基于烷基化反应的磺化聚砜的制备及质子交换膜性能
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摘要
以聚砜为基质材料,通过Friedel-Crafts烷基化反应引入环氧基团,然后与对羟基苯磺酸钠(HBS)反应,制备一种侧链型磺化聚砜,记为PS-BS。利用红外光谱(FT-IR)和核磁氢谱(1HNMR)对其结构进行表征,利用流延成膜法制备相应的质子交换膜(PEMs),初步研究温度对PEMs性能的影响规律。结果表明,在适宜的条件下,环氧基团键合量达到2. 28 mmol/g,磺酸基团键合量达到1. 43 mmol/g,由于亲水基团远离聚合物主链,能够形成明显的"微相分离"结构,该侧链型PEMs保持较好的尺寸稳定性、吸水率和质子传导率,PS-BS-4膜在25℃和80℃的溶胀率仅为15. 2%和44. 3%,低于商业化的Nafion115膜。同时,随着温度升高,磺酸基团的运动能力增强,PEMs的吸水率、吸水溶胀率和质子传导率增大。
Epoxy group is added onto the backbone of polysulfone via Friedel-Crafts alkylation reaction.Subsequently,a kind of side chain type sulfonated polysulfone,PS-BS,is obtained via macromolecule reaction with 4-hydroxybenzenesulfonate as reagent.After fully characterizing the chemical structure of PS-BS by FT-IR and1 H-NMR,PS-BS is used to prepare corresponding proton exchange membranes( PEMs) through solution casting method. The relationship between temperature and basic properties of PEMs are studied preliminarily. The experimental result shows that the bonding amount of sulfonic group reaches up to 1. 43 mmol·g-1 when the bonding amount of epoxy group reaches2. 28 mmol·g-1 under appropriate reaction conditions. PEMs keep excellent size stability,wateruptaking rate and proton conductivity mainly because they form obvious micro-phase separation structure due to faraway of hydrophilic groups from main chain of polymers.The swelling ratio of PS-BS-4 is only 15. 2% at 25℃ and 44. 3% at 80℃,lower than that of commercialized Nafion115 PEMs.Meanwhile,water uptaking,swelling ratio and proton conductivity of PEMs will increase with the enhancement of the movement ability of sulfonic group at a rising temperature.
Epoxy group is added onto the backbone of polysulfone via Friedel-Crafts alkylation reaction.Subsequently,a kind of side chain type sulfonated polysulfone,PS-BS,is obtained via macromolecule reaction with 4-hydroxybenzenesulfonate as reagent.After fully characterizing the chemical structure of PS-BS by FT-IR and1 H-NMR,PS-BS is used to prepare corresponding proton exchange membranes( PEMs) through solution casting method. The relationship between temperature and basic properties of PEMs are studied preliminarily. The experimental result shows that the bonding amount of sulfonic group reaches up to 1. 43 mmol·g-1 when the bonding amount of epoxy group reaches2. 28 mmol·g-1 under appropriate reaction conditions. PEMs keep excellent size stability,wateruptaking rate and proton conductivity mainly because they form obvious micro-phase separation structure due to faraway of hydrophilic groups from main chain of polymers.The swelling ratio of PS-BS-4 is only 15. 2% at 25℃ and 44. 3% at 80℃,lower than that of commercialized Nafion115 PEMs.Meanwhile,water uptaking,swelling ratio and proton conductivity of PEMs will increase with the enhancement of the movement ability of sulfonic group at a rising temperature.
引文
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[10]Pang J H,Zhang H B,Li X F,et al. Poly(arylene ether)s with pendant sulfoalkoxy groups prepared by direct copolymerization method for proton exchange membranes[J]. Journal of Membrane Science,2008,184:1-8.
[11]Bose S,Kuila T,Nguyen T X,et al. Polymer membranes for high temperature proton exchange membrane fuel cell:Recent advances and challenges[J]. Progress in Polymer Science,2011,36:813-843.
[12]Gao Y,Robertson G P,Guiver M D,et al.Proton exchange membranes based on sulfonatedpoly(phthalazinone ether ketone)s/aminated polymer blends B[J]. Solid State Ionics,2005,176:409-415.
[2]乔宗文,高保娇,陈涛.侧链磺化型聚砜质子交换膜的设计与制备及其性能研究[J].高分子学报,2015,143:571-580.
[3]陶应勇,张虚略,胡朝霞,等.侧链型含氟磺化聚醚砜/磺化聚酰亚胺共混质子交换膜的制备及性能[J].高等学校化学学报,2016,(4):793-800.
[4]Chen S L,Bocarsly A B,Benziger J.Nafion-layered sulfonated polysulfone fuel cell membranes[J]. Journal of Power Sources,2005,152:27-33.
[5]Kobayashi T,Rilukawa M,Sanui K,et al. Proton conducting polymers derived from poly(etheretherketone)and poly(4-phenoxybenzoyl-1,4-phenylene)[J]. Solid State Ionic,1998,106:219-225.
[6]Zhang Y,Wan Y,Zhao C J,et al.Novel side-chain-type sulfonated poly(arylene ether ketone)with pendant sulfoalkyl groups for direct methanol fuel cells[J].Polymer,2009,50:4471-4478.
[7]沈斌,汪称意,徐常,等.一类侧链型磺化聚芳醚砜质子交换膜的合成及表征[J].高分子学报,2016,10:1409-1417.
[8]乔宗文,高保娇,陈涛.侧链型磺化聚砜的制备及侧链链长对质子交换膜性能影响的研究[J].化学研究与应用,2015,10:1489-1497.
[9]Zhu Y Q,Manthiram A. Synthesis and characterization of polysulfone-containing sulfonated side chains for direct methanol fuel cells[J].Journal of Power Sources,2011,196:7481-7487.
[10]Pang J H,Zhang H B,Li X F,et al. Poly(arylene ether)s with pendant sulfoalkoxy groups prepared by direct copolymerization method for proton exchange membranes[J]. Journal of Membrane Science,2008,184:1-8.
[11]Bose S,Kuila T,Nguyen T X,et al. Polymer membranes for high temperature proton exchange membrane fuel cell:Recent advances and challenges[J]. Progress in Polymer Science,2011,36:813-843.
[12]Gao Y,Robertson G P,Guiver M D,et al.Proton exchange membranes based on sulfonatedpoly(phthalazinone ether ketone)s/aminated polymer blends B[J]. Solid State Ionics,2005,176:409-415.