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Crosslinked terpolymers of vinylidene fluoride, perfluoro-3,6-dioxa-4-methyl-7-octene sulfonyl fluoride, and cure site monomers for membranes in PEMFC applications†
Polymer Chemistry ( IF 4.1 ) Pub Date : 2019-03-22 00:00:00 , DOI: 10.1039/c9py00188c Maxime Colpaert 1, 2, 3, 4, 5 , Marta Zaton 1, 2, 3, 4, 5 , Vincent Ladmiral 1, 2, 3, 4, 5 , Deborah Jones 1, 2, 3, 4, 5 , Jacques Rozière 1, 2, 3, 4, 5 , Bruno Ameduri 1, 2, 3, 4, 5
Polymer Chemistry ( IF 4.1 ) Pub Date : 2019-03-22 00:00:00 , DOI: 10.1039/c9py00188c Maxime Colpaert 1, 2, 3, 4, 5 , Marta Zaton 1, 2, 3, 4, 5 , Vincent Ladmiral 1, 2, 3, 4, 5 , Deborah Jones 1, 2, 3, 4, 5 , Jacques Rozière 1, 2, 3, 4, 5 , Bruno Ameduri 1, 2, 3, 4, 5
Affiliation
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Radical terpolymerisations of perfluoro(8-cyano-5-methyl-3,6-dioxaoct-1-ene) (CNVE) or 2,2,3,3,4,4,5,5,6,6-decafluoro-6-[(1,2,2-trifluoroethenyl) oxy] hexanenitrile (MV5CN), vinylidene fluoride (VDF) and perfluoro(4-methyl-3,6-dioxaoct-7-ene) sulfonyl fluoride (PFSVE) are presented. Changing the monomer feed compositions of these terpolymerisations enabled the synthesis of different statistical-type poly(VDF-ter-PFSVE-ter-CNVE) terpolymers containing sulfonyl fluoride and nitrile side groups. Yields higher than 11% were reached in all cases. The hydrolysis of the sulfonyl fluoride groups into sulfonic acid functions, using potassium hydroxide (or lithium carbonate) under mild conditions, was achieved quantitatively without affecting the content of VDF, assuming that no dehydrofluorination of the VDF units occurred. These original terpolymers were then thermally crosslinked using cyclisation of the pendant nitrile functions to produce films insoluble in organic solvents such as acetone and dimethylformamide (that completely dissolved uncured terpolymers). The thermal stabilities of the crosslinked materials were higher than those of the uncured terpolymers. Depending on the sulfonic acid content in the terpolymers, the ion-exchange capacities ranged from 0.95 to 1.32 meq H+ per g. The proton conductivity at 80 °C and 100% relative humidity reached 58 mS cm−1 for a membrane crosslinked at 240 °C and having a hydration number of 33 H2O/SO3H, while excessive swelling was observed for membranes crosslinked at lower temperatures.
中文翻译：
偏二氟乙烯，全氟-3,6-二氧杂-4-甲基-7-辛烯磺酰氟的交联三元共聚物以及PEMFC应用中膜的固化位点单体†
全氟（8-氰基-5-甲基-3,6-二氧杂辛-1-烯）（CNVE）或2,2,3,3,4,4,5,5,6,6-十氟-6的自由基三元聚合提出了-[[（1,2,2-三氟乙烯基）氧基]己腈（MV5CN），偏二氟乙烯（VDF）和全氟（4-甲基-3,6-二氧杂八烷基-7-烯）磺酰氟（PFSVE）。改变这些三元聚合的单体进料组成使得能够合成不同统计类型的聚（VDF- ter -PFSVE- ter）-CNVE）含磺酰氟和腈侧基的三元共聚物。在所有情况下，收率均高于11％。假定不发生VDF单元的脱氟化氢，在不影响VDF含量的情况下，在不影响VDF含量的情况下，在温和条件下定量实现了磺酰氟基团水解为磺酸官能团的作用。然后使用侧基腈官能团的环化作用将这些原始三元共聚物进行热交联，以制得不溶于有机溶剂（如丙酮和二甲基甲酰胺）的膜（完全溶解未固化的三元共聚物）。交联材料的热稳定性高于未固化的三元共聚物。取决于三元共聚物中磺酸的含量，离子交换容量为0.95至1。每克+。对于在240°C交联且水合值为33 H 2 O / SO 3 H的膜，在80°C和100％相对湿度下的质子电导率达到58 mS cm -1，而在60°C交联的膜上观察到过度溶胀。较低的温度。
更新日期：2019-03-22
中文翻译：
偏二氟乙烯，全氟-3,6-二氧杂-4-甲基-7-辛烯磺酰氟的交联三元共聚物以及PEMFC应用中膜的固化位点单体†
全氟（8-氰基-5-甲基-3,6-二氧杂辛-1-烯）（CNVE）或2,2,3,3,4,4,5,5,6,6-十氟-6的自由基三元聚合提出了-[[（1,2,2-三氟乙烯基）氧基]己腈（MV5CN），偏二氟乙烯（VDF）和全氟（4-甲基-3,6-二氧杂八烷基-7-烯）磺酰氟（PFSVE）。改变这些三元聚合的单体进料组成使得能够合成不同统计类型的聚（VDF- ter -PFSVE- ter）-CNVE）含磺酰氟和腈侧基的三元共聚物。在所有情况下，收率均高于11％。假定不发生VDF单元的脱氟化氢，在不影响VDF含量的情况下，在不影响VDF含量的情况下，在温和条件下定量实现了磺酰氟基团水解为磺酸官能团的作用。然后使用侧基腈官能团的环化作用将这些原始三元共聚物进行热交联，以制得不溶于有机溶剂（如丙酮和二甲基甲酰胺）的膜（完全溶解未固化的三元共聚物）。交联材料的热稳定性高于未固化的三元共聚物。取决于三元共聚物中磺酸的含量，离子交换容量为0.95至1。每克+。对于在240°C交联且水合值为33 H 2 O / SO 3 H的膜，在80°C和100％相对湿度下的质子电导率达到58 mS cm -1，而在60°C交联的膜上观察到过度溶胀。较低的温度。
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