CN110615895B - Covalent triazine polymer and preparation method and application thereof - Google Patents

Covalent triazine polymer and preparation method and application thereof Download PDF

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CN110615895B
CN110615895B CN201910859588.9A CN201910859588A CN110615895B CN 110615895 B CN110615895 B CN 110615895B CN 201910859588 A CN201910859588 A CN 201910859588A CN 110615895 B CN110615895 B CN 110615895B
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covalent triazine
triazine polymer
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邓伟侨
李怡萌
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Abstract

The present disclosure provides a covalent triazine polymer and a preparation method thereofMethods and uses, covalent triazine polymers having repeating structural units of formula I:
Figure DDA0002199310020000011
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. The covalent triazine polymer provided by the disclosure as a catalyst for chemical conversion of carbon dioxide has the advantages of high catalytic activity, easy separation, no need of metal loading, no need of a cocatalyst and the like.

Description

Covalent triazine polymer and preparation method and application thereof
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 human emission of carbon dioxide is a major cause of global warming, which runs counter to the concept of sustainable development. 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:
Figure BDA0002199308000000021
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:
Figure BDA0002199308000000022
the triazine polymer has a repeating structural unit represented by formula I:
Figure BDA0002199308000000031
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:
Figure BDA0002199308000000032
the chemical structural formula of the cyclic carbonate is shown as IV:
Figure BDA0002199308000000041
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:
Figure BDA0002199308000000051
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.
Figure BDA0002199308000000053
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:
Figure BDA0002199308000000052
Figure BDA0002199308000000061
Figure BDA0002199308000000071
Figure BDA0002199308000000081
the connection mode is as follows:
Figure BDA0002199308000000091
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:
Figure BDA0002199308000000092
the triazine polymer has a repeating structural unit represented by formula I:
Figure BDA0002199308000000101
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
Figure BDA0002199308000000102
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:
Figure BDA0002199308000000111
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 the series of embodiments, the washing process comprises the steps of washing with water, washing with an acid solution, washing with water, and washing with tetrahydrofuran, so that complete removal of impurities can be ensured, wherein 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:
Figure BDA0002199308000000121
the chemical structural formula of the cyclic carbonate is shown as IV:
Figure BDA0002199308000000122
wherein R is13Selected from hydrogen, halogen, alkyl, substituted alkyl, phenyl, substituted phenyl, benzyl and substituted benzyl.
One or more embodiments of the present inventionIn the examples, 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 separately to pressure-resistant ampoules (3 × 15cm), the ampoules were evacuated, flame-sealed, placed in a muffle furnace at 400 ℃ for 40 hours, the ampoules were cooled to room temperature and opened, the crude product was washed with copious amounts of deionized water for 12 hours, 2 mol/L dilute HCl for 12 hours, deionized water for 12 hours, then THF for 4 hours, and dried in a vacuum oven at 90 ℃ for 12 hours to give a black, powdery covalent triazine polymer, designated 2,5-DCP-CTF-0, having an infrared absorption spectrum as shown in FIG. 1 at 2230cm-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 demonstration of covalent triazine polymersThe XRD spectrum of the structure (1) is 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 1.4nm
Figure BDA0002199308000000131
This corresponds to the actual measurement values, which indicate the presence of repeating structural units. Can prove the existence
Figure BDA0002199308000000132
Or 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
2,5-DCP and ZnCl are put under inert atmosphere2(2,5-DCP:ZnCl21:10) were transferred into pressure-resistant ampoules (3 × 15cm), the ampoules were evacuated, flame-sealed, placed in a muffle furnace at 600 ℃ for 40 hours, the ampoules were cooled to room temperature and opened, the crude product was washed with copious amounts of deionized water for 12 hours, 2 mol/L diluted HCl for 12 hours, deionized water for 12 hours, then THF for 4 hours, and dried in a vacuum oven at 90 ℃ for 12 hours to give a black, powdery covalent triazine polymer, designated 2,5-DCP-CTF-1, having 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 into pressure-resistant ampoules (3 × 15cm), the ampoules were evacuated and flame-sealed, placed in a muffle furnace at 400 ℃ for 20h and 600 ℃ for 20h, and the ampoules were cooled to room temperature and opened, the crude product was rinsed with a large amount of deionized water for 12 h, 2mol/L diluted HCl for 12 hours, deionized water for 12 hours, then THF for 4 hours, and dried in a vacuum oven at 90 ℃ 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 into pressure resistant ampoules (3 × 15cm) respectively, the ampoules were evacuated, flame sealed, placed in a muffle furnace at 400 ℃ for 20h, 600 ℃ for 20h, then the ampoules were cooled to room temperature and opened, the crude product was rinsed with copious amounts of deionized water, 2 mol/L dilute HCl for 12 h, deionized water for 12 h, then THF for 4 h, and dried in a vacuum oven at 90 ℃ for 12 h to give a black powder of the covalent triazine polymer designated 2,5-DCP-CTF-3, the infrared absorption spectrum is shown in figure 1 and the XRD spectrum is 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 into pressure resistant ampoules (3 × 15cm) respectively, the ampoules were evacuated, flame sealed, placed in a muffle furnace at 400 ℃ for 20h, 600 ℃ for 60h, then the ampoules were cooled to room temperature and opened, the crude product was rinsed with copious amounts of deionized water, 2 mol/L dilute HCl for 12 h, deionized water for 12 h, then THF for 4 h, and dried in a vacuum oven at 90 ℃ for 12 h to give a black powder of the covalent triazine polymer designated 2,5-DCP-CTF-4, the infrared absorption spectrum is shown in figure 1 and the XRD spectrum is shown in figure 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 (18)

1. A covalent triazine polymer characterized by having a repeating structural unit of formula I:
Figure FDA0002508492820000011
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:
Figure FDA0002508492820000012
Figure FDA0002508492820000021
Figure FDA0002508492820000031
Figure FDA0002508492820000041
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:
Figure FDA0002508492820000042
the triazine polymer has a repeating structural unit represented by formula I:
Figure FDA0002508492820000051
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 preparation method comprises the following steps: heating 2, 5-dicyanopyridine and a catalyst to a temperature of not less than 400 ℃ under a vacuum condition for reaction; the reaction temperature is 400 ℃, 450 ℃, 500 ℃, 550 ℃ and 600 ℃; the reaction time is 40-80 h; the catalyst is zinc chloride; the mass ratio of the catalyst to the 2, 5-dicyanopyridine is 5-12: 1.
4. A process for the preparation of a covalent triazine polymer according to claim 3, wherein the 2, 5-dicyanopyridine and the catalyst are evacuated under an inert atmosphere.
5. The method of claim 3, wherein the mass ratio of the catalyst to the 2, 5-dicyanopyridine is 9.5-10.5: 1.
6. A process according to claim 3, wherein the polymer is a covalent triazine polymer,
the chemical structure of the triazine ring trimer is one or more of the following chemical structural formulas:
Figure FDA0002508492820000061
7. the process according to claim 3, wherein the reaction mixture is washed and dried.
8. The method of claim 7, wherein the washing comprises: firstly, washing with water, then washing with an acid solution, then washing with water, and finally washing with tetrahydrofuran.
9. A preparation method of covalent triazine polymer is characterized in that 2, 5-dicyanopyridine and zinc chloride are heated to be not lower than 400 ℃ under vacuum condition for reaction; the reaction time is 40-80 h; the mass ratio of the zinc chloride to the 2, 5-dicyanopyridine is 5-12: 1.
10. The method of claim 9, wherein the mass ratio of zinc chloride to 2, 5-dicyanopyridine is 9.5-10.5: 1.
11. A covalent triazine polymer characterized by having pores with a diameter of less than 2nm, obtained by the process of claim 9 or 10.
12. Use of a covalent triazine polymer according to claim 1 or 2, a covalent triazine polymer obtained by a process according to any one of claims 3 to 8 or a covalent triazine polymer according to claim 11 for catalysing the chemical conversion of carbon dioxide.
13. 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 any one of claims 3 to 8, or the covalent triazine polymer of claim 11.
14. 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 according to claim 1 or 2, the covalent triazine polymer obtained by the production method according to any one of claims 3 to 8, the covalent triazine polymer according to claim 11, or the catalyst according to claim 13 to obtain a cyclic carbonate;
the chemical structural formula of the alkylene oxide is shown as III:
Figure FDA0002508492820000071
the chemical structural formula of the cyclic carbonate is shown as IV:
Figure FDA0002508492820000072
wherein R is13Selected from hydrogen, halogen, alkyl, substituted alkyl, phenyl, substituted phenyl, benzyl and substituted benzyl.
15. The method for synthesizing a cyclic carbonate according to claim 14, wherein R is13Selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, 2-chloroethyl, n-butyl, phenyl, benzyl and trifluoromethyl.
16. The method according to claim 14, wherein the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, epichlorohydrin, bromohydrin, 1, 2-butylene oxide, 1, 2-epoxyhexane, phenylethane, propylene oxide, epoxycyclohexane, 1, 2-epoxydodecane, 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, and mixtures thereof, 2-fluoroethylene oxide, 2-difluoroethylene oxide and 1,1, 1-trifluoro-2, 3-propylene oxide.
17. The method for synthesizing a cyclic carbonate according to claim 14, wherein the cycloaddition reaction conditions are as follows: the pressure of the carbon dioxide is 0.1-1.0 MPa, and the temperature is 25-130 ℃.
18. The method for synthesizing cyclic carbonate according to claim 14, wherein the mass ratio of the covalent triazine polymer to the alkylene oxide is 1:10 to 50.
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