WO2019113748A1 - Système de catalyseur pour l'oligomérisation sélective d'éthylène et procédé de réaction d'oligomérisation d'éthylène - Google Patents

Système de catalyseur pour l'oligomérisation sélective d'éthylène et procédé de réaction d'oligomérisation d'éthylène Download PDF

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WO2019113748A1
WO2019113748A1 PCT/CN2017/115490 CN2017115490W WO2019113748A1 WO 2019113748 A1 WO2019113748 A1 WO 2019113748A1 CN 2017115490 W CN2017115490 W CN 2017115490W WO 2019113748 A1 WO2019113748 A1 WO 2019113748A1
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group
catalyst system
compound
ethylene
activator
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PCT/CN2017/115490
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Chinese (zh)
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姜涛
张乐
陈延辉
阿兰⋅法赫
邵怀启
李健
闫冰
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天津科技大学
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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
    • B01J31/16—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
    • 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
    • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
    • 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
    • C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
    • 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 invention belongs to the technical field of catalysis, and relates to a catalyst system for selective oligomerization of ethylene and an ethylene oligomerization reaction method.
  • Linear alpha-olefins are an important class of organic chemicals that are widely used in homopolymerization and copolymerization to produce polyethylene, surfactants, lubricants and oil additives.
  • the light component (C 4 -C 8 ) can be copolymerized with ethylene as a comonomer to produce linear low density polyethylene.
  • high-purity 1-hexene and 1-octene can significantly improve the abrasion resistance and other chemical and mechanical properties of linear low-density polyethylene.
  • the industrial production methods of 1-hexene and 1-octene mainly include paraffin cracking, ethylene oligomerization and extraction separation, and the ethylene oligomerization method is the main method for producing 1-hexene and 1-octene.
  • US 6,184,428 discloses a nickel catalyst which employs a boron compound as a cocatalyst to catalyze the oligomerization of ethylene to give a mixture of linear alpha olefins wherein the content of 1-hexene is 22% and the content of 1-octene is 19%.
  • SHOP process US3676523, US Pat. No. 3,635,937
  • the content of 1-hexene in the ethylene oligomerization product accounts for 21%
  • the content of 1-octene accounts for 11%.
  • the central metal of the ethylene selective trimerization catalyst currently studied is mainly chromium and titanium, and the chromium catalyst is used for the trimerization of ethylene to prepare 1-hexene (US5550305, US5198563), which has been industrialized, and the main product 1
  • the content of hexene is generally greater than 90%, but the content of 1-octene is less than 3%.
  • the central metal of the ethylene tetramerization catalyst is mainly chromium.
  • the ethylene tetramerization three-way catalyst system is highly selective for the synthesis of 1-octene (WO2004/056478A1, US2006/0229480 and US2006/0173226), and the content of 1-octene in the desired product reaches 60%.
  • the ligand structure in the catalyst system plays an important role in the selective oligomerization of ethylene, and the structure of the ligand directly affects the selectivity of the ethylene selective oligomerization catalyst system.
  • the present invention aims to propose a catalyst system for selective oligomerization of ethylene to solve the technical problem that the total selectivity of 1-hexene and 1-octene in the ethylene oligomerization reaction is not high.
  • a catalyst system for the selective oligomerization of ethylene comprising three components:
  • transition metal compound b being a metal compound of Groups IVB to VIII;
  • the activator c is a compound containing a Group IIIA metal
  • the ligand a contains at least one phosphonium group as shown in the formula I, and the formula I is as follows:
  • the bridging group A is a bridging group containing a hetero atom and an alkyl group, an alkenyl group or an aryl group as a main chain, wherein the hetero atom is one of silicon, tin, boron, phosphorus, nitrogen, oxygen or sulfur. ; R 1 , R 2 and R 3 are each a substituent group on two phosphonamine groups, and R 1 , R 2 and R 3 are the same or different.
  • the bridging group A is -(CH 2 )n-Si R"R"'-(CH 2 ) m - or -(CH 2 )n-BR'-(CH 2 ) m -, wherein 0 ⁇ n ⁇ 3, 0 ⁇ m ⁇ 3; R", R"' and R' are each independently selected from methyl, isopropyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or 2,6-di Isopropyl phenyl.
  • substituent groups R 1 , R 2 , and R 3 are each independently selected from the group consisting of methyl, isopropyl, cyclopentyl, cyclohexyl, phenyl, o-methylphenyl, o-ethylphenyl, ortho Isopropylphenyl, 2,4-dimethylphenyl, 2,4-diethylphenyl, 2,4-diisopropylphenyl, 2,4-dibutylphenyl, 2,6 -diisopropylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-dibutylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triethylphenyl, 2,4,6-triisopropylphenyl, naphthyl, anthracenyl, biphenyl; preferably methyl, isopropyl, cyclohexyl, phen
  • the transition metal compound b contains one of chromium, molybdenum, tungsten, lead, cobalt, titanium, ruthenium, vanadium, zirconium, iron, nickel or palladium.
  • transition metal compound b is one of CrCl 3 (THF) 3 , CoCl 3 , PbCl 2 (COD), and Pb(Ac) 2 .
  • the activator c is one or a mixture of two or more of an alkyl aluminum compound, an alkyl aluminoxane compound, an organoboron compound, an organic salt, an inorganic acid or an inorganic salt, wherein the alkyl aluminum
  • the oxyalkylene compound includes an alkyl aluminoxane compound which removes volatile components.
  • the activator c is a mixture of an alkyl aluminum compound and an alkyl aluminoxane compound from which a volatile component is removed, wherein the alkyl aluminum compound is triethyl aluminum (TEAL), the alkyl group
  • TEAL triethyl aluminum
  • DMAO methylaluminoxane
  • the invention also provides a preparation method of a catalyst system, comprising the steps of pre-mixing the ligand a, the transition metal compound b, the activator c or directly into the reaction system for in-situ synthesis.
  • the present invention also provides an ethylene oligomerization reaction process comprising ethylene oligomerization carried out in the presence of the above catalyst system.
  • reaction is carried out in an inert solvent which is one or a mixture of two or more of an alkane, an aromatic hydrocarbon, an olefin or an ionic liquid.
  • the temperature of the reaction is from 0 ° C to 200 ° C.
  • the pressure of the reaction is from 0.1 MPa to 50 MPa.
  • the catalyst system for ethylene selective oligomerization described in the present invention has the following advantages:
  • the catalyst system has high catalytic activity, and the total selectivity of the target products 1-hexene and 1-octene is high, and the 1-butene and 1-C 10 + mass percentages are low, wherein the product is C 6 - C
  • the linear percentage of the linear alpha-olefin is >90%.
  • the catalyst system is simple in synthesis, low in cost, and long in catalyst life.
  • transition metal compound b being a metal compound of Groups IVB to VIII;
  • the activator c is a compound containing a Group IIIA metal
  • the ligand a contains at least one phosphonium group as shown in the formula I, and the formula I is as follows:
  • the bridging group A is a bridging group composed of an alkyl group, an alkenyl group or an aryl group and a hetero atom as a main chain, wherein the hetero atom is silicon, tin, boron, phosphorus, nitrogen, oxygen or sulfur.
  • R 1 , R 2 , and R 3 are each a substituent group on two phosphonamine groups, and R 1 , R 2 , and R 3 are the same or different.
  • Embodiments of the present invention provide a catalyst system for selective oligomerization of ethylene, comprising three components of a ligand a, a transition metal compound b, and an activator c.
  • the ligand a is a ligand containing at least one bisphosphine group as shown in Formula I
  • the transition metal compound b is a metal compound of Groups IVB to VIII, which is a central metal atom
  • the activator c is a group IIIA.
  • ligand a effectively regulates the electronic effect and steric hindrance effect of the ligand on the active center of the metal according to the length of the bridging group A and the abundant substituent groups on each hetero atom.
  • the catalyst system of the examples of the present invention can be used for selective oligomerization of ethylene with excellent total selectivity of 1-hexene and 1-octene.
  • the phosphonamine coordinating group is different from other monohetero atomic coordinating groups, and adopts a similar ⁇ 2 coordination mode with the metallocene compound ( ⁇ 5 ). It has stronger coordination ability, which makes the catalyst have better chemical stability.
  • the hetero atom in the bridging group A has stronger electronegativity than the carbon atom, and can also enhance the coordination of the ligand with the metal center. The ability to enhance its chemical stability; again, the length of the bridging group and the different substituent groups on each hetero atom have different steric hindrance effects on the metal active center, thereby affecting the selectivity of the catalyst.
  • an appropriate compound containing a Group IIIA metal is selected according to the difference in alkylation strength to achieve an optimum activation.
  • the metal compounds selected from the group IVB to VIII are selected from the group IVB to VIII.
  • the catalyst system provided by the embodiment of the invention has a ligand structure combined with a corresponding transition metal compound and an activator, which has an important influence on the catalytic activity of selective oligomerization of ethylene and the selectivity of 1-hexene and 1-octene, and the ligand structure
  • the type and number of the mesogenic groups and the type and length of the bridging group exert an influence on the metal active center from both the electronic effect and the steric hindrance effect, thereby affecting the catalytic activity and selectivity of the catalyst, so that the present invention is implemented.
  • the catalyst system provided by the example can achieve high selectivity of 1-hexene and 1-octene when ethylene oligomerizes.
  • the molar ratio of the ligand a to the transition metal compound b in the catalyst system may be from 1:0.5 to 100.
  • the molar ratio of the ligand a to the activator c in the catalyst system may be from 1:0.1 to 5,000, preferably from 1:1 to 1,000, more preferably from 1:1 to 200.
  • the molar ratio of the ligand a, the transition metal compound b, and the activator c is 1:0.5 to 100:0.1 to 5000; preferably, the molar ratio of the ligand a, the transition metal compound b, and the activator c is 1. 0.5 to 100: 0.1 to 1000; more preferably, the molar ratio of the ligand a, the transition metal compound b, and the activator c is 1:0.5 to 100:0.1 to 200.
  • the catalyst system further comprises an inert solvent, which may be an alkane, an aromatic hydrocarbon, an olefin or an ionic liquid, preferably methylcyclohexane.
  • an inert solvent which may be an alkane, an aromatic hydrocarbon, an olefin or an ionic liquid, preferably methylcyclohexane.
  • the bridging group A contains a hetero atom, which is one of silicon, tin, boron, phosphorus, nitrogen, oxygen or sulfur.
  • the bridging group A includes a bridging group of a linear alkane as a main chain, and the linear alkane is methane, ethane, propane, butane, pentane or hexane.
  • the bridging group A includes a bridging group of an aromatic hydrocarbon or an olefin group as a main chain, the olefin may be ethylene, propylene, butylene, and the aromatic hydrocarbon may be benzene or toluene.
  • the bridging group A main chain contains a hetero atom and a bridging group of an alkyl group, an alkenyl group or an aryl group of 1 to 8 carbon atoms. This distance is more favorable for coordination between atoms.
  • the bridging group A may be a linear bridging group containing a silicon atom or a boron atom -(CH 2 )n-SiR"R"'-(CH 2 ) m - or -(CH 2 )n- BR'-(CH 2 ) m -, wherein 0 ⁇ n ⁇ 3, 0 ⁇ m ⁇ 3; R", R"' and R' are independently selected from methyl, isopropyl, cyclohexyl, cyclopentyl, Phenyl, naphthyl or 2,6-diisopropylphenyl.
  • the bridging group A may be -(CH 2 ) n Sn(R 6 R 7 )(CH 2 ) m -, -(CH 2 ) n P(R 6 )(CH 2 ) m -, -(( CH 2 ) n N(R 6 )(CH 2 ) m -, -(CH 2 ) n O(CH 2 ) m - or -(CH 2 ) n S(CH 2 ) m -(0 ⁇ n ⁇ 4, 0 ⁇ m ⁇ 4), wherein R 6 and R 7 are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclopentyl, cyclohexyl, isobutyl, tert-butyl Base, adamantyl, vinyl, allyl, phenyl, benzyl, phenyl, tolyl, xylyl, 2,4,6
  • the substituent groups R 1 , R 2 , and R 3 are each independently selected from the group consisting of methyl, isopropyl, cyclopentyl, cyclohexyl, phenyl, o-methylphenyl, o-ethyl.
  • the substituent R 3 is selected from phenyl.
  • the substituent R 3 is independently selected from isopropyl, cyclopentyl, methyl or cyclohexyl.
  • the ligand a may be one or two or more units of the structure of the formula I, which are bonded together by groups, chemical bonds or intermolecular forces to obtain bridges, dendrites and stars.
  • the compound may also be a polymerized polymer formed by binding to a polymer chain.
  • the ligand a may be (R 2 ) 2 PNR 3 ANR 3 P(R 1 ) 2 , wherein A is a bridging group containing the above hetero atom; R 1 , R 2 , R 3 Respectively a substituent group on two phosphonamine groups, R 1 , R 2 , R 3 are the same or different and are independently selected from methyl, isopropyl, cyclohexyl, cyclopentyl, phenyl, 2, 6 - Diisopropylphenyl or naphthyl.
  • the ligand a may also be -[(R 2 ) 2 PNR 3 ANR 3 P(R 1 ) 2 ] n B, n ⁇ 2, wherein A is a bridging group containing the above hetero atom.
  • R 1 , R 2 , and R 3 are each a substituent group on two phosphonamine groups, and R 1 , R 2 , and R 3 are the same or different and are independently selected from methyl, isopropyl, cyclohexyl, Phenyl, 2,6-diisopropylphenyl or naphthyl;
  • B is a bridging group between formula I, which may be methyl, hexyl, propyl or butyl, or may be aryl and A bridging group containing a hetero atom.
  • the transition metal compound b contains one of chromium, molybdenum, tungsten, lead, cobalt, titanium, ruthenium, vanadium, zirconium, iron, nickel or palladium.
  • the transition metal compound b is one of CrCl 3 (THF) 3 , CoCl 3 , PbCl 2 (COD), and Pb(Ac) 2 .
  • the transition metal compound b is a transition metal compound containing chromium, zirconium or titanium.
  • the transition metal compound b is a chromium-containing transition metal compound.
  • the optional chromium compound includes a compound of the formula CrR n m wherein R n is an organic negative ion or a neutral molecule, R n usually contains 1 to 10 carbon atoms, n is an integer of 0 to 6, and chromium The price is 0 to 6.
  • R n groups are organic groups containing a carboxyl group, a ⁇ -diketone group, and a hydrocarbon group or a group thereof.
  • chromium compounds include chromium acetate, chromium isooctanoate, chromium n-octanoate, chromium acetylacetonate, chromium diisoprene, diphenylchromium, CrCl 3 (THF) 3 , CrCl. 2 (THF) 2 , (phenyl) tricarbonyl chromium, hexacarbonyl chromium.
  • the activator c is an alkyl aluminum compound, an alkyl aluminoxane compound, or an organic boron.
  • an alkyl aluminum compound an alkyl aluminoxane compound, or an organic boron.
  • the aluminum alkyl compound may be various trialkyl aluminums such as TEAL, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum or tri-n-octyl aluminum; alkyl aluminum compounds may also be used.
  • TEAL triisobutyl aluminum
  • tri-n-butyl aluminum tri-n-hexyl aluminum or tri-n-octyl aluminum
  • alkyl aluminum compounds may also be used.
  • alkyl aluminum halide an alkyl aluminum hydride or an alkyl aluminum sesquichloride such as AlEt 2 Cl and A1 2 Et 3 C1 3 ;
  • the alkyl aluminoxane compound may be selected from methyl aluminoxane (MAO) , ethyl aluminoxane, isobutyl aluminoxane, modified aluminoxane, and methyl aluminoxane to remove volatile components.
  • MAO methyl aluminoxane
  • the activator c is a mixture of an alkyl aluminum compound and an alkyl aluminoxane which removes a volatile component, wherein the alkyl aluminum compound is TEAL, and the alkyl aluminoxane compound is DMAO .
  • the molar ratio of TEAL to DMAO is from 0.01 to 100, preferably from 0.1 to 10.
  • an organic salt activator such as methyl lithium, methyl magnesium bromide or the like
  • an inorganic acid and an inorganic salt activator such as tetrafluoroborate etherate, tetrafluoroborate, hexafluorocarbon A phthalate or the like
  • the organoboron compound includes boroxine, sodium borohydride, triethylborane, tris(pentafluorophenyl)boron, tributylborate, and the like.
  • the bridging group A in the ligand a may be -(CH 2 )n-SiR"R"'-(CH 2 ) m - or -(CH 2 )n-BR'-(CH 2 ) m -, wherein 0 ⁇ n ⁇ 3, 0 ⁇ m ⁇ 3; R", R"' and R' are independently selected from methyl, isopropyl, Cyclohexyl, cyclopentyl, phenyl, naphthyl or 2,6-diisopropylphenyl, the bridging group A of the ligand a may also be -(CH 2 ) n Sn(R 6 R 7 )( CH 2 ) m -, -(CH 2 ) n P(R 6 )(CH 2 ) m -, -(CH 2 ) n N(R 6 )(CH 2 )
  • the substituent groups R 1 , R 2 and R 3 of the ligand a are each independently selected from methyl, isopropyl, cyclohexyl, phenyl, 2,6-diisopropylphenyl or naphthyl;
  • the transition metal compound b may be one of CrCl 3 (THF) 3 , CoCl 3 , PbCl 2 (COD), and Pb(Ac) 2 ; or may be chromium acetate, chromium isooctanoate, chromium n-octanoate, chromium acetylacetonate, One of diisoprene chromium, diphenylchromium, CrCl 3 (THF) 3 , CrCl 2 (THF) 2 , (phenyl) chromium tricarbonyl, chromium hexacarbonyl;
  • the activator c may be a trialkyl aluminum such as TEAL, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum or tri-n-octyl aluminum; or may be an alkyl aluminum halide or an alkyl aluminum hydrogenated Or an alkyl aluminum sesquichloride such as AlEt 2 Cl and A1 2 Et 3 C1 3 ;
  • the aluminoxane compound may be selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane and modification Aluminoxane and methylaluminoxane to remove volatile components.
  • the activator c may also be a mixture of one or more of the above, such as the activator c being a mixture of the TEAL and the DMAO, wherein the molar ratio of the TEAL to the DMAO is 0.01 to 100, preferably 0.1 to 10.
  • the activator c may also be an organic salt activator such as methyl lithium, methyl magnesium bromide or the like or an inorganic acid and an inorganic salt activator such as tetrafluoroborate etherate, tetrafluoroborate, hexafluoroantimony.
  • the acid salt or the like; or the organic boron compound includes boroxine, sodium borohydride, triethylborane, tris(pentafluorophenyl)boron, tributylborate or the like.
  • the synthesis of the ligand a comprises the following steps:
  • R 3 NHLi Preparation of R 3 NHLi. A certain amount of R 3 NH 2 is first dissolved in an appropriate amount of n-hexane, and then n-butyllithium is added dropwise at a certain temperature to form R 3 NHLi.
  • R 3 NHPR 1 2 (2) Preparation of R 3 NHPR 1 2 .
  • Appropriate amount of R 3 NHLi was dispersed in n-hexane; an appropriate amount of R 1 2 PCl solution in n-hexane was added, and it was slowly added dropwise to the hexane turbid solution of R 3 NHLi, stirred at room temperature overnight, and then filtered through a sand core funnel. After concentration in vacuo, crystallization treatment was carried out to obtain R 3 NHPR 1 2 .
  • R 3 NLiPR 1 2 Preparation of R 3 NLiPR 1 2 .
  • a certain amount of R 3 NHPR 1 2 was dissolved in n-hexane, cooled to -35 ° C, and a certain amount of n-butyl lithium n-hexane solution was slowly added dropwise to the above solution, and then naturally increased to room temperature after the completion of the addition, and continued.
  • the filter cake was the R 3 NLiPR 1 2 product.
  • the method for preparing the catalyst system comprises the following steps:
  • the components a, b, c are premixed or added directly to the reaction system for in situ synthesis. That is to say, the preparation of the catalyst is to premix the ligand a, the transition metal compound b, and the activator c which are connected by a bridging group containing a hetero atom; or to be linked by a chain group containing a hetero atom; The body a, the transition metal compound b, and the activator c are directly added to the reaction system for in situ synthesis;
  • the reaction mode of the ligand a, the transition metal compound b and the activator c which are linked by the hetero atom-containing bridging group described in the general formula I can be carried out by a liquid phase reaction, for example, under the action of a solvent.
  • the selected solvent such as toluene, benzene and its derivatives may also be reacted by a solid phase; or may be formed by in situ reaction during the oligomerization reaction.
  • the reaction described herein may be a reaction between one, two, and three compounds of the above hetero atom ligand, transition metal compound, and metal organic activator. The process of this reaction is also the aging (pre-complexation) process of the catalyst.
  • the present invention also provides an ethylene oligomerization reaction process comprising the ethylene oligomerization reaction carried out in the presence of the above catalyst system.
  • the reaction is carried out in an inert solvent which is one or more of an alkane, an aromatic hydrocarbon, an olefin or an ionic liquid.
  • Typical solvents include, but are not limited to, benzene, toluene, xylene, cumene, n-heptane, n-hexane, methylcyclohexane, cyclohexane, 1-hexene, 1-octene, ionic liquids, and the like. Methylcyclohexane is preferred.
  • the reaction temperature is from 0 ° C to 200 ° C, preferably from 50 ° C to 150 ° C.
  • the pressure of the ethylene oligomerization reaction may be carried out at a pressure of from 0.1 MPa to 50 MPa, preferably from 1.0 MPa to 10 MPa.
  • the concentration of the catalyst in the reaction system may be from 0.01 ⁇ mol of metal/L to 1000 ⁇ mol of metal/L, preferably 0.1 ⁇ mol of metal/L to 10 ⁇ mol of metal/L.
  • Lithium anilide (4.95 g, 0.050 mol) was dissolved in dehydrated n-hexane (100 ml) in a N 2 atmosphere glove box and added to a 250 mL reactor, cooled to -35 ° C, vigorously stirred; Isopropylphosphonium chloride (7.48g, 0.049mol) was slowly added dropwise to the above solution. After completion, it was naturally warmed to room temperature and stirring was continued overnight. After filtration, the volatile components in the filtrate were vacuumed to obtain a yellow liquid. Distillation was carried out, and a fraction of 145 ° C to 150 ° C was collected to obtain a colorless liquid product of 8.79 g (0.042 mol, 85%).
  • 1,1-diisopropyl-N-phenylphosphinoamine (8.37 g, 0.040 mol) was dissolved in dehydrated n-hexane (100 mL) and cooled to -35 ° C.
  • the n-butyllithium n-hexane solution (17.1 mL, 0.041 mol, 2.4 mol/L) was slowly added dropwise to the above solution while stirring. After the completion of the dropwise addition, stirring was continued overnight, and the filter cake was washed twice with 20 mL of n-hexane after filtration.
  • the 500 mL autoclave was heated to evacuation for 2 hours, replaced with nitrogen several times, charged with ethylene, cooled to a predetermined temperature, and dehydrated methylcyclohexane (200 mL) and the above catalyst were added.
  • the oligomerization reaction was carried out at 45 ° C under a pressure of 1 MPa, and after reacting for 30 minutes, the mixture was cooled with an ice bath, pressure was released, and the reaction was terminated with an acidified ethanol having a mass fraction of 10%.
  • the oligomerized product was 35.5 g and the catalyst activity was 2.15 x 10 6 g oligomer/mol Cr ⁇ h.
  • the distribution of oligomerized products is shown in Table 1.
  • Example 1 Same as Example 1. The difference is that R 1 and R 2 are each a phenyl group, and R 3 is a cyclopentyl group.
  • the oligomerized product was obtained in an amount of 83.2 g, and the catalyst activity was 5.04 ⁇ 10 6 g of oligomer/mol Cr ⁇ h.
  • the distribution of oligomerized products is shown in Table 1.
  • Example 1 Same as Example 1. The difference is that R 1 , R 2 and R 3 are all isopropyl groups, and A is a dimethylsilyl group (-Si(CH 3 ) 2 CH 2 -). 91.7 g of an oligomerization product was obtained, and the catalyst activity was 5.56 ⁇ 10 6 g oligomer/mol Cr ⁇ h. The distribution of oligomerized products is shown in Table 1.
  • A is a dimethyldimethylenesilyl group (-CH 2 Si(CH 3 ) 2 CH 2 -).
  • the oligomerized product 77.1 g was obtained, and the catalyst activity was 4.67 ⁇ 10 6 g oligomer/mol Cr ⁇ h.
  • the distribution of oligomerized products is shown in Table 1.
  • A is a methylcyclohexyldimethylenesilyl group (-CH 2 Si(CH 3 )(C 6 H 11 )CH 2 -). 65.7 g was obtained with a catalyst activity of 3.98 x 10 6 g oligomer/mol Cr ⁇ h. The distribution of oligomerized products is shown in Table 1.
  • A is a methylphenyl dimethylene silicon group (-CH 2 Si(CH 3 )(C 6 H 5 )CH 2 -). 82.9 g was obtained with a catalyst activity of 5.02 x 10 6 g oligomer/mol Cr ⁇ h. The distribution of oligomerized products is shown in Table 1.
  • A is a diphenyl dimethylene silicon group (-CH 2 Si(C 6 H 5 ) 2 CH 2 -). 85.2 g was obtained and the catalyst activity was 5.16 x 10 6 g oligomer/mol Cr ⁇ h.
  • the distribution of oligomerized products is shown in Table 1.
  • R 3 is an isopropyl group and A is a phenyl boron group (-B(C 6 H 5 )-).
  • the oligomerized product was obtained in an amount of 62.5 g, and the catalyst activity was 3.79 ⁇ 10 6 g of oligomer/mol Cr ⁇ h.
  • the distribution of oligomerized products is shown in Table 1.
  • the difference is that the ethylene pressure is 2 MPa.
  • the oligomerized product was obtained in an amount of 112.5 g, and the catalyst activity was 6.82 ⁇ 10 6 g of oligomer/mol Cr ⁇ h.
  • the distribution of oligomerized products is shown in Table 1.
  • the difference is that the cocatalyst is MAO.
  • the oligomerized product was obtained in an amount of 302.0 g, and the catalyst activity was 1.83 ⁇ 10 7 g oligomer/mol Cr ⁇ h.
  • the distribution of oligomerized products is shown in Table 1.
  • Example 11 Same as Example 11. The difference is that the chromium compound is CrCl 2 (THF) 2 .
  • the oligomerized product was obtained in an amount of 22.8 g, and the catalyst activity was 1.38 ⁇ 10 6 g of oligomer/mol Cr ⁇ h.
  • the distribution of oligomerized products is shown in Table 1.
  • the catalyst system can catalyze the highly selective trimerization and tetramerization of ethylene to hexene and octene, wherein 1-hexene and 1-octene have higher total selectivity.
  • R 3 is a phenyl group in Example 1
  • the steric hindrance is relatively large
  • the catalytic system catalyzes the highly selective trimerization of ethylene
  • the 1-C 6 selectivity is relatively high
  • R 3 is different.
  • the steric hindrance is relatively small, and the catalytic system catalyzes the highly selective tetramerization of ethylene.
  • Example 14 when the cocatalyst was MAO, the product became an S-F distribution, indicating that when the cocatalyst was mixed with DMAO and TEAL, the catalytic system catalyzed the best selectivity for ethylene trimerization and tetramerization. Because the TEAL alkylation ability is relatively weak, it is more suitable for the catalyst system proposed by the present invention; at the same time, DMAO can shield the influence of volatile components such as toluene on the complexation process of the catalyst, thereby improving the activity of the catalyst system.

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Abstract

L'invention concerne un système catalyseur pour l'oligomérisation sélective de l'éthylène, le système catalyseur appartenant au domaine des technologies de catalyse. Le système catalyseur comprend trois composants : un ligand a; un composé b de métal de transition, qui est un composé d'un métal des groupes IVB-VIII; et un activateur c, qui est un composé contenant un métal du groupe IIIA, le ligand a comprenant au moins un groupe phosphine ou amine tel que représenté par la formule générale I, et le groupe de pontage A étant un groupe de pontage constitué d'un groupe alkyle, d'un groupe alcényle ou d'un groupe aryle et d'un hétéroatome dans le squelette, l'hétéroatome étant un atome de silicium, d'étain, le bore, de phosphore, d'azote, d'oxygène ou de soufre; et R1, R2, et R3 représentent respectivement des substituants sur deux des groupes amine ou phosphine, avec R1, R2, et R3 étant identiques ou différents. La présente invention présente les effets bénéfiques du système catalyseur ayant une activité élevée, les sélectivités pour des produits cibles 1-hexène et 1-octène étant élevées, le pourcentage en masse de C6-C8 alpha-oléfines linéaires dans le produit étant > 90 %, et le catalyseur étant simple à synthétiser, de faible coût et de longue durée de vie.
PCT/CN2017/115490 2017-12-11 2017-12-11 Système de catalyseur pour l'oligomérisation sélective d'éthylène et procédé de réaction d'oligomérisation d'éthylène WO2019113748A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101351269A (zh) * 2005-11-21 2009-01-21 国际壳牌研究有限公司 烯烃单体的催化低聚
CN103100420A (zh) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 用于乙烯四聚的催化剂组合物及其中配体的制备方法
CN103402951A (zh) * 2010-12-01 2013-11-20 诺瓦化学品(国际)股份有限公司 乙烯低聚中的热管理
CN105683135A (zh) * 2014-06-18 2016-06-15 株式会社Lg化学 用于制备烯烃低聚物的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101351269A (zh) * 2005-11-21 2009-01-21 国际壳牌研究有限公司 烯烃单体的催化低聚
CN103402951A (zh) * 2010-12-01 2013-11-20 诺瓦化学品(国际)股份有限公司 乙烯低聚中的热管理
CN103100420A (zh) * 2011-11-09 2013-05-15 中国石油化工股份有限公司 用于乙烯四聚的催化剂组合物及其中配体的制备方法
CN105683135A (zh) * 2014-06-18 2016-06-15 株式会社Lg化学 用于制备烯烃低聚物的方法

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