissolved in toluene and added together to react for 1 hour. After the reaction was completed, 0.25 隱 of the metallocene catalyst prepared in Preparation Example 2 was dissolved in toluene, and then reaction was added for 1 hour. After the reaction, stop the stirring and remove the After separation and removal, 1.0 mmol of aninium borate (Ν, dimethyl ani l inium tetraki s (pentaf luorophenyDborate, AB) was added thereto, stirred for 1 hour, and then reduced to 50t to remove toluene. Example 1 Ethylene / Alpha-olefin Copolymer
상기 제조예 3에서 제조한 담지 촉매 50 mg을 드라이 박스에서 정량하여 50 mL의 유리병에 각각 담은 후ᅳ고무 격막으로 밀봉하여 드라이 박스에서 꺼내어 주입할 촉매를 준비하였다. 중합은 기계식 교반기가 장착된 온도 조절이 가능하고 고압에서 이용되는 2L 금속 합금 반웅기에서 수행하였다. 상기 반응기에 1.0 mmol 트리에틸알루미늄 (tr i ethyl aluminum)이 들어 있는 핵산 1 L와 1—핵센 5 mL을 주입하고， 상기 준비한 담지 촉매를 반웅기에 공기 접촉 없이 투입한 후， 80°C에서 기체 에틸렌 단량체를 9 kgf/cm2의 압력으로 계속적으로 가하면서 1시간 동안 중합하였다. 중합의 종결은 먼저 교반을 멈춘 후 에틸렌을 배기시켜 제거함으로써 완료시켰다. 상기 얻어진 중합체에서 중합 용매를 여과시켜 대부분 제거한 후 80°C 진공 오븐에서 4시간 동안 건조시켰다. 실시예 2: 에틸렌 /알파-을레핀 공중합체 50 mg of the supported catalyst prepared in Preparation Example 3 was quantified in a dry box, and each was placed in a 50 mL glass bottle, sealed with a rubber diaphragm, and taken out of the dry box to prepare a catalyst to be injected. The polymerization was carried out in a 2 L metal alloy reaction vessel, which was equipped with a mechanical stirrer and temperature controlled and used at high pressure. Inject 1 L of nucleic acid containing 1.0 mmol triethyl aluminum and 5 mL of 1—nuxene into the reactor, add the prepared supported catalyst to the reactor without air contact, and then gas at 80 ° C. The ethylene monomer was polymerized for 1 hour with continuous addition of pressure at 9 kgf / cm 2 . Termination of the polymerization was completed by first stopping stirring and then evacuating and removing ethylene. Most of the polymerization solvent in the polymer obtained was filtered off and then dried in an 80 ° C. vacuum oven for 4 hours. Example 2: Ethylene / Alpha-Lepine Copolymer
1-핵센 투입량을 5 mL 보다 작게하는 것을 제외하고， 상기 실시예 1과 동일한 방법으로 에틸렌 /알파-을레핀 공중합체를 제조하였다. 비교예  An ethylene / alpha-lephine copolymer was prepared in the same manner as in Example 1, except that the amount of 1-nuxene was less than 5 mL. Comparative example
하기의 제품들을 비교예로 사용하였다.  The following products were used as comparative examples.
비교예 1： 2010J (롯데케미칼)  Comparative Example 1: 2010J (Lotte Chemical)
비교예 2 : LUTENE-H ME8000 (엘지화학)  Comparative Example 2: LUTENE-H ME8000 (LG Chem)
비교예 3： Rigidex® HD6070UA ( INE0S) 실험예: 중합체의 물성 평가 Comparative Example 3: Rigidex® HD6070UA (INE0S) Experimental Example: Evaluation of Physical Properties of Polymers
상기 실시예에서 제조한 중합체 및 "비교예의 중합체를 하기의 방법으로 물성을 평가하였다. 1) 밀도: ASTM 1505 A polymer, and "Physical properties in the following manner to the comparative example polymers prepared in Examples were evaluated: 1) density:. ASTM 1505
2) 용융지수 (MFR, 5 kg/2.16 kg): 측정 온도 190°C, ASTM D12382) Melt Index (MFR, 5 kg / 2.16 kg): Measured temperature 190 ° C, ASTM D1238
3) MFRR(MFR5/MFR2.i6): MFR5 용융지수 (MI, 5kg 하중)를 MFR2.16(MI, 2.16kg하중)으로 나눈 비율이다. 3) MFRR (MFR 5 / MFR 2 .i 6 ): MFR5 melt index (MI, 5kg load) is set to MFR 2 . The ratio is divided by 16 (MI, 2.16kg load).
4) Mn, Mw, 匿 D, GPC 커브: 샘플을 PL—SP260을 이용하여 BHT 0.0125% 포함된 1，2，4— Trichlorobenzene에서 160 °C， 10시간 동안 녹여 전처리하고，4) Mn, Mw, 匿 D, GPC curve: The sample is pretreated by dissolving at 160 ° C for 10 hours in 1,2,4—trichlorobenzene containing 0.0125% of BHT using PL—SP260.
PL-GPC220을 이용하여 측정 온도 160°C에서 수 평균분자량 중량 평균분자량을 측정하였다. 분자량 분포는 중량 평균분자량과 수 평균분자량의 비로 나타내었다. The PL-GPC220 was used to measure the number average molecular weight weight average molecular weight 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) 구정의 크기: 샘플의 표면을 현미경으로 관찰하였다. 구체적으로, 구정의 직경은 에틸렌 /알파-을레핀 공중합체를 190°C에서 완전히 용융시킨 후, KTC/분 속도로 결정화 온도까지 도달시킨 후 측정하며， 이때 구정의 직경은 구정이 성장함에 따라 각각의 구정이 겹쳐질 때의 크기로 하였다. 5) Size of Chinese New Year: The surface of the sample was observed under a microscope. Specifically, the diameter of the spherical well is measured after completely melting the ethylene / alpha-levine copolymer at 190 ° C. and reaching the crystallization temperature at a rate of KTC / min. It was set as the size when Chinese New Year overlaps.
6) 반결정화 시간 (half crystallization time, τ 1/2 at 123 °C): 시차 주사 열량계 (Differential Calorimeter Analysis; DSC)를 이용하여 측정하며， 에틸렌 /알파-올레핀 공중합체를 190°C에서 완전히 용융시킨 후, 결정화 온도 (123°C)까지 급넁 (80°C/분)하여 1시간 동안 유지한 후 나타나는 열량 피크의 절반일 때의 시간으로 하였다. 상기 결과를 하기 표 1에 나타내었다. 또한， 각 공중합체의 구정의 관찰 결과를 도 1 내지 3에 나타내었다. 6) half crystallization time (τ 1/2 at 123 ° C): measured using differential calorimeter analysis (DSC) and completely melting the ethylene / alpha-olefin copolymer at 190 ° C. After making it, the temperature was rapidly increased to the crystallization temperature (123 ° C.) (80 ° C./min.), And maintained for 1 hour. The results are shown in Table 1 below. In addition, the observation result of the spherical structure of each copolymer is shown to FIGS.
【표 1】  Table 1
Figure imgf000030_0001
LCB 존재 0 0 X X X
Figure imgf000030_0001
LCB Present 0 0 XXX
Spherul i te 크기 urn < 20 < 20 > 20 > 20 > 20 τ 1/2 at 123 °C min 2.5 4. 1 1.8 8.9 9.2 상기 표 1에 나타난 바와 같이， 본 발명에 따른 실시예의 구정의 크기는 20 im 미만인 반면， '비교예의 구정의 크기는 20 를 초과한 것으로 나타났다. 또한， 반결정화 속도의 경우에도 본 발명의 실시예와 유사한 분자량 및 분자량 분포를 가지는 비교예 3에 비하여 현저히 빠름을 확인할 수 있었다. Spherul i te size urn <20 <20>20>20> 20 τ 1/2 at 123 ° C min 2.5 4. 1 1.8 8.9 9.2 As shown in Table 1, the size of the Chinese New Year of the embodiment according to the present invention is 20 While less than im, the size of the Chinese New Year of the Comparative Example was found to exceed 20. In addition, even in the case of a semi-crystallization rate it was confirmed that significantly faster than Comparative Example 3 having a molecular weight and molecular weight distribution similar to the embodiment of the present invention.

Claims

【특허청구범위】 [Patent Claims]
【청구항 1】  [Claim 1]
중량 평균 분자량 (g/mol)이 50,000 내지 150 ,000이고,  The weight average molecular weight (g / mol) is 50,000 to 150,000,
분자량 분포 (Mw/Mn)가 3 내지 8이고，  Molecular weight distribution (Mw / Mn) is 3 to 8,
밀도 (g/cuf)가 0.940 내지 0.970이고,  Density (g / cuf) is from 0.940 to 0.970,
구정 (spherulite)의 직경이 20 zm 이하이고， 및  The diameter of the spherulite is 20 zm or less, and
123°C에서 반결정화 시간 (half crystallization time)이 6분 이하인， 에틸렌 /알파-올레핀 공중합체. 【청구항 2】 Ethylene / alpha-olefin copolymer having a half crystallization time of 6 minutes or less at 123 ° C. [Claim 2]
제 1항에 있어서，  The method of claim 1,
상기 에틸렌 /알파 올레핀 공중합체의 고분자 사슬들이 다발로 모여 라멜라를 형성하고, 상기 라멜라의 3차원 성장에 의해 상기 구정이 정의되는，  Wherein the polymer chains of the ethylene / alpha olefin copolymer gather in a bundle to form a lamellae, the well being defined by three-dimensional growth of the lamellae,
에틸렌 /알파 올레핀 공중합체.  Ethylene / Alpha Olefin Copolymer.
【청구항 3】 [Claim 3]
제 1항에 있어서，  The method of claim 1,
123°C에서 반결정화 시간 (half crystallization time)이 5분 이하인, 에틸렌 /알파 -올레핀 공중합체. Ethylene / alpha-olefin copolymer having a half crystallization time of 5 minutes or less at 123 ° C.
【청구항 4】 [Claim 4]
거 U항에 있어서，  In U,
MFRR2.i6(ASTM D1238에 의거하여 190°C， 2.16kg 하중에서 측정한 용융 유동 지수)이 0.5 내지 10인， MFRR 2 .i 6 (melt flow index measured at 190 ° C, 2.16 kg load according to ASTM D1238) of 0.5 to 10,
에틸렌 /알파-올레핀 공중합체.  Ethylene / alpha-olefin copolymers.
【청구항 5】 [Claim 5]
게 1항에 있어서,  According to claim 1,
MFRR5/2.i6(ASTM D1238에 의거하여 190°C， 5kg 하중에서 측정한 용융 유동 지수를 190 °C , MFRR 5 /2.i6 (melt measured at 190 ° C, 5 kg load in accordance with ASTM D1238) Flow index of 190 ° C,
2.16 kg 하중에서 측정한 용융 유동 지수로 나눈 값) o 3 내지 8인， Divided by the melt flow index measured at a 2.16 kg load) o 3 to 8,
에틸렌 /알파-올레핀 공증합체,  Ethylene / alpha-olefin copolymer,
【청구항 6】 [Claim 6]
제 1항에 있어서,  The method of claim 1,
상기 알파 -을레핀은， 프로필렌， 1-부텐， 1-펜텐, 4-메틸 -1-펜텐， 1- 핵센， 1-헵텐， 1ᅳ옥텐， 1-데센， 1-운데센， 1-도데센， 1-테트라데센, 1- 핵사데센 및 1-아이토센으로 구성되는 군으로부터 선택되는 어느 하나 이상인，  The alpha-olepin, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene, 1 octactene, 1-decene, 1-undecene, 1-dodecene Or 1 or more selected from the group consisting of 1-tetradecene, 1-nucledecene and 1-aitocene,
에틸렌 /알파-을레핀 공중합체.  Ethylene / Alpha-Lepine Copolymer.
【청구항 7】 [Claim 7]
거 U항에 있어서，  In U,
상기 에틸렌 /알파-을레핀 공증합체는 하기 화학식 1로 표시되는 거 U 메탈로센 화합물 1종 이상; 및 하기 화학식 3 내지 5로 표시되는 화합물 중에서 선택되는 제 2 메탈로센 화합물 1종 이상의 존재 하에， 에틸렌 및 알파-올레핀을 중합시킴으로써 제조되는，  The ethylene / alpha-lepine co-polymer is one or more of a metal U metallocene compound represented by the following Formula 1; And a second metallocene compound selected from compounds represented by the following Chemical Formulas 3 to 5, prepared by polymerizing ethylene and an alpha-olefin in the presence of at least one compound.
에틸렌 /알파-올레핀 공중합체:  Ethylene / Alpha-olefin Copolymer:
Figure imgf000033_0001
Figure imgf000033_0001
상기 화학식 1에서,  In Chemical Formula 1,
A는 수소， 할로겐, d-20 알킬， C2-20 알케닐, C6-20 아릴， C7-20 알킬아릴，. Cy-20 아릴알킬， d-20 알콕시， C2-20 알콕시알킬 , C 20 헤테로시클로알킬 , 또는 C5-20 헤테로아릴이고; A is hydrogen, halogen, d- 20 alkyl, C 2 - 20 alkenyl Al, C 6 - 20 aryl, C 7 - 20 alkylaryl,. Cy- 2 0 arylalkyl, d- 20 alkoxy, C 2 - 20 alkoxyalkyl, C 20 heterocycloalkyl, or C 5 - 20 membered heteroaryl;
D는 — ()- , -S- , -N(R)- 또는 -SKRXR 1 )-이고， 여기서 R 및 R 1은 서로 동일하거나 상이하고, 각각 독립적으로 수소， 할로겐, d-20 알킬， C2-20 알케닐， 또는 C6-20 아릴이고; L은 d-10 직쇄 또는 분지쇄 알킬렌이고; D is — () —, —S—, —N (R) — or —SKRXR 1 ) —, where R and R 1 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;
B는 탄소， 실리콘 또는 게르마늄이고;  B is carbon, silicon or germanium;
Q는 수소， 할로겐， d-20 알킬, C2-20 알케닐， C6-20 아릴, C교 20 알킬아릴 , 또는 C7-20 아릴알킬이고; Q is hydrogen, halogen, d- 20 alkyl, C 2 - 20 alkenyl, C 6 - 20 aryl, C T 20 alkylaryl, or C 7 - 20 aryl-alkyl;
M은 4족 전이금속이며;  M is a Group 4 transition metal;
X1 및 X2는 서로 동일하거나 상이하고， 각각 독립적으로 할로겐， 알킬， C2-20 알케닐， C6-20 아릴， 니트로, 아미도， d-20 알킬실릴, ( 20 알콕시 또는 Cwo 술폰네이트이고; Alkenyl of 20 Al, C 6 - - X 1 and X 2 are the same or different and each independently halogen, alkyl, C 2 to each other 20 aryl, nitro, amido, d-20 alkyl silyl group, (20 alkoxy or Cwo sulfone carbonate ego;
C1 및 C2는 서로 동일하거나 상이하고， 각각 독립적으로 하기 화학식 2a , 화학식 2b 또는 하기 화학식 2c 증 하나로 표시되고， 단， C1 및 C2가 모두 화학식 2c인 경우는 제외하며 ; 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;
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000034_0001
Figure imgf000035_0001
상기 화학식 2a , 2b 및 2c에서， 내지 R17 및 내지 '는 서로 동일하거나 상이하고, 각각 독립적으로ᅵ 수소， 할로겐， d-20 알킬, C2-20 알케닐， 알킬실릴， d-20 실릴알킬, d-20 알콕시실릴， d-20 알콕시， C6-20 아릴， C7-20 알킬아릴 또는 C7-20 아릴알킬이며, 상기 0 내지 R17 중 서로 인접하는 2개 이상이 서로 연결되어 치환 또는 비치환된 지방족 또는 방향족 고리를 형성할 수 있고; In the general formula 2a, 2b and 2c, to R 17, and to "are the same or different and each is independently i hydrogen, halogen, d-20 alkyl, C 2 of each other - 20 alkenyl, alkylsilyl, d-20 silyl alkyl , d-20 alkoxysilyl, d-20 alkoxy, C 6 - 20 aryl, C 7 - 20 alkylaryl or C 7 - 20 aryl-alkyl, substituted are the 0 to R 17 of the two or more adjacent to each other are connected to each other Or may form an unsubstituted aliphatic or aromatic ring;
[화학식 3] ·
Figure imgf000035_0002
[Formula 3] ·
Figure imgf000035_0002
상기 화학식 3에서， ·  In Chemical Formula 3,
M1은 4족 전이금속이고; M 1 is a Group 4 transition metal;
Cp1 및 Cp2는 서로 동일하거나 상이하고， 각각 독립적으로 시클로펜타디엔닐， 인데닐, 4 , 5, 6， 7-테트라하이드로 -1-인데닐 및 플루오레닐 라디칼로 이루어진 군으로부터 선택된 어느 하나이고， 이들은 탄소수 1 내지 20의 탄화수소로 치환될 수 있으며; 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 They may be substituted with a hydrocarbon having 1 to 20 carbon atoms;
RA 및 RB는 서로 동일하거나 상이하고， 각각 독립적으로 수소， CHO 알킬, 에 알콕시 , C2-20 알콕시알킬, C6-20 아릴， C6-10 아릴옥시， C2-20 알케닐, C7-40 알킬아릴， C7-40 아릴알킬, C8-40 아릴알케닐， 또는 C2—10 알키닐이고; R A and R B are the same or different and each is independently hydrogen, CHO-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;
Z1은 할로겐 원자， d-20 알킬, C2-10 알케닐， C7— 40 알킬아릴， C7-40 아릴알킬， ( 20 아릴， 치환되거나 치환되지 않은 d-20 알킬리덴， 치환되거나 치환되지 않은 아미노， C2ᅭ 20 알킬알콕시， 또는 C7-40 아릴알콕시이고; Z 1 is a halogen atom, d-20 alkyl, C 2 - 10 alkenyl, C 7 - 40 alkylaryl, C 7 - 40 arylalkyl, (20 aryl, substituted or unsubstituted d-20 alkylidene, optionally substituted that is not amino, C 2 yo 20 alkyl alkoxy, or C 7 - 40 aryl-alkoxy;
n은 1 또는 0이고;  n is 1 or 0;
[화학식 4]
Figure imgf000036_0001
[Formula 4]
Figure imgf000036_0001
상기 화학식 4에서，  In Chemical Formula 4,
M2는 4족 전이 금속이고; M 2 is a Group 4 transition metal;
Cp3 및 Cp4는 서로 동일하거나 상이하고， 각각 독립적으로 5 시클로펜타디에닐， 인데닐， 4， 5， 6， 7-테트라하이드로 -1-인데닐 및 플루오레닐 라디칼로 이루어진 군으로부터 선택된 어느 하나이고, 이들은 탄소수 1 내지 20의 탄화수소로 차환될 수 있으며 ; Cp 3 and Cp 4 are the same as or different from each other, and are each independently selected from the group consisting of 5 cyclopentadienyl, indenyl, 4, 5, 6, 7-tetrahydro-1-indenyl and fluorenyl radicals; One, they may be substituted with hydrocarbons having 1 to 20 carbon atoms;
Rc 및 Rd는 서로 동일하거나 상이하고， 각각 독립적으로 수소, 알킬， 알콕시， C2-20 알콕시알킬， C6-20 아릴， C6-10 아릴옥시， C2-200 알케닐， C7-40 알킬아릴， C7-40 아릴알킬， Cs-40 아릴알케닐， 또는 C2-10 알키닐이고; R c and R d are the same or different, each independently represent hydrogen, alkyl, alkoxy, and C 2 of each other - 20 alkoxyalkyl, C 6 - 20 aryl, C 6 - 10 aryloxy, C 2 - 20 0 alkenyl, C 7-40 alkylaryl, C 7-40 aryl, Cs-40 aryl-alkenyl, or C 2 - 10 alkynyl;
Z2는 할로겐 원자， d-20 알킬， C2-10 알케닐， C7—40 알킬아릴， C7-40 아릴알킬 , C6-20 아릴， 치환되거나 치환되지 않은 d-20 알킬리덴， 치환되거나Z 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
' 치환되지 않은 아미노， C2-20 알킬알콕시， 또는 C7-40 아릴알콕시이고; "Unsubstituted amino, C 2 - 20 alkyl, an alkoxy, or a C 7 - 40 aryl-alkoxy;
5 B1은 Cp¾c 고리와 Cp4Rd 고리를 가교 결합시키거나， 하나의 Cp4Rd 고리를 M2에 가교 결합시키는， 탄소， 게르마늄， 규소， 인 또는 질소 원자 . 함유 라디칼 중 하나 이상 또는 이들의 조합이고; 5 B 1 is a carbon, germanium, silicon, phosphorus or nitrogen atom which crosslinks the Cp¾ c ring with the Cp 4 R d ring or crosslinks one Cp 4 R d ring with M 2 . At least one of the containing radicals or a combination thereof;
m은 1 또는 0이고;  m is 1 or 0;
[화학식 5] .  [Formula 5].
(Cp5Re)B2(J )M3Z3 2 (Cp 5 R e ) B 2 (J) M 3 Z 3 2
상기 화학식 5에서，  In Chemical Formula 5,
M3은 4족 전이 금속이고; M 3 is a Group 4 transition metal;
Cp5는 시클로펜타디에닐， 인데닐， 4，5，6，7-테트라하이드로 -1-인데닐 및 플루오레닐 라디칼로 이루어진 군으로부터 선택된 어느 하나이고，5 이들은 탄소수 1 내지 20의 탄화수소로 치환될 수 있으며; Cp 5 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals, 5 which are substituted with hydrocarbons having 1 to 20 carbon atoms Can be;
• Re는 수소， d-20 알킬， d-10 알콕시， C2-20 알콕시알킬 , C6-20 아릴， C6 • R e is hydrogen, d- 20 alkyl, d- 10 alkoxy, C 2 - 20 alkoxyalkyl, C 6 - 20 aryl, C 6
10 아릴옥시， C2—20 알케닐， C7-40 알킬아릴， C7-40 아릴알킬， C8-40 아릴알케닐, 또는 C2-10 알키닐이고; 10 aryloxy, C 2 - 20 alkenyl, C 7 - 40 alkylaryl, C 7 - 40 arylalkyl, C 8 - 40 arylalkenyl, or C 2 - 10 alkynyl;
Z3은 할로겐 원자， 알킬， C2-10 알케닐， C7-40 알킬아릴， C7-40 아릴알킬， C6 20 아릴， 치환되거나 치환되지 않은 d—20 알킬리덴， 치환되거나 치환되지 않은 아미노， C2-20 알킬알콕시 , 또는 C7-40 아릴알콕시이고; 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 d-20 alkylidene, substituted or Unsubstituted amino, C 2 - 20 alkyl, an alkoxy, or a C 7 - 40 aryl-alkoxy;
B2는 Cp¾e 고리와 J를 가교 결합시키는 탄소, 게르마늄， 규소， 인 또는 질소 원자 함유 라디칼중 하나 이상 또는 이들의 조합이고; 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;
J는 NRf , 0 , PRf 및 S로 이루어진 군에서 선택된 어느 하나이고， 상기 Rf는 Cno 알킬， 아릴， 치환된 알킬 또는 치환된 아릴이다. J is any one selected from the group consisting of NR f , 0, PR f and S, wherein R f is Cno alkyl, aryl, substituted alkyl or substituted aryl.
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US20110217499A1 (en) * 2008-08-29 2011-09-08 Basell Polyolefine Gmbh Polyethylene for Injection Moldings
KR20130113322A (en) * 2010-07-06 2013-10-15 셰브론 필립스 케미컬 컴퍼니 엘피 Catalysts for producing broad molecular weight distribution polyolefins in the absence of added hydrogen
US20140213734A1 (en) * 2013-01-30 2014-07-31 Exxonmobil Chemical Patents Inc. Polyethylene Copolymers with Vinyl Terminated Macromonomers as Comonomers
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