1种氢基发电系统用全氟膜材料制备新工艺
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摘要
采用全氟3,6-二氧杂-4-甲基-7-辛烯磺酰氟(PSVE)水乳液共聚TFE,可以提供高生产率,降低昂贵磺化单体的消耗并且具备成分均匀性,同时结合良好的加工性能,并允许为FC生产质子传导膜,性能不低于传统的Nafion膜。提出了TFE与PSVE共聚的机理,并通过动力学数据和拓扑化学的研究加以证实。
The process is based on the aqueous emulsion copolymerization of TFE with perfluoro-3,6-dioxa-4-methyl-7-octenesulfonylfluoride(PSVE) and affords a high productivity, reduced consumption of the expensive sulfonated monomer and compositional uniformity in combination with good processability and allow the production of proton conducting membranes for hydrogen fuel cells with the properties no worse relating to the conventional Nafion membranes. A mechanism of TFE copolymerization with PSVE is suggested and confirmed by the data of kinetic and topochemical studies.
The process is based on the aqueous emulsion copolymerization of TFE with perfluoro-3,6-dioxa-4-methyl-7-octenesulfonylfluoride(PSVE) and affords a high productivity, reduced consumption of the expensive sulfonated monomer and compositional uniformity in combination with good processability and allow the production of proton conducting membranes for hydrogen fuel cells with the properties no worse relating to the conventional Nafion membranes. A mechanism of TFE copolymerization with PSVE is suggested and confirmed by the data of kinetic and topochemical studies.
引文
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[2] SOUZY R, AMEDURI B. Functional fluoropolymers for fuel cell membranes[J]. Progr Polym Sci, 2005,30:644-687.
[3] BASCHUK J J, LI X. Modelling of polymer electrolyte membrane fuel cells with variable degrees of water flooding[J]. Journal of Power Sources, 2000,86(1/2):181-196.
[4] KREUER K D, PADDISON S J, SPOHR E, et al. Transport in proton conductors for fuel-cell applications:Simulations,elementary reactions, and phenomenology[J]. Chem Rev,2004,104(10):4637-4678.
[5] MEHTA V, COOPER J S. Review and analysis of PEM fuel cell design and manufacturing[J]. Journal of Power Sources,2003,114(1):32-53.
[6] BANERJEE S, CURTIN, D E. Nafion perfluorinated membranes in fuel cells[J]. J Fluorine Chem, 2004,125:1211-1216.
[7] VOLFKOVICH Y M, SOSENKIN V E, BAGOTSKY V S.Structural and wetting properties of fuel cell components[J]. Journal of Power Sources, 2010,195(17):5429-5441.
[8] HUGH H G, RICHARD N G. Fluorocarbon sulfonyl fluorides:US3041317[P]. 1962-06-26.
[9] DONALD J C, WILLIAM F G. Fluorocarbon vinyl ether polymers:US3282875[P]. 1966-11-01.
[10] ODINOKOV A S, BAZANOVA O S, SOKOLOV L F, et al. Kinetics of Copolymerization of tetrafluoroethylene with perfluoro(3,6-dioxa-4-methyl-7-octen)sulfonyl fluoride[J]. Russian Journal of Applied Chemistry, 2009,82(1):112-115.
[11] ELISEEVA V I, IVANCHEV S S, KUCHANOV S I, et al.Emulsion polymerization and its application in industry[M]. N-Y:Plenum Publ Corp, 1981:225.
[12] YOSHIMICHI N, MASAAKI Y. Perfluorocarbon copolymer containing functional groups and a method for producing it:US5608022[P]. 1997-03-04.
[13] GREGORY B P, BROWN F W. Free radical polymerization method for fluorinated copolymers:US6602968[P].2003-08-05.
[14] JOSEPH H S, MAE R L, GOWER I M G, et al. Polymer electrolyte membrane:US7348088[P]. 2008-03-25.