WO2020034476A1 - Porous organic cage ligand containing p and n and complex catalyst and application - Google Patents

Porous organic cage ligand containing p and n and complex catalyst and application 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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中国科学院大连化学物理研究所
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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

The present invention relates to a porous organic cage ligand containing P and N and preparation method for the porous organic cage ligand, and application of a corresponding complex catalyst in hydroformylation of olefin. A catalyst formed by the P and N porous organic cage ligand and a transition metal is in a homogeneous phase reaction state during reaction, reactants and catalytic centers are in full contact, and a good catalytic performance is ensured; an alcohol solvent is added after the reaction is finished, the P and N porous organic cage ligand complex catalyst is crystallized from a reaction system, and recycling of a catalyst is simply achieved. The porous organic cage ligand containing P and N is formed by crosslinking by using P and N ligands of which functional groups such as an aldehyde group and an amino group are functionalized as monomers and using corresponding polyamine or polyaldehyde as a comonomer. A complex catalyst formed by the P and N porous organic cage ligand and the transition metal in the present invention has a good performance in hydroformylation, a TOF value of the catalyst can reach 3000 h-1 or more, the selectivity of alkane of the obtained products is less than 1%, and the selectivity of aldehyde is 90% or more.

Description

一种含P、N多孔有机笼配体及络合物催化剂和应用P, N porous organic cage ligand and complex catalyst and application 技术领域Technical field
本发明属于催化及精细化工领域，具体涉及一种含P、N多孔有机笼配体及其制备方法和相应的络合物催化剂在氢甲酰化反应中的应用。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.
背景技术Background technique
醛是很常用的化学中间体，化学性质较为活泼，醛可以氧化生成羧酸及相应的酯，以及脂肪胺等；醛还可以通过加氢还原生成醇，醇可作为有机溶剂、增塑剂和表面活性剂等广泛应用于精细化工领域，醛本身及后续的衍生产品都是非常有用的化学中间体。工业上醛的合成方式有多种，烯烃氢甲酰化反应属于典型的原子经济反应，可将烯烃与合成气(CO/H 2)接近100％选择性地转化成产品醛，废物零排放，通过烯烃氢甲酰化反应绿色合成醛的过程越来越受到人们的重视。 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.
目前全世界通过氢甲酰化生产的醛约为1200万吨/年，其中50％左右的醛是丙烯氢甲酰化生产的丁醛。表1叙述了已经工业应用的五代催化剂的丙烯氢甲酰化生产工艺条件和催化性能比较，已经工业化的五代催化剂前四代为均相催化过程，第五代为两相催化过程，但是这五种过程始终没有解决反应过程中金属及配体的流失问题。At present, 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.
已经工业化的五代催化技术催化剂回收利用困难，金属及配体流失严重，生产成本较高。为了较为简易地实现催化剂的循环使用，人们在氢甲酰化催化剂均相催化多相化领域做了大量的工作但是传统的均相催化多相化方法暴露出一系列需要解决和克服的问题，尤其是多相化后催化剂稳定性差，活性组分流失严重等(Chemical reviews,2012,112(11):5675-5732.；Eur.J.Org.Chem.,2012,2012:6309-6320)。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. In order to realize the recycling of catalysts more easily, people have done a lot of work in the field of hydroformylation catalysts for heterogeneous catalysis and heterogeneous catalysis. However, 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).
P、N配体在过渡金属络合物催化的偶联反应、硅氢加成反应、加氢反应和CO 2环加成反应等反应同样面临着均相催化剂回收困难，而传统固载化手段制备的多相催化剂性能和稳定性出现大幅度下降的问题。 Reactions such as coupling reactions catalyzed by transition metal complexes with P and N ligands, hydrosilylation reactions, hydrogenation reactions, and CO 2 cycloaddition reactions also face difficulties in recovering homogeneous catalysts, and traditional immobilization methods The performance and stability of the prepared heterogeneous catalysts were greatly reduced.
2009年，英国利物浦大学的Cooper教授课题组(Nature materials,2009,8(12):973)首次成功合成了2+3和4+6的多孔有机笼Porous Organic Cages(POCs)。设计合成的POCs最大的比表面积可达730m 2g -1。在后续的研究中(Nature Reviews Materials,2016,1(9):16053)，作者发现该类型的POCs材料溶于二氯甲烷等溶剂，可在甲醇等溶液中结晶出来，POCs材料在气体分离，催化等领域展示出了很好的应用前景。 In 2009, Professor Cooper's group at the University of Liverpool (Nature materials, 2009, 8 (12): 973) successfully synthesized Porous Organic Cages (POCs) with porous organic cages of 2 + 3 and 4 + 6 for the first time. The maximum specific surface area of POCs designed and synthesized can reach 730m 2 g -1 . In subsequent research (Nature Reviews Materials, 2016, 1 (9): 16053), the authors found that this type of POCs material is soluble in solvents such as dichloromethane and can be crystallized out of solutions such as methanol. POCs materials are separated by gas. Catalysis and other fields show very good application prospects.
表1已经工业化的五代催化剂丙烯氢甲酰化生产工艺条件和催化性能比较 [a] Table 1 Comparison of process conditions and catalytic performance of propylene hydroformylation for five-generation catalysts that have been industrialized [a]
[根据细则26改正15.01.2019]　
Figure WO-DOC-FIGURE-table
[Corrected 15.01.2019 in accordance with Rule 26]
Figure WO-DOC-FIGURE-table
POCs从首次报道至今，还没有P、N配体功能化的多孔有机笼配体见诸于文献报道，P、N多孔有机笼配体的合成一直面临着巨大的挑战。合成P、N多孔有机笼配体具有重要的科学及应用意义，并且借用相应的P、N多孔有机笼配体与过渡金属配位形成的络合物催化剂在某些溶剂中溶解，某些溶剂中析出的特点，有望解决烯烃氢甲酰化反应，偶联反应、硅氢加成反应、加氢反应和CO 2环加成反应等反应均相络合物催化剂分离回收困难的问题。 Since POCs were first reported, no porous organic cage ligands functionalized with P and N ligands have been reported in the literature. The synthesis of P and N porous organic cage ligands has been facing great challenges. The synthesis of P and N porous organic cage ligands has important scientific and application significance, and the complex catalysts formed by the coordination of the corresponding P and N porous organic cage ligands with transition metals are dissolved in some solvents, and some solvents The characteristics of precipitation are expected to solve the problem of difficult separation and recovery of homogeneous complex catalysts such as olefin hydroformylation reaction, coupling reaction, hydrosilylation reaction, hydrogenation reaction and CO 2 cycloaddition reaction.
发明内容Summary of the Invention
为了解决上述问题，本发明的目的在于提供一种含P、N多孔有机笼配体及其制备方法和相应的络合物催化剂在氢甲酰化反应中的应用。该类催化剂TOF值可达3000h -1以上，得到的产物中烷烃选择性低于1％，醛的选择性在90％以上。本发明的技术方案为： In order to solve the above problems, 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:
一种含P、N多孔有机笼配体及其制备方法和相应的络合物催化剂在氢甲酰化反应中的应用，将含P和/或N多孔有机笼配体与过渡金属形成的络合物催化剂装入反应器中，通入反应混合气和原料烯烃，混合气的主要组分为H 2和CO，H 2/CO体积比为0.5～5.0，混合气气体空速为100～20000h -1优选范围为1000～20000h -1；原料烯烃为C 3～C 20的烯烃，反应温度为323～573K，反应压力为0.1～10.0MPa的条件下进行烯烃氢甲酰化反应。 P, N-containing porous organic cage ligand, preparation method thereof and application of corresponding complex catalyst in hydroformylation reaction, the complex formed by P and / or N-containing porous organic cage ligand and transition metal 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.
混合气中还可含有选自Ar、CO 2、He或N 2中的一种或二种以上的其余气体，混合气中H 2+CO的体积含量为20～90％；所述反应器为釜式反应器；烯烃质量纯度为20～100％，烯烃中可含有的其他成分为C 3～C 20的烷烃中的一种或二种以上；所述C 3～C 20烯烃优选为C 5～C 14的烯烃。 反应温度优选为353～423K，反应压力优选为0.5～2MPa；含P、N多孔有机笼配体与过渡金属形成的络合物催化剂以含P、N多孔有机笼配体作为配体，以金属Rh、Co、Ir、Pd或Pt中的一种或两种以上作为活性组分；其中含P、N多孔有机笼配体以醛基、氨基等官能团功能化的P和/或N配体为单体，以相应的多元胺或多元醛为共单体，在溶剂存在条件下，单体和共单体中的官能团充分反应，交联成具有特定结构的P、N多孔有机笼配体；含P、N多孔有机笼配体加入含有活性组分Rh、Co、Ir、Pd或Pt前驱体中的一种或两种以上的溶液中充分搅拌配位，即可得到含P、N多孔有机笼配体与过渡金属形成的络合物催化剂。 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. In the presence of solvents, the functional groups in the monomers and co-monomers fully react to crosslink to form P, N porous organic cage ligands with specific structures; 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.
所述的醛基、氨基等官能团功能化的P、N配体可为单齿或多齿配体一种或两种以上；共单体多元胺或多元醛为二元或者二元以上，共单体可为一种或两种以上；所述的P、N多孔有机笼配体具有特定的孔结构，比表面积为0～3000m 2/g，优选范围为10～1000m 2/g，孔容为0～10.0cm 3/g，优选为0.5～2.0cm 3/g，孔径分布在0.01～100.0nm，优选为0.5～20.0nm； 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;
含P和/或N多孔有机笼配体的制备方法为：将醛基、氨基等官能团功能化的P、N配体和多元胺或多元醛共单体在溶剂中充分溶解混合后，在特定温度下静置或者搅拌，使得P、N配体和共单体中的官能团充分反应，生成具有特定孔结构的P、N多孔有机笼配体；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;
含P、N多孔有机笼配体与过渡金属形成的络合物催化剂制备方法为：活性金属组分的前驱体与含P、N多孔有机笼配体在溶剂中充分搅拌，活性金属组分与含P、N多孔有机笼配体中裸露的P形成牢固的配位键，蒸去溶剂后，得到含P、N多孔有机笼配体与过渡金属形成的络合物催化剂。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.
含P、N多孔有机笼配体的具体合成步骤为：The specific synthetic steps of the porous organic cage ligands containing P and N are:
a)惰性气体气氛273～473K下，在溶剂中加入醛基、氨基等官能团功能化的P、N配体、多元胺或多元醛共单体、添加或不添加催化剂，将混合物静置或搅拌0.1～500小时，优选的静置或搅拌时间范围为10～60小时；a) In an inert gas atmosphere of 273 to 473K, add functional groups such as aldehyde groups and amino groups to functional P, N ligands, polyamines or polyaldehyde comonomers in the solvent, with or without the addition of a catalyst, and let the mixture stand or stir. 0.1 to 500 hours, and the preferred standing or stirring time range is 10 to 60 hours;
b)将步骤a)制得的含有P、N多孔有机笼配体的混合溶液浓缩，加入醇类溶剂，多孔有机笼配体结晶沉淀下来；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;
c)将步骤b)得到的P、N多孔有机笼配体沉淀过滤、洗涤并干燥后得到含P、N多孔有机笼配体产品；c) 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;
含P、N多孔有机笼配体与过渡金属形成的络合物催化剂的制备方法为：A method for preparing a complex catalyst containing a P, N porous organic cage ligand and a transition metal is:
d)惰性气体气氛273～473K下，在含有活性金属组分前驱体的溶剂中，加入步骤c)得到的多孔有机笼配体，搅拌0.1～100小时，优选搅拌时间范围0.1～20小时，之后，室温条件下真空抽除溶剂，得到P、N多孔有机笼配体与过渡金属形成的络合物催化剂。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.
步骤a)和d)中所述的溶剂为二氯甲烷、三氯甲烷、四氯化碳、乙酸乙酯、甲酸甲酯、苯、甲苯、二甲苯、正己烷、正庚烷、正辛烷、环己烷、二甲亚砜、N,N-二甲基甲酰胺或四氢呋喃中一种或两种以上；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 One or more of cyclohexane, dimethyl sulfoxide, N, N-dimethylformamide or tetrahydrofuran;
步骤b)中所述的醇类溶剂为水、甲醇、乙醇、正丙醇、异丙醇、正丁醇等中的一种或两种以上；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;
步骤c)中的洗涤溶剂可选水、甲醇、乙醇、正丙醇、异丙醇、正丁醇等中的一种或 两种以上，干燥方法可选常压干燥、减压干燥、喷雾干燥、沸腾干燥和冷冻干燥中的一种或两种以上。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.
步骤a)中所述的醛基、氨基等官能团功能化的P、N配体在溶剂中的浓度范围为0.01-1000g/L，优选为0.1-10g/L，醛基、氨基等官能团功能化的P、N与共单体的摩尔比为0.01:1～100:1，优选为0.1:1-10:1，在添加催化剂的条件下，催化剂可选为盐酸、醋酸、硫酸、磷酸、硝酸中的一种或两种以上，醛基、氨基等官能团功能化的P、N配体单体与催化剂的摩尔比为10000:1-100:1，步骤a)、b)和c)中所述惰性气体选自Ar、He、N 2和CO 2中的一种或两种以上。 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. Under the condition of adding a catalyst, 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 .
步骤d)中所述的活性组分为Rh、Co、Ni、Ir、Pd或Pt中的一种或两种以上，其中Rh的前驱体为RhH(CO)(PPh 3) 3、Rh(CO) 2(acac)、RhCl 3、Rh(CH 3COO) 2中的一种或两种以上；Co的前驱体为Co(CH 3COO) 2、Co(CO) 2(acac)、Co(acac) 2、CoCl 2中的一种或两种以上；Ni的前驱体为Ni(CH 3COO) 2、Ni(CO) 2(acac)、Ni(acac) 2、NiCl 2中的一种或两种以上；Ir的前驱体为Ir(CO) 3(acac)、Ir(CH 3COO) 3、Ir(acac) 3、IrCl 4中的一种或两种以上；Pd的前驱体为Pd(CH 3COO) 2、Pd(acac) 2、PdCl 2、Pd(PPh 3) 4、PdCl 2(CH 3CN) 2中的一种或两种以上；Pt的前驱体为Pt(acac) 2、PtCl 4、PtCl 2(NH 3) 2中的一种或两种以上；P、N配体多孔有机笼配体与活性组分的摩尔比为100:1-1:1，优选为10:1-1:1。 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 , Pd (PPh 3 ) 4 , PdCl 2 (CH 3 CN) 2 or more; one of the precursors of Pt is Pt (acac) 2 , PtCl 4. One or two or more of PtCl 2 (NH 3 ) 2 ; the molar ratio of the P, N ligand porous organic cage ligand to the active component is 100: 1-1: 1, preferably 10: 1- 1: 1.
本发明的反应原理：Reaction principle of the present invention:
含P、N多孔有机配体溶于某些极性较大的溶剂，而不溶于甲醇等醇类溶剂，因而P、N多孔有机笼配体形成的络合物催化剂具有均相反应和多相回收的特点。反应时P、N多孔有机笼配体与过渡金属形成的催化剂处于均相反应状态，反应物和催化中心充分接触，保证了良好的催化性能，反应结束后加入醇类溶剂，P、N多孔有机笼配体络合物催化剂从反应体系中结晶出来，实现催化剂的回收。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. During the reaction, 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. After the reaction, 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.
含P、N多孔有机笼配体以醛基、氨基等官能团功能化的P、N配体为单体，以相应的多元胺或多元醛为共单体交联而成。所合成的P、N多孔有机笼配体具有稳定的独特孔结构，可用于选择性吸附分离气体；P、N配体在过渡金属络合物催化的氢甲酰化反应、偶联反应、硅氢加成反应、加氢反应和CO 2环加成反应等反应中具有广泛的应用。含P、N多孔有机笼配体保留了P、N配体良好的配体性质，并且由于P、N多孔有机笼配体的特定构造，P、N多孔有机笼配体具有与相应的P、N配体不同的电子效应及立体效应，同时，P、N多孔有机笼配体的空腔具有浓集反应物的性质，因而P、N多孔有机笼配体与过渡金属形成的络合物催化剂展示出了比相应的P、N配体络合物催化剂更高效的催化性能。 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. 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.
本发明的有益效果为：The beneficial effects of the present invention are:
本发明制备的含P、N多孔有机笼配体中的P、N配体可与活性金属进行配位形成络合物催化剂。由于笼配体在二氯甲烷等溶剂中溶解性良好，在甲醇等溶剂中可结晶出来。因而P、N多孔有机笼配体形成的络合物催化剂具有均相反应和多相回收的特点，反应时P、N多孔有机笼配体与过渡金属形成的催化剂处于均相反应状态，反应物和催化中心充分接触，保证了良好的催化性能，反应结束后加入醇类溶剂，P、N多孔有机笼配体络合物催化剂从反应体系中结晶出来，通过这种简易的方法实现催化剂的回收。并且由于P、N多孔有机笼配体的特定构造，P、N多孔有机笼配体具 有与相应的P、N配体不同的电子效应及立体效应，同时，P、N多孔有机笼配体的NHx基团具有碱性改变腔体的化学环境，因而，P、N多孔有机笼配体与过渡金属形成的络合物催化剂(如，经典的三苯基膦的Rh-P催化剂体系)展示出了独特的催化性能。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. After the reaction, an alcoholic solvent is added, and the P and N porous organic cage ligand complex catalysts are crystallized from the reaction system. The catalyst recovery is achieved by this simple method. . And due to the specific structure of the P, N porous organic cage ligands, the P, N porous organic cage ligands have different electronic effects and stereo effects than the corresponding P, N ligands. At the same time, the P, N porous organic cage ligands have The NHx group has a basic ability to change the chemical environment of the cavity. Therefore, complex catalysts formed by P, N porous organic cage ligands and transition metals (eg, the classic Rh-P catalyst system of triphenylphosphine) exhibited It has unique catalytic performance.
本发明提供的P、N多孔有机笼配体与过渡金属形成的络合物催化剂在氢甲酰化反应中有很好的表现，催化剂TOF值可达3000h -1以上，得到的产物中烷烃选择性低于1％，醛的选择性在90％以上。 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%.
本发明提供的含P、N多孔有机笼配体及其相应的络合物催化剂的制备方法为烯烃氢甲酰化反应、偶联反应、硅氢加成反应、加氢反应和CO 2环加成反应等反应提供了新的工业化技术。 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.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1：典型的醛基官能团化的PPh 3单体的合成路线图 Figure 1: Synthesis of a typical aldehyde-functionalized PPh 3 monomer
图2：典型的含PPh 3多孔有机笼配体的合成技术路线示意图 Figure 2: Schematic diagram of the synthesis of typical PPh 3 porous organic cage ligands
图3：含P、N多孔有机笼配体合成所需单体的结构示意图，其中，L1-L62为醛基或氨基官能团化的P、N配体单体，L63-L74为多元醛和多元胺共单体Figure 3: Schematic diagram of the monomers required for the synthesis of porous organic cage ligands containing P and N. Among them, L1-L62 are aldehyde or amino-functionalized P and N ligand monomers, and L63-L74 are polyaldehyde and polyvalent Amine comonomer
图4：典型的醛基官能团化的PPh 3配体单体(附图3L1)的 1H谱图 Figure 4: 1 H spectrum of a typical aldehyde-functionalized PPh 3 ligand monomer (Figure 3L1)
图5：典型的醛基官能团化的PPh 3配体单体(附图3L1)的 13C谱图 Figure 5: 13 C spectrum of a typical aldehyde-functionalized PPh 3 ligand monomer (Figure 3L1)
图6：典型的醛基官能团化的PPh 3配体单体(附图3L1)的 31P谱图 Figure 6: 31 P spectrum of a typical aldehyde-functionalized PPh 3 ligand monomer (Figure 3L1)
图7：N 2氛围下实施例1合成的含PPh 3多孔有机笼配体热重曲线 Figure 7: Thermogravimetric curve of PPh 3 porous organic cage ligand synthesized in Example 1 under N 2 atmosphere
图8：N 2氛围下实施例1合成的含PPh 3多孔有机笼配体的 1H谱图 Figure 8: 1 H spectrum of PPh 3 porous organic cage ligand synthesized in Example 1 under N 2 atmosphere
图9：实施例1获得的PPh 3多孔有机笼配体的N 2物理吸附曲线 Figure 9: N 2 physical adsorption curve of PPh 3 porous organic cage ligand obtained in Example 1
图10：实施例1获得的PPh 3多孔有机笼配体的孔径分布曲线(NLDFT计算方法) Figure 10: Pore size distribution curve of PPh 3 porous organic cage ligand obtained in Example 1 (NLDFT calculation method)
图11：实施例1中合成的含PPh 3多孔有机笼配体的XRD衍射谱图，并且我们也测试了X射线单晶衍射，解析出结构后申请的CCDC号码为1857136 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
图12：实施例1中合成的含PPh 3多孔有机笼配体的圆二色光谱图，结果显示笼的骨架有手性 Figure 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
图13：实施例2中合成的含PPh 3多孔有机笼配体的圆二色光谱图，结果显示笼的骨架有手性，我们也做了实施例2中笼的X射线单晶衍射，解出结构后申请的CCDC号码为1857683。 Figure 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.
具体实施方式detailed description
下述实施例对本发明进行更好的说明，但不限制本发明所要保护的范围。The following examples better illustrate the present invention, but do not limit the scope of the present invention.
实施例1Example 1
醛基官能团化的PPh 3配体单体(附图3L1)的制备：醛基官能团化的PPh 3配体的合成路线如附图1所示。25g4-溴苯甲醛二乙酸醛(96mmol)用四氢呋喃稀释10倍(体积比)后缓慢滴加到4.4g镁屑中，制得格氏试剂。2.3g三氯化磷溶解于10倍(体积比)的四氢呋喃溶液后滴加如制得的格氏试剂中，充分反应后，加入等体积的5％的HCl溶液继续反应。反应完成后，油相减压蒸馏除去大部分溶剂，经5:1的石油醚：乙酸乙酯的洗脱剂过柱子后可得淡黄色固体产品6.5g，产率60％左右。附图4、附图5和附图6分别为制备出的醛基官能团化的PPh 3配体单体核磁 1H、 13C和 31P谱图。 Preparation of aldehyde-functionalized PPh 3 ligand monomer (Figure 3L1): The synthetic route of aldehyde-functionalized PPh 3 ligand is shown in Figure 1. 25 g of 4-bromobenzaldehyde diacetaldehyde (96 mmol) was diluted 10-fold (volume ratio) with tetrahydrofuran, and then slowly added dropwise to 4.4 g of magnesium dust to obtain a Grignard reagent. 2.3 g of phosphorus trichloride was dissolved in a 10-fold (volume ratio) tetrahydrofuran solution, and the solution was added dropwise to the Grignard reagent prepared. After the reaction was completed, an equal volume of 5% HCl solution was added to continue the reaction. After the reaction is completed, most of the solvent is distilled off under reduced pressure from the oil phase. After passing the column through a 5: 1 petroleum ether: ethyl acetate eluent, 6.5 g of a pale yellow solid product can be obtained with a yield of about 60%. Figures 4, 5, and 6 are NMR 1 H, 13 C, and 31 P spectra of the prepared aldehyde-functionalized PPh 3 ligand monomers, respectively.
含PPh 3多孔有机笼配体的制备：在318K和惰性气体保护氛围下，将4.29克醛 基官能团化的PPh 3单体(附图3，L1)溶于500.0ml四氢呋喃溶剂中，同时加入1,2环己二胺共单体2.12g(附图3中L64)，并加入1ml醋酸作为催化剂，混合溶液在该反应条件下静止60h可得含PPh 3多孔有机笼配体粗产品。 Preparation of porous organic cage ligands containing PPh 3 : 4.29 grams of aldehyde-functionalized PPh 3 monomer (Figure 3, L1) were dissolved in 500.0 ml of tetrahydrofuran solvent under the protection of 318K and an inert gas atmosphere, and 1 was added at the same time. 2,2 g of cyclohexanediamine comonomer (L64 in FIG. 3), and 1 ml of acetic acid was added as a catalyst, and the mixed solution was allowed to stand under the reaction conditions for 60 h to obtain a crude PPh 3 porous organic cage ligand crude product.
含PPh 3多孔有机笼配体配位的Rh基络合物催化剂的制备：称取25.8毫克乙酰丙酮羰基铑(Rh(CO) 2(acac))溶于10.0ml四氢呋喃溶剂中，加入277.8毫克上述制得的含PPh3多孔有机笼配体，将此混合物在298K和惰性气体保护氛围下搅拌24小时，室温条件下真空抽除溶剂，即获得适用于烯烃氢甲酰化反应的含PPh 3多孔有机笼配体配位的Rh基络合物催化剂。 Preparation of 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.
实施例2Example 2
在实施例2中，除了称取2.12克附图3L66为共单体替代2.12克附图3L64共单体外，其余的实施过程与实施例1相同。In 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.
实施例3Example 3
在实施例3中，除了不添加醋酸作为催化剂外，其余的实施过程与实施例1相同。In Example 3, the implementation process is the same as Example 1 except that acetic acid is not added as a catalyst.
实施例4Example 4
在实施例4中，除了用250.0ml四氢呋喃溶剂替代500.0ml四氢呋喃溶剂外，其余的实施过程与实施例1相同。In 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.
实施例5Example 5
在实施例5中，除了用500.0ml乙酸乙酯溶剂替代500.0ml四氢呋喃溶剂外，其余的实施过程与实施例1相同。In 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.
实施例6Example 6
在实施例6中，除了用298K反应温度替代318K反应温度外，其余的实施过程与实施例1相同。In 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.
实施例7Example 7
在实施例7中，除了用24h反应时间替代60h反应时间外，其余的实施过程与实施例1相同。In 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.
实施例8Example 8
在实施例8中，除了用1.06g附图3中的L64共单体和1.06g附图3中的L66共单体作为混合共单体替代2.12g附图3中的L64共单体外，其余的实施过程与实施例1相同。In 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.
实施例9Example 9
在实施例9中，除了用0.56g附图3中的L72共单体(n＝1)和0.67g附图3中的L74共单体(n＝1)作为混合共单体替代2.12g附图3中的L64共单体外，其余的实施过程与实施例1相同。In Example 9, in addition to using 0.56 g of the L72 comonomer (n = 1) in FIG. 3 and 0.67 g of the L74 comonomer (n = 1) in FIG. 3 as a mixed comonomer instead of 2.12 g of Except for the L64 comonomer in FIG. 3, the rest of the implementation process is the same as that of Example 1.
实施例10Example 10
在实施例10中,称取25.7毫克乙酰丙酮钴替代乙酰丙酮羰基铑溶于10.0ml四氢呋喃溶剂外，其余的实施过程与实施例1相同。In 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.
实施例11Example 11
在实施例11中,称取34.8毫克乙酰丙酮二羰基铱替代乙酰丙酮羰基铑溶于10.0ml四氢呋喃溶剂外，其余的实施过程与实施例1相同。In 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.
实施例12Example 12
在实施例12中，称取4.08g附图3中的L3替代实施例1中的L1，其余的实施过程与实施例1相同。In 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.
实施例13Example 13
在实施例13中，称取4.08g附图3中的L5替代实施例1中的L1，其余的实施过程与实施例1相同。In 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.
实施例14Example 14
为了便于对比，在实施例14中，我们制备了经典传统的三苯基膦配体与贵金属Rh配位的络合物催化剂。具体制备步骤为，称取25.8毫克乙酰丙酮羰基铑(Rh(CO) 2(acac))溶于10.0ml四氢呋喃溶剂中，加入157.2毫克PPh 3配体(保证与实施例1相同的P/Rh比)，将此混合物在298K和惰性气体保护氛围下搅拌24小时，室温条件下真空抽除溶剂，即获得适用于烯烃氢甲酰化反应的PPh 3配位的Rh基络合物催化剂。 In order to facilitate comparison, in 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.
实施例15Example 15
将上述制备的催化剂10mmol溶于50ml甲苯，并加入1000mol 1-辛烯，在373K，1MPa合成气(CO:H 2＝1:1)压力条件下进行氢甲酰化反应。反应5h后将反应釜冷却至室温，加入正丁醇作为内标，采用配有HP-5毛细管柱和FID检测器的Agilent-7890N气相色谱分析，反应结果列于表2。反应完成后加入50ml甲醇，含PPh 3多孔有机笼配体配位的Rh基络合物催化剂即可从反应体系中结晶出来，实现催化剂的回收。 10 mmol of the catalyst prepared above was dissolved in 50 ml of toluene, and 1000 mol of 1-octene was added, and the hydroformylation reaction was performed under the pressure of 373 K, 1 MPa synthesis gas (CO: H 2 = 1: 1). After 5 hours of reaction, the reaction kettle was cooled to room temperature, n-butanol was added as an internal standard, and an Agilent-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector was used for analysis. The reaction results are shown in Table 2. After the reaction is completed, 50 ml of methanol is added, and the Rh-based complex catalyst containing PPh 3 porous organic cage ligand can be crystallized from the reaction system to realize catalyst recovery.
实施例16Example 16
将上述制备的催化剂10mmol溶于50ml甲苯，并加入1000mol苯乙烯，在373K，1MPa合成气(CO:H 2＝1:1)压力条件下进行氢甲酰化反应。反应5h后将反应釜冷却至室温，加入正丁醇作为内标，采用配有HP-5毛细管柱和FID检测器的Agilent-7890B气相色谱分析，反应结果列于表3。反应完成后加入50ml甲醇，含PPh 3多孔有机笼配体配位的Rh基络合物催化剂即可从反应体系中结晶出来，实现催化剂的回收。 10 mmol of the catalyst prepared above was dissolved in 50 ml of toluene, 1000 mol of styrene was added, and a hydroformylation reaction was performed under the pressure of 373 K, 1 MPa synthesis gas (CO: H 2 = 1: 1). After 5 hours of reaction, the reaction kettle was cooled to room temperature, n-butanol was added as an internal standard, and an Agilent-7890B gas chromatography equipped with an HP-5 capillary column and a FID detector was used for analysis. The reaction results are shown in Table 3. After the reaction is completed, 50 ml of methanol is added, and the Rh-based complex catalyst containing PPh 3 porous organic cage ligand can be crystallized from the reaction system to realize catalyst recovery.
实施例17Example 17
将上述制备的催化剂10mmol溶于50ml甲苯，并加入1000mol2-辛烯，在373K，1MPa合成气(CO:H 2＝1:1)压力条件下进行氢甲酰化反应。反应5h后将反应釜冷却至室温，加入正丁醇作为内标，采用配有HP-5毛细管柱和FID检测器的Agilent-7890B气相色谱分析，反应结果列于表4。反应完成后加入50ml甲醇，含PPh 3多孔有机笼配体配位的Rh基络合物催化剂即可从反应体系中结晶出来，实现催化剂的回收。 10 mmol of the catalyst prepared above was dissolved in 50 ml of toluene, 1000 mol of 2-octene was added, and hydroformylation reaction was performed under the pressure of 373 K, 1 MPa synthesis gas (CO: H 2 = 1: 1). After 5 hours of reaction, the reaction kettle was cooled to room temperature, n-butanol was added as an internal standard, and an Agilent-7890B gas chromatography equipped with an HP-5 capillary column and a FID detector was used for analysis. The reaction results are shown in Table 4. After the reaction is completed, 50 ml of methanol is added, and the Rh-based complex catalyst containing PPh 3 porous organic cage ligand can be crystallized from the reaction system to realize catalyst recovery.
表2实施例1-14中合成的含P多孔有机笼配体比表面积和1-辛烯反应数据Table 2 Specific surface area of P-containing porous organic cage ligands synthesized in Examples 1-14 and 1-octene reaction data
Figure PCTCN2018116378-appb-000002
Figure PCTCN2018116378-appb-000002
实验条件为100℃，1MPa，TOF计算时认为所有的金属均是活性位点，催化剂回收使用10次，未出现催化性能的下降。**表示反应温度为230℃,实施例10的活性组分为Co,实施例11的活性组分为Ir。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.
表3实施例1-14中合成的含P多孔有机配体笼比表面积和苯乙烯反应数据Table 3 Specific surface area and styrene reaction data of P-containing porous organic ligand cages synthesized in Examples 1-14
Figure PCTCN2018116378-appb-000003
Figure PCTCN2018116378-appb-000003
*实验条件为100℃，1MPa，TOF计算时认为所有的金属均是活性位点，催化剂回收使用10次，未出现催化性能的下降。**表示反应温度为230℃，实施例10的活性组分为Co，实施例11的活性组分为Ir。* Experimental conditions are 100 ° C, 1MPa, all metals are considered as active sites when the TOF calculation is performed, and the catalyst is 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.
表4实施例1-14中合成的含P多孔有机笼配体比表面积和1-辛烯反应数据Table 4 Specific surface area of P-containing porous organic cage ligands synthesized in Examples 1-14 and 1-octene reaction data
Figure PCTCN2018116378-appb-000004
Figure PCTCN2018116378-appb-000004
*实验条件为100℃，1MPa，TOF计算时认为所有的金属均是活性位点，催化剂回收使用10次，未出现催化性能的下降。**表示反应温度为230℃,实施例10的活性组分为Co,实施例11的活性组分为Ir。* Experimental conditions are 100 ° C, 1MPa, all metals are considered as active sites when the TOF calculation is performed, and the catalyst is 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.

Claims (10)

  1. 一种含P、N多孔有机笼配体，其特征在于：以醛基和/或氨基官能团功能化的P和/或N配体为单体，以相应的(单体中醛基对应多元胺，单体中氨基对应多元醛)多元胺或多元醛为共单体，在溶剂存在条件下，单体和共单体中的官能团充分反应，交联成含P和/或N多孔有机笼配体。A porous organic cage ligand containing P and N, characterized in that a P and / or N ligand functionalized with an aldehyde group and / or an amino functional group is used as a monomer, and a corresponding (the aldehyde group in the monomer corresponds to a polyamine (The amino group in the monomer corresponds to a polyaldehyde) The polyamine or polyaldehyde is a co-monomer. In the presence of a solvent, the functional groups in the monomer and the co-monomer fully react and cross-link to form a porous organic cage containing P and / or N. body.
  2. 按照权利要求1所述的有机笼配体，其特征在于：所述的单体可为单齿或多齿配体一种或两种以上；共单体多元胺或多元醛中的多元可为二元或者三元以上，共单体可为一种或两种以上。The organic cage ligand according to claim 1, characterized in that: the monomer may be one or two or more kinds of monodentate or multidentate ligands; the polymonomer in the co-monomer polyamine or polyaldehyde may be Binary or ternary or more, the co-monomer may be one kind or two or more kinds.
  3. 按照权利要求1所述的有机笼配体，其特征在于：所述单体选自下述中的一种或二种以上：The organic cage ligand according to claim 1, wherein the monomer is selected from one or more of the following:
    Figure PCTCN2018116378-appb-100001
    Figure PCTCN2018116378-appb-100001
    Figure PCTCN2018116378-appb-100002
    Figure PCTCN2018116378-appb-100002
    Figure PCTCN2018116378-appb-100003
    Figure PCTCN2018116378-appb-100003
    Figure PCTCN2018116378-appb-100004
    Figure PCTCN2018116378-appb-100004
    Figure PCTCN2018116378-appb-100005
    Figure PCTCN2018116378-appb-100005
    Figure PCTCN2018116378-appb-100006
    Figure PCTCN2018116378-appb-100006
    Figure PCTCN2018116378-appb-100007
    Figure PCTCN2018116378-appb-100007
    所述共单体多元胺或多元醛选自下述中的一种或二种以上：The comonomer polyamine or polyaldehyde is selected from one or two or more of the following:
    Figure PCTCN2018116378-appb-100008
    Figure PCTCN2018116378-appb-100009
    n为正整数。
    Figure PCTCN2018116378-appb-100008
    Figure PCTCN2018116378-appb-100009
    n is a positive integer.
  4. 按照权利要求1所述的有机笼配体，其特征在于：所述的P、N多孔有机笼配体具有特定的孔结构，比表面积为0.1～3000m 2/g，优选范围为10～1000m 2/g，孔容为0～10.0cm 3/g，优选为0.5～2.0cm 3/g，孔径分布在0.01～100.0nm，优选为0.5～20.0nm；其可用于选择性吸附分离气体。 The organic cage ligand according to claim 1, wherein the P, N porous organic cage ligand has a specific pore structure, and has a specific surface area of 0.1 to 3000 m 2 / g, preferably in a range of 10 to 1000 m 2. / g, with a pore volume of 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; it can be used for selective adsorption and separation of gases.
  5. 按照权利要求1所述的有机笼配体，其特征在于：含P和/或N多孔有机笼配体 的制备方法为：将单体和多元胺或多元醛共单体在溶剂中充分溶解混合后，静置或者搅拌，使得P、N配体和共单体中的官能团充分反应，生成具有特定孔结构的P、N多孔有机笼配体；The organic cage ligand according to claim 1, characterized in that the preparation method of the porous organic cage ligand containing P and / or N is: fully dissolving and mixing the monomer and the polyamine or polyaldehyde comonomer in a solvent Then, let it stand or stir to make the P and N ligands and the functional groups in the comonomer fully react to form P and N porous organic cage ligands with a specific pore structure;
    含P、N多孔有机笼配体的具体合成步骤为：The specific synthetic steps of the porous organic cage ligands containing P and N are:
    a)惰性气体气氛273～473K下，在溶剂中加入单体、多元胺或多元醛共单体、添加或不添加催化剂，将混合物静置或搅拌0.1～500小时，优选的静置或搅拌时间范围为10～60小时；a) In an inert gas atmosphere of 273 to 473K, a monomer, a polyamine or a polyaldehyde comonomer is added to the solvent, and the catalyst is added or not added, and the mixture is allowed to stand or be stirred for 0.1 to 500 hours. The range is 10 to 60 hours;
    b)将步骤a)制得的含有P、N多孔有机笼配体的混合溶液浓缩，加入水和/或醇类溶剂，多孔有机笼配体结晶沉淀下来；b) concentrating the mixed solution containing the P and N porous organic cage ligands obtained in step a), adding water and / or alcohol solvents, and crystallizing the porous organic cage ligands;
    c)将步骤b)得到的P、N多孔有机笼配体沉淀过滤、洗涤并干燥后得到含P、N多孔有机笼配体产品；c) 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;
    步骤a)中所述的溶剂为二氯甲烷、三氯甲烷、四氯化碳、乙酸乙酯、甲酸甲酯、苯、甲苯、二甲苯、正己烷、正庚烷、正辛烷、环己烷、二甲亚砜、N,N-二甲基甲酰胺或四氢呋喃中一种或两种以上；The solvents described in step a) are dichloromethane, chloroform, carbon tetrachloride, ethyl acetate, methyl formate, benzene, toluene, xylene, n-hexane, n-heptane, n-octane, cyclohexane One or more of alkane, dimethyl sulfoxide, N, N-dimethylformamide or tetrahydrofuran;
    步骤b)中所述的醇类溶剂为水、甲醇、乙醇、正丙醇、异丙醇、正丁醇中的一种或两种以上；The alcohol solvent described in step b) is one or two or more of water, methanol, ethanol, n-propanol, isopropanol, and n-butanol;
    步骤c)中的洗涤溶剂可选水、甲醇、乙醇、正丙醇、异丙醇、正丁醇中的一种或两种以上，干燥方法可选常压干燥、减压干燥、喷雾干燥、沸腾干燥和冷冻干燥中的一种或两种以上；The washing solvent in step c) can be selected from one or more of water, methanol, ethanol, n-propanol, isopropanol, and n-butanol. The drying method can be selected from normal pressure drying, reduced pressure drying, spray drying, One or more of boiling drying and freeze drying;
    步骤a)中所述的单体在溶剂中的浓度范围为0.01-1000g/L，优选为0.1-10g/L，单体与共单体的摩尔比为0.01:1～100:1，优选为0.1:1-10:1，在添加催化剂的条件下，催化剂可选为盐酸、醋酸、硫酸、磷酸、硝酸中的一种或两种以上，单体与催化剂的摩尔比为10000:1-100:1；步骤a)、b)和c)中所述惰性气体选自Ar、He、N 2和CO 2中的一种或两种以上。 The concentration of the monomer in the solvent in step a) ranges from 0.01 to 1000 g / L, preferably from 0.1 to 10 g / L, and the molar ratio of the monomer to the co-monomer is from 0.01: 1 to 100: 1, preferably 0.1. : 1-10: 1, under the condition of adding the catalyst, the catalyst may be selected from one or more of hydrochloric acid, acetic acid, sulfuric acid, phosphoric acid, and nitric acid, and the molar ratio of the monomer to the catalyst is 10000: 1-100: 1; The inert gas in steps a), b) and c) is selected from one or two or more of Ar, He, N 2 and CO 2 .
  6. 一种络合物催化剂，其是以权利要求1-4中任一所述含P、N多孔有机笼配体作为配体，与过渡金属Rh、Co、Ir、Pd或Pt中的一种或两种以上作为活性组分，形成的络合物催化剂。A complex catalyst, comprising the P, N-containing porous organic cage ligand according to any one of claims 1-4 as a ligand, and one or more of transition metals Rh, Co, Ir, Pd or Pt or Two or more complex catalysts formed as active components.
  7. 按照权利要求6所述的络合物催化剂，其特征在于：将含P、N多孔有机笼配体加入含有活性组分Rh、Co、Ir、Pd或Pt前驱体中的一种或两种以上的溶液中充分搅拌配位，即可得到含P、N多孔有机笼配体与过渡金属形成的络合物催化剂；活性金属组分的前驱体与含P、N多孔有机笼配体在溶剂中充分搅拌，活性金属组分与含P、N多孔有机笼配体中裸露的P或N形成牢固的配位键，蒸去溶剂后，得到含P、N多孔有机笼配体与过渡金属形成的络合物催化剂；The complex catalyst according to claim 6, characterized in that: a porous organic cage ligand containing P and N is added to one or two or more precursors containing Rh, Co, Ir, Pd or Pt precursors The solution is stirred and coordinated sufficiently to obtain a complex catalyst formed by the P, N porous organic cage ligand and transition metal; the precursor of the active metal component and the P, N porous organic cage ligand are in a solvent. After fully stirring, the active metal component forms a strong coordination bond with the exposed P or N in the porous organic cage ligand containing P and N. After the solvent is distilled off, the P and N porous organic cage ligand and the transition metal are formed. Complex catalyst
    具体过程为：惰性气体气氛273～473K下，在含有活性金属组分前驱体的溶剂中，加入含P、N多孔有机笼配体，搅拌0.1～100小时，优选搅拌时间范围0.1～20小时，之后，室温条件下真空抽除溶剂，得到P、N多孔有机笼配体与过渡金属形成的络合物催化剂；The specific process is: under an inert gas atmosphere of 273 to 473K, in a solvent containing a precursor of an active metal component, adding a porous organic cage ligand containing P and N, and stirring for 0.1 to 100 hours, preferably for a stirring time range of 0.1 to 20 hours, Then, the solvent was removed under vacuum at room temperature to obtain a complex catalyst formed by P, N porous organic cage ligand and transition metal;
    所述的溶剂为二氯甲烷、三氯甲烷、四氯化碳、乙酸乙酯、甲酸甲酯、苯、甲苯、二甲苯、正己烷、正庚烷、正辛烷、环己烷、二甲亚砜、N,N-二甲基甲酰胺或四氢呋喃中一种或两种以上；The solvent is methylene chloride, chloroform, carbon tetrachloride, ethyl acetate, methyl formate, benzene, toluene, xylene, n-hexane, n-heptane, n-octane, cyclohexane, dimethyl One or two or more of sulfoxide, N, N-dimethylformamide or tetrahydrofuran;
    所述的活性组分为Rh、Co、Ni、Ir、Pd或Pt中的一种或两种以上，其中Rh的前驱体为RhH(CO)(PPh 3) 3、Rh(CO) 2(acac)、RhCl 3、Rh(CH 3COO) 2中的一种或两种以上；Co的前驱体为Co(CH 3COO) 2、Co(CO) 2(acac)、Co(acac) 2、CoCl 2中的一种或两种以上；Ni的前驱体为Ni(CH 3COO) 2、Ni(CO) 2(acac)、Ni(acac) 2、NiCl 2中的一种或两种以上；Ir的前驱体为Ir(CO) 3(acac)、Ir(CH 3COO) 3、Ir(acac) 3、IrCl 4中的一种或两种以上；Pd的前驱体为Pd(CH 3COO) 2、Pd(acac) 2、PdCl 2、Pd(PPh 3) 4、PdCl 2(CH 3CN) 2中的一种或两种以上；Pt的前驱体为Pt(acac) 2、PtCl 4、PtCl 2(NH 3) 2中的一种或两种以上；含P、N配体多孔有机笼配体与活性组分的摩尔比为100:1-1:1，优选为10:1-1:1。 The active component is one or more of Rh, Co, Ni, Ir, Pd or Pt, wherein the precursors of Rh are RhH (CO) (PPh 3 ) 3 , Rh (CO) 2 (acac ), RhCl 3 , Rh (CH 3 COO) 2 or two or more of them; the precursors of Co are Co (CH 3 COO) 2 , Co (CO) 2 (acac), Co (acac) 2 , CoCl Ni is one kind of precursor Ni (CH 3 COO) 2, Ni (CO) 2 (acac), 2, NiCl 2 in Ni (acac) or two or more;; 2, one or two or more of Ir The precursor is one or more of Ir (CO) 3 (acac), Ir (CH 3 COO) 3 , Ir (acac) 3 , IrCl 4 ; the precursor of Pd is Pd (CH 3 COO) 2 , Pd (acac) 2 , PdCl 2 , Pd (PPh 3 ) 4 , PdCl 2 (CH 3 CN) 2 or more; one of the precursors of Pt is Pt (acac) 2 , PtCl 4 , PtCl 2 One or two or more of (NH 3 ) 2 ; the molar ratio of the porous organic cage ligand containing P and N ligands to the active component is 100: 1-1: 1, preferably 10: 1-1: 1 .
  8. 一种权利要求6-7任一所述络合物催化剂的在氢甲酰化反应、偶联反应、硅氢加成反应、加氢反应或CO 2环加成反应中的应用。 An application of the complex catalyst according to any one of claims 6 to 7 in a hydroformylation reaction, a coupling reaction, a hydrosilylation reaction, a hydrogenation reaction or a CO 2 cycloaddition reaction.
  9. 按照权利要求8所述的应用，其特征在于：在催化氢甲酰化反应中应用，将含P、N多孔有机笼配体与过渡金属形成的络合物催化剂装入反应器中，通入反应混合气和原料烯烃，混合气的主要组分为H 2和CO，H 2/CO体积比为0.5～5.0，混合气气体空速为100～20000h -1优选范围为1000～20000h -1；原料烯烃为C 3～C 20的烯烃，反应温度为323～573K(反应温度优选为353～423K)，反应压力为0.1～10.0MPa(反应压力优选为0.5～5MPa)的条件下进行烯烃氢甲酰化反应。 The application according to claim 8, characterized in that: in the application of catalytic hydroformylation reaction, a complex catalyst formed by a porous organic cage ligand containing P and N and a transition metal is charged into a reactor, and Reacting mixed gas and raw olefin, the main components of the mixed gas are H 2 and CO, the volume ratio of H 2 / CO is 0.5 to 5.0, the space velocity of the mixed gas is 100 to 20000 h -1, and the preferred range is 1000 to 20000 h -1 ; The raw olefins are C 3 to C 20 olefins, the reaction temperature is 323 to 573K (the reaction temperature is preferably 353 to 423K), and the reaction pressure is 0.1 to 10.0 MPa (the reaction pressure is preferably 0.5 to 5 MPa). Acylation reaction.
  10. 按照权利要求9所述的应用，其特征在于：混合气中还可含有选自Ar、CO 2、He或N 2中的一种或二种以上的其余气体，混合气中H 2+CO的体积含量为20～90％；所述反应器为釜式反应器；烯烃质量纯度为20～100％，烯烃中可含有的其他成分为C 3～C 20的烷烃中的一种或二种以上；所述C 3～C 20烯烃优选为C 5～C 14的烯烃。 Use according to claim 9, characterized in that: the gas mixture may contain one selected from Ar, CO 2, He or N 2 gas or the remaining mixed gas of two or more of the H 2 + CO The volume content is 20 to 90%; the reactor is a kettle type reactor; the mass purity of the olefin is 20 to 100%, and the other components that may be contained in the olefin are one or two or more of C 3 to C 20 alkanes ; The C 3 to C 20 olefin is preferably a C 5 to C 14 olefin.
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CN114985002A (en) * 2022-05-31 2022-09-02 中海油天津化工研究设计院有限公司 Diphosphine polymer catalyst for olefin hydroformylation and preparation method and application thereof
CN114985002B (en) * 2022-05-31 2023-11-07 中海油天津化工研究设计院有限公司 Biphosphine polymer catalyst for olefin hydroformylation, preparation method and application thereof
CN114950551B (en) * 2022-05-31 2024-05-07 中国海洋石油集团有限公司 Monophosphite polymer catalyst for olefin hydroformylation, preparation method and application thereof

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