CN115521443A - Piperidine polymer with microporous structure, preparation method thereof, anion exchange membrane and fuel cell - Google Patents

Piperidine polymer with microporous structure, preparation method thereof, anion exchange membrane and fuel cell Download PDF

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CN115521443A
CN115521443A CN202211226244.2A CN202211226244A CN115521443A CN 115521443 A CN115521443 A CN 115521443A CN 202211226244 A CN202211226244 A CN 202211226244A CN 115521443 A CN115521443 A CN 115521443A
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piperidine
polymer
formula
anion exchange
exchange membrane
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CN115521443B (en
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秦国锐
王茜
张所波
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a piperidine polymer with a microporous structure, a preparation method thereof, an anion exchange membrane and a fuel cell. The structural formula of the repeating unit of the piperidine polymer is shown as a formula I or a formula II. The piperidine polymer provided by the invention has a pore structure, and is prepared by polymerizing a piperidine monomer and a carbonyl monomer through acid catalysis to obtain the piperidine polymer, and then sequentially performing quaternization treatment and ion exchange to obtain an anion exchange membrane. The piperidine type polymer provided by the invention has a simple synthetic route, the obtained polymer is used for preparing an anion exchange membrane, the anion exchange membrane has high-temperature alkali stability, the long-term application problem of an anion exchange membrane fuel cell can be solved, and the anion exchange membrane has high anion conductivity, low swelling rate and water absorption rate and good mechanical properties.

Description

Piperidine polymer with microporous structure, preparation method thereof, anion exchange membrane and fuel cell
Technical Field
The invention belongs to the technical field of anion exchange membranes, and particularly relates to a piperidine polymer with a microporous structure, a preparation method of the piperidine polymer, an anion exchange membrane and a fuel cell.
Background
The fuel cell can directly and efficiently convert chemical energy of fuel (such as hydrogen, hydrazine and methanol) into electric energy in an environment-friendly manner, is always regarded as an optimal energy conversion device to utilize hydrogen energy, is an important part of renewable clean energy and energy conversion technologies, and is receiving more and more attention. Among them, anion Exchange Membrane Fuel Cells (AEMFCs), operating under alkaline conditions, can use non-noble metals as electrocatalysts, have significant cost advantages over Proton Exchange Membrane Fuel Cells (PEMFCs). In recent years, researchers have conducted a series of studies on anion exchange membranes.
CN112608503B reported that under the condition of using biphenyl, N-methyl piperidone and methyl pyruvate as solvent, trifluoroacetic acid and trifluoromethanesulfonic acid were added to catalyze polymerization to obtain polymer, which was quaternized with methyl iodide, and ion-exchanged with potassium hydroxide to finally prepare anion-exchange membrane. Due to the introduction of the comonomer, the mechanical properties of the membrane can be improved to a certain extent, but the Ion Exchange Capacity (IEC) is reduced, and meanwhile, due to the existence of ester groups, the use performance of the membrane at the later stage is influenced.
CN114808028A reports that under the condition of using p-terphenyl, diphenylmethane and isatin as solvent, trifluoroacetic acid and trifluoromethanesulfonic acid are added to catalyze and polymerize to obtain polymer, and then a grafting method is used to introduce piperidine group into the side group. This method results in a polymer with a low IEC, and the presence of methylene groups in the main chain may affect the membrane lifetime, and in addition the long alkyl chains on the cationic group piperidine may reduce its base stability.
CN114854063A reports the preparation of polymers by photopolymerization of 2-bromoethyl acrylic acid dissolved in an organic solvent with the addition of 2- (butyltrithiocarbonate) propionic acid and a photocatalyst, followed by the introduction of a piperidine group. The performance and service life of the anion exchange membrane are influenced due to easily degradable ester groups and thiocarbonate groups contained in the polymer.
In conclusion, the current anion exchange membranes still face the problems of poor alkali stability and low conductivity, are easy to decompose in an alkaline environment, particularly under a high-temperature condition, and are not beneficial to the long-term application of the anion exchange membranes in AEMFCs.
Disclosure of Invention
In view of the above, the present invention aims to provide a piperidine type polymer having a microporous structure, a preparation method thereof, an anion exchange membrane and a fuel cell. The anion exchange membrane has the advantages of good mechanical property, high ion exchange capacity, high conductivity, low swelling rate and good alkali stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a piperidine type polymer having a microporous structure, wherein the structural formula of the repeating unit is represented by formula I or formula II below:
Figure BDA0003879943640000021
wherein, the structural formula of A is shown as a formula a or a formula b:
Figure BDA0003879943640000022
R 1 or R 2 Selected from H, substituted or unsubstituted C 1 ～C 6 Alkyl or substituted or unsubstituted C 6 ～C 10 And R is an aryl group of 1 And R 2 Not H at the same time;
the substituted group is selected from halogen, nitro, carboxyl or acyl;
R 3 selected from H, unsubstituted C 1 ～C 6 Alkyl, phenyl or
Figure BDA0003879943640000023
Z = 2-6,X is a halogen element or OH;
q is C, N or S, n = 1-5, m = 2-6, and at least two R 4 May form an aromatic ring with the carbon atom on which it is located.
Preferably, said R is 1 Or R 2 Selected from substituted or unsubstituted C 1 ～C 4 The substituted group is halogen.
Preferably, said R is 3 Selected from H, unsubstituted C 1 ～C 4 Alkyl or
Figure BDA0003879943640000031
Z =2 to 6,X is a halogen element.
Preferably Q is selected from C or N, more preferably N, with N = 2-4.
Preferably, m =2, two R 4 To form a benzene ring; or m =3, three R 4 A naphthalene ring; or m =4, four R 4 Forming two benzene rings.
More preferably, m =2, two R 4 To form a benzene ring.
Preferably, A is selected from any one of (formula A-1) to (formula A-5):
Figure BDA0003879943640000032
more preferably, the structural formula of the specific repeating unit of the piperidine type polymer is represented by (formula I-1) to (formula I-5) or (formula II-1) to (formula II-5):
Figure BDA0003879943640000033
Figure BDA0003879943640000041
in a second aspect, the present invention also provides a method for preparing the piperidine type polymer having a microporous structure, comprising the steps of:
polymerizing a piperidine aromatic monomer and an A = O monomer by using an acid catalyst to obtain a piperidine polymer;
wherein the piperidine aromatic monomer comprises 1 '-methylxanthene-9-spiro-4' -piperidine or 1 '-methylfluorene-9-spiro-4' -piperidine.
Preferably, the molar ratio of the piperidine aromatic monomer to the a = O monomer is 1 (1.0 to 1.5).
Preferably, the acid catalyst is selected from trifluoromethanesulfonic acid, methanesulfonic acid or eaton's reagent.
Preferably, the temperature of the polymerization reaction is-40-80 ℃, the reaction time is 0.1-48 h, and the concentration of the reaction system is 5-50%.
In a third aspect, the present invention provides an anion exchange membrane, which is made of the piperidine type polymer with a microporous structure according to the above technical scheme.
Preferably, the anion exchange membrane has a thickness of 10 to 60 μm.
In a fourth aspect, the present invention provides a fuel cell comprising the above anion exchange membrane.
Compared with the prior art, the invention has the beneficial effects that:
the piperidine polymer provided by the invention is stable under high-temperature alkaline conditions, is used for preparing an anion exchange membrane, is applied to a fuel cell, can solve the problem of long-term stability of the fuel cell, has pore channel structures with different specific surface areas, can reduce the swelling rate while keeping high ion exchange capacity, keeps the mechanical property of the anion exchange membrane, and is favorable for forming an ion channel due to the existence of the pore channel structures so as to improve the ion conductivity of the anion exchange membrane.
Drawings
FIG. 1 shows the NMR spectrum of 1 '-methylxanthene-9-spiro-4' -piperidine monomer (solvent: CDCl) 3 ,DMSO-d6)；
FIG. 2 shows the NMR spectrum of the piperidine type polymer obtained in example 1 (solvent: CDCl) 3 ,DMSO-d6)；
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum (solvent: CDCl) of the piperidine type polymer obtained in example 2 3 ,DMSO-d6)；
FIG. 4 shows a nuclear magnetic resonance hydrogen spectrum of the anion exchange membrane material obtained in example 11 (solvent: CDCl) 3 ,DMSO-d6)；
FIG. 5 shows the NMR spectrum of the anion exchange membrane material obtained in example 12 (solvent: CDCl) 3 ,DMSO-d6)；
Figure 6 is a graph of conductivity retention data for anion exchange membranes prepared in example 12.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
All the raw materials involved in the present invention are available from commercial sources or can be prepared according to conventional preparation methods well known to those skilled in the art, without particular limitation thereto.
The invention provides a piperidine polymer with a micropore structure, wherein a structural formula of a repeating unit of the polymer is shown as a formula I or a formula II:
Figure BDA0003879943640000051
Figure BDA0003879943640000061
in one embodiment of the present invention, the repeating unit of the piperidine type polymer has a structure represented by formula I or formula II;
wherein, the structural formula of A is shown as a formula a or a formula b:
Figure BDA0003879943640000062
R 1 or R 2 Selected from H, substituted or unsubstituted C 1 ～C 6 Alkyl or substituted or unsubstituted C 6 ～C 10 And R is an aryl group of 1 And R 2 Not H at the same time;
the substituted group is selected from halogen, nitro, carboxyl or acyl;
R 3 selected from H, unsubstituted C 1 ～C 6 Alkyl, phenyl or
Figure BDA0003879943640000063
Z = 2-6,X is a halogen element or OH;
q is C, N or S, n = 1-5;
m = 2-6, and at least two R 4 May form an aromatic ring with the carbon atom on which it is located.
In one embodiment of the present invention, the repeating unit of the piperidine type polymer has a structure represented by formula I or formula II, wherein R 1 Or R 2 Selected from substituted or unsubstituted C 1 ～C 4 The substituted group is halogen;
R 3 selected from H, unsubstituted C 1 ～C 4 Alkyl or
Figure BDA0003879943640000064
Z = 2-6,X is a halogen element;
q is selected from C or N, and N = 2-4;
m =2, two R 4 To form a benzene ring; or m =3, three R 4 A naphthalene ring; or m =4, four R 4 Forming two benzene rings.
In one embodiment of the present invention, the repeating unit of the piperidine type polymer has a structure represented by formula I or formula II, wherein R 1 Or R 2 Selected from substituted or unsubstituted C 1 ～C 4 The substituted group is halogen;
R 3 selected from H, unsubstituted C 1 ～C 4 Alkyl or
Figure BDA0003879943640000071
Z = 2-6,X is a halogen element;
q is selected from N, N = 2-4; m =2, two R 4 To form a benzene ring.
In one embodiment of the present invention, the repeating unit of the piperidine type polymer has a structure represented by formula I or formula II, wherein a is selected from any one of (formula a-1) to (formula a-5):
Figure BDA0003879943640000072
wherein R is 1 And R 3 The selection of the above technical solutions is not described in detail herein.
In one embodiment of the present invention, the specific repeating unit of the piperidine type polymer has a structural formula shown in (formula I-1) to (formula I-5) or (formula II-1) to (formula II-5):
Figure BDA0003879943640000073
Figure BDA0003879943640000081
it should be noted that, in the above technical solution, when the value of n is greater than 1, Q may be the same or different. In addition, in the present invention, the,
Figure BDA0003879943640000082
represents a linking site.
Through research, the piperidine polymer provided by the invention has pore channel structures with different specific surface areas, has an all-carbon skeleton, does not contain easily degradable groups such as ester groups and the like, does not have long alkyl chains on the piperidyl, is stable under a high-temperature alkaline condition, and can be used for preparing an anion exchange membrane for application to a fuel cell.
The invention also provides a preparation method of the piperidine polymer with the micropore structure, which comprises the following steps:
polymerizing a piperidine aromatic monomer and an A = O monomer by using an acid catalyst to obtain a piperidine polymer;
wherein the piperidine aromatic monomer comprises 1 '-methylxanthene-9-spiro-4' -piperidine or 1 '-methylfluorene-9-spiro-4' -piperidine.
The reaction technical route of the piperidine polymer with the repeating unit shown as the formula I is shown as follows:
Figure BDA0003879943640000083
the reaction technical route of the piperidine polymer with the repeating unit shown as the formula II is shown as follows:
Figure BDA0003879943640000084
according to the present invention, a mixed solution is obtained by dissolving a piperidine type aromatic monomer (i.e., 1 '-methylxanthene-9-spiro-4' -piperidine or 1 '-methylfluorene-9-spiro-4' -piperidine) and a carbonyl monomer (i.e., a = O monomer) in a solvent, the molar ratio of the piperidine type aromatic monomer to the a = O monomer being preferably 1 (1.0 to 1.5), more preferably 1 (1.0 to 1.2). The solvent is preferably Dichloromethane (DCM), nitrobenzene or trifluoroacetic acid (TFAc), more preferably Dichloromethane (DCM) or trifluoroacetic acid (TFAc), wherein the trifluoroacetic acid assists dichloromethane for adjusting solubility to make the reaction system sufficiently soluble. The A = O monomer has any one of the structures (formula 1) to (formula 5) (wherein R is 3 The following options are selected as described in the above technical solutions, and are not described herein:
Figure BDA0003879943640000091
adding an acid catalyst selected from the group consisting of trifluoromethanesulfonic acid (TFSA), methanesulfonic acid (MSA) or eaton's reagent (7.5 wt.% phosphorus pentoxide, methanesulfonic acid), more preferably trifluoromethanesulfonic acid), and subjecting the resulting mixed solution to a polymerization reaction at a temperature of-40 to 80 ℃, preferably-10 to 40 ℃, most preferably 0 to 25 ℃; the reaction time is 0.1 to 48 hours, preferably 0.5 to 5 hours; the concentration of the reaction system is preferably 5 to 50%, more preferably 25 to 30%. And (3) phase-converting the reaction product into a white polymer in absolute ethyl alcohol, repeatedly washing, filtering and drying to obtain the polymer. During the polymerization reaction, the piperidine aromatic monomer reacts with the carbonyl site of the carbonyl monomer, which has a high activity.
The preparation method of the piperidine polymer provided by the invention is simple, the piperidine aromatic monomer directly purchased and the A = O monomer are subjected to polymerization reaction under the catalysis of acid to obtain the piperidine polymer, the piperidine polymer is an all-carbon skeleton and has a pore structure, an anion exchange membrane can be prepared for a fuel cell, the problem of long-term stability of the fuel cell can be solved, and the pore structure of the piperidine polymer is favorable for forming an ion channel so as to improve the ionic conductivity of the anion exchange membrane.
The invention also provides an anion exchange membrane which is prepared from the piperidine polymer with the repeating unit shown as the formula I or the formula II in the technical scheme. The thickness of the anion exchange membrane is 10 to 60 μm, preferably 25 to 35 μm. The anion exchange membrane can be prepared by quaternizing the piperidine polymer obtained by the technical scheme and then performing a delayed flow method.
The quaternization treatment specifically comprises the following steps: reacting a piperidine type polymer with CH 3 I, reacting to obtain the quaternary amination polymer. The present invention preferably provides a solution of the piperidine-type polymer in a solvent selected from the group consisting of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), tetrahydrofuran (THF), dimethylsulfoxide (DMSO), or N-methylpyrrolidone (NMP), preferably Dimethylsulfoxide (DMSO), under exclusion of light. The resulting polymer solution was mixed with an excess of CH 3 I, reacting under the heating condition, wherein the reaction temperature is 50-70 ℃, preferably 60 ℃, and the reaction time is 2-12 h, preferably 2-5 h. After the reaction is finished, carrying out phase conversion in ethanol, filtering and drying to obtain the quaternary ammonium polymer.
In one embodiment of the invention, the quaternized polymer is dissolved in a solvent selected from the group consisting of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), or N-methylpyrrolidone (NMP) to provide a 3wt% casting solution, the casting solution is filtered and cast on a glass plate to form a film, the solvent is dried, and the counter ion is exchanged in a 1M aqueous metal hydroxide solution to OH - The metal hydroxide is selected from sodium hydroxide (NaOH), potassium hydroxide (KOH), cesium hydroxide (CsOH) or barium hydroxide (Ba (OH) 2 ) Preferably NaOH, to obtain an anion exchange membrane.
The invention also provides a fuel cell, which comprises the anion exchange membrane in the technical scheme. The fuel cell is composed of a cathode, an anode, the anion exchange membrane and an external circuit.
To further illustrate the present invention, the following examples are provided for illustration. The experimental starting materials used in the following examples of the present invention may be either commercially available or prepared according to conventional preparation methods well known to those skilled in the art.
Example 1
This example provides a piperidine-based polymer prepared as follows:
weighing 1 '-methylxanthene-9-spiro-4' -piperidine monomer (0.0018mol, 0.5g) and isatin (0.0022mol, 0.3g), adding into a 50mL eggplant-shaped bottle containing magnetons, adding 3mL DCM (dichloromethane), stirring until the monomers are completely dissolved, stirring for 10min, and mixing the system uniformly. Slowly adding 0.5mL of TFAc (trifluoroacetic acid) and 2mL of TFSA (trifluoromethanesulfonic acid) dropwise, stirring quickly, reacting at room temperature for 10h to obtain a polymer solution with a certain viscosity, phase-converting the polymer solution into a white filamentous polymer in a large amount of anhydrous ethanol after dilution, repeatedly washing, and drying for later use. Nuclear magnetic resonance hydrogen spectrogram (solvent: CDCl) for detecting polymer with Ubbelohde viscosity of 0.92,1 '-methylxanthene-9-spiro-4' -piperidine monomer 3 DMSO-d 6) is shown in FIG. 1, and the NMR spectrum of the obtained polymer (solvent: CDCl) 3 DMSO-d 6) is shown in FIG. 2, and the structural formula of the polymer is shown below (n represents the degree of polymerization):
Figure BDA0003879943640000101
example 2
This example provides a piperidine type polymer prepared as follows:
weighing 1 '-methylxanthene-9-spiro-4' -piperidine monomer (0.0018mol, 0.5g) and 1-methylisatin (0.0022mol, 0.3g), adding into a 50mL eggplant-shaped bottle containing magnetons, adding 2mL DCM (dichloromethane), stirring until the monomers are completely dissolved, stirring for 10min, and mixing the system uniformly. Slowly dropwise adding 1mL of TFAc (trifluoroacetic acid) and 3mL of TFSA (trifluoromethanesulfonic acid), quickly stirring, reacting at room temperature for 12h to obtain a polymer solution with a certain viscosity, diluting, phase-converting in a large amount of anhydrous ethanol to obtain a white filamentous polymer, repeatedly washing, and drying for later use. The polymer was examined for a Ubbelohde viscosity of 0.87 and a NMR hydrogen spectrum of the resulting polymer (solvent: CDCl) 3 DMSO-d 6) is shown in FIG. 3, and the structural formula of the polymer is shown below (n represents the degree of polymerization):
Figure BDA0003879943640000111
example 3
This example provides a piperidine type polymer prepared as follows:
weighing 1 '-methylxanthene-9-spiro-4' -piperidine monomer (0.0018mol, 0.5g) and 1-butyltrimethylammonium bromide isatin (0.0022mol, 0.7g) into a 50mL eggplant-shaped bottle containing magnetons, adding 1mL DCM (dichloromethane), stirring until the monomers are completely dissolved, stirring for 10min, and mixing the system uniformly. Slowly dropwise adding 2mL of TFAc (trifluoroacetic acid) and 3mL of TFSA (trifluoromethanesulfonic acid), quickly stirring, reacting at room temperature for 24h to obtain a polymer solution with a certain viscosity, diluting, phase-converting in a large amount of anhydrous ethanol to obtain a white filamentous polymer, repeatedly washing, and drying for later use. The Ubbelohde viscosity of the test polymer was 1.21. The structure of the polymer is shown below (n represents the degree of polymerization):
Figure BDA0003879943640000112
example 4
This example provides a piperidine type polymer prepared as follows:
weighing 1 '-methylxanthene-9-spiro-4' -piperidine monomer (0.0018mol, 0.5g), 1-butyltrimethylammonium bromide isatin (0.0011mol, 0.35g) and 1-methylisatin (0.0011mol, 0.15g), adding into a 50mL eggplant-shaped bottle containing magnetons, adding 2mL of DCM (dichloromethane), stirring until the monomers are completely dissolved, stirring for 10min, and mixing the system uniformly. Slowly dropwise adding 2mL of TFAc (trifluoroacetic acid) and 3mL of TFSA (trifluoromethanesulfonic acid), quickly stirring, reacting at room temperature for 24h to obtain a polymer solution with a certain viscosity, diluting, phase-converting in a large amount of anhydrous ethanol to obtain a white filamentous polymer, repeatedly washing, and drying for later use. The Ubbelohde viscosity of the test polymer was 1.31. The structural formula of the polymer is shown as follows (m and n respectively correspond to the polymerization degree of the repeating unit):
Figure BDA0003879943640000121
example 5
This example provides a piperidine type polymer prepared as follows:
weighing 1 '-methylxanthene-9-spiro-4' -piperidine monomer (0.0018mol, 0.5g) and 1,1,1-trifluoroacetone (0.0022mol, 0.25g), adding into a 50mL eggplant-shaped bottle containing magnetons, adding 0.5mL DCM (dichloromethane), stirring until the monomers are completely dissolved, stirring for 10min, and after the system is uniformly mixed. Slowly adding 0.5mL of TFAc (trifluoroacetic acid) and 2mL of TFSA (trifluoromethanesulfonic acid) dropwise, stirring rapidly, reacting at room temperature for 8h to obtain a polymer solution with a certain viscosity, diluting, phase-converting in a large amount of anhydrous ethanol to obtain a white filamentous polymer, repeatedly washing, and drying for later use. The Ubbelohde viscosity of the polymer was measured to be 0.85. The structural formula of the polymer is shown as follows (n represents polymerization degree):
Figure BDA0003879943640000122
example 6
This example provides a piperidine type polymer prepared as follows:
weighing 1 '-methylxanthene-9-spiro-4' -piperidine monomer (0.0018mol, 0.5g) and 2,2,2-trifluoroacetophenone (0.0022mol, 0.38g), adding into a 50mL eggplant-shaped bottle containing magnetons, adding 1mL DCM (dichloromethane), stirring until the monomers are completely dissolved, stirring for 10min, and mixing the system uniformly. Slowly adding 0.3mL of TFAc (trifluoroacetic acid) and 2mL of TFSA (trifluoromethanesulfonic acid) dropwise, stirring quickly, reacting at room temperature for 10h to obtain a polymer solution with a certain viscosity, phase-converting the polymer solution into a white filamentous polymer in a large amount of anhydrous ethanol after dilution, repeatedly washing, and drying for later use. The wustite viscosity of the test polymer was 0.76. The structural formula of the polymer is shown as follows (n represents polymerization degree):
Figure BDA0003879943640000131
example 7
This example provides a piperidine type polymer prepared as follows:
weighing 1 '-methylfluorene-9-spiro-4' -piperidine monomer (0.0018mol, 0.47g) and 2,2,2-trifluoroacetophenone (0.0022mol, 0.38g), adding into a 50mL eggplant-shaped bottle containing magnetons, adding 1mL DCM (dichloromethane), stirring until the monomers are completely dissolved, stirring for 10min, and mixing the system uniformly. Slowly adding 0.3mL of TFAc (trifluoroacetic acid) and 2mL of TFSA (trifluoromethanesulfonic acid) dropwise, stirring rapidly, reacting at room temperature for 10h to obtain a polymer solution with a certain viscosity, phase-converting the polymer solution into a white filamentous polymer in a large amount of anhydrous ethanol after dilution, repeatedly washing, and drying for later use. The Ubbelohde viscosity of the polymer was measured to be 1.15. The structural formula of the polymer is shown as follows (n represents polymerization degree):
Figure BDA0003879943640000132
example 8
This example provides a piperidine type polymer prepared as follows:
weighing 1 '-methylxanthene-9-spiro-4' -piperidine monomer (0.0018mol, 0.5g) and acenaphthenequinone (0.0022mol, 0.4g) and adding into a 50mL eggplant-shaped bottle containing magnetons, adding 2mL DCM (dichloromethane), stirring until the monomers are completely dissolved, stirring for 10min, and mixing the system uniformly. Slowly adding 0.5mL of TFSA (trifluoroacetic acid) and 3mL of TFSA (trifluoromethanesulfonic acid) dropwise, stirring quickly, reacting at room temperature for 24 hours to obtain a polymer solution with a certain viscosity, phase-converting the polymer solution into a white filamentous polymer in a large amount of anhydrous ethanol after dilution, repeatedly washing, and drying for later use. The Ubbelohde viscosity of the polymer was measured to be 1.02. The structural formula of the polymer is shown as follows (n represents polymerization degree):
Figure BDA0003879943640000141
example 9
This example provides a piperidine type polymer prepared as follows:
weighing 1 '-methylxanthene-9-spiro-4' -piperidine monomer (0.0018mol, 0.5g) and phenanthrenequinone (0.0022mol, 0.45g) and adding the mixture into a 50mL eggplant-shaped bottle containing magnetons, adding 2mL DCM (dichloromethane) and stirring until the monomers are completely dissolved, stirring for 10min, and mixing the system uniformly. Slowly adding 1mL of TFAc (trifluoroacetic acid) and 4mL of TFSA (trifluoromethanesulfonic acid) dropwise, stirring quickly, reacting at room temperature for 24h to obtain a polymer solution with a certain viscosity, diluting, phase-converting in a large amount of anhydrous ethanol to obtain a white filamentous polymer, repeatedly washing, and drying for later use. The Ubbelohde viscosity of the polymer was measured to be 0.99. The structural formula of the polymer is shown as follows (n represents polymerization degree):
Figure BDA0003879943640000142
example 10
This example provides a piperidine type polymer prepared as follows:
weighing 1 '-methylfluorene-9-spiro-4' -piperidine monomer (0.0018mol, 0.46g) and 1-methylisatron (0.0022mol, 0.3g), adding into a 50mL eggplant-shaped bottle containing magnetons, adding 1mL DCM (dichloromethane), stirring until the monomers are completely dissolved, stirring for 10min, and mixing the system uniformly. Slowly dropwise adding 2mL of TFAc (trifluoroacetic acid) and 3mL of TFSA (trifluoromethanesulfonic acid), quickly stirring, reacting at room temperature for 10h to obtain a polymer solution with a certain viscosity, diluting, phase-converting in a large amount of anhydrous ethanol to obtain a white filamentous polymer, repeatedly washing, and drying for later use. The Ubbelohde viscosity of the polymer was measured to be 1.21. The structural formula of the polymer is shown as follows (n represents polymerization degree):
Figure BDA0003879943640000143
and (3) viscosity testing: 125mg/25mL of the N, N-dimethylacetamide solution of the piperidine polymers obtained in examples 1 to 10 was prepared and tested at 30 ℃ with a Ubbelohde viscometer; and (3) testing molecular weight: 1mg/mL of the N, N-dimethylformamide solution of the piperidine type polymer obtained in examples 1 to 10 was prepared and measured by a GPC apparatus. The test results are shown in table 1 below:
TABLE 1
Group of η Mn(g/mol)
Example 1 0.92 121567
Example 2 0.87 84356
Example 3 1.21 -
Example 4 1.31 95364
Example 5 0.85 112354
Example 6 0.76 54983
Example 7 1.15 75369
Example 8 1.02 123647
Example 9 0.99 56394
Example 10 1.21 69713
As can be seen from table 1, by changing the structures of the piperidine type monomer and the carbonyl monomer, piperidine type polymers having different viscosities and high molecular weights can be obtained.
By using N 2 The adsorption method was used to test the BET surface area and the pore size distribution of the piperidine type polymers obtained in examples 1 to 10, and the test results are shown in Table 2 below:
TABLE 2
Figure BDA0003879943640000151
Figure BDA0003879943640000161
As can be seen from table 2, by changing the structures of the piperidine type monomer and the carbonyl monomer, the inherent pore piperidine type polymer having different specific surface areas can be obtained.
Example 11
This example provides an anion exchange membrane, which is prepared as follows:
1g of the piperidine type polymer obtained in example 1 was taken in a 100mL single-neck flask, dissolved in 20mL of dimethyl sulfoxide, and 1g of CH was added 3 And I, reacting for 3 hours at 60 ℃ in a dark place, performing phase conversion in ethanol, filtering, washing and drying to obtain the piperidine salt-containing anion exchange membrane material. Nuclear magnetic resonance hydrogen spectrogram of anion exchange membrane material (solvent: CDCl) 3 DMSO-d 6) is shown in FIG. 4.
Preparing 0.5g of anion exchange membrane material into 3wt% of membrane casting solution in a 100mL single-neck flask by using dimethyl sulfoxide, casting the membrane casting solution on a glass plate to form a membrane after filtering, drying a solvent, and exchanging counter ions in 1M NaOH aqueous solution to OH - Thus obtaining the anion exchange membrane.
Example 12
This example provides an anion exchange membrane, which is prepared as follows:
1g of the piperidine type polymer obtained in example 2 was taken in a 100mL single-neck flask, dissolved in 20mL of dimethyl sulfoxide, and 1g of CH was added 3 I, reacting for 3 hours at 60 ℃ in a dark place, performing phase conversion in ethanol, filtering, washing and drying to obtain piperidine salt-containing anionsA sub-exchange membrane material. Nuclear magnetic resonance hydrogen spectrogram of anion exchange membrane material (solvent: CDCl) 3 DMSO-d 6) is shown in FIG. 5.
Preparing 0.5g of anion exchange membrane material into 3wt% of membrane casting solution in a 100mL single-neck flask by using dimethyl sulfoxide, casting the membrane casting solution on a glass plate to form a membrane after filtering, drying a solvent, and exchanging counter ions in 1M NaOH aqueous solution to OH - Thus obtaining the anion exchange membrane.
The obtained anion exchange membrane is soaked in 2M NaOH aqueous solution at the temperature of 80 ℃, and the conductivity retention rate is measured to observe the alkali stability in the high-temperature environment. The results are shown in fig. 6, and it can be seen that the anion exchange membrane prepared in example 12 has conductivity retention higher than 85% within 40 days of soaking in 2M NaOH aqueous solution at 80 ℃, which indicates that it can be used stably and has good high temperature alkali stability.
Examples 13 to 20
This example provides 8 kinds of anion exchange membranes, which are different from example 11 only in that the piperidine type polymer obtained in example 1 was equally replaced with the piperidine type polymers obtained in examples 3 to 10, and the remaining parameters and steps were the same as those of example 11.
The anion exchange membranes prepared in examples 11 to 20 were measured for Ion Exchange Capacity (IEC), conductivity, water absorption, swelling ratio, tensile strength, and elongation at break.
The test method is as follows:
1) Titration of Ion Exchange Capacity (IEC)
The ion exchange capacity was tested by acid-base titration. The anion-exchange membranes obtained in examples 11 to 20 were used as membranes to be tested, dried in vacuo and weighed. The membrane was then placed in a volume of 0.1mol L -1 Soaking in HCl solution for 24h to realize OH in the film - With Cl - Is exchanged sufficiently. With 0.1mol L -1 The above solution was titrated with NaOH solution (phenolphthalein as indicator). The experimental value of the ion exchange capacity (mmol/g) was calculated by the following formula: IEC =0.1 · (V) HCl -V NaOH )/M；
Wherein, V HCl (mL) and V NaOH (mL) are the volumes of HCl solution and sodium hydroxide solution consumed, respectively, and M (g) is the mass of the anion exchange membrane dry film.
2) Characterization of the conductivity (σ)
Conductivity test the resistance of the membrane was measured with an electrochemical impedance meter and the conductivity of hydroxyl was calculated using a formula.
σ＝d/LWR；
Wherein σ is the conductivity (unit: S cm) -1 ) D represents the distance (1 cm) between two adjacent platinum electrodes, and L and W represent the thickness and width (unit: cm), R is the resistance value of the film (unit: Ω).
3) Characterization of Water absorption (WU) and Swelling Rate (SR)
Drying the film to be tested in a vacuum oven at 80 ℃ for 12h to constant weight, testing the mass and the transverse dimension of the film, and respectively recording the mass and the transverse dimension as W d And L d . Then soaking the dry film in deionized water, heating for 12h at a specific test temperature, taking out, quickly wiping water on the surface of the dry film by using filter paper, weighing, and recording as W w (ii) a The transverse dimension of the wet film is rapidly measured by a micrometer with the precision of 0.001mm and is recorded as L w 。
The water absorption (WU) and Swelling Ratio (SR) of the film were calculated, respectively:
WU(％)＝[(W w -W d )/M d ]×100％；
SR(％)＝[(L w -L d )/L d ]×100％；
4) Tensile strength and elongation at break
An Instron-1211 static mechanical property tester (testing film length 3cm X width 5mm, stretching speed 5mm min) -1 The test temperature was 25 ℃ and the test humidity was 50RH%. Three samples were taken for each film and the average of the three test results was taken).
The test results are shown in table 3 below:
TABLE 3
Figure BDA0003879943640000181
As can be seen from the data in table 3, the anion exchange membranes prepared in examples 11 to 20 all have high conductivity and ion exchange capacity, good conductivity, low water absorption and swelling degree, good use stability, high tensile strength, low elongation at break, and good mechanical properties.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A piperidine polymer having a microporous structure, wherein the repeating unit has the formula I or II:
Figure FDA0003879943630000011
wherein, the structural formula of A is shown as a formula a or a formula b:
Figure FDA0003879943630000012
R 1 or R 2 Selected from H, substituted or unsubstituted C 1 ～C 6 Alkyl or substituted or unsubstituted C 6 ～C 10 And R is an aryl group of 1 And R 2 Not H at the same time;
the substituted group is selected from halogen, nitro, carboxyl or acyl;
R 3 selected from H, unsubstituted C 1 ～C 6 Alkyl, phenyl or
Figure FDA0003879943630000013
Z = 2-6,X is a halogen element or OH;
q is C, N or S, n = 1-5, m = 2-6, and at least two R 4 May form an aromatic ring with the carbon atom in which it is located.
2. The piperidine-based polymer according to claim 1, wherein R is 1 Or R 2 Selected from substituted or unsubstituted C 1 ～C 4 The substituted group is halogen;
R 3 selected from H, unsubstituted C 1 ～C 4 Alkyl or
Figure FDA0003879943630000014
Z = 2-6,X is halogen;
q is selected from C or N, and N = 2-4;
m =2, two R 4 To form a benzene ring; or m =3, three R 4 A naphthalene ring; or m =4, four R 4 Forming two benzene rings.
3. The piperidine-based polymer having a microporous structure according to claim 2, wherein Q is selected from N, N = 2-4; m =2, two R 4 To form a benzene ring.
4. The piperidine type polymer according to claim 2, wherein a is selected from any one of formulae a-1 to a-5:
Figure FDA0003879943630000021
5. the piperidine type polymer according to claim 4, wherein the specific repeat unit has the following formula I-1 to formula I-5 or formula II-1 to formula II-5:
Figure FDA0003879943630000022
Figure FDA0003879943630000031
6. a process for preparing a piperidine type polymer having a microporous structure according to any one of claims 1 to 5, comprising the steps of:
polymerizing a piperidine aromatic monomer and an A = O monomer by using an acid catalyst to obtain a piperidine polymer;
wherein the piperidine aromatic monomer comprises 1 '-methylxanthene-9-spiro-4' -piperidine or 1 '-methylfluorene-9-spiro-4' -piperidine.
7. The method according to claim 6, wherein the molar ratio of the piperidine aromatic monomer to the A = O monomer is 1 (1.0-1.5).
8. The method of claim 6, wherein the acid catalyst is selected from the group consisting of trifluoromethanesulfonic acid, methanesulfonic acid, and eaton's reagent;
the temperature of the polymerization reaction is-40 to 80 ℃, the reaction time is 0.1 to 48 hours, and the concentration of the reaction system is 5 to 50 percent.
9. An anion exchange membrane, characterized in that it is made of the piperidine type polymer having a microporous structure according to any one of claims 1 to 5 or the piperidine type polymer having a microporous structure prepared by the preparation method according to any one of claims 6 to 8.
10. A fuel cell comprising the anion exchange membrane of claim 9.
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