萘磺酸型侧链磺化聚砜质子交换膜的性能
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摘要
以聚砜(PS)和自制的1,4-二氯甲氧基丁烷(BCD)为氯甲基化试剂通过Fridel-Crafts烷基反应制备氯甲基化聚砜(CPS),紧接着氯甲基与2-萘酚-6,8-二磺酸钾(NSK)试剂通过亲核取代反应制备一种萘磺酸型磺化聚砜(PS-NS),在用红外和核磁氢谱充分表征的基础上制备一系列磺酸基团键合量不同的PS-NS质子交换膜(分别为PS-NS-1,PS-NS-2,PS-NS-3)重点研究温度对质子交换膜性能的影响规律。研究结果表明:由于亲水基团与疏水主链距离较远,能够形成类似于Nafion膜的微相分离结构,使得该质子交换膜在高磺化度下仍能保持高的尺寸稳定性,同时随着温度升高,质子交换膜的吸水率、溶胀性以及质子传导率增加,PS-NS-3在25℃和85℃的吸水率为21. 3%和42. 7%,但是溶胀率仅为22. 2%和50. 3%,与商业化Nafion115膜(24. 9%和55. 0%)的性能十分接近,表现出很好的尺寸稳定性。
The chloromethylated polysulfone( CPS) was obtained by introducing chloromethyl group onto backbone of PS with 1,4-bischloromethyoxyl butane as reagent.Subsequently with 2-naphthol-6,8-disulfonic acid dipotassium as reagent,the sulfonated polysulfone( PS-NS) was prepared by Fridel-Crafts alkylation reaction.A series of PS-NS PEMs( PS-NS-1,PS-NS-2 and PS-NS-3) with different bonding amount of sulfonic acid group were obtained after fully characterizing their structures by the FT-IR and1 H-NMR.The effects of temperature on performance of PEMs were explored.The results showed that the PS-NS PEMs could form Micro-phase separation structure similar to Nafion membrane by locating the hydrophilic sulfonic acid group far away from hydrophobic polysulfone main chain.So the PEMs could keep excellent size stability at high wateruptaking.The wateruptaking,swelling ratio and proton conductivity of PEMs were increased with temperture increasing.The reaction was allowed to be carried out at 100 ℃ for 40 h with dimethyl sulfoxide as solvent. The bonding amount of sulfonate acid group was up to 1. 57 mmol·g-1. The proton exchange membranes( PEMs) were fabricated by solution casting method. The wateruptaking and proton conductivity of PEMs increased with the bonding amount increasing.The PS-NS-3 PEMs showed excellent size stability that the swelling ratio of were only 22. 2% at 25℃and 50. 3%at 85℃ when the wateruptaking were 21. 3% and 42. 7%. And the swelling ration was closed to the commercialization Nafion115 membranes( 24. 9%at 25℃ and 55. 0%at 85℃).
The chloromethylated polysulfone( CPS) was obtained by introducing chloromethyl group onto backbone of PS with 1,4-bischloromethyoxyl butane as reagent.Subsequently with 2-naphthol-6,8-disulfonic acid dipotassium as reagent,the sulfonated polysulfone( PS-NS) was prepared by Fridel-Crafts alkylation reaction.A series of PS-NS PEMs( PS-NS-1,PS-NS-2 and PS-NS-3) with different bonding amount of sulfonic acid group were obtained after fully characterizing their structures by the FT-IR and1 H-NMR.The effects of temperature on performance of PEMs were explored.The results showed that the PS-NS PEMs could form Micro-phase separation structure similar to Nafion membrane by locating the hydrophilic sulfonic acid group far away from hydrophobic polysulfone main chain.So the PEMs could keep excellent size stability at high wateruptaking.The wateruptaking,swelling ratio and proton conductivity of PEMs were increased with temperture increasing.The reaction was allowed to be carried out at 100 ℃ for 40 h with dimethyl sulfoxide as solvent. The bonding amount of sulfonate acid group was up to 1. 57 mmol·g-1. The proton exchange membranes( PEMs) were fabricated by solution casting method. The wateruptaking and proton conductivity of PEMs increased with the bonding amount increasing.The PS-NS-3 PEMs showed excellent size stability that the swelling ratio of were only 22. 2% at 25℃and 50. 3%at 85℃ when the wateruptaking were 21. 3% and 42. 7%. And the swelling ration was closed to the commercialization Nafion115 membranes( 24. 9%at 25℃ and 55. 0%at 85℃).
引文
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[10]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.
[11]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]. Polym,2009,50:4471-4478.
[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.
[13]Bose S,Kuila T,Nguyen T X,et al.Polymer membranes for high temperature proton exchange membrane fuel cell:Recent advances and challenges[J]. Progr Polym Sci,2011,36:813-843.
[14]Ekstr m H,Lafitte B,Ihonen J,et al. Evaluation of a sulfophenylated polysulfone membrane in a fuel cell at 60to 110°C[J].Solid State Ionics 2007,178:959-966.
[15]Wang G G,Weng Y M,Chu D,et al.Developing a polysulfone-based alkaline anion exchange membranefor improved ionic conductivity[J].J Memb Sci 2009,332:63-68.
[2]Feng S G,Shang Y M,Xie X F,et al.Synthesis and characterization of crosslinked sulfonated poly(arylene ether sulfone)membranes for DMFC applications[J]. J Memb Sci,2009,35:13-20.
[3]宫飞祥,齐永红,薛群翔.含氟磺化双三蝶烯型聚芳醚砜质子交换膜的制备及性能[J].高等学校化学学报,2014,2014,35:433-439.
[4]Mishra A K,Bose S,Kuila T,et al.Silicate-based polymernanocomposite membranes for polymer electrolyte membrane fuel cells[J].Prog Polym Sci,2012,37:842-869.
[5]荣倩,顾爽,贺高红等.SPEEK/P4VP酸碱复合质子交换膜的制备与性能[J].高分子材料科学与工程,2009,8:126-129.
[6]Lafitte B,Jannasch P. Proton-Conducting Aromatic Polymers Carrying Hypersulfonated Side Chains for Fuel Cell Applications[J].Adva Funct Mater,2007,17:2823-283
[7]Kobayashi T,Rilukawa M,Sanui K,et al.Proton conducting polymers derived from poly(ether-etherketone)and poly(4-phenoxybenzoyl-1,4-phenylene)[J]. Solid State Ionic,1998,106:219-225.
[8]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]. Polym,2009,50:4471-4478.
[9]乔宗文,高保娇,陈涛.侧链末端为磺酸根基团的磺化改性聚砜的制备及其阳离子交换膜的基本性能[J].功能高分子学报,2014,27(04):399-407.
[10]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.
[11]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]. Polym,2009,50:4471-4478.
[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.
[13]Bose S,Kuila T,Nguyen T X,et al.Polymer membranes for high temperature proton exchange membrane fuel cell:Recent advances and challenges[J]. Progr Polym Sci,2011,36:813-843.
[14]Ekstr m H,Lafitte B,Ihonen J,et al. Evaluation of a sulfophenylated polysulfone membrane in a fuel cell at 60to 110°C[J].Solid State Ionics 2007,178:959-966.
[15]Wang G G,Weng Y M,Chu D,et al.Developing a polysulfone-based alkaline anion exchange membranefor improved ionic conductivity[J].J Memb Sci 2009,332:63-68.