WO2016167568A1 - Copolymère éthylène/alpha-oléfine ayant une excellente aptitude au traitement - Google Patents

Copolymère éthylène/alpha-oléfine ayant une excellente aptitude au traitement Download PDF

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WO2016167568A1
WO2016167568A1 PCT/KR2016/003890 KR2016003890W WO2016167568A1 WO 2016167568 A1 WO2016167568 A1 WO 2016167568A1 KR 2016003890 W KR2016003890 W KR 2016003890W WO 2016167568 A1 WO2016167568 A1 WO 2016167568A1
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alkyl
aryl
ethylene
alpha
alkoxy
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PCT/KR2016/003890
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Korean (ko)
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선순호
승유택
조솔
권혁주
최이영
이기수
김우리
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주식회사 엘지화학
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Publication of WO2016167568A1 publication Critical patent/WO2016167568A1/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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene

Definitions

  • Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed for their respective characteristics.
  • 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 single active site, the homogeneous composition distribution 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.
  • Korean Patent Application No. 10-2003-0012308 discloses a method for controlling the molecular weight distribution by supporting a double-nucleated metallocene catalyst and a mononuclear metallocene catalyst on a carrier together with an activator to polymerize by changing the combination of catalysts in the reaction system. Disclosing the plan.
  • linear low density polyethylene is produced by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst, has a narrow molecular weight distribution and a short chain branch of a constant length ,. It is a resin without long chain branching.
  • the linear low density polyethylene film has the characteristics of general polyethylene, and has high breaking strength and elongation, and excellent tearing strength and fall stratification strength, so that the use of stretch film or overlap film, which is difficult to apply to the existing low density polyethylene or high density polyethylene, increases. Doing.
  • linear low density polyethylene using 1-butene or 1-nuxene as comonomers and sieves is mostly produced in a single vapor phase reactor or a single loop slurry semi-unger, and the productivity is high compared to a process using 1-octene comonomers. Due to the limitations of the catalyst technology and the process technology, the product is inferior to that of the 1-octene comonomer, and the molecular weight distribution is narrow.
  • U.S. Pat.No. 4,935,474 reports a method for producing polyethylene having a wide molecular weight distribution using two or more metallocene compounds.
  • U. S. Patent No. 6,828, 394 reports a method for producing polyethylene which is a good combination of good comonomer binding and not good comonomerability and is particularly suitable for films.
  • US Patent Registration No. 6,841,631, US Patent Registration No. 6,894, 128 to prepare a polyethylene having a bimodal or polycrystalline molecular weight distribution with a metallocene-based catalyst using at least two metal compounds, It is reported that it is applicable to the use of film, blow molding, pipe and the like.
  • the present invention is to provide an ethylene / alpha -olefin copolymer excellent in processability.
  • the present invention provides an ethylene / alpha-olefin copolymers satisfying the following conditions:
  • the weight average molecular weight (g / mol) is 50,000 to 150,000
  • Density (g / cin 3 ) is from 0.950 to 0.965
  • Ethylene / alpha-lephine copolymers according to the present invention have an advantage in injection molding.
  • Ethylene / alpha-olefin copolymer according to the present invention It is made of a metallocene catalyst as will be described later, in general, the polymer produced by the metallocene catalyst is excellent in mechanical properties, but there is a limit in manufacturing a product by injection molding is poor workability.
  • the present invention by using a metallocene catalyst as described below, by narrowing the middle molecular region in the molecular weight distribution, and by producing an ethylene / alpha -olefin copolymer having a high proportion of the polymer region, excellent mechanical properties and Together, there is a feature of improving workability.
  • the weight average molecular weight is 85, 000 to 100, 000 g / nl.
  • the molecular weight distribution is 4 to 10.
  • the ethylene / alpha-olefin copolymer according to the present invention is MFRR 5/2 . 16 (melt flow index measured at 190 ° C, 5kg load divided by 190 ° C, 2.
  • melt flow index measured at 16kg load) according to ASTM D1238 has a value of 2 to 10, preferably Is »3 ⁇ 43 ⁇ 4 / 2 . 16 is 3.5 to 5.
  • the ethylene / alpha-olepin copolymer according to the present invention has an Izod lattice strength of 7 to 15 kg-cm / cm.
  • the Izod layer strength may be measured according to ASTM D-256, and the Izod impact strength of the ethylene / alpha-olefin copolymer according to the present invention is 7 to 15 kg-cm / cm, preferably 7 to 13 kg-. Excellent mechanical properties in cm / cm.
  • the spiral flow length indicates the processability of the ethylene / alpha-olefin copolymer according to the present invention, and the larger the value, the better the processability.
  • the spiral flow length is applied to a spiral mold by applying a specific pressure and temperature to inject the polymer and accordingly melted and injected This can be assessed by measuring how far the polymer is pushed out.
  • a mold having a thickness of 1.5 kPa may be used, and an injection temperature of 190 ° C., a mold temperature of 50 ° C, and an injection pressure may be set to 90 bar.
  • the spiral flow length of the ethylene / alpha-olefin copolymer according to the invention is 25 to 40 cm, which shows excellent processability.
  • the ethylene / alpha -olefin copolymer according to the present invention in addition to the mechanical properties and workability as described above is characterized by excellent environmental stress cracking resistance (ESCR) and flexural modulus (flexural modulus).
  • alpha-olefin monomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene and 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 alpha-ullepin as the comonomer 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-olefinic copolymer as described above can be prepared using a metallocene catalyst.
  • the metallocene catalyst that can be used includes one or more metallocene compounds represented by the following Chemical Formula 1; And at least one compound selected from the compounds represented by the following Chemical Formulas 3 to 5 may be two metallocene compounds.
  • A is hydrogen, halogen, d- 20 alkyl, C 2 - 20 alkenyl, C 6 - 20 aryl, C 7 - 20 alkylaryl, C 7 - 20 arylalkyl, alkoxy, C 2 - 20 alkoxyalkyl, C 3 - 20 heterocycloalkyl, or C 5 - 20 membered heteroaryl;
  • D is -0-, -S-, -NCR)-or -SKR R ')-, wherein R and R' are the same as or different from each other, and are each independently hydrogen, halogen, d-20 alkyl, C 2- 20 alkenyl, or C 6 - 20 aryl;
  • L is d- 10 straight or branched chain alkylene
  • B is carbon, silicon or germanium
  • Q is hydrogen, halogen, d- 20 alkyl, C 2 - 20 alkenyl, C 6 - 20 aryl, C 7 -2o alkyl, aryl, or C 7 - 20 aryl-alkyl;
  • M is a Group 4 transition metal
  • 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, d-20-alkoxy, or sulfone carbonate ego;
  • C 1 and C 2 are the same as or different from each other, and are each independently represented by one of the following Chemical Formula 2a, Chemical Formula 2b, or Chemical Formula 2c, except that both C 1 and C 2 are Chemical Formula 2c;
  • R 17 and "to" are the same or different and are each independently hydrogen, halogen, alkyl, C 2 - 20 alkenyl, d- 20 alkylsilyl, alkyl silyl, (20 alkoxysilyl, C ⁇ o alkoxy, C 6 - 20 aryl, C 7 - 20 alkylaryl, or C 7 - 20 aryl-alkyl, wherein R 10 to R 17 of the two or more adjacent to each other are connected to each other substituted or unsubstituted To form a ringed 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, 7-tetrahydro-1-indenyl, and fluorenyl radicals One, they may be substituted with a hydrocarbon of 1 to 20 carbon atoms;
  • R 3 and R b are the same or different from each other, each independently hydrogen, d-20-alkyl, d-10 alkoxy, C 2 - 20 alkoxyalkyl, C 6 - 20 aryl, C 6 - 10 aryloxy, C 2 Al alkenyl, C 7 - 40 alkylaryl, C 7 - 40 arylalkyl, C 8 - 40 arylalkenyl, or C 2 - 10 alkynyl;
  • Z 1 is a halogen atom, d- 20 alkyl, C 2 - 10 alkenyl, C 7 - 40 alkylaryl, C 7 - 40 arylalkyl, C 20 aryl, substituted or unsubstituted d-20 alkylidene, optionally substituted that is not amino, 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 each independently selected from the group consisting of cyclopentadienyl, indenyl, 4, 5, 6,7-tetrahydro-1-indenyl and fluorenyl radicals One, they may be substituted with a hydrocarbon having 1 to 20 carbon atoms;
  • R c and R d are the same or different and each is independently hydrogen, alkyl, C -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 c 20 nyolkil alkylidene, substituted or unsubstituted amino, C 2 - 20 alkyl, an alkoxy, or a C 7 - 40 aryl-alkoxy;
  • B 1 is one or more of a carbon, germanium, silicon, phosphorus or nitrogen atom containing radical which crosslinks the Cp 3 R c ring with the Cp 4 R d ring or crosslinks one Cp 4 R d ring with M 2 Or a combination thereof;
  • 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 be;
  • R e is hydrogen, d- 20 alkyl, C - 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, C 2 -io or alkynyl;
  • Z 3 is a halogen atom, alkyl, C 2 - 10 alkenyl, C 7 - 40 alkylaryl, C 7 - 40 arylalkyl, C 6 20 aryl, substituted or unsubstituted (20 alkylidene, optionally substituted amino , C 2 - 20 alkyl, an alkoxy, or a C 7 - 40 aryl-alkoxy;
  • B 2 is carbon, germanium, silicon, phosphorus which crosslinks the Cp3 ⁇ 4 e ring and J. Or one or more or a combination of nitrogen atom containing radicals;
  • the CO alkyl may include linear or branched alkyl, and specifically methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, phenyl, nucleus, heptyl, octyl, etc. It is not limited.
  • the C 2 - to 20 alkenyl including alkenylene of straight or branched chain and, specifically allyl, ethenyl, propenyl, butenyl, pentenyl, and the like, but a pen, but is not limited thereto only.
  • the C 6 - 20 aryl includes a monocyclic or condensed polycyclic aryl, specifically phenyl, biphenyl, naphthyl, but are phenanthrenyl, fluorenyl deungol, but is not limited thereto.
  • the C 5 - 20 heteroaryl group include a monocyclic or condensed ring includes heteroaryl, carbazolyl, pyridyl, quinoline, isoquinoline, thiophenyl, furanyl, imidazole, oxazolyl, thiazolyl, triazine, tetrahydro Hydropyranyl, tetrahydrofuranyl, and the like, but is not limited thereto.
  • Examples of the alkoxy include, but are not limited to, methoxy, echoxy, phenyloxy, cyclonuclear oxy, and the like.
  • 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 'to R 9 ' are each independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, nucleus, heptyl, octyl, phenyl, Halogen, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, mesooxy, or ethoxy are more preferred, but not always limited thereto.
  • L of the general formula (1) is C 4 - 8 straight or branched chain alkylene of one to more preferred, but is not limited thereto only. Further, the alkylene group alkyl, C 2 - 20 alkenyl, or C 6 - can be unsubstituted or substituted with 20 aryl.
  • a in Formula 1 is hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, methoxymethyl, tert-subspecific methyl, 1-ethoxyethyl, 1-methyl- 1-special It is preferably, but not limited to, ethyl ethyl, tetrahydropyranyl, or tetrahydrofuranyl.
  • B of Formula 1 is preferably silicon, but is not limited thereto.
  • the first metallocene compound of Chemical Formula 1 forms a structure in which an indeno indole derivative and / or a fluorene (f luorene) derivative is crosslinked by a bridge, and is non-covalent to act as a Lewis base on the ligand structure. By having an electron pair, it is supported on the surface which has the Lewis acid characteristic of a support, and shows high polymerization activity even when it carries.
  • 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, thereby inhibiting the beta-hydrogen eliminat ion, thereby increasing the ultra-high molecular weight olefin polymer.
  • specific examples of the compound represented by Chemical Formula 2a may include a compound represented by one of the following structural formulas, but the present invention
  • specific examples of the compound represented by Formula 2c may include a compound represented by one of the following structural formulas,
  • specific examples of the first metallocene compound represented by Chemical Formula 1 may include a compound represented by one of the following structural formulas, but is not limited thereto.
  • the first metallocene compound of Chemical Formula 1 has excellent activity and may polymerize a high molecular weight ethylene / alpha-lepin copolymer. In particular, it shows high polymerization activity even when used on a carrier, and ultra high molecular weight ethylene / alpha- Olefin copolymers can be prepared. In addition, even when the polymerization reaction is performed including hydrogen to prepare an ethylene / alpha-olefin copolymer having a high molecular weight and a wide molecular weight distribution, the first metallocene compound of Formula 1 according to the present invention has a low hydrogen It exhibits reaction properties and still allows high polymerization of ultra high molecular weight ethylene / alpha-olefin copolymers.
  • an ethylene / alpha-olefin copolymer which satisfies high molecular weight properties without deterioration of activity even when used in combination with a catalyst having other characteristics can be prepared, and the polymer includes an ethylene / alpha-lephine copolymer. While the ethylene / alpha-olefin copolymer having a broad molecular weight distribution can be easily produced.
  • 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 carry out metal lat ion. Can be obtained.
  • the manufacturing method of the said crab 1 metallocene compound is demonstrated concretely in the Example mentioned later.
  • the compound represented by Formula 5 may be, for example, a compound represented by the following structural formula, but is not limited thereto.
  • the metallocene catalyst used in the present invention may be at least one of the first metallocene compounds represented by Formula 1, and at least 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 catalyst may induce the production of long chain branches (LCBs) in the ethylene / alpha-lephine copolymers produced.
  • the cocatalyst supported on the carrier for activating the metallocene compound is an organometallic compound containing a Group 13 metal, and polymerizes olefinol under a general metallocene catalyst. If it can be used when it is not particularly limited.
  • 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.
  • each R 18 is 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 boron in +3 oxidation state
  • G is independently 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 molecular weight distribution of the finally produced polyolefin can be made more uniform, and the polymerization activity can be improved.
  • the first cocatalyst of Chemical Formula 6 may be an alkylaluminoxane compound having a repeating unit bonded in a linear, circular, or reticular form.
  • Specific examples of the first cocatalyst include methylaluminoxane (MA0) and ethylalumina. Noxyl acid, isobutyl aluminoxane or butyl aluminoxane.
  • the Crab 2 cocatalyst of the formula (7) is trisubstituted ammonium salt, or Dialkyl ammonium salts, trisubstituted phosphonium salts.
  • a second cocatalyst include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate , Methyltetracyclooctadecylammonium tetraphenylborate , ⁇ , ⁇ -dimethylaninium tetraphenylborate, ⁇ , ⁇ -diethylaninynium tetraphenylborate, ⁇ , ⁇ -dimethyl (2
  • the mass ratio of the total transition metal to the carrier contained in the first 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, the optimum shape can be exhibited.
  • the mass ratio of the promoter compound to the carrier is 1 : May be from 1 to 1,000.
  • a carrier containing a hydroxy group on the surface may be used, and preferably, a semi-ungsung hydroxyl group and a siloxane group are dried to remove moisture on the surface.
  • the carrier which has is used for example, silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, and these are 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. If the dry silver of the carrier is less than 200 ° C, the water content is too much and the cocatalyst reacts, and if it exceeds 800 ° C, the surface area decreases as the pores on the surface of the carrier are combined, and the surface is hydroxy. It is not preferable because there is a lot of groups and only siloxane groups are left to decrease the reaction space with the promoter.
  • the amount of hydroxyl groups on the surface of the carrier is preferably from 0.1 to 10 kPa / 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 silver, 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, and if the amount of the hydroxy group is more than 10 ⁇ ol / g, it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle. Because it is not desirable.
  • the ethylene / alpha-olefin copolymer according to the present invention can be produced by polymerizing ethylene and alpha-lepin 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 reactor, a loop slurry reactor, 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 15 CTC.
  • the polymerization pressure may be about 1 to about 100 Kgf / cin 2 , preferably about 1 to about 50 Kgf / cin 2 , 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, air, or the like acting as a catalyst poison by treating a small amount of alkyl aluminum, and may be carried out by further using a promoter.
  • Ethylene / alpha-lephine copolymer according to the present invention is a combination of the catalyst of the formula (3) to 5 mainly to polymerize the low molecular weight polymer chain, and the catalyst of the formula (1) to mainly polymerize the high molecular weight chain, ethylene and Prepared by copolymerizing alpha-olefin monomers. Due to the interaction of two or more catalysts, a polymer having a broad molecular weight distribution as a whole and having a higher content of the polymer chains in the high molecular weight region can be obtained.
  • the ethylene / alpha-olefin copolymer according to the present invention has excellent mechanical properties and processability, and can be usefully applied to manufacture a product by injection molding.
  • the solution was changed to violet color at room temperature overnight.
  • the reaction solution was filtered to remove LiCl.
  • the toluene of the filtrate was removed by vacuum drying, and the nucleic acid was added and sonicated for 1 hour.
  • the slurry was filtered to obtain 6 g of a dark violet metallocene compound (Mw 758.02, 7.92 ⁇ ol, yield 66 mol%). Two isomers were observed on 1 H-NMR.
  • T-Butyl-0- (CH 2 ) 6 -Cl was prepared by the method shown in Tetrahedron Lett. 2951 (1988) using 6-chlorohexanol. NaCp was reacted to give t-Butyl-0- (CH 2 ) 6 -C 5 3 ⁇ 4 (yield 60%, bp 80 ° CI 0.1 mmHg).
  • t-Butyl-0- (CH 2 ) 6 -C 5 H 5 was dissolved in THF at -78 ° C, and normal butyllithium (n-BuLi) was added slowly, and then the temperature was raised to room temperature. I was. The solution was again mixed with a lithium salt solution pre-synthesized in a suspension solution of ZrCl 4 (THF) 2 (1.70 g, 4.50 ⁇ l) / THF (30 mL) at -78 ° C. Slowly added and reacted further for 6 hours at room temperature.
  • THF ZrCl 4
  • each of the supported catalysts prepared in Examples and Comparative Examples 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 for injection.
  • 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.
  • 1 L of nucleic acid containing 1.0 ⁇ ol triethylaluminum and 5 mL of 1—butene were injected, and each supported catalyst prepared above was introduced into the reactor without air contact, followed by 80 ° C.
  • MFR 5 melt index (MI, 5kg load) is set to MFR 2 . This is the ratio divided by 16 (MI, 2.16kg load).
  • the number average molecular weight and the weight average molecular weight were measured at a measurement temperature of 160 ° C.
  • the molecular weight distribution was expressed as the ratio of weight average molecular weight and number average molecular weight.
  • the embodiment has a narrower molecular weight distribution than the comparative example, which is a factor to further improve the Izod impact strength.
  • the example has a higher ratio than the comparative example. It was confirmed that this is a factor to further improve the Izod impact strength and ESCR.
  • a long chain branch (LCB) in the polymer region of the second region to enable a high spiral f low length, as can be seen in Table 1, to improve the workability with excellent mechanical properties compared to the comparative example Can be.

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Abstract

La présente invention concerne un copolymère éthylène/alpha-oléfine. Le copolymère éthylène/alpha-oléfine selon la présente invention offre d'excellentes propriétés mécaniques et une excellente aptitude au traitement, et peut donc être appliqué de manière intéressante à la fabrication de produits par moulage par injection.
PCT/KR2016/003890 2015-04-15 2016-04-14 Copolymère éthylène/alpha-oléfine ayant une excellente aptitude au traitement WO2016167568A1 (fr)

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US20200048381A1 (en) * 2016-11-15 2020-02-13 Lg Chem, Ltd. Ethylene/Alpha-Olefin Copolymer Having Excellent Environmental Stress Crack Resistance

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KR101856727B1 (ko) 2016-06-21 2018-05-10 주식회사 엘지화학 액정 배향제 조성물, 이를 이용한 액정 배향막의 제조 방법, 및 이를 이용한 액정 배향막
KR102228534B1 (ko) * 2016-10-27 2021-03-15 주식회사 엘지화학 내환경 응력 균열성이 우수한 에틸렌/알파-올레핀 공중합체
KR102039073B1 (ko) 2016-11-15 2019-10-31 주식회사 엘지화학 충격 강도가 우수한 폴리에틸렌 수지
KR102090812B1 (ko) * 2016-11-15 2020-03-18 주식회사 엘지화학 가공성이 우수한 에틸렌/알파-올레핀 공중합체
KR102180532B1 (ko) * 2016-11-28 2020-11-18 주식회사 엘지화학 내환경 응력 균열성이 우수한 폴리올레핀의 제조 방법
KR102072697B1 (ko) * 2016-12-09 2020-02-03 주식회사 엘지화학 가공성 및 기계적 물성이 우수한 에틸렌/1-헥센 공중합체
KR102215630B1 (ko) * 2016-12-13 2021-02-10 주식회사 엘지화학 혼성 담지 메탈로센 촉매
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