WO2020034476A1 - Ligand à effet de cage organique poreux contenant p et n, catalyseur complexe et utilisation - Google Patents

Ligand à effet de cage organique poreux contenant p et n, catalyseur complexe et utilisation Download PDF

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WO2020034476A1
WO2020034476A1 PCT/CN2018/116378 CN2018116378W WO2020034476A1 WO 2020034476 A1 WO2020034476 A1 WO 2020034476A1 CN 2018116378 W CN2018116378 W CN 2018116378W WO 2020034476 A1 WO2020034476 A1 WO 2020034476A1
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porous organic
organic cage
ligand
reaction
monomer
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丁云杰
李存耀
汪文龙
严丽
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
    • 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
    • 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
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2461—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring
    • B01J31/248—Bridged ring systems, e.g. 9-phosphabicyclononane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/228—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing six-membered aromatic rings, e.g. phenylacetaldehyde
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention belongs to the field of catalysis and fine chemical industry, and particularly relates to a porous organic cage ligand containing P and N, a preparation method thereof and application of a corresponding complex catalyst in a hydroformylation reaction.
  • Aldehydes are very commonly used chemical intermediates with relatively active chemical properties. Aldehydes can be oxidized to form carboxylic acids and corresponding esters, as well as fatty amines. Aldehydes can also be reduced by hydrogenation to form alcohols. Alcohols can be used as organic solvents, plasticizers, and Surfactants are widely used in the field of fine chemicals. The aldehyde itself and subsequent derivatives are very useful chemical intermediates. There are many industrial aldehyde synthesis methods. The olefin hydroformylation reaction is a typical atomic economic reaction. It can selectively convert olefins and synthesis gas (CO / H 2 ) to nearly 100% selectively into product aldehydes with zero waste emissions. The process of green aldehyde synthesis by olefin hydroformylation is receiving more and more attention.
  • the aldehyde produced by hydroformylation around the world is about 12 million tons per year, and about 50% of the aldehyde is butyraldehyde produced by propylene hydroformylation.
  • Table 1 describes the comparison of propylene hydroformylation production process conditions and catalytic performance of the fifth-generation catalysts that have been applied industrially.
  • the first four generations of the fifth-generation catalysts that have been industrialized are homogeneous catalysis processes and the fifth generation are two-phase catalysis processes. The process did not solve the problem of metal and ligand loss during the reaction.
  • the fifth-generation catalysis technology that has been industrialized is difficult to recycle the catalyst, the loss of metals and ligands is serious, and the production cost is high.
  • people have done a lot of work in the field of hydroformylation catalysts for heterogeneous catalysis and heterogeneous catalysis.
  • the traditional homogeneous catalyzed heterogeneous methods have exposed a series of problems to be solved and overcome. Especially after heterogeneous catalysts, the stability of the catalyst is poor, and the loss of active components is serious, etc. (Chemical reviews, 2012, 112 (11): 5675-5732 .; Eur. J. Org. Chem., 2012, 2012: 6309-6320).
  • an object of the present invention is to provide a P, N-containing porous organic cage ligand, a preparation method thereof, and application of a corresponding complex catalyst in a hydroformylation reaction.
  • the TOF value of this kind of catalyst can reach more than 3000h -1 , and the selectivity of alkane in the obtained product is less than 1%, and the selectivity of aldehyde is more than 90%.
  • the technical solution of the present invention is:
  • the composite catalyst is charged into the reactor, and the reaction mixture and the raw olefin are introduced.
  • the main components of the mixture are H 2 and CO, the H 2 / CO volume ratio is 0.5 to 5.0, and the space velocity of the mixed gas is 100 to 20000 h.
  • the preferred range of -1 is 1000 to 20000 h -1 ; the olefinic raw material is C 3 to C 20 olefin, the reaction temperature is 323 to 573K, and the reaction pressure is 0.1 to 10.0 MPa under conditions of hydroformylation of olefin.
  • the mixed gas may further contain one or two or more remaining gases selected from Ar, CO 2 , He or N 2 , and the volume content of H 2 + CO in the mixed gas is 20 to 90%; the reactor is Kettle reactor; mass purity of olefins is 20 to 100%, and other components that may be contained in the olefins are one or more of C 3 to C 20 alkanes; the C 3 to C 20 olefins are preferably C 5 ⁇ C 14 olefin.
  • the reaction temperature is preferably 353 to 423K, and the reaction pressure is preferably 0.5 to 2 MPa.
  • the complex catalyst formed by the P, N-containing porous organic cage ligand and transition metal uses P, N-containing porous organic cage ligand as the ligand, and the metal One or two or more of Rh, Co, Ir, Pd or Pt are used as active components; the P and N-containing porous organic cage ligands are functionalized P and / or N ligands with functional groups such as aldehyde groups and amino groups as Monomers, with corresponding polyamines or polyaldehydes as co-monomers.
  • P, N-containing porous organic cage ligands are added to a solution containing one or two or more of the active components Rh, Co, Ir, Pd or Pt precursors, and stirred and coordinated to obtain P, N-containing porous organic Complex catalyst formed by cage ligand and transition metal.
  • the P and N ligands functionalized with functional groups such as aldehyde group and amino group may be one or two or more kinds of monodentate or multidentate ligands; the co-monomer polyamine or polyaldehyde is binary or more than two.
  • the monomer may be one kind or two or more kinds;
  • the P, N porous organic cage ligands have a specific pore structure, and a specific surface area is 0 to 3000 m 2 / g, and a preferred range is 10 to 1000 m 2 / g. 0 to 10.0 cm 3 / g, preferably 0.5 to 2.0 cm 3 / g, and a pore size distribution of 0.01 to 100.0 nm, preferably 0.5 to 20.0 nm;
  • the preparation method of P and / or N-containing porous organic cage ligands is as follows: P, N ligands functionalized with functional groups such as aldehyde groups and amino groups, and polyamines or polyaldehyde comonomers are fully dissolved and mixed in a solvent. Allow to stand or stir at temperature to make the P and N ligands and the functional groups in the co-monomer fully react to form P and N porous organic cage ligands with a specific pore structure;
  • a method for preparing a complex catalyst formed by a porous organic cage ligand containing P and N and a transition metal is as follows: the precursor of the active metal component and the porous organic cage ligand containing P and N are fully stirred in a solvent, and the active metal component and the The bare P in the porous organic cage ligand containing P and N forms a strong coordination bond. After the solvent is distilled off, a complex catalyst formed by the porous organic cage ligand containing P and N and a transition metal is obtained.
  • step b) concentrating the mixed solution containing P and N porous organic cage ligands obtained in step a), adding an alcoholic solvent, and crystallizing the porous organic cage ligands;
  • step b filtering the P, N porous organic cage ligand obtained in step b), filtering, washing and drying to obtain a P, N porous organic cage ligand product;
  • a method for preparing a complex catalyst containing a P, N porous organic cage ligand and a transition metal is:
  • step d) Under an inert gas atmosphere of 273 to 473K, add the porous organic cage ligand obtained in step c) to a solvent containing a precursor of an active metal component, and stir for 0.1 to 100 hours, preferably for a stirring time range of 0.1 to 20 hours.
  • the solvent was removed under vacuum at room temperature to obtain a complex catalyst formed by P, N porous organic cage ligands and transition metals.
  • the solvents described in steps a) and d) are dichloromethane, chloroform, carbon tetrachloride, ethyl acetate, methyl formate, benzene, toluene, xylene, n-hexane, n-heptane, n-octane
  • cyclohexane dimethyl sulfoxide, N, N-dimethylformamide or tetrahydrofuran
  • the alcohol solvent described in step b) is one or two or more of water, methanol, ethanol, n-propanol, isopropanol, n-butanol and the like;
  • the washing solvent in step c) can be selected from one or more of water, methanol, ethanol, n-propanol, isopropanol, n-butanol, etc., and the drying method can be selected from normal pressure drying, reduced pressure drying, and spray drying. Or one or more of boiling drying and freeze drying.
  • the concentration of functionalized P, N ligands such as aldehyde groups and amino groups in step a) in the solvent ranges from 0.01 to 1000 g / L, preferably 0.1 to 10 g / L.
  • Functional groups such as aldehyde groups and amino groups are functionalized
  • the molar ratio of P, N and comonomer is 0.01: 1 to 100: 1, preferably 0.1: 1 to 10: 1.
  • the catalyst can be selected from hydrochloric acid, acetic acid, sulfuric acid, phosphoric acid, and nitric acid.
  • the molar ratio of P, N ligand monomer functionalized with aldehyde group, amino group and other functional groups to the catalyst is 10,000: 1-100: 1, as described in steps a), b) and c).
  • the inert gas is selected from one or two or more of Ar, He, N 2 and CO 2 .
  • the active component described in step d) is one or more of Rh, Co, Ni, Ir, Pd or Pt, wherein the precursor of Rh is RhH (CO) (PPh 3 ) 3 , Rh (CO ) 2 (acac), RhCl 3 , Rh (CH 3 COO) 2 or more than two kinds; the precursors of Co are Co (CH 3 COO) 2 , Co (CO) 2 (acac), Co (acac ) 2 or one or more of CoCl 2 ; the precursor of Ni is one or two of Ni (CH 3 COO) 2 , Ni (CO) 2 (acac), Ni (acac) 2 , NiCl 2 More than one species; one or two or more of Ir (CO) 3 (acac), Ir (CH 3 COO) 3 , Ir (acac) 3 , and IrCl 4 ; precursors of Pd are Pd (CH 3 COO) 2 , Pd (acac) 2 , PdCl 2 , P
  • P, N-containing porous organic ligands are soluble in some polar solvents, but insoluble in alcohol solvents such as methanol, so the complex catalyst formed by P, N porous organic cage ligands has homogeneous reactions and heterogeneous Recycling features.
  • the catalyst formed by the P, N porous organic cage ligands and the transition metal is in a homogeneous reaction state, and the reactants and the catalytic center are fully contacted to ensure good catalytic performance.
  • an alcohol solvent is added, and the P and N porous organic compounds are added.
  • the cage ligand complex catalyst is crystallized from the reaction system to realize catalyst recovery.
  • P, N-containing porous organic cage ligands are cross-linked with P, N ligands functionalized with functional groups such as aldehyde groups and amino groups, and corresponding polyamines or polyaldehydes as comonomers.
  • the synthesized P and N porous organic cage ligands have stable and unique pore structures and can be used for selective adsorption and separation of gases; P, N ligands catalyze the hydroformylation reaction, coupling reaction, silicon Hydrogenation reactions, hydrogenation reactions and CO 2 cycloaddition reactions have a wide range of applications.
  • Porous organic cage ligands containing P and N retain the good ligand properties of P and N ligands.
  • P and N porous organic cage ligands Due to the specific structure of P and N porous organic cage ligands, P and N porous organic cage ligands have the Different electronic and three-dimensional effects of N ligands. At the same time, the cavity of P and N porous organic cage ligands has the property of concentrating reactants, so the complex catalyst formed by P, N porous organic cage ligands and transition metals Showed more efficient catalytic performance than the corresponding P, N ligand complex catalyst.
  • the P and N ligands in the P and N-containing porous organic cage ligands prepared by the present invention can coordinate with the active metal to form a complex catalyst. Since the cage ligand has good solubility in solvents such as dichloromethane, it can crystallize out in solvents such as methanol. Therefore, the complex catalyst formed by P, N porous organic cage ligands has the characteristics of homogeneous reaction and heterogeneous recovery. During the reaction, the catalyst formed by P, N porous organic cage ligands and transition metals is in a homogeneous reaction state. Full contact with the catalytic center to ensure good catalytic performance.
  • the complex catalyst formed by the P and N porous organic cage ligands and transition metals provided by the present invention performs well in the hydroformylation reaction, and the TOF value of the catalyst can reach more than 3000 h -1 .
  • the alkane in the obtained product is selected The property is less than 1%, and the selectivity of aldehyde is more than 90%.
  • the preparation method of the P, N-containing porous organic cage ligands and the corresponding complex catalysts is prepared by olefin hydroformylation reaction, coupling reaction, hydrosilylation reaction, hydrogenation reaction and CO 2 cycloaddition. Reactions such as formation reactions provide new industrial technologies.
  • FIG. 2 Schematic diagram of the synthesis of typical PPh 3 porous organic cage ligands
  • FIG. 3 Schematic diagram of the monomers required for the synthesis of porous organic cage ligands containing P and N.
  • L1-L62 are aldehyde or amino-functionalized P and N ligand monomers
  • L63-L74 are polyaldehyde and polyvalent Amine comonomer
  • Figure 4 1 H spectrum of a typical aldehyde-functionalized PPh 3 ligand monomer (Figure 3L1)
  • Figure 5 13 C spectrum of a typical aldehyde-functionalized PPh 3 ligand monomer (Figure 3L1)
  • Figure 6 31 P spectrum of a typical aldehyde-functionalized PPh 3 ligand monomer ( Figure 3L1)
  • Figure 7 Thermogravimetric curve of PPh 3 porous organic cage ligand synthesized in Example 1 under N 2 atmosphere
  • Figure 8 1 H spectrum of PPh 3 porous organic cage ligand synthesized in Example 1 under N 2 atmosphere
  • Figure 10 Pore size distribution curve of PPh 3 porous organic cage ligand obtained in Example 1 (NLDFT calculation method)
  • Figure 11 XRD diffraction pattern of the PPh 3 porous organic cage ligand synthesized in Example 1, and we also tested X-ray single crystal diffraction, and the CCDC number applied after analyzing the structure is 1857136
  • FIG. 12 Circular dichroism spectrum of a PPh 3 porous organic cage ligand synthesized in Example 1, the results show that the cage skeleton has chirality
  • FIG. 13 Circular dichroism spectrum of a PPh 3 porous organic cage ligand synthesized in Example 2. The results show that the cage's skeleton has chirality. We also did X-ray single crystal diffraction of the cage in Example 2. The CCDC number applied for after the structure is 1856683.
  • Rh-based complex catalysts containing PPh 3 porous organic cage ligands Weigh 25.8 mg of acetylacetone carbonyl rhodium (Rh (CO) 2 (acac)) in 10.0 ml of tetrahydrofuran solvent and add 277.8 mg of the above The PPh3 porous organic cage ligand was prepared. The mixture was stirred under a protective atmosphere of 298K and inert gas for 24 hours, and the solvent was removed under vacuum at room temperature to obtain a PPh 3 porous organic compound suitable for hydroformylation of olefins. Cage ligand coordination Rh-based complex catalyst.
  • Example 2 except that 2.12 grams of Figure 3L66 as a comonomer were weighed instead of 2.12 grams of Figure 3L64 as a comonomer, the rest of the implementation process was the same as Example 1.
  • Example 3 the implementation process is the same as Example 1 except that acetic acid is not added as a catalyst.
  • Example 4 the implementation process is the same as that in Example 1 except that 250.0 ml of tetrahydrofuran solvent is used instead of 500.0 ml of tetrahydrofuran solvent.
  • Example 5 the same procedure as in Example 1 was performed except that 500.0 ml of ethyl acetate solvent was used instead of 500.0 ml of tetrahydrofuran solvent.
  • Example 6 the implementation process is the same as Example 1 except that the 298K reaction temperature is used instead of the 318K reaction temperature.
  • Example 7 the implementation process is the same as that in Example 1 except that the reaction time of 24 h is replaced by the reaction time of 24 h.
  • Example 8 except that 1.06 g of the L64 comonomer in FIG. 3 and 1.06 g of the L66 comonomer in FIG. 3 were used as the mixed comonomer instead of 2.12 g of the L64 comonomer in FIG. 3, The rest of the implementation process is the same as that of the first embodiment.
  • Example 10 25.7 mg of cobalt acetylacetonate was substituted for acetylacetone rhodium carbonyl rhodium and dissolved in 10.0 ml of a tetrahydrofuran solvent, and the rest of the implementation process was the same as in Example 1.
  • Example 11 34.8 mg of acetylacetone dicarbonyl iridium was weighed in place of acetylacetone carbonyl rhodium to dissolve in 10.0 ml of a tetrahydrofuran solvent, and the rest of the implementation process was the same as in Example 1.
  • Example 12 4.08 g of L3 in FIG. 3 is weighed to replace L1 in Example 1. The rest of the implementation process is the same as that of Example 1.
  • Example 13 4.08 g of L5 in FIG. 3 is substituted for L1 in Example 1.
  • the rest of the implementation process is the same as that in Example 1.
  • Example 14 we prepared a classic traditional triphenylphosphine ligand complexed with a precious metal Rh complex catalyst.
  • the specific preparation step is to weigh 25.8 mg of acetylacetone carbonyl rhodium (Rh (CO) 2 (acac)) in 10.0 ml of tetrahydrofuran solvent, and add 157.2 mg of PPh 3 ligand (to ensure the same P / Rh ratio as in Example 1). ), The mixture was stirred under a protective atmosphere of 298K and inert gas for 24 hours, and the solvent was removed under vacuum at room temperature to obtain a PPh 3 complex Rh-based complex catalyst suitable for hydroformylation of olefins.
  • Rh (CO) 2 (acac) acetylacetone carbonyl rhodium
  • the experimental conditions were 100 ° C and 1 MPa. All metals were considered as active sites when the TOF was calculated. The catalyst was recovered and used 10 times without degradation of catalytic performance. ** indicates that the reaction temperature is 230 ° C, the active component of Example 10 is Co, and the active component of Example 11 is Ir.

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Abstract

La présente invention concerne un ligand à effet de cage organique poreux contenant P et N ainsi qu'un procédé de préparation du ligand à effet de cage organique poreux, et l'utilisation d'un catalyseur complexe correspondant dans l'hydroformylation d'oléfine. L'invention concerne un catalyseur formé par le ligand à effet de cage organique poreux P et N, et un métal de transition qui est dans un état de réaction de phase homogène pendant la réaction, les réactifs et les centres catalytiques étant en contact complet, et une bonne performance catalytique étant assurée ; un solvant d'alcool étant ajouté à la fin de la réaction, le catalyseur complexe de ligand à effet de cage organique poreux P et N étant cristallisé à partir d'un système de réaction, permettant ainsi d'obtenir simplement un recyclage du catalyseur. Le ligand à effet de cage organique poreux contenant P et N est formé par réticulation à l'aide de ligands P et N dont des groupes fonctionnels tels qu'un groupe aldéhyde et un groupe amino sont fonctionnalisés en tant que monomères et à l'aide d'une polyamine ou un polyaldéhyde correspondant en tant que co-monomère. Le catalyseur complexe formé par le ligand à effet de cage organique poreux P et N et le métal de transition selon la présente invention a une bonne performance dans l'hydroformylation, une valeur TOF du catalyseur peut atteindre 3000 h-1 ou plus, la sélectivité de l'alcane des produits obtenus est inférieure à 1 %, et la sélectivité de l'aldéhyde est de 90 % ou plus.
PCT/CN2018/116378 2018-08-17 2018-11-20 Ligand à effet de cage organique poreux contenant p et n, catalyseur complexe et utilisation Ceased WO2020034476A1 (fr)

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CN110357925A (zh) * 2019-07-16 2019-10-22 东莞理工学院 碱性笼状化合物、其制备方法及催化剂
CN114522734A (zh) * 2020-11-23 2022-05-24 中国科学院大连化学物理研究所 一种催化剂及其制备和在合成气制混合醇醛中的应用
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