WO2016167548A1 - Copolymère éthylène/alpha-oléfine ayant une aptitude au traitement et des caractéristiques de surface excellentes - Google Patents

Copolymère éthylène/alpha-oléfine ayant une aptitude au traitement et des caractéristiques de surface excellentes Download PDF

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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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alkyl
aryl
ethylene
alpha
alkenyl
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PCT/KR2016/003848
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English (en)
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/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2017533912A priority Critical patent/JP6788590B2/ja
Priority to CN201680007527.4A priority patent/CN107207661B/zh
Priority to EP16780271.9A priority patent/EP3225638B1/fr
Priority to US15/549,103 priority patent/US10266626B2/en
Publication of WO2016167548A1 publication Critical patent/WO2016167548A1/fr

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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

La présente invention concerne un copolymère éthylène/alpha-oléfine. Le copolymère éthylène/alpha-oléfine selon la présente invention a une aptitude au traitement et des caractéristiques de surface excellentes, et peut donc être appliquée avantageusement à la fabrication de divers produits.
PCT/KR2016/003848 2015-04-13 2016-04-12 Copolymère éthylène/alpha-oléfine ayant une aptitude au traitement et des caractéristiques de surface excellentes WO2016167548A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2017533912A JP6788590B2 (ja) 2015-04-13 2016-04-12 加工性および表面特性に優れたエチレン／アルファ−オレフィン共重合体
CN201680007527.4A CN107207661B (zh) 2015-04-13 2016-04-12 具有优异的加工性能和表面特性的乙烯/α-烯烃共聚物
EP16780271.9A EP3225638B1 (fr) 2015-04-13 2016-04-12 Copolymère éthylène/alpha-oléfine ayant une aptitude au traitement et des caractéristiques de surface excellentes
US15/549,103 US10266626B2 (en) 2015-04-13 2016-04-12 Ethylene/alpha-olefin copolymer having excellent processability and surface characteristics

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KR10-2015-0051831 2015-04-13
KR20150051831 2015-04-13
KR1020160038476A KR101831418B1 (ko) 2015-04-13 2016-03-30 가공성 및 표면 특성이 우수한 에틸렌/알파-올레핀 공중합체
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Citations (4)

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US20110217499A1 (en) * 2008-08-29 2011-09-08 Basell Polyolefine Gmbh Polyethylene for Injection Moldings
KR20130113322A (ko) * 2010-07-06 2013-10-15 셰브론 필립스 케미컬 컴퍼니 엘피 수소 첨가없이 넓은 분자량 분포의 폴리올레핀 제조를 위한 촉매
US20140213734A1 (en) * 2013-01-30 2014-07-31 Exxonmobil Chemical Patents Inc. Polyethylene Copolymers with Vinyl Terminated Macromonomers as Comonomers
KR20150037520A (ko) * 2013-09-30 2015-04-08 주식회사 엘지화학 폴리올레핀의 제조 방법 및 이로부터 제조된 폴리올레핀

Patent Citations (4)

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US20110217499A1 (en) * 2008-08-29 2011-09-08 Basell Polyolefine Gmbh Polyethylene for Injection Moldings
KR20130113322A (ko) * 2010-07-06 2013-10-15 셰브론 필립스 케미컬 컴퍼니 엘피 수소 첨가없이 넓은 분자량 분포의 폴리올레핀 제조를 위한 촉매
US20140213734A1 (en) * 2013-01-30 2014-07-31 Exxonmobil Chemical Patents Inc. Polyethylene Copolymers with Vinyl Terminated Macromonomers as Comonomers
KR20150037520A (ko) * 2013-09-30 2015-04-08 주식회사 엘지화학 폴리올레핀의 제조 방법 및 이로부터 제조된 폴리올레핀

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