CN113321787B - Nitroxide free radical functionalized porous organic polymer nanotube and preparation method and application thereof - Google Patents
Nitroxide free radical functionalized porous organic polymer nanotube and preparation method and application thereof Download PDFInfo
- Publication number
- CN113321787B CN113321787B CN202110613887.1A CN202110613887A CN113321787B CN 113321787 B CN113321787 B CN 113321787B CN 202110613887 A CN202110613887 A CN 202110613887A CN 113321787 B CN113321787 B CN 113321787B
- Authority
- CN
- China
- Prior art keywords
- nitroxide
- free radical
- organic polymer
- reaction
- nitrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
-
- 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
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/76—Dehydrogenation
- B01J2231/763—Dehydrogenation of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/143—Side-chains containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/143—Side-chains containing nitrogen
- C08G2261/1432—Side-chains containing nitrogen containing amide groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/413—Heck reactions
Abstract
The invention discloses a nitroxide free radical functionalized porous organic polymer nanotube and a preparation method and application thereof. The method comprises the following steps: sequentially adding a palladium catalyst and cuprous iodide into a reaction bottle under the condition of nitrogen, adding an aromatic acetylene monomer and a nitroxide free radical functional monomer into the reaction bottle, and exhausting gas for 3-5 times; adding an organic solvent into the reaction system under the condition of nitrogen, freezing by using liquid nitrogen, exhausting gas for 3-5 times, stirring for 1-3 h at room temperature under the protection of nitrogen, slowly thawing to obtain a mixed solution, transferring the reaction system to an oven, heating to 70-90 ℃, and reacting for 68-76 h; washing the obtained product with an organic solvent, filtering, drying in vacuum, and collecting to obtain the nitroxide free radical functionalized porous organic polymer nanotube. The nitroxide free radical functionalized porous organic polymer nanotube material can efficiently and selectively oxidize various alcohols into corresponding aldehydes and ketones.
Description
Technical Field
The invention relates to a preparation method of a nitroxide free radical functionalized porous organic polymer nanotube catalyst and application of the nitroxide free radical functionalized porous organic polymer nanotube catalyst in catalyzing alcohol oxidation, and belongs to the technical field of nanocatalysis.
Background
Alcohol oxidation reaction is one of important functional group conversion reactions, and the traditional alcohol oxidation catalyst mostly contains heavy metals such as manganese, chromium and the like, has large environmental pollution and difficult reaction control and is often accompanied with the generation of a large amount of harmful wastes. Based on the concept of effective utilization of resources to the maximum and sustainable development, how to develop a green, efficient and high-selectivity catalyst in chemical experiments and production has important research significance.
The porous organic polymer is a novel macromolecular porous material which is formed by connecting organic structural units through covalent bonds and has a micropore or mesopore structure. Compared with the traditional inorganic porous and inorganic-organic hybrid porous materials, the organic porous material has comprehensive advantages of stable structure, strong modifiability and the like, so the organic porous material has wide application potential in the fields of catalysis, gas storage, pollutant capture, energy and the like. However, conventional porous organic polymers are typically spherical or bulk solid powders on the order of microns or even millimeters, which limit the rate of diffusion of substrates and products during catalytic reactions. Therefore, the preparation of the organic porous polymer with the nano-scale and hollow tubular structure can effectively improve the specific surface area of the organic porous polymer and the diffusion rate of the substrate and the product, and is expected to become a new generation of efficient heterogeneous catalyst.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of a nitroxide radical functionalized porous organic polymer nanotube catalyst.
The invention also aims to provide a functionalized hollow nanotube porous organic polymer catalyst.
It is a further object of the present invention to provide a catalyst for the catalytic oxidation of alcohols.
In order to achieve any one of the above objects, the present invention provides a method for preparing a nitroxide radical functionalized porous organic polymer nanotube catalyst, the method comprising the steps of:
sequentially adding a palladium catalyst and cuprous iodide into a reaction bottle under the condition of nitrogen, adding an aromatic acetylene monomer and a nitroxide free radical functionalized monomer into the reaction bottle, vacuumizing for 3-5 times, and vacuumizing for 1-3 hours; adding an organic solvent A into a reaction bottle under the condition of nitrogen, freezing by using liquid nitrogen, exhausting gas for 3-5 times, stirring at room temperature for 1-2 h under the protection of nitrogen, thawing to obtain a mixed solution, heating to 70-90 ℃ (preferably 80 ℃), transferring the reaction system into an oven, and reacting for 68-76 h to obtain a hollow nano-tube-shaped functionalized porous organic polymer material; wherein the molar ratio of the aromatic acetylene monomers to the nitroxide free radical functional monomers is 1:2-4:1, and the molar amount of the palladium catalyst or cuprous iodide is 3% -15% of that of the aromatic acetylene monomers; the concentration of the aromatic acetylene monomers in the organic solvent is 50 mmol/L-250 mmol/L;
and (3) washing the functionalized hollow nano-tube-shaped porous organic polymer material with an organic solvent B, and drying to obtain the hollow nano-tube-shaped functionalized porous organic polymer material.
The invention relates to a preparation method of a nitroxide free radical functionalized porous organic polymer nanotube catalyst, which is used for obtaining nitroxide free radical functionalized organic porous polymer hollow nanotubes with different sizes and hollow tube diameters by controlling the concentration of the catalyst, the concentration of aromatic alkynes and the polymerization reaction time. The hollow nanotube can be used for catalyzing alcohol oxidation reaction, the conversion rate can reach 100%, and the selectivity of the hollow nanotube on the generation of aldehyde by the catalytic oxidation of alcohol can reach more than 99%.
Further, the palladium catalyst used is selected from tetrakistriphenylphosphine palladium (Pd (PPh)3)4) Bis (triphenylphosphine) palladium dichloride (Pd (PPh)3)2Cl2) [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (Pd (dppf)2Cl2) One kind of (1).
Further, the organic solvent A is selected from two or three of triethylamine, toluene and methanol. Preferably, the mixed solution of triethylamine and toluene with the volume ratio of 1:5-10:1 is used as the organic solvent.
Further, the molar ratio of the aromatic acetylenic monomer to the nitroxide radical functional monomer is 1:1, 3:2, or 3: 4.
Further, the aromatic acetylene monomer is selected from one of 1, 4-diacetylene benzene, 1,3, 5-triacetylene benzene, tetra (4-ethynyl benzene) methane, tetra (4-ethynyl benzene) ethylene, 1,3, 5-tri (4-ethynyl phenyl) benzene and 1,3,6, 8-tetra-ethynyl pyrene. Wherein the structure of the acetylene monomer is shown in table 1.
TABLE 1
Further, the TEMPO-functional monomer (nitroxide-functional monomer) used is selected from the group consisting of 2, 5-dibromo-N- (2,2,6, 6-tetramethylpiperidine) benzamide (2, 5-dibromo-TEMPO), 2, 5-dibromo-N, N' -bis (2,2,6, 6-tetramethylpiperidine) p-dibenzoamide (2, 5-dibromo-TEMPO)2) (MaoHui Ling, Wang Chen, Yanmyi, Schaum, Shenyanming, Zhuangjingliang TEMPO functionalized conjugated microporous polymer as a highly effective alcohol catalytic oxidant [ J]Fine chemical engineering, 2020,37(05): 976-. The structural formula of the TEMPO free radical functionalized monomer is shown in Table 2.
TABLE 2
The invention also provides a nitroxide free radical functionalized hollow tubular organic porous polymer, which is obtained by the preparation method of the nitroxide free radical functionalized porous organic polymer nanotube catalyst. The nitroxide free radical functionalized hollow nano-tube-shaped organic porous polymer is a nano tube with the particle size of 50 nm-500 nm and the specific surface area of 50 m2/g-1000 m2/g。
The application comprises the following steps: the nitroxide free radical functionalized hollow tubular organic porous polymer can be used for catalytic oxidation of alcohol organic matters. When the nitroxide free radical functionalized hollow tubular organic porous polymer is used for catalytic oxidation of alcohol organic matters, a catalyst and a substrate are added into an organic solvent and react for 3 hours at 80 ℃.
Further, the adding proportion of the catalyst, the substrate and the organic solvent is 10-60 mg: 0.5 mmol-5 mmol: 1 mL-10 mL.
The invention has the following remarkable advantages: the concentration of oxygen and water in a reaction system is greatly reduced by using a liquid nitrogen freezing and gas exhausting process; in addition, the temperature is slowly raised at room temperature after the liquid nitrogen is frozen, and the time of the catalyst participating in the catalytic reaction can be regulated, so that the growth of the hollow nanotube is accurately regulated and controlled under the conditions of proper reaction substrate concentration and catalyst concentration, and the occurrence of solid microspheres or blocks is avoided. Firstly, the invention pumps the water and solvent in the system away by vacuumizing for two hours, and the system is in anhydrous and anaerobic condition by freezing and exhausting gas by liquid nitrogen. Secondly, the concentration of the acetylenic aromatic hydrocarbon is 133 mmol/L, the concentration of the nitroxide free radical functionalized monomer is 89 mmol/L, the concentration of the palladium catalyst is 9.4 mmol/L, and the concentration of cuprous iodide is 17.3 mmol/L. Thirdly, in the experimental process, the thawing condition is mild, the thawing time is 2 hours, the reaction system is uniformly mixed, and finally the reaction is carried out in a stable environment in an oven at the temperature of 80 ℃ for 72 hours to obtain the hollow nanotube 1.
In comparative example 1, the concentration of the acetylenic aromatic hydrocarbon substrate was 333 mmol/L, the concentration of the nitroxyl radical functionalized monomer was 500 mmol/L, the concentration of the palladium catalyst was 16.7 mmol/L, and the concentration of cuprous iodide was 33.3 mmol/L. The reaction was stirred at 80 ℃ for 24 hours to give only a rod-like and block-like conjugated microporous polymer.
Therefore, the invention vacuumizes the substrate and the catalyst system for two hours, adds the solvent, freezes the liquid nitrogen, exhausts the gas, unfreezes at room temperature, and reacts in an oven at 80 ℃ for 72 hours. The rapid diffusion of the catalyst is controlled in the reaction process, the catalyst is uniformly distributed in the solution, and the hollow nanotube 1 can be obtained in a stable reaction environment by reducing the concentration of the substrate and the concentration of the palladium catalyst.
The preparation method of the nitroxide free radical functionalized porous organic polymer nanotube catalyst can synthesize the functionalized porous organic polymer with a hollow tubular structure. The method has the advantages of simple reaction system, simple experimental operation, faster catalytic efficiency of the functionalized porous organic polymer and higher specific surface area.
Compared with spherical porous organic polymers, the hollow tubular functionalized organic porous polymer has the advantages that in the catalytic reaction, a substrate can enter the porous material through gaps of the porous material, so that the substrate and the functionalized oxygen free radicals on the porous material can have larger contact area, and the catalytic efficiency of the functionalized organic porous polymer in alcohol catalytic oxidation is further improved. And the catalyst can be used as a functionalized nitroxide radical heterogeneous loaded catalyst, and can be recovered through centrifugal separation after the catalysis is finished, so that the catalyst can be recycled.
Drawings
FIG. 1 is a TEM image of nitroxide radical functionalized organic porous polymer hollow nanotube 1 of example 1;
FIG. 2 is an SEM image of the nitroxide radical functionalized organic porous polymer hollow nanotube 1 of example 1;
FIG. 3 is a graph of the nitroxide radical functionalized organic porous polymer hollow nanotube 1 EPR of example 1;
FIG. 4 is a TEM image of the nitroxide radical functionalized hollow tubular organic porous polymer hollow nanotube 3 of example 3;
FIG. 5 is an SEM image of the nitroxide radical functionalized hollow tubular organic porous polymer hollow nanotube 3 of example 3;
FIG. 6 is an SEM image of bulk and rod hybrid CMP-3-TEMPO synthesized according to the non-optimized version of comparative example 1;
FIG. 7 is an SEM image of less than optimal synthesized microspheres of comparative example 2, CMP-4-TEMPO.
Detailed Description
The invention relates to a preparation method of a nitroxide free radical functionalized porous organic polymer nanotube catalyst, which comprises the following steps:
(a) adding a palladium catalyst and cuprous iodide into a reaction bottle under the condition of nitrogen, adding an aromatic acetylene monomer and a nitroxide free radical functional monomer into the reaction bottle, vacuumizing for 4 times, and vacuumizing for 2 hours;
(b) adding an organic solvent into the reaction system in the step (a) under the condition of nitrogen, freezing by using liquid nitrogen, exhausting gas for 4 times, stirring at room temperature for 2 hours under the protection of nitrogen, and unfreezing to obtain a mixed solution;
(c) and (c) heating the reaction system in the step (b) to 80 ℃, and transferring the reaction system to an oven for reaction for 72 hours. And after the reaction is finished, sequentially using chloroform, methanol, acetone and ethyl acetate to clean the product, drying, and collecting to obtain the nitroxide free radical functionalized hollow tubular organic porous polymer.
According to the preparation method of the nitroxide free radical functionalized porous organic polymer nanotube catalyst, the nitroxide free radical is functionalized, and the synthesis of the nitroxide free radical functionalized hollow nanotube organic porous polymer is realized by utilizing a Sonogashira-Hagihara coupling reaction and under the catalysis of metal Pd through the optimization of a scheme.
The nitroxide free radical functionalized hollow nanotube organic porous polymer material synthesized by the method can be used for catalytic oxidation reaction of alcohol, and specifically comprises the following steps: putting the hollow nanotube catalyst in an organic solvent, performing ultrasonic dispersion, adding an alcohol organic substrate, taking tert-butyl nitrite (TBN) as a cocatalyst, introducing oxygen into a reaction system, and reacting at 80 ℃.
Example 1
This example provides a method for preparing a hollow nanotube 1 catalyst, which includes the following steps:
(a) the catalyst Pd (PPh) is added under nitrogen3)2Cl2(0.07 mmol 50 mg) and CuI (0.13 mmol, 25 mg) were added to a round-bottomed flask, 1,3, 5-triacetylbenzene (1 mmol, 150 mg) and 2, 5-dibromo-TEMPO (0.67 mmol, 288.7 mg) were further added, the evacuation was carried out 4 times, and vacuum was evacuated for 2 hours;
(b) adding triethylamine (3.75 mL) and toluene (3.75 mL) into the reaction system in the step (a) under the nitrogen condition, freezing and exhausting gas for 4 times by using liquid nitrogen, stirring at room temperature for 2 h under the protection of nitrogen, thawing to obtain a mixed solution, heating the reaction system to 80 ℃, and transferring to an oven for reaction for 72 h.
(c) And (b) sequentially washing the product obtained in the step (b) with chloroform, methanol, acetone and ethyl acetate, filtering to obtain a product, drying in vacuum, and collecting to obtain the nitroxide radical functionalized organic porous polymer hollow nanotube 1, wherein a TEM is shown in figure 1, and an SEM is shown in figure 2, so that the synthesized hollow nanotube 1 catalyst has an obvious tubular structure and uniform size. The solid-state solid paramagnetic electron resonance spectrum (figure 3) can be observed to have an obvious single broad peak at a g-factor of 2.0, which indicates that a large amount of nitroxide radicals exist in the microporous structure of the hollow nanotube 1.
The hollow nanotube 1 (10 mg) nanotube catalyst was placed in a polytetrafluoroethylene reaction vessel, to which benzotrifluoride (0.5 mL) was added as a reaction solvent, and the catalyst was sufficiently dispersed in the solvent by ultrasound. And adding tert-butyl nitrite (TBN) serving as a cocatalyst into the mixture (3 mu L), performing ultrasonic dispersion, adding 5-hydroxymethylfurfural (5-HMF) (10 mu L) serving as a catalytic reaction substrate, and finally performing ultrasonic dispersion, and placing the reaction in an oven at 80 ℃ for reaction for several hours. After the reaction is finished, cooling the reaction kettle to room temperature, taking the reaction liquid for high-speed centrifugation (10000 rpm, 5 min), taking the supernatant, and analyzing the components in the reaction liquid by a gas-mass spectrometer to obtain the conversion rate and selectivity of converting 5-HMF into 2, 5-furandicarboxaldehyde (2, 5-DFF). The results are shown in Table 3.
TABLE 3 Performance Table for catalyzing alcohol Oxidation of hollow nanotube 1 samples prepared in Experimental example 1
Example 2
This example provides a method for preparing a hollow nanotube 2 catalyst, which includes the following steps:
(a) the catalyst Pd (PPh) is added under nitrogen3)2Cl2(50 mg) and CuI (25 mg) were added to a round-bottom flask, and 1, 4-diacetylene benzene (1 mmol, 126.15 mg) and 2, 5-dibromo-TEMPO (0.5 mmol, 215.5 mg) were added thereto, followed by evacuation for 3 to 5 times and evacuation for 2 hours;
(b) adding triethylamine (3.75 mL) and toluene (3.75 mL) into the reaction system in the step (a) under the nitrogen condition, freezing and exhausting gas for 3-5 times by using liquid nitrogen, stirring at room temperature for 2 h under the protection of nitrogen, thawing to obtain a mixed solution, heating the reaction system to 80 ℃, and transferring to an oven for reaction for 72 h.
(c) And (c) sequentially washing the product obtained in the step (b) by using chloroform, methanol, acetone and ethyl acetate, filtering to obtain a product, and drying and collecting to obtain the hollow nanotube 2 catalyst.
Example 3
This example provides a method for preparing a hollow nanotube 3 catalyst, which includes the following steps:
(a) the catalyst Pd (PPh) is added under nitrogen3)2Cl2(50 mg) and CuI (25 mg) were added to a round-bottom flask, and tetrakis (4-ethynylbenzene) methane (1 mmol, 416.51 mg) and 2, 5-dibromo-TEMPO (2 mmol, 862 mg) were added thereto, followed by evacuation of gas for 3-5 times and evacuation for 2 hours;
(b) adding triethylamine (3.75 mL) and toluene (3.75 mL) into the reaction system in the step (a) under the nitrogen condition, freezing and exhausting gas for 3-5 times by using liquid nitrogen, stirring at room temperature for 2 h under the protection of nitrogen, thawing to obtain a mixed solution, heating the reaction system to 80 ℃, and transferring to an oven for reaction for 72 h.
(c) And (c) sequentially washing the product obtained in the step (b) by using chloroform, methanol, acetone and ethyl acetate, filtering to obtain a product, and drying and collecting to obtain the hollow nanotube 3 catalyst.
Example 4
This example provides a method for preparing a hollow nanotube 4 catalyst, which includes the following steps:
(a) the catalyst Pd (PPh) is added under nitrogen3)2Cl2(50 mg) and CuI (25 mg) were added to a round-bottom flask, and tetrakis (4-ethynylstyrene) ethylene (1 mmol, 428.52 mg) and 2, 5-dibromo-TEMPO (2 mmol, 862 mg) were added thereto, followed by evacuation of gas for 3-5 times and evacuation for 2 hours;
(b) adding triethylamine (3.75 mL) and toluene (3.75 mL) into the reaction system in the step (a) under the nitrogen condition, freezing and exhausting gas for 3-5 times by using liquid nitrogen, stirring at room temperature for 2 h under the protection of nitrogen, thawing to obtain a mixed solution, heating the reaction system to 80 ℃, and transferring to an oven for reaction for 72 h.
(c) And (b) sequentially washing the product obtained in the step (b) with chloroform, methanol, acetone and ethyl acetate, filtering to obtain a product, and drying and collecting to obtain the hollow nanotube 4 catalyst.
Example 5
This example provides a method for preparing a hollow nanotube 5 catalyst, which includes the following steps:
(a) pd (PPh) catalyst was added under nitrogen3)2Cl2(50 mg) and CuI (25 mg) were charged into a round-bottomed flask, and 1,3, 5-tris (4-ethynylphenyl) benzene (1 mmol, 378.46 mg) and 2, 5-dibromo-TEMPO (0.67 mmol, 288.7 mg) were added thereto, followed by evacuation for 3 to 5 times and evacuation for 2 hours;
(b) adding triethylamine (3.75 mL) and toluene (3.75 mL) into the reaction system in the step (a) under the nitrogen condition, freezing and exhausting gas for 3-5 times by using liquid nitrogen, stirring at room temperature for 2 h under the protection of nitrogen, thawing to obtain a mixed solution, heating the reaction system to 80 ℃, and transferring to an oven for reaction for 72 h.
(c) And (c) sequentially washing the product obtained in the step (b) by using chloroform, methanol, acetone and ethyl acetate, filtering to obtain a product, and drying and collecting to obtain the hollow nanotube 5 catalyst.
Example 6
This example provides a method for preparing a hollow nanotube 6 catalyst, which includes the following steps:
(a) the catalyst Pd (PPh) is added under nitrogen3)2Cl2Adding 50 mg of the raw materials and 25 mg of CuI into a round-bottom flask, adding 1,3,6, 8-tetraacetylpyrene (1 mmol, 298.34 mg) and 2, 5-dibromo-TEMPO (2 mmol, 862 mg), evacuating for 3-5 times, and vacuumizing for 2 hours;
(b) adding triethylamine (3.75 mL) and toluene (3.75 mL) into the reaction system in the step (a) under the nitrogen condition, freezing and deflating by using liquid nitrogen for 3-5 times, stirring at room temperature for 2 h under the protection of nitrogen, thawing to obtain a mixed solution, heating the reaction system to 80 ℃, and transferring to an oven for reaction for 72 h.
(c) And (c) sequentially washing the product obtained in the step (b) by using chloroform, methanol, acetone and ethyl acetate, filtering to obtain a product, and drying and collecting to obtain the hollow nanotube 6 catalyst.
Example 7
This example provides a method for preparing a hollow nanotube 7 catalyst, which includes the following steps:
(a) the catalyst Pd (PPh) is added under nitrogen3)2Cl2(50 mg) and CuI (25 mg) were added to a round-bottom flask, and then tetrakis (4-ethynylstyrene) ethylene (1 mmol, 428.52 mg) and 2, 5-dibromo-N, N' -bis (2,2,6, 6-tetramethylpiperidine) p-benzamide (2 mmol, 1.260 g) were added, followed by 3-5 times of degassing and evacuation for 2 hours;
(b) adding triethylamine (3.75 mL) and toluene (3.75 mL) into the reaction system in the step (a) under the nitrogen condition, freezing and exhausting gas for 3-5 times by using liquid nitrogen, stirring at room temperature for 2 h under the protection of nitrogen, thawing to obtain a mixed solution, heating the reaction system to 80 ℃, and transferring to an oven for reaction for 72 h.
(c) And (c) sequentially washing the product obtained in the step (b) by using chloroform, methanol, acetone and ethyl acetate, filtering to obtain a product, and drying and collecting to obtain the hollow nanotube 7 catalyst.
Example 8
This example provides a method for preparing a hollow nanotube 8 catalyst, which is substantially the same as the steps in example 1, except that: the catalyst Pd (PPh)3)2Cl2(50 mg) was changed to palladium tetrakistriphenylphos-phate (Pd (PPh)3)4）（50 mg）。
Example 9
This example provides a method for preparing a hollow nanotube 9 catalyst, which is substantially the same as the steps in example 1, except that: the catalyst Pd (PPh)3)2Cl2(50 mg) was changed to [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (Pd (dppf)2Cl2）（25 mg）。
Example 10
The example provides a method of preparing a hollow nanotube 10 catalyst, which is substantially identical to the procedure of example 1, except that: the amount of triethylamine solvent used was changed to 1.5 mL.
Comparative example 1
The present comparative example provides a process for preparing a CMP-3-TEMPO catalyst comprising the steps of:
1,3, 5-Triethynylbenzene (150 mg, 1 mmol), Br2-Ph-TEMPO (636.5 mg, 1.5 mmol), tetrakis (triphenylphosphine) palladium (58 mg, 0.05 mmol), cuprous iodide (19 mg, 0.1 mmol) were dissolved in triethylamine (1.5 mL) and toluene (1.5 mL) and stirred at 80 ℃ for 24 h under nitrogen. After the reaction is finished, cooling to room temperature, washing the product with chloroform, methanol, acetone and ethyl acetate in sequence until the washing liquid is colorless, and drying in vacuum at 120 ℃ to obtain a brownish black solid. The obtained CMP-3-TEMPO catalyst for the conjugated microporous polymer has two shapes of a rod and a block, and the shapes are not uniform, and are shown in FIG. 6.
Comparative example 2
The present comparative example provides a process for the preparation of a CMP-4-TEMPO catalyst comprising the steps of:
tetrakis (4-ethynylbenzene) methane (156 mg, 0.375 mmol), Br2-Ph-TEMPO (215.5 mg, 0.5 mmol), tetrakis (triphenylphosphine) palladium (33 mg, 0.03 mmol), cuprous iodide (12 mg, 0.06 mmol) were dissolved in triethylamine (2 mL) and toluene (3 mL) and stirred under nitrogen at 80 ℃ for 24 h. Cooling to room temperature, washing the product with chloroform, methanol, acetone and ethyl acetate successively until the washing liquid is colorless, and vacuum drying at 60 deg.c to obtain brown yellow solid. The morphology of the obtained conjugated microporous polymer CMP-4-TEMPO catalyst is microspheres, which is shown in FIG. 7.
Comparative example 3
Comparative example 3 is essentially identical to the procedure in example 1, except that: the adopted functional monomer is N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide.
The catalytic experiments of example 1 were conducted using the above-mentioned materials of examples 1 to 10 and comparative examples 1 to 3 for a reaction time of 3 hours, and the conversion and selectivity (selectivity to 2, 5-furandicarboxaldehyde) of each material were measured. The results are shown in Table 4.
TABLE 4
The efficiency of catalyzing alcohol oxidation by the hollow nanotubes 1 prepared in example 1 is significantly higher than that of comparative examples 1 and 2. Therefore, the micropore and mesopore composite pore structure and the high specific surface area of the hollow nanotube 1 synthesized by the method are beneficial to substrate diffusion, and can more quickly perform catalytic oxidation on alcohol.
It can be seen from the above examples and comparative examples that the hollow nanotube catalyst prepared by the method of the present invention can effectively catalyze and oxidize alcohols.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A preparation method of a nitroxide free radical functionalized porous organic polymer nanotube is characterized by comprising the following steps:
(1) sequentially adding a palladium catalyst and cuprous iodide into a reaction bottle under the condition of nitrogen, adding an aromatic acetylene monomer and a nitroxide free radical functional monomer into the reaction bottle, vacuumizing for 3-5 times, and vacuumizing for 1-3 hours;
(2) adding an organic solvent into the reaction system in the step (1) under the condition of nitrogen, freezing by liquid nitrogen, exhausting gas for 3-5 times, stirring at room temperature for 1 h-3 h under the protection of nitrogen, thawing to obtain a mixed solution, heating to 70-90 ℃, and transferring the reaction to an oven for reaction for 68 h-76 h;
(3) washing the product obtained in the step (2) with an organic solvent, filtering, drying in vacuum, and collecting to obtain the nitroxide free radical functionalized porous organic polymer nanotube;
wherein the molar ratio of the aromatic acetylene monomers to the nitroxide free radical functional monomers is 1:2-4:1, and the molar usage of the palladium catalyst and cuprous iodide is 3% -15% of the usage of the aromatic acetylene monomers; the concentration of the aromatic acetylene monomers in the mixed solution in the step (2) is 50 mmol/L-250 mmol/L;
the nitroxide free radical functionalized monomer is selected from one of 2, 5-dibromo-N- (2,2,6, 6-tetramethylpiperidine) benzamide and 2, 5-dibromo-N, N' -bis (2,2,6, 6-tetramethylpiperidine) p-dibenzoamide;
the aromatic acetylene monomer is selected from one of 1, 4-diacetylene benzene, 1,3, 5-triacetylene benzene, 1,3, 5-tri (4-ethynyl phenyl) benzene, tetra (4-ethynyl phenyl) methane, tetra (4-ethynyl phenyl) ethylene and 1,3,6, 8-tetra-ethynyl pyrene.
2. The method according to claim 1, wherein the organic solvent in step (2) is selected from two or three of triethylamine, toluene and methanol; in the step (3), the organic solvent is selected from four or five of chloroform, methanol, acetone, normal hexane and ethyl acetate.
3. The method according to claim 2, wherein the organic solvent in the step (2) is a mixed solution of toluene and triethylamine in a volume ratio of 1:5-10: 1; the organic solvent washing operation in the step (3) is to wash the reaction product to be colorless by sequentially using chloroform, methanol, acetone and ethyl acetate.
4. The method according to claim 1, wherein the palladium catalyst is selected from one of tetrakistriphenylphosphine palladium, bis (triphenylphosphine) palladium dichloride, [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride.
5. The nitroxide radical-functionalized porous organic polymer nanotube prepared according to any one of claims 1 to 4, having a specific surface area of 50 m2/g-1000 m2/g。
6. The use of the nitroxide-functionalized porous organic polymer nanotube of claim 5, wherein the nitroxide-functionalized porous organic polymer nanotube is used for catalytic oxidation of organic alcohols.
7. The use of the nitroxide-functionalized porous organic polymer nanotube of claim 6, wherein the nitroxide-functionalized porous organic polymer nanotube is used for the specific operation of catalytic oxidation of organic alcohols by: putting the nitroxide free radical functionalized porous organic polymer nanotube catalyst in an organic solvent, performing ultrasonic dispersion, adding an alcohol organic substrate into the organic solvent, taking tert-butyl nitrite as a cocatalyst, introducing oxygen into a reaction system, and reacting at 80 ℃.
8. The application of the nitroxide radical functionalized porous organic polymer nanotube of claim 7, wherein the organic solvent is one or a combination of toluene, trifluorotoluene, acetonitrile, water, methoxypentane and 2-methylfuran.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110613887.1A CN113321787B (en) | 2021-06-02 | 2021-06-02 | Nitroxide free radical functionalized porous organic polymer nanotube and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110613887.1A CN113321787B (en) | 2021-06-02 | 2021-06-02 | Nitroxide free radical functionalized porous organic polymer nanotube and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113321787A CN113321787A (en) | 2021-08-31 |
| CN113321787B true CN113321787B (en) | 2022-06-17 |
Family
ID=77421455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110613887.1A Active CN113321787B (en) | 2021-06-02 | 2021-06-02 | Nitroxide free radical functionalized porous organic polymer nanotube and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113321787B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111454436B (en) * | 2020-04-27 | 2022-12-20 | 齐齐哈尔大学 | Preparation method of chiral conjugated microporous polymer containing (S) -N-sec-butylacetamide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102281948A (en) * | 2008-11-14 | 2011-12-14 | 堪萨斯大学 | Polymer-supported transition metal catalyst complexes and methods of use |
| WO2015015386A1 (en) * | 2013-08-01 | 2015-02-05 | Basf Se | Two-dimensional graphene-based porous polymer and the preparation thereof |
| CN112159515A (en) * | 2020-09-10 | 2021-01-01 | 贵州师范大学 | Based on SiO2Method for preparing TEMPO free radical functionalized hollow conjugated microporous polymer by using template and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012027242A1 (en) * | 2010-08-23 | 2012-03-01 | The Research Foundation Of State University Of New York | High flux microfiltration membranes with virus and metal ion adsorption capability for liquid purification |
-
2021
- 2021-06-02 CN CN202110613887.1A patent/CN113321787B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102281948A (en) * | 2008-11-14 | 2011-12-14 | 堪萨斯大学 | Polymer-supported transition metal catalyst complexes and methods of use |
| WO2015015386A1 (en) * | 2013-08-01 | 2015-02-05 | Basf Se | Two-dimensional graphene-based porous polymer and the preparation thereof |
| CN112159515A (en) * | 2020-09-10 | 2021-01-01 | 贵州师范大学 | Based on SiO2Method for preparing TEMPO free radical functionalized hollow conjugated microporous polymer by using template and application |
Non-Patent Citations (5)
| Title |
|---|
| Synthesis of a Macroporous Conjugated Polymer Framework: Iron Doping for Highly Stable, Highly Efficient Lithium–Sulfur Batteries;Pan Jia等;《ACS APPLIED MATERIALS & INTERFACES》;20181226;第11卷;第907--910页 * |
| Synthesis of TEMPO radical decorated hollow porous aromatic frameworks for selective oxidation of alcohols;Yan-Ming Shen等;《CHEMICAL COMMUNICATIONS》;20201216;第57卷(第7期);第3087-3097页 * |
| TEMPO功能化共轭微孔聚合物作为高效醇催化氧化剂;毛会玲等;《精细化工》;20200531;第35卷(第05期);第976-981页 * |
| 有机单体空间构型对共轭微孔聚合物催化性能的影响;王晨等;《过程工程学报》;20200531;第20卷(第05期);第576-582页 * |
| 自由基修饰共轭微孔聚合物应用于 5－羟甲基糠醛选择性氧化;毛会玲等;《分子催化》;20190630;第33卷(第3期);第245-252页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113321787A (en) | 2021-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Metal-free nitrogen-doped carbon nanosheets: a catalyst for the direct synthesis of imines under mild conditions | |
| Wang et al. | An efficient, soluble, and recyclable multiwalled carbon nanotubes-supported TEMPO for oxidation of alcohols | |
| CN112159515A (en) | Based on SiO2Method for preparing TEMPO free radical functionalized hollow conjugated microporous polymer by using template and application | |
| CN113578382B (en) | Thienyl-containing polymer photocatalyst with high photocatalytic water splitting hydrogen production activity and preparation method thereof | |
| CN113321787B (en) | Nitroxide free radical functionalized porous organic polymer nanotube and preparation method and application thereof | |
| CN111871466A (en) | Node-supported metal cluster catalyst in metal organic framework structure and preparation method and application thereof | |
| CN114522688A (en) | Porous carbon loaded bimetallic catalyst and preparation and application thereof | |
| CN112774663B (en) | Multistage pore catalyst for directly preparing ethylene from methane and preparation method and application thereof | |
| Li et al. | An Fe 3 O 4@ P4VP@ FeCl 3 core–shell heterogeneous catalyst for aerobic oxidation of alcohols and benzylic oxidation reaction | |
| CN114029047A (en) | Preparation method of array carbon nanotube supported catalyst | |
| CN101613534A (en) | Water-soluble nano-carrier and preparation method thereof | |
| CN111151301B (en) | Bifunctional heterogeneous Pd @ MIL-101@ SGO composite material and preparation method and application thereof | |
| CN106378189B (en) | Catalyst and its preparation method and application for synthesizing polymethoxy dimethyl ether | |
| CN109851596B (en) | Substituted graphene material with three-dimensional structure and preparation method thereof | |
| CN113398963B (en) | Preparation method of molybdenum carbide supported carbon-coated iron catalyst and application of molybdenum carbide supported carbon-coated iron catalyst in benzene ring selective hydroxylation reaction | |
| CN109110753A (en) | A kind of preparation method based on molysite catalyzed graphitization nitrogen-doped carbon nano material | |
| CN110252368A (en) | A kind of preparation method and application of porous carbon supported double noble metal catalysts | |
| Bian et al. | A novel poly (p-styrenesulfonic acid) grafted carbon nanotube/graphene oxide architecture with enhanced catalytic performance for the synthesis of benzoate esters and fatty acid alkyl esters | |
| CN113717351A (en) | Normal-temperature rapid preparation method of microporous organic polymer with high specific surface area | |
| Ding et al. | Novel sea urchin-like polyaniline microspheres-supported molybdenum catalyst: Preparation, characteristic and functionality | |
| CN108557798B (en) | Method for controllably preparing transition metal loaded nitrogen-containing porous carbon composite material by utilizing star polymer | |
| CN114736356B (en) | Dibenzo-thick dinaphthyl polymer photocatalyst for preparing hydrogen by photocatalytic decomposition of water and preparation method thereof | |
| CN114345388B (en) | Modification method of graphite-like phase carbon nitride | |
| CN114229828B (en) | Preparation method of gamma-graphite monoalkyne | |
| CN111377432B (en) | Method for preparing layered nano carbon material by coal solvent heat treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |