WO2016153275A1 - Polymère à base d'oléfine - Google Patents

Polymère à base d'oléfine Download PDF

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WO2016153275A1
WO2016153275A1 PCT/KR2016/002938 KR2016002938W WO2016153275A1 WO 2016153275 A1 WO2016153275 A1 WO 2016153275A1 KR 2016002938 W KR2016002938 W KR 2016002938W WO 2016153275 A1 WO2016153275 A1 WO 2016153275A1
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group
carbon atoms
polymer
olefin polymer
olefin
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PCT/KR2016/002938
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English (en)
Korean (ko)
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김효주
우지윤
박상은
이영우
이충훈
박해웅
최익제
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주식회사 엘지화학
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Priority claimed from KR1020160021825A external-priority patent/KR101847702B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201680002144.8A priority Critical patent/CN106795242B/zh
Priority to EP16769093.2A priority patent/EP3162817B1/fr
Priority to US15/500,859 priority patent/US10023669B2/en
Publication of WO2016153275A1 publication Critical patent/WO2016153275A1/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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

  • the present invention relates to olefinic polymers which exhibit good mechanical strength, in particular significantly improved impact strength.
  • CGC Constrained-Geometry Catalyst
  • the copolymer produced by such a CGC catalyst has a lower content of the portion having a lower molecular weight than the copolymer prepared by the conventional Ziegler-Natta-based catalyst is improved physical properties such as strength (strength).
  • the copolymer produced by the CGC or the like has a disadvantage in that the processability is lower than that of the polymer produced by the existing Ziegler-Natta catalysts.
  • U.S. Patent 5,539,076 discloses a metallocene / nonmetallocene mixed catalyst system for preparing certain peak high density copolymers.
  • the catalyst system is supported on an inorganic support.
  • the problem with the supported Ziegler-Natta and metallocene catalyst systems is that the supported hybrid catalysts are less active than homogeneous homocatalysts, making it difficult to produce olefinic polymers having properties suitable for the application.
  • the olefin-based polymer is produced in a single reactor, there is a fear that a gel generated in the blending method is produced, it is difficult to insert a comonomer in a high molecular weight portion, and the shape of the resulting polymer may be poor.
  • the two polymer components are not uniformly mixed, there is a fear that quality control becomes difficult.
  • the technical problem to be solved by the present invention is to provide an olefin-based polymer and a method for producing the same that can exhibit excellent mechanical strength, in particular significantly improved impact strength through the control of the crystal structure in the polymer.
  • a single peak is shown in gel permeation chromatography (GPC) analysis, and the temperature rising elution fraction (TREF) is measured at a temperature range of -20 ° C to 120 ° C.
  • GPC gel permeation chromatography
  • Te1 Elution temperature 1
  • Te2 Elution temperature 2
  • Te3 Elution temperature 3
  • the olefinic polymer according to the present invention exhibits a single peak in the GPC analysis through control of the crystal structure in the polymer, and has three elution temperatures, namely, Te1, Te2 and Te3 in the temperature rise elution fractionation measurement, thereby providing excellent mechanical strength, In particular, it can exhibit significantly improved impact strength. As a result, it can be used in various fields and uses, such as various packaging, construction, household goods, such as materials for automobiles, electric wires, toys, textiles, and medical.
  • FIG. 1 is a graph showing the results of temperature rise elution fractionation (TREF) measurement of the olefin polymer prepared in Example 1.
  • FIG. 1 is a graph showing the results of temperature rise elution fractionation (TREF) measurement of the olefin polymer prepared in Example 1.
  • FIG. 1 is a graph showing the results of temperature rise elution fractionation (TREF) measurement of the olefin polymer prepared in Example 1.
  • FIG. 2 is a graph showing the results of temperature rise elution fractionation (TREF) measurement of the olefin polymer prepared in Example 2.
  • FIG. 1 is a graph showing the results of temperature rise elution fractionation (TREF) measurement of the olefin polymer prepared in Example 2.
  • FIG. 1 is a graph showing the results of temperature rise elution fractionation (TREF) measurement of the olefin polymer prepared in Example 2.
  • thermostyrene resin is prepared in Comparative Example 1.
  • Figure 4 is a graph showing the results of temperature rise elution fractionation (TREF) measurement of the olefin polymer prepared in Comparative Example 4.
  • TREF temperature rise elution fractionation
  • FIG. 5 is a graph showing the results of gel permeation chromatography (GPC) analysis of the olefin polymer prepared in Example 1.
  • GPC gel permeation chromatography
  • an alkyl group refers to a straight and branched aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms.
  • the alkyl group includes a straight or branched alkyl group having 1 to 20 carbon atoms, more specifically 1 to 6 carbon atoms.
  • Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, iso-amyl group, hexyl group and the like. Can be mentioned.
  • an alkoxy group means the C1-C20 linear or branched alkyl group (-OR) couple
  • the alkoxy group includes an alkoxy group having 1 to 20 carbon atoms, and more specifically 1 to 6 carbon atoms. Specific examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group or t-butoxy group.
  • an alkenyl group means a C2-C20 linear and branched aliphatic unsaturated hydrocarbon group containing a carbon-carbon double bond.
  • the alkenyl group includes an alkenyl group having 2 to 6 carbon atoms.
  • Specific examples of the alkenyl group include an ethenyl group, propenyl group or butenyl group.
  • a cycloalkyl group means a C3-C20 cyclic saturated hydrocarbon group.
  • the cycloalkyl group includes a cycloalkyl group having 3 to 6 carbon atoms.
  • a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, etc. are mentioned.
  • an aryl group means a carbocyclic aromatic radical having 6 to 20 carbon atoms including one or more rings, and the rings may be attached or fused together in a pendant manner.
  • the aryl group includes an aryl group having 6 to 20 carbon atoms, more specifically, 6 to 12 carbon atoms.
  • Specific examples of the aryl group include a phenyl group, a naphthyl group or a biphenyl group.
  • an arylalkyl group means the functional group (Ar-R-) in which the aryl group (Ar) which is an aromatic hydrocarbon group was substituted by the carbon of a linear or branched alkyl group (R).
  • the arylalkyl group includes an arylalkyl group having 7 to 20 carbon atoms, more specifically, 7 to 12 carbon atoms.
  • Specific examples of the arylalkyl group include benzyl group, phenethyl group and the like.
  • an alkylaryl group means the functional group (R-Ar-) in which the linear or branched alkyl group (R) was substituted by the carbon of an aromatic hydrocarbon group (Ar).
  • the alkylaryl group includes an alkylaryl group having 7 to 20 carbon atoms, more specifically, 7 to 12 carbon atoms.
  • an aryloxy group means an aryl group (-OAr) bonded with oxygen, wherein the aryl group is as defined above.
  • the aryloxy group includes an aryloxy group having 6 to 20 carbon atoms, more specifically, 6 to 12 carbon atoms. Specific examples of the aryloxy group include phenoxy and the like.
  • a silyl group means a -SiH 3 radical derived from silane, and at least one of hydrogen atoms in the silyl group may be substituted with various organic groups such as an alkyl group or a halogen group. It may be.
  • the alkylamino group means a functional group in which at least one hydrogen in the amino group (-NH 2 ) is substituted with an alkyl group, wherein the alkyl group is as defined above.
  • the alkylamino group is —NR 2 (wherein R may each be a hydrogen atom or a straight or branched alkyl group having 1 to 20 carbon atoms, but not both R are hydrogen atoms).
  • an arylamino group means a functional group in which at least one hydrogen in the amino group (-NH 2 ) is substituted with an aryl group, wherein the aryl group is as defined above.
  • an alkylidene group means the bivalent aliphatic hydrocarbon group from which two hydrogen atoms were removed from the same carbon atom of an alkyl group.
  • the alkylidene group includes an alkylidene group having 1 to 20 carbon atoms, more specifically, 1 to 12 carbon atoms.
  • Specific examples of the alkylidene group include a propane-2-ylidene group.
  • a hydrocarbyl group has a carbon number of 1 to 60 containing only carbon and hydrogen regardless of its structure, such as an alkyl group, an aryl group, an alkenyl group, an alkylaryl group, an arylalkyl group, etc. It means a monovalent hydrocarbon group, and a hydrocarbylene group means a divalent hydrocarbon group having 1 to 60 carbon atoms.
  • a metalloid radical is a metalloid radical of group 14 (Group 4A) metal substituted by the C1-C20 hydrocarbyl group.
  • Metalloid radicals are electronically unsaturated and can act as Lewis acids.
  • the Group 14 metal may be silicon (Si), germanium (germanium), tin (tin) or arsenic (arsenic) and the like.
  • the metalloid radical may include silyl groups such as trimethylsilyl group, triethylsilyl group, triethylsilyl group, ethyldimethylsilyl group and methyldiethylsilyl group; Triphenylgermyl, trimethylgermyl, and the like.
  • polymer means a polymer compound prepared by polymerization of the same or different types of monomers.
  • the generic term “polymer” includes the terms “homopolymer”, “copolymer”, “terpolymer” as well as “interpolymer”.
  • the "interpolymer” means a polymer produced by the polymerization of two or more different types of monomers.
  • the term “interpolymer” is used generically to refer to polymers made from three different types of monomers, as well as to the term “copolymer” commonly used to refer to polymers made from two different monomers. Terpolymers ". This includes polymers made by the polymerization of four or more types of monomers.
  • the term "quasicrystalline” refers to primary transition temperature, crystal melting point (Tm), elution point, or the like measured by temperature rising elution fractionation (TREF), differential scanning calorimetry (DSC) or equivalent technique. It refers to a polymer having. As for the semi-crystalline, the density, Tm, elution point, etc. vary depending on the crystallinity.
  • the term “amorphous” refers to a polymer without a crystalline melting point, as measured by elevated temperature elution fractionation (TREF), differential scanning calorimetry (DSC), or equivalent technique.
  • the olefin-based polymer according to an embodiment of the present invention exhibits a single peak in the gel permeation chromatography analysis, and three elution temperatures in the temperature range of -20 ° C. to 120 ° C. when measuring the temperature rise elution fractionation (TREF), Te1, Te2. And Te3.
  • TEZ temperature rise elution fractionation
  • the present invention shows a single peak in GPC analysis and three elution temperatures in TREF measurement by controlling the crystal structure in the polymer using a catalyst composition containing a heterogeneous transition metal compound having excellent miscibility in preparing an olefin polymer.
  • Te1, Te2 and Te3 can be provided to provide olefinic polymers with good mechanical strength, in particular significantly improved impact strength.
  • the olefin polymer according to one embodiment of the present invention includes a first semicrystalline olefin polymer, a second semicrystalline olefin polymer, and a third semicrystalline olefin polymer, and temperature rising elution fractionation (TREF) measurement Having a first semicrystalline olefinic polymer peak (P1), a second semicrystalline olefinic polymer peak (P2) and a third semicrystalline olefinic polymer peak (P3) in the -20 ° C to 120 ° C temperature range.
  • the elution temperature (Te, Elution temperature) of each peak is represented by Te1, Te2 and Te3, respectively.
  • an olefinic polymer has one semicrystalline peak
  • an olefinic polymer according to an embodiment of the present invention may have three semicrystalline peaks, thereby increasing mechanical strength, particularly impact strength.
  • the measurement of the TREF can be measured using, for example, a TREF machine manufactured by PolymerChar, and can be measured while increasing the temperature from -20 ° C to 120 ° C using o-dichlorobenzene as a solvent.
  • Te1 when the olefin polymer is measured at a TREF, Te1 is present at a temperature lower than Te2, and Te2 is relatively lower than Te3.
  • Te2 is in the range of -20 °C to 100 °C
  • Te2 is in the range of 0 °C to 120 °C
  • Te3 may be present in the range of 20 °C to 120 °C.
  • Te Elution temperature
  • Te means the temperature of the highest point of each peak in the TREF elution curve expressed as elution with respect to temperature (dW / dT), fraction ratio can be calculated as the integral value of the temperature-dissolution graph have.
  • the olefin polymer has a density of 0.86 g / cc to 0.88 g / cc when the TREF is measured, the Te1 ranges from -20 ° C to 30 ° C, the Te2 ranges from 10 ° C to 80 ° C, and the Te3 May range from 40 ° C to 120 ° C.
  • the olefin polymer has a fraction ratio (area%) of the first semicrystalline olefin polymer peak (P1) of 5% to 90% when measured by TREF, and the second semicrystalline olefin polymer peak (P2)
  • the fractional ratio is 5% to 90%
  • the fractional ratio of the third semicrystalline olefin polymer peak (P3) may be 5% to 90%. More specifically, the fractional ratio of the first semicrystalline olefinic polymer peak (P1) is 30% to 80%, the fractional ratio of the second semicrystalline olefinic polymer peak (P2) is 5% to 40%, and the third quaternary
  • the fractional ratio of the crystalline olefinic polymer peak (P3) may be 5% to 50%.
  • the starting point of each peak in the elution rate (dW / dT) graph with respect to temperature is defined as the point at which the polymer starts to elute based on the base line, and the end point of each peak is based on the base line.
  • the polymer was defined as the point at which elution ends.
  • the point where the value of the elution amount (dW / DT) is lowest in the overlap region is determined by the end point of the peak of P1. It can be defined as the starting point of the P2 peak.
  • the peak expressed at -20 ° C to -10 ° C appears as a mixture of an amorphous polymer and a low crystalline polymer, the peak appearing at this position can be treated in addition to the fraction ratio of the P1 peak.
  • the olefin polymer may include Tc1, Tc2, and Tc3, which are crystallization temperatures (Tc) obtained from a differential scanning calorimetry (DSC) curve.
  • Tc crystallization temperatures
  • the olefin polymer may have a density of 0.850 g / cc to 0.910 g / cc, Tc1 of 5 ° C. or less, Tc2 of 0 ° C. to 60 ° C., and Tc3 of 80 ° C. to 130 ° C.
  • Tc means the peak of the cooling curve of the heat flow in the temperature-heat flow graph of the differential scanning calorimetry (DSC), that is, the exothermic peak temperature at the time of cooling.
  • DSC differential scanning calorimetry
  • the Tc is filled with about 0.5 mg to 10 mg of a sample in a measuring container with a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 6000) manufactured by PerKinElmer, and a nitrogen gas flow rate of 20 ml / min.
  • the temperature was raised from 0 ° C to 150 ° C at a heating rate of 20 ° C / min, then maintained for 2 minutes in that state, and again at a temperature of 10 ° C / min from 150 ° C to -100 ° C. It is the peak value of the cooling curve of the heat flow measured by DSC, cooling by.
  • the olefin polymer according to one embodiment of the present invention exhibits a low density of 0.850 g / cc to 0.910 g / cc as measured according to ASTM D-792.
  • the density of the olefin-based polymer is affected by the type and content of the monomers used in the polymerization, the degree of polymerization, and the like.
  • the density of the olefin polymer is largely affected by the content of the comonomer.
  • a large amount of comonomers can be introduced by using a mixed catalyst having a heterogeneous structure.
  • the olefin polymer according to one embodiment of the present invention has a low density in the range as described above, and as a result can exhibit excellent impact strength.
  • the olefin-based polymer may have a density of 0.86 g / cc to 0.88 g / cc, in this case, the effect of maintaining the mechanical properties and the impact strength improvement by the density control is more remarkable.
  • the olefin polymer according to one embodiment of the present invention has a melt index (MI) of 0.1 g / 10 min to 100 g / 10 min, more specifically 0.1 g measured at 190 ° C. and 2.16 kg load conditions according to ASTM D1238. / 10min to 50 g / 10min, even more specifically 0.1 g / 10min to 30 g / 10min.
  • MI melt index
  • the melt index (MI) affecting the mechanical properties, impact strength, and moldability of the olefin polymer can be controlled by controlling the amount of catalyst used in the polymerization process.
  • the olefin-based polymer according to an embodiment of the present invention may exhibit excellent impact strength by showing a melt index (MI) measured in the low density condition as described above in the above-described range.
  • the olefin-based polymer according to an embodiment of the present invention has at least three or more crystallization temperatures on a DSC curve by using heterogeneous catalysts having a characteristic structure, but is monomodal in a molecular weight distribution curve when measuring GPC. It has a peak and shows a narrow molecular weight distribution. As a result, excellent impact strength can be exhibited.
  • the olefin polymer may have a molecular weight distribution (MWD) of 1.5 to 4.0, specifically 1.5 to 3.0, which is the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn).
  • Mw molecular weight distribution
  • the olefin polymer may have a weight average molecular weight (Mw) of 10,000 g / mol to 500,000 g / mol, more specifically 20,000 g / mol to 200,000 g / mol within the above molecular weight distribution range.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene equivalent molecular weights analyzed by gel permeation chromatography (GPC).
  • the olefinic polymer according to one embodiment of the present invention may be one that satisfies the following requirements (1) to (4) simultaneously:
  • Temperature Elution Elution temperature Te1, Te2 and Te3 of three olefinic polymers are included in the temperature range of -20 ° C to 120 ° C for fractional measurement.
  • P1 is in the range of -20 ° C to 30 ° C
  • Te2 is in the range of 10 ° C to 80 ° C
  • Te3 is in the range of 40 ° C to 120
  • Olefin-based polymers satisfying the above-described physical properties exhibit excellent mechanical strength, particularly impact strength, and thus can be used for various packaging, construction, and household goods such as materials for automobiles, electric wires, toys, textiles, medical, and the like. It is useful for blow molding, extrusion molding or injection molding in various fields and applications.
  • the olefin polymer as described above may be obtained by polymerizing an olefin monomer using a catalyst composition comprising a transition metal compound of Formula 1 and a transition metal compound of Formula 2. Accordingly, according to another embodiment of the present invention, a method for preparing the olefin polymer is provided.
  • M 1 and M 2 are each independently a Group 4 transition metal
  • Q 1, Q 2 , Q 3 and Q 4 each independently represent a hydrogen atom, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl having 6 to 20 carbon atoms.
  • Group selected from the group consisting of an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylamido group having 1 to 20 carbon atoms, an arylamido group having 6 to 20 carbon atoms, and an alkylidene group having 1 to 20 carbon atoms Become,
  • R 1 to R 6 are each independently a hydrogen atom, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 7 carbon atoms.
  • at least two adjacent functional groups of R 1 to R 6 are connected to each other and selected from a group consisting of a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms;
  • R 21 to R 27 are each independently a group 14 metal substituted with a hydrogen atom, a halogen group, a C1-C20 hydrocarbyl group, a C1-C20 heterohydrocarbyl group, and a C1-C20 hydrocarbyl group It is selected from the group consisting of metalloid radical of, specifically R 21 to R 27 are each independently a hydrogen atom, a halogen group, a silyl group, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, 3 carbon atoms Metalloid radicals of Group 14 metals substituted with a cycloalkyl group of 20 to 20, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms, and a hydrocarbyl group of 1 to 20 carbon atoms. It is selected from the group consisting of;
  • X 1 to X 3 are each independently selected from the group consisting of a hydrogen atom, a halogen group, a hydrocarbyl group of 1 to 20 carbon atoms and a heterohydrocarbyl group of 1 to 20 carbon atoms, more specifically a hydrogen atom, a halogen group, Silyl group, amino group, (alkyl of 1 to 20 carbon atoms) amino group, alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms, cycloalkyl group of 3 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, 7 to 20 carbon atoms An alkylaryl group and an arylalkyl group having 7 to 20 carbon atoms; Or two or more adjacent functional groups of X 1 to X 3 are connected to each other, such as a halogen group, a silyl group, an amino group, an (alkyl having 1 to 20 carbon atoms) amino group, an alkyl group having
  • Z is phosphorus (P), arsenic (As) or antimony (Sb).
  • the metal site is linked by a cyclopentadienyl (Cp) ligand to which an amino group is linked to a phenylene bridge, so that the Cp-M 1 -N angle is structurally narrow, and a monomer is approached.
  • Q 1 -M 1 -Q 2 angle is characterized by keeping wide.
  • the seats are connected in order to form a more stable and rigid five-point ring structure.
  • the nitrogen atom of the amino group is connected to the phenylene bridge by two bonds in the form of a ring to have a more complex complex structure. Therefore, when these compounds are reacted with methylaluminoxane or a cocatalyst such as B (C 6 F 5 ) 3 to be activated and then applied to olefin polymerization, they exhibit characteristics such as high activity, high molecular weight and high copolymerization even at high polymerization temperatures. It is possible to produce polyolefins having.
  • low density polyethylene as well as a large amount of alpha-olefins can be introduced, so that a low density polyolefin air having a density of 0.910 g / cc or less, more specifically, a density of 0.855 g / cc to 0.910 g / cc
  • the preparation of the coalescence is possible.
  • the catalyst composition containing the transition metal compound it is possible to prepare a polymer having a narrow MWD compared to CGC, excellent copolymerizability, and high molecular weight even in a low density region.
  • the compound of Formula 1 is preferably used to prepare a catalyst for the polymerization of the olefin monomer, but is not limited thereto and may be applicable to all fields in which the transition metal compound may be used.
  • the transition metal compound of Formula 2 which is used in combination with the transition metal compound of Formula 1, is an imide-based ligand such as phosphinimide ligands connected to a derivative of cyclopentadiene having a heterocycle including sulfur.
  • the transition metal compound of Formula 2 when used as a catalyst when copolymerizing ethylene and olefinic polymers such as octene, hexene or butene, it exhibits high catalytic activity and enables the production of olefinic polymers having excellent physical properties such as high molecular weight and low density.
  • it is excellent in the miscibility with the transition metal compound of Formula 1 and uniformly mixed in the catalyst composition, it is possible to further improve the catalytic activity of the catalyst composition.
  • M 1 may be Ti, Hf or Zr.
  • Q 1 and Q 2 may be each independently selected from the group consisting of a hydrogen atom, a halogen group and an alkyl group having 1 to 6 carbon atoms.
  • R 1 and R 2 may be an alkyl group having 1 to 20 carbon atoms, more specifically, an alkyl group having 1 to 6 carbon atoms, and even more specifically, a methyl group.
  • R 3 to R 6 are each independently a hydrogen atom; An alkyl group having 1 to 20 carbon atoms; Or an alkenyl group having 2 to 20 carbon atoms, more specifically a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and even more specifically, a hydrogen atom.
  • R 7 to R 10 may be each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R 11 may be an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, wherein the substituent is a halogen group, carbon number It may be any one or two or more selected from the group consisting of an alkyl group of 1 to 20, an alkenyl group of 2 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, and an aryloxy group of 6 to 20 carbon atoms.
  • R 11 may be connected to R 10 adjacent to R 11 to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms.
  • the aliphatic ring or aromatic ring may be substituted with any one or two or more substituents selected from the group consisting of a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. have.
  • the transition metal compound is R 11 is an aryl group, or an alkyl aryl group having 7 to 20 in the alkyl group of the unsubstituted or substituted, having 1 to 20 carbon atoms, having 6 to 20 carbon atoms represented by the formula 1, e.
  • the compound may be represented by the following Chemical Formula, and any one or a mixture of two or more thereof may be used:
  • transition metal compound represented by the formula (1) are connected to each other and R 10 to R 11 are adjacent to the R 11 form a ring of 5 to 20 carbon atoms aliphatic ring or a carbon number of 6 to 20, to the general formula (3) It may be a compound represented:
  • M 1 , Q 1 , Q 2 , R 1 to R 9 are the same as defined in Chemical Formula 1,
  • Cy is an aliphatic ring group having 4 or 5 carbon atoms including nitrogen (N),
  • R, R 12 and R 13 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms.
  • m may be an integer of 0 to 2 when Cy is an aliphatic ring group having 4 carbon atoms, and may be an integer of 0 to 4 when Cy is an aliphatic ring having 5 carbon atoms.
  • R a to R d are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, And an arylalkyl group having 7 to 20 carbon atoms, and the remaining substituents are as defined in Chemical Formula 1,
  • R e and R f each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. It is selected from the group consisting of an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms, the remaining substituents are the same as defined in the formula (1).
  • transition metal compound of Formula 3 may be a compound represented by the following formula:
  • the transition metal compound of Formula 1 may be prepared by the following steps a) to d):
  • R ' is a hydrogen atom
  • R 0 is a protecting group
  • the compound including a protecting group in step a) may be trimethylsilyl chloride, benzyl chloride, t-butoxycarbonyl chloride, benzyloxycarbonyl chloride or carbon dioxide.
  • the compound of Formula 5 may be a lithium carbamate compound represented by Formula 5a:
  • Each substituent in Formula 5a is as defined in Formula 1 above.
  • the compound of Formula 1 may be prepared by the following Scheme 1.
  • the transition metal compound of Formula 2 may be a compound of Formula 2a.
  • M 2 may be the same as defined above, specifically, Ti, Hf or Zr,
  • Q 3 and Q 4 may be the same as defined above, specifically, each independently may be a halogen group or an alkyl group having 1 to 8 carbon atoms,
  • R 21 to R 27 may be the same as defined above, more specifically, R 21 to R 27 are each independently a hydrogen atom, a halogen group, a silyl group, an alkyl group having 1 to 8 carbon atoms, an alke having 2 to 6 carbon atoms Of a Group 14 metal substituted with a silyl group, a C3-12 cycloalkyl group, a C6-C18 aryl group, a C7-C18 alkylaryl group, a C7-C18 arylalkyl group, and a C1-C8 hydrocarbyl group Selected from the group consisting of metalloid radicals, and more specifically, R 21 to R 27 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms or 1 to 4 carbon atoms;
  • X 1 to X 3 may be the same as defined above, more specifically, X 1 to X 3 are each independently a hydrogen atom, a halogen group, a silyl group, an amino group, (alkyl having 1 to 8 carbon atoms), C 1 Selected from the group consisting of an alkyl group of 8 to 8, an alkenyl group of 2 to 6 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, an aryl group of 6 to 18 carbon atoms, an alkylaryl group of 7 to 18 carbon atoms, and an arylalkyl group of 7 to 18 carbon atoms Or; Or two adjacent functional groups of X 1 to X 3 are connected to each other to form a halogen group, a silyl group, an amino group, an (alkyl having 1 to 8 carbon atoms) amino group, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms and a carbon number A
  • the second transition metal compound of Chemical Formula 2 which is more preferred for controlling the electronic steric environment around the metal, may be the following compounds, and any one or a mixture of two or more thereof may be used.
  • Cy is a cyclohexyl group
  • tBu is a t-butyl group
  • Me is a methyl group
  • Ph is a phenyl group.
  • the transition metal compound of Formula 2 may have various structures within the range defined in Formula 2, and these compounds may exhibit equivalent functions and effects.
  • the transition metal compound of Chemical Formula 2 may be prepared using a known synthetic reaction.
  • the catalyst composition used to prepare the olefin-based polymer may specifically include the transition metal compounds of Formulas 1 and 2 in a weight ratio of 99: 1 to 1:99.
  • the catalyst composition may mix the transition metal compounds of Formulas 1 and 2 in a weight ratio of 50:50 to 80:20.
  • the catalyst composition may further include a promoter.
  • the promoter may be used without particular limitation as long as it is known in the art such as alkylaluminoxane, alkylaluminum or Lewis acid.
  • the promoter may include any one or a mixture of two or more selected from the group consisting of compounds represented by Formulas 9 to 12:
  • R 41 is a halogen group, a C 1-20 hydrocarbyl group or a C 1-20 hydrocarbyl group substituted with halogen, a is an integer of 2 or more,
  • D is aluminum or boron
  • each R 42 is independently a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen.
  • L is a neutral or cationic Lewis acid
  • H is a hydrogen atom
  • Z is a Group 13 element
  • each A independently has one to six carbon atoms of 1 to 20 hydrogen atoms may be substituted with a substituent. It is an aryl group or a C1-C20 alkyl group
  • the said substituent is a halogen group, a C1-C20 hydrocarbyl group, a C1-C20 alkoxy group, or a C6-C20 aryloxy group.
  • a method of preparing the catalyst composition comprising: first contacting the catalyst composition with a compound represented by Formula 9 or Formula 10 to obtain a mixture; And adding the compound represented by Formula 11 or 12 to the mixture.
  • the molar ratio of the compound represented by Formula 9 or Formula 10 with respect to the catalyst composition may be 1: 2 to 1: 5,000, respectively. Specifically 1:10 to 1: 1,000, and even more specifically 1:20 to 1: 500.
  • the molar ratio of the compound represented by Formula 11 or 12 with respect to the catalyst composition may be 1: 1 to 1:25, more specifically 1: 1 to 1:10, even more specifically 1: 1 To 1: 5.
  • the ratio of the compound represented by Formula 11 or 12 with respect to the total amount of the transition metal compounds of Formulas 1 and 2 is less than 1: 1, the amount of the activator is relatively small, resulting in incomplete activation of the metal compound. If there is a problem that the activity of the catalyst composition is deteriorated and if it is greater than 1:25, the metal compound is fully activated, but the excess amount of the activator does not economically cost or the purity of the polymer produced is poor. have.
  • the molar ratio of the compound represented by the formula (10) relative to the catalyst composition may be 1: 1 to 1: 500, more specifically 1: 1 to 1:50 And even more specifically, 1: 2 to 1:25.
  • the molar ratio is less than 1: 1, the amount of the activator is relatively small, so that the activation of the metal compound may not be completed, and thus the activity of the resulting catalyst composition may be inferior.
  • the cost of the catalyst composition is economically undesirable or the purity of the resulting polymer is poor with the remaining excess activator.
  • Aliphatic hydrocarbon solvents having 5 to 12 carbon atoms such as pentane, hexane or heptane, as a reaction solvent in the preparation of the catalyst composition described above; Hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene; Or aromatic hydrocarbon solvents such as benzene, toluene, etc. may be used, but are not necessarily limited thereto, and all solvents available in the art may be used.
  • 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 alkylaluminum, and may be carried out by further using a promoter.
  • the catalyst composition may further include an additive.
  • a compound containing a hetero atom may be included.
  • examples of the compound containing a hetero atom include a hetero ring compound; Or alkanes containing heteroatoms.
  • heterocyclic compound examples include aromatic rings containing heteroatoms; Heterocycloalkanes; Or heterocycloalkene.
  • alkanes containing the heteroatom examples include alkanes containing amine groups or ether groups.
  • the heteroaromatic ring; Heterocycloalkanes; Or heterocycloalkenes include 5- or 6-membered rings.
  • the compound containing the heteroatom may include O, S, Se, N, P or Si as a heteroatom.
  • the compound containing a heteroatom may include one heteroatom.
  • the compound containing the hetero atom may be substituted, and when the compound containing the hetero atom is substituted, it may be substituted with one or two or more from the group consisting of hydrogen, methyl, phenyl and benzyl.
  • Examples of the compound containing a hetero atom include pyridine, 3,5-dimethylpyridine, 2,4,6-trimethylpyridine, 2,6-dimethylpyridine, 2,4-dimethylpyridine, thiophene, 2-methylthiophene , 2,3-dimethylthiophene, piperidine, phosphinene, pyrrole, 2-methylpyrrole, aniline, para-toluidine, tetrahydrofuran, 2,3-dimethyltetrahydrofuran, 2,5-tetrahydrofuran, Selected from the group consisting of 3,4-dihydro-2H-pyrene, furan, 2-methylfuran, 2,3-dimethylfuran, 2,5-dimethylfuran, diethylether, methyl tertbutyl ether and triethylamine It may include any one or two or more, but is not limited thereto.
  • first and second transition metal compounds and the promoter may be used in a form supported on a carrier.
  • the carrier may be silica-alumina, silica-magnesia, or the like, and other carriers known in the art may be used.
  • such a carrier may be used in a dry state at a high temperature, and the drying temperature may be, for example, 180 ° C to 800 ° C. If the drying temperature is too low below 180 ° C., an excess portion on the carrier may react with the promoter to degrade the performance. If the drying temperature is too high above 800 ° C., the hydroxy group content on the surface of the carrier may be lowered to promote the promoter. The reaction site with and may decrease.
  • the compound represented by Formula 9 may be alkyl aluminoxane, specific examples thereof include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and more specifically, methyl aluminoxane. .
  • the compounds represented by the above formula (10) are specifically trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tri Cyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxy Seed, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, more specifically, may be selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum.
  • the compound of Formula 11 or 12 specifically triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, trimethyl Ammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammoniumtetrapentafluorophenylboron, N , N-diethylanilidedium tetrapetyl boron, N, N-diethylanilidedium tetraphenylboron, N, N-diethylanilinium
  • the monomers usable in the production of the olefin polymers include, for example, alpha-olefin monomers, cyclic olefin equivalents, diene olefin monomers, triene olefin monomers or styrene monomers.
  • One type of monomer may be homopolymerized, or two or more types may be mixed and copolymerized.
  • the alpha-olefin monomers include aliphatic olefins having 2 to 12 carbon atoms, specifically 2 to 8 carbon atoms, and more specifically ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 4,4-dimethyl-1-pentene, 4,4 -Diethyl-1-hexene, 3,4-dimethyl-1-hexene, etc. can be illustrated.
  • the alpha-olefins may be homopolymerized or alternating, random, or block copolymerized.
  • the copolymerization of the above-mentioned alpha-olefins is copolymerization of ethylene and an alpha-olefin having 2 to 12 carbon atoms, specifically 2 to 8 carbon atoms (ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 4 -Methyl-1-pentene, ethylene and 1-octene) and copolymerization of propylene with alpha-olefins having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms (propylene and 1-butene, propylene and 4-methyl-1-pentene , Propylene and 4-methyl-1-butene, propylene and 1-hexene, propylene and 1-octene).
  • the amount of other alpha-olefins may be up to 90% by weight of the total monomers. More specifically, the ethylene copolymer is 70% by weight or less, specifically 60% by weight or less, more specifically 50% by weight or less, and 1% to 90% by weight, specifically 5% by weight, for the propylene copolymer. To 90% by weight, more specifically 10% to 70% by weight.
  • the cyclic olefins may be used having 3 to 24 carbon atoms, specifically 3 to 18, more specifically cyclopentene (cyclopentene), cyclobutene, cyclohexene, 3-methylcyclohexene, cyclooctene, tetracyclo Decene, octacyclodecene, dicyclopentadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6- Dimethyl-2-norbornene, 5,5,6-trimethyl-2-norbornene or ethylene norbornene and the like.
  • cyclopentene cyclopentene
  • cyclobutene cyclohexene
  • 3-methylcyclohexene cyclooctene
  • cyclooctene tetracyclo Decene
  • the cyclic olefins may be copolymerized with the alpha-olefins, wherein the amount of the cyclic olefin may be 1 to 50 mol%, specifically 2 to 50 mol% with respect to the copolymer.
  • the dienes and triene may be a polyene having 4 to 26 carbon atoms having two or three double bonds, specifically 1,3-butadiene, 1,4-pentadiene, 1,4- Hexadiene, 1,5-hexadiene, 1,9-decadiene, 2-methyl-1,3-butadiene, and the like.
  • the styrenes may be styrene or styrene substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen group, an amine group, a silyl group, or a halogenated alkyl group.
  • the polymerization step may be carried out in solution phase, slurry phase, bulk phase or gas phase polymerization in a hydrocarbon solvent.
  • the catalyst composition is present in the form of a carrier or insoluble particles of the carrier, as well as the catalyst composition in a homogeneous solution, it may be carried out in a solution phase, a slurry phase, a bulk phase, or a gas phase polymerization.
  • each polymerization condition may vary depending on the state of the catalyst used (homogeneous or heterogeneous phase (supported)), the polymerization method (solution polymerization, slurry polymerization, gas phase polymerization), the desired polymerization result or the shape of the polymer. Can be. The degree of deformation thereof can be easily modified by anyone skilled in the art.
  • the hydrocarbon solvents include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene; Alternatively, any one or two or more dissolved or diluted in a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane or chlorobenzene may be mixed and injected.
  • 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 alkylaluminum, and may be carried out by further using a promoter.
  • alkylaluminum examples include trialkylaluminum, dialkyl aluminum halides, alkyl aluminum dihalides, aluminum dialkyl hydrides or alkyl aluminum sesqui halides, and more specifically, Al (C 2 H 5 ) 3 , Al (C 2 H 5 ) 2 H, Al (C 3 H 7 ) 3 , Al (C 3 H 7 ) 2 H, Al (iC 4 H 9 ) 2 H, Al (C 8 H 17 ) 3 , Al (C 12 H 25 ) 3 , Al (C 2 H 5 ) (C 12 H 25 ) 2 , Al (iC 4 H 9 ) (C 12 H 25 ) 2 , Al (iC 4 H 9 ) 2 H, Al ( iC 4 H 9 ) 3 , (C 2 H 5 ) 2 AlCl, (iC 3 H 9 ) 2 AlCl, or (C 2 H 5 ) 3 Al 2 Cl 3 .
  • Such organoaluminum compounds may be introduced continuously into each reactor and may be introduced
  • the polymerization step may be carried out in a batch reactor or a continuous reactor, more specifically, may be performed in a continuous reactor.
  • the polymerization step may be carried out in the presence of an inert gas, such as arcon or nitrogen gas.
  • an inert gas such as arcon or nitrogen gas.
  • the inert gas for example, may be used alone or in combination with nitrogen gas or hydrogen gas.
  • the use of the inert gas serves to prevent the activity of the catalyst due to the inflow of moisture or impurities in the air, and may be added so that the mass ratio of the inert gas to the olefin monomer is about 1:10 to 1: 100. It is not limited to this.
  • the amount of inert gas is used too little, the catalyst composition reacts rapidly, making it difficult to manufacture an olefin polymer having a molecular weight and molecular weight distribution, and when the amount of the inert gas is added, the activity of the catalyst composition is sufficiently realized. It may not be.
  • the polymerization temperature when copolymerizing alpha olefin as a comonomer with the catalyst may range from about 130 ° C. to about 250 ° C., specifically from about 140 ° C. to about 200 ° C.
  • the polymerization pressure may be about 1 bar to about 150 bar, specifically about 1 bar to about 120 bar, more specifically about 10 bar to about 120 bar.
  • the olefin polymer prepared by the above production method may be surface treated with an inorganic material such as talc, Ca or Si based on a conventional method. Accordingly, the olefin polymer according to the present invention may further include a coating layer including an inorganic material such as talc, Ca or Si based on the surface thereof.
  • a catalyst composition including the transition metal compound of Formula 1 and the transition metal compound of Formula 2 is useful for preparing the olefin polymer.
  • the catalyst composition is the same as described in the method for preparing the olefin polymer.
  • the ketone (1.9g, 8.8mmol) was diethyl ether (Diethyl ether). After stirring for 12 hours, the mixture was stirred at room temperature for 12 hours, 10mL of water was added, hydrochloric acid (2N, 60mL) was added, stirred for 2 minutes, organic solvent was extracted, neutralized with NaHCO 3 aqueous solution, and the organic solvent was extracted. Water was removed with MgSO 4. A yellow oil (1.83 g, 60% yield) was obtained through a silica gel column.
  • ethylene (0.87 kg / h) was introduced into the autoclave reactor and maintained at 160 ° C. for 30 minutes or more in a continuous process at a pressure of 89 bar, followed by a copolymerization reaction to produce an ethylene-1 octene copolymer as an olefin polymer.
  • ethylene 0.87 kg / h
  • the remaining ethylene gas was removed and the polymer solution was dried in a vacuum oven for at least 12 hours, and then physical properties were measured.
  • LG Chem's ethylene-1 octene copolymer (product name: LC170) prepared using only one metallocene catalyst was prepared.
  • ethylene (0.87 kg / h) was introduced into the autoclave reactor and maintained at 160 ° C. for 30 minutes or more in a continuous process at a pressure of 89 bar, followed by a copolymerization reaction to produce an ethylene-1 octene copolymer as an olefin polymer.
  • ethylene 0.87 kg / h
  • the remaining ethylene gas was removed and the polymer solution was dried in a vacuum oven for at least 12 hours, and then physical properties were measured.
  • TREF was measured using PolymerChar's TREF machine and measured in the range of -20 ° C to 120 ° C using o-dichlorobenzene as a solvent.
  • GPC peak number Observed through gel permeation chromatography (GPC) analysis.
  • FIG. 1 to 4 are temperature rise elution fractionation (TREF) graphs of the olefin polymers prepared in Examples 1 and 2 and Comparative Examples 1 and 4, respectively, and FIG. 5 is a gel of the olefin polymers prepared in Example 1.
  • FIG. It is a graph showing the results of permeation chromatography (GPC) analysis.
  • Example 1 0.869 10 98525 2.34 0.5 (70%) 41.4 (18%) 89.0 (12%) 3
  • Example 2 0.867 24.5 64738 2.68 -6.7 (58%) 38.8 (22%) 87.6 (20%) 3
  • Example 3 0.871 6.3 85088 2.60 0.3 (45%) 41.0 (22%) 88.0 (33%) 3
  • Example 4 0.873 1.7 103827 2.51 -20.0 (44%) 30.1 (14%) 89.6 (42%) 3
  • Example 5 0.872 5.6 89932 2.51 -20.0 (46%) 24.9 (13%) 88.9 (41%) 3
  • One Comparative Example 1 0.871 27.9 62115 2.28 33.2 (100%) - - One Comparative Example 2 0.873 4.9 97635 2.31 3
  • the olefinic polymers of Examples 1 to 5 according to the present invention showed three peaks of Te1, Te2 and Te3 on the TREF within a density of 0.850 g / cc to 0.910 g / cc.
  • the polymers of Comparative Examples 1 to 5 only found one or two peaks within the same density range.
  • the olefin polymers of Examples 1 to 5 according to the present invention showed a single peak on GPC and had a molecular weight distribution (MWD) of 2.3 to 2.7, which showed a narrow molecular weight distribution on the same level as the polymers of Comparative Examples 1 to 5. It was.

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Abstract

La présente invention concerne un polymère à base d'oléfine présentant une excellente résistance mécanique et, en particulier, une résistance au choc considérablement améliorée représentée par un pic unique dans l'analyse par chromatographie de perméation de gel et ayant des Te1, Te2 et Te3, qui sont les températures d'élution du polymère à base d'oléfine, dans une plage de températures de -20 °C à 120 °C lors du fractionnement par température croissante d'élution.
PCT/KR2016/002938 2015-03-26 2016-03-23 Polymère à base d'oléfine WO2016153275A1 (fr)

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CN113795524A (zh) * 2019-09-30 2021-12-14 株式会社Lg化学 聚丙烯基复合材料
EP3967728A4 (fr) * 2019-09-30 2022-08-31 Lg Chem, Ltd. Matériau composite à base de polypropylène

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EP3950824A4 (fr) * 2019-09-30 2022-08-24 Lg Chem, Ltd. Matériau composite à base de polypropylène
EP3967728A4 (fr) * 2019-09-30 2022-08-31 Lg Chem, Ltd. Matériau composite à base de polypropylène
CN113795524B (zh) * 2019-09-30 2023-10-03 株式会社Lg化学 聚丙烯基复合材料

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