A highly branched poly(arylene piperidine) cationic polymer and methods of making and using the same
By using the multifunctional branched monomer MFSC to prepare highly branched polyarylene piperidine cationic polymers, the problem of low crosslinking degree after modification with traditional branching agents is solved, realizing the anti-swelling and high-performance application of anion exchange membranes, which are suitable for electrochemical energy conversion devices.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHANGHAI BRIGHT-H TECHNOLOGY CO LTD
- Filing Date
- 2026-04-13
- Publication Date
- 2026-06-26
Smart Images
Figure CN122277834A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of polymer materials technology, and in particular to a highly branched polyarylene piperidine cationic polymer, its preparation method and application, specifically applicable to the preparation of anion exchange membranes, and further applied to electrochemical energy conversion devices such as anion exchange membrane water electrolysis and anion exchange membrane fuel cells, belonging to the field of novel polymer electrolyte materials and energy applications. Background Technology
[0002] Hydrogen, as a clean, efficient, and renewable new energy source, has become an important strategic approach to alleviating the global energy crisis and environmental pollution. Among numerous hydrogen production and utilization technologies, anion exchange membrane electrolysis (AEMWE) and anion exchange membrane fuel cells (AEMFC) have shown broad application prospects in the field of large-scale hydrogen production and utilization due to their cost advantage of using non-precious metal catalysts and their high-efficiency reaction kinetics under alkaline systems, making them a current research hotspot in the field of energy materials.
[0003] As a core component of AEMWE and AEMFC, the performance of polymer electrolytes directly determines the operating efficiency, stability, and safety of the device. In actual operation, polymer electrolytes are typically in a hydrated environment. However, traditional polymer electrolytes often exhibit significant swelling, especially when the polymer molecular weight is insufficient or the structural design is inappropriate. This swelling behavior leads to decreased dimensional stability of the polymer electrolyte, deformation or even damage to the membrane structure, thereby affecting the uniformity of ion conduction, gas barrier properties, and mechanical stability. This severely restricts the long-term stable operation of AEMWE and AEMFC, becoming a key technological bottleneck hindering their industrial application.
[0004] To address the aforementioned issues, researchers have focused on developing high-performance polymer electrolyte materials. Among them, polyarylene piperidine cationic polymers (PIPs) have emerged as one of the most promising polymer electrolyte materials for alkaline electrochemical conversion devices due to their excellent alkali stability and high ionic conductivity. To further improve their anti-swelling properties, researchers have attempted to structurally regulate PIPs using polyarylene piperidine cationic polymers such as triphenylbenzene and triphenylbenzene, hoping to construct a dense polymer network structure through branching modification to reduce membrane swelling. However, traditional polyarylene piperidine branching agents have a limited number of reaction sites, typically only three, resulting in a still low degree of crosslinking and insufficient molecular chain entanglement in the prepared polymer electrolytes. Consequently, the branched polymers still exhibit significant swelling in hydrated environments. This means that anion exchange membranes prepared based on these polymers still cannot meet practical application requirements in terms of gas barrier properties and mechanical strength, limiting their large-scale application in electrochemical energy conversion devices.
[0005] Therefore, developing novel branching agents with high density of multiple substitution sites and designing and preparing highly branched polyarylene piperidine cationic polymers to effectively suppress their swelling behavior while taking into account excellent electrochemical and mechanical properties has become a pressing technical problem to be solved in this field. Summary of the Invention
[0006] In view of the above-mentioned defects in the prior art, the technical problem to be solved by the present invention is that the existing polyarylene piperidine cationic polymers, after being modified by traditional branching agents, have low cross-linking degree and insufficient molecular chain entanglement, resulting in significant swelling of the anion exchange membranes prepared by them, and insufficient mechanical strength and gas barrier properties, which in turn affect the long-term operational stability and safety of devices such as AEMWE and AEMFC.
[0007] To achieve the above objectives, the present invention provides a highly branched polyarylene piperidine cationic polymer, which is composed of two parts: a centrally branched unit and a linear unit.
[0008] The central branching unit includes one or more of the following: branching agent residue MA unit, piperidine cationic unit, and nonfunctional monomer residue CA unit;
[0009] The linear unit Lm is one or more of Lm1 and Lm2, wherein Lm1 includes an aromatic ring monomer residue BA unit and a piperidine cationic unit, and Lm2 includes an aromatic ring monomer residue BA unit and a non-functional monomer residue CA unit.
[0010] The chemical structure of the polymer is as follows:
[0011] ;
[0012] Where m and n are any values between 0 and 1, and m + n = 1.
[0013] Preferably, the chemical structure of the branching agent residue MA unit is as follows:
[0014] .
[0015] Preferably, the chemical structure of the piperidine cation unit is as follows:
[0016] ;
[0017] Among them, R 1 and R 2 Independently selected from hydrocarbon groups containing 1-10 carbon atoms, or R 1 and R 2 They connect to form cycloalkyl groups consisting of 4 to 7 carbon atoms, resisting counterion A. -It is selected from one or more of halide ions, methyl sulfate ions, hydroxide ions, or bicarbonate ions.
[0018] Preferably, the aromatic ring monomer residue BA is independently selected from one or more of the following chemical structures:
[0019] (1) ;
[0020] (2) ;
[0021] (3) ;
[0022] (4) ;
[0023] (5) ;
[0024] (6) ;
[0025] (7) ;
[0026] (8) ;
[0027] (9) Where p = 1 - 10;
[0028] (10) Where o = 2 - 4.
[0029] Preferably, the chemical structure of the nonfunctional monomer residue CA unit is as follows:
[0030] k = 0 or 1;
[0031] Among them, each R 3 It is independently selected from hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 6 carbon atoms that are fully or partially fluorinated.
[0032] Preferably, the central unit is connected to the linear unit Lm1, the central unit includes an MA unit and a piperidine cation unit, and Lm1 includes a BA unit and a piperidine cation unit;
[0033] The chemical structure of the polymer is as follows:
[0034] .
[0035] Preferably, the central unit is connected to both linear units Lm1 and Lm2. The central unit includes an MA unit, a piperidine cation unit, and a CA unit. Lm1 includes a BA unit and a piperidine cation unit, and Lm2 includes a BA unit and a CA unit.
[0036] The chemical structure of the polymer is as follows:
[0037] .
[0038] This invention also provides a method for preparing the above-mentioned highly branched polyarylene piperidine cationic polymer, comprising the following steps:
[0039] S1, raw material MA', 1-R 4 Piperidin-4-one or its salt or hydrate, BA' are mixed and dissolved or dispersed in a first organic solvent, and polycondensation is carried out under the catalysis of a strong organic acid at -20 °C to 50 °C for 0.1-200 h to obtain a multi-aromatic polymer precursor solution or dispersion containing a piperidine structure.
[0040] S2. The piperidine-containing polyaromatic polymer precursor solution or dispersion obtained in S1 is added dropwise to precipitant one. After precipitation, the mixture is filtered to obtain fibrous polymer. After thorough washing and drying, the piperidine-containing polyaromatic polymer precursor is obtained.
[0041] S3. The piperidine-containing polyaromatic polymer precursor obtained in S2 is dispersed or dissolved in a second organic solvent. After adding an ionizing agent, an ionization reaction is carried out at 0-100 °C for 1-72 h to obtain a highly branched polyarylene piperidine cationic polymer solution or dispersion.
[0042] S4. Slowly add the highly branched polyarylene piperidine cationic polymer solution or dispersion obtained in S3 to precipitant II, filter and dry to obtain the highly branched polyarylene piperidine cationic polymer.
[0043] Among them, R in S1 4 It is independently selected from H atoms or methyl groups.
[0044] This invention also provides a second method for preparing the above-mentioned highly branched polyarylene piperidine cationic polymer, comprising the following steps:
[0045] S1, raw material MA', 1-R 4 Piperidin-4-one or its salt or hydrate, BA' and compound CA'' are mixed and dissolved or dispersed in a first organic solvent, and undergo a polycondensation reaction catalyzed by a strong organic acid at -20 °C to 50 °C for 0.1 to 200 h to obtain a multi-aromatic polymer precursor solution or dispersion containing a piperidine structure;
[0046] S2. The piperidine-containing polyaromatic polymer precursor solution or dispersion obtained in S1 is added dropwise to precipitant one. After precipitation, the mixture is filtered to obtain fibrous polymer. After thorough washing and drying, the piperidine-containing polyaromatic polymer precursor is obtained.
[0047] S3. The piperidine-containing polyaromatic polymer precursor obtained in S2 is dispersed or dissolved in a second organic solvent. After adding an ionizing agent, an ionization reaction is carried out at 0-100 °C for 1-72 h to obtain a highly branched polyarylene piperidine cationic polymer solution or dispersion.
[0048] S4. Slowly add the highly branched polyarylene piperidine cationic polymer solution or dispersion obtained in S3 to precipitant II, filter and dry to obtain the highly branched polyarylene piperidine cationic polymer.
[0049] 10. An application of a highly branched polyarylene piperidine cationic polymer according to any one of claims 1-7, characterized in that the highly branched polyarylene piperidine cationic polymer is used to prepare anion exchange membranes.
[0050] The technical effects of this invention are as follows:
[0051] (1) The highly branched polyarylene piperidine cationic polymer provided by the present invention uses multifunctional branched monomer MFSC as a branching agent. Its unique compliant twisted helical structure can provide 5 reaction sites. Compared with the traditional branching agent with 3 reaction sites, it can significantly improve the crosslinking density and molecular chain entanglement ability of the polymer, effectively suppress the water absorption and swelling of the high ion content membrane, and solve the technical problem of obvious electrolyte swelling of existing polymers.
[0052] (2) The preparation method of this polymer is simple to operate and the reaction conditions are mild. It does not require harsh conditions such as high temperature and high pressure, and it is easy to industrialize. Moreover, the reagents used in the preparation process are all conventional chemical raw materials, the cost is controllable, and the product yield is high.
[0053] (3) The highly branched polyarylene piperidine cationic polymer prepared by the present invention still has outstanding mechanical properties and anti-swelling properties under high ion exchange capacity. When applied to the preparation of anion exchange membranes, it exhibits excellent physical stability and retains good electrochemical performance and high ionic conductivity, which can meet the high performance requirements of electrolyte materials for devices such as AEMWE and AEMFC.
[0054] (4) The polymer of the present invention and the anion exchange membrane prepared therefrom have a wide range of applications and can be used in many fields such as water electrolysis to produce hydrogen and fuel cell power generation. They provide key material support for the large-scale development and utilization of hydrogen energy and have important industrial application value and market prospects.
[0055] The following will further explain the concept, specific structure, and technical effects of the present invention in conjunction with the accompanying drawings, so as to fully understand the purpose, features, and effects of the present invention. Attached Figure Description
[0056] Figure 1 This is a graph showing the change in hydroxide ion conductivity as a function of temperature for anion exchange membrane 1 in Application Example 1 and Comparative Example 1 of the present invention.
[0057] Figure 2 This is a graph showing the water absorption rate of anion exchange membrane 2 and Comparative Example 1 as a function of temperature in Application Example 1 of the present invention.
[0058] Figure 3 This is a graph showing the swelling ratio of anion exchange membrane 2 and Comparative Example 1 as a function of temperature in Application Example 1 of this invention.
[0059] Figure 4 This is a comparison diagram of the mechanical properties of anion exchange membrane 2 in Application Example 1 and Comparative Example 1 of the present invention;
[0060] Figure 5 This is a comparison chart of the electrolytic polarization performance of anion exchange membrane 1 and comparative example 1 in application example 1 of the present invention. Detailed Implementation
[0061] The following description, with reference to the accompanying drawings, illustrates several preferred embodiments of the present invention to make its technical content clearer and easier to understand. The present invention can be embodied in many different forms, and the scope of protection of the present invention is not limited to the embodiments mentioned herein.
[0062] In the accompanying drawings, components with the same structure are indicated by the same numerical designation, and components with similar structures or functions are indicated by similar numerical designations. The dimensions and thicknesses of each component shown in the drawings are arbitrary, and the present invention does not limit the dimensions and thicknesses of each component. To make the illustrations clearer, the thickness of some components has been appropriately exaggerated in the drawings.
[0063] Example 1
[0064] S1. MFSC (0.020 g, 0.051 mmol), 1-piperidin-4-one hydrochloride (0.38 g, 2.86 mmol) and p-terphenyl (0.58 g, 2.53 mmol) were mixed and dispersed in dichloromethane (4.0 mL). Polycondensation was carried out under the catalysis of trifluoromethanesulfonic acid (1.0 mL) at 25 °C for 5 h to obtain a viscous dispersion of a multi-aromatic polymer precursor containing a piperidine structure.
[0065] S2. The dispersion of the piperidine-containing polyaromatic polymer precursor obtained in S1 was added dropwise to a 1:1 (v / v) mixed solution of methanol and water. After precipitation, the mixture was filtered to obtain a white fibrous polymer. After filtration, the polymer was thoroughly washed and dried under vacuum to obtain 0.89 g of the piperidine-containing polyaromatic polymer precursor.
[0066] S3. Dissolve the piperidine-containing polyaromatic polymer precursor obtained in S2 in 18 mL of N-methylpyrrolidone, add 1.0 mL of iodomethane and 0.6 g of potassium carbonate, and carry out the ionization reaction at room temperature for 48 h to obtain a highly branched polyarylene piperidine cationic polymer solution.
[0067] S4. The highly branched polyarylene piperidine cationic polymer solution obtained in S3 is slowly added to diethyl ether, filtered, and dried to obtain 1.0 g of highly branched polyarylene piperidine cationic polymer one, the structure of which is shown below:
[0068] ;
[0069] Application Example 1
[0070] a. Preparation of anion exchange membranes
[0071] The highly branched polyarylene piperidine cationic polymer prepared in Example 1 was dissolved in 10 mL of dimethyl sulfoxide to obtain a highly branched polyarylene piperidine cationic polymer solution with a mass fraction of approximately 10%. The highly branched polyarylene piperidine cationic polymer solution was coated onto a clean glass plate using a casting method. The glass plate was placed in an 80 °C drying oven for 24 h to remove dimethyl sulfoxide. After the temperature cooled to room temperature, the glass plate was removed, placed in deionized water for demolding, and then thoroughly washed with deionized water to obtain an anti-ion of I. - Anion exchange membrane.
[0072] b. Replace the counterions in the anion exchange membrane in a.
[0073] Let the counter ion in a be I. - The anion exchange membrane was immersed in 1 mol / L NaOH solution for 48 h, and then thoroughly washed with deionized water to obtain an anion exchange membrane with an OH- counterion. - Anion exchange membrane one. The above counter ion is I. - The anion exchange membrane was immersed in 2 mol / L NaCl solution for 24 h, and then thoroughly washed with deionized water to obtain an anion exchange membrane with Cl- as the counter ion. - Anion exchange membrane II.
[0074] Using DMSO-d6 as solvent, a highly branched polyarylene piperidine cationic polymer with the structure shown above was obtained by detection using an Agilent 600 MHz nuclear magnetic resonance spectrometer. Figure 1 As shown, a highly branched polyarylene piperidine cationic polymer was successfully prepared.
[0075] Comparative Example 1
[0076] S1. A polymerization mixture consisting of 1-piperidin-4-one hydrochloride (0.38 g, 2.86 mmol) and p-terphenyl (0.6 g, 2.64 mmol) was placed in dichloromethane (4.0 mL), and trifluoromethanesulfonic acid (1.0 mL) was added to carry out a catalytic polycondensation reaction. The reaction was carried out at 25 °C for 10 h to obtain a viscous linear polymer precursor dispersion containing piperidine structure.
[0077] S2. The linear polymer precursor dispersion containing piperidine structure obtained in S1 was added dropwise to a 1:1 (v / v) mixed solution of methanol and water to obtain a pale yellow fibrous polymer. After filtration, thorough washing, and vacuum drying, 0.85 g of cationic polymer powder was obtained.
[0078] S3. Dissolve the cationic polymer powder from S2 in 18 mL of N-methylpyrrolidone, add 1.0 mL of iodomethane and 0.6 g of potassium carbonate, and carry out the ionization reaction at room temperature for 48 h to obtain a linear polyarylene piperidine cationic polymer solution.
[0079] S4. Slowly add the linear polyarylene piperidine cationic polymer solution from S3 to diethyl ether, filter and dry to obtain 0.91 g of linear polyarylene piperidine cationic polymer (PTP) powder. Prepare a PTP anion exchange membrane from the PTP powder, with an anti-counterion of I0.05. − Furthermore, it can be replaced with hydroxide ions or other counterions as needed, and the resulting structure is shown below.
[0080] ;
[0081] The counter ion is OH - .
[0082] Test Example 1
[0083] The slurries of anion exchange membrane 1, anion exchange membrane 2 and catalyst layer binder corresponding to Example 1 were subjected to the following tests to characterize their basic performance and to compare them with the PTP membrane in Comparative Example 1.
[0084] a. Conductivity test
[0085] The resistance R of the anion exchange membrane I in Application Example 1 and the anion exchange membrane PTP membrane in Comparative Example 1 were measured using a four-electrode AC impedance method. The anion exchange membrane I in Application Example 1 and the anion exchange membrane PTP membrane in Comparative Example 1 were both cut into 1 cm × 5 cm strips, clamped in a fixture, and then placed in a water bath filled with pure water. After installing the electrodes, the electrochemical workstation was connected. In constant current mode (0.1 mA), the scanning frequency range was 1 MHz – 100 Hz. The frequency range where impedance was stable was found on the Bode curve, and the resistance R of the anion exchange membrane I and the anion exchange membrane PTP membrane was then read from the corresponding curve.
[0086] The conductivity of hydroxide ions is calculated using the following formula:
[0087]
[0088] Where R is the resistance of the anion exchange membrane, L is the distance between the electrodes (1.0 cm), W is the width of the anion exchange membrane, and d is the thickness of the anion exchange membrane.
[0089] Based on the hydroxide ion conductivity measured at different temperatures, a curve showing the change in hydroxide ion conductivity of the anion exchange membrane as a function of temperature was obtained, as shown below. Figure 1 As shown. By Figure 1 It can be seen that, under 80 °C conditions, the hydroxide ion conductivity of the highly branched anion exchange membrane reaches 189 mS·cm. -1 It outperforms linear anion exchange membranes (PTP membranes) by 180 mS·cm. -1 The electrical conductivity.
[0090] b. Water absorption rate and swelling rate
[0091] The anion exchange membrane II from Application Example 1 and the PTP anion exchange membrane with chloride ions as counterions from Comparative Example 1 were cut into 1 cm × 8 cm strips, respectively. They were thoroughly dried in an oven, and the weight of the dried anion exchange membrane was recorded as W. dry The dried anion exchange membrane was then immersed in deionized water. Every 12 hours, the anion exchange membrane was removed, its surface dried, and the weight W of the anion exchange membrane after immersion at different temperatures (30–80 °C) was recorded. wet Water absorption rate (WU) is calculated using the following formula:
[0092]
[0093] Based on the calculated water absorption rates obtained at different temperatures, a curve showing the change in water absorption rate of the anion exchange membrane with temperature was generated, as shown below. Figure 2 As shown.
[0094] Swelling ratio (SR) is an important indicator of membrane dimensional stability, measured by the length (L) of the dry and wet anion exchange membrane. dry and L wet The calculation is obtained using the following formula:
[0095]
[0096] Based on the swelling ratios measured at different temperatures, the swelling ratio curves of anion exchange membrane II and PTP membrane (using chloride ions as counterions) as a function of temperature were obtained, as shown below. Figure 3 As shown.
[0097] c. Mechanical property testing
[0098] Using a CMT4506 electronic universal testing machine at a speed of 5 mm min -1 The tensile properties of the anion exchange membrane II in Application Example 1 and the PTP anion exchange membrane with chloride ions as counterions in Comparative Example 1 were determined by tensile speed measurement. All anion exchange membranes were cut into dumbbell shapes, 40 mm × 10 mm × 0.04 mm (length × width × thickness). Three parallel samples were set up for each group of samples. The samples were equilibrated in the test environment for 24 hours before use. The test results are as follows: Figure 4 As shown.
[0099] d. Performance testing of anion exchange membrane water electrolyzer
[0100] CAPist-L1 and Pt / C were used as the anode and cathode catalysts, respectively, with Pt loading in the cathode being 0.5 mg / cm³. -2 Membrane electrodes were prepared using catalyst-coated membrane technology. The polarization performance of the anion exchange membrane 1 in Application Example 1 and the PTP anion exchange membrane in Comparative Example 1 was measured in an anion exchange membrane water electrolyzer. Figure 5 As shown.
[0101] In summary, at 80 °C, the hydroxide ion conductivity of the highly branched anion exchange membrane reaches 189 mS·cm. -1 Anion exchange membrane type II exhibits lower water absorption and swelling rates, as well as better mechanical properties. Furthermore, in an anion exchange membrane water electrolyzer at 80 °C and 2 V, anion exchange membrane type I, with its highly branched structure, can achieve a viscosity of 6.28 A / cm². -2 High current density.
[0102] Example 2
[0103] S1. MFSC (0.043 g, 0.11 mmol), 1-piperidin-4-one hydrochloride (0.57 g, 4.29 mmol), 9,9-dimethylfluorene (0.35 g, 1.82 mmol) and p-terphenyl (0.41 g, 1.82 mmol) were mixed and dispersed in dichloromethane (6.0 mL). Polycondensation was carried out under the catalysis of trifluoromethanesulfonic acid (1.5 mL) at 25 °C for 8 h to obtain a viscous dispersion of a multi-aromatic polymer precursor containing a piperidine structure.
[0104] S2. The dispersion of the piperidine-containing polyaromatic polymer precursor obtained in S1 was added dropwise to a 1:1 (v / v) mixed solution of methanol and water. After precipitation, the mixture was filtered to obtain a white fibrous polymer. After filtration, the polymer was thoroughly washed and dried under vacuum to obtain 1.24 g of the piperidine-containing polyaromatic polymer precursor.
[0105] S3. The piperidine-containing polyaromatic polymer precursor obtained in S2 was dissolved in 26 mL of N-methylpyrrolidone, and 1.5 mL of iodomethane and 0.9 g of potassium carbonate were added. After ionization reaction at room temperature for 48 h, a highly branched polyarylene piperidine cationic polymer solution was obtained.
[0106] S4. The highly branched polyarylene piperidine cationic polymer solution obtained in S3 is slowly added to diethyl ether, filtered, and dried to obtain 1.36 g of highly branched polyarylene piperidine cationic polymer II, the structure of which is shown below:
[0107]
[0108] Application Example 2
[0109] a. Preparation of anion exchange membranes
[0110] The highly branched polyarylene piperidine cationic polymer II prepared in Example 2 was dissolved in 14 mL of dimethyl sulfoxide to obtain a highly branched polyarylene piperidine cationic polymer solution with a mass fraction of approximately 10%. The highly branched polyarylene piperidine cationic polymer solution was coated onto a clean glass plate using a casting method. The glass plate was placed in an 80 °C drying oven for 24 h to remove dimethyl sulfoxide. After the temperature cooled to room temperature, the glass plate was removed, placed in deionized water for demolding, and then thoroughly washed with deionized water to obtain an anti-ion of I. - Anion exchange membrane.
[0111] b. Replace the counterions in the anion exchange membrane in a.
[0112] Let the counter ion in a be I. -The anion exchange membrane was immersed in 1 mol / L NaOH solution for 48 h, and then thoroughly washed with deionized water to obtain an anion exchange membrane with an OH- counterion. - Anion exchange membrane. The counter ion is I. - The anion exchange membrane was immersed in 2 mol / L NaCl solution for 24 h, and then thoroughly washed with deionized water to obtain an anion exchange membrane with Cl- as the counter ion. - Anion exchange membrane.
[0113] Example 3
[0114] S1. MFSC (0.035 g, 0.09 mmol), 1-piperidin-4-one hydrochloride (0.55 g, 4.10 mmol), trifluoroacetophenone (0.13 g, 0.72 mmol) and p-terphenyl (1.02 g, 4.5 mmol) were mixed and dispersed in dichloromethane (7.0 mL). Polycondensation reaction was carried out under the catalysis of trifluoromethanesulfonic acid (1.7 mL) at 25 °C for 10 h to obtain a viscous multi-aromatic polymer precursor dispersion containing piperidine structure.
[0115] S2. The piperidine-containing polyaromatic polymer precursor dispersion obtained in S1 was added dropwise to a 1:1 (v / v) mixed solution of methanol and water. After precipitation, the mixture was filtered to obtain a white fibrous polymer. After filtration, the polymer was thoroughly washed and dried under vacuum to obtain 1.55 g of the piperidine-containing polyaromatic polymer precursor.
[0116] S3. The piperidine-containing polyaromatic polymer precursor obtained in S2 was dissolved in 31 mL of N-methylpyrrolidone, and 2.0 mL of iodomethane and 1.2 g of potassium carbonate were added. After ionization reaction at room temperature for 48 h, a highly branched polyarylene piperidine cationic polymer solution was obtained.
[0117] S4. The highly branched polyarylene piperidine cationic polymer solution obtained in S3 is slowly added to diethyl ether, filtered and dried to obtain 1.70 g of highly branched polyarylene piperidine cationic polymer III, the structure of which is shown below.
[0118]
[0119] Application Example 3
[0120] a. Preparation of anion exchange membranes
[0121] The highly branched polyarylene piperidine cationic polymer prepared in Example 3 was dissolved in 17 mL of dimethyl sulfoxide to obtain a highly branched polyarylene piperidine cationic polymer solution with a mass fraction of approximately 10%. The highly branched polyarylene piperidine cationic polymer solution was coated onto a clean glass plate using a casting method. The glass plate was placed in a forced-air drying oven at 80 °C for 24 h to remove dimethyl sulfoxide. After the temperature cooled to room temperature, the glass plate was removed, placed in deionized water for demolding, and then thoroughly washed with deionized water to obtain an anti-ion of I. - Anion exchange membrane.
[0122] b. Replace the counterions in the anion exchange membrane in a.
[0123] Let the counter ion in a be I. - The anion exchange membrane was immersed in 1 mol / L NaOH solution for 48 h, and then thoroughly washed with deionized water to obtain an anion exchange membrane with an OH- counterion. - Anion exchange membrane. The counter ion is I. - The anion exchange membrane was immersed in 2 mol / L NaCl solution for 24 h, and then thoroughly washed with deionized water to obtain an anion exchange membrane with Cl- as the counter ion. - Anion exchange membrane.
[0124] Example 4
[0125] S1. MFSC (0.03 g, 0.079 mmol), 1-piperidin-4-one hydrochloride (0.38 g, 2.86 mmol), and p-tetraphenyl (0.81 g, 2.63 mmol) were mixed and dispersed in dichloromethane (4.0 mL). Polycondensation was carried out under the catalysis of trifluoromethanesulfonic acid (1.0 mL) at 25 °C for 6 h to obtain a viscous dispersion of a multi-aromatic polymer precursor containing a piperidine structure.
[0126] S2. The dispersion of the piperidine-containing polyaromatic polymer precursor obtained in S1 was added dropwise to a 1:1 (v / v) mixed solution of methanol and water. After precipitation, the mixture was filtered to obtain a white fibrous polymer. After filtration, the polymer was thoroughly washed and dried under vacuum to obtain 1.02 g of the piperidine-containing polyaromatic polymer precursor.
[0127] S3. Dissolve the piperidine-containing polyaromatic polymer precursor obtained in S2 in 10 mL of N-methylpyrrolidone, add 1.2 mL of iodomethane and 0.75 g of potassium carbonate, and carry out the ionization reaction at room temperature for 48 h to obtain a highly branched polyarylene piperidine cationic polymer solution.
[0128] S4. The highly branched polyarylene piperidine cationic polymer solution obtained in S3 is slowly added to diethyl ether, filtered and dried to obtain 1.15 g of highly branched polyarylene piperidine cationic polymer four, the structure of which is shown below.
[0129]
[0130] Application Example 4
[0131] a. Preparation of anion exchange membranes
[0132] The highly branched polyarylene piperidine cationic polymer tetra prepared in Example 4 was dissolved in 11 mL of dimethyl sulfoxide to obtain a highly branched polyarylene piperidine cationic polymer solution with a mass fraction of approximately 10%. The highly branched polyarylene piperidine cationic polymer solution was coated onto a clean glass plate using a casting method. The glass plate was placed in an 80 °C drying oven for 24 h to remove dimethyl sulfoxide. After the temperature cooled to room temperature, the glass plate was removed, placed in deionized water for demolding, and then thoroughly washed with deionized water to obtain an anti-ion of I. - Anion exchange membrane.
[0133] b. Replace the counterions in the anion exchange membrane in a.
[0134] The anion exchange membrane with counter ion a was immersed in 1 mol / L NaOH solution for 48 h, and then thoroughly washed with deionized water to obtain the anion exchange membrane with counter ion OH. - Anion exchange membrane with the above counter ion was immersed in 2 mol / L NaCl solution for 24 h, and then thoroughly washed with deionized water to obtain an anion exchange membrane with the counter ion Cl. - Anion exchange membrane.
[0135] The preferred embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.
Claims
1. A highly branched polyarylene piperidine cationic polymer, characterized in that, It consists of two parts: centrally branched units and linear units; The central branching unit includes one or more of the following: branching agent residue MA unit, piperidine cationic unit, and nonfunctional monomer residue CA unit; The linear unit Lm is one or more of Lm1 and Lm2, wherein Lm1 includes an aromatic ring monomer residue BA unit and a piperidine cationic unit, and Lm2 includes an aromatic ring monomer residue BA unit and a non-functional monomer residue CA unit. The chemical structure of the polymer is as follows: ； Where m and n are any values between 0 and 1, and m + n = 1.
2. The highly branched polyarylene piperidine cationic polymer as described in claim 1, characterized in that, The chemical structure of the branching agent residue MA unit is as follows: 。 3. The highly branched polyarylene piperidine cationic polymer as described in claim 1, characterized in that, The chemical structure of the piperidine cation unit is as follows: ； Among them, R 1 and R 2 Independently selected from hydrocarbon groups containing 1-10 carbon atoms, or R 1 and R 2 They connect to form cycloalkyl groups consisting of 4 to 7 carbon atoms, resisting counterion A. − It is selected from one or more of halide ions, methyl sulfate ions, hydroxide ions, or bicarbonate ions.
4. The highly branched polyarylene piperidine cationic polymer as described in claim 1, characterized in that, The aromatic ring monomer residue BA is independently selected from one or more of the following chemical structures: （1） ； （2） ； （3） ； （4） ； （5） ； （6） ； （7） ； （8） ； (9) Where p = 1 - 10; (10) Where o = 2 - 4.
5. The highly branched polyarylene piperidine cationic polymer as described in claim 1, characterized in that, The chemical structure of the nonfunctional monomer residue CA unit is as follows: k = 0 or 1; Among them, each R 3 It is independently selected from hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 6 carbon atoms that are fully or partially fluorinated.
6. The highly branched polyarylene piperidine cationic polymer as described in claim 1, characterized in that, The central unit is connected to the linear unit Lm1. The central unit includes an MA unit and a piperidine cation unit, and Lm1 includes a BA unit and a piperidine cation unit. The chemical structure of the polymer is as follows: 。 7. The highly branched polyarylene piperidine cationic polymer as described in claim 1, characterized in that, The central unit is connected to both linear units Lm1 and Lm2. The central unit includes an MA unit, a piperidine cation unit, and a CA unit. Lm1 includes a BA unit and a piperidine cation unit. Lm2 includes a BA unit and a CA unit. The chemical structure of the polymer is as follows: 。 8. A method for preparing a highly branched polyarylene piperidine cationic polymer according to claim 6, characterized in that, Includes the following steps, S1, raw material MA', 1-R 4 Piperidin-4-one or its salt or hydrate, BA' are mixed and dissolved or dispersed in a first organic solvent, and polycondensation is carried out under the catalysis of a strong organic acid at -20 °C to 50 °C for 0.1-200 h to obtain a multi-aromatic polymer precursor solution or dispersion containing a piperidine structure. S2. The piperidine-containing polyaromatic polymer precursor solution or dispersion obtained in S1 is added dropwise to precipitant one. After precipitation, the mixture is filtered to obtain fibrous polymer. After thorough washing and drying, the piperidine-containing polyaromatic polymer precursor is obtained. S3. The piperidine-containing polyaromatic polymer precursor obtained in S2 is dispersed or dissolved in a second organic solvent. After adding an ionizing agent, an ionization reaction is carried out at 0-100 °C for 1-72 h to obtain a highly branched polyarylene piperidine cationic polymer solution or dispersion. S4. Slowly add the highly branched polyarylene piperidine cationic polymer solution or dispersion obtained in S3 to precipitant II, filter and dry to obtain the highly branched polyarylene piperidine cationic polymer. Among them, R in S1 4 It is independently selected from H atoms or methyl groups.
9. A method for preparing a highly branched polyarylene piperidine cationic polymer according to claim 7, characterized in that, Includes the following steps, S1, raw material MA', 1-R 4 Piperidin-4-one or its salt or hydrate, BA' and compound CA'' are mixed and dissolved or dispersed in a first organic solvent, and undergo a polycondensation reaction catalyzed by a strong organic acid at -20 °C to 50 °C for 0.1 to 200 h to obtain a multi-aromatic polymer precursor solution or dispersion containing a piperidine structure; S2. The piperidine-containing polyaromatic polymer precursor solution or dispersion obtained in S1 is added dropwise to precipitant one. After precipitation, the mixture is filtered to obtain fibrous polymer. After thorough washing and drying, the piperidine-containing polyaromatic polymer precursor is obtained. S3. The piperidine-containing polyaromatic polymer precursor obtained in S2 is dispersed or dissolved in a second organic solvent. After adding an ionizing agent, an ionization reaction is carried out at 0-100 °C for 1-72 h to obtain a highly branched polyarylene piperidine cationic polymer solution or dispersion. S4. Slowly add the highly branched polyarylene piperidine cationic polymer solution or dispersion obtained in S3 to precipitant II, filter and dry to obtain the highly branched polyarylene piperidine cationic polymer.
10. The application of a highly branched polyarylene piperidine cationic polymer according to any one of claims 1-7, characterized in that, The highly branched polyarylene piperidine cationic polymer is used to prepare anion exchange membranes.