WO2016093580A1 - 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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WO2016093580A1
WO2016093580A1 PCT/KR2015/013328 KR2015013328W WO2016093580A1 WO 2016093580 A1 WO2016093580 A1 WO 2016093580A1 KR 2015013328 W KR2015013328 W KR 2015013328W WO 2016093580 A1 WO2016093580 A1 WO 2016093580A1
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Prior art keywords
alkyl
aryl
alpha
ethylene
alkenyl
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PCT/KR2015/013328
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English (en)
Korean (ko)
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김중수
선순호
권오주
최이영
이기수
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주식회사 엘지화학
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Priority claimed from KR1020150161159A external-priority patent/KR101747401B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2016547588A priority Critical patent/JP6482564B2/ja
Priority to CN201580005067.7A priority patent/CN105916896B/zh
Priority to RU2016132145A priority patent/RU2671499C1/ru
Priority to US15/106,708 priority patent/US10155830B2/en
Priority to EP15866382.3A priority patent/EP3070108A4/fr
Publication of WO2016093580A1 publication Critical patent/WO2016093580A1/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
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • 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
    • 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

Definitions

  • the present invention relates to an ethylene / alpha-olepin copolymer having excellent processability.
  • the olefin polymerization catalyst system may, be divided into Ziegler-Natta and metallocene catalyst systems, the high activity catalyst systems of these two has been developed according to its characteristics.
  • Ziegler-Natta catalysts have been widely applied to existing commercial processes since the invention in the 50s, but are characterized by a wide molecular weight distribution of polymers because they are multi-active catalysts with multiple active sites. Since the composition distribution of the comonomer is not uniform, there is a problem that there is a limit in securing the 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 organometallic compounds composed mainly of aluminum.
  • Such a catalyst is a homogeneous complex catalyst, which is a single active site catalyst (s ingle si). te catalyst), single .
  • the polymer has a narrow molecular weight distribution and a homogeneous composition distribution of the comonomer according to the active site characteristics, and the stereoregularity, copolymerization characteristics, molecular weight, crystallinity, etc. of the polymer can be obtained by changing the ligand structure of the catalyst and changing the polymerization conditions. It has the property to change.
  • 5,914,289 describes a method for controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount and time of solvent used in preparing the supported catalyst This takes a lot, The hassle of having to support each of the metallocene catalysts to be used on a carrier was followed.
  • Korean Patent Application No. 10-2003-0012308 discloses a method of controlling molecular weight distribution by supporting a double-nucleated metallocene catalyst and a mononuclear metallocene catalyst on a carrier together with an activator to polymerize by changing the combination of catalysts in the reactor. Is starting.
  • 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.
  • 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 is mostly produced in a single gas phase reactor or a single loop slurry reactor, and is more productive than a process using 1-octene comonomers.
  • 6,894,128 produce polyethylene having bimodal or polycrystalline molecular weight distribution with a metallocene catalyst using at least two kinds of metal compounds to form films, blow moldings, and pipes. It is reported that it can be applied to such applications.
  • 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.
  • 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 is further required.
  • the present invention is to provide an ethylene / alpha-olefin copolymer excellent in processability.
  • the present invention provides an ethylene / alpha-lephine copolymer satisfying the following conditions:
  • Density (g / otf) is from 0.930 to 0.950
  • MFR 5 (g / 10 min, 19 (measured by ASTM 1238 in C)) is 0.1 to
  • Melt flow rate ratio (MFR2i. 6 / MFR 5 , measured by ASTM 1238 at 19CTC) is 10 to 200
  • the d value is 250,000 to 400,000.
  • C 2 value is -0.7 to -0.5
  • Ci value is 1,500,000 to 2,500, 000
  • C 2 value is 3 to 10
  • C 3 value is 0.2 to 0.3 persons Ethylene / Alpha-olefin-Polymer
  • Fully elastic materials deform in proportion to the elastic shear force (el ast ic shear st ress), which is called Hook's law.
  • deformation occurs in proportion to the v i scous shear stress, which is called Newton's law.
  • the material of the fully elastic can be deformed again when the elastic energy is accumulated and the elastic shear force is removed, and the fully viscous material does not recover even if the viscous shear force is removed, since the energy is all lost to the deformation.
  • the viscosity of the material itself does not change.
  • polymers in the molten state have a property of between a material of full elasticity and a viscous liquid, which is called viscoelastic (vi scoelast ici ty).
  • viscoelastic vi scoelast ici ty
  • the deformation is not proportional to the shear force, and the viscosity varies according to the shear force, which is also called a non-Newtonian fluid.
  • This property is due to the complexity of the deformation due to shear forces due to the large molecular size and complex intermolecular structure of the polymer.
  • shear thinning is considered to be important among the characteristics of non-Newtonian fluids.
  • Shear fluidization phenomenon means that as the shear rate increases It means a phenomenon that the viscosity of the polymer is reduced, the molding method of the polymer is determined according to the shear fluidization characteristics.
  • Shear fluidization characteristics are considered important.
  • Equation 1 is a Power Law model, x means frequency, y means complex viscosity, and two variables, ⁇ and C 2, are required. ( ⁇ Is the consistency index, C 2 is the CV index, C 2 is the slope of the graph.
  • TA Orchestrator which is an ARES measurement program of TA Instruments, may be used. Accordingly, when the complex viscosity graph according to the frequency of the ethylene / alpha-olefin copolymer according to the present invention is fitted with p Lawer Law of Equation 1, C 2 value is -0.7 to -0.5, and Cross of Equation 2 is When fitting with a model, the value of C 3 is 0.2 to 0.3.
  • the d value of the above formula (2) is preferably a zero point viscosity
  • the C 2 value of Equation 2 has a value in the range of 3 to 10 as the material constant, preferably has a value in the range of 5 to 8.
  • the complex viscosity value is lower than that of the comparative example, respectively, which is a high shear of the ethylene / alpha-olefin copolymer according to the present invention. Low viscosity in speed means that the workability is remarkably excellent.
  • the ethylene / alpha-olefin copolymer is. Density (g / cii)
  • the ethylene / alpha-olefin copolymer has an increased average molecular weight (g / mol) of 10,000 to 40,000.
  • the weight average molecular weight is 100,000 or more, 120,000 or more, 140,000 or more, 160,000 or more, 180,000 or more, or 200,000 or more, 380,000 or less, 360,000 or less, 340,000 or less, 320,000 or less, 300,000 or less, 280,000 or less, 260,000 or less Or 240,000 or less.
  • the ethylene / alpha-olepin copolymer has a molecular weight distribution (Mw / Mn, PDI) of 5 to 30.
  • the molecular weight distribution is 7 or more, 9 or more, 11 or more, 13 or more, 15 or more, or 17 or more, 29 or less, 28 or less, 27 or less, 26 or less, 25 or less, 24 or less, 23 or less, Or 22 or less.
  • the alpha -olepin that can be used for the copolymerization of the above ethylene / alpha-olephine is -butene, 1-pentene, 1-nuxene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene , One- Any one or more selected from the group consisting of tetradecene, 1-nuxadecene, 1-octadecene, and 1-eicosene can be used.
  • the content of alpha-lephine may be about 0.5% to about 10% by weight, preferably about 1% to about 5% by weight, but is not limited thereto.
  • 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 a mixture of one or more second metallocene compounds selected from compounds represented by the following Chemical Formulas 3 to 5.
  • A is hydrogen, halogen, alkyl, CHO, C 2 - 20 alkenyl, C 6 -20 aryl, C 7 - 20 alkylaryl, C 7 - 20 aryl-alkyl, d-20 alkoxy, C 2 - 20 alkoxyalkyl, C 20 heterocyclic cycloalkyl, or C 5 - 20 membered heteroaryl;
  • D is -0-, -S-, -N (R)-or -S RKR ')-, 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-) straight or branched alkylene
  • B is carbon, silicon or germanium
  • Q is hydrogen, halogen, d-20 alkyl, C 2 - 20 alkenyl, C 6 - 20 aryl, and C 20 alkylaryl, or C 7 - 20 aryl-alkyl;
  • M is a Group 4 transition metal
  • X 1 and X 2 are the same or different and are each independently halogen, d-20 alkyl, C 2 - alkenyl 20 Al, C 6 - 20 aryl, nitro, amido, d-20 alkyl silyl, d-20-alkoxy Or C-20 sulfonate;
  • c 1 and c 2 are the same as or different from each other, and are each independently represented by one of the following Formulas 2a, 2b, or 2c, except that C 1 and C 2 are both Formula 2c;
  • Ri to R 17 and "to" are the same or different and are each independently hydrogen, halogen, (20 alkyl, C 2 - 20 alkenyl, d- 20 alkyl silyl, alkyl silyl, alkoxysilyl CHO, d- 20 alkoxy , C 6 - 20 aryl, C 7 - 20 alkylaryl, or C 7 -2o aryl-alkyl, wherein 0 to R 17 of the two or more adjacent to each other are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring Can do it;
  • M 1 is a Group 4 transition metal
  • Cp 1 and Cp 2 are the same as or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals One, they may be substituted with a hydrocarbon of 1 to 20 carbon atoms;
  • R a and R b are the same or different, each independently represent a hydrogen, an alkyl, an alkoxy, and 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, an alkyl C 2 -io alkenyl, C 7 - 40 alkylaryl, C 7 - 40 arylalkyl, C 6 - 20 aryl, optionally substituted d-20 alkylidene, substituted or unsubstituted amino, C 2 - 20 alkyl, an alkoxy, or a C 7 - 40 aryl-alkoxy;
  • 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, which are 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, Cwo alkoxy, C 2 of each other - 20 alkoxyalkyl, C 6 - 20 aryl, C 6 - 10 aryloxy C 2 -20 alkenyl, C 7 - 40 alkylaryl, C 7 - 40 arylalkyl, C 8 - 40 arylalkenyl, or C 2 - 10 alkynyl;
  • Z 2 is a halogen atom, alkyl, C 2 - 10 alkenyl, C 7 - 40 alkylaryl, C 7 - 40 arylalkyl, C 6 - 20 aryl, alkyl substituted or unsubstituted alkylidene, substituted or unsubstituted amino, C 2 - 20 alkyl, an alkoxy, or 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 ; Combination;
  • 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, ;
  • R e is hydrogen, d- 20 alkyl, Cwo alkoxy, C 2 - 20 alkoxyalkyl, C 6 - 20 aryl, C 6 -
  • Z 3 is a halogen atom, alkyl, C 2 - 10 alkenyl, C 7 - 40 alkylaryl, C 7 - 40 arylalkyl, C 6 - 20 aryl, optionally substituted d-20 alkylidene, optionally substituted are amino, C 2 - 20 alkyl, an alkoxy, or 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 Cp 5 R e ring and J;
  • the ( 20 alkyl) includes a linear or branched alkyl, specifically methyl, ethyl, propyl, isopropyl, ⁇ -butyl, tert- butyl, pentyl, nuclear chamber, heptyl, octyl, etc. but it not limited to the C 2 -.
  • alkenyl include, including alkenylene of straight or branched chain, and allyl specifically, ethenyl, propenyl, butenyl, pen, but the like ethenyl, whereby only not limited to a C 6 -.
  • 20 aryl include, includes monocyclic or condensed ring aryl ol and, but, and the like More specifically, phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, whereby only limited but not the C 5 -.
  • heteroaryl group include a monocyclic or condensed ring includes heteroaryl, carbazolyl, pyridyl, quinoline, isoquinoline, thiophenyl, furanyl, imidazole, oxazolyl, thiazolyl, bit Azine, tetrahydropyranyl, tetrahydrofuranyl, etc., but is not limited thereto .
  • alkoxy include methoxy, ethoxy, phenyloxy, cyclonuxyloxy, 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 I to ' are each independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, phenyl, halogen, More preferably, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, mesooxy, or ethoxy are not limited thereto.
  • L of the general formula (1) is C 4 - 8 straight or branched chain alkylene of one to more preferred, but is not limited thereto only. Further, the alkylene group d-20 alkyl, C 2 - may be substituted or unsubstituted aryl as 20 - 20 alkenyl, or C 6.
  • A is hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, mesoxymethyl, tert-butoxymethyl, 1-ethoxyethyl, 1 ⁇ methyl— 1-meth Preferred is methoxyethyl, tetrahydropyranyl, or tetrahydrofuranyl, but is not limited thereto.
  • B of Formula 1 is preferably silicon, but is not limited thereto.
  • the crab 1 metallocene compound of Formula 1 may be a structure in which an indeno indol derivative and / or a fluorene derivative are crosslinked by a bridge, and may act as a Lewis base to the ligand structure.
  • an indeno indol derivative and / or a fluorene derivative are crosslinked by a bridge, and may act as a Lewis base to the ligand structure.
  • it is supported on the surface having the Lewis acid characteristic of the carrier and shows high polymerization activity even when supported.
  • it is highly active as it contains an electronically rich indeno indole group and / or fluorene group, and due to appropriate steric hindrance and the electronic effect of the ligand, the hydrogen reactivity is low and high activity is maintained even in the presence of hydrogen.
  • the beta-hydrogen of the polymer chain in which the nitrogen atom of the indeno indole derivative grows is stabilized by hydrogen bonding, thereby inhibiting beta-hydrogen el iminat ion, and thus, an ultra high molecular weight olefin type
  • the polymer can be polymerized.
  • specific examples of the compound represented by Chemical Formula 2a may include a compound represented by one of the following structural formulas.
  • specific examples of the compound represented by Chemical Formula 2b include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.
  • specific examples of the compound represented by Chemical Formula 2c may include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.
  • 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 Crab 1 metallocene compound of Chemical Formula 1 has excellent activity and may polymerize high molecular weight ethylene / alpha-lepin copolymer. In particular, even when used on a carrier, it shows high polymerization activity, and thus an ultra high molecular weight ethylene / alpha-lephine co-polymer can be prepared.
  • the first metallocene compound of formula 1 according to the present invention is low hydrogen It exhibits reactivity and still allows high polymerization of ultra high molecular weight ethylene / alpha-olefin copolymers. Therefore, an ethylene / alpha-olefin copolymer that satisfies high molecular weight characteristics can be produced without deterioration of activity even when used in combination with a catalyst having other characteristics, while containing an ethylene / alpha-olefin copolymer of a 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 innoindol derivative and / or a fluorene derivative with a bridge compound, and then a metal precursor is added to perform metallization. Can be obtained.
  • the manufacturing method of the said 1st metallocene compound is concretely demonstrated to the Example mentioned later.
  • Examples of the compound represented by Formula 3 include one of the following structural formulas
  • 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 one of the 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 formation of a long chain branch (LCB) in the ethylene / alpha—lepin copolymer prepared.
  • the cocatalyst supported on the carrier for activating the metallocene compound is an organometallic compound containing a Group 13 metal, and polymerizes the olefin under a general metallocene catalyst. If it can be used when it is not particularly limited.
  • the cocatalyst compound may include at least one of an aluminum-containing first cocatalyst of Formula 6, and a borate-based 2 cocatalyst of Formula 7 below.
  • R 18 in Formula 6 is each independently a halogen, a halogen substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, and k is an integer of 2 or more, [Formula 7]
  • T + is a + monovalent polyatomic ion
  • B is boron in +3 oxidation state
  • G is independently hydride, dialkylamido, halide, alkoxide, aryl oxide, hydrocarbyl, halocarbyl And. Selected from the group consisting of halo-substituted hydrocarbyl, wherein G has up to 20 carbons, but at up to one position G is a halide.
  • the first cocatalyst of Chemical Formula 6 may be an alkylaluminoxane compound having a repeating unit bonded in a linear, circular or reticulated form.
  • the promoter include methyl aluminoxane (MA0), ethyl aluminoxane, isobutyl aluminoxane or butyl aluminoxane.
  • the second cocatalyst of Formula 7 may be a borate-based compound in the form of a trisubstituted ammonium salt, or a dialkyl ammonium salt, a trisubstituted phosphonium salt.
  • Such 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, 4, 6-trimethylaninium Tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (
  • the mass ratio of the total transition metal to the carrier included in the first metallocene compound represented by the formula (1), or the C2 metallocene compound represented by the 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 may be from 1: 1 to 1: 100.
  • the carrier may be a carrier containing a hydroxy group on the surface, preferably a dry semi-reactive hydroxy group and a siloxane group which have been dried to remove moisture on the surface.
  • the carrier which has is used.
  • silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, and these are usually oxides, carbonates, sulfates, such as Na 2 0, 2 C0 3 , BaS0 4 , and Mg (N0 3 ) 2 . And nitrate components.
  • the drying temperature of the carrier is preferably 200 to 80CTC, more preferably 300 to 600 ° C, and most preferably 300 to 400 ° C.
  • the amount of hydroxy 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 hydroxy 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.
  • 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-olefin using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.
  • the polymerization temperature is about 25 to about 500 ° C, preferably about 25 to about . About 200 ° C., more preferably about 50 to about 15 CTC.
  • the polymerization pressure may be about 1 to about 100 Kgf / citf, preferably about 1 to about 50 Kgf / ciii 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 and chlorobenzene.
  • 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-lepine copolymer according to the present invention is a combination of the catalyst of formula 3 to 5 to polymerize low-molecular-weight polymer chains, and the catalyst of formula 1 mainly to polymerize high-molecular weight polymer chain, ethylene and Prepared by copolymerizing alpha-olefin monomers.
  • the ethylene / alpha-olefin copolymer may exhibit, for example, a molecular weight distribution curve as shown in FIG. 1 and may exhibit excellent processability. Due to the above-described physical layer, the ethylene / alpha -olefin copolymer according to the present invention can be preferably applied to large diameter pipes or composite pipes.
  • the ethylene / alpha-olefin copolymer ⁇ according to the present invention is excellent in workability and can be applied to large diameter pipes or composite pipes.
  • Figure 2 shows the result of fitting the complex viscosity graph according to the frequency of the copolymer prepared in Example 2 of the present invention, Power Law and Cross Model.
  • Figure 3 shows the result of fitting the complex viscosity graph according to the frequency of the copolymer prepared in Examples and Comparative Examples of the cross model.
  • 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 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 3 ⁇ 4-NMR.
  • 6-Chlorohexanol was used to prepare t_Butyl-0- (CH 2 ) 6 -Cl using the method presented in Tetrahedron Lett. 2951 (1988), whereupon NaCp was reacted to t- Buty ⁇ 0— (CH 2 ) 6 ⁇ C 5 3 ⁇ 4 (yield 60%, bp 80 VI 0.1 ⁇ Hg). Further, t-ButyK)-(C3 ⁇ 4) 6 -C 5 3 ⁇ 4 at -78t: was dissolved in THF, and normal butyllithium (n-BuLi) was slowly added, and the reaction mixture was heated to room temperature for 8 hours.
  • n-BuLi normal butyllithium
  • Catalyst Preparation Example 3 (20 g) was dissolved in toluene, charged into the reactor, and stirred at 200 rpm for 2 hours.
  • 70 g of the cocatalyst ani 1 inium tetrakis (pentaf luorophenyl) borate
  • the toluene slurry was transferred to a fil ter dryer and filtered. 3.0 kg of toluene was added and stirred for 10 minutes, and then stirring was stopped and filtered. 3.0 kg of nucleic acid was added to the reactor and stirred for 10 minutes, and then the stirring was stopped and filtered. Drying under reduced pressure at 50 ° C. for 4 hours to prepare a 500g-Si0 2 supported catalyst.
  • the olefin polymer was prepared by bimodal operation of two common supported metallocene catalysts prepared in Examples 1 and 2 using two hexane slurry slurry tank polymerizers. 1-butene was used as comonomer.
  • polymerization conditions using respective common supported metallocene catalysts are summarized in Table 1 below.
  • MFR 21 .6 / MFR 5 MFR 21 . 6 Melt index (MI ⁇ 21.6kg load) divided by MFR 5 (MI, 5kg lower).
  • Mn, Mw, ⁇ D, GPC curve Melt the sample in l, 2,4-Trichlorobenzene containing 0.0125% of BHT using PL-SP260 for 160 ° C for 10 hours, and use PL-GPC220. The number average molecular weight and the weight average molecular weight were measured at a measurement temperature of 160 ° C. The molecular weight distribution was expressed as the ratio of weight average molecular weight and number average molecular weight. -
  • FIG. 2 a graph of the complex viscosity according to the frequency of the copolymer prepared in Example 2 and a result of fitting this to the power law and the cross model are shown in FIG. 2.
  • FIG. 2 it was confirmed that the results of fitting the complex viscosity graph according to the frequency of the copolymer prepared in Example 2 and the result of fitting the power law and the cross model were very similar. It was confirmed that the model is suitable for quantitatively evaluating the flow characteristics of the copolymer according to the invention.
  • the copolymers prepared in Examples and Comparative Examples were fitted to Power Law and Cross Mode, and the values of the variables obtained are shown in Table 3 below.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Abstract

La présente invention concerne un copolymère éthylène/alpha-oléfine ayant une excellente aptitude au traitement. Le copolymère éthylène/alpha-oléfine selon la présente invention a une excellente aptitude au traitement en raison de sa faible viscosité complexe à une vitesse de cisaillement élevée, ce qui permet au copolymère d'être appliqué sur un tuyau de gros calibre ou un tuyau complexe et analogues.
PCT/KR2015/013328 2014-12-08 2015-12-07 Copolymère éthylène/alpha-oléfine ayant une excellente aptitude au traitement WO2016093580A1 (fr)

Priority Applications (5)

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JP2016547588A JP6482564B2 (ja) 2014-12-08 2015-12-07 加工性に優れたエチレン／アルファ−オレフィン共重合体
CN201580005067.7A CN105916896B (zh) 2014-12-08 2015-12-07 具有优良可加工性的乙烯/α‑烯烃共聚物
RU2016132145A RU2671499C1 (ru) 2014-12-08 2015-12-07 Этилен/альфа-олефиновые сополимеры, характеризующиеся превосходной перерабатываемостью
US15/106,708 US10155830B2 (en) 2014-12-08 2015-12-07 Ethylene/alpha-olefin copolymers having excellent processability
EP15866382.3A EP3070108A4 (fr) 2014-12-08 2015-12-07 Copolymère éthylène/alpha-oléfine ayant une excellente aptitude au traitement

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KR20140174985 2014-12-08
KR10-2014-0174985 2014-12-08
KR1020150161159A KR101747401B1 (ko) 2014-12-08 2015-11-17 가공성이 우수한 에틸렌/알파-올레핀 공중합체
KR10-2015-0161159 2015-11-17

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