WO2016186291A1 - Système catalyseur d'oligomérisation d'oléfines, et procédé d'oligomérisation d'oléfines l'utilisant - Google Patents

Système catalyseur d'oligomérisation d'oléfines, et procédé d'oligomérisation d'oléfines l'utilisant Download PDF

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WO2016186291A1
WO2016186291A1 PCT/KR2016/000238 KR2016000238W WO2016186291A1 WO 2016186291 A1 WO2016186291 A1 WO 2016186291A1 KR 2016000238 W KR2016000238 W KR 2016000238W WO 2016186291 A1 WO2016186291 A1 WO 2016186291A1
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group
chromium
catalyst system
oligomerization
iii
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PCT/KR2016/000238
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English (en)
Korean (ko)
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이용호
신은지
박진영
이기수
사석필
임슬기
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주식회사 엘지화학
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Priority claimed from KR1020150185319A external-priority patent/KR101959542B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP16796618.3A priority Critical patent/EP3260475B1/fr
Priority to CN201680025845.3A priority patent/CN107567465B/zh
Priority to JP2017546864A priority patent/JP6503472B2/ja
Priority to US15/570,133 priority patent/US10427991B2/en
Publication of WO2016186291A1 publication Critical patent/WO2016186291A1/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
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F4/69—Chromium, molybdenum, tungsten or compounds thereof

Definitions

  • the present invention relates to a catalyst system for an olefin oligomerization reaction and a method for levlein oligomerization, and more particularly, the carrying efficiency is further improved by a ligand compound, which can act as a tether on a support.
  • a catalyst system for olefin oligomerization reactions and a method for levine oligomerization which exhibits high activity in leulevine oligomerization reactions with only a small amount of catalyst composition and cocatalyst, allowing for the production of more efficient alpha-olepins. .
  • Linear alpha-olefin is used as a cleaning agent, lubricant, plasticizer, etc., and is especially used as a comonomer for controlling the density of polymers in the production of linear low-density polyethylene (LLDPE). .
  • LLDPE linear low-density polyethylene
  • LLDPE low density polyethylene
  • Conventional processes for the production of LLDPE include a mixture of alpha-elepine, e.g. 1-nuxene, 1-octene, in order to control the density by forming a branch in the polymer backbone with ethylene. Copolymerization with the monomer was made.
  • alpha-olefins have different types of business and market sizes
  • the ability to produce various olefins simultaneously is of great commercial importance and is a chromium catalyst for producing 1-nuxene, 1-octene, or polyethylene with specific selectivity through recent ethylene oligomerization reactions or polymerization of ethylene
  • chromium catalyst for producing 1-nuxene, 1-octene, or polyethylene with specific selectivity through recent ethylene oligomerization reactions or polymerization of ethylene
  • the present invention exhibits high catalytic activity in the olefin oligomerization reaction, while reducing the leaching phenomenon of the catalyst material, and high catalytic activity and linear alpha- even when a relatively small amount of promoter is added as compared to the liquid catalyst system. It is to provide a catalyst system for the relefin oligomerization reaction system that can implement the selectivity to the olefin.
  • the present invention is to provide a method for refring oligomerization using the catalyst system.
  • the present invention comprises a ligand compound comprising at least two diphosphine groups represented by the following formula (1) in the molecule, and comprising a linker (L) connecting between each group represented by the formula (1); Chromium source; And it provides a catalyst system for olefin oligomerization reaction comprising a support on which the ligand compound is supported.
  • p is a phosphorus atom
  • R1 to R4 are each independently the same or different and have a C1-C20 hydrocarbyl group, heterohydrocarbyl group, or hydrocarboheteryl group,
  • a non-covalent electron pair belonging to one or more diphosphine groups of two or more diphosphine groups included in the ligand compound may be coordinated to the crum atom.
  • two or more diphosphine groups included in the ligand compound may be preferably formed in a form in which one or more diphosphine groups are tethered to the support.
  • the mole number ratio of the creme atom to the mole number of the ligand compound is 1 or less.
  • the ligand compound may be represented by the following formula (2).
  • P is a phosphorus atom
  • N is a nitrogen atom
  • P is a nitrogen atom
  • R1 to R4 and R1 'to R4' are each independently the same or differently a hydrocarbyl group having 1 to 20 carbon atoms, heterohydrocarbyl group, or hydrocarboheteryl group,
  • L is a C2-C30 hydrocarbyl or heterohydrocarbyl group connecting between two or more diphosphine groups.
  • L is a linker having 4 to 10 carbon atoms in the shortest distance connecting the diphosphine group, an aliphatic linker having 1 to 20 carbon atoms, alicyclic linkage having 3 to 20 carbon atoms . Or an aromatic linking group having 6 to 20 carbon atoms.
  • the crum source is chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2-ethylnucleonoate, chromium (III) acetate, chromium (III) ) Butyrate, chromium (III) pentanoate, chromium (III) laurate, chromium (IN) tris (2,2,6,6-tetramethyl-3.5-heptanedionate), and chromium (III) stearate It may be one or more compounds selected from the group consisting of.
  • the olefin oligomerization reaction catalyst system may further include a promoter supported on the support.
  • the promoter is trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethyl aluminum sesquichloride, It may be at least one compound selected from the group consisting of diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and modified methylaluminoxane.
  • a method for oligomerizing ollefin comprising the step of proceeding the oligomerization reaction of the olefinic monomer in the presence of the catalyst system to form an alpha-olefin.
  • the olefin monomer may be preferably ethylene.
  • the oligomerization reaction of the olefinic monomer may be carried out at a temperature of about 5 to about 200 ° C, but may be preferably carried out at a pressure of about 1 to about 300 bar.
  • the promoter It can be uniformly distributed throughout the support, and can exhibit high activity even with a small amount of promoter.
  • one or more diphosphine groups present in the ligand compound molecule may be strongly bound to the support, thereby improving the carrying efficiency and reducing the leaching phenomenon of the catalyst composition.
  • the separation of the catalyst from the liquid reaction product and the product is easy, so that the formation of other isomers can be reduced, and since the generation of the solid alpha-olefin occurs at the support, the parling phenomenon that may occur on the surface of the reaction apparatus or the like. Can be prevented.
  • oligomerization means that the olefin is small polymerized.
  • it refers to multimerization, including trimerization or tetraactivity reactions, depending on the number of reps of polymerized ollepin, in particular, in the present specification, 1- used as the main comonomer of LLDPE from ethylene.
  • a hydrocarbyl group refers to a hydrocarbon compound, for example, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a cycloalkyl group, or the like. It can mean, unless otherwise specified, including both straight and branched chains, both substituted and unsubstituted.
  • alkylaryl group means an aryl group having at least one alkyl group as a substituent
  • aryl alkyl group means an alkyl group having at least one aryl group as a substituent
  • a hetero element means nitrogen, oxygen, sulfur, or phosphorus
  • a heterohydrocarbyl group refers to a hydrocarbyl group containing one or more hetero atoms.
  • the linking point to be functionalized is carbon, and when referred to as a heteryl group, such as a 'hydrocarboheteryl group' or an 'organoheteryl group', the linking point to be functionalized is a hetero atom Means to be.
  • the catalyst system according to an aspect of the present invention even when supported on a support such as silica, can not only produce alpha -lepine with high activity and selectivity. And easy separation from the product, thereby reducing the amount of isomers due to side effects or side reactions that may occur when the catalyst is not separated from the product.
  • the olefin oligomerization reaction can proceed in the pores and the like in the support, even if a solid alpha-olefin is produced, it can be fixed in the support, the morphology is maintained, and separation is easy. Therefore, it can be easily processed into high value-added low molecular weight PE products and can be produced by the by-products remaining in the reaction vessel. It is possible to prevent problems of parling and pipe clogging.
  • an olefin oligomerization reaction catalyst system includes at least two diphosphine groups represented by the following Chemical Formula 1 in a molecule, and is a linker connecting between the respective groups represented by Chemical Formula 1 above.
  • It includes a support on which the ligand compound is carried.
  • p is a phosphorus atom
  • A is nitrogen (N), arsenic (As), or antimony (Sb),
  • R1 to R4 are each independently the same or different and have a C1-C20 hydrocarbyl group, heterohydrocarbyl group, or hydrocarboheteryl group,
  • the ligand compound contains a diphosphino moiety in the molecule and can provide a lone pair of electrons to a ligand such as a creme due to the rich electron density of the A atom and the linking group.
  • the electrical and steric properties of the entire ligand compound may change, the bond between the ligand and the chromium atom may change, the structure of the catalyst may be more stable, or the existing metallacycloheptane, or metallai 2 p _ energy of transition state, ie activation of reactions / able to form alpha-olefins
  • R3 ——R2 ⁇ ! It may be represented by 2.
  • P is a phosphorus atom
  • N is a nitrogen atom
  • P is a nitrogen atom
  • R1 to R4 and R1 'to R4' are each independently the same or different and have a C1-C20 hydrocarbyl group, heterohydrocarbyl group, or hydrocarboheteryl group,
  • L is a C2-C30 hydrocarbyl or heterohydrocarbyl group connecting between two or more diphosphine groups.
  • R1 to R4 and R1 'to R4' may be, for example, an aryl group having 6 to 20 carbon atoms, a heteroaryl group, or an arylheteryl group; Or an alkylaryl group, a heteroalkylaryl group, an alkyl heteroaryl group, or an alkylaryl heteroaryl group having 7 to 20 carbon atoms.
  • linking group (L) may be a hydrocarbyl group, a heterohydrocarbyl group, or a hydrocarbyl heterotyl group having various structures, and the number of atoms of the shortest distance between diphosphine groups may be 2 to 30. Specifically, for example, carbon number
  • Aliphatic linking group having 2 to 20 carbon atoms having 2 to 20 carbon atoms
  • heteroaliphatic linking group having 2 to 20 carbon atoms having 2 to 20 carbon atoms
  • It may be a 3 to 20 alicyclic linking group, a hetero alicyclic linking group of 3 to 20 carbon atoms, an aromatic linking group of 6 to 20 carbon atoms, or a heteroaromatic linking group of 6 to 20 carbon atoms, the structure is not particularly limited.
  • the main chains of the linking groups may have substituents of various structures.
  • Non-limiting examples of the above-described linking group include those having the following structural formula.
  • the diphosphine groups represented by Formula 1 are represented by [A], [ ⁇ ′], or [ ⁇ ′′] for convenience, and each diphosphine group is the same as or different from each other. Can be different.
  • the connector (L) may be a first connector, a second connector or a third connector described below.
  • the first linker may be four carbon atoms of the shortest distance between the diphosphine group, an aliphatic linker having 1 to 20 carbon atoms, an alicyclic linker having 3 to 20 carbon atoms, and an aromatic linking group having 6 to 20 carbon atoms, Has the following structural formula:
  • RR is each independently an alkyl group having 1 to 5 carbon atoms
  • ⁇ is the number of substitutions in each ring, and may vary depending on the number of substitutions within an integer range of 1 to 4,
  • the plurality of RRs coupled to the ring in one may be the same or different from each other.
  • the second linking group has 5 to 8 carbon atoms at the shortest distance between the diphosphine groups, and is composed of aliphatic linking groups having 5 to 20 carbon atoms, or aliphatic having 1 to 20 carbon atoms and aromatic atoms having 6 to 20 carbon atoms. It may be made of a linking group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms at at least one end of the linking group.
  • the third linking group the shortest distance between the number of carbon atoms between the diphosphine group is 23 to 23, it may be represented by the following formula (3).
  • Q is represented by Formula 1, means a diphosphine group
  • X is alkylene having 1 to 20 carbon atoms or arylene having 6 to 14 carbon atoms
  • R5 to R 14 are each independently the same or differently, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, and 6 carbon atoms. It may be an aryl group of 14 to 14, an alkylaryl group of 7 to 18 carbon atoms, an arylalkyl group of 7 to 18 carbon atoms, or an alkoxyaryl group of 7 to 18 carbon atoms.
  • a representative example of the ligand compound may have the following structural formula.
  • the activity of the supported catalyst can be further improved, and the selectivity for the linear alpha-olefin may also be advantageous.
  • a non-covalent electron pair belonging to one or more diphosphine groups of two or more diphosphine groups included in the ligand compound is large It may be present in the form of an organic crum compound, coordinated to the atom.
  • At least one diphosphine group of two or more diphosphine groups included in the ligand compound may be formed in a form that is tethered to the support.
  • one or more diphosphine groups of two or more diphosphine groups included in the ligand compound may serve as a tethering group for the support, and one or more of the other diphosphine groups may be used to bind and coordinate Thus, it can serve as an active point of the reaction.
  • an electron pair donor for providing a valent valent lone pair of electrons of the diphosphine group serving as the tethering group, and a metal or nonmetallic element included in the support, for example, silicon or aluminum is an electron pair acceptor. acting as an acceptor), the Lewis acid-base form of the bond can be followed, the ligand compound and the support can be fixed with a strong binding force.
  • the supporting force can be improved as compared with other supported catalysts, and thus, the supporting efficiency can be improved, and the phenomenon in which the catalyst component is separated from the support during reaction or separation can be reduced.
  • the linker (L) may more preferably comprise a relatively flexible aliphatic linking group, so that each diphosphine group can be smooth to act as a tethering and active point.
  • the linking group is composed of only alicyclic or aromatic, not including aliphatic, the rigid bonds may result in extremely limited interactions, greatly lowering catalytic activity, and selectivity to linear alpha-olefins. It can also be degraded.
  • the ligand compound is, based on the weight in the state of the coordination, about 0.5 to about 20 parts by weight, preferably about 1 to about 15 parts by weight, more preferably about 100 parts by weight of the support It may be included in 1 to about 10 parts by weight.
  • the mole number ratio of the chromium atoms to the mole number of the ligand compound may be 1 or less, preferably, 1: 1 to 10: 1, preferably, 1: 1 to 5: 1 days Can be. That is, at least one or more of the diphosphine groups present in the ligand compound is preferably molar within the above range so that tethering with the support is possible.
  • the support has a specific surface area capable of sufficiently supporting the catalyst component, and a general support containing many pores therein may be used so that olefin oligomerization reaction can occur smoothly.
  • the support may be any metal or nonmetal, a salt thereof, or an oxide, which is usually used in a supported catalyst, without particular limitation.
  • silica, alumina, silica-alumina, silica-magnesia, or the like may be applied.
  • the present invention is not necessarily limited thereto.
  • Such a support may be dried at high temperatures, and may generally include materials such as oxides, carbonates, sulfates, or nitrates of metals, such as sodium oxide, potassium carbonate, barium sulfate, magnesium nitrate and the like.
  • the surface of the support preferably contains less hydroxy groups, it may be impossible to remove all the hydroxy groups, it may be important to control the amount of hydroxy groups by adjusting the drying conditions, etc. at the time of preparing the support .
  • a hydroxy group may be about 10 mmol / g or less, preferably about i mmol / g or less and more preferably about 0.5 mmol / g or less, based on the mass of the support.
  • the source of chromium is an organic or inorganic crescent compound in which the oxidation state of the crucible is 0 to 6, for example a crumble metal, or any compound in which any organic or inorganic radical is bound to the crumble.
  • the organic radical may be an alkyl, alkoxy, ester, ketone, amido, carboxylate radical, etc. having 1 to 20 carbon atoms per radical
  • the inorganic radical may be a halide, sulfate, oxide, or the like.
  • the crum source is chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium 2-ethylnucleoate, chromium (III) acetate, chromium (III) Butyrate, chromium (III) pentanoate, chromium (III) laurate, chromium (III) tris (2,2,6,6-tetramethyl-3.5- Heptanedionate), and at least one compound selected from the group consisting of chromium (III) stearate.
  • the catalyst system described above may further include a promoter supported on the support.
  • the promoter is an organometallic compound containing a Group 13 metal, and can be applied without particular limitation as long as it can be generally used when polymerizing olefins under a catalyst of a transition metal compound.
  • the promoter may be at least one compound selected from the group consisting of compounds represented by Formulas 4 to 6 below:
  • Rx is the same as or different from each other, and each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, c is an integer of 2 or more, '
  • D is aluminum or boron
  • Ry is C1-20 hydrocarbyl or halogen substituted by C1-20 carbonyl
  • L is a neutral Lewis base
  • [LH] + is brothsted acid
  • Q is boron or aluminum in the +3 type oxidation state
  • each E independently represents one or more hydrogen atoms halogen, a hydrocarbyl having 1 to 20 carbon atoms , An aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, unsubstituted or substituted with an alkoxy functional group or a phenoxy functional group.
  • the compound represented by Formula 4 is methyl aluminoxane, Alkyl aluminoxanes such as ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane.
  • the compound represented by Formula 5 is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, di Ethylchloroaluminum, triisopropylaluminum, tri-S-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trinuclear silaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-P -Laryl aluminum, dimethylaluminum methoxide, dimethylaluminum specialty, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron and
  • the compound represented by Formula 6 is triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium Tetra (P-Lyl) boron, tripropyl ammonium tetra (P-lryl) boron, triethyl ammonium tetra ( ⁇ , ⁇ -dimethylphenyl) boron, trimethyl ammonium tetra (e ⁇ - dimethylphenyl) boron, tributyl Ammonium tetra ( ⁇ -trifluoromethylphenyl) boron, trimethyl ammonium tetra ( ⁇ -trifluoromethylphenyl) boron,
  • Triphenylcarbonium tetrapentafluorophenylboron and the like Triphenylcarbonium tetrapentafluorophenylboron and the like.
  • the promoter may be an organoaluminum compound, an organoboron compound, an organic magnesium compound, an organozinc compound, an organolithium compound, or a combination thereof.
  • the promoter is preferably an organic aluminum compound, more preferably trimethyl aluminum, triethyl aluminum, triisoprapyl aluminum, triisobutyl aluminum (triisobutyl aluminum), ethylaluminum sesquichloride, diethylaluminum chloride, ethyl aluminum dichloride, methylaluminoxane, and modified methylaluminoxane It may be one or more compounds selected from the group consisting of ⁇
  • the content of each component is not particularly limited, but the molar ratio of the ligand compound and the promoter may be about 1: 5 to 1: 1,000, preferably May be from about 1:10 to about 1: 250.
  • the cocatalyst may be included in an amount of about 1 to about 1,000 parts by weight, preferably about 10 to about 100 parts by weight, and more preferably about 40 to about 150 parts by weight based on 100 parts by weight of the support.
  • the ligand compound coordinated with the chromium atom and the promoter may be supported on one support in a uniform composition, or may be supported on each of the different supports.
  • the supporting method is also not particularly limited, and a promoter may be first supported on a support, and then a ligand compound coordinated with chromium atoms may be supported. Can be. In this case, the promoter may be supported by dividing the amount to be finally supported by two.
  • the loading of the promoter and ligand compound may proceed for about 1 to about 20 hours in the temperature range of about 20 to about 120 ° C.
  • the temperature can be divided into one or more times by varying the temperature at the time of promoter input, and each input temperature can be lowered sequentially from the initial input temperature, for example, about At temperatures below 50 ° C. to about 150 ° C., the temperature may be sequentially lowered.
  • the promoter when the input is divided into one or more times, the temperature is gradually lowered at each input step, and the promoter and the support are brought into contact with each other, the promoter may be uniformly supported on the outside and the inside of the support. The amount of loss can be reduced, and finally, even if only a small amount of promoter is used, it is possible to maintain high activity in the leupine oligomer reaction.
  • a method for oligomerization of olefins comprising the step of proceeding to the oligomerization reaction of the olefinic monomers in the presence of the catalyst system described above to form an alpha-olefin.
  • the olefin monomer is ethylene.
  • the olefin oligomerization reaction can be carried out by applying conventional apparatus and contacting techniques.
  • a typical olefin oligomerization reaction is a homogeneous liquid reaction in the presence or absence of an inert solvent, or a slurry reaction in which the catalyst system is in some or incomplete form, or an alpha-olefin or polyethylene that is a product. It may be carried out in a bulk phase reaction, or in a gas phase reaction, serving as the main medium.
  • the oligomerization reaction is carried out in the pores in the supported catalyst as a solid supported catalyst, the stability of the catalyst is very high, and even if a solid alpha-olefin or the like is produced, the morphology of the oligomerization reaction can be maintained. have.
  • the diphosphine groups included in the ligand compound is strongly tethered with the support to reduce the leaching of the catalytically active component, it is possible to increase the efficiency of reaction and reduce the impurity content. Same as one.
  • the olepin oligomerization reaction may be performed under an inert solvent.
  • the inert solvent may be benzene, toluene, xylene, cumene, chlorobenzene, dichlorobenzene, heptane, cyclonucleic acid, methylcyclonucleic acid, methylcyclopentane, n-nucleic acid, 1-nuxene, 1-octene, etc. have.
  • the leupin oligomerization reaction may be performed at a temperature of about 0 to about 200 ° C, or about 0 to about 15 C C, or about 30 to about 100 ° C, or about 50 to about 100 ° C. .
  • the reaction may be performed under a pressure of about 1 to about 300 bar, or 2 to about 150 bar.
  • a ligand compound was prepared in the same manner as in Preparation Example 1, except that 1, 6-diphenylnucleic acid-1, 6-diamine was used instead of 4,4-methylenebis (2,6-diethylaniline). Prepared.
  • trivalent chromium acetate 224.5 mg, 0.7 mmol was prepared as a chromium source, placed in a flask so that each molar ratio was 1: 1, and 65 ml of toluene was added.
  • 7 g of the support prepared above was placed in a glass reactor at 40 ° C., and a methyl aluminoxane (MAO) solution containing 77 mmol of aluminum was added to the toluene solution.
  • MAO methyl aluminoxane
  • the oligomerization reaction was carried out in a 600 ml metal alloy reaction vessel equipped with a mechanical stirrer, adjustable in temperature, and operated at high pressure.
  • the supported catalyst prepared in Examples 1 to 3, Reference Example 1, and Comparative Examples 1 and 2 was weighed 30 mg in a dry box and placed in a 50 ml glass bottle. It was sealed with a rubber diaphragm, taken out of the dry box, and prepared to be injected into the reactor.
  • the reaction vessel was charged with 400 ml of nucleic acid (Hexane) containing I.Ommol triethylaluminum and the prepared supported catalyst so as not to come into contact with air, while continuously injecting gaseous ethylene monomer at a pressure of 30 bar at 80 ° C. For hours Oligomerization reaction was performed.
  • reaction solution was stirred by adding 409 ml of ethane / HCI (10 vol%) and filtering to obtain a polymer.
  • the polymer was dried in 6 (C vacuum Aubon for 12 hours or more and weighed.
  • the activity is about 10 times higher than the comparative example.
  • the reference example also shows a very high activity, which appears to be due to having two catalytic active sites in one ligand molecule using 2 moles of chromium relative to the ligand compound.
  • Comparative Examples 1 and 2 also, although used in the form of a supported catalyst, the tethering effect is insignificant, it can be seen that the catalyst activity is very low, about 10% of the examples.
  • Comparative Example 3 comparing the case of using the supported catalyst system and the case of using the liquid catalyst system for the same composition (Comparative Example 3) in the liquid catalyst system it can be seen that the catalyst activity is very low, about 1% compared to the embodiment.
  • a cocatalyst (based on the weight of aluminum) should be used at least 600 equivalents, preferably 900 to 1500 equivalents, relative to the number of moles of chromium in order to secure a certain amount of activity. It is thought to be due.
  • the catalyst activity is very good even when using a relatively small amount of promoter, compared to the general liquid catalyst system, and the selection for the linear alpha-olefin is also high. Number have. This is thought to be due to the fact that the promoter and the catalytically active component (ligand compound-chromium complex) are supported together on one support, the distance thereof is close, and the promoter can be uniformly distributed throughout the support and inside.
  • the promoter and the catalytically active component ligand compound-chromium complex

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne : un système catalyseur d'oligomérisation d'oléfines ; et un procédé d'oligomérisation d'oléfines et, plus spécifiquement : un système catalyseur d'oligomérisation d'oléfines, permettant une préparation plus efficace d'α-oléfines dans la mesure où l'efficacité de support est en outre améliorée par un composé ligand susceptible de servir d'attache sur le support, faisant preuve de là d'activité élevée dans l'oligomérisation d'oléfines uniquement avec une quantité plus petite d'une composition catalyseur et d'un co-catalyseur ; et un procédé d'oligomérisation d'oléfines.
PCT/KR2016/000238 2015-05-15 2016-01-11 Système catalyseur d'oligomérisation d'oléfines, et procédé d'oligomérisation d'oléfines l'utilisant WO2016186291A1 (fr)

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EP16796618.3A EP3260475B1 (fr) 2015-05-15 2016-01-11 Système catalyseur d'oligomérisation d'oléfines, et procédé d'oligomérisation d'oléfines l'utilisant
CN201680025845.3A CN107567465B (zh) 2015-05-15 2016-01-11 用于烯烃低聚的催化剂体系和使用其使烯烃低聚的方法
JP2017546864A JP6503472B2 (ja) 2015-05-15 2016-01-11 オレフィンオリゴマー化反応用触媒システムおよびこれを用いたオレフィンオリゴマー化方法
US15/570,133 US10427991B2 (en) 2015-05-15 2016-01-11 Catalyst system for olefin oligomerization and method for olefin oligomerization using the same

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KR10-2015-0068301 2015-05-15
KR20150068301 2015-05-15
KR1020150185319A KR101959542B1 (ko) 2015-05-15 2015-12-23 올레핀 올리고머화 반응용 촉매 시스템 및 이를 이용한 올레핀 올리고머화 방법
KR10-2015-0185319 2015-12-23

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EP3225637B1 (fr) * 2015-05-15 2020-02-05 LG Chem, Ltd. Système catalytique de réaction d'oligomérisation d'oléfine et procédé d'oligomérisation d'oléfine l'utilisant
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US10688473B2 (en) 2014-12-11 2020-06-23 Lg Chem, Ltd. Ligand compound, organic chromium compound, catalyst system for oligomerization of olefins, and method for oligomerizing olefins using the same
EP3225637B1 (fr) * 2015-05-15 2020-02-05 LG Chem, Ltd. Système catalytique de réaction d'oligomérisation d'oléfine et procédé d'oligomérisation d'oléfine l'utilisant
EP3190118A4 (fr) * 2015-05-26 2018-02-21 LG Chem, Ltd. Composé ligand, composé de chrome organique, système catalyseur pour l'oligomérisation d'oléfines, et procédé d'oligomérisation d'oléfines au moyen de ce dernier
CN113402554A (zh) * 2021-06-11 2021-09-17 万华化学集团股份有限公司 一种PNSiNP配体及其制备方法、乙烯齐聚催化剂及其应用
CN114920866A (zh) * 2022-05-23 2022-08-19 万华化学集团股份有限公司 一种聚烯烃热塑性弹性体的制备方法
CN114920866B (zh) * 2022-05-23 2023-07-14 万华化学集团股份有限公司 一种聚烯烃热塑性弹性体的制备方法

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