Poly(azulenylethylene) polymer and use thereof

Abstract

Disclosed in the present invention are a poly(azulenylethylene) polymer and a use thereof. The present invention provides a poly(azulenylethylene) polymer. The polymer has a general structural formula as represented by formula I. The poly(azulenylethylene) polymer provided by the present invention has structural diversity. The backbone of the polymer can be connected to different sites of an azulenyl unit, and a variety of different functional groups can be introduced at the remaining sites of the azulenyl unit. The polymer can be either a homopolymer of an azulenyl monomer or a copolymer of an azulenyl monomer and other monomers such as arylethylene and methacrylate. The poly(azulenylethylene) polymer provided by the present invention has good thermal stability, a relatively high glass transition temperature, reversible proton response, and good solution processability. The poly(azulenylethylene) polymer provided by the present invention is used for applications based on ion response or ion conduction, for example, can be used for preparing fuel cell proton exchange membranes, ion battery solid-state electrolytes, and metal corrosion protection, bacterial protection, and acidochromic devices.

Description

A polyvinyl alcohol polymer and its applications Technical Field

[0001] This invention relates to the field of polymers, and more specifically to a polyvinyl alcohol polymer and its applications. Background Technology

[0002] Polystyrene (PS) is one of the most representative general-purpose and functional polymers, combining excellent thermal, electrical, and optical properties. For example, it has low thermal conductivity and good insulation; high resistivity and good insulation; high light transmittance, allowing transmission of all wavelengths of visible light; and resistance to solvents, various alkalis, salts, and most acids. Therefore, PS has a wide range of applications, including disposable tableware, packaging, daily-use decoration, and optical instrument parts. Global demand for PS is high annually; according to Statista Research Department, global PS production capacity reached 15.44 million tons in 2022.

[0003] The benzene ring in the PS structure determines the physical properties and applications of polystyrene, and also enables PS to be further functionalized. Due to the mature and diverse synthetic methods of PS, researchers have long been committed to developing PS analogs with novel structures, such as directly functionalized PS derivatives (Ejima, H. et al. J. Am. Chem. Soc. 2022, 144, 2450; Zhu, Y.; Liu, B.; Li, S.; Lu, G. et al. Chem. Mater. 2022, 34, 6505; Coughlin, JE et al. J. Polym. Sci. Part A: Polym. Chem. 2013, 51, 2416.) and heteroatom-doped PS derivatives (Klausen, R.S. et al. Macromolecules 2018, 51, 6859; Liu, S.-Y.). F. et al. Macromolecules 2019, 52, 4500., polyarylethene heterocyclic ethylene (Goseki, R.; Ishizone, T. et al. Macromolecules 2021, 54, 8173.), etc., with the expectation of developing polymer materials with new properties and functions. Some functionalized PS derivatives have become research hotspots in industry and academia, among which sulfonated and chloromethylated PS are the most representative. Sulfonated PS has been widely used in wastewater treatment, ion exchange, semiconductors, medical fields, etc. For example, high-conductivity aqueous solutions prepared from polystyrene sulfonate (PSS) and poly(3,4-ethylenedioxythiophene) (PEDOT) can be used in organic light-emitting diodes, organic solar cells, supercapacitors, etc. Chloromethylated PS resin can be used for solid-phase peptide synthesis. Merrifield's pioneering research on this topic won the 1984 Nobel Prize in Chemistry, and the new discipline of solid-phase synthesis was born.

[0004] Therefore, developing PS-type polymer materials with novel structures and unique properties is of great significance for developing new functional applications.

[0005] Unlike the benzene ring in the PS structure, azurite is a non-benzene aromatic hydrocarbon composed of cyclopentadiene and cycloheptanetriene. It exhibits a beautiful deep blue color, a large molecular dipole moment (1.08D), non-mirror frontier molecular orbitals, anti-Kasha luminescence properties, reversible proton responsiveness, and multiple sites that can be functionalized. Due to its unique chemical structure and physicochemical properties, azurite and its derivatives have applications in organic electronic devices (Gao, X. et al. Angew. Chem. Int. Ed. 2018, 57, 1322; McNeill, CR; Gao, X. et al. ACS Macro Lett. 2023, 12, 487.), ion-selective electrodes (Lindfors, T. et al. Sens. Actuators B 2015, 207, 918; Gyurcsanyi, RE; Lindfors, T. et al. Analyst 2016, 141, 2990.), sensors (Zhu, L. et al. J. Phys. Chem. Lett. 2018, 9, 550.), photothermal therapy (Shi, Y.; Xu, H.; Gao, X. et al. ACS Appl. Mater. Interfaces 2022, 14, 19192; Ding D.; Gao, X. et al. Angew. Chem. Int. Ed. 2024, e202400372.) have shown great application potential in multiple fields. In recent years, research on azurite-based organic conjugated polymers in proton exchange membrane hydrogen fuel cells (Wang, J.; Gao, X. et al. ACS Macro Letters 2022, 11, 680; Wang, J.; Gao, X. et al. ACS Materials Lett. 2022, 4, 392) has further attracted the attention and interest of researchers. Summary of the Invention

[0006] The purpose of this invention is to provide a polyazine-based polymer and its applications. The polyazine-based polymer provided by this invention exhibits structural diversity; the polymer backbone can be connected to different sites of azurite units, and various functional groups can be introduced at the remaining sites of the azurite units. The polyazine-based polymer provided by this invention possesses good thermal stability, a high glass transition temperature, reversible proton responsiveness, and good solution processability. The polyazine-based polymer provided by this invention can fully utilize the proton responsiveness of azurite units, and can be used in applications based on proton response, ion response, and ion conduction, such as proton exchange membranes for fuel cells, solid electrolytes for ion batteries, metal corrosion protection, bacterial protection, and acid-chromic devices. When used in proton exchange membranes, the polyazine-based polymer can be loaded into a perfluorosulfonic acid resin (Nafion), and the resulting composite proton exchange membrane has a higher proton conductivity than a single Nafion membrane. Hydrogen fuel cells prepared using the composite proton exchange membrane show significantly higher performance than those prepared using a single Nafion membrane.

[0007] To achieve the above objectives, the technical method employed by this invention is as follows:

[0008] In a first aspect, the present invention provides a polyvinyl alcohol polymer having the following general structural formula:

[0009] In this context, the numbers "1 to 8" refer to the point numbers of each element in the azurite unit. It refers to the connection site between the azurite unit (Az) and the polymer backbone, which can be located at any position from position 1 to position 8 of the azurite unit;

[0010] “m” and “n” refer to the number of repeating units, where m is an integer from 0 to 5000 and n is an integer from 10 to 5000.

[0011] Monomers copolymerized with azulene monomers These are conventional polymerizable monomers in this field.

[0012] “R” represents an unsubstituted or substituted group selected from the group consisting of: H, -OC(O)C1-C6 alkyl, -COOC1-C6 alkyl, -CN, C6-C 10 Aryl, 5-10 aryl,

[0013] X and Y are each independently selected from the following group: H, methyl, or X and Y together with the carbon atom attached to them to form a substituted or unsubstituted five- or six-membered heterocyclic group;

[0014] Wherein, the substitution refers to one or more hydrogen atoms on the substituent group being substituted by a substituent selected from the group consisting of: H, OH, halogen, carbonyl; the heterocyclic group is saturated, partially unsaturated or aromatic, and has 1 to 5 heteroatoms selected from the group consisting of: N, S or O.

[0015] R′ refers to a substituent on the azurite five-membered ring, and each R′ is independently selected from the group consisting of: hydrogen, C1-C… 24 Alkoxy, C3-C 19 Glycol monomethyl ether group, chlorine, aldehyde group, nitro group, trifluoroacetyl group, C2-C 16 Acyl group, C2-C 16 Alkyl, C2-C 25 Ester group, C2-C 25 Amide group, sulfonic acid group, phenyl, naphthyl, azulel, pyridyl, thiophene group, quinolinyl, isoquinolinyl, benzothiophene group, acetyl, ethyl formate group, ethyl or tert-butyl group;

[0016] R″ refers to a substituent on the seven-membered ring of the azurite unit, and each R″ is independently selected from the group consisting of: phenyl, naphthyl, azuthyl, pyridyl, thiophene, quinolinyl, isoquinolinyl, benzothiophene, hydrogen, methyl, hydrogen, ethyl, isopropyl, cyano, methylthio, aldehyde, piperidinyl, diethylamino, morpholinyl, tetrahydropyrrole, C3-C 12 Straight-chain alkyl, C1-C 24 Alkoxy or C3-C 19 The glycol monomethyl ether group.

[0017] In another preferred embodiment, m is an integer from 0 to 3000, more preferably an integer from 0 to 1000; n is an integer from 10 to 3000, more preferably an integer from 0 to 1000.

[0018] In another preferred embodiment, when m = 0, the polyvinyl alcohol polymer is a homopolymer.

[0019] In another preferred embodiment, Selected from the following group: styrene, methyl methacrylate, methyl acrylate, acrylonitrile, vinyl acetate, maleic anhydride.

[0020] In another preferred embodiment, the polyvinyl alcohol polymer has the following general structural formula:

[0021] Wherein, m, n, R, X, Y, R′ and R″ are as described above.

[0022] In another preferred embodiment, the connection method between the azurite (Az) unit and the main chain is selected from the following group:

[0023] Among them, "1, 2 and 4-6" refer to the sites on the azurite units that are connected to the polymer backbone.

[0024] In another preferred embodiment, the polyvinyl alcohol polymer specifically has the following structural formula:

[0025] In the structural formulas I-1 and I-6, R 2 Each independently is hydrogen, C1-C 24 alkoxy, or C3-C 19 The glycol monomethyl ether group, preferably

[0026] In the structural formulas I-4, I-5 and I-6, R 1 and R 3 Independently, it can be hydrogen, chlorine, aldehyde, nitro, sulfonic acid, trifluoroacetyl, or C2-C. 16 Acyl group, C2-C 16 Alkyl, C2-C 25 amide group, or C2-C 25 Ester group, preferred Trifluoroacetyl, ethyl, tert-butyl, or

[0027] In the structural formulas I-4 and I-5, R 7 Independently, it is phenyl, naphthyl, azulel, pyridyl, thienyl, quinolinyl, isoquinolinyl, or benzothienyl;

[0028] In the structural formula I-1, R 3 It can be hydrogen, chlorine, aldehyde, nitro, sulfonic acid, trifluoroacetyl, or C2-C. 16 Acyl group, C1-C 16 Alkyl, C2-C 25 amide group, C2-C 25 Ester, phenyl, naphthyl, azulel, pyridyl, thiophene, quinolinyl, isoquinolinyl, benzothiophene, preferably Trifluoroacetyl, methyl, ethyl, tert-butyl, or

[0029] R 4 and R 8 Independently hydrogen or methyl;

[0030] R 5 The derivatives are hydrogen, ethyl, isopropyl, phenyl, naphthyl, azulel, pyridyl, thienyl, quinolinyl, isoquinolinyl, and benzothienyl.

[0031] R 6 It can be hydrogen, methyl, cyano, methylthio, aldehyde, piperidinyl, diethylamino, morpholino, tetrahydropyrrolyl, or C3-C.12 Straight-chain alkyl, C1-C 24 Alkoxy, C3-C 19 The glycol monomethyl ether group, phenyl, naphthyl, azulel, pyridyl, thiophene, quinolinyl, isoquinolinyl, benzothiophene, preferably n-octyl,

[0032] R 7 The radicals are hydrogen, phenyl, naphthyl, azulel, pyridyl, thiophene, quinolinyl, isoquinolinyl, and benzothiophene.

[0033] In the aforementioned structural formula I-2, R 1 and R 3 Independently, it can be hydrogen, chlorine, aldehyde, nitro, trifluoroacetyl, sulfonic acid, acetyl, ethyl, ethyl formate, N-ethylformamido, tert-butyl, R 1 and R 3 It can be methyl but not simultaneously methyl;

[0034] R 4 and R 8 It can be hydrogen or methyl, but not both simultaneously methyl;

[0035] R 5 and R 7 It can be hydrogen, ethyl, or isopropyl, but not simultaneously ethyl or isopropyl;

[0036] R 6 It is hydrogen, cyano, methylthio, aldehyde, piperidinyl, diethylamino, morpholino, tetrahydropyrrole, C3-C 12 Straight-chain alkyl, C1-C 24 Alkoxy, C3-C 19 The glycol monomethyl ether group, phenyl, naphthyl, azulel, pyridyl, thiophene, quinolinyl, isoquinolinyl, benzothiophene, preferably n-octyl,

[0037] In the aforementioned structural formula I-5, R 6 It is methyl;

[0038] In the aforementioned structural formula I-6, R 4 and R 7 It can be either hydrogen or methyl;

[0039] In the structural formulas I-1, I-2, I-4, I-5 and I-6, n is selected from 10 to 1000.

[0040] In another preferred embodiment, when R in the structural formulas I-1 and I-6 2 Independently for C1-C 24 When alkoxy is present, the "C1-C" 24"Alkoxy" refers to C1-C8 alkoxy groups;

[0041] And / or, when R in the structural formula I-1 2 and R 6 R in I-2 6 And R in I-6 2 Independently for C3-C 19 When the glycol monomethyl ether group is present, the "C3-C" 19 The glycol monomethyl ether group is C7-C 19 Glycol monomethyl ether group;

[0042] And / or, when R in the structural formula I-1 3 R in I-4, I-5 and I-6 1 and R 3 Independently for C2-C 16 When acyl, the "C2-C" 16 The acyl group is a C2-C8 acyl group;

[0043] And / or, when R in the structural formula I-1 3 R in I-4, I-5 and I-6 1 and R 3 Independently for C2-C 25 When the amide group is present, the "C2-C" 25 The "amide group" is a C2-C9 amide group;

[0044] And / or, when R in the structural formula I-1 3 R in I-4, I-5 and I-6 1 and R 3 Independently for C2-C 25 When esterified, the "C2-C" group is mentioned. 25 The "ester group" is a C2-C9 ester group;

[0045] And / or, when R in the structural formulas I-4, I-5 and I-6 1 and R 3 Independently for C2-C 16 When alkyl, the "C2-C" 16 "alkyl" refers to C2-C8 alkyl groups;

[0046] And / or, when R in the structural formula I-1 3 For C1-C 16 When alkyl, the "C1-C" 16 "alkyl" refers to C1-C8 alkyl groups;

[0047] And / or, when R in the structural formulas I-1 and I-2 6Independently for C3-C 12 When the chain is linear alkyl, the "C3-C" 12 "Straight-chain alkyl" refers to C3-C8 straight-chain alkyl;

[0048] And / or, when R in the structural formulas I-1 and I-2 6 Independently for C1-C 24 When alkoxy is present, the "C1-C" 24 "Alkoxy" is C1-C 12 Alkoxy;

[0049] And / or, when R in the structural formula I-1 3 When it is methyl, R in the structural formula I-1 8 For methyl, R 5 It is ethyl or isopropyl, R 4 R 6 and R 7 Both are hydrogen;

[0050] And / or, when R in the structural formula I-1 6 When it is methyl, R in the structural formula I-1 4 and R 8 Both are methyl groups, R 5 and R 7 Both are hydrogen;

[0051] And / or, when R in the structural formula I-2 1 When it is methyl, R in the structural formula I-2 4 For methyl, R 7 It is isopropyl or ethyl, R 3 R 5 R 6 and R 8 Both are hydrogen.

[0052] In another preferred embodiment, when R in the structural formulas I-1 and I-6 2 Independently for C1-C 24 When alkoxy is present, the "C1-C" 24 "alkoxy" is

[0053] And / or, when R in the structural formula I-1 2 and R 6 R in I-2 6 And R in I-6 2 Independently for C3-C 19 When the glycol monomethyl ether group is present, the "C3-C" 19 The glycol monomethyl ether group is

[0054] And / or, when R in the structural formula I-1 3 R in I-4, I-5 and I-6 1 and R 3 Independently for C2-C 16 When acyl, the "C2-C" 16 "Acyl" is

[0055] And / or, when R in the structural formulas I-4, I-5 and I-6 1 and R 3 Independently for C2-C 16 When alkyl, the "C2-C" 16 "alkyl" refers to tert-butyl or ethyl;

[0056] And / or, when R in the structural formulas I-1 and I-2 6 Independently for C1-C 24 When alkoxy is present, the "C1-C" 24 "alkoxy" is

[0057] In another preferred embodiment, R in structural formula I-1 3 It can be hydrogen, chlorine, aldehyde, nitro, sulfonic acid, trifluoroacetyl, or C2-C. 16 Acyl group, C1-C 16 Alkyl, C2-C 25 Ester group, C2-C 25 Amide, phenyl, naphthyl, azulel, pyridyl, thiophene, quinolinyl, isoquinolinyl, or benzothiophene, preferably. Trifluoroacetyl, Aldehyde, methyl, ethyl, tert-butyl, or When R in the aforementioned structural formula I-1 3 When it is methyl, R in the structural formula I-1 8 For methyl, R 5 It is ethyl or isopropyl, R 4 R 6 and R 7 Both are hydrogen.

[0058] In another preferred embodiment, R in structural formula I-1 6 It can be hydrogen, methyl, cyano, methylthio, aldehyde, piperidinyl, diethylamino, morpholino, tetrahydropyrrolyl, or C3-C. 12 Straight-chain alkyl, C1-C 24 Alkoxy, C3-C 19 The glycol monomethyl ether group, phenyl, naphthyl, azulel, pyridyl, thiophene, quinolinyl, isoquinolinyl, or benzothiophene, preferably n-octyl, When R in the aforementioned structural formula I-1 6 When it is methyl, R in the structural formula I-1 4 and R 8 Both are methyl groups, R 5 and R 7 Both are hydrogen.

[0059] In another preferred embodiment, in the structural formula I-2, R 1 and R 3 Each group independently represents hydrogen, chlorine, aldehyde, nitro, sulfonic acid, trifluoroacetyl, acetyl, ethyl, ethyl formate, tert-butyl, N-ethylformamido, R 1 and R 3 It is methyl but not simultaneously methyl, when R in the structural formula I-2 1 When it is methyl, R in the structural formula I-2 4 For methyl, R 7 It is isopropyl or ethyl, R 3 R 5 R 6 and R 8 Both are hydrogen.

[0060] In another preferred embodiment, the azurite unit may be any of the following structures:

[0061] In another preferred embodiment, the average degree of polymerization (n) of the polyvinyl alcohol polymer is 10 to 5000, more preferably 10 to 3000, and even more preferably 10 to 1000;

[0062] And / or, the polydispersity index of the polyvinyl alcohol polymer. The value ranges from 1.0 to 5.0.

[0063] In another preferred embodiment, the average degree of polymerization (n) of the polyvinyl alcohol polymer may independently be 10 to 500, more preferably 10 to 300, more preferably 10 to 150, and even more preferably 10 to 50, 100 to 150, or 250 to 300, for example 15, 22, 23, 27, 30, 33, 109, 121, 142, 155, 258, 273, or 289.

[0064] In another preferred embodiment, the polydispersity index of the polyvinyl alcohol polymer is... It can be independently 1.0 to 4.0, preferably 1.21, 1.37, 1.44, 1.53, 1.62, 1.65, 1.71, 1.94, 1.95, 2.25, 3.06 or 3.57.

[0065] In another preferred embodiment, the polyvinyl alcohol polymer is any of the following polymers:

[0066] Where m is an integer from 0 to 5000; n is an integer from 10 to 5000.

[0067] In another preferred embodiment, the number average molecular weight of the polyvinyl alcohol polymer is 3,000 to 500,000, more preferably 5,000 to 500,000, and even more preferably 10,000 to 500,000.

[0068] In another preferred embodiment, the polydispersity index of the polyvinyl alcohol polymer is 1.0 to 4.0, more preferably 1.0 to 3.0, and even more preferably 1.0 to 2.0.

[0069] In another preferred embodiment, the polyvinyl alcohol polymer may be any of the following polymers:

[0070] 1. Number average molecular weight M n The range is 3,000 to 500,000, with a high degree of dispersion. The value is 1.0 to 2.0;

[0071] 2. Number average molecular weight M n The range is 3,000 to 500,000, with a high degree of dispersion. The value is 1.0 to 2.0;

[0072] 3. Number average molecular weight M n The range is 3,000 to 500,000, with a high degree of dispersion. The value is 1.0 to 2.0;

[0073] 4. Number average molecular weight M n The range is 5000 to 500000, with a high degree of dispersion. The value ranges from 1.0 to 4.0.

[0074] 5.' Number average molecular weight M n The range is 10,000 to 500,000, with a high degree of dispersion. The value is 1.0 to 2.0;

[0075] 6. Number average molecular weight M n The range is 5000 to 500000, with a high degree of dispersion. The value is 1.0 to 2.0;

[0076] 7. Number average molecular weight M nThe range is 5000 to 500000, with a high degree of dispersion. The value is 1.0 to 2.0;

[0077] 8. Number average molecular weight M n The range is 3,000 to 500,000, with a high degree of dispersion. The value is 1.0 to 2.0;

[0078] 9. Number average molecular weight M n The range is 5000 to 500000, with a high degree of dispersion. It ranges from 1.0 to 2.0.

[0079] In another preferred embodiment, the polyvinyl alcohol polymer may be any of the following polymers:

[0080] 1. Number average molecular weight M n The multiplicity index is 4677. It is 1.44;

[0081] 2. Number average molecular weight M n The value is 4374, which is the multi-dispersion index. It is 1.62;

[0082] 3. Number average molecular weight M n The multi-dispersion index is 4491. It is 1.65;

[0083] 4. Number average molecular weight M n The value is 30450, which is the multi-dispersion index. It is 1.71;

[0084] 5. Number average molecular weight M n The multi-dispersion index is 19942. It is 1.95;

[0085] 6. Number average molecular weight M n The value is 7074, which is the multi-dispersion index. It is 1.37;

[0086] 7. Number average molecular weight M n The dispersion index is 9487. It is 1.71;

[0087] 8. Number average molecular weight Mn The multi-dispersion index is 3378. It is 1.60;

[0088] 9. Number average molecular weight M n The value is 5073, which is the multi-dispersion index. It is 1.46.

[0089] A second aspect of the present invention provides a method for preparing polyvinyl alcohol polymers as described in the first aspect of the present invention, comprising the following steps:

[0090] In an inert gas atmosphere, the azulene monomers shown in the following formula are homopolymerized or copolymerized with optional conventional polymeric monomers in the art to obtain the polyazolene polymers described above.

[0091] Wherein, R′ and R″ are defined as described in the first aspect of the present invention, and the vinyl group can be located at any position on the azurite unit (on a five-membered ring or a seven-membered ring);

[0092] The conventional polymeric monomers described herein are as defined in the first aspect of this invention.

[0093] In another preferred embodiment, the polymerization reaction is carried out in solution, and the solvent is one or more of aromatic solvents, ether solvents, alcohol solvents, amide solvents, and water.

[0094] In another preferred embodiment, the copolymerization reaction includes a free radical polymerization reaction.

[0095] In another preferred embodiment, the aromatic solvent may be a conventional aromatic solvent for this type of reaction in the art, such as benzene or toluene.

[0096] In another preferred embodiment, the ether solvent may be a conventional ether solvent for this type of reaction in the art, such as tetrahydrofuran or anisole.

[0097] In another preferred embodiment, the alcohol solvent may be a conventional alcohol solvent for this type of reaction in the art, such as 2,2,2-trifluoroethanol.

[0098] In another preferred embodiment, the amide solvent may be a conventional amide solvent for this type of reaction in the art, such as N,N-dimethylformamide.

[0099] In another preferred embodiment, the mass-to-volume ratio of the polymeric monomer to the solvent can be a conventional mass-to-volume ratio for this type of reaction in the art, preferably 50 g / L to 2000 g / L, more preferably 500 g / L to 1000 g / L or 1500 g / L to 2000 g / L, more preferably 1600 g / L to 1900 g / L, for example about 1800 g / L.

[0100] In another preferred embodiment, the copolymerization reaction is carried out in the absence of a solvent.

[0101] In another preferred embodiment, the polymerization reaction is carried out in the presence of an initiator.

[0102] In another preferred embodiment, the initiator is a conventional initiator for this type of reaction in the art, such as azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO).

[0103] In another preferred embodiment, the molar ratio of the initiator to the polymerizing monomer may be a conventional molar ratio for this type of reaction in the art, for example, 0.5% to 5%, or for example, 0.5%, 0.7%, 1%, 2% or 3%.

[0104] In another preferred embodiment, the temperature of the free radical polymerization reaction is 60°C to 120°C, for example, about 70°C, 80°C or 110°C.

[0105] In another preferred embodiment, the polymeric monomer (azulene monomer) may be copolymerized with polymeric monomers conventional in the art, such as styrene, methyl methacrylate, methyl acrylate, acrylonitrile, vinyl acetate, or maleic anhydride.

[0106] In another preferred embodiment, without violating common sense in the art, the above preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0107] In a third aspect, the present invention provides a use of the polyvinyl alcohol polymer described in the first aspect of the present invention for preparing materials based on proton transport and proton response, or cationic and / or anionic conductive materials.

[0108] In another preferred embodiment, the polyvinyl alcohol polymer is used to prepare proton exchange membranes for fuel cells, anion exchange membranes, solid electrolytes for ion batteries, metal corrosion protection, bacterial protection, and acid-induced color-changing devices.

[0109] In another preferred embodiment, the polyvinyl alcohol polymer is used as an additive to Nafion perfluorosulfonic acid resin in the preparation of proton exchange membranes for hydrogen fuel cells.

[0110] In another preferred embodiment, the cation is selected from the group consisting of lithium ions, sodium ions, potassium ions, or calcium ions; and the anion is selected from the group consisting of chloride ions or hydroxide ions. Attached Figure Description

[0111] Figure 1 shows the thermogravimetric analysis curves of polymers P1-P6.

[0112] Figure 2 shows the differential scanning calorimetry curves of polymers P1-P6.

[0113] Figure 3 shows the UV-Vis absorption spectra of polymers P1-P6 before and after protonation.

[0114] Figure 4 shows the color changes of the polymer P1-P6 solution before protonation, after protonation, and after deprotonation.

[0115] Figure 5 shows the change in proton conductivity as a function of temperature for intrinsic Nafion membrane, Nafion / P1, Nafion / P2, and Nafion / P4-P6 composite membrane at 0% relative humidity.

[0116] Figure 6 shows the variation of proton conductivity with temperature at 100% relative humidity for intrinsic Nafion membrane, Nafion / P1, Nafion / P2, and Nafion / P4-P6 composite membrane.

[0117] Figure 7 shows the variation of proton conductivity with relative humidity at 80℃ for intrinsic Nafion membrane, Nafion / P1, Nafion / P2, and Nafion / P4-P6 composite membrane.

[0118] Figure 8 shows the current density-voltage / power density relationship of hydrogen fuel cells prepared using intrinsic Nafion membranes and Nafion / P6 composite membranes at 80℃ and 25% relative humidity.

[0119] Figure 9 shows the current density-voltage / power density relationship of hydrogen fuel cells prepared using intrinsic Nafion membranes and Nafion / P6 composite membranes at 80℃ and 100% relative humidity. Detailed Implementation

[0120] To facilitate understanding of the invention, certain technical and scientific terms are specifically defined below. Unless otherwise expressly defined herein, all other technical and scientific terms used herein have the meanings commonly understood by one of ordinary skill in the art to which this invention pertains. Before describing the invention, it should be understood that the invention is not limited to the specific methods and experimental conditions described, as such methods and conditions can vary. It should also be understood that the terminology used herein is intended only to describe particular embodiments and is not intended to be restrictive; the scope of the invention will be limited only by the appended claims.

[0121] As used herein, the term “comprising” or its variations such as “including” or “comprising” are understood to include the said element or component without excluding other elements or other components.

[0122] The term “about” can refer to a value or composition within an acceptable margin of error for a particular value or composition as determined by a person skilled in the art, depending in part on how the value or composition is measured or determined. For example, as used herein, the expression “about 100” includes all values ​​between 99 and 101 (e.g., 99.1, 99.2, 99.3, 99.4, etc.).

[0123] As used herein, unless otherwise stated, any concentration range, percentage range, proportion range, or integer range shall be understood to include any integer value within the range and, where appropriate, its fractional value (e.g., one-tenth and one-hundredth of an integer).

[0124] As used herein, the term “and / or” refers to and covers any and all possible combinations of one or more of the related listed items.

[0125] The term "C1-C" 24 "Alkoxy group" refers to a straight-chain or branched alkoxy group having 1-24 carbon atoms. The C1-C... 24 Alkoxy groups are preferred, C1-C. 12 Alkoxy groups, more preferably C2-C8 alkoxy groups, such as ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, and their various isomers.

[0126] The term "C3-C" 19 "Glycol monomethyl ether group" refers to a glycol monomethyl ether group having 3-19 carbon atoms. n is selected from 1 to 9). The C3-C mentioned above... 19 The glycol monomethyl ether group is preferably C7-C. 19 Glycol monomethyl ether group, more preferably C7-C 13 Glycol monomethyl ether groups, such as triethylene glycol monomethyl ether group, tetraethylene glycol monomethyl ether group, pentaethylene glycol monomethyl ether group, and hexaethylene glycol monomethyl ether group.

[0127] The term "C2-C" 16 "Acyl" refers to a straight-chain or branched acyl group having 2-16 carbon atoms. The C2-C... 16 The acyl group is preferably a C2-C8 acyl group, such as acetyl, n-butyryl, n-octanoyl, or 2-ethylhexanoyl.

[0128] The term "C2-C" 25 "Ester group" refers to an ester group formed by the esterification of formic acid and a straight-chain or branched alcohol having 1-24 carbon atoms. The C2-C... 25 The preferred ester group is a C2-C9 ester group, such as methyl formate or ethyl formate.

[0129] The term "C2-C" 25"Amide group" refers to an amide group formed by the amidation of formic acid and a straight-chain or branched amine having 1-24 carbon atoms. The C2-C... 25 The amide group is preferably a C2-C9 amide group, such as N-ethylformamido or N-hexylformamido.

[0130] The term "C1-C" 16 "Alkyl" refers to a straight-chain or branched alkyl group having 1-16 carbon atoms. The C1-C... 16 The alkyl group is preferably a C1-C8 alkyl group, such as methyl, ethyl, n-butyl, n-octyl, or 2-ethylhexyl.

[0131] The term "C3-C" 12 "Straight-chain alkyl" refers to a straight-chain alkyl group having 3-12 carbon atoms. The C3-C... 12 The straight-chain alkyl group is preferably a C3-C8 straight-chain alkyl group, such as n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl.

[0132] The term "polymer" encompasses all monomer polymerizations, including oligomers and high polymers.

[0133] The term "number-average molecular weight (M)" n ")" refers to the average molecular weight calculated based on the amount of substance.

[0134] The term "weight-average molecular weight (M)" w ")" refers to the statistical average molecular weight by mass.

[0135] The term "multi-dispersion index" "This refers to the ratio of weight-average molecular weight to number-average molecular weight."

[0136] The term "average degree of polymerization (n)" refers to the average number of repeating units in each polymer molecule.

[0137] The present invention has the following advantages and beneficial effects:

[0138] The polyazine-based polymers provided by this invention can fully utilize the low symmetry of azurite, allowing different sites of azurite units to be connected to the polymer backbone, and introducing a variety of different functional groups at the remaining sites of azurite units. Therefore, the polyazine-based polymers have rich chemical structures.

[0139] The polyvinyl alcohol polymers provided by this invention have good thermal stability, high glass transition temperature, reversible proton responsiveness, and good solution processability.

[0140] The polyaluminum ethylene polymer provided by this invention can fully utilize the proton-responsive characteristics of azurite and its derivatives. This polyaluminum ethylene polymer can be used in applications based on proton response, ion response, and ion conduction, for example, in proton exchange membranes. When used in proton exchange membranes, the polyaluminum ethylene polymer can be loaded into a perfluorosulfonic acid resin (Nafion) to form a composite proton exchange membrane. The composite proton exchange membrane exhibits a higher proton conductivity than a single Nafion membrane. Hydrogen fuel cells prepared using the composite proton exchange membrane show significantly higher performance than those prepared using a single Nafion membrane. Specifically, the composite proton exchange membrane prepared by loading P1, P2, P4, P5, and P6 into Nafion exhibits excellent performance, with a proton conductivity of up to 251.62 mS / cm measured at 100% relative humidity and 80°C. -1 The hydrogen fuel cell can output a power of up to 367.2 mW / cm². -2 The maximum current density can reach 1219.5 mA cm⁻¹ -2 Compared to Nafion membranes alone, these figures represent improvements of 80%, 60%, and 54%, respectively.

[0141] The reagents and raw materials used in this invention are all commercially available.

[0142] In this application, the molecular weight determination method is as follows: The test was performed on a Waters 1515 gel permeation chromatograph using a Waters 2410 differential refractometer as the detector. Tetrahydrofuran was used as the eluent, with a flow rate of 1.00 mL / min. The test temperature was 35°C. The test measures the relative molecular weight of the polymer, using polystyrene as a standard.

[0143] Example 1

[0144] 1.1,2-Vinylazine M1

[0145] Compound S1 (20.7 mg, 0.10 mmol), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (22.0 mg, 0.03 mmol), and potassium hydroxide (16.8 mg, 0.30 mmol) were added sequentially to a 10 mL Schlenk tube. The tube was purged with nitrogen three times to remove air. Under a nitrogen atmosphere, deoxygenated tetrahydrofuran (3.0 mL) and water (0.3 mL) were added, followed by pinacol ester of vinylborate (23.1 mg, 0.15 mmol). The reaction mixture was stirred in an oil bath at 60 °C for 1 hour. After cooling to room temperature, the reaction mixture was poured into water and extracted three times with dichloromethane. The combined organic phases were dried over anhydrous sodium sulfate, evaporated to dryness, and then subjected to column chromatography (silica gel, petroleum ether elution) to obtain a blue solid M1 (11.2 mg, 74% yield).

[0146] Melting point: 104–105℃. 1H NMR spectrum: 1 ¹H NMR (400MHz, CDCl₃) δ 8.21 (d, J = 9.5Hz, 2H), 7.48 (t, J = 9.9Hz, 1H), 7.39 (s, 2H), 7.17–7.03 (m, 3H), 6.07 (d, J = 17.6Hz, 1H), 5.48 (d, J = 10.7Hz, 1H). Carbon NMR spectrum: 13 C10 NMR (100MHz, CDCl3) δ 148.5, 141.1, 136.4, 135.9, 133.1, 123.8, 118.2, 115.5. Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1 )ν:3084,3045,2999,1818,1611,1569,1532,1471,1449,1415,1400,1375,1312,1297,1266,1204,1145,1103,1043,1011,989,948,905,824,727,601,587,546,452. High-resolution mass spectrometry: HRMS(DART) m / z: calculated value: C 12 H 11 [M+H] + :155.0855, Actual value: 155.0855.

[0147] 1.2, Poly(2-azine)P1

[0148] Compound M1 (551.6 mg, 3.58 mmol) and azobisisobutyronitrile (5.9 mg, 35.8 μmol) were added to a 10 mL Schlenk tube. Nitrogen gas was purged three times to remove air from the tube. Redistilled tetrahydrofuran (0.5 mL) was added under nitrogen atmosphere. The reaction mixture was frozen-purged-thawed three times to further remove air from the tube. The reaction system was stirred in a 70 °C oil bath for 12 hours. The reaction was stopped by rapid cooling with liquid nitrogen. After thawing, the precipitate was added dropwise to methanol. The precipitate was filtered and dried to obtain a blue-purple solid, P1 (conversion 63%).

[0149] 1H NMR spectrum: 1 ¹H NMR (400MHz, CD₂Cl₂) δ 8.33–7.24 (m, 3H), 6.95 (s, 2H), 6.83–5.91 (m, 2H), 2.44 (br, 1H), 2.00–1.62 (m, 2H). Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1)ν:3061,3007,2974,2919,2845,1961,1695,1573,1538,1496,1478,1450,1399,1380,1346,1290,1214,1201,1141,1009,966,942,904,852,807,725,670,583,442,409. Number-average molecular weight M n :4677, average degree of polymerization n:30, polydispersity index 1.44.

[0150] Example 2

[0151] 1.1, 2-Bromo-6-ethoxyazine S3

[0152] A fresh sodium ethoxide solution was prepared by adding sodium wire (1.0 g, 43.70 mmol) in portions to anhydrous ethanol (100.0 mL). Then, compound S2 (2.5 g, 8.74 mmol) was added. The reaction mixture was stirred in an oil bath at 80 °C for 9 hours. After cooling to room temperature, a red solid precipitated. The solid was filtered, washed with ethanol, collected, and the filtrate was evaporated to dryness and then subjected to column chromatography (silica gel, petroleum ether elution) to separate the red solid S3 (2.2 g total, 98% yield).

[0153] Melting point: 131–132℃. 1H NMR spectrum: 1 ¹H NMR (400MHz, CDCl₃) δ 8.09 (d, J = 11.0 Hz, 2H), 7.21 (s, 2H), 6.84 (d, J = 10.9 Hz, 2H), 4.17 (q, J = 6.9 Hz, 2H), 1.49 (t, J = 7.0 Hz, 3H). Carbon NMR spectrum: 13 C10 NMR (100MHz, CDCl3) δ 166.9, 135.7, 135.0, 122.0, 119.5, 112.4, 64.6, 14.9. Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1 )ν:3094,2983,2937,2887,2437,1931,1580,1540,1489,1474,1447,1404,1376,1355,1298,1255,1232,1193,1110,1072,1029,969,904,844,819,795,754,689,594,481. High-resolution mass spectrometry: HRMS(DART) m / z: calculated value: C 12 H 12 OBr[M+H] +:251.0066, Actual value: 251.0066.

[0154] 1.2, 2-Vinyl-6-ethoxyazine M2

[0155] In a 10 mL Schlenk tube, compound S3 (62.8 mg, 0.25 mmol), palladium acetate (2.2 mg, 0.01 mmol), 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (8.2 mg, 0.02 mmol), and potassium phosphate (159.2 mg, 0.75 mmol) were added sequentially. The tube was purged with nitrogen three times to remove air. Under a nitrogen atmosphere, 1.0 mL of deoxygenated 1,4-dioxane and 22.6 μL of water (1.25 mmol) were added, followed by pinacol vinylborate (43.1 mg, 0.28 mmol). The reaction mixture was stirred in an oil bath at 80 °C for 1 hour. After the reaction was cooled to room temperature, the reaction system was transferred to a round-bottom flask with dichloromethane, dried by rotary evaporation, and then subjected to column chromatography (neutral alumina, petroleum ether / dichloromethane 50:1 elution) to obtain purple solid M2 (39.3 mg, yield 79%).

[0156] Melting point: 135–136℃. ¹H NMR spectrum: 1 ¹H NMR (500MHz, CDCl₃) δ 8.06 (d, J = 11.0 Hz, 2H), 7.27 (s, 2H), 7.00 (dd, J = 17.6, 10.7 Hz, 1H), 6.75 (d, J = 10.9 Hz, 2H), 5.94 (dd, J = 17.6, 1.2 Hz, 1H), 5.36 (dd, J = 10.7, 1.3 Hz, 1H), 4.15 (q, J = 7.0 Hz, 2H), 1.48 (t, J = 7.0 Hz, 3H). Carbon NMR spectrum: 13 C10 NMR (125MHz, CDCl3) δ 166.2, 144.3, 136.7, 135.4, 133.2, 116.4, 116.0, 111.6, 64.4, 15.0. Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1 )ν:3086,3004,2982,2933,2888,2365,1811,1621,1582,1540,1494,1482,1470,1442,1420,1395,1359,1312,1289,1255,1230,1189,1128,1108,1032,992,957,904,890,841,818,765,718,705,606,555,498,403. High-resolution mass spectrometry: HRMS(DART) m / z: calculated value: C 14 H15 O[M+H] + :199.1117, Actual value: 199.1117.

[0157] 1.3, Poly(6-ethoxy-2-azine)P2

[0158] Add compound M2 (2.5 g, 12.61 mmol) and azobisisobutyronitrile (20.5 mg, 126.1 μmol) to a 10 mL Schlenk tube. Purge the tube three times with nitrogen to remove air. Add redistilled tetrahydrofuran (4.0 mL) under nitrogen atmosphere. Perform a freeze-purge-thaw cycle three times to further remove air from the tube. Stir the reaction mixture in a 70 °C oil bath for 10 hours. Stop the reaction by rapid cooling with liquid nitrogen. After thawing, precipitate the precipitate dropwise into methanol. Filter and dry the precipitate to obtain a purple-red solid P2 (conversion 48%).

[0159] 1H NMR spectrum: 1 ¹H NMR (400MHz, CD₂Cl₂) δ 8.20–7.15 (m, 2H), 7.09–5.86 (m, 4H), 4.03 (br, 2H), 2.46 (br, 1H), 1.78 (br, 2H), 1.41 (br, 3H). Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1 )ν:3064,2976,2923,2357,1579,1545,1496,1474,1442,1409,1360,1291,1243,1185,1109,1086,1033,911,836,814,761,699,670. Number-average molecular weight M n :4374, average degree of polymerization n:23, polydispersity index 1.62.

[0160] Example 3

[0161] 1.1, 1,3-Di-tert-butyl-6-bromoazine S5

[0162] Compound S4 (100.0 mg, 0.48 mmol), anhydrous diethyl ether (2.0 mL), and tert-butanol (2.0 mL) were added sequentially to a 25 mL round-bottom flask. The reaction flask was then placed in an ice bath, and the tetrafluoroborate diethyl ether complex (777.3 mg, 4.80 mmol) was added. The ice bath was removed, and the reaction mixture was stirred at room temperature for 2 hours. The reaction solution was quenched in anhydrous methanol. After rotary evaporation to dryness, column chromatography (silica gel, petroleum ether elution) was performed to separate the blue solid S5 (142.1 mg, 92% yield).

[0163] Melting point: 135–136℃. ¹H NMR spectrum: 1 1H NMR (400MHz, CDCl3) δ 8.26 (d, J = 10.8 Hz, 2H), 7.76 (s, 1H), 7.26 (d, J = 10.8 Hz, 2H), 1.55 (s, 18H). Carbon NMR spectrum: 13 C10 NMR (100MHz, CDCl3) δ 139.4, 135.7, 134.4, 133.9, 133.2, 123.1, 33.5, 32.3. Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1 )ν:3117,3048,2976,2961,2901,2866,1753,1559,1509,1475,1457,1423,1406,1391,1362,1243,1209,1026,993,877,818,807,663,607,558,534,524. High-resolution mass spectrometry: HRMS(DART) m / z: calculated value: C 18 H 24 Br[M+H] + :319.1056, Actual value: 319.1056.

[0164] 1.2, 1,3-Di-tert-butyl-6-vinylazine M3

[0165] Compound S5 (1.0 g, 3.13 mmol), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (687.8 mg, 0.94 mmol), and potassium hydroxide (526.9 mg, 9.39 mmol) were added sequentially to a 100 mL Schlenk tube. The tube was purged with nitrogen three times to remove air. Under a nitrogen atmosphere, 20.0 mL of deoxygenated tetrahydrofuran and 2.0 mL of water were added, followed by pinacol ester of vinylborate (964.2 mg, 6.26 mmol). The reaction mixture was stirred in an oil bath at 60 °C for 12 hours. After cooling to room temperature, the reaction mixture was poured into water and extracted three times with petroleum ether. The combined organic phases were dried over anhydrous sodium sulfate, evaporated to dryness, and then subjected to column chromatography (silica gel, petroleum ether elution) to obtain a blue-green solid M3 (781.1 mg, 94% yield).

[0166] Melting point: 92–93℃. 1H NMR spectrum: 11H NMR (400MHz, CDCl3) δ 8.52 (d, J = 10.5Hz, 2H), 7.68 (s, 1H), 7.08 (d, J = 10.5Hz, 2H), 6.85 (dd, J = 17.4, 10.9Hz, 1H), 5.93 (d, J = 17.4Hz, 1H), 5.41 (d, J = 10.8Hz, 1H), 1.57 (s, 18H). Carbon NMR spectrum: 13 C10 NMR (100MHz, CDCl3) δ 145.1, 141.2, 137.5, 135.0, 134.3, 118.6, 116.9, 33.4, 32.4. Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1 )ν:3103,3086,3052,3006,2958,2901,2865,2363,1846,1746,1702,1618,1570,1512,1478,1457,1427,1411,1385,1362,1305,1236,1211,1197,1027,1019,982,922,874,845,828,724,715,660,555,542. High-resolution mass spectrometry: HRMS(DART) m / z: calculated value: C 20 H 27 [M+H] + :267.2107, Actual value: 267.2107.

[0167] 1.3, Poly(1,3-di-tert-butyl-6-azine)P3

[0168] Compound M3 (588.4 mg, 2.21 mmol) and azobisisobutyronitrile (3.6 mg, 22.1 μmol) were added to a 10 mL Schlenk tube. Nitrogen gas was purged three times to remove air from the tube. Redistilled tetrahydrofuran (0.4 mL) was added under nitrogen atmosphere. The reaction mixture was frozen-purged-thawed three times to further remove air from the tube. The reaction mixture was stirred in a 70 °C oil bath for 8.5 hours. The reaction was stopped by rapid cooling with liquid nitrogen. After thawing, the precipitate was added dropwise to methanol. The precipitate was filtered and dried to give a blue solid, P3 (conversion 48%).

[0169] 1H NMR spectrum: 1 ¹H NMR (400MHz, CD₂Cl₂) δ 8.21 (br, 2H), 7.57 (s, 1H), 6.37 (br, 2H), 2.72–0.50 (m, 21H). Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1)ν:3107,3053,2952,2903,2868,1574,1513,1459,1412,1388,1363,1242,1212,983,874,828,683,537,419. Number-average molecular weight M n 7074, average degree of polymerization n: 27, polydispersity index 1.37.

[0170] Example 4

[0171] 1.1, 1-Acetyl-6-bromoazine S6

[0172] Compound S4 (1.6 g, 7.56 mmol) was dissolved in dichloromethane (100.0 mL). The reaction flask was transferred to an ice-salt bath, and acetyl chloride (593.5 mg, 7.56 mmol) and aluminum trichloride (1.1 g, 8.31 mmol) were added. The reaction system was allowed to return to room temperature and stirred at room temperature for 12 hours. The reaction solution was poured into water and extracted three times with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and evaporated to dryness before column chromatography (silica gel, petroleum ether / ethyl acetate 10:1 elution) to obtain a deep purple solid S6 (797.9 mg, yield 42%), and S4 (775.3 mg) was recovered.

[0173] Melting point: 65–66℃. 1H NMR spectrum: 1 ¹H NMR (400MHz, CDCl₃) δ 9.56 (d, J = 10.8 Hz, 1H), 8.29 (d, J = 4.2 Hz, 1H), 8.18 (d, J = 10.6 Hz, 1H), 7.91 (dd, J = 10.7, 1.9 Hz, 1H), 7.78 (dd, J = 10.5, 1.7 Hz, 1H), 7.29 (d, J = 4.2 Hz, 1H), 2.71 (s, 3H). Carbon NMR spectrum: 13 C10 NMR (100MHz, CDCl3) δ 195.8, 143.3, 141.0, 138.5, 137.7, 137.2, 136.7, 132.6, 130.8, 126.6, 119.4, 29.4. Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1)ν:3063,2924,2270,1805,1651,1567,1525,1487,1438,1409,1363,1315,1288,1235,1216,1149,1065,1029,974,910,873,858,825,787,723,619,559,516,463. High-resolution mass spectrometry: HRMS(DART) m / z: calculated value: C 12 H 10 BrO[M+H] + :248.9910, Actual value: 248.9912.

[0174] 1.2, 1-Acetyl-6-vinylazine M4

[0175] Compound S6 (124.6 mg, 0.50 mmol), potassium vinyltrifluoroborate (67.0 mg, 0.50 mmol), palladium dichloride (1.8 mg, 0.01 mmol), triphenylphosphine (7.9 mg, 0.03 mmol), and cesium carbonate (488.7 mg, 1.50 mmol) were added sequentially to a 10 mL Schlenk tube. The tube was purged with nitrogen three times to remove air. Tetrahydrofuran (0.9 mL) and water (0.1 mL) were added under a nitrogen atmosphere to remove oxygen. The reaction mixture was stirred in an oil bath at 85 °C for 5 hours. After cooling to room temperature, the reaction mixture was transferred to a round-bottom flask with dichloromethane, evaporated to dryness, and then subjected to column chromatography (silica gel, petroleum ether / ethyl acetate 20:1 elution) to obtain a deep purple oily liquid M4 (61.5 mg, yield 63%).

[0176] 1H NMR spectrum: 1 ¹H NMR (400MHz, CDCl₃) δ 9.78 (d, J = 10.5 Hz, 1H), 8.40 (d, J = 10.3 Hz, 1H), 8.20 (d, J = 4.1 Hz, 1H), 7.67 (dd, J = 10.5, 1.4 Hz, 1H), 7.58 (dd, J = 10.3, 1.1 Hz, 1H), 7.20 (d, J = 4.1 Hz, 1H), 6.95 (dd, J = 17.4, 10.9 Hz, 1H), 6.04 (d, J = 17.4 Hz, 1H), 5.57 (d, J = 10.9 Hz, 1H), 2.70 (s, 3H). Carbon NMR spectrum: 13 C10 NMR (100MHz, CDCl3) δ 195.6, 148.2, 144.0, 140.5, 140.4, 139.2, 138.7, 137.6, 127.9, 125.6, 125.5, 119.5, 118.0, 29.2. Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹)-1 )ν:3089,3008,2301,1839,1637,1577,1548,1494,1443,1401,1349,1323,1292,1257,1237,1216,1146,1039,1018,988,916,885,855,777,724,712,623,575,500. High-resolution mass spectrometry: HRMS(ESI) m / z: calculated value: C 14 H 13 O[M+H] + :197.0961, Actual value: 197.0960.

[0177] 1.3, Poly(1-acetyl-6-azine)P4

[0178] Compound M3 (537.3 mg, 2.74 mmol) and azobisisobutyronitrile (4.5 mg, 27.4 μmol) were added to a 25 mL Schlenk tube. The tube was subjected to a freeze-evacuation-thawing cycle three times to remove air. The reaction mixture was then stirred in a 70 °C oil bath for 12 hours. The reaction was stopped by rapid cooling with liquid nitrogen. After thawing, the precipitate was added dropwise to methanol. The precipitate was filtered and dried to obtain a purple solid, P4 (conversion 91%).

[0179] 1H NMR spectrum: 1 ¹H NMR (400MHz, CD₂Cl₂) δ 9.78–8.51 (m, 1H), 8.35–5.89 (m, 5H), 2.58 (s, 3H), 1.64 (br, 3H). Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1 )ν:2924,1636,1578,1548,1492,1443,1403,1351,1322,1291,1239,1216,1146,1041,1015,991,915,885,844,776,722,622,571. Number-average molecular weight M n 30450, average degree of polymerization n: 155, polydispersity index 1.71.

[0180] Example 5

[0181] 1.1, 2-ethoxy-6-vinylazine M5

[0182] In a 100 mL Schlenk tube, compound S6 (1.8 g, 7.17 mmol), palladium acetate (65.1 mg, 0.29 mmol), 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (234.0 mg, 0.57 mmol), and potassium phosphate (4.6 g, 21.51 mmol) were added sequentially. The tube was purged with nitrogen three times to remove air. Under a nitrogen atmosphere, deoxygenated 1,4-dioxane (30.0 mL) and water (0.65 mL, 35.85 mmol) were added, followed by pinacol vinylborate (1.2 g, 7.89 mmol). The reaction mixture was stirred in an oil bath at 80 °C for 2 hours. After the reaction was cooled to room temperature, the reaction system was transferred to a round-bottom flask with dichloromethane, dried by rotary evaporation, and then subjected to column chromatography (neutral alumina, petroleum ether / dichloromethane 50:1 elution) to obtain purple solid M5 (1.4 g, yield 97%).

[0183] Melting point: 114–115℃. 1H NMR spectrum: 1 ¹H NMR (400MHz, CDCl₃) δ 8.02 (d, J = 10.1 Hz, 2H), 7.33 (d, J = 10.1 Hz, 2H), 6.88 (dd, J = 17.3, 10.9 Hz, 1H), 6.77 (s, 2H), 5.87 (d, J = 17.4 Hz, 1H), 5.36 (d, J = 10.8 Hz, 1H), 4.30 (q, J = 6.8 Hz, 2H), 1.51 (t, J = 6.9 Hz, 3H). Carbon NMR spectrum: 13 CNMR (100MHz, CDCl3) δ 168.9, 141.5, 141.0, 139.4, 130.9, 123.1, 115.6, 102.2, 66.2, 15.0. Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1 )ν:2975,2935,1943,1828,1617,1574,1547,1510,1473,1454,1414,1389,1340,1291,1242,1232,1185,1171,1153,1138,1106,1041,991,973,963,913,878,847,783,762,677,654,634,551,462,411. High-resolution mass spectrometry: HRMS(DART) m / z: calculated value: C 14 H 15 O[M+H] + :199.1117, Actual value: 199.1117.

[0184] 1.2, Poly(2-ethoxy-6-azine)P5

[0185] Add compound M5 (2.2 g, 11.10 mmol) and azobisisobutyronitrile (18.4 mg, 111.0 μmol) to a 10 mL Schlenk tube. Purge the tube three times with nitrogen to remove air. Add 2.7 mL of redistilled tetrahydrofuran under nitrogen atmosphere. Perform a freeze-purge-thaw cycle three times to further remove air from the tube. Stir the reaction mixture in a 70 °C oil bath for 10 hours. Stop the reaction by rapid cooling with liquid nitrogen. After thawing, precipitate the precipitate dropwise into methanol. Filter and dry the precipitate to obtain a pink solid, P5 (45% conversion).

[0186] 1H NMR spectrum: 1 ¹H NMR (400MHz, CD₂Cl₂) δ 8.25–7.04 (m, 2H), 7.03–5.58 (m, 4H), 4.25 (br, 2H), 2.26–1.27 (m, 6H). Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1 )ν:2975,2926,1578,1547,1508,1471,1409,1385,1362,1338,1288,1234,1146,1108,1088,1041,984,906,879,833,776,648,601,407. Number-average molecular weight M n : 4491, average degree of polymerization n: 22, polydispersity index 1.65.

[0187] Example 6

[0188] 1.1, 2-Triethylene glycol methyl ether-6-bromoazine S9

[0189] Compound S8 (3.3 g, 14.84 mmol), potassium iodide (246.3 mg, 1.48 mmol), potassium carbonate (4.1 g, 29.68 mmol), and N,N-dimethylformamide (50.0 mL) were added sequentially to a 250 mL round-bottom flask. Then, diethylene glycol-2-bromoethyl methyl ether (4.0 g, 17.81 mmol) dissolved in N,N-dimethylformamide (50.0 mL) was added. The reaction mixture was stirred in an oil bath at 60 °C for 11 hours. After cooling to room temperature, the reaction solution was poured into water and extracted three times with ethyl acetate. The combined organic phases were dried over anhydrous sodium sulfate, evaporated to dryness, and then subjected to column chromatography (silica gel, petroleum ether / ethyl acetate 1:1 elution) to obtain a red solid S9 (3.8 g, yield 69%).

[0190] Melting point: 38–39℃. ¹H NMR spectrum: 11H NMR (400MHz, CDCl3) δ 7.75 (d, J = 10.8 Hz, 2H), 7.48 (d, J = 10.7 Hz, 2H), 6.82 (s, 2H), 4.35 (t, J = 4.7 Hz, 2H), 3.92 (t, J = 4.7 Hz, 2H), 3.77–3.72 (m, 2H), 3.71–3.66 (m, 2H), 3.66–3.61 (m, 2H), 3.55–3.50 (m, 2H), 3.36 (s, 3H). Carbon NMR spectrum: 13 C10 NMR (100MHz, CDCl3) δ 168.8, 138.4, 130.0, 128.7, 127.5, 103.7, 71.9, 70.9, 70.7, 70.6, 69.8, 69.6, 59.1. Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1 )ν:3088,2871,1927,1584,1567,1531,1499,1446,1404,1376,1362,1352,1337,1288,1248,1225,1196,1164,1128,1100,1055,1029,994,966,951,934,898,877,838,827,795,750,653,641,514,477,409. High-resolution mass spectrometry: HRMS(ESI) m / z: calculated value: C 17 H 22 O4Br[M+H] + :369.0696, Actual value: 369.0698.

[0191] 1,2,2-Triethylene glycol methyl ether-6-vinylazine M6

[0192] Compound S9 (89.0 mg, 0.24 mmol), palladium acetate (2.2 mg, 0.01 mmol), 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (7.9 mg, 0.02 mmol), and potassium phosphate (152.8 mg, 0.72 mmol) were added sequentially to a 25 mL Schlenk tube. The tube was purged with nitrogen three times to remove air. Under a nitrogen atmosphere, 2.0 mL of deoxygenated 1,4-dioxane and 21.7 μL of water (1.20 mmol) were added, followed by pinacol ester of vinylborate (40.0 mg, 0.26 mmol). The reaction mixture was stirred in an oil bath at 80 °C for 10 hours. After cooling to room temperature, the reaction mixture was transferred to a round-bottom flask with dichloromethane, evaporated to dryness, and then subjected to column chromatography (silica gel, petroleum ether / ethyl acetate 2:1 elution) to obtain a purple solid M6 (68.2 mg, 89% yield).

[0193] Melting point: 58–59℃. ¹H NMR spectrum: 1 ¹H NMR (400MHz, CDCl₃) δ 8.02 (d, J = 10.5 Hz, 2H), 7.33 (d, J = 10.4 Hz, 2H), 6.88 (dd, J = 17.4, 10.9 Hz, 1H), 6.78 (s, 2H), 5.87 (d, J = 17.4 Hz, 1H), 5.36 (d, J = 10.9 Hz, 1H), 4.39 (t, J = 4.8 Hz, 2H), 3.94 (t, J = 4.7 Hz, 2H), 3.80–3.73 (m, 2H), 3.72–3.68 (m, 2H), 3.69–3.62 (m, 2H), 3.58–3.51 (m, 2H), 3.37 (s, 3H). Carbon NMR spectrum: 13 CNMR (100MHz, CDCl3) δ 168.48, 141.39, 141.13, 139.15, 131.09, 123.04, 115.64, 102.21, 71.96, 70.91, 70.71, 70.63, 69.75, 69.70, 59.11. Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1 )ν:3090,2985,2872,1830,1614,1572,1546,1505,1473,1447,1409,1377,1353,1340,1289,1244,1233,1185,1164,1130,1102,1056,1030,990,973,951,914,879,845,797,758,684,652,641,551,527,419,405. High-resolution mass spectrometry: HRMS(ESI) m / z: calculated value: C 19 H 25 O4[M+H] + :317.1747, Actual value: 317.1749.

[0194] 1.3, Poly(2-triethylene glycol methyl ether-6-azine) P6

[0195] Add compound M6 (1.8 g, 5.69 mmol) and azobisisobutyronitrile (9.3 mg, 56.9 μmol) to a 10 mL Schlenk tube. Purge the tube three times with nitrogen to remove air. Add redistilled tetrahydrofuran (1.0 mL) under nitrogen atmosphere. Perform a freeze-purge-thaw cycle three times to further remove air from the tube. Stir the reaction mixture in a 70 °C oil bath for 18 hours. Stop the reaction by rapid cooling with liquid nitrogen. After thawing, precipitate the precipitate dropwise into methanol. Filter and dry the precipitate to obtain a pink solid, P6 (conversion 34%).

[0196] 1H NMR spectrum: 1 ¹H NMR (400MHz, CD₂Cl₂) δ 8.42–5.46 (m, 6H), 4.33 (br, 2H), 4.05–3.18 (m, 13H), 1.71 (br, 3H). Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1 )ν:3094,2873,1932,1578,1547,1506,1449,1409,1339,1288,1237,1198,1107,1054,987,942,879,836,779,648,535,419,408. Number-average molecular weight M n : 9487, average degree of polymerization n: 30, polydispersity index 1.71.

[0197] Example 7

[0198] 1.1, 1-Aldehyde-6-bromoazine S10

[0199] Compound S4 (1.7 g, 8.21 mmol) was dissolved in N,N-dimethylformamide (32.0 mL). The reaction flask was placed in an ice-water bath, and phosphorus oxychloride (15.1 g, 98.52 mmol) was slowly added. The ice-water bath was removed, and the reaction system was stirred at room temperature for 30 minutes. The reaction solution was poured into ice water, and 2.0 M sodium hydroxide aqueous solution was added dropwise to adjust the pH to neutral. The mixture was extracted three times with dichloromethane, and the organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and then subjected to column chromatography (silica gel, petroleum ether / ethyl acetate 10:1 elution) to obtain a pale purple solid S10 (1.4 g, yield 74%).

[0200] Melting point: 80–81℃. ¹H NMR spectrum: 1 1H NMR (400MHz, CDCl3) δ 10.36 (s, 1H), 9.30 (d, J = 10.5 Hz, 1H), 8.29 (d, J = 4.1 Hz, 1H), 8.22 (d, J = 10.6 Hz, 1H), 7.95 (dd, J = 10.5, 1.9 Hz, 1H), 7.85 (dd, J = 10.6, 1.9 Hz, 1H), 7.36 (d, J = 4.1 Hz, 1H). Carbon NMR spectrum: 13 C10 NMR (125MHz, CD2Cl2) δ 186.9, 144.4, 142.6, 138.7, 137.7, 137.4, 135.8, 132.8, 131.9, 127.7, 120.9. Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm2)-1 )ν:3050,2959,2849,1667,1575,1526,1485,1450,1405,1374,1330,1291,1249,1229,1200,1028,987,955,883,820,787,776,756,715,674,646,543,512,458. High-resolution mass spectrometry: HRMS(ESI) m / z: calculated value: C 11 H8BrO[M+H] + :234.9753, Actual value: 234.9753.

[0201] 1.2, 1-Aldehyde-6-vinylazine M7

[0202] Compound S10 (754.0 mg, 3.21 mmol), potassium vinyltrifluoroborate (515.7 mg, 3.85 mmol), palladium acetate (35.9 mg, 0.16 mmol), triphenylphosphine (83.9 mg, 0.32 mmol), and cesium carbonate (2.9 g, 8.99 mmol) were added sequentially to a 350 mL Schlenk flask. Nitrogen gas was purged three times to remove air from the tube. Tetrahydrofuran (29.0 mL) and water (3.2 mL) were added under a nitrogen atmosphere to remove oxygen. The reaction mixture was stirred in an oil bath at 85 °C for 18 hours. After cooling to room temperature, the reaction mixture was transferred to a round-bottom flask with dichloromethane, concentrated, and then subjected to column chromatography (silica gel, petroleum ether / ethyl acetate 10:1 elution) to obtain a blue solid M7 (419.6 mg, 72% yield).

[0203] 1H NMR spectrum: 1 ¹H NMR (500MHz, CD₂Cl₂) δ 10.32 (s, 1H), 9.43 (d, J = 10.3 Hz, 1H), 8.43 (d, J = 10.2 Hz, 1H), 8.18 (d, J = 4.1 Hz, 1H), 7.68 (dd, J = 10.3, 1.7 Hz, 1H), 7.63 (dd, J = 10.3, 1.7 Hz, 1H), 7.28 (d, J = 4.2 Hz, 1H), 6.97 (dd, J = 17.4, 10.9 Hz, 1H), 6.07 (d, J = 17.4 Hz, 1H), 5.59 (d, J = 10.8 Hz, 1H). Carbon NMR spectrum: 13C10 NMR (125MHz, CD2Cl2) δ 186.56, 148.98, 145.22, 141.62, 140.60, 139.63, 138.46, 136.75, 128.21, 126.82, 126.78, 120.12, 119.58. Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm2Cl2) -1 )ν:2832,2761,1851,1644,1571,1497,1452,1421,1396,1310,1289,1233,1187,1029,1010,977,926,870,854,802,784,725,716,679,648,593. High-resolution mass spectrometry: HRMS(ESI) m / z: calculated value: C 13 H 11 O[M+H] + :183.0804, Actual value: 183.0805.

[0204] 1.3, Poly(1-aldehyde-6-azevinyl)P7

[0205] Add compound M7 (419.6 mg, 2.30 mmol) and azobisisobutyronitrile (43.8 mg, 23.0 μmol) to a 10 mL Schlenk tube. Perform a freeze-evacuation-thawing cycle three times to remove air from the tube. Place the reaction mixture in an 80°C oil bath and stir for 12 hours. Stop the reaction by rapid cooling with liquid nitrogen. After thawing, precipitate the precipitate dropwise into toluene. Filter the precipitate and dry it to obtain a purple solid, P7 (conversion 98%).

[0206] 1H NMR spectrum: 1 ¹H NMR (400MHz, DMSO-d6) δ 10.05 (s, 1H), 9.50–5.80 (m, 6H), 1.77 (br, 3H). Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1 )ν:2926,2804,2731,1644,1579,1547,1495,1449,1400,1368,1333,1287,1238,1186,1090,1022,845,800,785,720,648,587. Number-average molecular weight M n :19942, average degree of polymerization n:109, polydispersity index 1.95.

[0207] Example 8

[0208] 1. Styrene–1-aldehyde-6-vinylazine copolymer P8

[0209] Compound M7 (565.2 mg, 2.88 mmol), styrene (300.0 mg, 2.88 mmol), and azobisisobutyronitrile (4.7 mg, 28.8 μmol) were added to a 25 mL Schlenk tube. The tube was subjected to a freeze-evacuation-thawing cycle three times to remove air from the tube. The reaction mixture was then stirred in a 70 °C oil bath for 12 hours. The reaction was stopped by rapid cooling with liquid nitrogen. After thawing, the precipitate was added dropwise to methanol. The precipitate was filtered and dried to give a purple solid, P8 (466.0 mg, yield 54%).

[0210] 1H NMR spectrum: 1 ¹H NMR (400MHz, CD₂Cl₂) δ 10.00–8.79 (m, 1H), 8.68–5.73 (m, 6.10H), 2.59 (s, 3H), 1.66 (br, 3.66H). Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1 )ν:2923,1637,1579,1548,1492,1443,1403,1351,1322,1291,1238,1215,1146,1040,1015,991,915,885,844,775,722,702,622,570. Number-average molecular weight M n 5073, Diversity Index 1.46, the content of azurite unit is 82 mol%.

[0211] Example 9

[0212] 1. Styrene–1-aldehyde-6-vinylazine copolymer P9

[0213] Compound M1 (503.0 mg, 3.26 mmol), styrene (339.5 mg, 3.26 mmol), and azobisisobutyronitrile (5.4 mg, 32.6 μmol) were added to a 25 mL Schlenk tube. The tube was subjected to a freeze-evacuation-thawing cycle three times to remove air from the tube. The reaction mixture was then stirred in a 70 °C oil bath for 12 hours. The reaction was stopped by rapid cooling with liquid nitrogen. After thawing, the precipitate was added dropwise to methanol. The precipitate was filtered and dried to give a blue solid, P9 (74.9 mg, 9% yield).

[0214] 1H NMR spectrum: 1 ¹H NMR (400MHz, CD₂Cl₂) δ 8.46–5.96 (m, 7.35H), 2.43 (br, 1H), 1.81 (br, 2.21H). Fourier transform infrared spectrum: FT-IR (potassium bromide pellet, cm⁻¹) -1)ν:3063,3009,2923,2850,1573,1538,1496,1451,1399,1380,1349,1291,1201,943,904,809,727,701,675,583. Number-average molecular weight M n 3378, Diversity Index 1.60, with an azurite unit content of 93 mol%.

[0215] Example 1: Thermogravimetric Analysis Test

[0216] Thermogravimetric analysis test method: The test was performed on a TGA Q500 thermogravimetric analyzer in a nitrogen atmosphere, with a temperature range from room temperature to 500℃ and a heating rate of 10℃ / min.

[0217] Figure 1 shows the thermogravimetric analysis curves of polymers P1-P6. The thermal decomposition temperatures of polymers P1-P6 under a nitrogen atmosphere with a 5% weight loss are 321℃, 322℃, 298℃, 337℃, 308℃, and 337℃, respectively.

[0218] Example 2: Differential Scanning Calorimetry Test

[0219] Differential scanning calorimetry test method: The test was conducted on a DSC Q2000 or DSC2A-01318 differential scanning calorimeter in a nitrogen atmosphere. The temperature range was from room temperature to 250 to 350℃, and the heating and cooling rates were both 10℃ / min.

[0220] Figure 2 shows the differential scanning calorimetry (DSC) curves of polymers P1-P6. The glass transition temperatures of polymers P1-P6 are 141℃, 142℃, 181℃, 210℃, 118℃, and 210℃, respectively.

[0221] Example 3: Proton Response Test

[0222] Proton responsiveness test method: Polymers P1-P6 were prepared in concentrations of 1.0 × 10⁻⁶. -5 A mol / L dichloromethane solution was prepared, and equal volumes of the solution were placed in cuvettes. Equal volumes or equivalent amounts of trifluoroacetic acid (TFA), concentrated hydrochloric acid (HCl), or trifluoromethanesulfonic acid (TFSA) were then added. The UV-Vis absorption spectra before and after the addition of acid were measured using a Hitachi U-3900 UV-Vis spectrophotometer. Figure 3 shows the UV-Vis absorption spectra of polymers P1-P6 before and after the addition of acid.

[0223] Example 4: Proton Response Reversibility Test

[0224] Proton response reversibility test method: Trifluoroacetic acid was added dropwise to a dichloromethane solution of polymers P1-P6, followed by triethylamine (TEA). Figure 4 shows the color changes of polymers P1-P6 before protonation, after protonation, and after deprotonation. Polymers P1-P6 all exhibit reversible proton response.

[0225] Example 5: Preparation of composite proton exchange membranes using polymers P1, P2, and P4-P6 supported in a Nafion matrix.

[0226] Preparation method of proton exchange membrane: A solution casting method was used. A commercially available 5% Nafion solution was placed in a vacuum drying oven at 60°C to remove the solvent. The resulting Nafion resin was redissolved in N,N-dimethylformamide to prepare a 5% solution. Polymers P1, P2, and P4-P6 were dissolved in chloroform and added to the freshly prepared Nafion solution. The resulting solution was cast onto a glass plate and dried in a vacuum drying oven at 80°C for 12 hours, then heated to 120°C and dried for 4 hours. Finally, the membrane was peeled off the glass plate and immersed in 1.0 mol / L sulfuric acid at room temperature for 12 hours, followed by rinsing with deionized water until neutral. The loading mass fraction of polymers P1, P2, and P4-P6 was 3%.

[0227] Proton conductivity was measured on a ParStat MC 1000 electrochemical workstation using AC impedance spectroscopy. Test temperature and humidity were controlled using an MTS-740 proton exchange membrane conductivity meter. Before testing, all membranes were immersed in deionized water for 24 hours, followed by equilibration at the appropriate test temperature and humidity for at least 30 minutes. Experimental results are shown in Tables 1-1 to 1-3 and Figures 5 to 7.

[0228] Table 1-1 Proton conductivity (mS / cm) at different temperatures with 0% relative humidity

[0229] Table 1-2 Proton conductivity (mS / cm) at different temperatures with 100% relative humidity

[0230] Table 1-3 Proton conductivity (mS / cm) at different relative humidities at 80℃

[0231] Example 6: Performance testing of intrinsic Nafion membrane and Nafion / P6 composite membrane in hydrogen fuel cells.

[0232] Hydrogen fuel cell performance testing method: Both cathode and anode use platinum / carbon catalyst (60% platinum, 0.25 mg / cm³). 2The membrane electrode area was 2.0 cm × 2.0 cm. The flow rates of hydrogen and oxygen were 90 and 120 mL / min, respectively. Before testing, the battery was activated in deionized water for 1 hour. Single-cell performance testing was conducted on the Greenlight G20 fuel cell testing system. The experimental results are shown in Table 2 and Figures 8-9.

[0233] Table 2. Test data of hydrogen fuel cells at 80℃ and 25% and 100% relative humidity.

[0234] All documents mentioned in this invention are incorporated herein by reference as if each document were individually incorporated by reference. Furthermore, it should be understood that after reading the foregoing teachings of this invention, those skilled in the art can make various alterations or modifications to this invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. A polyvinyl alcohol polymer, characterized in that, The polyvinyl alcohol polymer has the following general structural formula: Here, the numbers "1 to 8" refer to the numbers of each point in the azurite unit. It refers to the connection site between the azurite unit (Az) and the polymer backbone, which can be located at any position from position 1 to position 8 of the azurite unit; m and n refer to the number of repeating units, where m is an integer from 0 to 5000 and n is an integer from 10 to 5000. Monomers copolymerized with azulene monomers These are conventional polymerizable monomers in this field. R is a group selected from the group consisting of unsubstituted or substituted groups: H, -OC(O)C1-C6 alkyl, -COOC1-C6 alkyl, -CN, C6-C 10 Aryl, 5-10 heteroaryl; X and Y are each independently selected from the following group: H, methyl; or X and Y together with the carbon atom attached to them form a substituted or unsubstituted five- or six-membered heterocyclic group; Wherein, the substitution refers to one or more hydrogen atoms on the substituent group being substituted by a substituent selected from the group consisting of: H, OH, halogen, carbonyl; the heterocyclic group is saturated, partially unsaturated or aromatic, and has 1 to 5 heteroatoms selected from the group consisting of: N, S or O. R′ refers to a substituent on the azurite five-membered ring, and each R′ is independently selected from the group consisting of: hydrogen, C1-C… 24 Alkoxy, C3-C 19 Glycol monomethyl ether group, chlorine, aldehyde group, nitro group, trifluoroacetyl group, sulfonic acid group, C2-C 16 Acyl group, C2-C 16 Alkyl, C2-C 25 Ester group, C2-C 25 Amide, phenyl, naphthyl, azulel, pyridyl, thiophene, quinolinyl, isoquinolinyl, benzothiophene, acetyl, ethyl formate, ethyl or tert-butyl; R″ refers to a substituent on the seven-membered ring of the azurite unit, and each R″ is independently selected from the group consisting of: phenyl, naphthyl, azuthyl, pyridyl, thiophene, quinolinyl, isoquinolinyl, benzothiophene, hydrogen, methyl, hydrogen, ethyl, isopropyl, cyano, methylthio, aldehyde, piperidinyl, diethylamino, morpholinyl, tetrahydropyrrole, C3-C 12 Straight-chain alkyl, C1-C 24 Alkoxy or C3-C 19 The glycol monomethyl ether group.

2. The polyvinyl alcohol polymer as described in claim 1, characterized in that, The connection method between the azurite (Az) unit and the main chain is selected from the following group: "1, 2 and 4-6" refer to sites on azurite units that are connected to the polymer backbone.

3. The polyvinyl alcohol polymer as described in claim 1, characterized in that, The polyvinyl alcohol polymer has the following structure: In the structural formulas I-1 and I-6, R 2 Each independently is hydrogen, C1-C 24 alkoxy, or C3-C 19 Glycol monomethyl ether group; In the structural formulas I-4, I-5 and I-6, R 1 and R 3 Each group independently consists of hydrogen, chlorine, aldehyde, nitro, sulfonic acid, trifluoroacetyl, or C2-C groups. 16 Acyl group, C2-C 16 Alkyl, C2-C 25 amide group, or C2-C 25 Ester group; In the structural formulas I-4 and I-5, R 7 Each can be independently phenyl, naphthyl, azulel, pyridyl, thiophene, quinolinyl, isoquinolinyl, or benzothiophene; In the structural formula I-1, R 3 It can be hydrogen, chlorine, aldehyde, nitro, sulfonic acid, trifluoroacetyl, or C2-C. 16 Acyl group, C1-C 16 Alkyl, C2-C 25 Ester group, C2-C 25 Amide, phenyl, naphthyl, azulel, pyridyl, thiophene, quinolinyl, isoquinolinyl, or benzothiophene; R 4 and R 8 Each can be either hydrogen or methyl; R 5 It can be hydrogen, ethyl, isopropyl, phenyl, naphthyl, azulel, pyridyl, thiophene, quinolinyl, isoquinolinyl, or benzothiophene; R 6 It can be hydrogen, methyl, cyano, methylthio, aldehyde, piperidinyl, diethylamino, morpholino, tetrahydropyrrolyl, or C3-C. 12 Straight-chain alkyl, C1-C 24 Alkoxy, C3-C 19 The glycol monomethyl ether group, phenyl, naphthyl, azulel, pyridyl, thiophene, quinolinyl, isoquinolinyl, or benzothiophene; R 7 It can be hydrogen, phenyl, naphthyl, azulel, pyridyl, thiophene, quinolinyl, isoquinolinyl, or benzothiophene; In the aforementioned structural formula I-2, R 1 and R 3 Each group can be independently hydrogen, chlorine, aldehyde, nitro, sulfonic acid, trifluoroacetyl, acetyl, ethyl formate, N-ethylformamido, ethyl, or tert-butyl. R 1 and R 3 It is methyl but not simultaneously methyl; R 4 and R 8 It can be hydrogen or methyl, but not both methyl; R 5 and R 7 It is hydrogen, ethyl, or isopropyl, but not simultaneously ethyl or isopropyl; R 6 It is hydrogen, cyano, methylthio, aldehyde, piperidinyl, diethylamino, morpholino, tetrahydropyrrole, C3-C 12 Straight-chain alkyl, C1-C 24 Alkoxy, C3-C 19 The glycol monomethyl ether group, phenyl, naphthyl, azulel, pyridyl, thiophene, quinolinyl, isoquinolinyl, or benzothiophene; In the aforementioned structural formula I-5, R 6 It is methyl; In the aforementioned structural formula I-6, R 4 and R 7 It can be either hydrogen or methyl; In the structural formulas I-1, I-2, I-4, I-5, and I-6, n is an integer from 10 to 5000.

4. The polyvinyl alcohol polymer as described in claim 3, characterized in that, When R in the aforementioned structural formulas I-1 and I-6 2 Independently for C1-C 24 When alkoxy is present, the "C1-C" 24 "Alkoxy" refers to C1-C8 alkoxy groups; And / or, when R in the structural formula I-1 2 and R 6 R in I-2 6 And R in I-6 2 Independently for C3-C 19 When the glycol monomethyl ether group is present, the "C3-C" 19 The glycol monomethyl ether group is C7-C 19 Glycol monomethyl ether group; And / or, when R in the structural formula I-1 3 R in I-4, I-5 and I-6 1 and R 3 Independently for C2-C 16 When acyl, the "C2-C" 16 The acyl group is a C2-C8 acyl group; And / or, when R in the structural formula I-1 3 R in I-4, I-5 and I-6 1 and R 3 Independently for C2-C 25 When esterified, the "C2-C" group is mentioned. 25 The "ester group" is a C2-C9 ester group; And / or, when R in the structural formula I-1 3 R in I-4, I-5 and I-6 1 and R 3 Independently for C2-C 25 When the amide group is present, the "C2-C" 25 The "amide group" is a C2-C9 amide group; And / or, when R in the structural formulas I-4, I-5 and I-6 1 and R 3 Independently for C2-C 16 When alkyl, the "C2-C" 16 "alkyl" refers to C2-C8 alkyl groups; And / or, when R in the structural formula I-1 3 For C1-C 16 When alkyl, the "C1-C" 16 "alkyl" refers to C1-C8 alkyl groups; And / or, when R in the structural formulas I-1 and I-2 6 Independently for C3-C 12 When the chain is straight-chain alkyl, the "C3-C" 12 "Straight-chain alkyl" refers to C3-C8 straight-chain alkyl; And / or, when R in the structural formulas I-1 and I-2 6 Independently for C1-C 24 When alkoxy is present, the "C1-C" 24 "Alkoxy" is C1-C 12 Alkoxy; And / or, when R in the structural formula I-1 3 When it is methyl, R in the structural formula I-1 8 For methyl, R 5 It is ethyl or isopropyl, R 4 R 6 and R 7 Both are hydrogen; And / or, when R in the structural formula I-1 6 When it is methyl, R in the structural formula I-1 4 and R 8 Both are methyl groups, R 5 and R 7 Both are hydrogen; And / or, when R in the structural formula I-2 1 When it is methyl, R in the structural formula I-2 4 For methyl, R 7 It is isopropyl or ethyl, R 3 R 5 R 6 and R 8 Both are hydrogen.

5. The polyvinyl alcohol polymer as described in claim 3, characterized in that, When R in the aforementioned structural formulas I-1 and I-6 2 Independently for C1-C 24 When alkoxy is present, the "C1-C" 24 "alkoxy" is And / or, when R in the structural formula I-1 2 and R 6 R in I-2 6 And R in I-6 2 Independently for C3-C 19 When the glycol monomethyl ether group is present, the "C3-C" 19 The glycol monomethyl ether group is And / or, when R in the structural formula I-1 3 R in I-4, I-5 and I-6 1 and R 3 Independently for C2-C 16 When acyl, the "C2-C" 16 "Acyl" is And / or, when R in the structural formulas I-4, I-5 and I-6 1 and R 3 Independently for C2-C 16 When alkyl, the "C2-C" 16 "alkyl" refers to tert-butyl or ethyl; And / or, when R in the structural formulas I-1 and I-2 6 Independently for C1-C 24 When alkoxy is present, the "C1-C" 24 "alkoxy" is 6. The polyvinyl alcohol polymer as described in claim 1, characterized in that, Az is selected from the following group:

7. The polyvinyl alcohol polymer as described in claim 1, characterized in that, The average degree of polymerization (n) of the polyvinyl alcohol polymer is 10 to 5000; And / or, the polydispersity index of the polyvinyl alcohol polymer. The value ranges from 1.0 to 5.

0.

8. The polyvinyl alcohol polymer as described in claim 1, characterized in that, The average degree of polymerization (n) of the polyvinyl alcohol polymer is 10 to 3000.

9. The polyvinyl alcohol polymer as described in claim 1, characterized in that, The average degree of polymerization (n) of the polyvinyl chloride polymer is 10 to 1000.

10. The polyvinyl alcohol polymer as described in claim 3, characterized in that, The polyvinyl alcohol polymer is any of the following polymers: Where m is an integer from 0 to 5000; n is an integer from 10 to 5000.

11. The method for preparing polyvinyl alcohol polymers as described in claim 1, characterized in that, Includes the following steps: In an inert gas atmosphere, the azulene monomers shown in the following formula are homopolymerized or copolymerized with optional conventional polymeric monomers in the art to obtain the polyazolene polymers described above. Wherein, R′ and R″ are defined as described in claim 1, and the vinyl group can be located at any position on the azurite unit (on a five-membered ring or a seven-membered ring); The definition of conventional polymeric monomers in this art is as described in claim 1.

12. Use of the polyvinyl alcohol polymer as described in any one of claims 1 to 8, characterized in that, Used to prepare materials based on proton transport and proton response, or cation and / or anion conductive materials.

13. The use as described in claim 12, characterized in that, The polyvinyl chloride polymers are used to prepare proton exchange membranes for fuel cells, anion exchange membranes, solid electrolytes for ion batteries, metal corrosion protection, bacterial protection, memristors, and acid-induced color-changing devices.

14. The use as described in claim 12, characterized in that, The polyvinyl chloride polymers are used as additives in Nafion perfluorosulfonic acid resins to prepare proton exchange membranes for hydrogen fuel cells.

15. The use as described in claim 12, characterized in that, The cation is selected from the group consisting of lithium ion, sodium ion, potassium ion, or calcium ion; the anion is selected from the group consisting of chloride ion or hydroxide ion.

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