Preparation method and application of crystalline sp2 carbon conjugated two-dimensional polymer film

Abstract

The invention discloses a preparation method and application of a crystalline sp2 carbon conjugated two-dimensional polymer film. The thin film comprises a multi-element annular molecular structure formed by alternately polymerizing a first monomer and a second monomer, the first monomer is an amphiphilic methyl monomer with a functional side chain; the second monomer is a multi-aldehyde monomer. The preparation method comprises the following step: under the catalytic action of a catalyst, carrying out interfacial polymerization reaction on the first monomer and the second monomer at the interface of the first liquid phase and the second liquid phase. A methyl monomer is subjected to side chain modification to successfully realize an interfacial polymerization reaction to generate a single-layer or multi-layer crystalline film, side chain modification and amphipathy can stabilize an interfacial reaction system and reduce a reaction energy barrier, a condensation reaction of an interface can be effectively promoted, and various sp2 carbon conjugated two-dimensional polymer films are further synthesized; the preparation method provided by the invention has a large-scale prospect, and is green, simple, economical and environment-friendly to operate.

Description

Technical Field

[0001] This invention relates to the field of conjugated polymer technology, and more particularly to a crystalline sp... 2 Preparation methods and applications of carbon conjugated two-dimensional polymer films. Background Technology

[0002] Two-dimensional polymers are crystalline polymer materials in which units are integrated into a periodic framework via covalent bonds. They possess characteristics such as π-delocalized conjugation, designable topology, precisely tunable thickness, and functionalized pores, making them widely applicable in mass separation, energy conversion, and organic electronics. Currently, monolayer or few-layer two-dimensional polymers linked by boronic ester bonds, imine bonds, or carbon-carbon single bonds have been synthesized at the interface via Boronic ester reactions, Schiff-base reactions, and Suzuki reactions. Compared to two-dimensional polymers linked by boronic ester bonds or imine bonds, two-dimensional conjugated polymers linked by carbon-carbon double bonds (sp... 2 Carbon conjugated polymers (CCPs) possess extended π-electron delocalization, excellent physicochemical stability, and photoelectric and magnetic properties, making them promising for applications in photocatalysis / electrocatalysis, semiconductor devices, and other fields.

[0003] Currently, sp 2 Carbon-conjugated polymers can be successfully synthesized under solvothermal conditions via cyano-induced Nevon's condensation and pyridine derivative-induced aldol condensation. These synthetic processes typically involve vacuum sealing and high-temperature, high-pressure environments, and require the use of large amounts of organic solvents (such as o-dichlorobenzene, mesitylene, and dioxane) and strong acid-base catalysts (such as trifluoroacetic acid, sodium hydroxide, potassium hydroxide, and piperidine). Limited by the finite variety of monomers and stringent synthetic conditions, existing interfacial reaction systems are insufficient to meet the requirements of sp... 2 The limited availability of carbon-conjugated two-dimensional polymer thin films restricts their application in membrane separation, functional devices, and organic semiconductors. The design and development of novel sp... 2 The preparation of carbon conjugated two-dimensional polymer films and green, simple, and scalable interface methods is an urgent problem to be solved. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a crystalline sp 2 Preparation methods and applications of carbon conjugated two-dimensional polymer films.

[0005] To achieve the aforementioned objectives, the technical solution adopted by this invention includes:

[0006] Firstly, the present invention provides a crystalline sp 2A method for preparing a carbon conjugated two-dimensional polymer film includes: forming a periodic porous molecular structure by polymerizing a first monomer and a second monomer through an aldol condensation reaction; the first monomer is an amphiphilic methyl monomer with functional side chains, wherein the number of methyl functional groups of the amphiphilic methyl monomer is multiple; and the second monomer is an aldehyde monomer, wherein the number of aldehyde functional groups of the aldehyde monomer is multiple.

[0007] Furthermore, the preparation method specifically includes: dissolving the first monomer and the second monomer in immiscible first liquid phase and second liquid phase, respectively;

[0008] Under the catalytic action of the catalyst, the first monomer and the second monomer undergo an interfacial polymerization reaction at the interface between the first liquid phase and the second liquid phase to generate the crystalline sp. 2 Carbon conjugated two-dimensional polymer film.

[0009] Secondly, the present invention also provides crystalline sp prepared by the above-described preparation method. 2 Applications of carbon conjugated two-dimensional polymer films in material separation or energy conversion.

[0010] Based on the above technical solution, compared with the prior art, the beneficial effects of the present invention include at least the following:

[0011] 1) This invention prepares sp 2 A method for preparing carbon-conjugated two-dimensional polymer films was developed. By modifying the side chains of methyl monomers, an interfacial polymerization reaction was successfully achieved between amphiphilic methyl monomers and polyaldehyde monomers to generate monolayer crystalline films. Functional side chain modification and amphiphilicity stabilize the interfacial reaction system and lower the reaction energy barrier, effectively promoting the aldol condensation reaction at the interface, thereby synthesizing various sp... 2 Carbon-conjugated two-dimensional polymer films. However, current technologies cannot achieve monolayer crystalline sp from aldol condensation. 2 Preparation of carbon conjugated two-dimensional polymer films.

[0012] 2) The preparation of sp provided by the present invention 2 The method of carbon conjugated two-dimensional polymer thin films can synthesize a series of size-controllable ionic conjugated porous polymer thin films on a large scale by selecting appropriate aldehyde monomers and interfacial reaction systems. These films can be widely used in photocatalysis, sensing, separation, energy conversion and other fields.

[0013] 3) In view of the problem of harsh reaction conditions in existing technologies, this invention does not involve vacuum sealing and high temperature and high pressure reaction environment. It uses an aqueous phase and a small amount of organic phase as reaction solvent, and can synthesize a series of thin films under various synthesis conditions. The operation is green, simple and economical.

[0014] The above description is merely an overview of the technical solution of the present invention. In order to enable those skilled in the art to better understand the technical means of this application and to implement it in accordance with the contents of the specification, the preferred embodiments of the present invention are described below in conjunction with detailed drawings. Attached Figure Description

[0015] Figure 1 SP provided for some typical implementation examples of the present invention 2 Schematic diagram of the synthesis route for carbon conjugated two-dimensional polymer films;

[0016] Figure 2 SP provided as a typical embodiment of the present invention 2 Carbon conjugated two-dimensional polymer films sp 2 c-2DP DF Scanning probe microscope images;

[0017] Figure 3 SP provided as a typical embodiment of the present invention 2 Carbon conjugated two-dimensional polymer films sp 2 c-2DP DB Infrared spectral images;

[0018] Figure 4 SP provided as a typical embodiment of the present invention 2 Carbon conjugated two-dimensional polymer films sp 2 c-2DP DB Small-angle X-ray scattering images;

[0019] Figure 5 SP provided as a typical embodiment of the present invention 2 Carbon conjugated two-dimensional polymer films sp 2 c-2DP DB Solid-state carbon NMR spectrum;

[0020] Figure 6 SP provided as a typical embodiment of the present invention 2 Carbon conjugated two-dimensional polymer films sp 2 c-2DP DB The salt concentration gradient energy conversion performance test diagram. Detailed Implementation

[0021] In view of the shortcomings of the prior art, the inventors of this invention, through long-term research and extensive practice, have proposed the technical solution of this invention. The following will further explain and illustrate this technical solution, its implementation process, and its principles.

[0022] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and therefore the scope of protection of the invention is not limited to the specific embodiments disclosed below.

[0023] Moreover, relational terms such as “first” and “second” are used merely to distinguish one component or method step from another that has the same name, without necessarily requiring or implying any such actual relationship or order between these components or method steps.

[0024] See Figure 1 As shown, the embodiments of the present invention first provide a single-layer, crystalline sp 2 A carbon conjugated two-dimensional polymer film comprising a multi-cyclic molecular structure formed by alternating polymerization of a first monomer and a second monomer; the first monomer is an amphiphilic methyl monomer with alkyl functional side chains, wherein the number of methyl functional groups of the amphiphilic methyl monomer is multiple; the second monomer is an aldehyde monomer, wherein the number of aldehyde functional groups of the aldehyde monomer is multiple.

[0025] Regarding the specific molecular structure and membrane structure characteristics, in some implementation schemes, the sp... 2 Carbon conjugated two-dimensional polymer films have a fully conjugated structure.

[0026] In some implementations, the monolayer, crystalline sp 2 The thickness of the carbon conjugated two-dimensional polymer film is 1–200 nm.

[0027] In some implementations, the sp 2 The area of ​​carbon conjugated two-dimensional polymer films ranges from 1 to 100 cm². 2 .

[0028] In some implementations, the main chain carbon number of the functional side chain is 2-16.

[0029] See also Figure 1 As shown, in order to prepare the above-mentioned thin film, a second aspect of the present invention also provides the above-mentioned monolayer, crystalline sp. 2 A method for preparing carbon conjugated two-dimensional polymer films, comprising the following steps:

[0030] The first monomer and the second monomer are dissolved in the first liquid phase and the second liquid phase, which are immiscible, respectively.

[0031] Under the catalytic action of the catalyst, the first monomer and the second monomer undergo interfacial polymerization at the interface between the first liquid phase and the second liquid phase to generate a monolayer, crystalline sp. 2 Carbon conjugated two-dimensional polymer film.

[0032] The first monomer is an amphiphilic methyl monomer with a long-chain alkyl functional side chain, and the number of methyl functional groups of the amphiphilic methyl monomer is multiple; the second monomer is an aldehyde monomer, and the number of aldehyde functional groups of the aldehyde monomer is multiple.

[0033] As some typical application examples, the specific reaction process includes, for instance: dissolving the amphiphilic methyl monomer, aldehyde monomer, and catalyst in different solvents, and assembling them to form an interfacial reaction system; heating the homogeneous mixed reaction system at a specific temperature to promote the aldol condensation reaction, thereby obtaining sp. 2 Carbon conjugated two-dimensional polymer film.

[0034] Based on the above technical solutions, the main objective of this invention is to provide a solution suitable for SP. 2 Amphiphilic methyl monomers of carbon conjugated two-dimensional polymer films can be synthesized on a large scale by selecting appropriate aldehyde monomers and reaction conditions to produce a series of large-area conjugated two-dimensional polymer films with high stability and ionization channels.

[0035] The mechanism by which this invention selects amphiphilic methyl monomers with chosen structures is as follows: these pyridine derivatives contain electron-rich atoms such as nitrogen, which can be modified into side chains through quaternization reactions. Furthermore, the electron-withdrawing ability of the nitrogen sites can activate adjacent methyl sites, and the ordered structure formed by the monomers can promote hydroxyl condensation reactions at the interface to synthesize sp. 2 Carbon conjugated two-dimensional polymer film.

[0036] Through long-term practice, the inventors of this invention have concluded that the key technical means in the above technical solution lies in the modification of the first monomer (methyl monomer) to make it a methyl monomer with a long carbon chain side chain and amphiphilicity. The above characteristics enable the monomer to have an interfacial stabilizing effect and a lowering effect on the reaction energy barrier during the interfacial reaction. Under the combined effect, the reaction can proceed smoothly, and finally a single-layer film is successfully prepared.

[0037] While some existing technologies provide technical solutions for preparing two-dimensional polymer films using Schiff base condensation reactions, the aldol condensation reaction indicated by these technologies cannot directly achieve interfacial polymerization of the film. Furthermore, the aldol condensation reaction requires relatively high reaction temperatures (120–200°C), making it difficult to construct films at the two-phase interface under mild conditions. Through practical experience, the inventors of this invention have discovered that without the aforementioned modifications and alterations, it is difficult to obtain products using the same interfacial polymerization reaction method, and it is completely impossible to obtain products in film morphology (especially monolayer films).

[0038] Regarding the specific choice of monomer, in some embodiments, the first monomer includes any one or more combinations of compounds shown in the following formula:

[0039]

[0040] Wherein, X is selected from any one or a combination of two or more of carbon, sulfur, oxygen, nitrogen, and hydrogen; Y is selected from any one or a combination of two of bromine and iodine; R represents the functional side chain, including C2 to C3. 16 Alkyl chains, alkoxy chains, perfluoroalkyl chains, and alkyl chains linked by oxygen or benzene rings.

[0041] In some embodiments, the long-chain alkyl side chain R comprises any one or more combinations of the molecular structures shown in the following formula:

[0042]

[0043] In some embodiments, the first monomer is obtained by modifying a precursor with a side chain, said precursor comprising 2,6-dimethylpyridine, 3,5-dimethylpyridine, 3,6-dimethylpyridazine, 2,5-dimethylpyridine, 3,6-dimethyl-3,6-dihydro-1,2,4,5-tetraazine, 2,3-dimethylpyridine, 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, 2,3,5,6-tetramethylpyridine, 2,3,5,6-tetramethylpyridine, 2,2′,6,6′-tetramethyl-4,4′-bipyridine, 3,5-dimethyl-4H-1,2,4-triazole, 2,5-dimethyl-1,3,4-thiadiazole, 2,5-dimethyl-1,3,4-oxadiazole, 3,5-dimethyl-1,2′-tri ... 4-Thiadiazole, 3,5-dimethyl-1,2,4-oxadiazole, 4,7-dimethyl-[1,2,5]thiadiazolo[3,4-d]pyridazine, 1,4-dimethylthieno[3,4-d]pyridazine, 4,7-dimethyl-[1,2,5]oxadiazolo[3,4-d]pyridazine, 4,7-dimethyl-2H-imidazo[4,5-d]pyridazine, 1,4-dimethyl-6H-cyclopenta[d]pyridazine, 2-methyl-5-(5-methyl-1,3,4-thiadiazol-2-yl)-1,3,4-oxadiazole, 5,5′-dimethyl-2,2′-bis(1,3,4-thiadiazole), 5,5′-dimethyl-2,2′-bis(1,3,4-oxadiazole), 2-methyl-5-(5-methyl- 4H-1,2,4-triazol-3-yl)-1,3,4-thiadiazole, 2-methyl-5-(5-methyl-4H-1,2,4-triazol-3-yl)-1,3,4-oxadiazole, 5,5′-dimethyl-4H,4′H-3,3′-bis(1,2,4-triazole), 2,6-dimethylbenzo[1,2-d:5,4-d′]bis(oxazole), 2,6-dimethylbenzo[1,2-d:4,5-d′]bis(oxazole), 2,6-dimethylbenzo[1,2-d:5,4-d′]bis(thiazole), 2,6-dimethylbenzo[1,2-d:4,5-d′]bis(thiazole), 2,6-dimethyl-1,7-dihydrobenzo[1,2-d:4,5-d′]diimidazole 2,6-Dimethyl-1,5-dihydrobenzo[1,2-d:4,5-d′]diimidazole, 2,5,8-trimethylbenzo[1,2-d:3,4-d′:5,6-d"]tri(oxazole), 1,3,5-tris(2-methyloxazol-5-yl)benzene, 2,5,8-trimethylbenzo[1,2-d:3,4-d′:5,6-d"]tri(thiazole), 1,3,5-tris(2-methyl-1H-imidazol-5-yl)benzene, 2,5,8-trimethyl-4,7-dihydro-1H-benzo[1,2-d:3,4-d′:5,6-d"]triimidazole, 1,3,5-tris(6-methylpyridin-3-yl)benzene, 1,3,5-tris(5-methylpyrazin-2-yl)benzene, 1,3,5-Tris(6-methylpyridazin-3-yl)benzene, 5,10,15,20-tetra(2-methyloxazol-5-yl)porphyrin, 5,10,15,20-tetra(2-methyl-4H-114-thiazo-5-yl)porphyrin, 5,10,15,20-tetra(2-methyl-4H-imidazol-5-yl)porphyrin, 5,10,15,20-tetra(6-methylpyridin-3-yl)porphyrin, 5,10,15,20-tetra(5-methylpyridazin-2-yl)porphyrin, 5,10,15,20-tetra(6-methylpyridazin-3-yl)porphyrin, 1,3,6,8-tetra(6-methylpyridazin-3-yl)porphyrin The following are possible combinations of one or more of the following: pyridine-3-yl)pyrene, 1,3,6,8-tetra(5-methylpyrazin-2-yl)pyrene, 1,3,6,8-tetra(6-methylpyridazin-3-yl)pyrene, 5,5′,5″,5″′-(1,10-dihydroperylene-2,5,8,11-tetrayl)tetra(2-methylpyridine), 5,5′,5″,5″′-(1,10-dihydroperylene-2,5,8,11-tetrayl)tetra(2-methylpyrazine), and 6,6′,6″,6″′-(1,10-dihydroperylene-2,5,8,11-tetrayl)tetra(3-methylpyridazine), and are not limited thereto.

[0044] As typical examples of the above technical solutions, the amphiphilic methyl monomers for side chain modification are preferably selected from 1-hexyl-2,6-dimethylpyridinium, 1-hexyl-3,5-dimethylpyridinium, 1-hexyl-3,6-dimethylpyridinium, 1-hexyl-3,6-dimethyl-3,6-dihydro-1,2,4,5-tetraazinium, 1-hexyl-2,3-dimethylpyridinium, 1-hexyl-3,5-dimethylpyridinium, 1-hexyl-2,4,6-trimethylpyridinium, 1-hexyl-2,3,5,6-tetramethylpyridinium, 1 -decyl-2,6-dimethylpyridinium, 1-decyl-3,5-dimethylpyridinium, 1-decyl-3,6-dimethylpyridazinium, 1-decyl-2,5-dimethylpyridinium, 1-decyl-2,3-dimethylpyridinium, 1-decyl-3,5-dimethylpyridinium, 1-decyl-2,4,6-trimethylpyridinium, 1-decyl-2,3,5,6-tetramethylpyridinium, 1,1′-dihexyl-2,2′,6,6′-tetramethyl-[4,4′-bipyridine]bitonium, 1,1′-didecyl-2,2′ 6,6′-Tetramethyl-[4,4′-Bipyridine]bitonium, 3-hexyl-2,5-dimethyl-1,3,4-thiadiazolium, 3-decyl-2,5-dimethyl-1,3,4-thiadiazolium, 3,5-dihexyl-2,6-dimethylbenzo[1,2-d:5,4-d′]bis(thiazolium)bitonium, 3,5-dihexyl-2,6-dimethylbenzo[1,2-d:5,4-d′]bis(oxazole)bitonium, 3,5-didecyl-2,6-dimethylbenzo[1,2-d:5,4-d′]bis( The bis(thiazole)bitonium, 3,5-didecyl-2,6-dimethylbenzo[1,2-d:5,4-d′]bis(thiazole)bitonium, 3,7-dihexyl-2,6-dimethylbenzo[1,2-d:4,5-d′]bis(thiazole)bitonium, 3,7-didecyl-2,6-dimethylbenzo[1,2-d:4,5-d′]bis(thiazole)bitonium, and 3,7-didecyl-2,6-dimethylbenzo[1,2-d:4,5-d′]bis(thiazole)bitonium, or any one or more combinations thereof, and not limited thereto. The side chain is an alkyl chain, but the type of side chain is not limited thereto.

[0045] In some embodiments, the second monomer comprises pyromellitic pyrrolizaldehyde, 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine, 2,2′-bipyridine-4,4′-dicarboxaldehyde, [2,2′-bipyridine]-6,6′-dicarboxaldehyde, 5′-(4-formylphenyl)-[1,1′:3′,1″-triphenyl]-4,4"-dicarboxaldehyde, trialdehyde-resorcinol, [1,1′-biphenyl]-3,3′,5,5′-tetracarboxaldehyde, 3,3′-dihydroxy-[1,1′-biphenyl]-4,4′-dicarboxaldehyde, 1,3,6,8-tetra(4-formylphenyl)pyrene, 4,4′,4″,4″′-(ethylene-1,1,2,2-tetrayl)tetrabenzaldehyde, 4, The following are all possible combinations of 4′,4″-(pyrimidin-2,4,6-triyl)tribenzaldehyde, 1,3,5-tris(3,3″,3″′-trifluoro-4′,4″,4″′-tri(p-formylphenyl)benzene, 2,5-difluoro-terephthalaldehyde, 2,5-dihydroxy-terephthalaldehyde, 5,5′,5″-(benzene-1,3,5-triyl)tri(thiophene-2-carboxaldehyde), pyrazine-2,5-dicarboxaldehyde, 1,3,5-tris(2-formylpyridin-5-yl)benzene, 5,5′,5″-(benzene-1,3,5-triyl)tri(pyridine-2-carboxaldehyde), 3,3′-bipyridine-6,6′-dicarboxaldehyde, and 2,3,5,6-tetrafluoro-terephthalaldehyde, and are not limited thereto.

[0046] In some embodiments, the catalyst comprises, but is not limited to, any one or a combination of two or more of trifluoroacetic acid, trifluoromethanesulfonic acid, trichloroacetic acid, trichloromethanesulfonic acid, p-toluenesulfonic acid, p-chlorobenzenesulfonic acid, m-methylbenzoic acid, trimesic acid, terephthalic acid, piperidine, pyridine, pyrrole, 4-dimethylaminopyridine, pyrrolidine, sodium hydroxide, potassium hydroxide, calcium hydroxide, and cesium carbonate.

[0047] Regarding the specific material ratios and reaction conditions, in some implementation schemes, the temperature of the interfacial polymerization reaction is 2–80°C and the time is 2–120 h.

[0048] In some implementations, the molar ratio of the first monomer to the second monomer is 1:(0.5 to 6).

[0049] In some embodiments, the molar ratio of the first monomer to the catalyst is 1:(0.5 to 10).

[0050] As a typical example of the above technical solutions, the present invention provides a green and simple sp 2 A method for preparing carbon conjugated two-dimensional polymer films is proposed, which uses an aqueous phase and a small amount of organic phase as reaction solvents. A series of films can be synthesized under various synthesis conditions. The method is simple, economical and environmentally friendly.

[0051] Specifically, this may include: adding amphiphilic methyl monomers and aldehyde monomers to two solvents respectively, ultrasonically dispersing the solvent-containing glass bottle for 2-30 minutes to form a homogeneous system, then mixing them to form an interfacial reaction system and adding a catalyst, and then heating the reaction system to achieve an interfacial polymerization reaction.

[0052] Furthermore, regarding post-reaction processing, in some embodiments, the preparation method further includes, after the interfacial polymerization reaction is completed, processing the obtained monolayer, crystalline sp... 2 The steps of cleaning and vacuum drying carbon conjugated two-dimensional polymer films.

[0053] The above preparation method can produce a stable, highly active, fully conjugated sp3 carbon-carbon double bond-linked sp3 carbon-carbon double bond with good stability. 2 Carbon conjugated two-dimensional polymer thin film materials have large lateral dimensions and adjustable thickness.

[0054] The third aspect of the present invention also provides a single-layer, crystalline sp... provided or obtained by any of the above embodiments. 2 Applications of carbon conjugated two-dimensional polymer films in material separation or energy conversion.

[0055] In some implementations, the material separation includes seawater desalination and ion sieving, and the energy conversion includes salt concentration gradient energy conversion.

[0056] As some typical examples, the sp-linked carbon-carbon double bond 2 The output power converted from the salt concentration gradient of carbon conjugated two-dimensional polymer films can reach 51.4 W / m- 2 .

[0057] The technical solution of the present invention will be further described in detail below with reference to several preferred embodiments and accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. It should be noted that the following embodiments are intended to facilitate the understanding of the present invention, and do not constitute any limitation thereof. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions or according to the conditions recommended by the manufacturer. Unless otherwise specified, the experimental materials used in the embodiments below can be purchased from conventional biochemical reagent companies.

[0058] Example 1

[0059] This embodiment is an example sp 2 Carbon conjugated two-dimensional polymer films sp 2 The preparation of c-2DPDB includes the following steps:

[0060] (1) System assembly: 1-decyl-2,4,6-trimethylpyridinium (0.02 mmol) and 3,3′-dihydroxy-[1,1′-biphenyl]-4,4′-dicarboxaldehyde (0.014 mmol) were dissolved in 10 mL of water and o-dichlorobenzene, respectively. After the monomers were ultrasonically dispersed evenly, they were mixed in a 20 mL glass bottle to form a liquid-liquid interface reaction system. Then piperidine (0.03 mmol) was added and the glass bottle was heated at 80 °C for 72 hours.

[0061] (2) Post-reaction treatment: After the reaction was completed, the product was washed with ethanol, acetone and tetrahydrofuran solvent, and dried under vacuum to obtain sp. 2 c-2DP DB .

[0062] The sp obtained in this embodiment 2 Infrared spectral characterization results of carbon conjugated two-dimensional polymer films are as follows: Figure 3 As shown, 970cm -1 And 1631cm -1 The infrared vibrational peak at the sp position indicates the formation of a carbon-carbon double bond. 2 c-2DP DB Small-angle X-ray scattering spectra as follows Figure 4 As shown in the figure, the film exhibits good crystallinity. Figure 5 For sp 2 c-2DP DB The solid-state carbon NMR spectrum shows that the peak positions match the theoretical structure, proving that carbon sp. 2 c-2DP DB Successful preparation of thin films. Figure 6 Photocurrent testing shows that sp 2 c-2DP DB It exhibits excellent salt concentration gradient energy conversion performance, with an output power density reaching 51.4 W / m³. -2 .

[0063] Comparative Example 1

[0064] This comparative example is largely the same as Example 1, with the main difference being:

[0065] The methyl monomer was replaced with 2,4,6-trimethylpyridine, which is equivalent to the precursor of the methyl monomer in Example 1 without side chain R modification.

[0066] As a result, the reaction temperature needs to be raised to 100°C but the interfacial polymerization reaction still cannot occur; and apart from the temperature difference, the other reaction processes, ratios and other conditions are kept the same, and ultimately a thin film product cannot be obtained.

[0067] Comparative Example 2

[0068] This comparative example is largely the same as Example 1, with the main difference being:

[0069] The methyl monomer was replaced with 3-decyl-2,4,6-trimethylpyridine, which has the same side chain R modification and a similar trimethyl structure as the methyl monomer in Example 1, but is not amphiphilic.

[0070] In the comparative cases above, the monomers whose functional side chains are not attached to nitrogen atoms lack amphiphilicity, resulting in insufficient reactivity. Based on theoretical experience, they require temperatures of approximately 150°C to react and form a powder product, which exceeds the temperature range used in liquid-liquid interface systems (the boiling point of water). Consequently, even raising the reaction temperature to 100°C did not allow interfacial polymerization to occur; furthermore, aside from the temperature difference, all other reaction processes and formulations remained consistent, ultimately failing to yield a thin film product.

[0071] Example 2

[0072] This embodiment is an example sp 2 Carbon conjugated two-dimensional polymer films sp 2 c-2DP DF The preparation of [the substance] includes the following steps:

[0073] (1) System assembly: 1-decylalkyl-2,4,6-trimethylpyridinium (0.02 mmol) and 2,3,5,6-tetrafluoroterephthalaldehyde (0.12 mmol) were dissolved in 10 mL of water and o-dichlorobenzene, respectively. After the monomers were ultrasonically dispersed evenly, they were mixed in a 20 mL glass bottle to form a liquid-liquid interface reaction system. Then 4-dimethylaminopyridine (0.04 mmol) was added and the glass bottle was reacted at 25 °C for 3 minutes.

[0074] (2) Post-reaction treatment: After the reaction was completed, the product was washed with ethanol, acetone and tetrahydrofuran solvent, and dried under vacuum to obtain sp. 2 c-2DP DF .

[0075] The single-layer sp obtained in this embodiment 2 The thickness of the carbon conjugated two-dimensional polymer film is ~1 nm (e.g. Figure 2 (As shown)

[0076] Example 3

[0077] This embodiment is an example sp 2 Carbon conjugated two-dimensional polymer films sp 2 The preparation of c-2DP-3 includes the following steps:

[0078] (1) System assembly: 1-decyl-2,4,6-trimethylpyridinium (0.02 mmol) and 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine (0.02 mmol) were dissolved in 10 mL of water and o-dichlorobenzene, respectively. After the monomers were ultrasonically dispersed evenly, they were mixed in a 20 mL glass bottle to form a liquid-liquid interface reaction system. Then piperidine (0.03 mmol) was added and the glass bottle was heated at 80 °C for 72 hours.

[0079] (2) Post-reaction treatment: After the reaction was completed, the product was washed with ethanol, acetone and tetrahydrofuran solvent, and dried under vacuum to obtain sp. 2 c-2DP-3.

[0080] Example 4

[0081] This embodiment is an example sp 2 Carbon conjugated two-dimensional polymer films sp 2 The preparation of c-2DP-4 includes the following steps:

[0082] (1) System assembly: 1-hexadecyl-2,4,6-trimethylpyridinium (0.02 mmol) and 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine (0.01 mmol) were dissolved in 10 mL of water and o-dichlorobenzene, respectively. After the monomers were ultrasonically dispersed evenly, they were mixed in a 20 mL glass bottle to form a liquid-liquid interface reaction system. Then piperidine (0.03 mmol) was added and the glass bottle was reacted at 2C for 120 hours.

[0083] (2) Post-reaction treatment: After the reaction was completed, the product was washed with ethanol, acetone and tetrahydrofuran solvent, and dried under vacuum to obtain sp. 2 c-2DP-4.

[0084] Example 5

[0085] This embodiment is an example sp 2 Carbon conjugated two-dimensional polymer films sp 2 The preparation of c-2DP-5 includes the following steps:

[0086] (1) System assembly: 1-hexadecyl-2,4,6-trimethylpyridinium (0.02 mmol) and 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine (0.01 mmol) were dissolved in 10 mL of water and o-dichlorobenzene, respectively. After the monomers were ultrasonically dispersed evenly, they were mixed in a 20 mL glass bottle to form a liquid-liquid interface reaction system. Then piperidine (0.03 mmol) was added and the glass bottle was reacted at 25 °C for 72 hours.

[0087] (2) Post-reaction treatment: After the reaction was completed, the product was washed with ethanol, acetone and tetrahydrofuran solvent, and dried under vacuum to obtain sp. 2 c-2DP-5.

[0088] Example 6

[0089] This embodiment is an example sp 2 Carbon conjugated two-dimensional polymer films sp 2 The preparation of c-2DP-6 includes the following steps:

[0090] (1) System assembly: 1-decyl-3,6-dimethylpyridazine-1-onium (0.03 mmol) and 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine (0.02 mmol) were dissolved in 10 mL of water and o-dichlorobenzene, respectively. After the monomers were ultrasonically dispersed evenly, they were mixed in a 20 mL glass bottle to form a liquid-liquid interface reaction system. Then piperidine (0.03 mmol) was added and the glass bottle was heated at 80 °C for 72 hours.

[0091] (2) Post-reaction treatment: After the reaction was completed, the product was washed with ethanol, acetone and tetrahydrofuran solvent, and dried under vacuum to obtain sp. 2 c-2DP-6.

[0092] Example 7

[0093] This embodiment is an example sp 2 Carbon conjugated two-dimensional polymer films sp 2 The preparation of c-2DP-7 includes the following steps:

[0094] (1) System assembly: 1-ethyl-2,4,6-trimethylpyridinium (0.02 mmol) and 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine (0.02 mmol) were dissolved in 10 mL of water and mesitylene, respectively. After the monomers were ultrasonically dispersed evenly, they were mixed in a 20 mL glass bottle to form a liquid-liquid interface reaction system. Then piperidine (0.03 mmol) was added and the glass bottle was heated at 80 °C for 72 hours.

[0095] (2) Post-reaction treatment: After the reaction was completed, the product was washed with ethanol, acetone and tetrahydrofuran solvent, and dried under vacuum to obtain sp. 2 c-2DP-7.

[0096] Example 8

[0097] This embodiment is an example sp 2 Carbon conjugated two-dimensional polymer films sp 2 The preparation of c-2DP-8 includes the following steps:

[0098] (1) System assembly: 1-hexadecyl-2,6-dimethylpyridinium (0.03 mmol) and 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine (0.02 mmol) were dissolved in 10 mL of water and o-dichlorobenzene, respectively. After the monomers were ultrasonically dispersed evenly, they were mixed in a 20 mL glass bottle to form a liquid-liquid interface reaction system. Then piperidine (0.015 mmol) was added and the glass bottle was heated at 80 °C for 2 hours.

[0099] (2) Post-reaction treatment: After the reaction was completed, the product was washed with ethanol, acetone and tetrahydrofuran solvent, and dried under vacuum to obtain sp. 2 c-2DP-8.

[0100] Example 9

[0101] This embodiment is an example sp 2 Carbon conjugated two-dimensional polymer films sp 2 The preparation of c-2DP-9 includes the following steps:

[0102] (1) System assembly: 1-hexadecyl-2,3,5,6-tetramethylpyrazine (0.02 mmol) and 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine (0.01 mmol) were dissolved in 10 mL of water and o-dichlorobenzene, respectively. After the monomers were ultrasonically dispersed evenly, they were mixed in a 20 mL glass bottle to form a liquid-liquid interface reaction system. Then 4-dimethylaminopyridine (0.04 mmol) was added and the glass bottle was heated at 80 °C for 72 hours.

[0103] (2) Post-reaction treatment: After the reaction was completed, the product was washed with ethanol, acetone and tetrahydrofuran solvent, and dried under vacuum to obtain sp. 2 c-2DP-9.

[0104] Example 10

[0105] This embodiment is an example sp 2 Carbon conjugated two-dimensional polymer films sp 2 The preparation of c-2DP-9 includes the following steps:

[0106] (1) System assembly: 1-hexadecyl-2,4,6-trimethylpyridinium (0.02 mmol) and 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine (0.02 mmol) were dissolved in 10 mL of water and mesitylene, respectively. After the monomers were ultrasonically dispersed evenly, they were mixed in a 20 mL glass bottle to form a liquid-liquid interface reaction system. Then sodium hydroxide (0.2 mmol) was added and the glass bottle was heated at 80 °C for 72 hours.

[0107] (2) Post-reaction treatment: After the reaction was completed, the product was washed with ethanol, acetone and tetrahydrofuran solvent, and dried under vacuum to obtain sp. 2 c-2DP-10.

[0108] The various sp prepared in the above embodiments 2 The carbon conjugated two-dimensional polymer films all possess the characteristics of being ultrathin and having high crystallinity. Furthermore, the inventors of this invention also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the foregoing embodiments, and obtained relatively ideal results in all cases.

[0109] Based on the above embodiments and comparative examples, it can be clearly understood that the sp used in the embodiments of the present invention 2 A method for preparing carbon-conjugated two-dimensional polymer films involves quaternization reactions to modify the side chains of various functional monomers, thereby synthesizing amphiphilic methyl monomers. These methyl monomers are applicable to various interfaces and catalytic systems, leading to the synthesis of various sp... 2 Carbon conjugated two-dimensional polymer films were used to obtain a series of conjugated porous polymers with excellent thermal stability and active sites, which can be widely used in photoelectrocatalysis, sensing, separation, energy conversion and other fields.

[0110] It should be understood that the above embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A crystalline sp 2 A method for preparing carbon conjugated two-dimensional polymer films, characterized in that, include: A periodic porous molecular structure formed by polymerizing the first and second monomers through an aldol condensation reaction; The first monomer is an amphiphilic methyl monomer with a functional side chain, and the amphiphilic methyl monomer has multiple methyl functional groups; The second monomer is an aldehyde monomer, and the aldehyde monomer has multiple aldehyde functional groups.

2. The preparation method according to claim 1, characterized in that, The sp 2 Carbon conjugated two-dimensional polymer films have a fully conjugated structure; And / or, the crystalline sp 2 The thickness of carbon conjugated two-dimensional polymer films ranges from 1 to 200 nm; Preferably, the crystalline sp 2 Carbon-conjugated two-dimensional polymer films can be selectively prepared as monolayers or multilayers, wherein the monolayer crystalline sp 2 The thickness of the carbon conjugated two-dimensional polymer film is 1 nm; And / or, the sp 2 The area of ​​carbon conjugated two-dimensional polymer films ranges from 1 to 100 cm². 2 ; And / or, the functional side chain has an alkyl chain, the alkyl chain having 2-16 carbon atoms.

3. The preparation method according to claim 1, characterized in that, Specifically, it includes: The first monomer and the second monomer are dissolved in a first liquid phase and a second liquid phase that are immiscible, respectively; Under the catalytic action of the catalyst, the first monomer and the second monomer undergo an interfacial polymerization reaction at the interface between the first liquid phase and the second liquid phase to generate the crystalline sp. 2 Carbon conjugated two-dimensional polymer film.

4. The preparation method according to claim 1 or 3, characterized in that, The first monomer includes any one or more of the compounds shown in the following formula: Wherein, X is selected from any one or a combination of two or more of carbon, sulfur, oxygen, nitrogen, and hydrogen; Y is selected from any one or a combination of two of bromine and iodine; R represents the functional side chain, including C2 to C3. 16 Alkyl chains, alkoxy chains, perfluoroalkyl chains, and alkyl chains linked by oxygen or benzene rings.

5. The preparation method according to claim 1, characterized in that, The functional side chain R includes any one or more combinations of the molecular structures shown in the following formula:

6. The preparation method according to claim 1, characterized in that The second monomer includes pyromellitic pyrrolizaldehyde, 2,4,6-tris(4-aldehydephenyl)-1,3,5-triazine, 2,2′-bipyridine-4,4′-dicarboxaldehyde, [2,2′-bipyridine]-6,6′-dicarboxaldehyde, 5′-(4-formylphenyl)-[1,1′:3′,1″-triphenyl]-4,4"-dicarboxaldehyde, trialdehyde-resorcinol, [1,1′-biphenyl]-3,3′,5,5′-tetracarboxaldehyde, 3,3'-dihydroxy-[1,1′-biphenyl]-4,4'-dicarboxaldehyde, 1,3,6,8-tetra(4-formylphenyl)pyrene, 4,4′,4″,4″′-(ethylene-1,1,2,2-tetrayl)tetrabenzaldehyde, 4,4 ′,4″-(pyrimidin-2,4,6-triyl)tribenzaldehyde, 1,3,5-tris(3,3″,3″′-trifluoro-4′,4″,4″′-tri(p-formylphenyl)benzene, 2,5-difluoroterephthalaldehyde, 2,5-dihydroxyterephthalaldehyde, 5,5′,5″-(benzene-1,3,5-triyl)tri(thiophene-2-carboxaldehyde), pyrazine-2,5-dicarboxaldehyde, 1,3,5-tris(2-formylpyridin-5-yl)benzene, 5,5′,5″-(benzene-1,3,5-triyl)tri(pyridine-2-carboxaldehyde), 3,3′-bipyridine-6,6′-dicarboxaldehyde, 2,3,5,6-tetrafluoroterephthalaldehyde, or any combination of two or more of these.

7. The preparation method according to claim 1, characterized in that, The catalyst comprises any one or a combination of two or more of the following: trifluoroacetic acid, trifluoromethanesulfonic acid, trichloroacetic acid, trichloromethanesulfonic acid, p-toluenesulfonic acid, p-chlorobenzenesulfonic acid, m-methylbenzoic acid, pyromellitic acid, terephthalic acid, piperidine, pyridine, pyrrole, 4-dimethylaminopyridine, pyrrolidine, sodium hydroxide, potassium hydroxide, calcium hydroxide, and cesium carbonate.

8. The preparation method according to claim 1, characterized in that, The interfacial polymerization reaction is carried out at a temperature of 2–80°C for a time of 2–120 h. And / or, the molar ratio of the first monomer to the second monomer is 1:(0.5-6); And / or, the molar ratio of the first monomer to the catalyst is 1:(0.5 to 10).

9. The preparation method according to claim 1, characterized in that, It also includes, after the interfacial polymerization reaction is completed, the obtained crystalline sp 2 The steps of cleaning and vacuum drying carbon conjugated two-dimensional polymer films.

10. The crystalline sp prepared by the preparation method according to any one of claims 1-9 2 Applications of carbon conjugated two-dimensional polymer films in material separation or energy conversion; Preferably, the substance separation includes seawater desalination and ion sieving, and the energy conversion includes salt concentration gradient energy conversion.

Images