Synthesis of polycyanic organic porous polymers and their catalytic applications for organic transformations

Abstract

The application discloses synthesis of a polycyanine organic porous polymer and catalytic organic conversion application thereof, and belongs to the technical field of high-molecular organic porous catalytic materials. In the application, 2,6-diamino-11,11,12,12-tetracyano anthraquinone dimethyl is used as a structural unit, 2,4,6-trihydroxybenzene-1,3,5-trimethyl formaldehyde is used as a crosslinking agent, and a porous organic polymer is obtained under the catalysis of a Lewis acid catalyst. It is proved by the Fourier infrared spectrum of the porous organic polymer material that the material is indeed obtained by the reaction of 2,6-diamino-11,11,12,12-tetracyano anthraquinone dimethyl and the crosslinking agent. The method has the advantages of mild reaction conditions, simple operation, short reaction time, and the like, and the material is successfully prepared. The material has good catalytic activity, can realize visible light photocatalytic oxidation of sulfides into sulfoxides, improves the overall reaction rate, shortens the waiting time, and has good application prospect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high-molecular organic porous catalytic materials, and particularly relates to synthesis of a polycyanine organic porous polymer and catalytic organic conversion application thereof. BACKGROUND

[0002] Sulfur oxides (SOx) produced by combustion of sulfur compounds in fuel oil are one of the main sources of air pollution such as acid rain and particulate matter. In addition to separating SOx from combustion products by selective capture before being discharged into the atmosphere, a viable alternative solution to reduce the sulfur content in fuels of the environment and energy industry is to oxidize them into sulfoxides and sulfones, because these oxidation products are more easily removed by extraction than the corresponding sulfides. In addition, the oxidation of sulfides is also a very important reaction in synthetic chemistry, because the product sulfoxide of sulfides is not only widely used in drug synthesis, but also used as an essential biologically active ingredient in the pharmaceutical industry.

[0003] In the past decade, the use of solar energy to promote selective reactions has attracted increasing attention. In fact, heterogeneous photocatalytic reactions driven by visible light are considered as a renewable and environmentally friendly method that can be used for the conversion of sulfur compounds and the production of high-value chemicals. Molecular photocatalysts, such as inorganic materials, metal complexes, and organic dyes, have been widely studied in photocatalysis.

[0004] However, these catalysts are hindered in improving their catalytic ability and practical application due to disadvantages such as toxicity, poor stability, and difficulty in separation. SUMMARY

[0005] The purpose of the present application is to solve the above-mentioned problems, and to provide a synthesis of a polycyanine organic porous polymer and catalytic organic conversion application thereof.

[0006] The technical scheme adopted by the present application is as follows: a synthesis method of a polycyanine organic porous polymer, the synthesis method comprising the following steps:

[0007] S1: dissolving or dispersing 2,6-diamine-11,11,12,12-tetracyanoanthraquinone dimethyl, 2,4,6-trihydroxybenzene-1,3,5-triformyl and anhydrous ferric chloride in an organic solvent to obtain a solution or dispersion;

[0008] S2: adding an aqueous acetic acid solution as a catalyst, mixing uniformly, and stirring the obtained mixture at 40-90 DEG C for 12-72 hours;

[0009] S3: after the reaction is completed, the system is cooled to room temperature, the generated solid is filtered, washed, and vacuum dried to obtain a brown-red porous organic polymer material;

[0010] The reaction formula is:

[0011]

[0012] In a preferred embodiment, the Lewis acid catalyst is FeCl3.

[0013] In a preferred embodiment, the 2,6-diamino-11,11,12,12-tetracyanoanthraquinone dimethane has the following structure:

[0014]

[0015] In a preferred embodiment, the synthesis method of the 2,6-diamino-11,11,12,12-tetracyanoanthraquinone dimethane comprises the following steps:

[0016] S1: first, the synthesis of 2,6-diamino trifluoro diacetate anthraquinone, 2,6-diamino anthraquinone and sodium trifluoroacetate are dispersed in tetrahydrofuran solvent, and trifluoroacetic anhydride protective agent is added to obtain 2,6-diamino trifluoro diacetate anthraquinone;

[0017] S2: the synthesis of 2,6-diamino-11,11,12,12-tetracyanoanthraquinone dimethane trifluoro diacetate, 2,6-diamino trifluoro diacetate anthraquinone is subjected to a Claisen condensation reaction catalyzed by a Leimert reagent to obtain 2,6-diamino-11,11,12,12-tetracyanoanthraquinone dimethane trifluoro diacetate;

[0018] S3: the synthesis of 2,6-diamino-11,11,12,12-tetracyanoanthraquinone dimethane, 2,6-diamino-11,11,12,12-tetracyanoanthraquinone dimethane trifluoro diacetate is dispersed in a mixed solvent of ethyl acetate / hydrochloric acid to obtain 2,6-diamino-11,11,12,12-tetracyanoanthraquinone dimethane.

[0019] In a preferred embodiment, the synthesis reaction formula of the 2,6-diamino-11,11,12,12-tetracyanoanthraquinone dimethane is as follows:

[0020]

[0021] In a preferred embodiment, the Leimert reagent is a mixture of malononitrile, titanium tetrachloride and pyridine.

[0022] In a preferred embodiment, the porous organic polymer material has the following structure:

[0023]

[0024] In a preferred embodiment, the organic solvent in step S1 is preferably acetonitrile and dichloromethane.

[0025] In a preferred embodiment, the stirring time in step S1 is preferably 24 hours, and the reaction temperature is preferably 60℃.

[0026] In a preferred embodiment, the application of the polycyanine organic porous polymer of claim 1 in catalytic organic conversion applications includes the application in visible light photocatalytic oxidation of sulfides into sulfoxides, wherein the catalyst is uniformly dispersed in a liquid mixed solvent containing a thioether substrate, and the thioether and oxygen are catalytically reacted under the action of the catalyst under visible light irradiation to generate sulfoxides.

[0027] In summary, due to the adoption of the above technical solutions, the present application has the following advantages:

[0028] 1、In the present application, a method with relatively mild reaction conditions, simple operation and short reaction time is successfully used to prepare the material, and the obtained material has good catalytic activity, can realize visible light photocatalytic oxidation of sulfides into sulfoxides, improve the overall reaction rate, shorten the waiting time, and has good application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 is the infrared spectrum of materials I and V;

[0030] Figure 2 is the gas adsorption graph of polymer V;

[0031] Figure 3 is the effect graph of visible light photocatalytic oxidation of sulfides;

[0032] Figure 4 is the selectivity and conversion rate diagram of visible light catalytic organic conversion of the example after 4 cycles of experiments. DETAILED DESCRIPTION

[0033] In order to make the purpose, technical scheme and advantages of the present application clearer, the present application will be further described in detail below in combination with the drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application, and are not used to limit the present application.

[0034] REFERENCE Figures 1-4 ,

[0035] Example 1:

[0036] A synthesis method of a polycyanine organic porous polymer, the synthesis method comprising the following steps:

[0037] S1: 2,6-diamine-11,11,12,12-tetracyano anthraquinone dimethane, 2,4,6-trihydroxybenzene-1,3,5-triformyl and anhydrous ferric chloride are dissolved or dispersed in an organic solvent to obtain a solution or dispersion;

[0038] S2: an aqueous acetic acid solution is added as a catalyst, mixed, and the obtained mixture is stirred at 40-90°C for 12-72 hours;

[0039] S3: after the reaction is completed, the system is cooled to room temperature, and the generated solid is filtered, washed, and vacuum dried to obtain a brown-red porous organic polymer material;

[0040] The reaction formula is as follows:

[0041]

[0042] The Lewis acid catalyst is FeCl3.

[0043] 2,6-diamine-11,11,12,12-tetracyano anthraquinone dimethane has the following structure:

[0044]

[0045] The synthesis method of 2,6-diamine-11,11,12,12-tetracyano anthraquinone dimethane comprises the following steps:

[0046] S1: first, the synthesis of 2,6-diamine trifluoro diacetate anthraquinone is performed, 2,6-diamino anthraquinone and sodium trifluoroacetate are dispersed in a tetrahydrofuran solvent, and a trifluoroacetic anhydride protective agent is added to obtain 2,6-diamine trifluoro diacetate anthraquinone;

[0047] S2: the synthesis of 2,6-diamine-11,11,12,12-tetracyano anthraquinone dimethane trifluoro diacetate is performed, and 2,6-diamine trifluoro diacetate anthraquinone is subjected to a Claisen-Schmidt condensation reaction catalyzed by a Lieben reagent to obtain 2,6-diamine-11,11,12,12-tetracyano anthraquinone dimethane trifluoro diacetate;

[0048] S3: the synthesis of 2,6-diamine-11,11,12,12-tetracyano anthraquinone dimethane is performed, and 2,6-diamine-11,11,12,12-tetracyano anthraquinone dimethane trifluoro diacetate is dispersed in an ethyl acetate / hydrochloric acid mixed solvent to obtain 2,6-diamine-11,11,12,12-tetracyano anthraquinone dimethane.

[0049] The reaction formula is as follows:

[0050]

[0051]

[0052] The Leimann reagent is a mixture of malononitrile, titanium tetrachloride and pyridine.

[0053] The porous organic polymer material has a structure shown in the following formula:

[0054]

[0055] In step S1, the organic solvent is preferably acetonitrile and dichloromethane.

[0056] In step S1, the stirring time is preferably 24 hours, and the reaction temperature is preferably 60°C.

[0057] A catalytic organic conversion application of the polycyanine organic porous polymer as claimed in claim 1, the application method comprising: in the application of photocatalytic oxidation of sulfide to sulfoxide under visible light, uniformly dispersing the catalyst in a liquid mixed solvent containing a thioether substrate, and under visible light irradiation, allowing the thioether and oxygen to catalyze and react under the action of the catalyst to generate a sulfoxide.

[0058] Example 2

[0059] The preparation of the organic porous polymer material comprises the following steps:

[0060] 2,6-diamine-11,11,12,12-tetracyanoanthraquinone dimethane (60 mg, 0.18 mmol), 2,4,6-trihydroxybenzene-1,3,5-triformaldehyde (26 mg, 0.12 mmol) and anhydrous ferric chloride (15 mg, 0.09 mmol) were dispersed in 5 mL of acetonitrile and 4 mL of dichloromethane, the solids were fully dispersed in the organic solvent by ultrasonic for 5 min, an aqueous acetic acid solution (2 mL, 6 mol / L) was added as a catalyst, ultrasonic for 2 min, mixed well, and reacted at 60°C for 24 hours to obtain a red powder.

[0061] The specific surface area was detected by a specific surface area and micropore analyzer (BSD-PM / 2), and the specific surface area was 555 m2·g-1.

[0062] Example 3

[0063] The photocatalytic oxidation of sulfide comprises the following steps:

[0064] The organic porous polymer (10 mg) and anisyl thioether (12 μL, 0.1 mmol) were dispersed in a glass test tube containing 3 mL of methanol, the solids were fully dispersed in the organic solvent by ultrasonic for 5 min, a stirring rod was added, and stirred at room temperature and in the dark for 1 h, and then stirred for a period of time under light. After the reaction was completed, the supernatant was collected for analysis of the conversion rate, and the catalyst was collected by centrifugation, and the results are shown in Table 1. Figure 3 Table 1

[0065] Figure 4 The selectivity and conversion rate of visible light catalytic organic conversion of the example 3 after 4 cycles are shown in the schematic diagram, and it is found that the catalyst shows excellent light catalytic durability and repeatability after four cycles, indicating that the photocatalyst has high stability.

[0066] In the embodiments of the present application, it is confirmed by determining the Fourier infrared spectrum of the porous organic polymer material of the present application that the material is indeed obtained by reacting 2,6-diamino-11,11,12,12-tetracyanoanthraquinone dimethyl with a crosslinking agent; the specific surface area of the polycyanogen organic porous polymer material of the present application is calculated by determining the N2 adsorption-desorption curve; and the catalytic activity is proved by catalytic experiments.

[0067] Porous organic polymers (POPs) are a new type of porous material in the past decade, which have high porosity, low density, multiple components, easy functionalization and high thermal / chemical stability. Porous organic polymers have been proven to be competitive in various applications, such as adsorption / separation, energy storage, biomedical applications, optical devices and catalysis, due to the above characteristics. In addition, as a metal-free heterogeneous catalyst, porous organic polymers have the advantages of easy recovery and reusability.

[0068] From the experimental data, it can be seen that in the present application, the method is successfully prepared with relatively mild reaction conditions, relatively simple operation and less reaction time, and the obtained material has good catalytic activity, can realize visible light photocatalytic oxidation of sulfide to sulfoxide, and has good application prospect.

[0069] It should be noted that, in this document, relational terms such as first and second and the like can be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises", "comprising", or any other variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without more limitations, an element preceded by "comprises... " does not, without more constraints, foreclose the existence of additional identical elements in the process, method, article, or apparatus that comprises the element.

[0070] The foregoing description enables one of ordinary skill in the art to make or use the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein can be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for synthesizing a polycyano-based organic porous polymer, characterized in that: The synthesis method includes the following steps: S1: Dissolve or disperse 2,6-diamine-11,11,12,12-tetracyanoanthraquinone dimethyl ether, 2,4,6-trihydroxybenzene-1,3,5-tricarboxaldehyde and anhydrous ferric chloride in an organic solvent to obtain a solution or dispersion; S2: Add acetic acid aqueous solution as a catalyst, mix well, and stir the resulting mixture at 40-90℃ for 12-72 hours; S3: After the reaction is complete, the system is cooled to room temperature, and the generated solid is filtered, washed, and vacuum dried to obtain a brownish-red porous organic polymer material. The reaction formula is: 。 2. The method for synthesizing a polycyano-organic porous polymer as described in claim 1, characterized in that: The 2,6-diamino-11,11,12,12-tetracyanoanthraquinone dimethane has the structure shown in the following formula: 。 3. The method for synthesizing a polycyano-organic porous polymer as described in claim 1, characterized in that: The method for synthesizing the 2,6-diamino-11,11,12,12-tetracyanoanthraquinone dimethane includes the following steps: S1: First, the synthesis of 2,6-diamine trifluorodiacetate anthraquinone is carried out. 2,6-diamine anthraquinone and sodium trifluoroacetate are dispersed in tetrahydrofuran solvent, and trifluoroacetic anhydride is added as a protecting agent to obtain 2,6-diamine trifluorodiacetate anthraquinone. S2: To synthesize 2,6-diamine-11,11,12,12-tetracyanoanthraquinone dimethyl trifluorodiacetate, the anthraquinone 2,6-diamine trifluorodiacetate was prepared by Knauvengel condensation reaction catalyzed by Lenard reagent to give 2,6-diamine-11,11,12,12-tetracyanoanthraquinone dimethyl trifluorodiacetate; S3: To synthesize 2,6-diamine-11,11,12,12-tetracyanoanthraquinone dimethyl ester, 2,6-diamine-11,11,12,12-tetracyanoanthraquinone dimethyl ester was dispersed in an ethyl acetate / hydrochloric acid mixed solvent and reacted to obtain 2,6-diamine-11,11,12,12-tetracyanoanthraquinone dimethyl ester.

4. The method for synthesizing a polycyano-based organic porous polymer as described in claim 3, characterized in that: The reaction formula is as follows: ； ； 。 5. The method for synthesizing a polycyano-organic porous polymer as described in claim 3, characterized in that: The Lenard reagent is a mixture of malononitrile, titanium tetrachloride, and pyridine.

6. The method for synthesizing a polycyano-organic porous polymer as described in claim 1, characterized in that: The porous organic polymer material has the structure shown in the following formula: 。 7. The method for synthesizing a polycyano-organic porous polymer as described in claim 1, characterized in that: In step S1, the organic solvent is preferably acetonitrile and dichloromethane.

8. The method for synthesizing a polycyano-organic porous polymer as described in claim 1, characterized in that: In step S2, the stirring time is preferably 24 hours, and the reaction temperature is preferably 60°C.

9. The application of the polycyano-organic porous polymer as described in claim 1 in catalytic organic conversion, characterized in that: The application of the polycyano-organic porous polymer in the visible light photocatalytic oxidation of sulfides to sulfoxides includes the following method: uniformly dispersing the polycyano-organic porous polymer as a catalyst in a liquid mixed solvent containing a sulfide substrate, and catalyzing the sulfide and oxygen to generate sulfoxides under visible light irradiation.

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