降冰片烯类季铵型阴离子交换膜的制备
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摘要
通过环状烯烃双键打开,首尾相接形成聚合物的方法,设计合成了含有季铵阳离子作为功能化基的降冰片烯衍生物单体QRPh NB,通过开环异位聚合(ROMP)制备得到阴离子交换膜材料,流延成膜后的分析结果表明:当单体与降冰片二烯1:2投料时所得到的阴离子交换膜的IEC值为1.26 mequiv·g-1,其最高离子传导率为20.05m S·cm-1;吸水率为14.3%。
In this paper, monomers QRPh NB norbornene derivatives were designed and synthesized, which containing quaternary ammonium cation as a function of the group using a method to open the cyclic olefinic double bond, and end to end to form polymer. An anion exchange membrane material was prepared, through the ring-opening polymerization of ectopic(ROMP). The membrane results showed that when the molar ratio of the monomer and norbornadiene was 1:2, the obtained anion-exchange membrane IEC values was 1.26 mequiv·g-1, the highest ionic conductivity was 20.05 m S·cm-1; water uptake was 14.3%.
In this paper, monomers QRPh NB norbornene derivatives were designed and synthesized, which containing quaternary ammonium cation as a function of the group using a method to open the cyclic olefinic double bond, and end to end to form polymer. An anion exchange membrane material was prepared, through the ring-opening polymerization of ectopic(ROMP). The membrane results showed that when the molar ratio of the monomer and norbornadiene was 1:2, the obtained anion-exchange membrane IEC values was 1.26 mequiv·g-1, the highest ionic conductivity was 20.05 m S·cm-1; water uptake was 14.3%.
引文
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[13]Majchrzak M,Hine P J,Khosravi E.An autonomous self-healing system based on ROMP of norbornene dicarboximide monomers[J].Polymer,2012,53(23):5251-5257.
[14]Khosravi E,Iqbal F,Musa O M.Thermosetting ROMP materials with thermally degradable linkages[J].Polymer,2011,52(2):243-249.
[15]You Z,Song W,Zhang S,Jin O,Xie M.Polymeric microstructures and dielectric properties of polynorbornenes with3,5-bis(trifluoromethyl)biphenyl side groups by ring-opening metathesis polymerization[J].Journal of Polymer Science Part A:Polymer Chemistry,2013,51(22):4786-4798.
[16]Gauna G A,Cobice D,Awruch J.Efficient diborane-mediated synthesis of phthalocyanines carrying amino groups near the macrocycle[J].Polyhedron,2012,46(1):90-94.
[2]Li W,Wang S,Zhang X,Wang W,Xie X,Pei P.Degradation of guanidinium-functionalized anion exchange membrane during alkaline environment[J].International Journal of Hydrogen Energy,2014,39(25):13710-13717.
[3]Wang W,Wang S,Xie X,Lv Y,Ramani V.Density functional theory study of hydroxide-ion induced degradation of imidazolium cations[J].International Journal of Hydrogen Energy,2014,39(26):14355-14361.
[4]Li C,Zhang S,Wang S,Xie X,Deng C,Pei P.A novel cross-linked anion exchange membrane with conjugated and non-conjugated pyridine groups[J].International Journal of Hydrogen Energy,2014,39(26):14362-14369.
[5]Liu G,Shang Y,Xie X,Wang S,Wang J,Wang Y,et al.Synthesis and characterization of anion exchange membranes for alkaline direct methanol fuel cells[J].International Journal of Hydrogen Energy,2012,37(1):848-853.
[6]Truett W L,Johnson D R,Robinson I M,Montague B A.Polynorbornene by coordination polymerization[J].Journal of the American Chemical Society,1960,82(9):2337-2340.
[7]Gilliom L R,Grubbs R H.Titanacyclobutanes derived from strained cyclic olefins—the living polymerization of norbornene[J].Journal of the American Chemical Society,1986,108(4):733-742.
[8]Dias E L,Nguyen S T,Grubbs R H.Well-defined ruthenium olefin metathesis catalysts:mechanism and activity[J].Journal of the American Chemical Society,1997,119(17):3887-3897.
[9]Nguyen S T,Grubbs R H,Ziller J W.Syntheses and activities of new single-component,ruthenium-based olefin metathesis catalysts[J].Journal of the American Chemical Society,1993,115(21):9858-9859.
[10]Zha Y,Disabb-Miller M L,Johnson Z D,Hickner M A,Tew G N.Metal-cation-based anion exchange membranes[J].Journal of the American Chemical Society,2012,134(10):4493-6.
[11]Robertson N J,KostalikⅣH A,Clark T J,Mutolo P F,Abru?a H D,Coates G W.Tunable high performance cross-linked alkaline anion exchange membranes for fuel cell applications[J].Journal of the American Chemical Society,2010,132(10):3400-3404.
[12]Clark T J,Robertson N J,KostalikⅣH A,Lobkovsky E B,Mutolo P F,Abru?a H D,Coates G W.A ring-opening metathesis polymerization route to alkaline anion exchange membranes:development of hydroxide-conducting thin films from an ammonium-functionalized monomer[J].Journal of the American Chemical Society,2009,131(36):12888-12889.
[13]Majchrzak M,Hine P J,Khosravi E.An autonomous self-healing system based on ROMP of norbornene dicarboximide monomers[J].Polymer,2012,53(23):5251-5257.
[14]Khosravi E,Iqbal F,Musa O M.Thermosetting ROMP materials with thermally degradable linkages[J].Polymer,2011,52(2):243-249.
[15]You Z,Song W,Zhang S,Jin O,Xie M.Polymeric microstructures and dielectric properties of polynorbornenes with3,5-bis(trifluoromethyl)biphenyl side groups by ring-opening metathesis polymerization[J].Journal of Polymer Science Part A:Polymer Chemistry,2013,51(22):4786-4798.
[16]Gauna G A,Cobice D,Awruch J.Efficient diborane-mediated synthesis of phthalocyanines carrying amino groups near the macrocycle[J].Polyhedron,2012,46(1):90-94.