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WO2019168249A1 - Ligand, catalyseur d'oligomérisation le comprenant, et procédé de production d'oligomère d'éthylène à l'aide d'un catalyseur d'oligomérisation - Google Patents

Ligand, catalyseur d'oligomérisation le comprenant, et procédé de production d'oligomère d'éthylène à l'aide d'un catalyseur d'oligomérisation Download PDF

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Publication number
WO2019168249A1
WO2019168249A1 PCT/KR2018/012025 KR2018012025W WO2019168249A1 WO 2019168249 A1 WO2019168249 A1 WO 2019168249A1 KR 2018012025 W KR2018012025 W KR 2018012025W WO 2019168249 A1 WO2019168249 A1 WO 2019168249A1
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WO
WIPO (PCT)
Prior art keywords
ligand
ethylene
formula
catalyst
oligomerization catalyst
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PCT/KR2018/012025
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English (en)
Korean (ko)
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WO2019168249A8 (fr
Inventor
이호성
조용남
Original Assignee
에스케이이노베이션 주식회사
에스케이종합화학 주식회사
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Priority claimed from KR1020180119906A external-priority patent/KR102605188B1/ko
Application filed by 에스케이이노베이션 주식회사, 에스케이종합화학 주식회사 filed Critical 에스케이이노베이션 주식회사
Priority to US16/771,857 priority Critical patent/US11224870B2/en
Priority to JP2020512872A priority patent/JP7210552B2/ja
Priority to CN201880057196.4A priority patent/CN111094308B/zh
Priority to EP18907972.6A priority patent/EP3760634A4/fr
Publication of WO2019168249A1 publication Critical patent/WO2019168249A1/fr
Publication of WO2019168249A8 publication Critical patent/WO2019168249A8/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention is a ligand for preparing a highly active and highly selective ethylene oligomerization catalyst for use in oligomerization reactions such as trimerization or tetramerization of ethylene, oligomerization catalyst comprising the same and 1-hexene or 1 using the same It relates to a production method of octene.
  • Oligomers in particular 1-hexene and 1-octene, are important commercial raw materials widely used in the polymerization process as monomers or comonomers for the production of linear low density polyethylene, obtained by purifying products produced by oligomerization of ethylene. .
  • the existing ethylene oligomerization reaction has been an inefficient aspect of producing a considerable amount of butenes, higher oligomers and polyethylene together with 1-hexene and 1-octene.
  • This conventional oligomerization technique of ethylene generally produces a variety of ⁇ -olefins depending on the Schulze-Flory or Poisson product distribution, thus limiting the yield of the desired product.
  • WO 02/04119 discloses a chromium-based catalyst using a ligand of the general formula (R 1 ) (R 2 ) XYX (R 3 ) (R 4 ) as an ethylene trimerization catalyst, wherein X is phosphorus, arsenic, or antimony, Y is a linking group such as -N (R 5 )-, and at least one of R 1 , R 2 , R 3 and R 4 has a polar or electron-donating substituent.
  • Korean Patent Publication No. 2006-0002741 uses a PNP ligand containing a nonpolar substituent on the ortho position of a phenyl ring attached to phosphorus such as (o-ethylphenyl) 2 PN (Me) P (o-ethylphenyl) 2. It is known that excellent ethylene trimerization activity and selectivity are indeed possible.
  • WO 04/056479 discloses that the selectivity is improved by tetramerization of ethylene by a chromium-based catalyst containing a PNP ligand in which a phenyl ring attached to phosphorus is omitted. It is known, and (phenyl) 2 PN (isopropyl) P (phenyl) 2 and the like are disclosed as examples of the hetero atom ligands used in the tetramerization catalyst for these ethylene tetramerization.
  • This prior art has a selectivity of greater than 70% by mass of chromium-based catalysts containing heteroatom ligands having nitrogen and phosphorus as heteroatoms, tetramers of ethylene without polar substituents to hydrocarbyl or heterohydrocarbyl groups bonded to the phosphorus atom. It was disclosed that 1-octene can be produced.
  • the prior art is specifically related to the structure of a ligand containing a hetero atom in which form can be highly selectively tetramerized ethylene to produce 1-octene or ethylene trimerized to produce 1-hexene.
  • PNPs such as (R 1 ) (R 2 ) P- (R 5 ) NP (R 3 ) (R 4 ) as ligands with 1-octene selectivity of about 70% by mass. Only the structure of the type skeleton is given, and the types of substituents that can be substituted in the heteroatom ligands are also limited.
  • the tetramerization catalyst system is inevitably interrupted due to a decrease in catalytic activity resulting in a decrease in the production and selectivity of olefins, especially 1-octene, and the formation of by-products resulting in clogging and fouling. This causes serious problems in the olefin polymerization process.
  • an oligomerization catalyst having a structure capable of producing 1-hexene or 1-octene by oligomerizing high activity and high selectivity without degrading the olefin oligomerization catalytic activity at high temperature.
  • the present invention provides a novel ligand capable of oligomerizing ethylene at high temperatures and at high temperatures for use in oligomerization of olefins, specifically trimerization or tetramerization of ethylene. It is represented by Formula (1).
  • R 1 is hydrocarbyl
  • R 2 and R 3 are each independently hydrocarbyl
  • p and q are each independently integers of 0 to 5;
  • n and n are each independently integers of 0 to 5, where 1 ⁇ m + n ⁇ 10.
  • the ligand may be represented by the following formula (2).
  • R 1 , m and n are the same as defined in Formula 1.
  • the ligand may be represented by the following formula (3), (4) or (5).
  • R 1 , R 2 , R 3 , p, and q are the same as defined in Formula 1 above.
  • R 1 may be C1-C7 alkyl or C6-C12 aryl.
  • the present invention also provides an ethylene oligomerization catalyst comprising the ligand of Formula 1 and a transition metal.
  • the oligomerization catalyst may be mononuclear or dinuclear.
  • the transition metal is not particularly limited, but may be a Group 4, Group 5 or Group 6 transition metal.
  • the transition metal may be chromium, molybdenum, tungsten, titanium, tantalum, vanadium or zirconium.
  • the transition metal may be chromium.
  • the present invention provides a method for producing an ethylene oligomer using a catalyst composition comprising the ethylene oligomerization catalyst, it is possible to prepare an ethylene oligomer by contacting the ethylene oligomerization catalyst composition with ethylene.
  • the catalyst composition may further include a promoter.
  • the promoter may be an organoaluminum compound, an organic boron compound, an organic salt, or a mixture thereof, but is not limited thereto.
  • the organoaluminum compound is an aluminoxane compound, AlR 3 (wherein R is independently C 1 -C 12 alkyl, C 6 -C 20 aryl, C 2 -C 10 al Kenyl, C 2 -C 10 alkynyl, C 1 -C 12 alkoxy or halogen) or LiAlH 4 , and the like, and the promoter may specifically be methylaluminoxane (MAO), modified methylaluminoxane (mMAO), Ethylaluminoxane (EAO), tetraisobutylaluminoxane (TIBAO), isobutylaluminoxane (IBAO), trimethylaluminum (TMA), triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-octyl It may be aluminum, methylaluminum dich
  • the ethylene oligomer may be 1-hexene, 1-octene or a mixture thereof.
  • an aliphatic hydrocarbon may be used as a reaction solvent.
  • the aliphatic hydrocarbon is hexane, heptane, octane, nonene, decane, undecane, dodecane, tetradecane, 2,2-dimethylpentane, 2,3 -Dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2,2,4-trimethylpentane, 2,3,4-trimethylpentane, 2-methylhexane, 3-methylhexane, 2,2- Dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,4-dimethylhexane, 2-methylheptane, 4-methylheptane, cyclohexane, methylcyclohexane, ethylcyclohexane, isopropylcyclohexane, It may be one or
  • At least one fluorine is substituted for phenyl bonded to a phosphorus atom in bis (diphenylphosphino) ethene, and one carbon atom is substituted with a substituted or unsubstituted hydrocarbyl group other than hydrogen.
  • It contains the ligand of the formula (1) of the asymmetric form is excellent in catalytic activity and selectivity even at high temperature during ethylene oligomerization.
  • the oligomerization catalyst of the present invention is excellent in catalytic activity even at high temperatures, and does not require fouling and clogging caused by polymers, which are by-products during mass production of oligomers.
  • the oligomer manufacturing method of the present invention can produce the oligomer with high activity and high selectivity even at high temperature, and does not occur fouling and clogging, thereby making it possible to prepare the olefin in a very efficient process.
  • hydrocarbyl or “heterohydrocarbyl” refers to a radical having one bonding position derived from a hydrocarbon or heterohydrocarbon, and “hetero” means that the carbon is selected from O, S and N atoms. It means substituted by one or more atoms.
  • substituted refers to a group or moiety having one or more substituents attached to the structural backbone of the group or moiety.
  • Alkyl as used herein is a monovalent straight or pulverized saturated hydrocarbon radical consisting solely of carbon and hydrogen atoms and is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, nonyl and the like. It includes, but is not limited to.
  • the alkyl radicals described in this invention have 1 to 10 carbon atoms, preferably 1 to 7, more preferably 1 to 5 carbon atoms.
  • aryl described herein is a monovalent organic radical derived from an aromatic hydrocarbon by one hydrogen removal, each ring containing, for example, 4 to 7, preferably 5 or 6 ring atoms It includes a single or fused ring system, and includes a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like.
  • the aryl radicals described herein also have 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms.
  • ethylene oligomerization refers to small polymerization of ethylene and is called trimerization and tetramerization depending on the number of ethylene polymerized.
  • trimerization and tetramerization depending on the number of ethylene polymerized.
  • LLDPE linear low density polyethylene
  • oligomerization catalyst is defined to include both the form of the ligand and the transition metal complex and the form of the ligand and the transition metal composition.
  • oligomerization catalyst composition is defined as further comprising a cocatalyst or an additive in the above “oligomerization catalyst”.
  • the present invention provides a ligand for preparing an oligomerization catalyst that maintains high activity even at a high temperature unlike a conventional catalyst, the ligand of the present invention is represented by the following formula (1).
  • R 1 is substituted or unsubstituted hydrocarbyl
  • R 2 and R 3 are each independently hydrocarbyl
  • p and q are each independently integers of 0 to 5;
  • n and n are each independently integers of 0 to 5, where 1 ⁇ m + n ⁇ 10.
  • the ligand of the present invention is substituted with at least one fluorine in phenyl bonded to a phosphorus atom in bis (diphenylphosphino) ethene, and substituted in one carbon atom other than hydrogen or Asymmetrically substituted ligand of Formula 1 in which an unsubstituted hydrocarbyl group is substituted. Due to the ligand of Formula 1 including at least one fluorine-substituted phenyl, it has excellent catalytic activity and selectivity even at high temperature during ethylene oligomerization. Has an advantage.
  • the ligand may be represented by the following formula (2).
  • R 1 , m and n are the same as defined in Formula 1.
  • the ligand may be represented by the following formula (3), (4) or (5).
  • R 1 , R 2 , R 3 , p, and q are the same as defined in Formula 1 above.
  • n and n are each independently an integer of 0 to 1, may be 1 ⁇ m + n ⁇ 2, fluorine is substituted in the ortho-position Can be.
  • n may be 1.
  • n may be 0.
  • n may be 1.
  • R 2 and R 3 may be each independently C1-C10 alkyl, C6-C20 aryl, C6-C20 arylC1-C10 alkyl or C1-C10 alkylC6-C20 aryl, p and q may each independently be an integer of 0 to 2.
  • p and q may be each independently an integer of zero.
  • R 1 may be C1-C10 alkyl, C6-C20 aryl, C6-C20 arylC1-C10 alkyl or C1-C10 alkylC6-C20 aryl, more preferably R 1 may be C 1 -C 7 alkyl or C 6 -C 12 aryl.
  • the ligand according to an embodiment of the present invention may be exemplified by the following structure, but is not limited thereto.
  • the present invention also provides an ethylene oligomerization catalyst comprising the ligand of Formula 1 and a transition metal.
  • the transition metal is not particularly limited, but may be a Group 4, 5 or 6 transition metal, preferably selected from chromium, molybdenum, tungsten, titanium, tantalum, vanadium or zirconium, more preferably chromium to be.
  • the transition metal may be derived from a transition metal precursor.
  • the transition metal precursor is specifically a Group 4, Group 5 or Group 6 transition metal precursor, preferably may be selected from chromium, molybdenum, tungsten, titanium, tantalum, vanadium or zirconium precursors. More preferred.
  • the chromium precursor is not particularly limited, but is preferably selected from the group consisting of chromium (III) acetylacetonate, chromium trichloride tristetrahytrofuran and chromium (III) 2-ethylhexanoate.
  • the oligomerization catalyst according to the present invention may be a mononuclear or heteronuclear oligomerization catalyst in which a heteroatom ligand of Formula 1 is coordinated to a transition metal or transition metal precursor, and specifically ML 1 (L) a (X) b or M It may be represented by 2 X 1 2 L 1 2 (L) y (X) z , wherein M is a transition metal, L 1 is a ligand of Formula 1, X and X 1 are each independently from a transition metal precursor
  • the functional group to be derived is, for example, halogen, L is an organic ligand, a is an integer of 0 or more, b is an integer of (oxidation number of a-M), y is an integer of 0 or more, and z is (2 x M May be an integer of) -2-y.
  • the oligomerization catalyst according to the present invention coordinates a ligand having p and q 0 in chromium or chromium precursor in Chemical Formula 3, Chemical Formula 4 or Chemical Formula 5 so as to stably maintain the oligomerization activity, It is possible to prepare 1-hexene and 1-octene in high activity, high selectivity.
  • the oligomerization catalyst according to the present invention may be specifically exemplified by the following structure, but is not limited thereto.
  • R 1 is C1-C7 alkyl or C6-C12 aryl
  • X is halogen
  • L is organic ligand
  • a is an integer from 0 to 3
  • c and d are each independently 0 to 2 Is an integer.
  • organic ligand L may be selected from the following structural formula, but is not limited thereto.
  • R 41 and R 42 are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and R 43 is hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or Substituted heterohydrocarbyl;
  • R 44 and R 45 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl.
  • Ligands constituting the oligomerization catalyst according to the present invention can be prepared using various methods known to those skilled in the art.
  • the oligomerization catalyst according to an embodiment of the present invention has excellent catalytic activity, very high selectivity upon oligomerization of olefins, control of catalyst input amount, and excellent activity is maintained even at high temperature, thus preventing clogging of the olefin manufacturing process and No fouling occurs, very economical and efficient.
  • the present invention provides a method for producing a high activity and highly selective 1-hexene or 1-octene from ethylene using a catalyst composition comprising the oligomerization catalyst, the ethylene oligomerization catalyst composition Contact may be made to the ethylene oligomer.
  • the ethylene oligomerization catalyst composition according to one embodiment of the present invention may further include a promoter for more effective activity and high selectivity.
  • the ethylene oligomerization catalyst composition may be an oligomerization catalyst system including an oligomerization catalyst and a promoter comprising a transition metal or a transition metal precursor and a ligand of Formula 1.
  • the cocatalyst may in principle be any compound that activates the transition metal complex to which the ligand of Formula 1 is coordinated. Cocatalysts can also be used in mixtures. Suitable compounds as cocatalysts include organoaluminum compounds, organic aluminoxanes, organoboron compounds, organic salts and the like.
  • Organoaluminum compounds suitable for use as activators in the ethylene oligomerization catalyst composition according to one embodiment of the present invention are AlR 3 (wherein R is independently C 1 -C 12 alkyl, C 6 -C 20 aryl, C 2 -C 10 alkenyl , C 2 -C 10 alkynyl, C 1 -C 12 alkoxy or halogen) or LiAlH 4 or the like.
  • the organoaluminum compound is trimethylaluminum (TMA), triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum One, two or more mixtures selected from chloride, aluminum isopropoxide, ethylaluminum sesquichloride, methylaluminum sesquichloride, and aluminoxanes.
  • Organic aluminoxanes suitable for use as activators in the ethylene oligomerization catalyst composition according to one embodiment of the present invention are oligomeric compounds which can be prepared by adding water to water and alkylaluminum compounds, for example trimethylaluminum.
  • the aluminoxane oligomeric compounds can be linear, cyclic, cages or mixtures thereof.
  • the organic aluminoxanes are alkylaluminoxanes such as methylaluminoxane (MAO), ethylaluminoxane (EAO), tetraisobutylaluminoxane (TIBAO) and isobutyl aluminoxane (IBAO) as well as modified alkyl aluminoxanes, such as For example, it may be selected from modified methylaluminoxane (MMAO).
  • Modified methyl aluminoxanes (manufactured by Akzo Nobel) contain, in addition to methyl groups, mixed alkyl groups such as isobutyl or n-octyl groups.
  • methyl aluminoxane MAO
  • modified methyl aluminoxane MMAO
  • EAO ethyl aluminoxane
  • TIBAO tetraisobutyl aluminoxane
  • IBAO isobutyl aluminoxane
  • Organic boron compounds suitable for use as activators in the ethylene oligomerization catalyst composition according to one embodiment of the present invention are boroxine, NaBH 4 , triethyl borane, triphenylborane, triphenylborane ammonia complex, tributylborate, triiso Propylborate, tris (pentafluorophenyl) borane, trityl (tetrapentafluorophenyl) borate, dimethylphenylammonium (tetrapentafluorophenyl) borate, diethylphenylammonium (tetrapentafluorophenyl) borate, methyldi Phenylammonium (tetrapentafluorophenyl) borate, ethyldiphenylammonium (tetrapentafluorophenyl) borate, or mixtures thereof, and the organoboron compounds thereof may be used in a mixture with the organo
  • the promoter is methylaluminoxane (MAO), modified methylaluminoxane (mMAO), ethylaluminoxane (EAO), tetraisobutylaluminoxane (TIBAO), isobutyl aluminoxane (IBAO), trimethylaluminum (TMA) , Triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, aluminum isopropoxide, ethylaluminum It may be one or two or more mixtures selected from the group consisting of sesquichloride and methylaluminum sesquichloride, preferably methylaluminoxane (MAO) or modified methylaluminoxane (mMAO).
  • MAO
  • the ratio of the oligomerization catalyst and the promoter is 1: 1 to 10,000: 1 based on the molar ratio of metal to transition metal of the promoter, and more preferably 1: 1 to 2,000: 1.
  • the ratio of the oligomerization catalyst and the aluminoxane cocatalyst may be 1: 1 to 10,000: 1 based on the molar ratio of aluminum to transition metal, and more preferably 1: 1 to 1,000: 1. .
  • the ethylene oligomerization catalyst composition may further comprise other components possible as long as the ethylene oligomerization catalyst and promoter are not detrimental to the nature of the present invention.
  • the individual components of the ethylene oligomerization catalyst composition, the oligomerization catalyst and the promoter can be combined simultaneously or sequentially in any order in the presence of a solvent to provide the active catalyst.
  • the mixing of each component of the catalyst composition can be carried out at a temperature of -20 to 250 ° C., and the presence of the olefins during the mixing of each component can generally exhibit a protective effect to provide improved catalyst performance.
  • the range of more preferable temperature is 20-160 degreeC.
  • reaction products disclosed herein in other words ethylene oligomers, in particular 1-hexene or 1-octene, are homogeneous in the presence of an inert solvent using conventional apparatus and contacting techniques with the oligomerization catalyst or oligomerization catalyst composition according to the invention.
  • Liquid phase reactions or two-phase liquid / liquid reactions or product olefins may be prepared in bulk phase or gas phase reactions serving as the main medium, but homogeneous liquid phase reactions are preferred in the presence of an inert solvent.
  • the oligomer preparation method according to one embodiment according to the present invention may be performed in an inert solvent. That is, any inert solvent which does not react with the oligomerization catalyst and the promoter of the present invention may be used, and the inert solvent may be an aliphatic hydrocarbon in terms of improving the catalytic activity.
  • the oligomerization catalyst system according to the present invention not only easily adjusts the amount of catalyst in the continuous dosing of the catalyst solution but also shows excellent catalytic activity.
  • the aliphatic hydrocarbon is preferably a saturated aliphatic hydrocarbon, Linear saturated aliphatic hydrocarbons represented by C n H 2n +2 (wherein n is an integer from 1 to 15), alicyclic saturated aliphatic hydrocarbons represented by C m H 2m (wherein m is an integer from 3 to 8), and
  • the lower alkyl group having 1 to 3 carbon atoms may include a linear or cyclic saturated aliphatic hydrocarbon substituted with one or more carbon atoms.
  • the oligomerization reaction according to one embodiment of the present invention may be carried out at a temperature of -20 to 250 °C, preferably at a temperature of 20 to 160 °C, more preferably at a temperature of 60 to 160 °C, the reaction pressure is atmospheric pressure It can be carried out at a pressure of from 100 bar, preferably at a pressure of 10 to 70 bar.
  • the oligomer may be 1-hexene, 1-octene or a mixture thereof.
  • 1-octene is preferably at least 60% by weight, preferably at least 70% by weight, and more preferably, based on the total weight of the C8 product formed from ethylene through the oligomerization reaction. Can be obtained in an amount of at least 80 wt%. Yield in this case means the weight percent of 1-octene formed relative to the total weight of the C8 product formed.
  • 1-hexene is 50 wt% or more, preferably 70 wt% or more, more preferably 1 to hexene relative to the total weight of the C6 product formed from ethylene through the oligomerization reaction. Can be obtained in more than 90% by weight. Yield in this case means the weight percent of 1-hexene formed relative to the total weight of the C6 product formed.
  • the oligomer preparation method according to one embodiment of the present invention can be carried out in a plant comprising any type of reactor.
  • reactors include, but are not limited to, batch reactors, semi-batch reactors and continuous reactors.
  • the plant may comprise a reactor, an inlet of an olefin reactor and an oligomerization catalyst composition therein, a combination of the oligomerization reaction product from the reactor and a line for effluent and at least one separator for separating the oligomerization reaction product,
  • the catalyst composition may include an oligomerization catalyst and a promoter disclosed in the present invention, or may include a transition metal or a transition metal precursor, a ligand of Formula 1, and a promoter.
  • the oligomerization catalyst or oligomerization catalyst composition according to the invention can be used to maintain the activity of the catalyst even at high temperatures during ethylene oligomerization to produce 1-hexene, 1-octene or mixtures thereof in high activity and high selectivity.
  • N, N-diethylaminochloro (phenyl) phosphine was prepared with reference to known literature (M. Oliana et. Al., J. Org. Chem., 2006, p. 2472-2479).
  • reaction temperature of the mixture was raised to room temperature, the volatiles were removed under reduced pressure, diluted with a hexane: dichloromethane (1: 1 v / v) solution, and filtered through silica to obtain the title compound as a colorless transparent liquid (8.967 g, 85.7%). .
  • N, N-diethyl-1- (2-fluorophenyl) -1-phenylphosphinamine (8.967 g, 32.6 mmol) obtained above was added to anhydrous diethyl ether (70 mL). After dilution 1 M hydrogen chloride / diethyl ether (68.4 mL) was added slowly. After the mixture was reacted for at least 1 hour, activated alumina was filtered to obtain the title compound as a colorless transparent liquid (7.377 g, 94.9%).
  • chloro (2-fluorophenyl) phenylphosphine (2.3863 g, 10 mmol) obtained in Preparation Example A was diluted in n-hexane (20 mL), followed by trimethyltin hydride (4.0163 g). , 11 mmol) was added slowly. The mixture was reacted for 30 minutes, and then filtered through celite to remove the volatiles under reduced pressure to obtain the title compound as a liquid (2.0418 g, 100%).
  • ligand (1) was purified by silica column with a solution of n-hexane: ethyl acetate (9: 1 v / v) to give ligand (1) as a colorless transparent oil (0.2236 g, 95.1%).
  • the mixture was purified by silica column with a solution of n-hexane: ethyl acetate (9: 1 v / v) to give ligand (3) as a colorless transparent oil (0.2282 g, 100.0%).
  • Ligand (1) except that (2-fluorophenyl) (1-hexynyl) (phenyl) phosphine was used instead of (3,3-dimethyl-1-butynyl) (2-fluorophenyl) phenylphosphine as starting material
  • the reaction was carried out in the same manner as in the preparation of, to obtain the ligand (5) (51.01%).
  • Ligand (1) except for using (2-fluorophenyl) (phenyl) (phenylethynyl) phosphine in place of (3,3-dimethyl-1-butynyl) (2-fluorophenyl) phenylphosphine as starting material
  • the reaction was carried out in the same manner as in the preparation of, to obtain the ligand (7) (97.13%).
  • the title compound was obtained in the same manner as in the preparation of the ligand (3), except that ethynylbenzene was used instead of 3-methyl-1-butyne as the starting material (7.865 g, 92.29%).
  • the 2.1 L autoclave reactor was washed with nitrogen and vacuum, 1.0 L of methylcyclohexane was added, and 1.0 mL (1.87 mmol) of mMAO-3A (7 wt% -Al) sold by Akzo Nobel was added, followed by 500 Stirred at a stirring speed of rpm.
  • 1.9 mg (3 ⁇ mol) of the oligomerization catalyst I prepared above was added to 10 mL of methylcyclohexane in 20 mL of vial, and dispersed, and then charged into the autoclave reactor.
  • the temperature in the autoclave reactor was raised to 100 ° C., and ethylene was charged to 30 bar to start the oligomerization reaction.
  • the reactor was cooled with a cooling coil inside the reactor to maintain a constant temperature of 100 ° C. throughout the operation. After 60 minutes, the ethylene feed to the reactor was stopped, the stirring was stopped to stop the reaction, and after the excess ethylene was discharged in the reactor, the reactor was cooled to 10 ° C. or less. After the reaction was discharged into a discharge vessel containing 1.5 mL of 2-ethylhexanol, a small amount of the organic layer sample was passed through a micron syringe filter and analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax / polymer product. After drying these solid products overnight in an oven at 100 ° C., the obtained product was recorded.
  • Table 1 The product distribution of this example by GC analysis is summarized in Table 1 below.
  • the catalyst II was prepared in the same manner as in Example 1 using the ligand (2) instead of the ligand (1), and then the oligomerization reaction was performed in the same manner as in Example 1.
  • the product distribution of this example is summarized in Table 1 below.
  • Catalyst III was prepared in the same manner as in Example 1, and oligomerization was carried out in the same manner as in Example 1.
  • the product distribution of this example is summarized in Table 1 below.
  • the catalyst V was prepared in the same manner as in Example 1 using the ligand (5) instead of the ligand (1), and then the oligomerization reaction was performed in the same manner as in Example 1.
  • the product distribution of this example is summarized in Table 1 below.
  • catalyst (VII) was prepared using ligand (7) in the same manner as in Example 1, and then oligomerization reaction was performed in the same manner as in Example 1.
  • the product distribution of this example is summarized in Table 1 below.
  • catalyst (VIII) was prepared using ligand (8) in the same manner as in Example 1, followed by oligomerization reaction in the same manner as in Example 1.
  • the product distribution of this example is summarized in Table 1 below.
  • Catalyst IX was prepared in the same manner as in Example 1, followed by an oligomerization reaction in the same manner as in Example 1.
  • the product distribution of this example is summarized in Table 1 below.
  • the catalyst A was prepared in the same manner as in Example 1 using the ligand (A) having the following structure instead of the ligand (1), and then the oligomerization reaction was performed in the same manner as in Example 1.
  • the product distribution of this comparative example is summarized in Table 1 below.
  • the catalyst B was prepared in the same manner as in Example 1 using the ligand (B) having the following structure instead of the ligand (1), and then the oligomerization reaction was performed in the same manner as in Example 1.
  • the product distribution of this comparative example is summarized in Table 1 below.
  • the catalyst C was prepared in the same manner as in Example 1 using the ligand (C) having the following structure instead of the ligand (1), and then the oligomerization reaction was performed in the same manner as in Example 1.
  • the product distribution of this comparative example is summarized in Table 1 below.
  • the catalyst D was prepared in the same manner as in Example 1 using the ligand (D) having the following structure instead of the ligand (1), and then the oligomerization reaction was performed in the same manner as in Example 1.
  • the product distribution of this comparative example is summarized in Table 1 below.
  • the oligomerization catalyst of the present invention is substituted with fluorine at the ortho-position of phenyl bonded to phosphorus atom in bis (diphenylphosphino) ethene, and at one carbon atom.
  • fluorine at the ortho-position of phenyl bonded to phosphorus atom in bis (diphenylphosphino) ethene, and at one carbon atom.
  • it contains a ligand of the asymmetric form substituted with a hydrocarbyl group, it can be seen that it has a very good activity at high temperatures in comparison with the comparative example.
  • the oligomerization catalyst of the present invention exhibited at least 3.04 times more catalytic activity at a higher temperature than the catalyst of Comparative Example 4 containing a PNP ligand bonded to a phosphorus atom of phenyl substituted with fluorine at the ortho-position.
  • the oligomerization catalyst of the present invention remains catalytically active even at high temperatures, there are few by-products and there is no clogging and fouling, and thus it is very economical because the operation of the polymerization process for removing them is not necessary.
  • the oligomerization catalyst of the present invention is very excellent in catalytic activity even at high temperature, and has the advantage of preparing oligomers even when using a small amount of catalyst and a small amount of promoter in the oligomerization process of the olefin, but also active at high temperatures. This does not decrease and excellent selectivity, it is possible to manufacture 1-hexene or 1-octene from ethylene with high selectivity.
  • At least one fluorine is substituted for phenyl bonded to a phosphorus atom in bis (diphenylphosphino) ethene, and one carbon atom is substituted with a substituted or unsubstituted hydrocarbyl group other than hydrogen.
  • It contains the ligand of the formula (1) of the asymmetric form is excellent in catalytic activity and selectivity even at high temperature during ethylene oligomerization.
  • the oligomerization catalyst of the present invention is excellent in catalytic activity even at high temperatures, and does not require fouling and clogging caused by polymers, which are by-products during mass production of oligomers.
  • the oligomer manufacturing method of the present invention can produce the oligomer with high activity and high selectivity even at high temperature, and does not occur fouling and clogging, thereby making it possible to prepare the olefin in a very efficient process.

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Abstract

La présente invention concerne un ligand, un catalyseur d'oligomérisation d'éthylène le comprenant, et un procédé de production sélective de 1-hexène ou de 1-octène à partir d'éthylène à l'aide du catalyseur. Le ligand selon la présente invention est un bis(diphénylphosphino)éthane avec un atome de phosphore substitué par un phényle à substitution fluoro, et lorsque le ligand est utilisé pour l'oligomérisation de l'éthylène, l'activité à haute température du catalyseur peut être augmentée.
PCT/KR2018/012025 2018-02-27 2018-10-12 Ligand, catalyseur d'oligomérisation le comprenant, et procédé de production d'oligomère d'éthylène à l'aide d'un catalyseur d'oligomérisation WO2019168249A1 (fr)

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US16/771,857 US11224870B2 (en) 2018-02-27 2018-10-12 Ligand, oligomerization catalyst comprising same, and method for producing ethylene oligomer by using oligomerization catalyst
JP2020512872A JP7210552B2 (ja) 2018-02-27 2018-10-12 リガンド、それを含むオリゴマー化触媒、およびそれを用いたエチレンオリゴマーの製造方法
CN201880057196.4A CN111094308B (zh) 2018-02-27 2018-10-12 配体、包含其的低聚催化剂以及使用低聚催化剂制备乙烯低聚物的方法
EP18907972.6A EP3760634A4 (fr) 2018-02-27 2018-10-12 Ligand, catalyseur d'oligomérisation le comprenant, et procédé de production d'oligomère d'éthylène à l'aide d'un catalyseur d'oligomérisation

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CN111905832A (zh) * 2020-07-23 2020-11-10 天津科技大学 乙烯选择性齐聚的催化剂体系、反应方法及其应用
CN114163475A (zh) * 2021-12-01 2022-03-11 浙江智英石化技术有限公司 含吡咯基刚性结构多位点配体的催化剂体系、制备方法及应用
CN116328832A (zh) * 2021-12-24 2023-06-27 中国石油化工股份有限公司 有机聚合物载体和主催化剂及乙烯聚合催化剂组合物及其应用

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