WO2019123028A1 - Complexe métal-ligand, composition catalytique comprenant celui-ci pour une polymérisation à base d'éthylène et procédé de préparation de polymère à base d'éthylène faisant appel à celle-ci - Google Patents

Complexe métal-ligand, composition catalytique comprenant celui-ci pour une polymérisation à base d'éthylène et procédé de préparation de polymère à base d'éthylène faisant appel à celle-ci Download PDF

Info

Publication number
WO2019123028A1
WO2019123028A1 PCT/IB2018/054644 IB2018054644W WO2019123028A1 WO 2019123028 A1 WO2019123028 A1 WO 2019123028A1 IB 2018054644 W IB2018054644 W IB 2018054644W WO 2019123028 A1 WO2019123028 A1 WO 2019123028A1
Authority
WO
WIPO (PCT)
Prior art keywords
ethylene
alkyl
polymerization
metal
added
Prior art date
Application number
PCT/IB2018/054644
Other languages
English (en)
Korean (ko)
Inventor
한용규
오연옥
김미지
장현민
Original Assignee
사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180070243A external-priority patent/KR102100142B1/ko
Application filed by 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 filed Critical 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디
Priority to CN201880082390.8A priority Critical patent/CN111491942B/zh
Priority to US16/956,513 priority patent/US11505563B2/en
Priority to CA3083892A priority patent/CA3083892A1/fr
Priority to RU2020123959A priority patent/RU2783262C2/ru
Priority to ES18892906T priority patent/ES2928602T3/es
Priority to EP18892906.1A priority patent/EP3730501B1/fr
Priority to JP2020530990A priority patent/JP7163389B2/ja
Publication of WO2019123028A1 publication Critical patent/WO2019123028A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • 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
    • C08F10/02—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
    • 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
    • C08F4/52—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 selected from boron, aluminium, gallium, indium, thallium or rare earths
    • 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
    • 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
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound

Definitions

  • the present invention relates to metal-ligand complexes, a catalyst composition for ethylenic polymerization comprising the same, and a process for producing an ethylene polymer using the same.
  • copolymers of ethylene and alpha-olefins or copolymers of ethylene and olefins-dienes generally employ the so-called Ziegler-Natta catalyst system consisting of the main catalyst component of titanium or vanadium compound and the cocatalyst component of alkylaluminum compound come.
  • European Patent Publication Nos. 320,762, 372,632 or 63-092621, Nos. 02-84405 and 03-2347 disclose that Cp 2 TiCl 2 , Cp 2 ZrCl 2 , Cp (Mw / Mn) in the range of 1.5 to 2.0, by polymerizing ethylene in a high activity by activating the metallocene compound with the promoter methyl aluminoxane in the presence of a catalyst such as 2 ZrMeCl, Cp 2 ZrMe 2 , ethylene (IndH 4 ) 2 ZrCl 2 , Polyethylene can be produced.
  • a catalyst such as 2 ZrMeCl, Cp 2 ZrMe 2 , ethylene (IndH 4 ) 2 ZrCl 2 , Polyethylene
  • the present invention provides a metal-ligand complex having a specific substituent and a catalyst composition for ethylenic polymerization containing the same, in order to solve the above problems.
  • the present invention also provides a process for producing an ethylene polymer using the catalyst composition for ethylene polymerization according to the present invention.
  • the present invention provides a metal-ligand complex in which solubility in an organic solvent, particularly an aliphatic hydrocarbon, is remarkably improved, and the metal-ligand complex of the present invention is represented by the following formula (1).
  • M is a transition metal of Group 4 on the Periodic Table
  • R 'and R &quot are independently from each other (C1-C20) alkyl
  • R 1 and R 2 are independently of each other halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy or halo (C 1 -C 20) alkyl;
  • R 3 is linear (C 8 -C 20) alkyl
  • R 3 in formula (1) may be linear (C 8 -C 20) alkyl.
  • R 3 is an alkyl, straight-chain (C8-C20), M is titanium, zirconium or hafnium, R 'and R''are independently (C1-C5 each other ) alkyl, R 1 and R 2 are the same halogen, (C1-C8) alkyl or (C1-C8) alkoxy each other, m may be an integer of 3.
  • Formula 1 according to one embodiment of the present invention may be represented by Formula 2 below.
  • M is titanium, zirconium or hafnium
  • R 'and R &quot are independently from each other (C1-C5) alkyl
  • R 1 and R 2 are, independently of each other, halogen, (C 1 -C 8) alkyl or (C 1 -C 8) alkoxy;
  • R 3 is linear (C 8 -C 12) alkyl.
  • a catalyst composition for ethylenic polymerization comprising the metal-ligand complex of the present invention and the cocatalyst of the present invention.
  • the cocatalyst according to an embodiment of the present invention may be an aluminum compound cocatalyst, a boron compound cocatalyst, or a mixture thereof, and may be used in an amount of 0.5 to 10000 moles per mole of the metal-ligand complex.
  • the present invention also provides a process for producing an ethylene polymer comprising polymerizing ethylene or an alpha-olefin with ethylene or an alpha-olefin in the presence of the ethylene-based polymerization catalyst composition of the present invention to produce an ethylene polymer.
  • the polymerization according to one embodiment of the present invention can be carried out at 170 to 250 ° C.
  • the metal-ligand complex according to an embodiment of the present invention can dramatically improve the solubility in a solvent by introducing a specific functional group having a controlled number of carbon atoms and form, thereby improving the polymerization process more efficiently.
  • the metal-ligand complex according to an embodiment of the present invention has excellent activity of the catalyst due to the introduction of a specific functional group at a specific position, and is capable of polymerization even at a high polymerization temperature, and does not lower the activity of the catalyst.
  • the metal-ligand complex according to an embodiment of the present invention has an advantage of being capable of easily polymerizing with high reactivity with olefins and capable of producing an ethylene polymer having a high molecular weight at a high polymerization temperature.
  • the metal-ligand complex according to one embodiment of the present invention and the catalyst composition containing the metal-ligand complex can be very usefully used in the production of an ethylene polymer having excellent physical properties.
  • substituents comprising "alkyl” and “alkoxy” as well as other “alkyl” moieties described herein include both straight-chain or branched forms and, unless otherwise stated, have 1 to 20 carbon atoms, preferably 1 to 15 , More preferably from 1 to 10 carbon atoms.
  • the "(C8-C20) alkyl" which includes at least one of a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom described in the present specification refers to an alkyl group having from 8 to 20 carbon atoms and includes a nitrogen atom, an oxygen atom, A nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom may be present between the carbon and carbon of the alkyl group, and may be present as a substituent of the alkyl group. Examples include, but are not limited to, alkoxy, aminoalkyl, secondary amines, and ether compounds.
  • Haloalkyl as described herein is one in which at least one hydrogen of the alkyl group is replaced by a halogen, and the alkyl group may contain one or more halogens.
  • the present invention relates to a process for producing a polyolefin resin, which has improved solubility, excellent thermal stability and high catalytic activity even at a high polymerization temperature by introducing a substituent having a controlled shape and carbon number at a specific position, And a metal-ligand complex represented by the general formula (1).
  • M is a transition metal of Group 4 on the Periodic Table
  • R 'and R &quot are independently from each other (C1-C20) alkyl
  • R 1 and R 2 are independently of each other halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy or halo (C 1 -C 20) alkyl;
  • R 3 is linear (C 8 -C 20) alkyl
  • the metal-ligand complex according to an embodiment of the present invention is represented by the above formula (1), and it can be produced by introducing straight chain (C8-C20) alkyl which is a substituent intentionally controlled to R 3 in formula
  • the solubility is remarkably improved, and the catalyst activity is extremely high even at a high polymerization temperature.
  • the metal-ligand complex according to an embodiment of the present invention is excellent in thermal stability, and can be produced at a high yield, with high polymerization activity and good polymerization reactivity with other olefins while maintaining high catalytic activity even at a high temperature.
  • Commercial viability is higher than that of metallocene and non-metallocene single point catalysts.
  • R 3 in formula (1) may be straight chain (C 8 -C 20) alkyl, more preferably straight chain (C 8 -C 12) alkyl.
  • R 3 is linear (C 8 -C 20) alkyl
  • M is titanium, zirconium or hafnium
  • R 1 and R 2 are the same halogen, (C1-C8) alkyl or (C1-C8) alkoxy each other
  • m may be an integer of 3.
  • the compound of formula (1) in order to improve solubility, catalytic activity and reactivity with olefins, may be represented by the following formula (2).
  • M is titanium, zirconium or hafnium
  • R 'and R &quot are independently from each other (C1-C5) alkyl
  • R 1 and R 2 are, independently of each other, halogen, (C 1 -C 8) alkyl or (C 1 -C 8) alkoxy;
  • R 3 is linear (C 8 -C 12) alkyl.
  • R 3 in formula (2) may be linear (C 8 -C 12) alkyl, more preferably R 3 may be n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
  • the metal-ligand complex according to an embodiment of the present invention may be a compound selected from the following structures, but is not limited thereto.
  • M is titanium, zirconium or hafnium; PrO-, BuO-, PentylO-, HexylO-, HeptylO-, OctylO-, Pr-, Butyl-, Pentyl-, Hexyl-, Heptyl- and Octyl- Includes both straight chain and branched chain.
  • the present invention also provides a catalyst composition for ethylenic polymerization comprising a metal-ligand complex of the present invention and a cocatalyst.
  • the promoter according to one embodiment of the present invention may be a boron compound promoter, an aluminum compound promoter, and a mixture thereof.
  • the cocatalyst according to an embodiment of the present invention may be contained in a molar ratio of 0.5 to 10000 to 1 mole of the metal-ligand complex.
  • the boron compound which can be used as a cocatalyst in the present invention is a boron compound which is known in U.S. Patent No. 5,198,401, and can be specifically selected from the compounds represented by the following formulas (11) to (13).
  • B is a boron atom
  • R 21 is a phenyl group, and the phenyl group is a fluorine atom, (C1-C20) alkyl group, substituted by fluorine atoms (C1-C20) alkyl, (C1-C20) substituted with an alkoxy group or a fluorine atom, (C1-C20 ) Alkoxy group; < / RTI &gt
  • R 22 is a (C 5 -C 7) aromatic radical or a (C 1 -C 20) alkyl (C 6 -C 20) aryl radical or a (C 6 -C 20) aryl (C 1 -C 20) alkyl radical such as triphenylmethylium, Radical
  • Z is a nitrogen or phosphorus atom
  • R 23 is an (Cl-C20) alkyl radical or an anilinium radical substituted with two (C1-C10) alkyl groups
  • boron-based co-catalysts include trityl tetrakis (pentafluorophenyl) borate, tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) (2,3,4,5-tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) Tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetra (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate or tetrakis (triphenyl
  • these compounds include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, tri (Pentafluorophenyl) borate, triphenylmethylniniumtetrakis (3,5-bistrifluoromethylphenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium (Pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis , N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
  • An example of an aluminum compound that can be used as a cocatalyst in a catalyst composition according to an embodiment of the present invention is an aluminoxane compound of Formula 14 or 15, an organoaluminum compound of Formula 16 or an organoaluminum alkyloxide of Formula 17 or Formula 18 Or an organoaluminum aryloxide compound.
  • R 26 is Al (OR 27 ) 2
  • R 24 is a (C 1 -C 20) alkyl group, preferably a methyl group or an isobutyl group, m and q are each independently an integer of 5 to 20; R 25 and R 26 independently from each other are a (C 1 -C 20) alkyl group; E is a hydrogen atom or a halogen atom; r is an integer from 1 to 3; R 27 is (C 1 -C 20) alkyl group or (C 6 -C 30) aryl group.
  • the aluminum compound that can be used include aluminoxane compounds such as methyl aluminoxane, modified methyl aluminoxane, and tetraisobutyl aluminoxane;
  • organoaluminum compound include trialkylaluminum including trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum;
  • Dialkyl aluminum chlorides including dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride, and dihexyl aluminum chloride;
  • Alkylaluminum dichlorides including methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, and hexylaluminum dichloride;
  • Dialkylaluminum hydrides including dimethyl
  • the preferred range of the ratio between the metal-ligand complex of the present invention and the cocatalyst is that the aluminum compound cocatalyst is a transition metal (M) :
  • Aluminum atom (Al) may be from 1:50 to 1: 5,000 based on the molar ratio.
  • a process for preparing an ethylene polymer using the catalyst composition for ethylenic polymerization comprising reacting the metal-ligand complex, the cocatalyst, and the ethylene or, if necessary, the vinyl polymer Can be carried out by contacting the comonomer.
  • the catalyst and the catalyst component which are metal-ligand complexes, may be separately introduced into the reactor or may be preliminarily mixed with each other and introduced into the reactor. There is no particular limitation on the mixing conditions such as the order of introduction, temperature or concentration.
  • Preferred organic solvents that may be used in the above process are C3-C20 hydrocarbons. Specific examples thereof include butane, isobutane, pentane, hexane, heptane, octane, isooctane, nonane, decane, dodecane, cyclohexane, methylcyclohexane , Benzene, toluene, xylene, and the like.
  • C3-C18? -Olefins may be used as comonomers together with ethylene, preferably propylene, 1-butene, Pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 1-octadecene. More preferably, 1-butene, 1-hexene, 1-octene, or 1-decene and ethylene can be copolymerized.
  • the preferable ethylene pressure and the polymerization reaction temperature may be 1 to 1000 atm for pressure, and more preferably 10 to 150 atm. It is also effective that the polymerization reaction is carried out at a temperature of 170 to 250 ° C, preferably 180 to 200 ° C.
  • the copolymer prepared according to the process of the present invention usually contains not less than 50% by weight of ethylene, preferably contains not less than 60% by weight of ethylene, more preferably contains from 60 to 99% by weight of ethylene do.
  • the linear low density polyethylene (LLDPE) prepared by using C4 to C10 alpha -olefin as the comonomer has a density region of 0.940 g / cc or less and an ultra low density polyethylene (VLDPE or ULDPE) or an olefin elastomeric region.
  • VLDPE or ULDPE ultra low density polyethylene
  • hydrogen may be used as a molecular weight modifier and has a weight average molecular weight (Mw) usually in the range of 80,000 to 500,000.
  • the ethylene-propylene-diene copolymer has an ethylene content of 30 to 80% by weight, a propylene content of 20 to 70% , And an ethylene-propylene-diene copolymer having a diene content of 0 to 15% by weight can be prepared.
  • the diene monomer which can be used in the present invention has two or more double bonds.
  • Examples thereof include 1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6- Octadiene, 1,7-octadiene, 1,7-nonadiene, 1,8-nonadiene, 1,8-decadiene, 1,9-decadiene, 1,12-tetradecadiene, 1 Methyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3-ethyl-1,4-hexadiene, 3-ethyl- , 3,3-dimethyl-1,4-hexadiene, 3,3-dimethyl-1,5-hexadiene, 5-vinyl-2-norbornene, 5-norbornadiene, 7-ethyl-2,5-norbornadiene, 7-propyl-2,5-norbornadiene, Norbornadiene, 7-hexyl-2,5-norbornadiene, 7,7-dimethyl
  • the preferred reactor pressure and temperature are from 1 to 1000 atm for pressure, more preferably from 5 to 100 atm. It is also effective to carry out the polymerization reaction at a temperature of 170 to 250 ° C, preferably 180 to 200 ° C.
  • the ethylene content is 30 to 80 wt%
  • the olefin content is 20 to 70 wt%
  • the diene content is 0 to 15 wt% have.
  • the molecular weight of the copolymer is lowered when the content of propylene is increased.
  • the ethylene-propylene-diene copolymer according to the present invention It was possible to produce a product having a relatively high molecular weight without decreasing the molecular weight, even if it increased to 50%.
  • the catalyst composition presented in the present invention is present in a uniform form in a polymerization reactor, it is preferable to apply to a solution polymerization process carried out at a temperature above the melting point of the polymer.
  • it may also be used for slurry polymerization or gas-phase polymerization in the form of a non-uniform catalyst composition obtained by supporting a metal-ligand complex catalyst and a cocatalyst on a porous metal oxide support as disclosed in U.S. Patent No. 4,752,597.
  • Cyclohexane a polymerization solvent
  • the polymerized polymer was analyzed by the method described below.
  • MI Melt Flow Index
  • the solvent used herein was 1,2,4-trichlorobenzene, and the measurement temperature was 120 ⁇ ⁇ .
  • Catalyst WC04 was prepared in the same manner as in Example 1, except that ligand WC04L was used instead of ligand WC03L in Example 1.
  • Catalyst WC01 was prepared in the same manner as in Example 1 except that ligand WC01L was used instead of ligand WC03L in Example 1.
  • Catalyst WC02 was prepared in the same manner as in Example 1, except that ligand WC02L was used instead of ligand WC03L in Example 1.
  • Catalyst WB02 was prepared in the same manner as in Example 1 except that ligand WB02L was used instead of ligand WC03L in Example 1.
  • Ligand WD01L was prepared in the same manner as in Example 1 except that 2-Iodo-4-octylphenol (Compound 3-1) was replaced with 2-Iodo-4-n-butylphenol.
  • Catalyst WD01 was prepared in the same manner as in Example 1 except that ligand WD01L was used instead of ligand WC03L in Example 1.
  • Ligand WD02L was prepared in the same manner as in Example 1 except that 2-Iodo-4-octylphenol (Compound 3-1) was replaced with 2-Iodo-4-n-hexylphenol.
  • Catalyst WD02 was prepared in the same manner as in Example 1 except that the ligand WD02L was used instead of the ligand WC03L in Example 1.
  • the polymerization was carried out in a temperature-controlled continuous polymerization reactor equipped with a mechanical stirrer.
  • a methyl cyclohexane solvent, 1-octene and ethylene monomer were fed to a 1.0 L continuously stirred reactor preheated at a temperature of 130 to 200 ° C at a pressure of 40 bar.
  • WC03 Example 1
  • TTB Tetrakis-pentafluorophenyl Borate
  • TiBAO Tetraisobutyl aluminoxane
  • Methylcyclohexane as a reaction solvent was injected into the reactor in an amount of 5 kg per hour, and the reactor was injected into the reactor at a C2 / MCH ratio of 10 for a residence time of about 8 minutes and an ethylene amount of about 400 to 600 g per hour .
  • the polymerization was carried out at a relatively high temperature of 180 ° C., 190 ° C. and 200 ° C., and the amount of the catalyst was supplied to the reactor while adjusting the feed temperature and the temperature difference between the reactor temperature and the reactor. After the pressure was reduced to 3 bar at the rear end, it was sent to a solvent separator, and most of the solvent was removed by a solvent separation process.
  • Example 3 The polymerization was carried out in the same manner as in Example 3, except that WCO4 synthesized in Example 2 was used as a catalyst. The maximum temperature reached 158 ⁇ for a reaction time of 3 minutes, and 77 g of a polymer polymer was obtained. Polymerization reaction conditions and polymerization results are shown in Table 1 below.
  • Example 3 The procedure of Example 3 was repeated except that WB02 synthesized in Comparative Example 3 was used as a precatalyst.
  • the polymerization reaction conditions and polymerization results are shown in Table 2 below.
  • Example 3 The procedure of Example 3 was repeated except that WC01 synthesized in Comparative Example 1 was used as a precatalyst.
  • the polymerization reaction conditions and polymerization results are shown in Table 2 below.
  • Example 3 The procedure of Example 3 was repeated except that WC02 synthesized in Comparative Example 2 was used as a precatalyst.
  • the polymerization reaction conditions and polymerization results are shown in Table 2 below.
  • Example 3 The procedure of Example 3 was repeated except that WD01 synthesized in Comparative Example 4 was used as a precatalyst.
  • the polymerization reaction conditions and polymerization results are shown in Table 2 below.
  • Example 3 The procedure of Example 3 was repeated except that WD02 synthesized in Comparative Example 5 was used as a precatalyst.
  • the polymerization reaction conditions and polymerization results are shown in Table 2 below.
  • the catalysts of the present invention (WC03 and WC04), in which a controlled number of carbon atoms and a specific type of substituent were introduced into R 3 of Formula 1 according to an embodiment of the present invention
  • the reactivity with the active and comonomers is remarkably superior to that of the conventional WB02, WC01, WC02, WD01 and WD02, which are comparative examples.
  • the prepolymers of the present invention can produce copolymers of ethylene and 1-octene with higher molecular weights than the precursors of the present invention.
  • the copolymer prepared by copolymerizing ethylene and 1-octene at 180 DEG C had a molecular weight of 37,000 g / mole and 95,000 g / mole, respectively, while the copolymer of WC03 and WC04 of the present invention
  • the molecular weight of the copolymer produced in one polymerization is 131,000 g / mole and 135,000 g / mole, respectively, and a copolymer having a high molecular weight is obtained in comparison with the comparative example.
  • the catalysts WB02 and WC02 of the comparative examples produce copolymers having molecular weights of 69,000 g / mole and 67,000 g / mole, respectively, (WC03 and WC04) have a high molecular weight of 100,000 g / mole or more.
  • the WC03 of the present invention exhibits excellent properties in the production of a product having a low density because of higher catalytic activity and comonomer reactivity at a high polymerization temperature of 200 DEG C .
  • the WDO and WDO2 catalysts exhibiting the catalytic activities exhibit values of 2.2 and 2.3 at 200 ° C, respectively, while the WC03 of the present invention has a relatively low catalyst consumption of 1.7, indicating that the catalytic activity is excellent .
  • the density of the polymer obtained at a polymerization temperature of 200 ° C using WD01 and WD02 as the precatalysts was 0.901 and 0.900 g / cm 3 , respectively, while the polymer obtained from the same polymerization conditions using WC03 of the present invention as a precursor And 0.8895 g / cm < 3 >, respectively.
  • the metal-ligand complex according to an embodiment of the present invention can dramatically improve the solubility in a solvent by introducing a specific functional group having a controlled number of carbon atoms and form, thereby improving the polymerization process more efficiently.
  • the metal-ligand complex according to an embodiment of the present invention has excellent activity of the catalyst due to the introduction of a specific functional group at a specific position, and is capable of polymerization even at a high polymerization temperature, and does not lower the activity of the catalyst.
  • the metal-ligand complex according to an embodiment of the present invention has an advantage of being capable of easily polymerizing with high reactivity with olefins and capable of producing an ethylene polymer having a high molecular weight at a high polymerization temperature.
  • the metal-ligand complex according to one embodiment of the present invention and the catalyst composition containing the metal-ligand complex can be very usefully used in the production of an ethylene polymer having excellent physical properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La présente invention concerne un complexe métal-ligand, une composition catalytique comprenant celui-ci pour une polymérisation à base d'éthylène et un procédé de préparation de polymère à base d'éthylène faisant appel à celle-ci. Le complexe métal-ligand selon la présente invention dans lequel un groupe fonctionnel particulier est introduit à un emplacement particulier présente une solubilité élevée et une activité catalytique supérieure, et ainsi la composition catalytique comprenant celui-ci pour une polymérisation à base d'éthylène peut produire un polymère à base d'éthylène ayant d'excellentes propriétés physiques.
PCT/IB2018/054644 2017-12-21 2018-06-25 Complexe métal-ligand, composition catalytique comprenant celui-ci pour une polymérisation à base d'éthylène et procédé de préparation de polymère à base d'éthylène faisant appel à celle-ci WO2019123028A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CN201880082390.8A CN111491942B (zh) 2017-12-21 2018-06-25 金属-配体配合物、催化剂组合物及利用其的制造方法
US16/956,513 US11505563B2 (en) 2017-12-21 2018-06-25 Metal-ligand complex, catalyst composition for ethylene-based polymerization including the same, and method for preparing ethylene-based polymer using the same
CA3083892A CA3083892A1 (fr) 2017-12-21 2018-06-25 Complexe metal-ligand, composition catalytique comprenant celui-ci pour une polymerisation a base d'ethylene et procede de preparation de polymere a base d'ethylene faisant appela celle-ci
RU2020123959A RU2783262C2 (ru) 2017-12-21 2018-06-25 Металлолигандный комплекс, каталитическая композиция для полимеризации на основе этилена, включающая в себя указанный комплекс, и способ получения полимера на основе этилена с использованием указанного комплекса
ES18892906T ES2928602T3 (es) 2017-12-21 2018-06-25 Complejo de metal-ligando, composición catalizadora que lo comprende para la polimerización a base de etileno, y método para preparar un polímero a base de etileno que los utiliza
EP18892906.1A EP3730501B1 (fr) 2017-12-21 2018-06-25 Complexe métal-ligand, composition catalytique comprenant celui-ci pour une polymérisation à base d'éthylène et procédé de préparation de polymère à base d'éthylène faisant appel à celle-ci
JP2020530990A JP7163389B2 (ja) 2017-12-21 2018-06-25 金属－リガンド錯体、これを含むエチレン系重合用の触媒組成物およびこれを用いたエチレン系重合体の製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20170177345 2017-12-21
KR10-2017-0177345 2017-12-21
KR1020180070243A KR102100142B1 (ko) 2017-12-21 2018-06-19 금속-리간드 착체, 이를 포함하는 에틸렌계 중합용 촉매 조성물 및 이를 이용한 에틸렌계 중합체의 제조방법
KR10-2018-0070243 2018-06-19

Publications (1)

Publication Number Publication Date
WO2019123028A1 true WO2019123028A1 (fr) 2019-06-27

Family

ID=66993166

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2018/054644 WO2019123028A1 (fr) 2017-12-21 2018-06-25 Complexe métal-ligand, composition catalytique comprenant celui-ci pour une polymérisation à base d'éthylène et procédé de préparation de polymère à base d'éthylène faisant appel à celle-ci

Country Status (1)

Country Link
WO (1) WO2019123028A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022173905A1 (fr) * 2021-02-15 2022-08-18 Dow Global Technologies Llc Catalyseurs de polymérisation de biphénylphénol

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3594330A (en) 1967-08-31 1971-07-20 Solvay Process for the polymerization of alpha-olefins
US3676415A (en) 1968-06-27 1972-07-11 Hoechst Ag Process for polymerizing {60 -olefins
JPS6392621A (ja) 1986-10-08 1988-04-23 Mitsubishi Petrochem Co Ltd エチレン共重合体の製造法
US4752597A (en) 1985-12-12 1988-06-21 Exxon Chemical Patents Inc. New polymerization catalyst
EP0320762A2 (fr) 1987-12-18 1989-06-21 Hoechst Aktiengesellschaft Procédé pour la préparation d'un composé métallocène chiral stéréorigide
JPH0284405A (ja) 1988-09-20 1990-03-26 Mitsubishi Petrochem Co Ltd エチレン重合体の製造法
EP0372632A1 (fr) 1988-12-02 1990-06-13 Shell Internationale Researchmaatschappij B.V. Procédé de conversion d'hydrocarbures
JPH032347A (ja) 1989-02-22 1991-01-08 Sumitomo Electric Ind Ltd 窒素含有サーメット合金
US5198401A (en) 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
KR20130100140A (ko) * 2010-08-25 2013-09-09 다우 글로벌 테크놀로지스 엘엘씨 중합성 올레핀의 중합 방법 및 그를 위한 촉매
KR20140112488A (ko) * 2011-12-29 2014-09-23 다우 글로벌 테크놀로지스 엘엘씨 저분자량 에틸렌- 및 α-올레핀-계 물질의 제조 방법
KR20150100694A (ko) * 2012-12-27 2015-09-02 다우 글로벌 테크놀로지스 엘엘씨 올레핀 중합을 위한 촉매계
KR20150100844A (ko) * 2012-12-27 2015-09-02 다우 글로벌 테크놀로지스 엘엘씨 에틸렌계 중합체
KR20150103082A (ko) * 2012-12-27 2015-09-09 다우 글로벌 테크놀로지스 엘엘씨 에틸렌계 중합체를 제조하기 위한 중합 방법

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3594330A (en) 1967-08-31 1971-07-20 Solvay Process for the polymerization of alpha-olefins
US3676415A (en) 1968-06-27 1972-07-11 Hoechst Ag Process for polymerizing {60 -olefins
US4752597A (en) 1985-12-12 1988-06-21 Exxon Chemical Patents Inc. New polymerization catalyst
JPS6392621A (ja) 1986-10-08 1988-04-23 Mitsubishi Petrochem Co Ltd エチレン共重合体の製造法
US5198401A (en) 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
EP0320762A2 (fr) 1987-12-18 1989-06-21 Hoechst Aktiengesellschaft Procédé pour la préparation d'un composé métallocène chiral stéréorigide
JPH0284405A (ja) 1988-09-20 1990-03-26 Mitsubishi Petrochem Co Ltd エチレン重合体の製造法
EP0372632A1 (fr) 1988-12-02 1990-06-13 Shell Internationale Researchmaatschappij B.V. Procédé de conversion d'hydrocarbures
JPH032347A (ja) 1989-02-22 1991-01-08 Sumitomo Electric Ind Ltd 窒素含有サーメット合金
KR20130100140A (ko) * 2010-08-25 2013-09-09 다우 글로벌 테크놀로지스 엘엘씨 중합성 올레핀의 중합 방법 및 그를 위한 촉매
KR20140112488A (ko) * 2011-12-29 2014-09-23 다우 글로벌 테크놀로지스 엘엘씨 저분자량 에틸렌- 및 α-올레핀-계 물질의 제조 방법
KR20150100694A (ko) * 2012-12-27 2015-09-02 다우 글로벌 테크놀로지스 엘엘씨 올레핀 중합을 위한 촉매계
KR20150100844A (ko) * 2012-12-27 2015-09-02 다우 글로벌 테크놀로지스 엘엘씨 에틸렌계 중합체
KR20150103082A (ko) * 2012-12-27 2015-09-09 다우 글로벌 테크놀로지스 엘엘씨 에틸렌계 중합체를 제조하기 위한 중합 방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3730501A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022173905A1 (fr) * 2021-02-15 2022-08-18 Dow Global Technologies Llc Catalyseurs de polymérisation de biphénylphénol

Similar Documents

Publication Publication Date Title
WO2017188602A1 (fr) Catalyseur hybride de type métallocène supporté et résine polyoléfinique présentant une excellente aptitude au traitement et l'utilisant
WO2015046932A1 (fr) Polymère à base d'oléfine
WO2019125050A1 (fr) Polymère oléfinique
WO2017099491A1 (fr) Polymère à base d'oléfine
WO2020171631A1 (fr) Polymère à base d'oléfine
WO2017176074A1 (fr) Résine à base d'un copolymère de propylène-diène présentant une remarquable tension de fusion
WO2012169812A2 (fr) Procédé de préparation d'un copolymère éthylène-α-oléfine-diène
WO2015046930A1 (fr) Composition catalytique et procédé de préparation d'un polymère contenant cette composition
WO2019038605A1 (fr) Nouveau composé de métal de transition, composition de catalyseur le contenant, et procédé de préparation d'homopolymère ou de copolymère d'éthylène et d'alpha-oléfine l'utilisant
WO2020101373A1 (fr) Catalyseur supporté pour la polymérisation de propylène et procédé de production de résine de polypropylène l'utilisant
WO2017003261A1 (fr) Composé de métal de transition et composition de catalyseur le contenant
WO2019093630A1 (fr) Procédé de préparation d'une résine de polypropylène à haute résistance à l'état fondu
WO2021111282A1 (fr) Composé de métal de transition, composition de catalyseur le comprenant, et procédé de production de polymère d'oléfine à l'aide de la composition de catalyseur
WO2019132471A1 (fr) Polymère oléfinique
WO2023191519A1 (fr) Composé de métal de transition pour catalyseur de polymérisation d'oléfine, catalyseur de polymérisation d'oléfine le comprenant et polyoléfine polymérisée l'utilisant
WO2019123028A1 (fr) Complexe métal-ligand, composition catalytique comprenant celui-ci pour une polymérisation à base d'éthylène et procédé de préparation de polymère à base d'éthylène faisant appel à celle-ci
WO2018097468A1 (fr) Catalyseur de polyoléfine et procédé de préparation d'une polyoléfine l'utilisant
WO2019234637A1 (fr) Mélange de polymère d'éthylène, son procédé de préparation et article moulé l'utilisant
WO2017003262A1 (fr) Composé de métal de transition et composition de catalyseur le contenant
WO2018127772A1 (fr) Nouveau composé de métal de transition, composition de catalyseur contenant celui-ci, procédé de production d'homopolymère d'éthylène ou de copolymère d'éthylène et d'une alpha-oléfine l'utilisant
WO2022071744A1 (fr) Copolymère d'éthylène/hex-1-ène présentant d'excellentes propriétés de constructibilité et d'aptitude au traitement
WO2021066486A1 (fr) Polymère à base d'oléfine
WO2018122693A1 (fr) NOUVEAU COMPOSÉ À BASE DE MÉTAL DE TRANSITION DE CYCLOPENTA[B]THIOPHÉNYL, COMPOSITION DE CATALYSEUR À BASE DE MÉTAL DE TRANSITION, PROCÉDÉ DE PRÉPARATION D'HOMOPOLYMÈRES OU DE COPOLYMÈRES D'ÉTHYLÈNE ET DE α-OLÉFINES L'UTILISANT
WO2021020778A1 (fr) Composé de métal de transition pour catalyseur de polymérisation d'oléfine, catalyseur de polymérisation d'oléfine le comprenant, et polyoléfine polymérisée à l'aide de celui-ci
WO2020122371A1 (fr) Polyoléfine et son procédé de préparation

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18892906

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 3083892

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 2020530990

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2018892906

Country of ref document: EP

Effective date: 20200721