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EP-4520775-B1 - NITROGEN-CONTAINING HETEROCYCLIC POLYMER, AND POLYMER FILM AND USE THEREOF

EP4520775B1EP 4520775 B1EP4520775 B1EP 4520775B1EP-4520775-B1

Inventors

  • LI, MING
  • LIU, Junyu
  • LIAO, YUNLAN

Dates

Publication Date
20260506
Application Date
20231025

Claims (13)

  1. A class of nitrogen-containing heterocyclic polymers, wherein comprising a following general structural unit: and R 1 and R 2 are respectively hydrogen atom, methyl group, ethyl group, trifluoromethyl group, pyridyl group, phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group or mesitylene group; a is any integer greater than or equal to 1; b is any integer greater than or equal to 0; and A group is selected from following structural formulas: wherein, B group is a nitrogen-containing heterocycle and is selected from following structural formulas: and R 3 is a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclopropyl group, isopropyl group, isobutyl group, tert butyl group, cyclopentyl group, cyclohexyl group, or N, N, N-trimethylpentamine group; and When both A and B are multiple groups, a combination of A and B in A-B is random, and an arrangement of different combinations is also random.
  2. The nitrogen-containing heterocyclic polymers according to claim 1 are prepared by following methods, wherein in presence of an acid catalyst, a nitrogen-containing heterocyclic monomer C undergoes a Friedel-Crafts reaction with an aromatic monomer D, and the nitrogen-containing heterocyclic polymers are obtained.
  3. The nitrogen-containing heterocyclic polymers according to claim 1 are prepared by following methods, wherein in presence of an acid catalyst, a nitrogen-containing heterocyclic monomer C, an aromatic monomer D, and a ketone monomer E undergo a Friedel-Crafts reaction, and the nitrogen-containing heterocyclic polymers are obtained; and the ketone monomer E is selected from one or more combinations of following structures: and R 1 and R 2 are respectively hydrogen atom, methyl group, ethyl group, trifluoromethyl group, pyridine group, phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group or mesitylene group.
  4. The nitrogen-containing heterocyclic polymers according to claim 1 are prepared by following methods, wherein in presence of an acid catalyst, a nitrogen-containing heterocyclic monomer C, an aromatic monomer D, and an aromatic crosslinking agent monomer F undergo a Friedel-Crafts reaction, and the nitrogen-containing heterocyclic polymers are obtained; and the aromatic crosslinking agent monomer F is one or more combinations of triphenylmethane, 1,3,5-triphenylbenzene, triptycene, 9,9'-spirobifluorene, tetraphenyl ethylene, tetraphenylmethane, and hexaphenylbenzene.
  5. The nitrogen-containing heterocyclic polymers according to any one of claims 2 to 4, wherein: the nitrogen-containing heterocyclic monomer C is one or more combinations of and the aromatic monomer D is one or more combinations of benzene, biphenyl, 4,4-dimethylbiphenyl, fluorene, 9,9-dimethylfluorene, para-triphenyl, meta-triphenyl, ortho-triphenyl, diphenylmethane, 1,2-diphenylethane, 1,3-diphenylpropane, para-xylene dimer, 2,2-bis (3,4-dimethylphenyl) hexafluoropropane, 2,3-dimethyl-2,3-diphenylbutane, and 1,2-di (1-naphthyl) ethane; and the acid catalyst is one or more combinations of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methylsulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, and perfluorosulfonic acid resin.
  6. Quaternary ammonium salt polymers, a difference between a structure of the quaternary ammonium salt polymers and the nitrogen-containing heterocyclic polymers as claimed in claim 1 is: a nitrogen-containing heterocyclic ring of the quaternary ammonium salt polymers is one of structures of quaternary ammonium nitrogen heterocyclic rings as follows: R 4 is any one of methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cyclopropyl group, isopropyl group, isobutyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, and N, N, N-trimethylpentamine group.
  7. A preparation method of the quaternary ammonium salt polymers as claimed in claim 6 comprises following steps, wherein: in presence of alkali or no alkali, a quaternization reaction is carried out between the nitrogen-containing heterocyclic polymers as claimed in claim 1 and a monohalogenated compound, with a molar ratio of 1-20:1 between the monohalogenated compound and the N site, to obtain the quaternary ammonium salt polymer; and the monohalogenated compound is one or more combinations of iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, iodoheptane, iodooctane, iodononane, iododecane, bromomethane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromoheptane, bromooctane, bromononane, bromodecane, 2-bromoethylamine, 2-bromoethyl alcohol, cyclopropyl iodine, isopropyl iodine, isobutyl iodine, cyclopentyl iodine, cyclohexyl iodine and (5-bromopentyl) trimethylammonium bromide; and the alkali is one or more combinations of sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, trimethylamine, triethylamine, N,N-dimethylethylenediamine and N, N-diisopropylethylamine.
  8. Quaternary ammonium cross-linked polymers prepared by following method, wherein: in presence of alkali or no alkali, a quaternized cross-linking reaction is carried out between the nitrogen-containing heterocyclic polymers as claimed in claim 1 and a polyhalogenated compound, and nitrogen sites involved in the quaternized cross-linking reaction accounted for 0.001-10% of all nitrogen sites; after the reaction is completed, partial ammoniated cross-linked intermediate polymers are obtained, and then, remaining nitrogen sites of the intermediate polymer undergo quaternization without crosslinking reaction with a monohalogenated compound, to obtain the quaternary ammonium crosslinked polymers; or in presence of alkali or no alkali, a quaternized reaction without cross-linking is carried out between the nitrogen-containing heterocyclic polymers as claimed in claim 1 and a monohalogenated compound, and nitrogen sites participating in the quaternized reaction without cross-linking accounted for 0.90-99.999% of all nitrogen sites; after the reaction is completed, partial quaternized intermediate polymers are obtained; a quaternized cross-linking reaction is carried out between remaining nitrogen sites of the intermediate polymers and a polyhalogenated compound, to obtain the quaternary ammonium crosslinked polymers; or in presence of alkali or no alkali, a quaternized cross-linking reaction is carried out between the nitrogen-containing heterocyclic polymers as claimed in claim 1, a polyhalogenated compound and a monohalogenated compound at the same time, and nitrogen sites participating in the quaternized cross-linking reaction account for 0.001-10% of all nitrogen sites; after the reaction is completed, the quaternary ammonium crosslinked polymers are obtained; and the polyhalogenated compound is selected from one or more combinations of following structures: wherein, Y is F, Cl, Br or I, and n is an integer between 0 and 12; and the monohalogenated compound is one or more combinations of iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, iodoheptane, iodooctane, iodononane, iododecane, bromomethane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromoheptane, bromooctane, bromononane, bromodecane, cyclopropyl iodine, isopropyl iodine, isobutyl iodine, cyclopentyl iodine, cyclohexyl iodine and (5-bromopentyl) trimethylammonium bromide; and the alkali is one or more combinations of sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, trimethylamine, triethylamine, N, N-dimethylethylenediamine and N, N-diisopropylethylamine.
  9. A polymer flat membrane, wherein prepared by following method: dissolving any one or more of the nitrogen-containing heterocyclic polymers as claimed in claim 1, the quaternary ammonium salt polymers as claimed in claim 6, and the quaternary ammonium crosslinked polymers as claimed in claim 8 in an organic solvent, obtaining a polymer solution; or dissolving at least one of the nitrogen-containing heterocyclic polymers as claimed in claim 1 and the intermediate polymers as claimed in claim 8 in an organic solvent with the monohalogenated compound and/or the polyhalogenated compound, obtaining a polymer solution; and casting or moulding the polymer solution onto a substrate, drying to obtain the polymer flat membrane; and the organic solvent is one or more combinations of dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene, and ethyl acetate; and the substrate is a glass sheet, a copper sheet, an iron sheet, a ceramic sheet, a polytetrafluoroethylene sheet, a polyethylene terephthalate membrane, a polyamide membrane, a polytetrafluoroethylene membrane, a polyethylene membrane, a polypropylene membrane, a polyimide membrane, a carbon fiber membrane, or a glass fiber membrane.
  10. A polymer hollow fiber membrane, wherein prepared by following method: dissolving any one or more of the nitrogen-containing heterocyclic polymers as claimed in claim 1, the quaternary ammonium salt polymers as claimed in claim 6, and the quaternary ammonium crosslinked polymers as claimed in claim 8 in an organic solvent, obtaining a polymer solution; or dissolving at least one of the nitrogen-containing heterocyclic polymers as claimed in claim 1 and the intermediate polymers as claimed in claim 8 in an organic solvent with the monohalogenated compound and/or the polyhalogenated compound as claimed in claim 8, obtaining a polymer solution; and soaking a hollow fiber base membrane in the polymer solution, removing after soaking, and drying to obtain the polymer hollow fiber membrane; or using the polymer solution to prepare the polymer hollow fiber membrane by dry-wet spinning method; and the organic solvent is one or more combinations of dimethyl sulfoxide, N, N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene, and ethyl acetate; and the hollow fiber membrane comprises one of a ceramic hollow fiber membrane, a polytetrafluoroethylene hollow fiber membrane, a polyvinylidene fluoride hollow fiber membrane, a polyethylene terephthalate based hollow fiber membrane, a polyamide hollow fiber membrane, a polyethylene hollow fiber membrane, a polypropylene hollow fiber membrane, a carbon fiber hollow fiber membrane, and a glass hollow fiber membrane.
  11. A proton exchange membrane, wherein prepared by following method: soaking the polymer flat membrane as claimed in claim 9 and the polymer hollow fiber membrane as claimed in claim 10 in phosphoric acid aqueous solution respectively, a concentration of the phosphoric acid aqueous solution is 0.1-20M, and a soaking temperature is 0-90 °C, to obtain the proton exchange film.
  12. An anion exchange membrane, wherein prepared by following method: Soaking the polymer flat membrane as claimed in claim 9 or the polymer hollow fiber membrane as claimed in claim 10 in aqueous hydroxide solution, bromide solution, chloride solution, fluoride solution, nitrate solution or bicarbonate solution, and cleaning with pure water after soaking, obtain the anion exchange membrane; and the hydroxide is one or more combinations of lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, and ammonium hydroxide; and the bromide is one or more combinations of sodium bromide, potassium bromide, cesium bromide, ammonium bromide, magnesium bromide, and calcium bromide; and the chloride is one or more combinations of sodium chloride, potassium chloride, cesium chloride, ammonium chloride, magnesium chloride, and calcium chloride; and the fluoride is one or more combinations of sodium fluoride, potassium fluoride, cesium fluoride, ammonium fluoride, magnesium fluoride, and calcium fluoride; and the nitrate is one or more combinations of sodium nitrate, potassium nitrate, cesium nitrate, ammonium nitrate, magnesium nitrate, and calcium nitrate; and the bicarbonate is one or more combinations of sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, ammonium bicarbonate, magnesium bicarbonate, and calcium bicarbonate.
  13. Applications of the polymer flat membrane as claimed in claim 9, the polymer hollow fiber membrane as claimed in claim 10, the proton exchange membrane as claimed in claim 11, and the anion exchange membrane as claimed in claim 12 in alkaline fuel cells, alkaline water electrolysis hydrogen production, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, nickel hydrogen batteries, zinc manganese batteries, acid separation, salt lake lithium extraction, electrodialysis, water treatment, and membrane humidification, respectively.

Description

TECHNICAL FIELD The present invention relates to a technical field of polymer functional materials, and in particular to a class of nitrogen-containing heterocyclic polymers, a class of polymer membranes and applications thereof. BACKGROUND Fuel cells, hydrogen production from electrolytic water, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, acid separation, lithium extraction from salt lakes, etc., depend on functional polymer film materials, and the essence of such films lies in the selective permeability of ions. However, at present, such films are still very lacking, especially the highly stable and highly selective ion exchange membranes suitable for strong acid and alkali environments. The ion exchange membrane is composed of a polymer containing ion groups, and its stability is determined by the polymer chain skeleton and the ion groups on the skeleton. In recent years, it has been proposed to use carbon chains as the chain skeleton of polymers to solve the stability of the skeleton. Various quaternary ammonium salt ions have also been developed as anion exchange groups. However, the majority of quaternary ammonium salt ions have low stability. In recent years, it has been found that N-methylpiperidinium quaternary ammonium salt ions have good stability. However, N-methylpiperidinium quaternary ammonium salt ions are generally only stable in medium concentration of alkali solutions or at room temperature. For example, Jannasch et al. reported that a class of linear poly (aryl N-methylpiperidinium) electrolyte in 2M sodium hydroxide aqueous solution could exist stably for 15 days at 60°C, but a cationic degradation is 5% within 15 days at 90°C (reference: Jannasch P., et al., Adv. Funct.Mater. 2017, 1702758; DOI: 10.1002/adfm.201702758). Hu et al. reported that a class of branched poly (aryl N-methylpiperidinium) electrolyte could stably exist for 1500 hours at 80°C in 1M aqueous potassium hydroxide solution, but 17% of the cations were degraded in 3M aqueous potassium hydroxide solution at 80°C for 1500 hours (literature: Hu X., et al., Angew. Chem. Int. Ed. 2022, 61, e202114892; DOI: 10.1002/anie. 202114892). Chinese patent CN202011577765.3 also reported a cross-linked poly (aryl N-methylpiperidinium) electrolyte, soaking in 4M aqueous sodium hydroxide solution at 80°C for 10 days, and a cation degradation occurred by 4.6%. Therefore, it is necessary to explore new quaternary ammonium ions in order to further develop new ion exchange membranes with excellent comprehensive properties, especially excellent alkaline stability. CN 107 910 576 A, CN 111 269 401 A, WO 2022/170022 A1, and US 2021/009726 A1 disclose the use of polymers containing aryl- and piperidine units in anion exchange membranes. SUMMARY In order to solve problems in prior art, the present invention provides a class of nitrogen-containing heterocyclic polymers, a class of polymer membranes and applications thereof. The nitrogen-containing heterocycles in this kind of nitrogen-containing heterocyclic polymers have large steric hindrance and electron donating groups, which are conducive to further improving stability of materials. This class of polymer films has advantages of large size, thin thickness, high stability and high ionic conductivity, and can be used in many fields. A technical solution adopted to achieve the objectives of the present invention is: A class of nitrogen-containing heterocyclic polymers, comprising a following general structural unit: wherein: R1 and R2 are respectively hydrogen atom, methyl group, ethyl group, trifluoromethyl group, pyridyl group, phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group or mesitylene group; a is any integer greater than or equal to 1; b is any integer greater than or equal to 0, generally within 10 million. A group is selected from following structural formulas: B group is a nitrogen-containing heterocyclic ring and is selected from following structural formulas: wherein: R3 is a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclopropyl group, isopropyl group, isobutyl group, tert butyl group, cyclopentyl group, cyclohexyl group, or N, N, N-trimethylpentamine group. When both A and B are multiple groups, a combination of A and B in A-B is random, and an arrangement of different combinations is also random. Furthermore, the class of nitrogen-containing heterocyclic polymers are prepared by following methods: In presence of an acid catalyst, a nitrogen-containing heterocyclic monomer C undergoes a Friedel-Crafts reaction with an aromatic monomer D, and a molar ratio of the nitrogen-containing heterocyclic monomer C to the aromatic monomer D is 0.5-1.5:1, and the nitrogen-containing heterocyclic polymers are obtained. Furthermore, the class of nitrogen-containing heterocyclic polymers are prepared by following methods: In presence of an acid catalyst, a nitrogen-containin