摘要
采取"二锅二步"的聚合方法以双酚芴、4,4'-二氯二苯砜、双酚AF型二氮杂萘酮、二氟二苯酮磺酸钠为原料制备了含芴-聚芳醚砜憎水链段和双酚AF型二氮杂萘酮-磺化聚芳醚酮亲水链段的两亲嵌段聚芳醚砜酮离聚物,通过调整4种单体的比例以及预聚合、再缩合聚合工艺制备了一系列具有不同链段尺寸的芴-双酚AF型氮杂萘酮-两亲嵌段聚芳醚砜酮离聚物质子交换膜材料.通过黏度测试、傅里叶变换红外光谱(FTIR)、氢谱(1H-NMR)、热失重(TGA)等分析方法,对离聚物的结构和性能进行了表征,用蒸发溶剂法制备了质子交换膜,并考察膜的各种性能.实验结果表明,该系列离聚物的结构可控,热稳定性良好,5 wt%热失重温度均高于250℃;由其制备的质子交换膜具有良好的耐醇性和耐甲醇渗透性能、优异的抗氧化性和水解稳定性、以及适当的质子导电率和吸水率,室温下该系列膜的甲醇渗透率在0.23×10-6～0.28×10-6cm2/s,比Nafion 117具有更好的耐甲醇渗透性能;80℃下该系列膜的质子导电率与30℃时相比呈现倍增趋势,离聚物8e膜的质子导电率在80℃下达到了1.83×10-3S/cm.
A series of block ionomers containing sulfonated poly （phthalazinone ether ketone） hydrophilic segments and poly （fluorene ether sulfone） hydrophobic segments were synthesized via two-pot two-step nucleophilic polycondensation. Bis （4-ehlorophenyl） sulfone and 9,9-bis （4-hydroxyphenyl） fluorene （BHF） were used as eomonomers for hydrophobic blocks. Bisphthalazinone and sulfonated 4,4-difluorobenzophenone （SDFBP） were used to synthsize hydrophilic blocks. Ionomers with different segment sizes were synthesized by adjusting the molar ratios and prepolymerization and polyeondensation. The structure of the ionomers was characterized by ^1H-NMR and FTIR. The spectra and data indicated that these ploymers were in accordance with the designed backbone structure well. The TGA measurements of the ploymers were performed under a nitrogen atmosphere from 50℃ to 600℃ , and results demonstrated that the so-made polymers exhibited good thermal stabilities with 5% weight loss temperature over 250℃. The polymers were soluble in common aprotic solvents, such as DMS~, DMAc,dimethylformamide （DMF） , N-methylpyrroridone （NMP） and tetramethylene sulfone. The inherent viscosity of the synthesized polymers ranged from 0.40 dL/g to 0.71 dL/g,demonstrating high molecular weight of the resulted polymers. The water uptakes of the eopolymers with blocks of varying size were moderate. Moreover, these copolymers demonstrated greatly improved oxidative stabilities and hydrolysis resistance. Polymers 8c -8e with block size bigger than eighteen repeat units were undegradable after 720 h and unhydrolyzable after 480 h. The hydrolysis resistance of the resulted membrances were much better than that of Nation 117. The copolymers had strong alcohol resistance at refluxing temperature. The methanol penetrabilities of the prepared membranes varied from 0.23×10^-6 cm^2/s to 0. 28 × 10^-6 cm^2/s,while that of Nation 117 was 1.32 × 10^-6 cm^2/s under the identical conditions. Especially, polymer 8e gave the proton conductivity of 1.83 × 10^-3 S/cm at 80℃. It is a promising proton exchange membrane material for proton exchange membrane fuel cell using methanol or ethanol as fuel.
出处
《高分子学报》
SCIE
CAS
CSCD
北大核心
2012年第8期902-909,共8页
Acta Polymerica Sinica
基金
国家自然科学基金(基金号51173045)
广东省低碳化学与过程节能重点实验室开放基金(基金号20100103)
广东省燃料电池技术重点实验室研究基金(基金号201104)资助项目
关键词
离聚物
嵌段聚芳醚砜酮
双酚芴
氮杂萘酮
质子交换膜燃料电池
Keywords Ionomer, Poly（ ether sulfone） -b-poly（ ether ketone） , Fluorene bisphenol, Phthalazinone, Protonexchange membrane fuel cell
