CN110615895A - Covalent triazine polymer and preparation method and application thereof - Google Patents
Covalent triazine polymer and preparation method and application thereof Download PDFInfo
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Abstract
The disclosure provides a covalent triazine polymer, a preparation method and an application thereof, wherein the covalent triazine polymer has a repeating structural unit shown in a formula I:wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12Are all selected from carbon, nitrogen, R1And R2In a different sense, R3And R4In a different sense, R5And R6In a different sense, R8And R9In a different sense, R11And R12Different. Chemistry employing covalent triazine polymers provided by the present disclosure as carbon dioxideThe converted catalyst has the advantages of high catalytic activity, easy separation, no need of metal load, no need of cocatalyst and the like.
Description
Technical Field
The disclosure belongs to the field of catalysts, and relates to a covalent triazine polymer, and a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The carbon dioxide which is artificially emitted is the main cause of global warming, which is sustainableThe concept of development runs counter. Due to CO2Is safe and nontoxic, and can be used as a rich and cheap C1 raw material, CO2Has attracted a great deal of attention from countries around the world. Reduction of atmospheric CO2The content method mainly comprises two types: adsorption capture and chemical conversion. CO conversion using a suitable catalyst2Conversion to more valuable organic chemicals has been considered to reduce CO2A rather important method of discharge. In the present study, CO is utilized2The synthesis of cyclic carbonates via cycloaddition reactions with cyclic alkanes is one of the most prominent routes.
Cyclic carbonates are an important industrial raw material for printing and dyeing, textiles, electrochemistry, polymer synthesis, highly polar solvents, and even in the synthesis of pharmaceutical or fine chemical intermediates, exhibit unique values. To date, various catalysts developed in this field have been reported, including ionic liquids, Zeolitic Imidazolate Frameworks (ZIFs), nanomaterials, Metal Organic Frameworks (MOFs), Porous Organic Polymers (POPs), carbonaceous materials, and the like. However, the inventors of the present disclosure have found that the current catalysts for chemical conversion of carbon dioxide still have the disadvantages of low catalytic activity, difficult separation, coordination of noble metals required for most heterogeneous catalysts, toxic promoters required for most heterogeneous catalysts, and the like.
Disclosure of Invention
In order to solve the defects of the prior art, the present disclosure aims to provide a covalent triazine polymer, and a preparation method and an application thereof, wherein the covalent triazine polymer is adopted as a catalyst for chemical conversion of carbon dioxide, and has the advantages of high catalytic activity, easy separation, no need of metal loading, no need of a cocatalyst, etc.
In order to achieve the purpose, the technical scheme of the disclosure is as follows:
in one aspect, the present disclosure provides a covalent triazine polymer having a repeating structural unit represented by formula I:
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12Are all selected from carbon, nitrogen, R1And R2In a different sense, R3And R4In a different sense, R5And R6In a different sense, R8And R9In a different sense, R11And R12Different.
On the other hand, the disclosure provides a preparation method of covalent triazine polymer, 2, 5-dicyanopyridine is used as raw material to carry out cyanocyclization reaction to obtain triazine ring tripolymer, and the triazine ring tripolymer is continuously carried out with cyanocyclization reaction to obtain covalent triazine polymer;
the chemical structure of the triazine ring trimer is shown as formula II:
the triazine polymer has a repeating structural unit represented by formula I:
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R1′、R2′、R3′、R4′、R5′、R6' are all selected from carbon, nitrogen, R1And R2In a different sense, R3And R4In a different sense, R5And R6In a different sense, R8And R9In a different sense, R11And R12In a different sense, R1' and R2' different, R3' and R4' different, R5' and R6' different.
In a third aspect, the disclosure provides a method for preparing a covalent triazine polymer, 2, 5-dicyanopyridine and zinc chloride are heated to not less than 400 ℃ under vacuum condition for reaction.
In a fourth aspect, the present disclosure provides a covalent triazine polymer, obtained by the above preparation method, having pores with a diameter of less than 2 nm.
In a fifth aspect, the present disclosure provides a use of the above covalent triazine polymer for catalyzing the chemical conversion of carbon dioxide.
The covalent triazine polymer is used as a catalyst for chemical conversion of carbon dioxide for the first time, and the catalyst has the advantages of high catalytic activity, easiness in separation, no need of metal load, no need of a cocatalyst and the like.
In a sixth aspect, the present disclosure provides a catalyst, the active ingredient being the above covalent triazine polymer.
In a seventh aspect, the present disclosure provides a method for synthesizing cyclic carbonate, in which alkylene oxide and carbon dioxide undergo cycloaddition reaction under the catalysis of the above covalent triazine polymer or catalyst to obtain cyclic carbonate;
the chemical structural formula of the alkylene oxide is shown as III:
the chemical structural formula of the cyclic carbonate is shown as IV:
wherein R is13Selected from hydrogen, halogen, alkyl, substituted alkyl, phenyl, substituted phenyl, benzyl and substituted benzyl.
The synthesis method of the cyclic carbonate provided by the disclosure does not need a solvent, has high product yield, is simple and convenient, and has lower cost.
The beneficial effect of this disclosure does:
1. the covalent triazine polymer provided by the present disclosure as a catalyst can catalyze the reaction of carbon dioxide and cyclic alkane to form cyclic carbonate under the conditions of no solvent, no promoter and no metal load.
2. The preparation method of the covalent triazine polymer provided by the disclosure is stable and reliable, has shorter steps, and is beneficial to saving the preparation cost.
3. The covalent triazine polymers provided by the present disclosure can be reused multiple times as catalysts.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure and are not to limit the disclosure.
FIG. 1 is a chart of the infrared absorption spectra of covalent triazine polymers prepared in examples 1-5 of the present disclosure;
FIG. 2 is an XRD pattern of covalent triazine polymers prepared in examples 1-5 of the present disclosure;
FIG. 3 is a high resolution transmission electron micrograph of a covalent triazine polymer prepared according to example 1 of the present disclosure, A is a surface and B is a cross section;
FIG. 4 shows N of covalent triazine polymers prepared in examples 1-5 of the present disclosure2An adsorption curve;
FIG. 5 is a graph of the pore size distribution of a covalent triazine polymer prepared in example 1 of the present disclosure;
figure 6 is a model picture of a covalent triazine polymer prepared in example 1 of the present disclosure.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the defects that the existing catalyst for chemical conversion of carbon dioxide still has the defects that a homogeneous catalyst has low catalytic activity and is not easy to separate, most heterogeneous catalysts need coordination of noble metal, a toxic cocatalyst is needed, and the like, the disclosure provides a covalent triazine polymer and a preparation method and application thereof.
In one exemplary embodiment of the present disclosure, a covalent triazine polymer is provided having a repeating structural unit represented by formula I:
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12Are all selected from carbon, nitrogen, R1And R2In a different sense, R3And R4In a different sense, R5And R6In a different sense, R8And R9In a different sense, R11And R12Different.
Indicates the position of attachment of the repeating structural unit.
In one or more embodiments of this embodiment, there are one or more of the following repeating structural units:
the connection mode is as follows:
in another embodiment of the disclosure, a preparation method of a covalent triazine polymer is provided, which comprises the steps of carrying out a cyanocyclization reaction on 2, 5-dicyanopyridine as a raw material to obtain a triazine ring trimer, and continuing to carry out the cyanocyclization reaction on the triazine ring trimer to obtain the covalent triazine polymer;
the chemical structure of the triazine ring trimer is shown as formula II:
the triazine polymer has a repeating structural unit represented by formula I:
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R1′、R2′、R3′、R4′、R5′、R6' are all selected from carbon, nitrogen, R1And R2In a different sense, R3And R4In a different sense, R5And R6In a different sense, R8And R9In a different sense, R11And R12In a different sense, R1' and R2' different, R3' and R4' different, R5' and R6' different.
The chemical structural formula of the 2, 5-dicyanopyridine is
In one or more embodiments of this embodiment, the steps are: 2, 5-dicyanopyridine reacts with a catalyst under vacuum conditions by heating to a temperature of not less than 400 ℃.
In order to ensure complete removal of oxygen from the reaction system, in this series of examples, 2, 5-dicyanopyridine and the catalyst were evacuated under an inert atmosphere.
In the series of examples, the reaction temperature is 350-650 ℃. The reaction can be carried out at a specific temperature in the reaction process, such as 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ and the like; or the reaction can be continued by first reacting at a specific temperature for a period of time and then heating to a specific temperature, for example, first reacting at 400 ℃ for a period of time and then heating to 500 ℃, or first reacting at 400 ℃ for a period of time and then heating to 600 ℃, or first reacting at 500 ℃ for a period of time and then heating to 600 ℃, and the like. When the reaction temperature is 395-405 ℃, the cracking of nitrile and the decomposition of triazine ring can be greatly reduced, so that the damage of catalytic sites is avoided, and the covalent triazine polymer has higher catalytic activity.
In order to ensure the reaction to be complete, the reaction time is 40-80 h in the series of examples.
In this series of examples, the catalyst was zinc chloride.
In the series of embodiments, the mass ratio of the catalyst to the 2, 5-dicyanopyridine is 5-12: 1. When the mass ratio of the catalyst to the 2, 5-dicyanopyridine is 9.5-10.5: 1, the damage of catalytic sites can be further avoided, so that the catalytic activity of the covalent triazine polymer is further improved.
In one or more embodiments of this embodiment, the chemical structure of the trimer of the triazine ring is one or more of the following chemical structures:
in one or more embodiments of this embodiment, the reacted material is washed and dried in order to increase the purity of the covalent triazine polymer.
In this series of examples, the washing process was: firstly, washing with water, then washing with an acid solution, then washing with water, and finally washing with tetrahydrofuran. Can ensure complete removal of impurities. The acid solution is a dilute acid solution, such as 1.5-2.5 mol/L hydrochloric acid.
In a third embodiment of the disclosure, a method for preparing a covalent triazine polymer is provided, wherein 2, 5-dicyanopyridine and zinc chloride are heated to not less than 400 ℃ under vacuum condition for reaction.
In one or more embodiments of this embodiment, the reaction temperature is 350 to 650 ℃. The reaction can be carried out at a specific temperature in the reaction process, such as 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ and the like; or the reaction can be continued by first reacting at a specific temperature for a period of time and then heating to a specific temperature, for example, first reacting at 400 ℃ for a period of time and then heating to 500 ℃, or first reacting at 400 ℃ for a period of time and then heating to 600 ℃, or first reacting at 500 ℃ for a period of time and then heating to 600 ℃, and the like. When the reaction temperature is 395-405 ℃, the cracking of nitrile and the decomposition of triazine ring can be greatly reduced, so that the damage of catalytic sites is avoided, and the covalent triazine polymer has higher catalytic activity.
In one or more embodiments of this embodiment, the reaction time is 40 to 80 hours.
In one or more embodiments of this embodiment, the mass ratio of zinc chloride to 2, 5-dicyanopyridine is 5-12: 1. When the mass ratio of the zinc chloride to the 2, 5-dicyanopyridine is 9.5-10.5: 1, the catalytic sites can be further prevented from being damaged, so that the catalytic activity of the covalent triazine polymer is further improved.
In a fourth embodiment of the present disclosure, there is provided a covalent triazine polymer, obtained by the above preparation method, having pores with a diameter of less than 2 nm.
In a fifth embodiment of the disclosure, there is provided a use of the above covalent triazine polymer to catalyze the chemical conversion of carbon dioxide.
In a sixth embodiment of the present disclosure, a catalyst is provided, wherein the active ingredient is the above covalent triazine polymer.
In a seventh embodiment of the present disclosure, a method for synthesizing cyclic carbonate is provided, in which alkylene oxide and carbon dioxide undergo cycloaddition reaction under the catalysis of the covalent triazine polymer or the catalyst to obtain cyclic carbonate;
the chemical structural formula of the alkylene oxide is shown as III:
the chemical structural formula of the cyclic carbonate is shown as IV:
wherein R is13Selected from hydrogen, halogen, alkyl, substituted alkyl, phenyl, substituted phenyl, benzyl and substituted benzyl.
In one or more embodiments of this embodiment, R13Selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, 2-chloroethyl, n-butyl, phenyl, benzyl and trifluoromethyl.
In one or more embodiments of this embodiment, the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, epichlorohydrin, bromopropylene oxide, 1, 2-butylene oxide, 1, 2-cyclohexene oxide, phenylethylene oxide, propylene oxide, cyclohexene oxide, 1, 2-dodecane oxide, 1, 2-epoxy-5-hexene, 2, 3-epoxypropylpropargyl ether, 1,2,7, 8-diepoxyoctane, 1, 2-epoxy-2-methylpropane, trans-2, 3-butylene oxide, trans-1, 2-diphenylethylene oxide, 1-allyloxy-2, 3-propylene oxide, 1, 2-epoxy-3-phenoxypropane, 2-fluoroethylene oxide, 2, 2-difluoroethylene oxide and 1,1, 1-trifluoro-2, 3-propylene oxide.
In one or more embodiments of this embodiment, the cycloaddition reaction conditions are: the pressure of the carbon dioxide is 0.1-1.0 MPa, and the temperature is 25-130 ℃.
In one or more embodiments of this embodiment, the mass ratio of the covalent triazine polymer to the alkylene oxide is 1:10 to 50.
In order to make the technical solutions of the present disclosure more clearly understood by those skilled in the art, the technical solutions of the present disclosure will be described in detail below with reference to specific embodiments.
Example 1
2,5-DCP and ZnCl are put under inert atmosphere2(2,5-DCP:ZnCl21:10) were transferred to pressure-resistant ampoules (3 × 15cm), and the ampoules were evacuated and flame-sealed. The reaction was left in a muffle furnace at 400 ℃ for 40 hours, and then the ampoule was cooled to room temperature and opened. The crude product was washed with copious amounts of deionized water for 12 hours, 2mol/L dilute HCl for 12 hours, deionized water for 12 hours, then THF for 4 hours, and dried in a vacuum oven at 90 deg.C for 12 hours to give a black powder of covalent triazine polymer, designated 2,5-DCP-CTF-0, with an infrared absorption spectrum of 2230cm as shown in FIG. 1-1The absorption peak of cyano group obviously disappears and is 1548cm-1And 1280cm-1The absorption peak at (a) indicates that trimerization is complete, thus enabling the structure of the covalent triazine polymer to be demonstrated, with the XRD pattern shown in figure 2. Meanwhile, the pore size distribution of 2,5-DCP-CTF-0 is shown in FIG. 5, and as can be seen from the pore size distribution, the pores of 2,5-DCP-CTF-0 are mostly smaller than 2nm, and the 2,5-DCP-CTF-0 is modeled by Materials studio, as shown in FIG. 6, and the measured pore size is 1.4nmThis corresponds to the actual measurement values, which indicate the presence of repeating structural units. Can prove the existenceOr the like.
From XRD and HR-TEM, it can be seen that 2,5-DCP-CTF-0 has a graphene-like layered structure.
N of 2,5-DCP-CTF-02The adsorption curve is shown in FIG. 4, and the specific surface area is 544m2·g-1。
Example 2
In an inert atmosphere2,5-DCP and ZnCl2(2,5-DCP:ZnCl21:10) were transferred to pressure-resistant ampoules (3 × 15cm), and the ampoules were evacuated and flame-sealed. The reaction was left in a muffle furnace at 600 ℃ for 40 hours, and then the ampoule was cooled to room temperature and opened. The crude product was rinsed with copious amounts of deionized water for 12 hours, 2mol/L dilute HCl for 12 hours, deionized water for 12 hours, then THF for 4 hours, and dried in a vacuum oven at 90 deg.C for 12 hours to give a black powder of covalent triazine polymer, designated 2,5-DCP-CTF-1, with an infrared absorption spectrum as shown in FIG. 1 and an XRD spectrum as shown in FIG. 2.
N of 2,5-DCP-CTF-12The adsorption curve is shown in FIG. 4, and the specific surface area is 1332m2·g-1。
Example 3
2,5-DCP and ZnCl are put under inert atmosphere2(2,5-DCP:ZnCl21:12) were transferred to pressure-resistant ampoules (3 × 15cm), and the ampoules were evacuated and flame-sealed. The reaction mixture was left in a muffle furnace at 400 ℃ for 20h and at 600 ℃ for 20h, and then the ampoule was cooled to room temperature and opened. The crude product was rinsed with copious amounts of deionized water for 12 hours, 2mol/L dilute HCl for 12 hours, deionized water for 12 hours, then THF for 4 hours, and dried in a vacuum oven at 90 deg.C for 12 hours to give a black powder of covalent triazine polymer, designated 2,5-DCP-CTF-2, with an infrared absorption spectrum as shown in FIG. 1 and an XRD spectrum as shown in FIG. 2.
N of 2,5-DCP-CTF-22The adsorption curve is shown in FIG. 4, the specific surface area is 1768m2·g-1。
Example 4
2,5-DCP and ZnCl are put under inert atmosphere2(2,5-DCP:ZnCl21:10) were transferred to pressure-resistant ampoules (3 × 15cm), and the ampoules were evacuated and flame-sealed. The reaction mixture was left in a muffle furnace at 400 ℃ for 20h and at 600 ℃ for 20h, and then the ampoule was cooled to room temperature and opened. The crude product was rinsed with copious amounts of deionized water for 12 hours, 2mol/L dilute HCl for 12 hours, deionized water for 12 hours, then THF for 4 hours, and dried in a vacuum oven at 90 deg.C for 12 hours to give a black powder of the covalent triazine polymer, designated 2,5-DCPCTF-3, infrared absorption spectrum as shown in figure 1, XRD spectrum as shown in figure 2.
N of 2,5-DCP-CTF-32The adsorption curve is shown in FIG. 4, the specific surface area is 1707m2·g-1。
Example 5
2,5-DCP and ZnCl are put under inert atmosphere2(2,5-DCP:ZnCl21:10) were transferred to pressure-resistant ampoules (3 × 15cm), and the ampoules were evacuated and flame-sealed. The reaction mixture was left in a muffle furnace at 400 ℃ for 20h and at 600 ℃ for 60h, and then the ampoule was cooled to room temperature and opened. The crude product was rinsed with copious amounts of deionized water for 12 hours, 2mol/L dilute HCl for 12 hours, deionized water for 12 hours, then THF for 4 hours, and dried in a vacuum oven at 90 deg.C for 12 hours to give a black powder of covalent triazine polymer, designated 2,5-DCP-CTF-4, with an infrared absorption spectrum as shown in FIG. 1 and an XRD spectrum as shown in FIG. 2.
N of 2,5-DCP-CTF-42The adsorption curve is shown in FIG. 4, and the specific surface area is 1447m2·g-1。
Example 6
100mg of 2,5-DCP-CTF-0, 18mmol of epoxy chloropropane and 3.0MPa of carbon dioxide are reacted for 3 hours at 130 ℃, and the yield of the chlorinated propylene carbonate is 95 percent.
Example 7
100mg of 2,5-DCP-CTF-1, 18mmol of epichlorohydrin and 3.0MPa of carbon dioxide, and reacting for 3h at 130 ℃ to obtain the chlorinated propylene carbonate with the yield of 64%.
Example 8
100mg of 2,5-DCP-CTF-2, 18mmol of epichlorohydrin and 3.0MPa of carbon dioxide, and reacting for 3h at 130 ℃ to obtain the chlorinated propylene carbonate with the yield of 63%.
Example 9
100mg of 2,5-DCP-CTF-3, 18mmol of epichlorohydrin and 3.0MPa of carbon dioxide, and reacting for 3h at 130 ℃ to obtain the chlorinated propylene carbonate with the yield of 63%.
Example 10
100mg of 2,5-DCP-CTF-4, 18mmol of epoxy chloropropane and 3.0MPa of carbon dioxide are reacted for 3 hours at 130 ℃, and the yield of the chlorinated propylene carbonate is 55 percent.
Example 11
100mg of 2,5-DCP-CTF-0, 18mmol of epoxy bromopropane and 3.0MPa of carbon dioxide are reacted for 3 hours at 130 ℃, and the yield of the bromo-propylene carbonate is 83 percent.
Example 12
100mg of 2,5-DCP-CTF-0, 18mmol of propylene oxide and 3.0MPa of carbon dioxide are reacted for 3 hours at 130 ℃, and the yield of the propylene carbonate is 41 percent.
Example 13
100mg of 2,5-DCP-CTF-0, 18mmol of phenyloxirane and 3.0MPa of carbon dioxide are reacted at 130 ℃ for 3h to obtain the phenyl cyclic carbonate with a yield of 49%.
Example 14
Catalysis of CO with 2,5-DCP-CTF-02Repeated experiments with alkylene oxide reaction were as follows:
for the first time: 100mg of 2,5-DCP-CTF-0, 18mmol of epoxy chloropropane and 3.0MPa of carbon dioxide, and reacting for 3h at 130 ℃ to obtain the propylene carbonate with the yield of 99.06 percent;
and (3) for the second time: 100mg of 2,5-DCP-CTF-0, 18mmol of epoxy chloropropane and 3.0MPa of carbon dioxide, and reacting for 3h at 130 ℃ to obtain the propylene carbonate with the yield of 99.02 percent;
and thirdly: 100mg of 2,5-DCP-CTF-0, 18mmol of epoxy chloropropane and 3.0MPa of carbon dioxide, and reacting for 3h at 130 ℃ to obtain the propylene carbonate with the yield of 99 percent;
fourth time: 100mg of 2,5-DCP-CTF-0, 18mmol of epoxy chloropropane and 3.0MPa of carbon dioxide, and reacting for 3h at 130 ℃ to obtain the propylene carbonate with the yield of 98.84%;
fifth step: 100mg of 2,5-DCP-CTF-0, 18mmol of epichlorohydrin and 3.0MPa of carbon dioxide, and reacting for 3h at 130 ℃ to obtain the propylene carbonate with the yield of 98.44%.
And sixth time: 100mg of 2,5-DCP-CTF-0, 18mmol of epoxy chloropropane and 3.0MPa of carbon dioxide are reacted for 3 hours at 130 ℃, and the yield of the propylene carbonate is 97.9 percent.
The above description is only a preferred embodiment of the present disclosure and is not intended to limit the present disclosure, and various modifications and changes may be made to the present disclosure by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.
Claims (10)
1. A covalent triazine polymer characterized by having a repeating structural unit of formula I:
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12Are all selected from carbon, nitrogen, R1And R2In a different sense, R3And R4In a different sense, R5And R6In a different sense, R8And R9In a different sense, R11And R12Different.
2. The covalent triazine polymer of claim 1, having one or more of the following repeating structural units:
3. a preparation method of covalent triazine polymer is characterized in that 2, 5-dicyanopyridine is used as raw material to carry out cyanocyclization reaction to obtain triazine ring tripolymer, and the triazine ring tripolymer is continuously carried out with cyanocyclization reaction to obtain covalent triazine polymer;
the chemical structure of the triazine ring trimer is shown as formula II:
the triazine polymer has a repeating structural unit represented by formula I:
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R1′、R2′、R3′、R4′、R5′、R6' are all selected from carbon, nitrogen, R1And R2In a different sense, R3And R4In a different sense, R5And R6In a different sense, R8And R9In a different sense, R11And R12In a different sense, R1' and R2' different, R3' and R4' different, R5' and R6' different.
4. A process for the preparation of a covalent triazine polymer according to claim 3, characterized by the steps of: heating 2, 5-dicyanopyridine and a catalyst to a temperature of not less than 400 ℃ under a vacuum condition for reaction;
preferably, 2, 5-dicyanopyridine and the catalyst are vacuumized under an inert atmosphere;
preferably, the reaction temperature is 350-650 ℃, and further preferably 395-405 ℃;
preferably, the reaction time is 40-80 h;
preferably, the catalyst is zinc chloride;
preferably, the mass ratio of the catalyst to the 2, 5-dicyanopyridine is 5-12: 1, and further preferably, the mass ratio of the catalyst to the 2, 5-dicyanopyridine is 9.5-10.5: 1;
or, the chemical structure of the trimer of the triazine ring is one or more of the following chemical structural formulas:
or washing and drying the reacted materials;
preferably, the washing process is as follows: firstly, washing with water, then washing with an acid solution, then washing with water, and finally washing with tetrahydrofuran.
5. A process for preparing covalent triazine polymer features that 2, 5-dicyanopyridine and zinc chloride are heated to 400 deg.C or higher in vacuum condition for reaction.
6. The method of claim 5, wherein the reaction temperature is 350 to 650 ℃; preferably, the reaction temperature is 395-405 ℃;
or the reaction time is 40-80 h;
or the mass ratio of the zinc chloride to the 2, 5-dicyanopyridine is 5-12: 1; preferably, the mass ratio of the zinc chloride to the 2, 5-dicyanopyridine is 9.5-10.5: 1.
7. A covalent triazine polymer, characterized by having pores with a diameter of less than 2nm, obtained by the production process according to claim 5 or 6.
8. Use of a covalent triazine polymer according to claim 1 or 2, a covalent triazine polymer obtained by a process according to claim 3 or 4, or a covalent triazine polymer according to claim 7 for catalyzing the chemical conversion of carbon dioxide.
9. A catalyst, characterized in that the active ingredient is the covalent triazine polymer of claim 1 or 2, the covalent triazine polymer obtained by the production process of claim 3 or 4, or the covalent triazine polymer of claim 7.
10. A method for synthesizing a cyclic carbonate, characterized in that an alkylene oxide is subjected to a cycloaddition reaction with carbon dioxide under the catalysis of the covalent triazine polymer of claim 1 or 2, the covalent triazine polymer obtained by the production method of claim 3 or 4, the covalent triazine polymer of claim 7, or the catalyst of claim 9 to obtain a cyclic carbonate;
the chemical structural formula of the alkylene oxide is shown as III:
the chemical structural formula of the cyclic carbonate is shown as IV:
wherein R is13Selected from hydrogen, halogen, alkyl, substituted alkyl, phenyl, substituted phenyl, benzyl, substituted benzyl;
preferably, R13Selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, 2-chloroethyl, n-butyl, phenyl, benzyl, trifluoromethyl;
preferably, the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, epichlorohydrin, bromopropylene oxide, 1, 2-butylene oxide, 1, 2-cyclohexene oxide, phenyl ethylene oxide, propylene oxide, cyclohexene oxide, 1, 2-dodecane oxide, 1, 2-epoxy-5-hexene, 2, 3-glycidyl propargyl ether, 1,2,7, 8-diepoxyoctane, 1, 2-epoxy-2-methylpropane, trans-2, 3-butylene oxide, trans-1, 2-diphenylethylene oxide, 1-allyloxy-2, 3-propylene oxide, 1, 2-epoxy-3-phenoxypropane, 2-fluoroethylene oxide, 2-difluoroethylene oxide, and, 1,1, 1-trifluoro-2, 3-epoxypropane;
preferably, the cycloaddition reaction conditions are: the pressure of carbon dioxide is 0.1-1.0 MPa, and the temperature is 25-130 ℃;
preferably, the mass ratio of the covalent triazine polymer to the alkylene oxide is 1: 10-50.
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| CN111548487A (en) * | 2020-05-13 | 2020-08-18 | 广州大学 | Porous organic polymer and preparation method and application thereof |
| CN113292724A (en) * | 2021-05-17 | 2021-08-24 | 天津工业大学 | Preparation method of pyridine-rich cationic covalent triazine polymer |
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| CN111548487A (en) * | 2020-05-13 | 2020-08-18 | 广州大学 | Porous organic polymer and preparation method and application thereof |
| CN111548487B (en) * | 2020-05-13 | 2022-08-30 | 广州大学 | Porous organic polymer and preparation method and application thereof |
| CN113292724A (en) * | 2021-05-17 | 2021-08-24 | 天津工业大学 | Preparation method of pyridine-rich cationic covalent triazine polymer |
| CN113292724B (en) * | 2021-05-17 | 2022-03-25 | 天津工业大学 | Preparation method of pyridine-rich cationic covalent triazine polymer |
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