COMB-SHAPED STRUCTURE POLYBENZIMIDAZOLE ANION EXCHANGE MEMBRANE WITH HIGH CONDUCTIVITY AND PREPARATION METHOD THEREOF

Abstract

The present invention belongs to the field of alkaline polymer electrolyte membranes, and relates to a comb-shaped structure polybenzimidazole anion exchange membrane with high conductivity and preparation method thereof. In the invention, firstly, polybenzimidazole is grafted with the non-cationic side chains to the max grafting rate to synthesize the de-protonated comb-shaped polybenzimidazole material, avoiding the N—H in benzimidazole forms ionic binding with cationic functional groups, which will reduce the reactivity and mobility of cationic groups; then react de-protonated comb-shaped polybenzimidazole with quaternization reagent to attach the pendent side chain with cationic functional groups, making it easy to aggregate to form ion clusters and hydrophilic/hydrophobic microphase separation. The anion exchange membrane prepared in this invention has excellent conductivity, mechanical properties and alkaline stability.

Claims

1. (canceled)

2. (canceled)

3. A preparation method of comb-shaped polybenzimidazole anion exchange membrane with high conductivity, comprising the steps as follows: (1) synthesis of deprotonated comb-shaped side chain grafted polybenzimidazole material: dissolving polybenzimidazole in solvent A to form a solution with a mass fraction of 1-5 wt. %, and then adding acid binding agent and side chain ##STR00007## without quaternary ammonium cations; molar ratio of the side chain ##STR00008## and acid binding agent to N—H proton is both greater than 1:1; reacting at −18° C. to 100° C. for 48-168 h until a bright yellow liquid is formed; the bright yellow liquid produced by the reaction is precipitated in precipitator B to obtain a solid, which is filtered and dried in vacuum at room temperature for 12-24 h to obtain a deprotonated comb-shaped side chain grafted polybenzimidazole material; the side chain ##STR00009## without quaternary ammonium cation, wherein R2 is halogen, aldehyde group or epoxy group; (2) preparation of comb-shaped structure polybenzimidazole anion exchange membrane with high conductivity: dissolving the deprotonated comb-shaped side chains grafted polybenzimidazole material obtained in step (1) in DMSO solvent to form a solution with a mass fraction of 1-5 wt. %, followed by adding quaternization reagent and reacting at 40° C. to 100° C. for 24-48 h, and obtaining the reaction solution; pouring the reaction solution into precipitator C, a solid product is precipitated, filtered and dried at room temperature for 12-24 h, the comb-shaped structure polybenzimidazole material with high conductivity is obtained, dissolving the comb-shaped structure polybenzimidazole material with high conductivity in DMSO solvent to form a casting solution with a mass fraction of 1-5 wt. %, and then casting the casting solution into a membrane, which is dried under the condition of 60° C. for 48-96 h; immersing the membrane in 1M KOH solution for 24-72 h, and then washing to neutral in deionized water to obtain a comb-shaped structure polybenzimidazole anion exchange membrane with high conductivity; the solvent A is a mixture of one or more of DMF, DMAc, NMP or DMSO; the precipitant B is one or more of water, ethyl acetate or acetone; and the precipitant C is ethyl acetate or acetone or a mixture of both; the specific reaction formula is as follows: ##STR00010## molecular structure of the comb-shaped structure polybenzimidazole anion exchange membrane with high conductivity is as follows: ##STR00011## wherein 0<x≤1; structure of —R1- is as follow, and the structure is the same or different: ##STR00012## R3 is a carbon chain containing ether oxygen bond, with a total length of 1-14 atoms; R3 is the same or different; R4 is a hydrogen atom or halogen; R4 is the same or different; R5 is a quaternary ammonium cation, and R5 is the same or different.

4. The preparation method of the comb-shaped structure polybenzimidazole anion exchange membrane with high conductivity according to claim 3, wherein deprotonation refers to grafting polybenzimidazole with the side chain without cationic groups to max grafting rate, thereby removing all N—H protons from the main chain of polybenzimidazole, and each polybenzimidazole repeat unit is grafted with a functional side chain to form the comb-shaped structure.

5. The preparation method of the comb-shaped structure polybenzimidazole anion exchange membrane with high conductivity according to claim 3, wherein the acid binding agent is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydroxide or potassium hydride; the quaternization reagent is one or more mixtures of trimethylamine, 1-methylimidazole, 1-dimethylimidazole, N-methylpiperidine or N-methylmorpholine.

6. The preparation method of the comb-shaped structure polybenzimidazole anion exchange membrane with high conductivity according to claim 4, wherein the acid binding agent is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydroxide or potassium hydride; the quaternization reagent is one or more mixtures of trimethylamine, 1-methylimidazole, 1-dimethylimidazole, N-methylpiperidine or N-methylmorpholine.

Description

DESCRIPTION OF DRAWINGS

[0022] FIG. 1 shows the .sup.1H-NMR spectra of comb-shaped structure PBI anion exchange membranes. Characteristic peaks at δ=7.4 ppm-8.0 ppm appear in all three embodiments, corresponding to H.sub.a,b,c′ and H.sub.e,f,′ protons in the main chain of PBI, respectively. In the high field (δ<4.5 ppm), the characteristic peaks of side chain are appeared, in which the H.sub.1′ proton appears at δ=4.5 ppm, and the other protons on the side chain appear at δ=3.5 ppm-4.0 ppm. The characteristic peaks of different cationic groups appear at different positions. In embodiments 1, the characteristic peaks of quaternary ammonium cation, H.sub.7,8,9 appear at δ=2.98 ppm; in embodiments 2, the characteristic peaks of imidazole cation, H.sub.10, appears at δ=9.0 ppm; in embodiments 3, the characteristic peak of piperidine cation, H.sub.15, 17 appears at δ=1.6-1.8 ppm. .sup.1H-NMR spectra shows that the comb-shaped structure PBI anion exchange membranes were successfully synthesized in the three embodiments.

[0023] FIG. 2 shows the mechanical properties of the hydrated comb-shaped structure PBI anion exchange membrane. The elongation and tensile strength of the quaternary ammonium cation functionalized PBI anion exchange membrane synthesized in embodiment 1 reaches 41% and 14.5 MPa, respectively. While the elongation and tensile strength of the imidazole cation functionalized PBI anion exchange membrane in embodiment 2 reach 96.3% and 23.0 MPa respectively. The breaking elongation and tensile strength of the piperidine cation functionalized PBI anion exchange membrane synthesized in embodiment 3 reached 88.5% and 21.3 MPa, respectively. The anion exchange membranes synthesized in the three embodiments all exhibit excellent mechanical properties.

[0024] FIG. 3 shows the conductivity of comb-shaped structure PBI anion exchange membrane. The conductivity of the comb-shaped structure PBI anion exchange membranes synthesized in three embodiments increases with the increase of temperature. In 80° C., the conductivity of imidazole cation functionalized PBI anion exchange membrane synthesized in embodiment 2 is the highest, which reaches 86.1 mS cm.sup.−1, while the conductivity of quaternary ammonium cation functionalized PBI anion exchange membrane synthesized in embodiment 1 is slightly lower than that in embodiment 2, reaching 76.3 mS cm.sup.−1. In embodiment 3, the conductivity of piperidine cation functionalized PBI anion exchange membrane synthesized in embodiment 3 is slightly affected by water swelling at 80° C., but still reaches 54.6 mS cm.sup.−1. The anion exchange membranes prepared in the three embodiments all exhibit excellent conductivity.

DETAILED DESCRIPTION

[0025] The present invention is further described in detail in combination with an implementation case below, but the embodiment of the invention is not limited to this.

[0026] Embodiment 1: preparation of comb-shaped structure PBI anion exchange membrane with quaternary ammonium cation functionalized ether bond containing side chain

[0027] Synthesis of deprotonated comb-shaped structure PBI material: 1 g ether bond containing PBI (OPBI) was dissolved in 100 ml DMAc, followed by adding 30 ml non-cationic side chain 1,2-bis (2-chloroethoxy)ethane and 5 g KOH as acid binding agent and stirring at room temperature for 168 h to form a bright yellow liquid. The reaction solution was precipitated in water to obtain a yellowish solid, and then washed and precipitated repeatedly with water and acetone for three times. The obtained yellowish solid was filtered and dried at room temperature in a vacuum oven for 12 hours to obtain deprotonated comb-shaped PBI material.

[0028] Preparation of comb-shaped structure PBI anion exchange membrane with high conductivity: 0.1 g deprotonated comb-shaped PBI material was dissolved in 10 ml DMSO, followed by adding 1 ml 33% trimethylamine aqueous solution, stirred and refluxed under 60° C. for 24 hours.

[0029] A white solid was precipitated by pouring the reaction solution into ethyl acetate, and the comb-shaped structure PBI material with quaternary ammonium cation functionalized ether bond containing side chain was obtained by washing and precipitating repeatedly with water and acetone for three times, and then filtering and drying at room temperature in a vacuum oven for 12 hours. 0.06 g comb-shaped structure PBI material with quaternary ammonium cation functionalized ether bond containing side chain was dissolved in 6 ml DMSO to form a casting solution, which was centrifuged and cast in a glass plate, dried at 60° C. for 48 h, and the polymer membrane was obtained. After soaking in 1 M KOH solution for 24 h, the membrane was washed to neutral in deionized water to obtain the comb-shaped structure PBI anion exchange membrane with quaternary ammonium cation functionalized ether bond containing side chain.

[0030] The performance of the membrane was tested, and the quaternary ammonium cation functionalized PBI anion exchange membrane prepared in this embodiment shows the conductivity of 76.1 mS cm.sup.−1, water absorption of 72.4% and swelling degree of 18.2% at 80° C. The tensile strength of membrane is 14.5 MPa and the elongation at break is 41.4%. After soaking in 2 M KOH solution at 60° C. for 720 h, the conductivity of membrane still remains 81.4%.

[0031] Embodiment 2: preparation of comb-shaped structure PBI anion exchange membrane with imidazole cation functionalized ether bond containing side chain.

[0032] Synthesis of deprotonated comb-shaped structure PBI material: 1 g ether bond containing PBI (OPBI) was dissolved in 50 ml DMF, followed by adding 20 ml non-cationic side chain 1,2-bis (2-chloroethoxy)ethane and 2 g NaH as acid binding agent and stirring at −18° C. for 168 h to form a bright yellow liquid. The reaction solution was precipitated in acetone to obtain a yellowish solid, and then washed and precipitated repeatedly with water and acetone for three times. The obtained yellowish solid was filtered and dried at room temperature in a vacuum oven for 18 hours to obtain deprotonated comb-shaped PBI material.

[0033] Preparation of comb-shaped structure PBI anion exchange membrane with high conductivity: 0.1 g deprotonated comb-shaped PBI material was dissolved in 4 ml DMSO, followed by adding 1 ml 1-methylimidazole, stirred and refluxed under 80° C. for 36 hours; A white solid was precipitated by pouring the reaction solution into ethyl acetate, and the comb-shaped structure PBI material with imidazole cation functionalized ether bond containing side chain was obtained by washing and precipitating repeatedly with water and acetone for three times, and then filtering and drying at room temperature in a vacuum oven for 18 hours. 0.1 g comb-shaped structure PBI material with quaternary ammonium cation functionalized ether bond containing side chain was dissolved in 4 ml DMSO to form a casting solution, which was centrifuged and cast in a glass plate, dried at 60° C. for 72 h, and the polymer membrane was obtained. After soaking in 1 M KOH solution for 48 h, the membrane was washed to neutral in deionized water to obtain the comb-shaped structure PBI anion exchange membrane with quaternary ammonium cation functionalized ether bond containing side chain.

[0034] The performance of the membrane was tested, and the imidazole cation functionalized PBI anion exchange membrane prepared in this embodiment shows the conductivity of 86.3 mS cm.sup.−1, water absorption of 92.5% and swelling degree of 32.9% at 80° C. The tensile strength of membrane is 23.0 MPa and the elongation at break is 96.3%. After soaking in 2 M KOH solution at 60° C. for 720 h, the conductivity of membrane still remains 37.3%.

[0035] Embodiment 3: preparation of comb-shaped structure PBI anion exchange membrane with piperidine cation functionalized ether bond containing side chain.

[0036] Synthesis of deprotonated comb-shaped structure PBI material: 1 g ether bond containing PBI (OPBI) was dissolved in 20 ml NMP, followed by adding 30 ml non-cationic side chain 1,2-bis (2-chloroethoxy)ethane and 5 g K.sub.2CO.sub.3 as acid binding agent and stirring at 100° C. for 48 h to form a bright yellow liquid. The reaction solution was precipitated in acetone to obtain a yellowish solid, and then washed and precipitated repeatedly with water and acetone for three times, filtered and dried at room temperature in a vacuum oven for 24 hours to obtain deprotonated comb-shaped PBI material.

[0037] Preparation of comb-shaped structure PBI anion exchange membrane with high conductivity: 0.3 g deprotonated comb-shaped PBI material was dissolved in 6 ml DMSO, followed by adding 1 ml N-methyl piperidine, stirred and refluxed under 100° C. for 48 h; A white solid was precipitated by pouring the reaction solution into ethyl acetate, and the comb-shaped structure PBI material with piperidine cation functionalized ether bond containing side chain was obtained by washing and precipitating repeatedly with water and acetone for three times, and then filtering and drying at room temperature in a vacuum oven for 24 hours. 0.3 g comb-shaped structure PBI material with piperidine cation functionalized ether bond containing side chain was dissolved in 6 ml DMSO to form a casting solution, which was centrifuged and cast in a glass plate, dried at 60° C. for 96 h, and the polymer membrane was obtained. After soaking in 1 M KOH solution for 72 h, the membrane was washed to neutral in deionized water to obtain the comb-shaped structure PBI anion exchange membrane with piperidine cation functionalized ether bond containing side chain.

[0038] The performance of the membrane was tested, and the piperidine cation functionalized PBI anion exchange membrane prepared in this embodiment shows the conductivity of 54.6 mS cm.sup.−1, water absorption of 298.5% and swelling degree of 51.5% at 80° C. The tensile strength of membrane is 21.3 MPa and the elongation at break is 88.5%. After soaking in 2 M KOH solution at 60° C. for 720 h, the conductivity of membrane still remains 90.2%.