WO2016129847A1 - Procédé de préparation d'un système catalytique d'oligomérisation et système catalytique d'oligomérisation préparé par celui-ci - Google Patents

Procédé de préparation d'un système catalytique d'oligomérisation et système catalytique d'oligomérisation préparé par celui-ci Download PDF

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WO2016129847A1
WO2016129847A1 PCT/KR2016/001146 KR2016001146W WO2016129847A1 WO 2016129847 A1 WO2016129847 A1 WO 2016129847A1 KR 2016001146 W KR2016001146 W KR 2016001146W WO 2016129847 A1 WO2016129847 A1 WO 2016129847A1
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group
carbon atoms
formula
catalyst system
groups
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PCT/KR2016/001146
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Korean (ko)
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임슬기
이용호
신은지
박진영
사석필
이기수
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주식회사 엘지화학
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Priority claimed from KR1020150118964A external-priority patent/KR101679515B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/528,576 priority Critical patent/US10870104B2/en
Priority to EP16749387.3A priority patent/EP3257873B1/fr
Priority to CN201680004065.0A priority patent/CN107001499B/zh
Publication of WO2016129847A1 publication Critical patent/WO2016129847A1/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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • 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
    • 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
    • C08F4/607—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/609—Catalysts containing a specific non-metal or metal-free compound organic
    • 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 specification relates to a method for preparing an oligomerization catalyst system and a oligomerization catalyst system produced thereby, which can maintain activity even at high temperature oligomerization reaction.
  • Linear alpha-olefins are widely used commercially as important materials for comonomers, detergents, lubricants, plasticizers, etc.
  • 1-hexene and 1-octene are used in the production of linear low density polyethylene (LLDPE). It is often used as a comonomer to control the density.
  • LLDPE Linear Low-Density Polyethylene
  • a chromium-based catalyst using a ligand of the general formula (R1) (R2) X-Y-X (R3) (R4) as a trimerization catalyst of ethylene has been proposed.
  • R1 phosphorus, arsenic or antimony
  • Y is a linking group such as -N (R5)-and at least one of R1, R2, R3 and R4 has a polar or electron-donating substituent.
  • a (o- ethylphenyl) 2 PN (Me) P ( o- ethyl does not have a polar substituent on at least one of R1, R2, R3 and R4 compound as a ligand which does not exhibit catalytic activity for 1-hexene under catalytic conditions Phenyl) 2 ( Chem . Commun . , 2002, 858 ).
  • the ligands including the heteroatoms of the prior art described above are still in need for high multi-selective activity and consistent multimerization activity during the reaction of 1-octene or 1-hexene preparation.
  • the present specification provides a method for preparing an oligomerization catalyst system which can be maintained without degrading activity even at high temperatures during the oligomerization reaction by controlling the activation temperature and time of the catalyst composition and the catalyst composition including the ligand compound and the transition metal compound. It is an object of the present invention to provide a prepared oligomerization catalyst system, and to provide an oligomerization method which can have various process advantages due to the wide temperature range that can be controlled in the oligomerization reaction.
  • the step of preparing a catalyst composition by mixing a ligand compound and a transition metal compound comprising a diphosphine moiety represented by the formula (1); And a cocatalyst and the catalyst composition are mixed and activated at a temperature of -40 to 80 ° C. to provide an oligomerization catalyst system.
  • A is N, As or Sb, and R1 to R4 are each independently a hydrocarbyl group, heterohydrocarbyl group or hydrocarbyl heterotyl group having 1 to 20 carbon atoms.
  • the activation time of the promoter and the catalyst composition may be less than 5 minutes.
  • the activation time of the promoter and the catalyst composition may be 3 minutes or less.
  • the activation temperature may be 20 to 80 °C.
  • the catalyst system may have an activity of 100,000 kg / molCr / hr or more.
  • the catalyst system when the oligomerization reaction temperature is in the range of 30 to 150 °C, the activity reduction rate according to the temperature rise may be less than 6%.
  • the ligand compound includes two or more diphosphine moieties represented by the following Chemical Formula 2, and the linking group connecting the two or more diphosphine moieties is a hydrocarbyl group.
  • the shortest distance between the phosphine moieties may be 2 to 30 carbon atoms.
  • R1 to R4 are the same as in Formula 1, and * is a linking group connecting two or more diphosphine moieties.
  • the linking group may include an aliphatic group having 1 to 20 carbon atoms, a heteroaliphatic group having 2 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, a heteroalicyclic group having 3 to 20 carbon atoms, and carbon atoms
  • One or more groups selected from the group consisting of 6 to 20 aromatic groups and 6 to 20 carbon atoms are combined, an aliphatic group having 1 to 20 carbon atoms, a heteroaliphatic group having 2 to 20 carbon atoms, and 3 to 20 carbon atoms.
  • an oligomerization catalyst system having at least one group selected from the group consisting of an alicyclic group, a heterocyclic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and a heteroaromatic group having 6 to 20 carbon atoms. Manufacturing method.
  • the ligand compound may include a compound represented by the following Formula 3.
  • R1 to R4 are the same as those of Formula 1,
  • R5 is an alkyl group having 1 to 20 carbon atoms
  • R 6 is a straight chain group which is an alkyl group having 2 or 3 carbon atoms, an alkenyl group, a heteroalkyl group, a heteroalkenyl group, or a heteryl group thereof; Alkyl groups, alkenyl groups, arylalkyl groups, arylalkenyl groups, heteroalkyl groups, heteroalkenyl groups, heteroarylalkyl groups, heteroarylalkenyl groups, or heteryl groups thereof having 4 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group, an arylcycloalkyl group, an arylcycloalkenyl group heterocycloalkyl group, heterocycloalkenyl group, heteroarylcycloalkyl group, heteroarylcycloalkenyl group, or a heteryl group thereof; C6-C20 aryl group, heteroaryl group, heteroaryl group, hetero
  • R6 is an alkyl group having 2 to 20 carbon atoms, alkenyl group, arylalkyl group, arylalkenyl group, heteroalkyl group, heteroalkenyl group, heteroarylalkyl group, heteroarylalkenyl group or these Heteryl group;
  • R7 to R9 are each independently hydrogen; An alkyl group, alkenyl group, arylalkyl group, or arylalkenyl group having 1 to 20 carbon atoms; A cycloalkyl group, a cycloalkenyl group, an arylcycloalkyl group, or an arylcycloalkenyl group having 3 to 20 carbon atoms; Aryl groups having 6 to 20 carbon atoms; Or an alkylaryl group having 7 to 20 carbon atoms.
  • R7 to R9 of Chemical Formula 3 may be hydrogen.
  • the transition metal compound may include an organochrome compound, and the organochrome compound may be chromium (III) acetyl acetonate, chromium tris tetrahydrofuran, chromium (III) -2- Ethylhexanoate, chromium (III) tris (2,2,6,6-tetramethyl-3,5-heptanedionate), chromium (III) benzoyl acetonate, chromium (III) hexafluoro-2,4 At least one member selected from the group consisting of pentanedionate and chromium (III) acetate hydroxide.
  • organochrome compound may be chromium (III) acetyl acetonate, chromium tris tetrahydrofuran, chromium (III) -2- Ethylhexanoate, chromium (III) tris (2,2,6,6-tetramethyl-3,5
  • the promoter may be at least one selected from the group consisting of compounds represented by the following Chemical Formulas 4 to 6.
  • R 5 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
  • R 6 is the same as or different from each other, and each independently hydrogen or halogen, hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
  • L is a neutral Lewis base
  • [LH] + is a Bronsted acid
  • Q is boron or aluminum in a +3 type oxidation state
  • each E is independently at least one hydrogen atom is 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 which is unsubstituted or substituted with an alkoxy functional group or a phenoxy functional group.
  • the olefin multimerization reaction in the range of the reaction temperature of 30 to 150 °C provided is an olefin oligomerization method comprising the step of.
  • the reaction temperature may be in the range of 60 to 130 ° C.
  • the activity of the catalyst system in the entire reaction temperature range may be 100,000 kg / molCr / hr or more in a batch process, and 100,000 kg / molCr or more in a continuous process.
  • the catalyst system in the entire reaction temperature range, may have an activity lowering rate of less than 6% due to a temperature increase.
  • the selectivity of 1-hexene and 1-octene with respect to the total amount of the product may be 80% by weight or more.
  • the catalyst composition comprising a ligand compound and a transition metal compound is lowered in contact and aging temperature of the catalyst, and a short time is activated to activate the catalyst system. It is possible to provide an oligomerization catalyst system that can be maintained as it is without deterioration. Accordingly, even in the oligomerization reaction, the temperature control range is more free, and thus, various process advantages can be provided.
  • the terms “comprise”, “comprise” or “have” are intended to indicate that there is a feature, number, step, component, or combination thereof, that is, one or more other features, It should be understood that it does not exclude in advance the possibility of the presence or addition of numbers, steps, components, or combinations thereof.
  • catalyst system means a three component comprising a transition metal source, a ligand compound and a promoter, or alternatively, two components of the transition metal compound and a promoter It means a state which can be added simultaneously or in any order to obtain an active catalyst composition.
  • Three or two components of the catalyst system may be added in the presence or absence of a solvent and a monomer, and the three terms may be used interchangeably.
  • the term 'oligomerization' means that the olefin is small polymerized. Depending on the number of olefins to be polymerized, it is called trimerization and tetramerization, which is collectively called multimerization. In particular, it is meant herein to selectively prepare 1-hexene and 1-octene which are the main comonomers of LLDPE from ethylene.
  • the hydrocarbyl group refers to all compounds consisting of only carbon and hydrogen, and examples thereof include an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, and the like. As long as there is no, it can mean both straight and branched chain, it can mean both unsubstituted and substituted.
  • a group which is an alkyl group having 1 to 20 carbon atoms may mean methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, neopentyl group, etc.
  • the aryl group having 6 to 20 carbon atoms includes, for example, a phenyl group, a naphthyl group, an anthracenyl group, and the like, but is not limited thereto.
  • an alkylaryl group means an aryl group having at least one alkyl group as a substituent
  • an arylalkyl group means an alkyl group having at least one aryl group as a substituent.
  • the hetero element refers to N, O, S, and P
  • the heterohydrocarbyl group may mean a hydrocarbyl group including one or more hetero atoms. That is, a heteroalkyl group may mean that any one carbon of the constituent carbons of the alkyl group is substituted with a hetero atom, or a hetero atom is included as a substituent, and the heteroaryl group, like a pyridyl group, any one of the carbons in the aromatic ring is a hetero atom. It may mean substituted. The same may also apply to other heteroarylalkyl groups, heteroalkylaryl groups, heteroalkenylaryl groups, and the like.
  • connection point to be functionalized is carbon, but the 'heterolyl group' such as 'hydrocarboheteryl group', 'organoheteryl group', and 'heteryl group' refers to the point of functionalization. It may mean the case of a hetero atom.
  • preparing a catalyst composition by mixing a ligand compound and a transition metal compound including a diphosphine moiety represented by Formula 1 below; It provides a method for producing an oligomerization catalyst system comprising a; and a catalyst and the catalyst composition is activated by mixing at a temperature -40 to 80 °C.
  • A is N, As or Sb, and R1 to R4 are each independently a hydrocarbyl group, heterohydrocarbyl group or hydrocarbyl heterotyl group having 1 to 20 carbon atoms.
  • the catalyst composition includes a ligand compound and a transition metal compound, and the method for preparing an oligomerization catalyst system according to the present disclosure may first induce a metallization reaction between two compounds by first mixing a ligand compound and a transition metal compound.
  • the metallization reaction may be a reaction in which a transition metal compound is coordinated to a ligand compound, and the configuration of the ligand compound and the transition metal compound, an active point of the ligand compound, and the like will be described later.
  • the step of activating by mixing the catalyst composition and the promoter may be performed.
  • the activation may mean activation as an oligomerization catalyst system through contacting and aging of the catalyst composition with the promoter.
  • Activation of the catalyst composition and the promoter may be performed at a temperature of -40 to 80 °C. Preferably it may be carried out at a temperature of 20 to 80 °C, or 25 to 60 °C.
  • contact and aging of the catalyst composition and the promoter for the activation are performed at a high temperature of more than 80 ° C., the ligand and the transition metal of the catalyst composition are excessively activated by the metal alkyl which can be used as a promoter, resulting in oligomerization. Excessive activity can cause side reactions or premature deactivation.
  • the catalyst composition for the activation and the contact and aging of the catalyst is made at a cryogenic temperature of less than -40 °C can not supply the energy required to activate the catalyst can not activate the catalyst.
  • Activation of the catalyst composition and the promoter may be one that is mixed with the organic solvent and the catalyst and the catalyst composition present in solution contact and aged for a predetermined time, and the activation is particularly limited in its form such as stirring and simple mixing. If the catalyst composition and the promoter is in contact with the oligomerization catalyst system can be applied to any form that can generate activity.
  • the organic solvent includes, for example, heptane, toluene, cyclohexane, methylcyclohexane, 1-hexene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone, and the like. It is not limited.
  • the time taken from the time when the promoter and the catalyst composition first contact each other (the temperature at this time is called a temperature) and before the contact with the reactant (eg, ethylene) is called A time
  • the catalyst When the time taken to raise the oligomerization reaction temperature (reaction temperature referred to as b temperature) in the state where the composition, the promoter and the reactant are all mixed is B time, the activation time of the promoter and the catalyst composition is A If the start time of A time and the start time of B time are different, and if the time started first ends first, the time from the start time of the first time started to the end time of the next time started. May mean, or if another time is included within the longer time spent (e.g., A time is completely included in B time, or B If the liver is fully included in the time A) it may mean a longer period of time.
  • the activation of such catalyst composition and promoter can be carried out for less than 5 minutes, preferably for up to 3 minutes.
  • the contact and aging of the catalyst composition and the promoter for the activation are performed for a time of 5 minutes or more, the oligomerization catalyst system may be over-activated in the same manner as the activation at high temperature. It may be advantageous.
  • the ligand compound and the transition metal compound of the oligomerization catalyst system when the activation is performed for a short time at low temperature, the ligand compound and the transition metal compound of the oligomerization catalyst system The coordination bond is stabilized, so that the thermal stability of the catalyst system may be increased, and even though the reaction proceeds at a high temperature (about 60 ° C. to 120 ° C.) during the oligomerization reaction, the catalyst system is structurally durable and has no change in physical properties. This can be maintained continuously.
  • the activity of the catalyst system prepared under the activation conditions may be about 100,000 kg / molCr / hr or more in a batch process, preferably 120,000 kg / molCr / hr or more, more preferably 150,000 kg / molCr / hr or more have. Further, in a continuous process, it may be about 100,000 kg / molCr or more, preferably 120,000 kg / molCr or more, and more preferably 150,000 kg / molCr or more.
  • the activity of the catalyst system may be maintained without deterioration even at a high temperature, and the activity deterioration rate may be less than 6% due to the increase in the oligomerization reaction temperature.
  • the oligomerization reaction temperature is 30 to 150 ° C. and 60 ° C. To 130 ° C, or 70 to 110 ° C.
  • the promoter is mixed in the organic solvent and introduced into the reactor, the catalyst composition is introduced with the reactant olefin, directly into the reactor, or the promoter In the middle of the incoming line is introduced into the reactor.
  • the promoter and catalyst composition are introduced into the reactor in a separate line separately, and the reactants are also introduced directly into the reactor in a separate line. Accordingly, it may be possible to maintain activity even at high temperatures as the time for contacting the reactants is shortened.
  • the oligomerization catalyst system has a molar ratio of the ligand compound: transition metal compound: promoter about 0.5: 1: 1 to about 10: 1: 10,000 days. And preferably from about 0.5: 1: 100 to about 5: 1: 3,000.
  • the oligomerization catalyst system according to the present specification is not limited thereto.
  • any PNP-based ligand compound may be applied without particular limitation, but when the following ligand compound is applied, an excellent effect may be obtained.
  • the ligand compound may contain a diphosphine moiety represented by Formula 1 below.
  • A is N, As or Sb, and R1 to R4 are each independently an aryl group having 6 to 20 carbon atoms or an alkylaryl group having 7 to 20 carbon atoms.
  • the ligand compound containing the diphosphine moiety represented by Chemical Formula 1 may include two or more diphosphine moieties represented by the following Chemical Formula 2.
  • R1 to R4 are the same as in Formula 1, and * is a linking group connecting two or more diphosphine moieties.
  • the ligand compound may include a compound represented by Formula 2a.
  • R1 to R4 and R1 ⁇ to R4 ⁇ may be selected from the same group as R1 to R4 of Formula 1 or 2, respectively, and L may be a linking group connecting two diphosphine moieties. have.
  • the linking group (L) is a linking group connecting between two or more diphosphine moieties may be a hydrocarbyl group of a variety of structures, the shortest distance between the diphosphine moieties may be 2 to 30 carbon atoms. That is, a hydrocarbyl group exists between two or three or more of the diphosphine moieties, and the number of carbon atoms connected at a shortest distance between the diphosphine moieties in the hydrocarbyl group is 2 To eight.
  • the linking group which is a hydrocarbyl group, an aliphatic group having 2 to 20 carbon atoms, a heteroaliphatic group having 2 to 20 carbon atoms, a cycloaliphatic group having 3 to 20 carbon atoms, a heteroalicyclic group having 3 to 20 carbon atoms, and 6 to 20 carbon atoms
  • One or more groups selected from the group consisting of an aromatic group and a hetero aromatic group having 6 to 20 carbon atoms may be combined, and the structure is not particularly limited as long as it satisfies this.
  • the linking group (L) is an aliphatic group having 2 to 20 carbon atoms (eg, an alkylene group, an alkenylene group) connecting 2 to 30 carbon atoms, respectively, between two or more groups represented by Formula 1 above.
  • Non-limiting examples of the above-described linking group include a hydrocarbyl group having the following structure.
  • the diphosphine moiety represented by Formula 1 is represented by [A], [A '] or [A "] for convenience, and according to a group selected from R1 to R4, [A], [A '] And [A "] may be the same or different from each other.
  • the group connecting by four carbon atoms may not interact with the chromium complexes of the two or more diphosphine moieties. It may be desirable to include flexible aliphatic groups to facilitate smoothing.
  • diphosphine moiety represented by two or more Formula 1 is connected by four carbon atoms, it does not include an aliphatic group as in the case where the diphosphine moiety is connected to positions 1 and 4 of the cyclohexane
  • the interactions are extremely limited, resulting in significantly lower activity per unit PNP-Cr, and selection for low carbon number alpha-olefins such as 1-hexene and 1-octene Degrees may be degraded.
  • the ligand compound represented by Formula 2 or 2a may be synthesized by the same method as in Scheme 1, but is not limited thereto.
  • each A is the same as or different from each other, and is the same as the definition of R 1 to R 4 of Formula 1, 2, or 2a, and R is a linking group connected to 2 to 8 carbon atoms, wherein Formula 2 or As defined in 2a, X is halogen.
  • the ligand compound may include a compound represented by Formula 3 below.
  • R1 to R4 are each independently an aryl group having 6 to 20 carbon atoms or an alkylaryl group having 7 to 20 carbon atoms, and R5 may be an alkyl group having 1 to 20 carbon atoms.
  • R 6 is a straight chain group which is an alkyl group having 2 or 3 carbon atoms, an alkenyl group, a heteroalkyl group, a heteroalkenyl group, or a heteryl group thereof; Alkyl groups, alkenyl groups, arylalkyl groups, arylalkenyl groups, heteroalkyl groups, heteroalkenyl groups, heteroarylalkyl groups, heteroarylalkenyl groups, or heteryl groups thereof having 4 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group, an arylcycloalkyl group, an arylcycloalkenyl group heterocycloalkyl group, heterocycloalkenyl group, heteroarylcycloalkyl group, heteroarylcycloalkenyl group, or a heteryl group thereof; C6-C20 aryl group, heteroaryl group, heteroaryl group, hetero
  • R 6 is a heteroalkyl group having 2 to 20 carbon atoms, a heteroalkenyl group, a heteroarylalkyl group, a heteroarylalkenyl group or a heteryl group thereof; A heterocycloalkyl group, a heterocycloalkenyl group, a heteroarylcycloalkyl group, a heteroarylcycloalkenyl group, or a heteryl group thereof having 3 to 20 carbon atoms; C6-C20 aryl group, heteroaryl group, or these heteroaryl group; Or an alkylaryl group, heteroalkylaryl group, or a heteroaryl group thereof having 7 to 20 carbon atoms.
  • R6 is an alkyl group having 2 to 20 carbon atoms, alkenyl group, arylalkyl group, arylalkenyl group, heteroalkyl group, heteroalkenyl group, heteroarylalkyl group, heteroarylalkenyl group or these Heteryl group;
  • R7 to R9 are each independently hydrogen; An alkyl group, alkenyl group, arylalkyl group or arylalkenyl group having 1 to 20 carbon atoms; A cycloalkyl group, a cycloalkenyl group, an arylcycloalkyl group or an arylcycloalkenyl group having 3 to 20 carbon atoms; Aryl groups having 6 to 20 carbon atoms; Or an alkylaryl group having 7 to 20 carbon atoms.
  • the ligand compound represented by Chemical Formula 3 may be, for example, a compound in which carbons 2 and 6 of the aniline compound are substituted with R5 and R6, and a group substituted with carbons 2 and 6 Accordingly, the properties of the ligand compound and the oligomerization catalyst system including the same may be changed.
  • a group different from the group substituted at the carbon position 2 may be substituted at the carbon position 6 to form an asymmetric structure.
  • a straight chain group which is an alkyl group having 2 or 3 carbon atoms, an alkenyl group, a heteroalkyl group, a heteroalkenyl group or a heteryl group thereof may be substituted; Alkyl, alkenyl, arylalkyl, arylalkenyl, heteroalkyl, heteroalkenyl, heteroarylalkyl, heteroarylalkenyl or heteryl groups of 4 to 20 carbon atoms may be substituted.
  • a cycloalkyl group, a cycloalkenyl group, an arylcycloalkyl group, an arylcycloalkenyl group heterocycloalkyl group, a heterocycloalkenyl group, a heteroarylcycloalkyl group, a heteroarylcycloalkenyl group or a heteroaryl group thereof having 3 to 20 carbon atoms may be substituted.
  • An aryl group, heteroaryl group or heteryl group having 6 to 20 carbon atoms may be substituted;
  • An alkylaryl group, a heteroalkylaryl group, or a heteroaryl group thereof having 7 to 20 carbon atoms; may be substituted.
  • an alkyl group, alkenyl group, arylalkyl group, arylalkenyl group, heteroalkyl group, heteroalkenyl group, heteroarylalkyl group, heteroarylalkenyl group or a heteroaryl group thereof may be substituted;
  • a C3-C20 cycloalkyl group, cycloalkenyl group, arylcycloalkyl group, arylcycloalkenyl group heterocycloalkyl group, heterocycloalkenyl group, heteroarylcycloalkyl group, heteroarylcycloalkenyl group or a heteroaryl group thereof may be substituted;
  • An aryl group or heteroaryl group having 6 to 20 carbon atoms or a heteroaryl group thereof may be substituted;
  • an alkylaryl group, heteroalkylaryl group, or a heteroaryl group thereof having 7 to 20 carbon atoms may be substituted.
  • the catalyst system including the ligand compound can easily interact with PNP-Cr according to various conditions such as the electronic and three-dimensional environment around the transition metal, resulting in a high oligomer
  • the amount of 1-hexene isomers that significantly affect the product, even in small amounts in oligomerization can be greatly reduced.
  • the increase of 1-hexene and the decrease of 1-hexene isomers it can also bring about the effect of energy savings as separation may not be necessary.
  • the ligand compound may be synthesized in the same manner as in Scheme 2, but is not limited thereto.
  • G1 may be a phenyl group having R5 to R9 of Formula 3
  • G2 and G3 may each be R1 to R4 of Formula 3
  • X may be a halogen group.
  • Scheme 2 is a general scheme for synthesizing the ligand compound represented by Formula 3, may be a reaction in which the amine and the phosphine reacts to produce diphosphinoamine. That is, the amine may be a reaction in which the leaving group represented by X of the phosphine as a nucleophile is substituted and substituted, and the X is not particularly limited as long as it is stable and easy to leave. Br, or I may be present.
  • the catalyst system used in the olefin oligomerization reaction includes a transition metal compound serving as a main catalyst and a cocatalyst, wherein the structure of the active catalyst can be changed according to the chemical structure of the ligand, and thus the olefin selectivity, The amount of activity or by-products may be different.
  • the transition metal compound of the oligomerization catalyst system serves as a main catalyst, and may be in a coordination state with a ligand compound as described above.
  • the ligand compound including two or more diphosphine moieties represented by the transition metal compound and the formula (2) can be coordinated as shown by the formula (2-1).
  • R1 to R4 are the same as in Formula 1, * is the same as in Formula 2,
  • M may be a transition metal, preferably Cr,
  • Xn is H, F, Cl, Br, I, or may be an alkyl group, alkenyl group, arylalkyl group, heteroalkyl group, heteroalkenyl group or heteroarylalkyl group, or halogen group having 1 to 6 carbon atoms, or may be an acetate group or an acetyl acetonate group
  • m is an oxidation number of M and may be a natural number.
  • transition metal compound and the ligand compound represented by Formula 2a may be coordinated as represented by the following Formula 2a-1.
  • R1 to R4, Xn, m, and M are as defined in Formula 2-1, and R1 ⁇ to R4 ⁇ and Xn ⁇ are also the same as R1 to R4.
  • transition metal compound and the ligand compound represented by Chemical Formula 3 may be coordinated as represented by the following Chemical Formula 3-1.
  • the transition metal compound may include an organic chromium compound
  • the organic chromium compound may be, for example, chromium (III) acetylacetonate, chromium trichloride trihydrotrafuran, chromium (III) -2-ethyl Hexanoate, chromium (III) tris (2,2,6,6-tetramethyl-3,5-heptanedionate), chromium (III) benzoylacetonate, chromium (III) hexafluoro-2,4- It may be at least one selected from the group consisting of pentanedionate and chromium (III) acetate hydroxide.
  • the cocatalyst is an organometallic compound including a Group 13 metal, and is not particularly limited as long as it can be used in the multimerization of olefins under a transition metal compound catalyst. Specifically, the cocatalyst may be used at least one selected from the group consisting of compounds represented by the following formulas (4) to (6).
  • R 5 is the same as or different from each other, and each independently represent 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, and c is an integer of 2 or more.
  • D is aluminum or boron
  • R 6 is the same as or different from each other, and each independently hydrogen or halogen, hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
  • L is a neutral Lewis base
  • [LH] + is a Bronsted acid
  • Q is boron or aluminum in a +3 type oxidation state
  • each E is independently at least one hydrogen atom is 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 which is unsubstituted or substituted with an alkoxy functional group or a phenoxy functional group.
  • MMAO modified methyl aluminoxane
  • MAO methyl aluminoxane
  • ethyl aluminoxane isobutyl aluminoxane
  • butyl aluminoxane and the like.
  • alkyl metal compound represented by Formula 5 examples include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum and diethyl.
  • Chloro aluminum triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p- Tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron and the like.
  • triethyl ammonium tetraphenyl boron for example, triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p -Tolyl) boron, tripropylammonium tetra (p-tolyl) boron, triethylammonium tetra (o, p-dimethylphenyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium Tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrap
  • aluminoxane may be preferably used, and more preferably methylaluminoxane (MAO) or modified methylaluminoxane (MMAO) may be used.
  • MAO methylaluminoxane
  • MMAO modified methylaluminoxane
  • an oligomerization catalyst system prepared through the above method is provided.
  • the reaction temperature of the oligomerization reaction when the reaction temperature of the oligomerization reaction is 60 ° C. or more, the activity may be maintained at the reaction temperature of 30 to 150 ° C. Therefore, the oligomerization reaction carried out in the presence of the oligomerization catalyst system can be more free of the control of temperature, can be produced in the oligomerization by applying a variety of methods to produce 1-hexene and 1-octene, various advantages accordingly Can have
  • a method for preparing an olefin oligomer comprising the step of multimerizing olefins in the presence of the oligomerization catalyst system.
  • the catalyst system for olefin oligomerization of the above embodiment it is possible to provide a method for oligomerization of olefins having improved reaction activity and selectivity.
  • the olefin may include ethylene.
  • the olefin oligomerization process of the olefin is carried out in a product comprising 1-hexene and 1-octene in the presence of an oligomerization catalyst system comprising a ligand compound, a transition metal compound and a promoter.
  • Multi-reacting the olefins by controlling the reaction temperature in the range of 30 to 150 ° C. such that the molar ratio of 1-hexene to 1-octene has a predetermined value; comprising 1-hexene to 1-octene in the product.
  • the predetermined value of the molar ratio of may be selected from the range of 1: 0.5 to 1: 7.
  • the olefin oligomerization method is a method of controlling the ratio of alpha olefin as the main product, by selecting a means of controlling the reaction temperature to control the reaction temperature, thereby controlling 1-hexene and 1 in a desired ratio.
  • Can produce octene Accordingly, by controlling only the reaction temperature, it is possible to easily obtain 1-hexene and 1-octene in desired ratios, and thus the convenience and / or economic efficiency of the process may be greatly increased.
  • the range of the reaction temperature to be controlled may be 30 to 150 ° C, or may be in the range of 60 to 130 ° C, or may be in the range of 70 to 110 ° C.
  • the reaction temperature in the above temperature range, it is possible to determine the desired ratio of 1-hexene and 1-octene before the oligomerization reaction to obtain 1-hexene and 1-octene of the predetermined values.
  • the weight ratio of 1-hexene and 1-octene, which may be predetermined may range from 1: 0.5 to 1: 7, or may range from 1: 0.9 to 1: 6.6.
  • the weight ratio of 1-hexene and 1-octene may be in the range of about 1: 2 to 1: 7, preferably 1: 3 to 1: 7.
  • 1-octene may be produced in excess of 1-hexene.
  • the ratio of 1-hexene may be increased, and the activity of the catalyst system is maintained even when the reaction temperature exceeds 80 ° C., thus producing ratios of 1-hexene and 1-octene up to about 150 ° C. Can be adjusted by temperature control only.
  • the activity of the catalyst system can be maintained even in a wide range of temperatures, especially at high temperatures, and thus the ratio of 1-hexene and 1-octene in a wide temperature range, such as 30 to 150 ° C. Can be adjusted.
  • linear alpha olefin mixed products having more varied weight ratios can be prepared, and the total amount of 1-hexene and 1-octene (ie, linear alpha olefin selectivity) will be maintained as the catalyst system remains active in this temperature range. It can be.
  • the selectivity to the total amount of the product of 1-hexene and 1-octene produced can be maintained at 80% by weight or more over the entire reaction temperature range.
  • the application of the method of controlling the production rate of 1-hexene and 1-octene by controlling the reaction temperature to the olefin oligomerization method may be performed in various forms, and specifically, the practical application may be as follows. have.
  • the results of the weight ratio of 1-hexene and 1-octene produced according to the reaction temperature are obtained by repeating the experiment several times, and the data on the average ratio of 1-hexene and 1-octene produced at a specific reaction temperature After classifying, build a library with the classified data.
  • the temperature of the multimerization reaction is controlled using a library built in advance through the repeated experiments, and the predetermined value of 1-hexene and 1-octene is determined as an intended value according to various conditions such as demand. You can get the production rate.
  • a method of viewing the ratio of 1-hexene and 1-octene produced during the process and changing the reaction temperature at that time for changing the ratio in the desired direction can be applied. have.
  • the change of the production rate of 1-hexene and 1-octene according to the control of the reaction temperature tends to increase the production rate of 1-hexene as the temperature of the multimerization reaction increases in oligomerization. This can be applied in practice.
  • the method for preparing an olefin oligomer comprising the step of multimerizing olefins in the presence of the oligomerization catalyst system may provide a method for oligomerization of olefins having improved activity and selectivity using the catalyst system for olefin oligomerization.
  • the olefin may include ethylene.
  • the olefin oligomerization method according to the present specification is a homogeneous liquid phase reaction in the presence or absence of an inert solvent, a slurry reaction in which the catalyst system is partially or completely insoluble using the oligomerization catalyst system and conventional apparatus and contacting techniques.
  • Biphasic liquid / liquid reactions, or bulk or gas phase reactions in which the product olefins serve as the main medium, and homogeneous liquid phase reactions may be preferred.
  • the olefin oligomerization process can be carried out in any inert solvent that does not react with the catalyst compound and the active agent.
  • suitable inert solvents include, but are not limited to, benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, hexane, pentane, butane, isobutane and the like.
  • the solvent may be used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum.
  • the olefin oligomerization reaction may be carried out at a pressure of about 1 bar to about 300 bar, preferably at a pressure of about 2 bar to about 150 bar.
  • the range of the pressure conditions may be a condition of the family register for multimerizing the olefin, and when the olefin is multimerized within the pressure range, the selectivity may be excellent for the desired alpha-olefin, and the amount of by-products is reduced. It can increase efficiency and reduce costs in process operation.
  • a 600 ml Parr reactor was prepared and vacuumed at 180 for 2 hours, after which the inside was replaced with argon and the temperature was lowered to 60, which was to react the temperature. Thereafter, 140 g of methylcyclohexane was injected into the reactor, and 6.6 ml (2.5 umol) of the premixed solution (oligomerization catalyst system) were injected into the reactor. Immediately after injection, the valve of the ethylene line set to 60 bar was opened to fill the reactor with ethylene, and then stirred for 15 minutes at a reaction temperature of 60 ° C. at 500 rpm.
  • the ethylene line valve was shut off, the reactor was cooled to zero using a dry ice / acetone bath, slowly unvented ethylene was vented and 1 ml of nonane (GC internal standard) was added. Thereafter, a small portion of the liquid portion of the reactor was quenched with water, and the organic layer was filtered with a PTFE syringe filter to perform GC analysis.
  • GC internal standard nonane
  • the preparation, oligomerization, GC analysis and weight measurement of the polymer were carried out in the same manner as in Example 1 except that the activation temperature was 60 ° C.
  • the preparation, oligomerization, GC analysis and weighing of the obtained polymer were carried out in the same manner as in Example 1 except that the oligomerization reaction temperature was 80 ° C.
  • the catalyst system was prepared, oligomerized, GC analyzed and obtained in the same manner as in Example 1 except that the activation temperature was 80 ° C and the oligomerization reaction temperature was 80 ° C. Weighing of the polymer was performed.
  • Example 1 in Examples 1 to 4 in which the promoter and the catalyst composition were activated at an aging temperature of ⁇ 40 to 80 ° C. and less than 5 minutes of aging time, Comparative Example 1 in which aging was performed for 5 minutes or more. It was confirmed that the activity of the catalyst system is much superior to that of 4 to 4. That is, the activation conditions of the catalyst composition and the promoter can be seen that the aging temperature is -40 to 80 °C, the aging time should be short time to less than 5 minutes.
  • cyclohexane and ethylene were continuously added to the 2 L CSTR reactor at a flow rate of 1.2 kg / hr and 1.75 kg / hr, respectively, so that the pressure was maintained at 60 bar.
  • the ligand and Cr (acac) 3 prepared in Preparation Example were added at a molar ratio of 0.55: 1, and then a catalyst solution diluted to 0.05 m in cyclohexane was introduced into the reactor at a rate of 5.8 ml / min.
  • a solution in which the promoter MMAO was diluted in cyclohexane was continuously added to the amount of the catalyst solution so that the Al: Cr ratio was 1200: 1.
  • the reaction temperature was adjusted to 60 ° C. by continuously adding water at room temperature to the reactor jacket. Under the condition that the reaction proceeds stably for 2 hours, the discharged reactant was collected for 1 hour, quenched with 5 mL of water, quenched with water, and the organic layer was filtered with a PTFE syringe filter to perform GC analysis. Table 2 shows.
  • the ethylene line valve was shut off, the reactor was cooled to zero using a dry ice / acetone bath, slowly unvented ethylene was vented and 1 ml of nonane (GC internal standard) was added. Thereafter, a small portion of the liquid portion of the reactor was quenched with water, and the organic layer was filtered with a PTFE syringe filter to perform GC analysis.
  • GC internal standard nonane
  • Example 6 the reaction was carried out with the temperature of the oligomerization reaction at 70 ° C, the ratio of 1-hexene to 1-octene was about 1: 3, and the reaction temperature was 70 ° C.
  • the reaction was carried out gradually increasing from to 110 ° C., the production ratio of 1-hexene and 1-octene was changed with tendency, and the weight ratio of 1-hexene and 1-octene was about 1: 3 to about 1: It was confirmed that gradually changes to about 0.9.
  • the production rate of 1-hexene and 1-octene was controlled by the mixing ratio of 1-hexene production catalyst and 1-octene production catalyst, so that the production rate could not be easily changed when the plant was in operation.
  • There are many problems such as by-products generated by the action, lowering the activity or overactivation, but in the oligomerization method provided herein, the production of 1-hexene and 1-octene by controlling only the temperature of the oligomerization reaction
  • the ratio can be controlled simply, which can be controlled from the intermediate or initial setting at which the process is running, and it has been found to have significant advantages.

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Abstract

La présente invention concerne un procédé de préparation d'un système catalytique d'oligomérisation, comprenant spécifiquement les étapes consistant à : préparer une composition catalytique en mélangeant un composé de ligand à base de PNP et un composé de métal de transition et à mélanger la composition catalytique avec un cocatalyseur à une température de -40 °C à 80 °C et à activer celle-ci. Le système catalytique d'oligomérisation préparé par le procédé ne perd pas son activité mais il peut la conserver même à haute température au cours d'une réaction d'oligomérisation, ce qui facilite la régulation de la température pour la réaction d'oligomérisation et présente éventuellement divers avantages en termes de traitement.
PCT/KR2016/001146 2015-02-12 2016-02-02 Procédé de préparation d'un système catalytique d'oligomérisation et système catalytique d'oligomérisation préparé par celui-ci WO2016129847A1 (fr)

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US15/528,576 US10870104B2 (en) 2015-02-12 2016-02-02 Method for preparing oligomerization catalyst system and oligomerization catalyst system prepared thereby
EP16749387.3A EP3257873B1 (fr) 2015-02-12 2016-02-02 Procédé de préparation d'un système catalytique d'oligomérisation et système catalytique d'oligomérisation préparé par celui-ci
CN201680004065.0A CN107001499B (zh) 2015-02-12 2016-02-02 用于制备低聚催化剂体系的方法以及由此制备的低聚催化剂体系

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07310078A (ja) * 1994-03-24 1995-11-28 Chevron Chem Co オリゴマーの製造方法
US20080207857A1 (en) * 2006-07-25 2008-08-28 Chevron Phillips Chemical Company Lp Olefin Oligomerization Catalysts and Methods of Using Same
KR20130126518A (ko) * 2012-05-10 2013-11-20 주식회사 엘지화학 에틸렌 올리고머화 방법
KR20130142151A (ko) * 2010-12-29 2013-12-27 셰브론 필립스 케미컬 컴퍼니 엘피 올레핀 올리고머화 촉매 및 제조 및 사용방법
KR20140063346A (ko) * 2012-11-15 2014-05-27 주식회사 엘지화학 리간드 화합물, 유기크롬 화합물, 에틸렌 올리고머화용 촉매계, 이의 제조 방법 및 이를 이용한 에틸렌 올리고머화 방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07310078A (ja) * 1994-03-24 1995-11-28 Chevron Chem Co オリゴマーの製造方法
US20080207857A1 (en) * 2006-07-25 2008-08-28 Chevron Phillips Chemical Company Lp Olefin Oligomerization Catalysts and Methods of Using Same
KR20130142151A (ko) * 2010-12-29 2013-12-27 셰브론 필립스 케미컬 컴퍼니 엘피 올레핀 올리고머화 촉매 및 제조 및 사용방법
KR20130126518A (ko) * 2012-05-10 2013-11-20 주식회사 엘지화학 에틸렌 올리고머화 방법
KR20140063346A (ko) * 2012-11-15 2014-05-27 주식회사 엘지화학 리간드 화합물, 유기크롬 화합물, 에틸렌 올리고머화용 촉매계, 이의 제조 방법 및 이를 이용한 에틸렌 올리고머화 방법

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