WO2020034477A1 - Porous organic cage ligand containing p and n, preparation therefor and use thereof - Google Patents

Porous organic cage ligand containing p and n, preparation therefor and use thereof Download PDF

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WO2020034477A1
WO2020034477A1 PCT/CN2018/116379 CN2018116379W WO2020034477A1 WO 2020034477 A1 WO2020034477 A1 WO 2020034477A1 CN 2018116379 W CN2018116379 W CN 2018116379W WO 2020034477 A1 WO2020034477 A1 WO 2020034477A1
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porous organic
organic cage
monomer
ligand
reaction
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PCT/CN2018/116379
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Chinese (zh)
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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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    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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Definitions

  • the invention belongs to the field of material synthesis, and particularly relates to a porous organic cage ligand containing P and N, and a preparation method and application thereof.
  • P and N ligands are widely used in reactions such as hydroformylation reactions, coupling reactions, hydrosilylation reactions, hydrogenation reactions, and CO 2 cycloaddition reactions catalyzed by transition metal complexes.
  • hydroformylation reaction the olefin hydroformylation reaction is considered to be the most successful model for the implementation of the homogeneous catalysis industry.
  • This reaction process converts the raw olefins and synthesis gas (CO / H 2 ) to nearly 100% selective conversion.
  • Aldehydes are widely used chemical intermediates, and their subsequent conversion products such as alcohols, acids, esters, and fatty amines are very important fine chemical products. They are widely used as organic solvents, plasticizers, and surfactants.
  • 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.
  • a lot of work has been done in the field of hydroformylation catalysts for heterogeneous catalysis and heterogeneous catalysis, but the traditional homogeneous catalyzed heterogeneous methods have exposed a series of problems to be solved and overcome. , Especially poor catalyst stability after heterogeneous, serious loss of active components, etc. (J. Mol. Catal. A-Chem., 2002, 182: 107-123; Eur. J. Org. Chem., 2012, 2012: 6309-6320).
  • an object of the present invention is to provide a porous organic cage ligand containing P and N, and a preparation method and application thereof.
  • N ligands functionalized with aldehyde groups, amino groups, and other polyamines or polyaldehyde comonomers in a solvent they are allowed to stand or stir at a specific temperature to make the P, N ligands and comonomers
  • the functional groups in the body react sufficiently to form P, N porous organic cage ligands with a specific pore structure.
  • the P and N porous organic cage ligands have a specific pore structure, a specific surface area of 0 to 3000 m 2 / g, preferably a range of 10 to 1000 m 2 / g, and a pore volume of 0 to 10.0 cm 3 / g, preferably 0.5 to 2.0 cm 3 / g, and the pore size distribution is 0.01 to 100.0 nm, preferably 0.5 to 20.0 nm.
  • step b) concentrating the mixed solution containing P and / or N porous organic cage ligand prepared in step a), adding an alcohol solvent, and crystallizing the porous organic cage ligand;
  • 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 formed by 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
  • the complex catalyst formed by the P, N-containing porous organic cage ligand and transition metal is suitable for hydroformylation reaction, coupling reaction, hydrosilylation reaction, hydrogenation reaction and CO 2 cycloaddition of olefins. Formation 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.
  • an alcohol solvent is added, and the P and N porous organic
  • the cage ligand complex catalyst is crystallized from the reaction system, and the catalyst can be easily recovered.
  • the electronic and three-dimensional effects of the P and N ligands can be adjusted to control the performance of the complex catalysts that are finally formed, so as to be suitable for different substrates and different processes.
  • the P, N-containing porous organic cage ligand prepared by the present invention retains good ligand properties of the P, N ligand, and due to the specific structure of the P, N porous organic cage ligand, the P, N porous organic cage ligand has the same properties as Corresponding P and N ligands have different electronic effects and steric effects.
  • the NHx groups of P and N porous organic cage ligands have a basic effect on changing the chemical environment of the cavity. Therefore, the P, N porous organic cage ligands and Complex catalysts formed by transition metals, such as the classic Rh-P catalyst system of triphenylphosphine, exhibit unique catalytic properties.
  • the complex catalyst formed by P, N porous organic cage ligands has the characteristics of homogeneous reaction and heterogeneous recovery.
  • the catalyst formed by P, N porous organic cage ligands and transition metals is in a homogeneous reaction state.
  • the catalytic center is fully contacted to ensure good catalytic performance.
  • an alcohol solvent is added, and the P, N porous organic cage ligand complex catalyst is crystallized from the reaction system, and the catalyst can be easily recovered.
  • the beneficial effect of the present invention is that the P and N ligands in the P and N-containing porous organic cage ligands prepared by the present invention can effectively coordinate with the active metal to form a complex catalyst. Since the porous organic 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 ensures good catalytic performance.
  • 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
  • Figure 3 Schematic diagram of monomers required for the synthesis of porous organic cage ligands containing P and N, where L1-L53 are aldehyde or amino-functionalized P and N ligand monomers, and L54-L65 are polyaldehydes and polyvalents 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 The XRD diffraction spectrum of the PPh 3 porous organic cage ligand synthesized in Example 1, and we also tested the X-ray single crystal diffraction. After analyzing the structure, the CCDC number applied was 1857136.
  • 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 PPh 3 porous organic cage ligand was prepared, and 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 porous material suitable for hydroformylation of olefins. Rh-based complex catalysts coordinated by organic cage ligands.
  • Example 2 the same implementation process as in Example 1 was performed except that 2.12 grams of Figure 3L57 of Figure 3L57 was used as a comonomer instead of 2.12 grams of Figure 3L55.
  • 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 L55 comonomer in FIG. 3 and 1.06 g of the L57 comonomer in FIG. 3 were used as the mixed comonomer instead of 2.12 g of the L55 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 instead of acetylacetone 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 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 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

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Abstract

Disclosed in the present invention are a porous organic cage ligand containing P and N, a preparation method therefor, and use thereof. The porous organic cage ligand containing P and N is formed by cross-linking a P and N ligand functionalized with functional groups such as aldehyde group and amino group as a monomer, and a corresponding polyamine or polyaldehyde as a comonomer. The synthesized porous organic cage ligand containing P and N has a stable unique pore structure, and can be used to selectively adsorb separated gases. The complex catalyst formed by the porous organic cage ligand containing P and N has the characteristics of homogeneous reaction and heterogeneous recovery. During a reaction, the catalyst formed by the porous organic cage ligand containing P and N and a transition metal is in a homogeneous reaction state, and reactants and the catalytic center are sufficiently contacted to ensure good catalytic performance. After the reaction is completed, an alcoholic solvent is added, and the complex catalyst of porous organic cage ligand containing P and N is crystallized from the reaction system, so that the catalyst can be recovered more easily.

Description

一种含P、N多孔有机笼配体及其制备和应用P, N porous organic cage ligand, preparation and application thereof 技术领域Technical field
本发明属于材料合成领域，具体涉及一种含P、N多孔有机笼配体及其制备方法和应用。The invention belongs to the field of material synthesis, and particularly relates to a porous organic cage ligand containing P and N, and a preparation method and application thereof.
背景技术Background technique
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.
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。以氢甲酰化反应为例，烯烃氢甲酰化反应被认为是均相催化工业实施最成功的典范，该反应过程将原料烯烃和合成气(CO/H 2)接近100％选择性的转化为比原料烯烃多一个碳原子的醛。醛是用途广泛的化学中间体，其后续转化产品醇，酸，酯和脂肪胺等都是非常重要的精细化工产品，广泛用作有机溶剂、增塑剂和表面活性剂等。 P and N ligands are widely used in reactions such as hydroformylation reactions, coupling reactions, hydrosilylation reactions, hydrogenation reactions, and CO 2 cycloaddition reactions catalyzed by transition metal complexes. Taking the hydroformylation reaction as an example, the olefin hydroformylation reaction is considered to be the most successful model for the implementation of the homogeneous catalysis industry. This reaction process converts the raw olefins and synthesis gas (CO / H 2 ) to nearly 100% selective conversion. An aldehyde having one more carbon atom than the starting olefin. Aldehydes are widely used chemical intermediates, and their subsequent conversion products such as alcohols, acids, esters, and fatty amines are very important fine chemical products. They are widely used as organic solvents, plasticizers, and surfactants.
目前全世界通过氢甲酰化生产的醛约为1200万吨/年，这里面有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。为了能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(J.Mol.Catal.A-Chem.,2002,182:107-123；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 facilitate the recycling of catalysts, a lot of work has been done in the field of hydroformylation catalysts for heterogeneous catalysis and heterogeneous catalysis, but the traditional homogeneous catalyzed heterogeneous methods have exposed a series of problems to be solved and overcome. , Especially poor catalyst stability after heterogeneous, serious loss of active components, etc. (J. Mol. Catal. A-Chem., 2002, 182: 107-123; 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。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的问题。然而，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配体多孔有机笼配体的合成一直面临着巨大的挑战。 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. By taking advantage of the complex catalyst formed by the coordination of the corresponding P and N porous organic cage ligands and transition metals in certain solvents, the characteristics of precipitation in some solvents are expected to solve the hydroformylation reactions of olefins, coupling reactions, The problem of separation and recovery of homogeneous complex catalysts such as hydrosilylation reaction, hydrogenation reaction and CO 2 cycloaddition reaction. However, since the first report of POCs, no porous organic cage ligands functionalized with P and N ligands have been reported in the literature. The synthesis of porous organic cage ligands with P and N ligands has been facing great challenges.
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]
Figure PCTCN2018116379-appb-000001
Figure PCTCN2018116379-appb-000001
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应用。In order to solve the above problems, an object of the present invention is to provide a porous organic cage ligand containing P and N, and a preparation method and application thereof.
本发明的技术方案为：The technical solution of the present invention is:
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。After fully dissolving and mixing the P, N ligands functionalized with aldehyde groups, amino groups, and other polyamines or polyaldehyde comonomers in a solvent, they are allowed to stand or stir at a specific temperature to make the P, N ligands and comonomers The functional groups in the body react sufficiently to form P, N porous organic cage ligands with a specific pore structure.
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 porous organic cage ligands have a specific pore structure, a specific surface area of 0 to 3000 m 2 / g, preferably a range of 10 to 1000 m 2 / g, and a pore volume of 0 to 10.0 cm 3 / g, preferably 0.5 to 2.0 cm 3 / g, and the pore size distribution is 0.01 to 100.0 nm, preferably 0.5 to 20.0 nm.
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和/或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 / or N porous organic cage ligand prepared in step a), adding an alcohol solvent, and crystallizing the porous organic cage ligand;
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;
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 formed by 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.
本发明提供的含P、N多孔有机笼配体与过渡金属形成的络合物催化剂适用于烯烃的氢甲酰化反应、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。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，可容易的实现催化剂的回收。并且可以通过调变P、N多孔有机笼配体的构造结构进而调节P、N配体的电子效应和立体效应，控制最终形成的络合物催化剂的性能，以适用于不同底物，不同工艺的氢甲酰化反应、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。 The complex catalyst formed by the P, N-containing porous organic cage ligand and transition metal is suitable for hydroformylation reaction, coupling reaction, hydrosilylation reaction, hydrogenation reaction and CO 2 cycloaddition of olefins. Formation reaction. 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 The cage ligand complex catalyst is crystallized from the reaction system, and the catalyst can be easily recovered. In addition, by adjusting the structure of the P and N porous organic cage ligands, the electronic and three-dimensional effects of the P and N ligands can be adjusted to control the performance of the complex catalysts that are finally formed, so as to be suitable for different substrates and different processes. Hydroformylation reaction, coupling reaction, hydrosilylation reaction, hydrogenation reaction and CO 2 cycloaddition reaction.
本发明的原理为：The principle of the invention is:
本发明制备的含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, N-containing porous organic cage ligand prepared by the present invention retains good ligand properties of the P, N ligand, and due to the specific structure of the P, N porous organic cage ligand, the P, N porous organic cage ligand has the same properties as Corresponding P and N ligands have different electronic effects and steric effects. At the same time, the NHx groups of P and N porous organic cage ligands have a basic effect on changing the chemical environment of the cavity. Therefore, the P, N porous organic cage ligands and Complex catalysts formed by transition metals, such as the classic Rh-P catalyst system of triphenylphosphine, exhibit unique catalytic properties.
P、N多孔有机笼配体形成的络合物催化剂具有均相反应、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，可容易实现催化剂的回收。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. The catalytic center is fully contacted to ensure good catalytic performance. After the reaction is completed, an alcohol solvent is added, and the P, N porous organic cage ligand complex catalyst is crystallized from the reaction system, and the catalyst can be easily recovered.
本发明的有益效果为：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有效的配位形成络合物催化剂。由于多孔有机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、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，可较为容易实现催化剂的回收。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。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 beneficial effect of the present invention is that the P and N ligands in the P and N-containing porous organic cage ligands prepared by the present invention can effectively coordinate with the active metal to form a complex catalyst. Since the porous organic 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 ensures good catalytic performance. After the reaction is completed, alcohol solvents are added, and the P and N porous organic cage ligand complex catalysts are crystallized from the reaction system, which makes it easier to recover the catalyst. 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. 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-L53为醛基或氨基官能团化的P、N配体单体，L54-L65为多元醛和多元胺共单体Figure 3: Schematic diagram of monomers required for the synthesis of porous organic cage ligands containing P and N, where L1-L53 are aldehyde or amino-functionalized P and N ligand monomers, and L54-L65 are polyaldehydes and polyvalents 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: The XRD diffraction spectrum of the PPh 3 porous organic cage ligand synthesized in Example 1, and we also tested the X-ray single crystal diffraction. After analyzing the structure, the CCDC number applied was 1857136.
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。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L55)，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 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. 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 (L55 in FIG. 3), and 1 ml of acetic acid was added as a catalyst, and the mixed solution was allowed to stand for 60 hours under the reaction conditions 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PPh 3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 PPh 3 porous organic cage ligand was prepared, and 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 porous material suitable for hydroformylation of olefins. Rh-based complex catalysts coordinated by organic cage ligands.
实施例2Example 2
在实施例2中，除了称取2.12克附图3L57为共单体替代2.12克附图3L55共单体外，其余的实施过程与实施例1相同。In Example 2, the same implementation process as in Example 1 was performed except that 2.12 grams of Figure 3L57 of Figure 3L57 was used as a comonomer instead of 2.12 grams of Figure 3L55.
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L55共单体和1.06g附图3中的L57共单体作为混合共单体替代2.12g附图3中的L55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 L55 comonomer in FIG. 3 and 1.06 g of the L57 comonomer in FIG. 3 were used as the mixed comonomer instead of 2.12 g of the L55 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L63共单体(n＝1)和0.67g附图3中的L65共单体(n＝1)作为混合共单体替代2.12g附图3中的L55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 L63 comonomer (n = 1) in FIG. 3 and 0.67 g of the L65 comonomer (n = 1) in FIG. 3 as a mixed comonomer instead of 2.12 g of Except for the L55 comonomer in FIG. 3, the rest of the implementation process is the same as in 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 instead of acetylacetone 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.
对比实施例13Comparative Example 13
为了对比，在实施例13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。 For comparison, in Example 13, 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14Example 14
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-7890B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-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 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.
表2实施例1-13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 1-13 and 1-octene reaction data
Figure PCTCN2018116379-appb-000002
Figure PCTCN2018116379-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。* 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：含P、N多孔有机笼配体以醛基和/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 is characterized in that the porous organic cage ligand containing P and N uses P and / or N ligands functionalized with aldehyde groups and / or amino functional groups as monomers, and correspondingly (The aldehyde group in the monomer corresponds to the polyamine, and the amino group in the monomer corresponds to the polyaldehyde.) The polyamine or polyaldehyde is a comonomer. In the presence of a solvent, the functional groups in the monomer and the comonomer fully react and crosslink to form a monomer. P and / or N porous organic cage ligand.
  2. 按照权利要求1所述的含P、N多孔有机笼配体，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；优选：所述单体中的官能团优选为三个醛基或者三个氨基；共单体多元胺或多元醛优选为二元胺或二元醛。The porous organic cage ligand containing P and N according to claim 1, characterized in that: the monomer may be one or two or more kinds of monodentate or multidentate ligands; a co-monomer polyamine or polyaldehyde The multi-element in can be binary or ternary, and the co-monomer can be one or two or more; preferably: the functional group in the monomer is preferably three aldehyde groups or three amino groups; the co-monomer polyamine or The polyaldehyde is preferably a diamine or a dialdehyde.
  3. 按照权利要求1或2所述的含P、N多孔有机笼配体，其特征在于：所述单体选自下述中的一种或二种以上：The porous organic cage ligand containing P and N according to claim 1 or 2, wherein the monomer is selected from one or two or more of the following:
    Figure PCTCN2018116379-appb-100001
    Figure PCTCN2018116379-appb-100001
    Figure PCTCN2018116379-appb-100002
    Figure PCTCN2018116379-appb-100002
    Figure PCTCN2018116379-appb-100003
    Figure PCTCN2018116379-appb-100003
    Figure PCTCN2018116379-appb-100004
    Figure PCTCN2018116379-appb-100004
    Figure PCTCN2018116379-appb-100005
    Figure PCTCN2018116379-appb-100005
    Figure PCTCN2018116379-appb-100006
    Figure PCTCN2018116379-appb-100006
    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 PCTCN2018116379-appb-100007
    Figure PCTCN2018116379-appb-100007
    Figure PCTCN2018116379-appb-100008
    Figure PCTCN2018116379-appb-100008
    n为正整数。n is a positive integer.
  4. 按照权利要求1所述的含P、N多孔有机笼配体，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。 The porous organic cage ligand containing P and N according to claim 1, wherein the porous organic cage ligand containing P and N has a specific pore structure and a specific surface area of 0.1 to 3000 m 2 / g, preferably in a range. is 10 ~ 1000m 2 / g, a pore volume of 0 ~ 10.0cm 3 / g, preferably of 0.5 ~ 2.0cm 3 / g, a pore size distribution of 0.01 ~ 100.0nm, preferably 0.5 ~ 20.0nm.
  5. 一种权利要求1-4任一所述的含P、N多孔有机笼配体的制备方法，其特征在于：含P、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和/或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。A method for preparing a porous organic cage ligand containing P and N according to any one of claims 1-4, characterized in that the method for preparing a porous organic cage ligand containing P and N is: combining a monomer and a polyamine or After the polyaldehyde comonomer is sufficiently dissolved and mixed in the solvent, it is allowed to stand or stir, so that the P and / or 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. .
  6. 按照权利要求5所述的制备方法，其特征在于：含P、N多孔有机笼配体的具体合成步骤为：The preparation method according to claim 5, characterized in that the specific synthetic steps of the porous organic cage ligand containing P and N are:
    a)惰性气体气氛273～473K下，在溶剂中加入醛基和/或氨基等官能团功能化的P 和/或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 / or amino groups to functional P and / or N ligands, polyamines or polyaldehyde comonomers, and add or not add catalysts to the solvent. Allow to stand or stir for 0.1 to 500 hours, and the preferred time for standing or stirring is 10 to 60 hours;
    b)将步骤a)制得的含有P和/或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 / or N porous organic cage ligand prepared in step a), adding an alcohol solvent, and crystallizing the porous organic cage ligand;
    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) P, N porous organic cage ligands obtained in step b) are filtered, washed and dried to obtain P, N porous organic cage ligand products.
  7. 按照权利要求6所述的制备方法，其特征在于：The preparation method according to claim 6, characterized in that:
    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.
  8. 按照权利要求6所述的制备方法，其特征在于：步骤a)中所述的醛基和/或氨基等官能团功能化的P和/或N配体在溶剂中的浓度范围为0.01-1000g/L，优选为0.1-10g/L，醛基和/或氨基等官能团功能化的P和/或N配体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，醛基和/或氨基等官能团功能化的P和/或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 preparation method according to claim 6, characterized in that the concentration range of the functionalized P and / or N ligands of functional groups such as aldehyde group and / or amino group in the solvent in step a) is 0.01-1000 g / L is preferably 0.1-10 g / L, and the molar ratio of P and / or N ligand monomer functionalized with functional groups such as aldehyde group and / or amino group to the co-monomer is 0.01: 1 to 100: 1, preferably 0.1: 1 -10: 1, under the condition of adding a catalyst, the catalyst may be selected from one or more of hydrochloric acid, acetic acid, sulfuric acid, phosphoric acid, and nitric acid, and functional groups such as aldehyde and / or amino functional P and / or N The molar ratio of the ligand monomer to the catalyst is 10000: 1-100: 1, and the inert gas in steps a), b) and c) is selected from one or two of Ar, He, N 2 and CO 2 the above.
  9. 一种权利要求1-4任一所述的含P、N多孔有机笼配体在选择性吸附分离气体中，或在氢甲酰化反应、偶联反应、硅氢加成反应、加氢反应或CO 2环加成反应等反应中的应用；反应采用的催化剂为权利要求1-4任一所述含P、N多孔有机笼配体与过渡金属形成的络合物催化剂。 A porous organic cage ligand containing P and N according to any one of claims 1 to 4 in a selective adsorption separation gas, or in a hydroformylation reaction, a coupling reaction, a hydrosilylation reaction, and a hydrogenation reaction Or CO 2 cycloaddition reaction; the catalyst used in the reaction is a complex catalyst formed by a P, N-containing porous organic cage ligand and a transition metal according to any one of claims 1-4.
  10. 按照权利要求9所述的应用，其特征在于：络合物催化剂的制备过程为：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；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；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 application according to claim 9, characterized in that the preparation process of the complex catalyst is: adding a porous organic cage containing P and N in a solvent containing an active metal component precursor under an inert gas atmosphere of 273-473K; The ligand is stirred for 0.1 to 100 hours, preferably for a stirring time range of 0.1 to 20 hours, and then the solvent is removed under vacuum at room temperature to obtain a complex catalyst formed by the P, N porous organic cage ligand and the transition metal; The solvents are dichloromethane, chloroform, carbon tetrachloride, ethyl acetate, methyl formate, benzene, toluene, xylene, n-hexane, n-heptane, n-octane, cyclohexane, dimethylsulfoxide, One, two or more of N, N-dimethylformamide or tetrahydrofuran; the active component is one or two or more of Rh, Co, Ni, Ir, Pd or Pt, among which the precursor of Rh The body is one or more of RhH (CO) (PPh 3 ) 3 , Rh (CO) 2 (acac), RhCl 3 , and Rh (CH 3 COO) 2 ; the precursor of Co is Co (CH 3 COO ) 2 , one or more of Co (CO) 2 (acac), Co (acac) 2 , CoCl 2 ; the precursors of Ni are Ni (CH 3 COO) 2 , Ni (CO) 2 (acac ), Ni (acac) 2 , NiCl 2 or more; the precursors of Ir are Ir (CO) 3 (acac), Ir (CH 3 COO) 3 , Ir (acac) 3 , IrCl 4 One or two or more; the precursor of Pd is one of Pd (CH 3 COO) 2 , Pd (acac) 2 , PdCl 2 , Pd (PPh 3 ) 4 , PdCl 2 (CH 3 CN) 2 or Two or more kinds; the precursors of Pt are one or more of Pt (acac) 2 , PtCl 4 , PtCl 2 (NH 3 ) 2 ; moles of P, N ligand porous organic cage ligand and active component The ratio is 100: 1-1: 1, and preferably 10: 1-1: 1.
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