An sp derived from a carbonyl monomer 2 Carbon conjugated polymers, methods for their preparation and use

Abstract

This invention relates to an sp derived from a carbonyl monomer. 2 -Carbon conjugated polymers, their preparation methods, and applications belong to the field of polymer material preparation technology. The preparation method includes: carrying out a polymerization reaction on a mixed reaction system comprising a carbonyl monomer, an aldehyde monomer, and a catalyst to obtain sp... derived from the carbonyl monomer. 2 -Carbon conjugated polymers. The prepared sp 2 -Carbon conjugated polymers have excellent photoelectric activity and can be widely used in gas storage and separation, sensor technology, photoelectrocatalysis, batteries and electrochemical energy storage.

Description

Technical Field

[0001] This invention relates to an sp derived from a carbonyl monomer. 2 - Carbon conjugated polymers, their preparation methods and applications, belong to the field of polymer material preparation technology. Background Technology

[0002] Due to the depletion of traditional energy sources and the increasing global energy demand, the development of alternative energy sources has received considerable attention. Obtaining energy chemicals from renewable biomass resources, reducing reliance on petroleum and other petrochemical resources, has significant scientific importance and application prospects. Carbohydrates are a major component of biomass resources; through hydrolysis and dehydration, bio-based platform compounds, namely, high-molecular-weight chemical monomers such as cyclopentanone and cyclohexanone, can be efficiently obtained. Furthermore, the technology for preparing cyclopentanone and cyclohexanone from waste, inexpensive biomass resources (such as corn cobs, sugarcane bagasse, and cottonseed hulls) is gradually maturing.

[0003] Conjugated porous polymers are a class of organic porous polymer materials linked by covalent bonds, characterized by low density, large specific surface area, good thermal stability, abundant active sites, and ordered structure. Through monomer design and geometric configuration design, conjugated polymers can achieve complete pre-control of structure and pre-design of functional groups, making them widely applicable in gas storage and separation, catalysis, energy storage and conversion, semiconductors, luminescence, sensing, and drug delivery.

[0004] In recent years, conjugated porous polymers have developed rapidly. Among them, borate ester-linked conjugated porous polymers formed by boric acid condensation have high crystallinity, but these boronic acid ester-linked polymers are unstable in water and decompose completely. Similarly, dynamically reversible imine-linked conjugated polymers formed by Schiff base reactions cannot resist hydrolysis in strong acids and bases. In contrast, carbon-carbon double-bonded conjugated porous polymers formed by Knauvengel condensation and aldol condensation have strong chemical stability, and their reaction systems have gradually matured and are widely used. However, the limited number of reaction systems restricts the development of applicable monomers and polymer types, making it difficult to meet the diverse needs of polymer materials. In addition, current reaction systems use single and expensive monomers, require harsh reaction conditions, and have long reaction times. Therefore, introducing new, simple, and rapid chemical reactions, developing new conjugated polymer reaction systems, and expanding the application fields of conjugated polymers is an urgent problem to be solved. Summary of the Invention

[0005] To address the aforementioned problems in the prior art, the present invention aims to provide an sp derived from a carbonyl monomer. 2 - Carbon conjugated polymers, their preparation methods and applications, to overcome the shortcomings of existing technologies.

[0006] One objective of this invention is achieved through the following technical solution:

[0007] A sp derived from carbonyl monomers 2 A method for preparing a carbon conjugated polymer includes: subjecting a mixed reaction system comprising a carbonyl monomer, an aldehyde monomer, and a catalyst to a polymerization reaction to obtain a carbonyl monomer-derived sp... 2 -Carbon conjugated polymer;

[0008] The carbonyl monomer is a cyclic ketone;

[0009] The aldehyde monomer is a compound containing a cyclic structure and two or more aldehyde groups.

[0010] Preferably, the carbonyl monomer is a cyclic ketone derived from biomass.

[0011] Preferably, the cyclic ketone is cyclopentanone and / or cyclohexanone.

[0012] Preferably, the aldehyde monomer is a compound containing a cyclic structure and two aldehyde groups, including one or more of the following structures:

[0013]

[0014] Wherein, R1 is selected from one of fluorine, chlorine, bromine, methyl, methoxy, ethoxy, and hydroxyl; R2 is selected from one of fluorine, chlorine, bromine, hydroxyl, and nitro; and X is selected from one of N, O, and S.

[0015] Alternatively, the aldehyde monomer is a compound containing a cyclic structure and three aldehyde groups, including one or more of the following structures:

[0016]

[0017] Wherein, R is selected from one of fluorine, chlorine, bromine, methoxy, ethoxy, and hydroxyl, X is C and / or N, and Y is N and / or P;

[0018] Alternatively, the aldehyde monomer is a compound containing a cyclic structure and four aldehyde groups, including one or more of the following structures:

[0019]

[0020] Preferably, the aldehyde monomer includes terephthalaldehyde, 2,5-dimethylbenzene-1,4-dicarboxaldehyde, 2,5-dihydroxyterephthalaldehyde, 2,5-difluoroterephthalaldehyde, 2,5-dichloroterephthalaldehyde, 2,5-diethoxyterephthalaldehyde, 2,5-dibromobenzene-1,4-dicarboxaldehyde, 2,5-dimethoxybenzene-1,4-dicarboxaldehyde, 1-pyrrole-2,5-dicarboxaldehyde, 2,5-dicarboxylofuran, thiophene-2,5-dicarboxaldehyde, 2-hydroxyterephthalaldehyde, 2-nitroterephthalaldehyde, 2-bromoterephthalaldehyde, naphthalene-2,6-dicarboxaldehyde, 9,10-anthracitedicarboxaldehyde, thieno[3,2-b]thiophene-2,5-dicarboxaldehyde, and 4,4'-(thiazo[5,4-d]thiazolyl-2,5-dicarboxaldehyde). -diyl)dibenzaldehyde, 4,4'-(acetyl-1,2-diyl)dibenzaldehyde, 4,4'-(but-1,3-diyne-1,4-diyl)dibenzaldehyde, [1,1':4',1”-terphenyl]-4,4”-dicarbaldehyde, 4,4'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzaldehyde, 4,4'-( Anthracene-9,10-diyl)dibenzaldehyde, 4,4'-(pyrene-1,6-diyl)dibenzaldehyde, pyromellitic pyrogallol, trialdehyde-2,4,6-tricarboxymethylbenzene, 2,4,6-trichlorophenyl-1,3,5-tricarboxaldehyde, 4,4',4”-phosphotrimethyltribenzaldehyde, 4,4',4”-nitrotribenzaldehyde, Benzo[1,2-b:3,4-b':5,6-b']trithiophene-2,5,8-trialdehyde, 5'-(4-formylphenyl)-[1,1':3',1”-triphenyl]-4,4”-dicarboxaldehyde (also known as 1,3,5-tris(p-formylphenyl)benzene, 5,5',5”-(benzene-1,3,5-triyl)tri(pyridine-2-carboxaldehyde), 4,4',4”-(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde, 4,4',4”-((1,3,5-triazine-2,4,6-triyl)tri(oxy))tribenzaldehyde, 4,4',4”-[benzene-1,3,5-triyltri(acetylene-2,1-diyl)]tribenzaldehyde, 5,5',5”-(benzene-1,3 ,5-triyl)tri(thiophene-2-carboxaldehyde), 5,5',5”-(triazine-2,4,6-triyl)tri([1,1'-biphenyl]-4-carboxaldehyde)), tri(4-aldehyde-biphenyl)amine, 4',4”',4””'-(1,3,5-triazine-2,4,6-triyl)tri(([1,1'-biphenyl]-4-carboxaldehyde)), [1,1'-biphenyl]-3,3',5,5'-tetracarboxaldehyde, 5,5'-(ynyne-1,2-diyl)di-m-phenylenedialdehyde, [1,1':4',1”-triphenyl]-3,3”,5,5”-tetracarboxaldehyde, 5,5'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)di-m-phenylenedialdehyde, 5,5'-(1,4-phenylenebis(acetylene-2,1-Dimethyl))di-isophthalaldehyde, [1,1':4',1”:4”,1”'-tetraphenyl]-3,3”',5,5”'-tetracarboxaldehyde, 4,4',4”,4”'-(ethylene-1,1,2,2-tetramethyl)tetrabenzaldehyde, 1,2,4,5-tetra(4-formylphenyl)benzene, 4,4',4”,4”'-([1,1'-biphenyl]-4,4'-dimethylbis( The following are all of the following: (azatriyl)tetrabenzaldehyde, 2,3,6,7-tetra(4-formylphenyl)tetrathiofulvalene, 1,3,6,8-tetra(4-formylphenyl)pyrene, and 4”,5”-bis(4'-formyl-[1,1'-biphenyl]-4-yl)-[1,1':4',1”:2”,1”':4”',1””-pentaphenyl]-4,4””-dicarboxaldehyde.

[0021] Preferably, the catalyst is an alkaline catalyst; more preferably, the alkaline catalyst includes any one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, pyridine, and piperidine.

[0022] Preferably, the molar ratio of carbonyl monomer to aldehyde monomer is (1-50):1.

[0023] Preferably, the molar ratio of carbonyl monomer to alkaline catalyst is 1:(0.1-100).

[0024] Preferably, the polymerization reaction is carried out under one or more of the following conditions: shaking, ultrasound, and microwave.

[0025] Preferably, the polymerization reaction is carried out at a temperature of 0–100°C for a time of 1–1000 s.

[0026] More preferably, the polymerization reaction is carried out at a temperature of 5–80°C for a time of 2–600 s.

[0027] Preferably, the sp prepared by the preparation method 2 - Carbon conjugated polymers generate photocurrent densities of 1–100 μA / cm² under illumination with wavelengths >400 nm. 2 .

[0028] The second objective of this invention is achieved through the following technical solution:

[0029] A sp derived from carbonyl monomers 2 -Carbon conjugated polymer, the sp 2 - Carbon conjugated polymers are obtained by polymerization in a mixed reaction system including carbonyl monomers, aldehyde monomers and catalysts;

[0030] The carbonyl monomer is a cyclic ketone;

[0031] The aldehyde monomer is a compound containing a cyclic structure and two or more aldehyde groups.

[0032] Preferably, the sp 2 - Carbon conjugated polymers generate photocurrent densities of 1–100 μA / cm² under illumination with wavelengths >400 nm. 2 .

[0033] The third objective of this invention is achieved through the following technical solution:

[0034] The aforementioned sp derived from carbonyl monomers 2 Applications of carbon conjugated polymers in gas storage and separation, optoelectronic devices, photocatalysts, and energy storage.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) This invention is based on the preparation of sp from carbonyl monomers. 2 - In carbon-conjugated polymers, the O atom in the carbonyl group of the carbonyl monomer strongly attracts electrons. Therefore, the electron cloud of the carbon-oxygen double bond is concentrated around the oxygen atom, while the carbon atom is relatively electron-depleted, making it more susceptible to nucleophilic substitution. This facilitates the preparation of sp... 2 - Carbon conjugated polymers offer possibilities.

[0037] (2) The carbonyl monomer used in this invention can be derived from cheap and abundant biomass resources, and the entire preparation method is more green and environmentally friendly.

[0038] (3) This invention uses carbonyl monomers as raw materials, selects suitable aldehyde monomers and alkaline catalysts, and can synthesize a series of sps with electrochemical properties. 2 - Carbon conjugated polymer.

[0039] (4) The polymerization reaction of the present invention can be completed rapidly, through the rapid synthesis of sp 2 The carbonyl groups on the sp2-carbon conjugated polymer backbone can form poles, which are delocalized into the entire backbone to form a p-electron conjugated structure, thereby improving the photoelectric activity of the synthesized sp2-carbon conjugated polymer.

[0040] (5) The sp2-carbon conjugated polymer prepared by this invention has the characteristics of high specific surface area, porous structure, low density, and good stability. The carbonyl groups on its polymer backbone can form polar delocalization to form a p-electron conjugated structure throughout the entire backbone, which improves the synthesized sp2-carbon conjugated structure. 2 The photoelectric activity of carbon conjugated polymers enables the preparation of a series of sp... 2 - Carbon conjugated polymers can be widely used in gas storage and separation, sensor technology, photoelectrocatalysis, batteries and electrochemical energy storage. Attached Figure Description

[0041] Figure 1The sp prepared in Example 1 of this invention 2 - The 1H NMR spectrum of the carbon conjugated polymer POP-DF;

[0042] Figure 2 The sp prepared in Example 1 of this invention 2 -Infrared spectrum of carbon conjugated polymer POP-DF;

[0043] Figure 3 The sp prepared in Example 1 of this invention 2 -UV-Vis absorption spectrum of carbon conjugated polymer POP-DF;

[0044] Figure 4 The sp prepared in Example 1 of this invention 2 -Thermogravimetric diagram of carbon conjugated polymer POP-DF;

[0045] Figure 5 The sp prepared in Example 1 of this invention 2 - Photocurrent density-time curve of carbon conjugated polymer POP-DF. Detailed Implementation

[0046] In view of the problems of existing technologies, the inventors, through long-term research and extensive practice, have proposed the technical solution of this invention. Its main function is to provide suitable carbonyl monomers, and by selecting appropriate aldehyde monomers and alkaline catalysts, a series of sps with electrochemical properties can be synthesized. 2 - Carbon conjugated porous polymer. The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments, and the disclosure of the present invention is not limited thereto.

[0047] One aspect of the present invention provides an sp derived from a carbonyl monomer. 2 A method for preparing a carbon conjugated polymer, the method comprising: subjecting a mixed reaction system including a carbonyl monomer, an aldehyde monomer, and a catalyst to a polymerization reaction to obtain a sp from the carbonyl monomer. 2 -Carbon conjugated polymer;

[0048] The carbonyl monomer is a cyclic ketone; the aldehyde monomer is a compound containing a cyclic structure and two or more aldehyde groups.

[0049] In some embodiments of the present invention, the carbonyl monomer is a cyclic ketone derived from biomass.

[0050] By way of example, the cyclic ketone may be one or more of cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone.

[0051] Preferably, the cyclic ketone is cyclopentanone and / or cyclohexanone.

[0052] In some embodiments of the present invention, the aldehyde monomer is a compound containing a cyclic structure and two aldehyde groups, including but not limited to one or more combinations of the following structures:

[0053]

[0054] R1 is selected from one of fluorine, chlorine, bromine, methyl, methoxy, ethoxy, and hydroxyl; R2 is selected from one of fluorine, chlorine, bromine, hydroxyl, and nitro; and X is selected from one of N, O, and S.

[0055] In some embodiments of the present invention, the aldehyde monomer is a compound containing a cyclic structure and three aldehyde groups, including but not limited to one or more combinations of the following structures:

[0056]

[0057] Wherein, R is selected from one of fluorine, chlorine, bromine, methoxy, ethoxy, and hydroxyl, X is C and / or N, and Y is N and / or P.

[0058] In some embodiments of the present invention, the aldehyde monomer is a compound containing a cyclic structure and four aldehyde groups, including but not limited to one or more combinations of the following structures:

[0059]

[0060] In some more specific embodiments of the present invention, the aldehyde monomer includes, but is not limited to, terephthalaldehyde, 2,5-dimethylbenzene-1,4-dicarboxaldehyde, 2,5-dihydroxyterephthalaldehyde, 2,5-difluoroterephthalaldehyde, 2,5-dichloroterephthalaldehyde, 2,5-diethoxyterephthalaldehyde, 2,5-dibromobenzene-1,4-dicarboxaldehyde, 2,5-dimethoxybenzene-1,4-dicarboxaldehyde, 1-pyrrole-2,5-dicarboxaldehyde, 2,5-dicarboxylated furan, thiophene-2,5-dicarboxaldehyde, 2-hydroxyterephthalaldehyde, 2-nitroterephthalaldehyde, 2-bromoterephthalaldehyde, naphthalene-2,6-dicarboxaldehyde, 9,10-anthracitedicarboxaldehyde, thieno[3,2-b]thiophene-2,5-dicarboxaldehyde, 4,4'-( Thiazolo[5,4-d]thiazolyl-2,5-diyl)dibenzaldehyde, 4,4'-(acetylene-1,2-diyl)dibenzaldehyde, 4,4'-(but-1,3-diyne-1,4-diyl)dibenzaldehyde, [1,1':4',1”-terphenyl]-4,4”-dicarboxaldehyde, 4,4'-(benzo[c][1,2,5]thiadiazole-4,7) 4,4'-(anthracene-9,10-diyl)diphenylaldehyde, 4,4'-(pyrene-1,6-diyl)diphenylaldehyde, pyromellitic trimethylaldehyde, trialdehyde-2,4,6-tricarboxymethylbenzene, 2,4,6-trichlorophenyl-1,3,5-trimethylbenzene, 4,4',4”-phosphotrimethyltriphenylaldehyde, 4,4',4”-Nitrogen-based tribenzaldehyde, benzo[1,2-b:3,4-b':5,6-b']trithiophene-2,5,8-trialdehyde, 5'-(4-formylphenyl)-[1,1':3',1”-triphenyl]-4,4”-dicarboxaldehyde (also known as 1,3,5-tris(p-formylphenyl)benzene, 5,5',5”-(benzene-1,3,5-triyl)tri(pyridine-2-carboxaldehyde), 4,4',4”-(1,3,5-triazinecyclo-2,4,6-triyl)tribenzaldehyde, 4,4',4”-((1,3,5-triazine-2,4,6-triyl)tri(oxy))tribenzaldehyde, 4,4',4”-[benzene-1,3,5-triyltri(acetylene-2,1-diyl)]tribenzaldehyde, 5 ,5',5”-(benzene-1,3,5-triyl)tri(thiophene-2-carboxaldehyde), 5,5',5”-(nitrotri(benzene-4,1-diyl))tri(thiophene-2-carboxaldehyde), tri(4-aldehyde-biphenyl)amine, 4',4”',4””'-(1,3,5-triazine-2,4,6-triyl)tri(([1,1'-biphenyl]-4-carboxaldehyde)), [1,1'-biphenyl]-3,3',5,5'-tetracarboxaldehyde, 5,5'-(ynyne-1,2-diyl)di-m-phenylenedialdehyde, [1,1':4',1”-terphenyl]-3,3”,5,5”-tetracarboxaldehyde, 5,5'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)di-m-phenylenedialdehyde, 5,5'-(1,4-Phenylidene bis(acetylene-2,1-diyl))di-m-phenylenedialdehyde, [1,1':4',1”:4”,1”'-tetraphenyl]-3,3”',5,5”'-tetracarboxaldehyde, 4,4',4”,4”'-(ethylene-1,1,2,2-tetraphenyl)tetrabenzaldehyde, 1,2,4,5-tetra(4-formylphenyl)benzene, 4,4',4”,4”'-([1,1'-biphenyl]-4,4 The following are any one or more of the following: '-dimethylbis(azatriyl))tetrabenzaldehyde, 2,3,6,7-tetra(4-formylphenyl)tetrathiofulvalene, 1,3,6,8-tetra(4-formylphenyl)pyrene, 4”,5”-bis(4'-formyl-[1,1'-biphenyl]-4-yl)-[1,1':4',1”':4”',1””-pentaphenyl]-4,4””-dicarboxaldehyde.

[0061] Further, the aldehyde monomer is any one or more of terephthalaldehyde, 2,5-dicarboxyfuran, naphthalene-2,6-dicarboxaldehyde, pyromellitic pyrogallol, trialdehyde-resorcinol, 2,4,6-trichlorophenyl-1,3,5-tricarboxaldehyde, 4,4',4”-(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde, 5'-(4-formylphenyl)-[1,1':3',1”-triphenyl]-4,4”-dicarboxaldehyde, [1,1'-biphenyl]-3,3',5,5'-tetracarboxaldehyde, and 1,3,6,8-tetra(4-formylphenyl)pyrene.

[0062] In some embodiments of the present invention, the catalyst is a basic catalyst, which includes inorganic basic catalysts and / or organic basic catalysts. The basic catalyst includes, but is not limited to, any one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, pyridine, and piperidine.

[0063] In some embodiments of the present invention, the catalyst is optionally added in solution form, that is, the catalyst is first dissolved in water to form a catalyst aqueous solution, and then the catalyst aqueous solution is added.

[0064] In some embodiments of the present invention, the molar ratio of carbonyl monomer to aldehyde monomer is (1-50):1, for example, it can be 1:1, 2:1, 5:1, 8:1, 10:1, 15:1, 18:1, 20:1, 23:1, 25:1, 30:1, 35:1, 38:1, 40:1, 43:1, 45:1, 48:1, or 50:1, but is not limited to the listed values; other unlisted ratios within the numerical range are also applicable. The molar ratio of carbonyl monomer to aldehyde monomer is specifically determined according to the number of aldehyde groups in the aldehyde monomer.

[0065] Furthermore, the molar ratio of carbonyl monomer to aldehyde monomer is (1-5):1.

[0066] In some embodiments of the present invention, the molar ratio of the carbonyl monomer to the basic catalyst is 1:(0.1 to 100). For example, it can be 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, 1:5, 1:8, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, 1:80, 1:85, 1:90, 1:95, or 1:100, but is not limited to the listed values; other unlisted ratios within the numerical range are also applicable.

[0067] Furthermore, the molar ratio of carbonyl monomer to alkaline catalyst is 1:(0.5-50).

[0068] In some embodiments of the present invention, the mixed reaction system further includes a solvent. Optionally, the solvent is one or more selected from water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, o-dichlorobenzene, 1,4-dioxane, mesitylene, etc.

[0069] In some embodiments of the invention, the polymerization reaction is carried out under one or more of the following conditions: shaking, ultrasonication, and microwave.

[0070] The shaking speed can be listed as 10 to 5000 r / min, for example, it can be 10, 20, 30, 40, 50, 60, 80, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 2000, 3000, 4000 or 5000 r / min.

[0071] The power of ultrasound can be listed from 10 to 1000W, for example, 10, 50, 80, 100, 150, 180, 200, 220, 250, 280, 300, 330, 350, 380, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950 or 1000W. The frequency of ultrasound can be listed from 20 to 100kHz, for example, 20, 30, 40, 50, 60, 70, 80, 90 or 100kHz.

[0072] Microwave power can be listed in the range of 50 to 1000W, for example, it can be 50, 80, 100, 150, 180, 200, 220, 250, 280, 300, 330, 350, 380, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950 or 1000W.

[0073] The parameters for shaking, ultrasound, and microwave are listed above only and are not intended to limit the scope of protection of this invention.

[0074] In some embodiments of the present invention, the temperature of the polymerization reaction is 0 to 100°C, for example, it can be 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 70, 80, 90, or 100°C.

[0075] Optionally, the polymerization reaction temperature is 5–80°C; alternatively, the polymerization reaction temperature is 5–40°C. The polymerization reaction of the present invention can be carried out at room temperature.

[0076] In some embodiments of the present invention, the polymerization reaction time is 1 to 1000 s, for example, it can be 1, 2, 5, 8, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 500, 800 or 1000 s.

[0077] Optionally, the polymerization reaction time is 2–600 s; alternatively, the polymerization reaction time is 3–60 s. The raw materials of the present invention complete the polymerization reaction in an extremely short time, resulting in the rapid synthesis of sp... 2 The carbonyl groups on the sp2-carbon conjugated polymer backbone can form poles, which are delocalized into the entire backbone to form a p-electron conjugated structure, thereby improving the photoelectric activity of the synthesized sp2-carbon conjugated polymer.

[0078] In some embodiments of the present invention, the preparation method includes: mixing a carbonyl monomer, an aldehyde monomer, and a catalyst, then adding a solvent to dissolve them to form a mixed reaction system, and subjecting the mixed reaction system to a polymerization reaction under one or more of the following conditions: shaking, ultrasound, and microwave, thereby obtaining sp derived from the carbonyl monomer. 2 - Carbon conjugated polymer.

[0079] In some embodiments of the present invention, after the polymerization reaction is completed, solid-liquid separation is performed to obtain a solid, which is then washed and dried to obtain the final product.

[0080] In some embodiments of the present invention, the sp prepared by the preparation method 2 - Carbon conjugated polymers generate photocurrent densities of 1–100 μA / cm² under illumination with wavelengths >400 nm. 2 .

[0081] Another aspect of the present invention provides an sp derived from a carbonyl monomer. 2 -Carbon conjugated polymer, the sp 2 - Carbon conjugated polymers are obtained by polymerization in a mixed reaction system including carbonyl monomers, aldehyde monomers and catalysts;

[0082] The carbonyl monomer is a cyclic ketone; the aldehyde monomer is a compound containing a cyclic structure and two or more aldehyde groups.

[0083] The specific descriptions of carbonyl monomers, aldehyde monomers, catalysts, and polymerization reactions are the same as above.

[0084] In some embodiments of the present invention, the sp 2 - Carbon conjugated polymers have a porous structure with a specific surface area of ​​100–3000 m². 2 / g, with a pore size distribution of 0.5–10 nm.

[0085] In some embodiments of the present invention, the sp 2 - Carbon conjugated polymers generate photocurrent densities of 1–100 μA / cm² under illumination with wavelengths >400 nm. 2 .

[0086] The third aspect of the present invention provides the aforementioned sp derived from carbonyl monomers. 2 Applications of carbon conjugated polymers in gas storage and separation, optoelectronic devices, photocatalysts, and energy storage.

[0087] The technical solution of the present invention will be further described and illustrated below with reference to specific embodiments and accompanying drawings. It should be understood that the specific embodiments described herein are only for the purpose of helping to understand the present invention and are not intended to limit the specific scope of the present invention. Furthermore, the accompanying drawings used herein are merely for better illustrating the content disclosed in the present invention and do not limit the scope of protection. Unless otherwise specified, the raw materials used in the embodiments of the present invention are all commonly used in the art, and the methods used in the embodiments are all conventional methods in the art.

[0088] In the following embodiments:

[0089] The ultrasonic cleaner used was a KQ5200DE CNC ultrasonic cleaner from Kunshan Ultrasonic Instrument Co., Ltd., with a power of 200W.

[0090] The microwave oven used is a Galanz-P70F20CL-DG(B0) microwave oven with an output power of 700W and a microwave frequency of 2450MHz;

[0091] The shaking was performed using a THZ-103B constant temperature incubator shaker from Shanghai Yiheng Scientific Instruments Co., Ltd., with a power of 450W, a frequency of 50Hz, and a rotation speed of 120rpm.

[0092] Cyclopentanone and cyclohexanone are derived from biomass, meaning they are prepared using biomass resources as raw materials.

[0093] Example 1

[0094] In this embodiment, sp2 The preparation of the carbon conjugated polymer POP-DF includes the following steps:

[0095] (1) Polymerization reaction: Add 4,4',4”-(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde (0.1 mmol) and cyclopentanone (0.15 mmol) to a quartz glass tube and mix well. Then add 1 ml of methanol reagent and 0.5 ml of 4M sodium hydroxide aqueous solution to the quartz glass tube. Shake at room temperature for 5 seconds to turn it into a yellow solid.

[0096] (2) Post-reaction processing: After the reaction is completed, the solid and liquid are separated. The obtained solid product is ground into powder and washed several times with anhydrous ethanol, tetrahydrofuran and acetone. Then, it is dried under vacuum at 60°C for 12 hours to obtain POP-DF.

[0097] The POP-DF 1H NMR spectrum characterization results are as follows: Figure 1 As shown, the position of its proton spectrum peak matches the theoretical structure, proving the successful synthesis of the model molecule. The infrared spectrum of POP-DF is shown below. Figure 2 As shown, 1625cm -1 The infrared vibrational peaks indicate the formation of carbon-carbon double bonds. The UV-Vis absorption spectrum of POP-DF is shown below. Figure 3 As shown, POP-DF can absorb ultraviolet-visible light in the 496nm band. The thermogravimetric diagram of POP-DF is shown below. Figure 4 As shown, POP-DF is stable below 300℃. Figure 5 Photocurrent tests show that POP-DF exhibits good photoelectric response under illumination with wavelengths >400 nm, with a photocurrent reaching 8 μA·cm⁻¹. -2 .

[0098] Example 2

[0099] In this embodiment, sp 2 The preparation of the carbon conjugated polymer POP-AF includes the following steps:

[0100] (1) Polymerization reaction: Add 0.1 mmol of pyromellitic aldehyde and 0.15 mmol of cyclopentanone to a quartz glass tube and mix well. Then add 1 ml of methanol reagent and 0.5 ml of 4M potassium hydroxide aqueous solution to the quartz glass tube and sonicate for 5 seconds to turn it into a yellow solid.

[0101] (2) Post-reaction processing: After the reaction is completed, the solid and liquid are separated. The obtained solid product is ground into powder and washed several times with anhydrous ethanol, tetrahydrofuran and acetone. Then it is dried under vacuum at 60°C for 12 hours to obtain POP-AF.

[0102] Example 3

[0103] In this embodiment, sp 2 The preparation of the carbon conjugated polymer POP-CF includes the following steps:

[0104] (1) Polymerization reaction: Add 1,3,5-tris(p-formylphenyl)benzene (0.1 mmol) and cyclopentanone (0.15 mmol) to a quartz glass tube and mix well. Then add 1 ml of ethanol reagent and 0.5 ml of 4M sodium hydroxide aqueous solution to the quartz glass tube. Microwave for 5 seconds to turn it into a yellow solid.

[0105] (2) Post-reaction processing: After the reaction is completed, the solid and liquid are separated. The obtained solid product is ground into powder and washed several times with anhydrous ethanol, tetrahydrofuran and acetone. Then, it is dried under vacuum at 60°C for 12 hours to obtain POP-CF.

[0106] Example 4

[0107] In this embodiment, sp 2 The preparation of the carbon conjugated polymer POP-AG includes the following steps:

[0108] (1) Polymerization reaction: Add 0.1 mmol of pyromellitic aldehyde and 0.15 mmol of cyclohexanone to a quartz glass tube and mix well. Then add 1 ml of methanol reagent and 0.5 ml of 4 M pyridine aqueous solution to the quartz glass tube. Shake at room temperature for 5 seconds to turn into a yellow solid.

[0109] (2) Post-reaction processing: After the reaction is completed, the solid and liquid are separated. The obtained solid product is ground into powder and washed several times with anhydrous ethanol, tetrahydrofuran and acetone. Then it is dried under vacuum at 60°C for 12 hours to obtain POP-AG.

[0110] Example 5

[0111] In this embodiment, sp 2 The preparation of the carbon conjugated polymer POP-CG includes the following steps:

[0112] (1) Polymerization reaction: Add 1,3,5-tris(p-formylphenyl)benzene (0.1 mmol) and cyclohexanone (0.2 mmol) to a quartz glass tube and mix well. Then add 1 ml of methanol reagent and 1 ml of 4M sodium hydroxide aqueous solution to the quartz glass tube. Microwave for 10 seconds to turn it into a yellow solid.

[0113] (2) Post-reaction processing: After the reaction is completed, the solid and liquid are separated. The obtained solid product is ground into powder and washed several times with anhydrous ethanol, tetrahydrofuran and acetone. Then it is dried under vacuum at 60°C for 12 hours to obtain POP-CG.

[0114] Example 6

[0115] In this embodiment, sp 2 The preparation of the carbon conjugated polymer POP-DG includes the following steps:

[0116] (1) Polymerization reaction: Add 4,4',4”-(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde (0.1 mmol) and cyclohexanone (0.15 mmol) to a quartz glass tube and mix well. Then add 1 ml of n-butanol reagent and 0.5 ml of 4M sodium hydroxide aqueous solution to the quartz glass tube. Shake at room temperature for 15 seconds to turn it into a yellow solid.

[0117] (2) Post-reaction processing: After the reaction is completed, the solid and liquid are separated. The obtained solid product is ground into powder and washed several times with anhydrous ethanol, tetrahydrofuran and acetone. Then it is dried under vacuum at 60°C for 12 hours to obtain POP-DG.

[0118] Example 7

[0119] In this embodiment, sp 2 The preparation of the carbon conjugated polymer POP-MF includes the following steps:

[0120] (1) Polymerization reaction: Add 0.1 mmol of terephthalaldehyde and 0.3 mmol of cyclopentanone to a quartz glass tube and mix well. Then add 1 ml of methanol reagent and 1.5 ml of 4M sodium hydroxide aqueous solution to the quartz glass tube and sonicate for 10 seconds to turn it into a yellow solid.

[0121] (2) Post-reaction processing: After the reaction is completed, the solid and liquid are separated. The obtained solid product is ground into powder and washed several times with anhydrous ethanol, tetrahydrofuran and acetone. Then it is dried under vacuum at 60°C for 12 hours to obtain POP-MF.

[0122] Example 8

[0123] In this embodiment, sp 2 The preparation of the carbon conjugated polymer POP-MG includes the following steps:

[0124] (1) Polymerization reaction: Mix 0.1 mmol of terephthalaldehyde and 0.15 mmol of cyclohexanone in a quartz glass tube, then add 1 ml of methanol reagent and 0.5 ml of 4 M sodium hydroxide aqueous solution to the quartz glass tube, and shake at room temperature for 5 seconds to turn it into a yellow solid.

[0125] (2) Post-reaction processing: After the reaction is completed, the solid and liquid are separated. The obtained solid product is ground into powder and washed several times with anhydrous ethanol, tetrahydrofuran and acetone. Then it is dried under vacuum at 60°C for 12 hours to obtain POP-MG.

[0126] Example 9

[0127] In this embodiment, sp 2 The preparation of the carbon conjugated polymer POP-MMF includes the following steps:

[0128] (1) Polymerization reaction: Add [1,1'-biphenyl]-3,3',5,5'-tetracarboxaldehyde (0.1 mmol) and cyclopentanone (0.15 mmol) to a quartz glass tube and mix well. Then add 1 ml of methanol reagent and 0.5 ml of 4M sodium hydroxide aqueous solution to the quartz glass tube. Shake at room temperature for 10 seconds to turn it into a yellow solid.

[0129] (2) Post-reaction processing: After the reaction is completed, the solid and liquid are separated. The obtained solid product is ground into powder and washed several times with anhydrous ethanol, tetrahydrofuran and acetone. Then it is dried under vacuum at 60°C for 12 hours to obtain POP-MMF.

[0130] All aspects, embodiments, and features of this invention should be considered illustrative in all respects and not limiting of the invention; the scope of the invention is defined only by the claims. Other embodiments, modifications, and uses will become apparent to those skilled in the art without departing from the spirit and scope of the invention as claimed.

[0131] In the preparation method of this invention, the order of the steps is not limited to the listed order. For those skilled in the art, variations in the order of the steps without creative effort are also within the scope of protection of this invention. Furthermore, two or more steps or actions can be performed simultaneously.

[0132] Finally, it should be noted that the specific embodiments described herein are merely illustrative examples of the invention and are not intended to limit the implementation of the invention. Those skilled in the art can make various modifications or additions to the described specific embodiments or use similar methods to replace them; it is neither necessary nor possible to exemplify all embodiments here. However, these obvious variations or modifications derived from the essential spirit of the invention still fall within the scope of protection of the invention, and interpreting them as any additional limitation would contradict the spirit of the invention.

Claims

1. A sp hybridized carbon monomer derived sp 2 - Process for the preparation of a carbon conjugated polymer, characterized in that, The preparation method comprises: performing a polymerization reaction on a mixed reaction system comprising a carbonyl monomer, an aldehyde group monomer, and a catalyst, thereby obtaining sp 2 a carbon conjugated polymer; The catalyst is a basic catalyst; The carbonyl monomer is a cyclic ketone derived from biomass, and the cyclic ketone is one or more of cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone; The aldehyde monomer is a compound containing a cyclic structure and two aldehyde groups, including one or a combination of two or more of the following structures: ， wherein R1 is selected from one of fluorine, chlorine, bromine, methyl, methoxy, ethoxy, and hydroxyl, R2 is selected from one of fluorine, chlorine, bromine, hydroxyl, and nitro, and X is selected from one of N, O, and S; Alternatively, the aldehyde monomer is a compound containing a cyclic structure and three aldehyde groups, including one or a combination of two or more of the following structures: ， wherein R is selected from one of fluorine, chlorine, bromine, methoxy, ethoxy, and hydroxyl, X is C and / or N, and Y is N and / or P; Alternatively, the aldehyde monomer is a compound containing a cyclic structure and four aldehyde groups, including one or a combination of two or more of the following structures: 。 2. The carbonyl monomer-derived sp according to claim 1. 2 A method for producing a carbon conjugated polymer, characterized by, The aldehyde monomers include terephthaldehyde, 2,5-dimethylbenzene-1,4-dialdehyde, 2,5-dihydroxyterephthaldehyde, 2,5-difluoroterephthaldehyde, 2,5-dichloroterephthaldehyde, 2,5-diethoxyterephthaldehyde, 2,5-dibromobenzene-1,4-dialdehyde, 2,5-dimethoxybenzene-1,4-dialdehyde, 1-pyrrole-2,5-dialdehyde, 2,5-diformylfuran, thiophene-2,5-dialdehyde, 2-hydroxyterephthaldehyde, 2-nitroterephthaldehyde, 2-bromoterephthaldehyde, naphthalene-2,6-dialdehyde, 9,10-anthracene dicarboxaldehyde, thieno[3,2-b]thiophene-2,5-dialdehyde, 4,4'-(thiazolo[5,4-d]thiazole-2,5-diyl)dibenzaldehyde, 4,4'-(ethyne-1,2-diyl)dibenzaldehyde, 4,4'-(but-1,3-diyn-1,4-diyl)dibenzaldehyde, [1,1':4',1''-terphenyl]-4,4''-dialdehyde, 4,4'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzaldehyde, 4,4'-(anthracene-9,10-diyl)dibenzaldehyde, 4,4'-(pyrene-1,6-diyl)dibenzaldehyde, trimesaldehyde, triformylphloroglucinol, 1,3,5-trimethoxy-2,4,6-triformylbenzene, 2,4,6-trichlorophenyl-1,3,5-triformaldehyde, 4,4',4''-phosphinidynetrisbenzaldehyde, 4,4',4''-azinidynetrisbenzaldehyde, benzo[1,2-b:3,4-b':5,6-b']trithiophene-2,5,8-trialdehyde, 5'-(4-formylphenyl)-[1,1':3',1''-terphenyl]-4,4''-dialdehyde, 5,5',5''-(benzene-1,3,5-triyl)tris(pyridine-2-carbaldehyde), 4,4',4''-(1,3,5-triazine-2,4,6-triyl)trisbenzaldehyde, 4,4',4''-((1,3,5-triazine-2,4,6-triyl)tris(oxy))trisbenzaldehyde, 4,4',4''-[benzene-1,3,5-triyltris(ethyne-2,1-diyl)]trisbenzaldehyde, 5,5',5''-(benzene-1,3,5-triyl)tris(thiophene-2-carbaldehyde), 5,5',5''-(nitrilotris(phen-4,1-diyl))tris(thiophene-2-carbaldehyde), tris(4-formylbiphenyl)amine, 4',4''',4'''''-(1,3,5-triazine-2,4,6-triyl)tris(([1,1'-biphenyl]-4-carbaldehyde)), [1,1'-biphenyl]-3,3',5,5'-tetraaldehyde, 5,5'-(ethyne-1,2-diyl)diphthaldehyde, [1,1':4',1''-terphenyl]-3,3'',5,5''-tetraaldehyde, 5,5'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)diphthaldehyde, 5,5'-(1,4-phenylenebis(ethyne-2,1-diyl))diphthaldehyde, [1,1 :4', 1 ":4", 1 "-quaterphenyl]-3,3",5,5"-tetraformal, 4,4',4",4"'-(ethene- 1, 1,2,2- tetrayl) tetrakisbenzaldehyde, 1,2,4,5-tetrakis(4-formylphenyl)benzene, 4,4',4",4"'- ([1, 1 '-biphenyl]-4,4"-diylbis(azanetriyl))tetrakisbenzaldehyde, 2,3,6,7- tetrakis(4-formylphenyl)thiophene, 1,3,6,8-tetrakis(4-formylphenyl)pyrene, 4",5"- bis(4'-formyl-[1, 1 '-biphenyl]-4-yl)-[1, 1 ':4', 1 ":2", 1 ":4", 1 ":4", 1 "-quaterphenyl]-4,4"- dimethylformal, or any one or more of the following:

3. The sp derived from carbonyl monomers according to claim 1 2 A method for preparing a carbon conjugated polymer, characterized in that, The basic catalyst includes any one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, pyridine, and piperidine.

4. The sp derived from carbonyl monomers according to claim 1 2 A method for preparing a carbon conjugated polymer, characterized in that, The molar ratio of the carbonyl monomer to the aldehyde monomer is (1-50):

1.

5. The sp derived from carbonyl monomers according to claim 1 2 A method for preparing a carbon conjugated polymer, characterized in that, The molar ratio of the carbonyl monomer to the basic catalyst is 1:(0.1-100).

6. The sp derived from carbonyl monomers according to claim 1 2 A method for preparing a carbon conjugated polymer, characterized in that, The polymerization reaction is carried out under the condition of one or more of shaking, ultrasonic, and microwave. And / or, the temperature of the polymerization reaction is 0-100 ℃, and the time is 1-1000 s.

7. The carbonyl monomer-derived sp according to claim 1 or 6. 2 A method for producing a carbon conjugated polymer, characterized by, The temperature of the polymerization reaction is 5-80 ℃, and the time is 2-600 s.

8. A sp derived from carbonyl monomers 2 - A carbon conjugated polymer, characterized in that... The sp 2 - a carbon conjugated polymer prepared by the method of any one of claims 1 to 7.

9. A carbonyl monomer-derived sp according to claim 8. 2 - carbon conjugated polymers characterized in that, The sp 2 - the carbon conjugated polymer generates a photocurrent density of 1 to 100 μA / cm 2 .

10. The sp derived from carbonyl monomer as described in claim 8 2 Applications of carbon conjugated polymers in gas storage and separation, optoelectronic devices, photocatalysts, and energy storage.

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