Flexible carbon skeleton cross-linked polymer, flexible polymer membrane, ion exchange membrane and application thereof

Abstract

The invention discloses a flexible carbon skeleton cross-linked polymer, a flexible polymer membrane, a proton exchange membrane and application of the flexible carbon skeleton cross-linked polymer, the flexible polymer membrane and the proton exchange membrane, a selected diacetyl monomer has two benzene rings, and a flexible chain is arranged between the two benzene rings, so that the prepared polymer has the characteristics of hardness and softness. The polymer is good in flexibility, good in mechanical property and large in specific surface area, and can be well applied to industrial production. The polymer is prepared into a film, and the obtained film has the advantages of good chemical stability, good structural stability, good flexibility, abundant pores and the like, and can be used in the fields of gas adsorption, nanofiltration separation, ion screening, fuel cells, hydrogen production by electrolysis of water, flow batteries, carbon dioxide reduction, supercapacitors, electrodialysis, water treatment and the like.

Description

Technical Field

[0001] This invention relates to the field of polymer functional materials technology, specifically to a class of flexible carbon skeleton crosslinked polymers, a class of flexible polymer membranes, ion exchange membranes and their applications. Background Technology

[0002] Cross-linked polyaromatic materials and their membranes, with an aromatic hydrocarbon framework, possess advantages such as good chemical stability, high structural stability, and abundant porosity, leading to their wide applications in gas adsorption, nanofiltration, fuel cells, hydrogen production via water electrolysis, flow batteries, carbon dioxide reduction, supercapacitors, electrodialysis, and water treatment. However, the rigidity of their framework results in high brittleness and poor mechanical properties, limiting their application in industrial production.

[0003] Therefore, improving these materials so that they can maintain the advantages of good chemical stability, high structural stability, and abundant porosity, while also possessing a certain degree of flexibility, is of great theoretical and practical significance for the continued development of this field. Summary of the Invention

[0004] Based on the above-mentioned prior art, the present invention provides a type of flexible carbon skeleton crosslinked polymer, a type of flexible polymer membrane, an ion exchange membrane and their applications. The monomers of this type of polymer have flexible chains between benzene rings, which makes the prepared polymer have the characteristics of both rigidity and flexibility. This makes the polymer have good flexibility and mechanical properties, and can be well applied in industrial production.

[0005] The technical solution adopted to achieve the above-mentioned objectives of this invention is as follows:

[0006] A class of diacetyl monomers, characterized by the following general structural formula:

[0007]

[0008] R1 and R2 are selected from one of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, and trifluoromethyl, respectively, and n is a positive integer, n≤20000.

[0009] A method for preparing a class of diacetyl monomers, characterized by comprising the following steps:

[0010] In the presence of an acylation catalyst, diphenyl compounds and acetyl halides undergo a Friedel-Crafts acylation reaction to generate diacetyl monomers, as shown in the following reaction formula:

[0011]

[0012] R1 and R2 are selected from one of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, and trifluoromethyl, respectively, n is a positive integer, and X is a halogen atom.

[0013] A method for preparing a class of flexible carbon skeleton crosslinked polymers includes the following steps:

[0014] In the presence of an acid catalyst and an organic solvent, at least one of the diacetyl flexible monomers undergoes an acetyl trimerization reaction to obtain the flexible backbone crosslinked polymer, as shown in the following reaction formula:

[0015]

[0016] Wherein, R1 and R2 are selected from one of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, and trifluoromethyl, respectively, and n is a positive integer;

[0017] Alternatively, in the presence of an acid catalyst and an organic solvent, at least one of the diacetyl flexible monomers undergoes a copolymerization reaction with a ketone monomer to obtain the aforementioned flexible carbon skeleton cross-linked polymer.

[0018] The ketone monomer is selected from at least one of the following compounds:

[0019]

[0020] The acid catalyst is selected from at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, perfluorosulfonic acid resin, p-toluenesulfonic acid, titanium chloride, tin tetrachloride, tetrachlorosilane, boron trifluoride, 4-dodecylbenzenesulfonic acid, sulfuric acid, bismuth trifluoromethanesulfonate, boron sulfate, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, tungstate sulfate, Amberlyst-15, and Zirconocene bis(perfluorooctane-sulfonate).

[0021] The organic solvent is at least one selected from dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, and ethyl acetate.

[0022] A method for preparing a type of flexible polymer film includes the following steps:

[0023] In the presence of an acid catalyst and an organic solvent, at least one of the diacetyl flexible monomers undergoes an acetyl trimerization reaction to obtain a prepolymer solution. The prepolymer solution is coated onto a substrate, heated and repolymerized, washed and dried to obtain the flexible polymer film.

[0024] Alternatively, in the presence of an acid catalyst and an organic solvent, at least one of the diacetyl flexible monomers undergoes a copolymerization reaction with a ketone monomer to obtain a prepolymer solution. The prepolymer solution is then coated onto a substrate, heated, and repolymerized. After washing and drying, the flexible polymer film is obtained.

[0025] The ketone monomer is selected from at least one of the following compounds:

[0026]

[0027] The acid catalyst is selected from at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, perfluorosulfonic acid resin, p-toluenesulfonic acid, titanium chloride, tin tetrachloride, tetrachlorosilane, boron trifluoride, 4-dodecylbenzenesulfonic acid, sulfuric acid, bismuth trifluoromethanesulfonate, boron sulfate, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, tungstate sulfate, Amberlyst-15, and Zirconocene bis(perfluorooctane-sulfonate).

[0028] The organic solvent is at least one selected from dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, and ethyl acetate.

[0029] A method for preparing a type of polymer hollow fiber membrane, characterized by comprising the following steps:

[0030] The hollow fiber base membrane is immersed in the prepolymer solution, and after immersion, it is dried to obtain the polymer hollow fiber membrane.

[0031] Alternatively, the prepolymer solution can be used to prepare polymer hollow fiber membranes using a dry-wet spinning method;

[0032] The hollow fiber base membrane is selected from one of the following: ceramic hollow fiber membrane, polytetrafluoroethylene hollow fiber membrane, polyvinylidene fluoride hollow fiber membrane, polyethylene terephthalate hollow fiber membrane, polyamide hollow fiber membrane, polyethylene hollow fiber membrane, polypropylene hollow fiber membrane, carbon fiber hollow fiber membrane, and glass hollow fiber membrane.

[0033] A type of cross-linked ion-exchange polymer resin or proton exchange membrane has structural units of the following general formula:

[0034]

[0035] R1 and R2 are selected from one of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, and trifluoromethyl, respectively. R1 and R2 can be different in different repeating units, and n is a positive integer. A is selected from sulfonic acid group (-SO3H) or phosphate group (-PO3H2) and can be at any position on any benzene ring in the structural unit.

[0036] A method for preparing a type of cross-linked ionomer resin includes the following steps:

[0037] The flexible carbon skeleton crosslinked polymer is grafted with acid groups in an acidifying agent. After the reaction is complete, the crosslinked ionomer resin is obtained.

[0038] Alternatively, in the presence of an acid catalyst, an acidifying agent, and an organic solvent, at least one of the diacetyl flexible monomers undergoes an acetyl trimerization reaction to obtain the cross-linked ionic polymer resin described above.

[0039] Alternatively, in the presence of an acid catalyst, an acidifying agent, and an organic solvent, at least one of the diacetyl flexible monomers undergoes a copolymerization reaction with a ketone monomer to obtain the cross-linked ionic polymer resin described above.

[0040] The ketone monomer is selected from at least one of the following compounds:

[0041]

[0042] The acidifying agent is selected from at least one of sulfur trioxide, concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, a mixture of sulfur dioxide and chlorine, a mixture of sulfur dioxide and oxygen, and sodium sulfite.

[0043] The acid catalyst is selected from at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, perfluorosulfonic acid resin, p-toluenesulfonic acid, titanium chloride, tin tetrachloride, tetrachlorosilane, boron trifluoride, 4-dodecylbenzenesulfonic acid, sulfuric acid, bismuth trifluoromethanesulfonate, boron sulfate, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, tungstate sulfate, Amberlyst-15, and Zirconocene bis(perfluorooctane-sulfonate).

[0044] The organic solvent is at least one selected from dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, and ethyl acetate.

[0045] A method for preparing a type of proton exchange flat sheet membrane includes the following steps:

[0046] Acid groups were grafted onto the flexible polymer membrane in an acidifying reagent. After the reaction was complete, the membrane was washed and dried to obtain the proton exchange plate membrane.

[0047] Alternatively, in the presence of an acid catalyst, an acidifying agent, and an organic solvent, at least one of the diacetyl flexible monomers undergoes an acetyl trimerization reaction to obtain a prepolymer solution. The prepolymer solution is then coated onto a substrate, heated, and repolymerized. After washing and drying, the proton exchange flat sheet membrane is obtained.

[0048] Alternatively, in the presence of an acid catalyst, an acidifying agent, and an organic solvent, at least one of the diacetyl flexible monomers undergoes a copolymerization reaction with a ketone monomer to obtain a prepolymer solution. The prepolymer solution is then coated onto a substrate, heated, and repolymerized. After washing and drying, the proton exchange flat sheet membrane is obtained.

[0049] The ketone monomer is selected from at least one of the following compounds:

[0050]

[0051] The acidifying agent is selected from at least one of sulfur trioxide, concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, a mixture of sulfur dioxide and chlorine, a mixture of sulfur dioxide and oxygen, and sodium sulfite.

[0052] The acid catalyst is selected from at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, perfluorosulfonic acid resin, p-toluenesulfonic acid, titanium chloride, tin tetrachloride, tetrachlorosilane, boron trifluoride, 4-dodecylbenzenesulfonic acid, sulfuric acid, bismuth trifluoromethanesulfonate, boron sulfate, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, tungstate sulfate, Amberlyst-15, and Zirconocene bis(perfluorooctane-sulfonate).

[0053] The organic solvent is at least one selected from dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, and ethyl acetate.

[0054] A method for preparing a type of proton exchange hollow fiber membrane includes the following steps:

[0055] The polymer hollow fiber membrane was grafted with acid groups in an acidifying reagent. After the reaction was complete, it was washed and dried to obtain the proton exchange hollow fiber membrane.

[0056] Alternatively, the hollow fiber membrane can be immersed in the prepolymer solution obtained during the preparation of the proton exchange flat sheet membrane, and after immersion, it can be dried to obtain the polymer hollow fiber membrane.

[0057] Alternatively, the prepolymer solution obtained during the preparation of proton exchange flat sheet membranes may be used to prepare polymer hollow fiber membranes using a dry-wet spinning method;

[0058] The acidifying agent is selected from at least one of sulfur trioxide, concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, a mixture of sulfur dioxide and chlorine, a mixture of sulfur dioxide and oxygen, and sodium sulfite.

[0059] Applications of a class of flexible carbon skeleton cross-linked polymers or flexible polymer membranes or polymer hollow fiber membranes, and a class of cross-linked ion polymer resins or proton exchange membranes in gas adsorption, nanofiltration separation, fuel cells, water electrolysis for hydrogen production, flow batteries, carbon dioxide reduction, supercapacitors, electrodialysis, and water treatment.

[0060] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows:

[0061] The diacetyl monomer selected in this invention has two benzene rings with a flexible chain between them, giving the prepared polymer a combination of rigidity and flexibility. This results in polymers with good flexibility, good mechanical properties, and a large specific surface area, making them well-suited for industrial applications. When these polymers are used to form thin films, the resulting films exhibit advantages such as good chemical stability, good structural stability, good flexibility, and abundant porosity. These films can be used in fields such as gas adsorption, nanofiltration separation, ion sieving, fuel cells, water electrolysis for hydrogen production, flow batteries, carbon dioxide reduction, supercapacitors, electrodialysis, and water treatment. Detailed Implementation

[0062] The present invention will now be described in detail with reference to specific embodiments, but these embodiments are not to be construed as limiting the scope of protection of the present invention in any sense.

[0063] Example 1

[0064] 1. 2.38 g (10 mmol) of 1,1-biphenylhexane (CAS No.: 1530-04-7), 2.36 g (30 mmol) of acetyl chloride, and 1.33 g (10 mmol) of aluminum trichloride were mixed in 25 mL of dimethyl sulfoxide and stirred at 50 °C for 20 hours. After the reaction was completed, the resulting mixture was centrifuged, the precipitate was washed with water and filtered, the filter cake was extracted with dichloromethane, and the organic phase was dried to obtain 2.85 g of monomer M1 (1,1'-(hexane-1,1-dimethylbis(4,1-phenylene))bis(ethane-1-one)) white powder, with a yield of 89%.

[0065] 1 ¹H NMR (600 MHz, ppm) δH = 7.32 (4H, benzene ring), 6.75 (4H, benzene ring), 3.89 (1H, tertiary hydrogen), 1.89 (2H, methylene), 1.27 (6H, methylene), 0.85 (3H, methyl).

[0066]

[0067] 2. Dissolve 0.322 g (1 mmol) of M1 in 15 mL of tetrahydrofuran, and slowly add 0.5 mL of trifluoromethanesulfonic acid dropwise. After the addition is complete, stir at 50 °C for 30 hours. Then, centrifuge the resulting mixture to obtain a precipitate. Wash the precipitate with water, filter, and dry to obtain 0.25 g of flexible carbon skeleton crosslinked polymer.

[0068]

[0069] 1 ¹H NMR (600 MHz, ppm) δH = 6.72-7.31 (benzene ring), 3.85 (tertiary hydrogen), 1.91 (methylene), 1.30-0.81 (methylene, methyl).

[0070] The BET specific surface area of ​​polymer P1a is 450 m². 2 The pore size is 0.8-4.2 nm. At 80℃ and normal pressure, the iodine vapor adsorption capacity of polymer P1a is 2.2 g / g. At 77 K and 10 bar, the hydrogen adsorption capacity of polymer P1a is 25 g / L.

[0071] Example 2

[0072] 1. Dissolve 0.266 g (1 mmol) of 4,4'-diacetyldiarylethane (CAS No.: 793-06-6) in 10 mL of N,N-dimethylacetamide, and slowly add 1 mL of trifluoromethanesulfonic acid. After the addition is complete, stir at 40 °C for 30 hours. Then, centrifuge the resulting mixture to obtain a precipitate. Wash the precipitate with water, filter, and dry to obtain 0.23 g of flexible backbone crosslinked polymer P2a.

[0073] 1 ¹H NMR (600 MHz, ppm) δH = 7.72-7.31 (benzene ring), 2.78 (methylene).

[0074] The BET specific surface area of ​​polymer P2a is 500 m². 2 The pore size is 1.2-6.5 nm. At 80℃ and normal pressure, the iodine vapor adsorption capacity of polymer P2a is 2.6 g / g. At 77 K and 10 bar, the hydrogen adsorption capacity of polymer P2a is 28 g / L.

[0075]

[0076] 2. Dissolve 0.266 g (1 mmol) of 4,4'-diacetyldiarylethane (CAS No.: 793-06-6) in 20 mL of N,N-dimethylformamide, then stir at 0 °C while slowly adding 1 mL of trifluoromethanesulfonic acid. After the addition is complete, continue stirring at 40 °C for 20 hours to obtain a viscous prepolymer solution. Coat the prepolymer solution onto a glass plate, then polymerize it at 150 °C. Wash the glass plate by immersing it in water and dry it to obtain a flexible polymer film F1a (IR spectrum: 3010, 2850, 2790, 1610, 1405, 1315 cm⁻¹). -1 The tensile strength of F1a is 35 MPa, and the elongation at break is 38%. Through dead-end filtration, the permeability of F1a to ethanol is 120 L / (m³). 2 (·h·bar). In ethanol solution, F1a has a retention rate of up to 99% for molecules with a molecular weight below 800 Da.

[0077] 3. Dissolve chlorosulfonic acid in dichloromethane to obtain a 0.1M chlorosulfonic acid-dichloromethane solution. Then, soak 0.2g of P2a in the 0.1M chlorosulfonic acid-dichloromethane solution at room temperature for 20 hours. After soaking, filter, wash the filter cake with water, and dry it to obtain 0.23g of cross-linked ionomer resin P1b (infrared spectrum: 3005, 2845, 2795, 1613, 1200, 1010 cm⁻¹). -1 The mass exchange capacity of P1b is 5.2 mmol / g, and the volume exchange capacity is 2.2 mmol / mL.

[0078] 4. Dissolve chlorosulfonic acid in dichloromethane to obtain a 0.1M chlorosulfonic acid-dichloromethane solution. Then, immerse F1a in the 0.1M chlorosulfonic acid-dichloromethane solution at room temperature for 20 hours. After immersion, wash with water and dry to obtain the proton exchange plate membrane F1b (infrared spectrum: 3012, 2856, 2802, 1605, 1205, 1015 cm⁻¹). -1 At 30°C, the proton conductivity of F1b is 30 mS / cm; at 80°C, the proton conductivity of F1b is 120 mS / cm. F1b has a water absorption rate of 10% and a water swelling rate of 5%. Using F1b as a membrane in a hydrogen-oxygen fuel cell at 80°C and 2 atmospheres, the maximum power density of the cell is 2.5 W / cm². 2 When F1b was used as a diaphragm for water electrolysis, the current density was 2.5 A / cm³ at 80℃ and 1.75V. 2 .

[0079] 5. Dissolve phosphorus oxychloride in dichloromethane to obtain a 0.1M phosphorus oxychloride dichloromethane solution. Then, immerse F1a in the 0.1M phosphorus oxychloride dichloromethane solution at room temperature for 20 hours. After immersion, wash with water and dry to obtain the proton exchange plate membrane F1c (infrared spectrum: 3007, 2852, 2800, 1600, 1205, 1036 cm⁻¹). -1 At 120°C, the proton conductivity of F1c is 95 MS / cm. Using F1c as a membrane in a hydrogen-oxygen fuel cell at 120°C and 2 atmospheres, the maximum power density of the cell is 1.9 W / cm². 2 When F1c is used in the separator of a full vanadium redox flow battery, the vanadium ion permeability is 5 × 10⁻⁶. -10 cm 2 / s, at 80℃, F1c is immersed in 1.5M VO 2+ After 30 days in a 3M H2SO4 solution, the conductivity decreased by only 3%. When assembled into a full vanadium redox flow battery, the coulombic efficiency was 98.8%.

[0080] 6. Dissolve 0.266 g (1 mmol) of 4,4'-diacetyldiarylethane (CAS No.: 793-06-6) in 20 mL of N,N-dimethylformamide. Stir at 0 °C while slowly adding 1 mL of trifluoromethanesulfonic acid. After the addition is complete, continue stirring for 20 hours to obtain a viscous prepolymer solution. Immerse a bundle of polyvinylidene fluoride (PVDF) hollow fiber membranes in the prepolymer solution for 10 hours, then remove and dry at 150 °C for 30 hours to obtain polymer hollow fiber membrane F1d. At room temperature, F1d is used for desalination of 1 M NaCl brine, and the NaCl concentration in the filtrate is less than 1 ppm.

[0081] 7. At 30°C, F1d was immersed in a 1M chlorosulfonic acid-dichloromethane solution for 20 hours to obtain a proton exchange hollow fiber membrane F1e. At room temperature, F1e separated NaOH and Na2SO4 with a flux ratio of 52.

[0082] 8. Dissolve 0.266 g (1 mmol) of 4,4'-diacetyldiarylethane (CAS No.: 793-06-6) in 20 mL of N,N-dimethylformamide. Stir at 0 °C while slowly adding 1 mL of trifluoromethanesulfonic acid. After the addition is complete, continue stirring for 20 hours to obtain a viscous prepolymer solution. Use a dry-wet spinning process to prepare polymer hollow fiber membranes F1f from this prepolymer solution. At room temperature, the permeability of F1f to ethanol is 136 L / (m³). 2 (·h·bar). In ethanol solution, F1f has a retention rate as high as 98% for molecules with a molecular weight below 450 Da.

[0083] 9. At 30°C, F1f was immersed in a 1M phosphorus oxychloride dichloromethane solution for 20 hours, followed by washing in a 0.1M NaOH aqueous solution, and then immersed in a 1M sulfuric acid aqueous solution to obtain the proton exchange hollow fiber membrane F1g. At room temperature, F1g separated NaOH and Na2SO4 with a flux ratio of 56.

[0084] Example 3

[0085] 8. At 0℃, 0.266 g (1 mmol) of 4,4'-diacetyldiarylethane (CAS No.: 793-06-6) and 0.166 g (1 mmol) of 1,4-diacetylbenzene (CAS No.: 1009-61-6) were dissolved in 20 mL of N,N-dimethylformamide. While stirring, 1 mL of trifluoromethanesulfonic acid was slowly added dropwise. After the addition was complete, the mixture was stirred at 40℃ for 20 hours to obtain a viscous prepolymer solution. The prepolymer solution was coated onto a glass plate, and then polymerized again at 150℃. The glass plate was washed in water and dried to obtain a flexible polymer film F2a (IR spectrum: 3008, 2852, 2793, 1608, 1412, 1319 cm⁻¹). -1 The tensile strength of F2a is 40 MPa, and its elongation at break is 32%. Through dead-end filtration, the permeability of F2a to ethanol is 100 L / (m³). 2 (·h·bar). In ethanol solution, F2a has a retention rate of up to 99% for molecules with a molecular weight below 1000 Da.

[0086] Example 4

[0087] 1. 2.38 g (10 mmol) of 2,3-dimethyl-2,3-diphenylbutane (CAS No.: 1889-67-4), 2.36 g (30 mmol) of acetyl chloride, and 1.33 g (10 mmol) of aluminum trichloride were mixed in 25 mL of dimethyl sulfoxide and stirred at 50 °C for 20 hours. After the reaction was completed, the resulting mixture was centrifuged, the precipitate was washed with water and filtered, the filter cake was extracted with dichloromethane, and then the organic phase was dried to obtain 2.92 g of monomer M2 (1,1'-((2,3-dimethylbutane-2,3-diyl)bis(4,1-phenylene))bis(ethane-1-one)), white powder, with a yield of 91%.

[0088] 1 ¹H NMR (600 MHz, ppm) δH = 7.45 (4H, benzene ring), 6.71 (4H, benzene ring), 2.53 (6H, methyl), 2.53 (12H, methyl).

[0089] 2. Dissolve 0.322 g (1 mmol) monomer M2 and 0.172 g (1 Mmol) p-toluenesulfonic acid in 10 mL of dimethyl sulfoxide and stir at 80 °C for 50 hours. Centrifuge the resulting mixture, wash the precipitate with water and filter to obtain 0.22 g of flexible carbon skeleton crosslinked polymer P3a.

[0090] 1 ¹H NMR (600 MHz, ppm) δH = 7.69-7.28 (benzene ring), 1.39 (methyl).

[0091] The BET specific surface area of ​​polymer P3a is 450 m². 2 The pore size is 0.8-4.5 nm. At 80℃ and normal pressure, the iodine vapor adsorption capacity of polymer P3a is 2.9 g / g. At 77 K and 10 bar, the hydrogen adsorption capacity is 31 g / L.

[0092]

[0093] 3. Dissolve 0.322 g (1 mmol) of monomer M2 in 30 mL of N,N-dimethylacetamide, and add 1 mL of trifluoromethanesulfonic acid dropwise at 0 °C. After the addition is complete, continue stirring for 20 hours to obtain a viscous prepolymer solution. Coat the prepolymer solution onto a ceramic plate, and then polymerize it at 160 °C. Wash the ceramic plate by immersing it in water and then dry it to obtain a flexible polymer film F3a. The tensile strength of F3a is 42 MPa, and the elongation at break is 42%. After dead-end filtration, the methanol permeability of F3a is 150 L / (m³). 2 (·h·bar). In methanol solution, F3a has a retention rate of up to 99% for molecules with a molecular weight below 500 Da.

[0094] 4. P3a was soaked in 2 mL of fuming sulfuric acid at room temperature for 20 hours, filtered, and the filter cake was washed with water and dried to obtain 0.35 g of cross-linked ionomer resin P2b. The mass exchange capacity of P2b was 4.8 mmol / g and the volume exchange capacity was 1.9 mmol / mL.

[0095] 5. Chlorosulfonic acid was dissolved in dichloromethane to obtain a 0.1M chlorosulfonic acid-dichloromethane solution. F3a was then immersed in this solution at room temperature for 30 hours. After removal, it was washed with water and dried to obtain the proton exchange flat sheet membrane F3b. At 80°C, the proton conductivity of F3b was 89 MS / cm. The water absorption rate of F3b was 6%, and its water swelling rate was 8%. Using F3b as a membrane in a hydrogen-oxygen fuel cell at 80°C and 2 atmospheres, the maximum power density of the cell was 2.3 W / cm². 2When F3b was used as a diaphragm for water electrolysis, the current density was 2.3 A / cm³ at 80℃ and 1.75V. 2 .

[0096] Example 5

[0097] 1. At 0℃, 0.266 g (1 mmol) of 4,4'-diacetyldiarylethane (CAS No.: 793-06-6) was dissolved in 20 mL of N,N-dimethylformamide. While stirring, 1 mL of trifluoromethanesulfonic acid and 0.5 mL of chlorosulfonic acid were slowly added dropwise. After the addition was complete, stirring was continued at 40℃ for 20 hours to obtain a viscous prepolymer solution. The prepolymer solution was coated onto a PET substrate, and then repolymerized at 120℃. The PET substrate was washed in water and dried to obtain a proton exchange flat sheet membrane F4a. The tensile strength of F4a was 42 MPa, and the elongation at break was 39%. At 30℃, the proton conductivity of F4a was 35 mS / cm; at 80℃, the proton conductivity of F4b was 218 mS / cm. At room temperature, the water absorption rate of F4a was 10%, and the water swelling rate was 3%. At 80°C and 2 atmospheres, using F4a as the membrane in a hydrogen-oxygen fuel cell, the maximum power density of the cell is 2.3 W / cm². 2 When F4a was used as a diaphragm for water electrolysis, the current density was 2.1 A / cm³ at 80℃ and 1.75V. 2 .

[0098] 2. At 0℃, 0.266 g (1 mmol) of 4,4'-diacetyldiarylethane (CAS No.: 793-06-6) was dissolved in 20 mL of tetrahydrofuran. While stirring, 1 mL of trifluoromethanesulfonic acid and 0.5 mL of phosphorus oxychloride were slowly added dropwise. After the addition was complete, the mixture was stirred at 40℃ for 30 hours to obtain a viscous prepolymer solution. The prepolymer solution was coated onto a glass plate, and then polymerized again at 150℃. The glass plate was washed successively by immersing it in a 1M sodium hydroxide aqueous solution and a 1M hydrochloric acid aqueous solution, and then dried to obtain a proton exchange plate membrane F4b (infrared spectrum: 3012, 2856, 2803, 1608, 1209, 1032 cm⁻¹). -1 The tensile strength of F4b is 39 MPa, and its elongation at break is 36%. At 30°C, the proton conductivity of F4b is 29 mS / cm; at 80°C, it is 92 mS / cm; and at 150°C, it is 168 mS / cm. At room temperature, F4b has a water absorption rate of 25% and a water swelling rate of 6%. When F4b is used as a membrane in a hydrogen-oxygen fuel cell at 160°C and 2 atmospheres, the maximum power density of the cell is 3.2 W / cm². 2 .

[0099] 3. At 0℃, 0.266 g (1 mmol) of 4,4'-diacetyldiarylethane (CAS No.: 793-06-6) was dissolved in 20 mL of N,N-dimethylformamide. While stirring, 1 mL of trifluoromethanesulfonic acid and 0.5 mL of chlorosulfonic acid were slowly added dropwise. After the addition was complete, stirring was continued at 40℃ for 20 hours to obtain a viscous prepolymer solution. A bundle of polyvinylidene fluoride (PVDF) hollow fiber membranes was immersed in the prepolymer solution for 35 hours, then removed and dried at 120℃ for 50 hours to obtain proton exchange hollow fiber membrane F4c. At room temperature, F4c separated NaOH and Na2SO4 with a flux ratio of 36.

[0100] 4. At 0℃, 0.266 g (1 mmol) of 4,4'-diacetyldiarylethane (CAS No.: 793-06-6) was dissolved in 30 mL of N,N-dimethylformamide. While stirring, 2 mL of trifluoromethanesulfonic acid and 1 mL of chlorosulfonic acid were slowly added dropwise. After the addition was complete, stirring was continued at 40℃ for 20 hours to obtain a viscous prepolymer solution. This prepolymer solution was then used to fabricate a proton exchange hollow fiber membrane, F4d, using a dry-wet spinning process. At room temperature, F4d separated NaOH and Na₂SO₄ at a flux ratio of 50.

[0101] 5. At room temperature, 0.266 g (1 mmol) of 4,4'-diacetyldiarylethane (CAS No.: 793-06-6), 1 mL of trifluoromethanesulfonic acid, and 0.5 mL of chlorosulfonic acid were dissolved in 10 mL of tetrahydrofuran. The mixture was stirred at 40 °C for 40 hours. After the reaction was complete, the resulting mixture was centrifuged. The precipitate was washed three times with 100 mL of pure water and 50 mL of ethyl acetate to obtain 0.221 g of crosslinked ionomer resin P5a (IR spectra: 3008, 2851, 2792, 1610, 1209, 1015 cm⁻¹). -1 The mass ion exchange capacity of P5a is 5.5 mmol / g, and the volume ion exchange capacity is 2.7 mmol / mL.

[0102] 6. At room temperature, 0.266 g (1 mmol) of 4,4'-diacetyldiarylethane (CAS No.: 793-06-6), 0.166 g (1 mmol) of 1,4-diacetylbenzene (CAS No.: 1009-61-6), 2 mL of trifluoromethanesulfonic acid, and 1 mL of chlorosulfonic acid were dissolved in 10 mL of dimethyl sulfoxide. The mixture was stirred at 50 °C for 100 hours. After the reaction was completed, the resulting mixture was centrifuged. The precipitate was washed three times with 200 mL of pure water and 100 mL of chloroform to obtain 0.410 g of cross-linked ionomer resin P5b (IR spectra: 3013, 2856, 2785, 1615, 1212, 1012 cm⁻¹). -1The mass ion exchange capacity of P5b is 5.1 mmol / g, and the volume ion exchange capacity is 2.5 mmol / mL.

Claims

1. A class of diacetyl monomers, characterized in that... Its general structural formula is as follows: R1 and R2 are selected from one of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, and trifluoromethyl, respectively, and n is a positive integer.

2. A type of flexible carbon skeleton crosslinked polymer, flexible polymer membrane, or polymer hollow fiber membrane, characterized in that... Structural units with the following general formula: R1 and R2 are selected from one of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, and trifluoromethyl, respectively. R1 and R2 can be different in different repeating units, and n is a positive integer.

3. A method for preparing the flexible carbon skeleton crosslinked polymer as described in claim 2, characterized in that... Includes the following steps: In the presence of an acid catalyst and an organic solvent, at least one of the diacetyl flexible monomers undergoes an acetyl trimerization reaction to obtain the flexible backbone crosslinked polymer, as shown in the following reaction formula: Wherein, R1 and R2 are selected from one of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, and trifluoromethyl, respectively, and n is a positive integer; Alternatively, in the presence of an acid catalyst and an organic solvent, at least one of the diacetyl flexible monomers undergoes a copolymerization reaction with a ketone monomer to obtain the aforementioned flexible backbone cross-linked polymer. The ketone monomer is selected from at least one of the following compounds: The acid catalyst is selected from at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, perfluorosulfonic acid resin, p-toluenesulfonic acid, titanium chloride, tin tetrachloride, tetrachlorosilane, boron trifluoride, 4-dodecylbenzenesulfonic acid, sulfuric acid, bismuth trifluoromethanesulfonate, boron sulfate, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, tungstate sulfate, Amberlyst-15, and Zirconocene bis(perfluorooctane-sulfonate). The organic solvent is at least one selected from dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, and ethyl acetate.

4. A method for preparing the flexible polymer film according to claim 2, characterized in that... Includes the following steps: In the presence of an acid catalyst and an organic solvent, at least one of the diacetyl flexible monomers undergoes an acetyl trimerization reaction to obtain a prepolymer solution. The prepolymer solution is coated onto a substrate, heated and repolymerized, washed and dried to obtain the flexible polymer film. Alternatively, in the presence of an acid catalyst and an organic solvent, at least one of the diacetyl flexible monomers undergoes a copolymerization reaction with a ketone monomer to obtain a prepolymer solution. The prepolymer solution is then coated onto a substrate, heated, and repolymerized. After washing and drying, the flexible polymer film is obtained. The ketone monomer is selected from at least one of the following compounds: The acid catalyst is selected from at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, perfluorosulfonic acid resin, p-toluenesulfonic acid, titanium chloride, tin tetrachloride, tetrachlorosilane, boron trifluoride, 4-dodecylbenzenesulfonic acid, sulfuric acid, bismuth trifluoromethanesulfonate, boron sulfate, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, tungstate sulfate, Amberlyst-15, and Zirconocene bis(perfluorooctane-sulfonate). The organic solvent is at least one selected from dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, and ethyl acetate.

5. A method for preparing a polymer hollow fiber membrane according to claim 2, characterized in that... Includes the following steps: The hollow fiber membrane is immersed in the prepolymer solution described in claim 4, and after immersion, it is dried to obtain the polymer hollow fiber membrane. Alternatively, the prepolymer solution described in claim 4 can be used to prepare a polymer hollow fiber membrane using a dry-wet spinning method; The hollow fiber base membrane is selected from one of the following: ceramic hollow fiber membrane, polytetrafluoroethylene hollow fiber membrane, polyvinylidene fluoride hollow fiber membrane, polyethylene terephthalate hollow fiber membrane, polyamide hollow fiber membrane, polyethylene hollow fiber membrane, polypropylene hollow fiber membrane, carbon fiber hollow fiber membrane, and glass hollow fiber membrane.

6. A type of cross-linked ionomer resin or proton exchange membrane, characterized in that... Structural units with the following general formula: R1 and R2 are selected from one of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, and trifluoromethyl, respectively. R1 and R2 can be different in different repeating units, and n is a positive integer. A is selected from sulfonic acid group (-SO3H) or phosphate group (-PO3H2) and can be at any position on any benzene ring in the structural unit.

7. A method for preparing the cross-linked ionomer resin according to claim 6, characterized in that... Includes the following steps: The flexible carbon skeleton crosslinked polymer of claim 2 is grafted with acid groups in an acidifying agent. After the reaction is complete, the crosslinked ionomer resin is obtained. Alternatively, in the presence of an acid catalyst, an acidifying agent, and an organic solvent, at least one of the diacetyl flexible monomers undergoes an acetyl trimerization reaction to obtain the cross-linked ionic polymer resin described above. Alternatively, in the presence of an acid catalyst, an acidifying agent, and an organic solvent, at least one of the diacetyl flexible monomers undergoes a copolymerization reaction with a ketone monomer to obtain the cross-linked ionic polymer resin described above. The ketone monomer is selected from at least one of the following compounds: The acidifying agent is selected from at least one of sulfur trioxide, concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, a mixture of sulfur dioxide and chlorine, a mixture of sulfur dioxide and oxygen, and sodium sulfite. The acid catalyst is selected from at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, perfluorosulfonic acid resin, p-toluenesulfonic acid, titanium chloride, tin tetrachloride, tetrachlorosilane, boron trifluoride, 4-dodecylbenzenesulfonic acid, sulfuric acid, bismuth trifluoromethanesulfonate, boron sulfate, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, tungstate sulfate, Amberlyst-15, and Zirconocene bis(perfluorooctane-sulfonate). The organic solvent is at least one selected from dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, and ethyl acetate.

8. A method for preparing a proton exchange flat sheet membrane as described in claim 6, characterized in that... Includes the following steps: The flexible polymer membrane of claim 2 is grafted with acid groups in an acidifying agent. After the reaction is complete, it is washed and dried to obtain the proton exchange plate membrane. Alternatively, in the presence of an acid catalyst, an acidifying agent, and an organic solvent, at least one of the diacetyl flexible monomers undergoes an acetyl trimerization reaction to obtain a prepolymer solution. The prepolymer solution is then coated onto a substrate, heated, and repolymerized. After washing and drying, the proton exchange flat sheet membrane is obtained. Alternatively, in the presence of an acid catalyst, an acidifying agent, and an organic solvent, at least one of the diacetyl flexible monomers undergoes a copolymerization reaction with a ketone monomer to obtain a prepolymer solution. The prepolymer solution is then coated onto a substrate, heated, and repolymerized. After washing and drying, the proton exchange flat sheet membrane is obtained. The ketone monomer is selected from at least one of the following compounds: The acidifying agent is selected from at least one of sulfur trioxide, concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, a mixture of sulfur dioxide and chlorine, a mixture of sulfur dioxide and oxygen, and sodium sulfite. The acid catalyst is selected from at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, perfluorosulfonic acid resin, p-toluenesulfonic acid, titanium chloride, tin tetrachloride, tetrachlorosilane, boron trifluoride, 4-dodecylbenzenesulfonic acid, sulfuric acid, bismuth trifluoromethanesulfonate, boron sulfate, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, tungstate sulfate, Amberlyst-15, and Zirconocene bis(perfluorooctane-sulfonate). The organic solvent is at least one selected from dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, and ethyl acetate.

9. A method for preparing a proton exchange hollow fiber membrane as described in claim 6, characterized in that... Includes the following steps: The polymer hollow fiber membrane of claim 5 is grafted with acid groups in an acidifying agent. After the reaction is complete, it is washed and dried to obtain the proton exchange hollow fiber membrane. Alternatively, the hollow fiber membrane can be immersed in the prepolymer solution described in claim 8, and after immersion, dried to obtain the proton exchange hollow fiber membrane. Alternatively, the prepolymer solution described in claim 8 can be used to prepare a proton exchange hollow fiber membrane using a dry-wet spinning method; The acidifying agent is selected from at least one of sulfur trioxide, concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, a mixture of sulfur dioxide and chlorine, a mixture of sulfur dioxide and oxygen, and sodium sulfite.

10. Applications of the flexible carbon skeleton cross-linked polymer or flexible polymer membrane or polymer hollow fiber membrane as described in claim 2, and the cross-linked ion polymer resin or proton exchange membrane as described in claim 6 in gas adsorption, nanofiltration separation, fuel cells, water electrolysis for hydrogen production, flow batteries, carbon dioxide reduction, supercapacitors, electrodialysis, and water treatment.

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