Sulfuryl bridge connection side chain sulfonated polyimide, preparation method thereof and application

A technology of sulfonated polyimide and sulfonated polyimide copolymer, which is applied in electrochemical generators, final product manufacturing, sustainable manufacturing/processing, etc., can solve the problem of reducing the acidity and difficulty of sulfonic acid groups Phase separation structure, affecting performance and other issues, to achieve the effect of high molecular weight, simple preparation process, and easy control of reaction conditions

CN107417915AInactive Publication Date: 2017-12-01张远男
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Patent Information

Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Publication Date
2017-12-01
Estimated Expiration
Not applicable · inactive patent

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Abstract

The invention discloses sulfuryl bridge connection side chain sulfonated polyimide, a preparation method thereof and a method for preparing proton exchange membranes by applying the sulfonated polyimide. The sulfuryl bridge connection side chain sulfonated polyimide is structurally characterized in that a side chain with a sulfonic acid group is connected onto a polyimide main chain through sulfuryl serving as a bridge connection group, the sulfuryl serves as the bridge connection group, so that flexibility of the side chain and acidity of the sulfonic acid group are ensured, and an obtained polymer has high molecular weight and good hydrolytic stability. A preparation process of the sulfonated polyimide is simple and applicable to industrial production, and reaction conditions are easily operated and controlled. The proton exchange membranes prepared by the sulfuryl bridge connection side chain sulfonated polyimide have high proton conductivity and potential application prospects.
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Description

technical field

[0001] The invention relates to the field of polymer materials, in particular to a side chain type sulfonated polyimide with sulfone group as a bridging group, a preparation method thereof, and a preparation method of a proton exchange membrane. Background technique

[0002] Polyimide (PI) is currently one of the polymer materials with the best comprehensive performance, which has excellent thermal stability, excellent mechanical properties, good film-forming properties and good chemical stability. Sulfonated polyimide (SPI) retains the excellent properties of polyimide to a certain extent, and is a research hotspot in the field of proton exchange membranes. However, the structural characteristics of this type of sulfonated polyimide make its hydrolytic stability poor, which can usually be improved by adjusting the structure of the molecular chain, among which the introduction of side chain type sulfonated diamine monomer is a very effective method . Litera...

Examples

Embodiment 1

[0035] Example 1: Synthesis of a sulfone-bridged side-chain sulfonated polyimide homopolymer NTDA-BSBSDA and preparation of a proton exchange membrane

[0036] Under the protection of nitrogen and mechanical stirring, add 2,2'-bis(3-sulfonic acid benzenesulfonyl)-4,4'-diaminobiphenyl (BSBSDA, 10mmol) into a 250mL dry three-necked flask 6.24g, 2.02-3.03g (20-30mmol) of triethylamine, and 45-90mL of m-cresol. Preferably, the optimal addition amounts in this embodiment are 2.42g (24mmol) and 60mL respectively. After completely dissolving, add 2.68g (NTDA, 10mmol) of 1,4,5,8-naphthalene tetracarboxylic dianhydride and 2.72-4.08g (20-30mmol) of phenylacetic acid, preferably, the optimal addition amount in this example It is 3.26g (22mmol). Under the protection of nitrogen, first raise the temperature of the reaction system to 50-120°C for 1-8h, and then continue to heat up to 150-200°C for 8-24h. Preferably, the two temperatures in this example are 80°C and 180°C respectively. ℃,...

Embodiment 2

[0038] Example 2: Synthesis of a sulfone group-bridged side-chain sulfonated polyimide copolymer NTDA-BSBSDA / ODA (1 / 1) and preparation of a proton exchange membrane

[0039] Under the protection of nitrogen and mechanical stirring, 3.12 g of 2,2'-bis(3-sulfobenzenesulfonyl)-4,4'-diaminobiphenyl (BSBSDA, 5mmol), triethylenediamine 1.12-1.68g (10-15mmol) and m-cresol 34-68mL, preferably, the optimal addition amount in this embodiment is 1.34g (12mmol) and 50mL. After the solid is completely dissolved, add 1.00 g of 4,4'-diaminodiphenyl ether (ODA, 5 mmol), 2.68 g of 1,4,5,8-naphthalene tetracarboxylic dianhydride (NTDA, 10 mmol) and 2.44-3.66 g of benzoic acid g (20-30mmol), preferably, the optimal addition amount in the present embodiment is 2.68g (22mmol). Under the protection of nitrogen, first raise the temperature of the reaction system to 50-120°C for 1-8h, then continue to heat up to 150-200°C for 8-24h, preferably, the optimum temperature points in this embodiment are 1...

Embodiment 3

[0041] Example 3: Synthesis of a sulfone group-bridged side-chain sulfonated polyimide copolymer NTDA-BSBSDA / ODA (2 / 1) and preparation of a proton exchange membrane

[0042] Under the protection of nitrogen and mechanical stirring, 2,2'-bis(3-sulfonic acid benzenesulfonyl)-4,4'-diaminobiphenyl 3.74g (BSBSDA, 6mmol), triethylamine 1.21-1.81g (12-18mmol) and m-cresol 34-68mL, preferably, the optimum addition amount of this embodiment is 1.41g (14mmol) and 45mL. After complete dissolution, add 0.60g of 4,4'-diaminodiphenyl ether (ODA, 3mmol), 2.41g of 1,4,5,8-naphthalene tetracarboxylic dianhydride (NTDA, 9mmol) and 2.20-3.29g of benzoic acid ( 18-27mmol), preferably, the optimum addition amount in the present embodiment is 2.44g (20mmol). Under the protection of nitrogen, first raise the temperature of the reaction system to 50-120°C for 1-8h, and then continue to heat up to 150-200°C for 8-24h. Preferably, the two temperatures in this example are 80°C and 180°C respectively. ...