CN115260390A - Preparation of novel polymerized N-heterocyclic carbene catalyst and application of catalyst in furoic acid synthesis process - Google Patents
Preparation of novel polymerized N-heterocyclic carbene catalyst and application of catalyst in furoic acid synthesis process Download PDFInfo
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- 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
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Abstract
The invention relates to the technical field of furoic acid synthesis, and discloses a synthetic method of a polymerized N-heterocyclic carbene catalyst, a synthesized catalyst and application thereof in preparing furoic acid, wherein N, N '-bis (acryloyl) cystamine is used as a polymerized carbene monomer, N' -bis (acryloyl) cystamine is used as an adhesive, azobisisobutyronitrile is used as an initiator, and N, N-dimethylformamide is used as a reaction solvent, and the polymerization reaction is carried out by heating under the conditions of degassing and sealing; wherein the N-heterocyclic carbene is 1-vinyl-3-butyl imidazole bromide or 1-methyl-3-allyl imidazole bromide. The invention has the beneficial effects that: the synthesized polymer N-heterocyclic carbene catalyst is an organic polymer, so that the problem of environmental pollution caused by preparing furoic acid by catalyzing and oxidizing furfural with a heavy metal catalyst is solved, the raw materials are cheap and easy to obtain, the catalytic efficiency is high, and the yield of the furoic acid can reach more than 98%; the method has good cyclic catalysis effect, the yield of the furoic acid after five times of cycle is still more than 90%, and the method is suitable for realizing industrial production and has great development potential in the preparation of the furoic acid.
Description
Technical Field
The invention relates to the technical field of furoic acid synthesis, in particular to a synthesis method of a polymerized N-heterocyclic carbene catalyst, the synthesized catalyst and application of the synthesized catalyst in preparation of furoic acid.
Background
The furoic acid is one of the deep processing products of the furfural, and can be used for synthesizing methyl furan, furfuryl amide, furoate spices and the like; useful in the plastics industry as plasticizers, thermosetting resins, and the like; as a preservative in the food industry; also useful as an intermediate for paint additives, medicines, perfumes, etc.
Furoic acid is usually prepared from furfural by oxidation, and two synthesis methods are commonly used: one is catalytic oxidation of furfural by adding NaClO to furfural in neutral or alkaline medium3Or KMnO4Oxidizing furfural as a catalyst, and acidifying to obtain furoic acid. The other method is a furfural air-liquid phase oxidation method, which uses O in air2As oxidant, cuO or Ag2And O is used as a catalyst to oxidize the furfural to prepare furoic acid.
For example, chinese patent publication No. CN109485624A discloses a method for preparing furoic acid by oxidizing furfural, which uses a complex nano metal oxide catalyst to catalyze furfural. But still has the problems that the catalytic efficiency of the catalyst to furfural is low, and the post-treatment of the metal catalyst is difficult and easy to cause environmental pollution.
Disclosure of Invention
The technical problem to be solved by the invention is how to provide a synthesis method of a polymerization N-heterocyclic carbene catalyst, so as to solve the problems that the catalyst in the prior art has low catalytic efficiency on furfural, and the post-treatment of a metal catalyst is difficult and easy to cause environmental pollution.
The invention solves the technical problems through the following technical means:
the invention provides a synthetic method of a polymerized N-heterocyclic carbene catalyst, which comprises the steps of taking N-heterocyclic carbene as a polymerized carbene monomer, taking N, N' -bis (acryloyl) cystamine as an adhesive, taking azobisisobutyronitrile as an initiator and taking N, N-dimethylformamide as a reaction solvent, and heating the mixture under the conditions of degassing and sealing to carry out polymerization reaction;
wherein the N-heterocyclic carbene is 1-vinyl-3-butyl imidazole bromide or 1-methyl-3-allyl imidazole bromide.
Has the beneficial effects that: when the azacyclo-carbene catalyst is synthesized, the adopted polymeric carbene monomer, the adhesive, the initiator and the solvent are all organic matters, and the synthesized catalyst is also an organic polymer, so that the problem of environmental pollution caused by the use of a heavy metal catalyst in the preparation of furoic acid by catalytic oxidation of furfural in the prior art is solved; the raw material furfural is cheap and easy to obtain, the preparation cost of furoic acid is effectively reduced, the catalytic oxidation efficiency of furfural is high, and the furfural is a low-cost, environment-friendly and efficient organic catalyst.
Preferably, the molar ratio of the azacyclo-carbene to the N, N' -bis (acryloyl) cystamine to the azobisisobutyronitrile is 1.1.
Preferably, the synthesis method of the polymerized N-heterocyclic carbene catalyst comprises the following steps:
(1) Mixing a polymerized carbene monomer, N' -bis (acryloyl) cystamine, azodiisobutyronitrile and N, N-dimethylformamide, degassing, sealing, and stirring at 60 ℃ for reaction for 12 hours;
(2) And after the reaction is finished, adding saturated salt water into the reaction system, standing to separate out suspended matters, filtering, washing, and drying in a vacuum drying oven to obtain the polymeric N-heterocyclic carbene catalyst.
Has the advantages that: according to the method, a polymeric carbene monomer, an adhesive, an initiator and a solvent are mixed in the same container, a saturated salt solution is added after heating and stirring reaction in a closed environment, and suspended matters precipitated by standing are filtered, washed and dried, so that the polymeric azacyclo-carbene catalyst can be synthesized.
Preferably, the degassing treatment in the step (1) is performed by bubbling an inert gas into the mixed solution for 30 minutes.
Preferably, the heating and the reaction in the step (1) are carried out in an oil bath.
The second aspect of the invention provides a polymer N-heterocyclic carbene catalyst synthesized by the synthesis method.
The third aspect of the invention provides an application of the polymer N-heterocyclic carbene catalyst synthesized by the synthesis method in preparing furoic acid, which comprises the following steps:
(1) Mixing furfural, anhydrous potassium carbonate and deionized water, placing the mixture into a storage tank, placing a polymerized N-heterocyclic carbene catalyst into a heated reactor, and carrying out air oxidation reaction for 24 hours at 80 ℃;
(2) And after the reaction is finished, taking out the reaction solution, adjusting the pH value to be 1-2, filtering and drying to obtain the furoic acid.
Has the advantages that: heating furfural and anhydrous potassium carbonate serving as raw materials in an air atmosphere, and carrying out catalytic oxidation on the furfural by adopting a polymerization N-heterocyclic carbene catalyst to obtain furoic acid; the preparation method has the advantages of simple process, low requirements on preparation conditions, high yield of the furoic acid which can reach more than 98 percent, low cost, high efficiency and small environmental pollution, and is beneficial to realizing industrial production, and the used N-heterocyclic carbene catalyst is an environment-friendly catalyst.
Preferably, in the step (1), the molar ratio of the furfural to the anhydrous potassium carbonate to the polymerized N-heterocyclic carbene catalyst is 1.
Preferably, the preparation of the furoic acid is carried out in a circulating system, the circulating system comprises a storage tank, a reactor, a circulating pump and a vacuum pump which are communicated with each other, the furfural and the anhydrous potassium carbonate are stored in the storage tank, the catalyst is placed in the reactor, air is pumped into the circulating system through the vacuum pump, and the circulating pump is started to circulate so that the materials flow in the circulating system and carry out circulating reaction.
Has the advantages that: the preparation of this application furoic acid goes on in circulation system, arranges the catalyst in the reactor, and the raw materials is deposited in the storage tank, starts the circulating pump circulation and can make the material flow in circulation system to contact repeatedly with the catalyst in the reactor and react, go into the air through the vacuum pump to circulation system in the while, with this catalytic oxidation preparation furoic acid to furfural that realizes, easy operation, and furoic acid's yield is high, has further improved the production efficiency of industrial preparation furoic acid.
Preferably, a condensation pipe positioned at the discharge end of the reactor is also arranged in the circulating system.
Has the advantages that: this application is cooled down through the material of condenser pipe to reactor output, has solved because of the higher problem that leads to the air to be difficult to pump into circulation system of reactor temperature, is favorable to controlling catalytic oxidation reaction's oxygen supply volume.
Preferably, after the reaction solution is taken out in the step (2), the polymerized N-heterocyclic carbene catalyst is still left in the reactor, and furfural, anhydrous potassium carbonate and deionized water are continuously added into the storage tank, so that the operations in the steps (1) and (2) are repeated, and the catalyst can be recycled for multiple times.
Has the advantages that: after the reaction solution is taken out, furfural, anhydrous potassium carbonate and deionized water are continuously added into a reaction system containing a polymerization N-heterocyclic carbene catalyst, so that the cyclic reaction can be performed again, and the catalyst can be recycled for multiple times; the catalyst is convenient to recover and separate, has a good circulating catalysis effect, the yield of the furoic acid after five times of circulation is still more than 90%, and has great development potential in a furoic acid synthesis process.
The invention has the advantages that:
1. when the azacyclo-carbene catalyst is synthesized, the adopted polymerized carbene monomer, the adhesive, the initiator and the solvent are all organic matters, and the synthesized catalyst is also an organic polymer, so that the problem of environmental pollution caused by the use of a heavy metal catalyst in the preparation of furoic acid by catalytic oxidation of furfural in the prior art is solved; the raw material furfural is cheap and easy to obtain, the preparation cost of furoic acid is effectively reduced, the catalytic oxidation efficiency of furfural is high, and the furfural is an organic catalyst which has low cost, simple process, convenient operation, environmental friendliness and high efficiency;
2. heating furfural and anhydrous potassium carbonate serving as raw materials in an air atmosphere for reaction, and carrying out catalytic oxidation on the furfural by adopting a polymerized N-heterocyclic carbene catalyst to obtain furoic acid; the preparation method has simple process and low requirement on preparation conditions, the used N-heterocyclic carbene catalyst is an environment-friendly catalyst, the yield of the furoic acid is high and can reach more than 98 percent, and the method has the advantages of low cost, high efficiency and small environmental pollution and is beneficial to realizing industrial production;
3. the preparation of the furoic acid is carried out in a circulating system, a catalyst is placed in a reactor, raw materials are stored in a storage tank, a circulating pump is started to circulate, so that the materials can flow in the circulating system, and repeatedly contact with the catalyst in the reactor to react, and air is pumped into the circulating system through a vacuum pump, so that the catalytic oxidation of furfural is realized to prepare the furoic acid, the operation is simple, the yield of the furoic acid is high, and the production efficiency of industrial preparation of the furoic acid is further improved;
4. after the reaction solution is taken out, furfural, anhydrous potassium carbonate and deionized water are continuously added into a reaction system containing a polymerization N-heterocyclic carbene catalyst, so that the cyclic reaction can be carried out again, and the catalyst can be recycled for multiple times; the catalyst is convenient to recover and separate, has a good circulating catalysis effect, the yield of the furoic acid after five times of circulation is still more than 90%, and has great development potential in a furoic acid synthesis process.
Drawings
FIG. 1 is an infrared spectrum of a polymerized 1-vinyl-3-butylimidazolium bromide catalyst in example 1 of this application;
FIG. 2 is a reaction diagram of a recycle system for producing furoic acid in example 1 of the present application;
FIG. 3 is a nuclear magnetic hydrogen spectrum of furoic acid in example 1 of the present application;
FIG. 4 is a nuclear magnetic carbon spectrum of furoic acid in example 1 of the present application;
FIG. 5 is an infrared spectrum of a catalyst for polymerizing 1-methyl-3-allylimidazolium bromide in example 3 of this application.
Description of reference numerals: 1. a material storage tank; 2. a reactor; 3. a circulation pump; 4. a vacuum pump; 5. a condenser tube.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
In one aspect, this embodiment provides a method for synthesizing a polymerized N-heterocyclic carbene catalyst, including the following steps:
(1) Weighing 1.16g of 1-vinyl-3-butylimidazolium bromide (1.0equiv, 5 mmol) as a carbene monomer, 1.43g of N, N' -bis (acryloyl) cystamine (1.1equiv, 5.5 mmol) as an adhesive, 164mg of azobisisobutyronitrile (0.2equiv, 1mmol) as an initiator, weighing 30mL of N, N-dimethylformamide as a reaction solvent, and putting the compound into a round-bottomed flask with a stirrer; then, introducing nitrogen into the flask, and bubbling the mixed solution for 30 minutes to degas; after the degassing was completed, a rubber stopper was attached to the flask, and the opening of the flask was closed with a sealing film, and then the flask was put in an oil bath at 60 ℃ and stirred for reaction for 12 hours.
(2) After the reaction is finished, adding 30mL of saturated saline solution into the reaction system, standing the reaction system to separate out suspended substances in the reaction bottle, and filtering the reaction solution and washing the filter cake with water when the separated suspended substances are not increased any more, wherein the amount of washing water is 20mL each time, and the washing is carried out for 3 times in total; collecting the filter cake, and placing the filter cake in a vacuum drying oven for drying to obtain the polymerized 1-vinyl-3-butylimidazolium bromide catalyst.
Infrared spectroscopy analysis was performed on the polymer synthesized above, and the obtained infrared spectrum is shown in FIG. 1. As can be seen in the figure, 3280cm-1Absorption of stretching vibration at N-H bond 3100cm-1Absorption of stretching vibration at bond = C-H, 2920cm-1Absorption of stretching vibration at C-H bond, 1620cm-1Absorption of stretching vibration at C = O key, 1530cm-1Bending vibration absorption at the position of N-H bond, 1400cm-1The expansion vibration absorption of the C-N bond indicates that the synthesized product is a polymerized 1-vinyl-3-butylimidazolium bromide catalyst.
In another aspect, this embodiment provides an application of the azacyclo-carbene polymer catalyst synthesized by the above synthesis method in the preparation of furoic acid, where the preparation process is performed in a circulation system.
As shown in fig. 2, the circulation system includes a storage tank 1, a reactor 2, a circulation pump 3, and a vacuum pump 4. The reactor 2 is a tubular reactor 2 with a heating function, the storage tank 1 is used for storing reaction raw materials, and a discharge port of the storage tank 1 is communicated with a feed port of the reactor 2 and a discharge port of the reactor 2 is communicated with a feed port of the storage tank 1 through pipelines. Circulating pump 3 installs on the pipeline between the discharge gate of storage tank 1 and the feed inlet of reactor 2, starts circulating pump 3 and can go into reactor 2 with the material pump and react, continues to go into storage tank 1 by reactor 2's discharge gate pump after the reaction to this realizes that the material flows and carries out the circulation reaction in the circulation system. The vacuum pump 4 is arranged on a pipeline between the discharge hole of the reactor 2 and the feed inlet of the storage tank 1 and is close to the feed inlet of the storage tank 1, so that air required by reaction is pumped into the circulating system. Still install condenser pipe 5 on the pipeline between the discharge gate of reactor 2 and the feed inlet of storage tank 1, and condenser pipe 5 is close to the discharge gate setting of reactor 2 to this cools down the material of reactor 2 output, is favorable to vacuum pump 4 to the air of circulation system pump income.
The preparation of furoic acid comprises the following steps:
(1) 1.55g of a polymerization 1-vinyl-3-butylimidazolium bromide catalyst (0.03equiv, 3mmol) was charged in a reactor 2, and 3.45g of anhydrous potassium carbonate (1.0 equiv, 100mmol), 9.6g of furfural (1.0 equiv, 100mmol) and 100mL of deionized water were weighed out and charged in a storage tank 1. And (3) heating the reactor 2 to 80 ℃, starting the circulating pump 3, the vacuum pump 4 and the condenser pipe 5, and reacting the anhydrous potassium carbonate, the furfural and the deionized water in the air atmosphere of the circulating system for 24 hours.
(2) After the reaction, the reaction solution was taken out from the storage tank 1, a hydrochloric acid solution was added to the reaction solution, the pH =1-2 of the reaction solution was adjusted, and after filtration and drying, a filter cake was taken out and subjected to nuclear magnetic analysis, and the results are shown in fig. 3 and 4.1H NMR(600MHz,CDCl3)δ10.87(s,1H),7.65(d,J＝0.7Hz,1H),7.34(d,J＝3.5Hz,1H),6.56(dd,J＝3.5,1.7Hz,1H)ppm；13C NMR(151MHz,CDCl3) Delta 163.6,147.4,143.8,120.1,112.2ppm, and the product prepared above was furoic acid as determined by nuclear magnetic hydrogen and carbon spectrum analysis.
The collected filter cake was placed in a vacuum oven for drying and weighed after 12 hours to obtain 11.1g of furoic acid with a yield of 99%. The polymerization 1-vinyl-3-butylimidazolium bromide catalyst prepared by the method can efficiently catalyze furfural to oxidize so as to prepare furoic acid.
(3) According to the operation of the step (1), 3.45g of anhydrous potassium carbonate (1.0 equiv, 100mmol), 9.6g of furfural (1.0 equiv, 100mmol) and 100mL of deionized water are weighed and added into the storage tank 1, and the circulating pump 3, the vacuum pump 4 and the condenser pipe 5 are started to perform a second circulation reaction; and (3) taking out the reaction solution, adjusting the pH =1-2, and filtering to obtain a second recycled product, namely, the furoic acid, according to the operation of the step (2). The operation cycle is repeated for five times, the yield of the furoic acid still reaches over 90 percent, and the result shows that the polymerization 1-vinyl-3-butyl imidazole bromide catalyst has good cyclic catalysis effect in the preparation of the furoic acid by catalyzing the oxidation of furfural.
Example 2
In one aspect, this embodiment provides a method for polymerizing azacyclo-carbene catalysts, which is the same as in embodiment 1, and synthesizes and polymerizes 1-vinyl-3-butylimidazolium bromide catalyst for further use.
In another aspect, this embodiment provides a use of the azacyclo-carbene catalyst synthesized by the above synthesis method in the preparation of furoic acid, wherein the preparation process is performed in the same cycle system as in embodiment 1.
The preparation of furoic acid comprises the following steps:
(1) 2.58g of a polymerization 1-vinyl-3-butylimidazolium bromide catalyst (0.05equiv, 5mmol) was charged into the reactor 2, and 3.45g of anhydrous potassium carbonate (1.0equiv, 100mmol), 9.6g of furfural (1.0equiv, 100mmol) and 100mL of deionized water were weighed and charged into the storage tank 1. And (3) heating the tubular reactor 2 to 80 ℃, starting the circulating pump 3, the vacuum pump 4 and the condenser pipe 5, and carrying out oxidation reaction on anhydrous potassium carbonate, furfural and deionized water for 24 hours in the air atmosphere of the circulating system.
(2) And after the reaction is finished, taking out the reaction solution from the material storage tank 1, adding a hydrochloric acid solution into the reaction solution, adjusting the pH =1-2 of the reaction solution, and filtering to obtain a filter cake, namely obtaining the furoic acid. The collected filter cake is placed in a vacuum drying oven for drying, and the weight is weighed after the filter cake is dried for 12 hours, so that 11.1g of furoic acid is obtained, and the yield is 99%, which indicates that the polymerized 1-vinyl-3-butylimidazolium bromide catalyst prepared by the method can efficiently catalyze furfural to prepare furoic acid through oxidation.
(3) According to the operation of the step (1), 3.45g of anhydrous potassium carbonate (1.0 equiv, 100mmol), 9.6g of furfural (1.0 equiv, 100mmol) and 100mL of deionized water are weighed and added into the storage tank 1, and the circulating pump 3, the vacuum pump 4 and the condenser pipe 5 are started to perform a second circulation reaction; and (3) taking out the reaction solution, adjusting the pH =1-2, and filtering to obtain a second recycled product, namely, the furoic acid, according to the operation of the step (2). The operation cycle is repeated for five times, the yield of the furoic acid still reaches over 90 percent, and the result shows that the polymerization 1-vinyl-3-butyl imidazole bromide catalyst has good cyclic catalysis effect in the preparation of the furoic acid by catalyzing the oxidation of furfural.
Example 3
In one aspect, the present invention provides a method for synthesizing a polymerized N-heterocyclic carbene catalyst, including the following steps:
(1) Weighing 1.02g of 1-methyl-3-allyl imidazole bromide (1.0 equiv,5 mmol) as a carbene monomer, 1.43g of N, N' -bis (acryloyl) cystamine (1.1 equiv,5.5 mmol) as an adhesive and 164mg of azobisisobutyronitrile (0.2 equiv,1 mmol) as an initiator, measuring 30mL of N, N-dimethylformamide as a reaction solvent, and putting the compounds into a round-bottom flask with a stirrer; then, nitrogen gas was introduced into the flask, and the mixed solution was bubbled for 30 minutes to conduct degassing; after the degassing was completed, a rubber stopper was attached to the flask, and the opening of the flask was closed with a sealing film, and then the flask was put in an oil bath at 60 ℃ and stirred for reaction for 12 hours.
(2) After the reaction is finished, adding 30mL of saturated saline solution into the reaction system, standing the reaction system to separate out suspended substances in the reaction bottle, and filtering the reaction solution and washing the filter cake with water when the separated suspended substances are not increased any more, wherein the amount of washing water is 20mL each time, and the washing is carried out for 3 times in total; collecting the filter cake, and placing the filter cake in a vacuum drying oven for drying to obtain the polymerized 1-methyl-3-allyl imidazole bromide catalyst.
The infrared spectrum analysis of the synthesized product is carried out, and the obtained infrared spectrum is shown in figure 5. As can be seen in the figure, 3280cm-1Stretching vibration absorption at position of N-H bond, 3100cm-1Absorption of stretching vibration at bond = C-H, 2920cm-1Absorption of stretching vibration at C-H bond, 1620cm-1Absorption of stretching vibration at C = O key, 1530cm-1Bending vibration absorption at the position of N-H bond, 1400cm-1The stretching vibration absorption of the C-N bond shows that the synthesized product is a polymerized 1-methyl-3-allyl imidazole bromide catalyst.
In another aspect, this embodiment provides a use of the azacyclo-carbene catalyst synthesized by the above synthesis method in the preparation of furoic acid, wherein the preparation process is performed in the same cycle system as in embodiment 1.
The preparation of furoic acid comprises the following steps:
(1) 1.42g of a polymerization 1-methyl-3-allylimidazole bromide catalyst (0.03equiv, 3mmol) was charged in the tubular reactor 2, and 3.45g of anhydrous potassium carbonate (1.0 equiv, 100mmol), 9.6g of furfural (1.0 equiv, 100mmol) and 100mL of deionized water were weighed out and charged in the tubular reactor 2. And (3) heating the tubular reactor 2 to 80 ℃, starting the circulating pump 3, the vacuum pump 4 and the condenser pipe 5, and carrying out oxidation reaction on anhydrous potassium carbonate, furfural and deionized water for 24 hours in the air atmosphere of the circulating system.
(2) After the reaction is finished, taking out the reaction solution from the storage tank 1, adding a hydrochloric acid solution into the reaction solution, adjusting the pH of the reaction solution to be =1-2, filtering and drying, taking a filter cake, and performing nuclear magnetic analysis, wherein the result is consistent with that in figures 3 and 4, and the prepared product is furoic acid.
The collected filter cake was placed in a vacuum oven for drying and weighed after 12 hours to obtain 11.0g of furoic acid with a yield of 98%. The prepared polymerized 1-methyl-3-allyl imidazole bromide catalyst can efficiently catalyze furfural to oxidize and prepare furoic acid.
(3) According to the operation of the step (1), weighing 3.45g of anhydrous potassium carbonate (1.0 equiv, 100mmol) and 9.6g of furfural (1.0 equiv, 100mmol) again, weighing 100mL of deionized water, adding the deionized water into the storage tank 1, and starting the circulating pump 3, the vacuum pump 4 and the condenser pipe 5 to perform a second circulating reaction; and (3) taking out the reaction solution, adjusting the pH =1-2, and filtering to obtain a second recycled product, namely, the furoic acid, according to the operation of the step (2). The operation is repeated for five times, the yield of the furoic acid still reaches over 90 percent, and the result shows that the catalyst for polymerizing the 1-methyl-3-allyl imidazole bromide has good cyclic catalysis effect in preparing the furoic acid by catalyzing the oxidation of furfural.
The implementation principle of the application is as follows: when the azacyclo-carbene catalyst is synthesized, the adopted polymeric carbene monomer, the adhesive, the initiator and the solvent are all organic matters, and the synthesized catalyst is also an organic polymer, so that the problem of environmental pollution caused by the use of a heavy metal catalyst in the preparation of furoic acid by catalytic oxidation of furfural in the prior art is solved; the raw material furfural is cheap and easy to obtain, the preparation cost of the furoic acid is effectively reduced, the catalytic oxidation efficiency of the furfural is high, and the yield of the furoic acid can reach more than 98 percent; the method has good cyclic catalysis effect, the yield of the furoic acid after five times of cycle is still more than 90%, and the furoic acid is a low-cost, environment-friendly and efficient organic catalyst, is suitable for realizing industrial production, and has great development potential in the preparation of the furoic acid.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A synthetic method of a polymerized N-heterocyclic carbene catalyst is characterized by comprising the following steps: the method comprises the steps of taking azacyclo-carbene as a polymeric carbene monomer, taking N, N' -bis (acryloyl) cystamine as an adhesive, taking azobisisobutyronitrile as an initiator and taking N, N-dimethylformamide as a reaction solvent, and heating the mixture under the degassing and sealing conditions for polymerization reaction;
wherein the N-heterocyclic carbene is 1-vinyl-3-butyl imidazole bromide or 1-methyl-3-allyl imidazole bromide.
2. The method for synthesizing a polymeric azacyclo-carbene catalyst according to claim 1, wherein the method comprises the following steps: the molar ratio of the N-heterocyclic carbene to the N, N' -bis (acryloyl) cystamine to the azobisisobutyronitrile is 1.1.
3. The method for synthesizing a polymeric azacyclo-carbene catalyst according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) Mixing N-heterocyclic carbene monomer, N' -bis (acryloyl) cystamine, azodiisobutyronitrile and N, N-dimethylformamide, degassing, sealing, and stirring at 60 deg.C for 12 hr;
(2) And after the reaction is finished, adding saturated salt water into the reaction system, standing to separate out suspended substances, filtering, washing, and drying in a vacuum drying oven to obtain the polymeric N-heterocyclic carbene catalyst.
4. The method for synthesizing a polymeric azacyclo-carbene catalyst according to claim 3, wherein the method comprises the following steps: in the step (1), inert gas is introduced into the mixed solution for 30 minutes to carry out bubbling, so that degassing treatment is realized; the heating and the reaction in the step (1) are carried out in an oil bath kettle.
5. The polymeric azacyclo-carbene catalyst synthesized by the synthesis method according to any one of claims 1 to 4.
6. The application of the polymerized N-heterocyclic carbene catalyst synthesized by the synthesis method according to any one of claims 1 to 4 in the preparation of furoic acid is characterized in that: the method comprises the following steps:
(1) Mixing furfural, anhydrous potassium carbonate and deionized water, placing the mixture into a storage tank, placing a polymerized N-heterocyclic carbene catalyst into a heated reactor, and performing air oxidation reaction for 24 hours at the temperature of 80 ℃;
(2) And after the reaction is finished, taking out the reaction solution, adjusting the pH value to be 1-2, filtering and drying to obtain the furoic acid.
7. The application of the polymeric azacyclo-carbene catalyst synthesized by the synthesis method of claim 6 in the preparation of furoic acid is characterized in that: in the step (1), the molar ratio of the furfural to the anhydrous potassium carbonate to the polymerized N-heterocyclic carbene catalyst is 1.
8. The application of the polymeric azacyclo-carbene catalyst synthesized by the synthesis method of claim 6 in the preparation of furoic acid is characterized in that: the preparation of the furoic acid is carried out in a circulating system, the circulating system comprises a storage tank, a reactor, a circulating pump and a vacuum pump which are communicated with each other, the furfural and the anhydrous potassium carbonate are stored in the storage tank, the catalyst is placed in the reactor, air is pumped into the circulating system through the vacuum pump, and the circulating pump is started to circulate so that the materials flow in the circulating system and carry out circulating reaction.
9. The use of a polymeric azacyclo-carbene catalyst synthesized by the synthesis method of claim 8 in the preparation of furoic acid, wherein: and a condensing pipe positioned at the discharge end of the reactor is also arranged in the circulating system.
10. The use of a polymeric azacyclo-carbene catalyst synthesized by the synthesis method of claim 8 in the preparation of furoic acid, wherein: and (3) after the reaction solution is taken out in the step (2), keeping the polymerized N-heterocyclic carbene catalyst in the reactor, and continuously adding furfural, anhydrous potassium carbonate and deionized water into the reaction system, so that the operations in the steps (1) and (2) are repeated, and the catalyst can be recycled for multiple times.
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