Fluorinated sulfonated polyimides

P. Sarkar, A.K. Mohanty, P. Bandyopadhyay, S. Chattopadhyay, S. Banerjee, Proton exchange properties of flexible diamine-based new fluorinated sulfonated polyimides, RSC Adv. 4 (23) (2014) 11848-11858. 

The vast catalogue of polymeric materials reviewed here included Nafion composite with inorganic and organic fillers, and non-fluorinated proton conducting membranes such as sulfonated polyimides, poly(arylene ether)s, polysulfones, poly (vinyl alcohol), polystyrenes, and acid-doped polybenzimidazoles. Anion-exchange membranes are also discussed because of the facile electro-oxidation of alcohols in alkaline media and because of the minimizatirHi of alcohol crossover in alkaline direct alcohol fuel cells. 

Considerable attention has been devoted to the preparation of fluorine-containing polymers because of their unique properties and high temperature performance (I). Recently we reported the preparation and characterization of novel fluorine-containing polyimides and polyethers which exhibit low moisture absorption and low dielectric constants (2, 3). Fluorinated polyimides absorb 1 wt% water and have dielectric constants of about 2.8 (all dielectric constants reported in this paper were measured at 10 kHz) vtdiereas their non-fluorinated analogs absorb as much as 3 wt% water and have dielectric constants of about 3.2. Fluorinated polyarylethers, which are free of polar groups such as ketones, imides and sulfones, absorb as little as 0.1 wt% water and have dielectric constants less than 2.8. 

Cuo, X., Fang, J., Watari, T., Tanaka, K., Kita, H., Okamoto, K., Novel sulfonated polyimides as polyelectrolytes for fuel ceU appUcation. 2. Synthesis and proton conductivity of polyimides from 9,9-h is(4-aminophenyl)fluorine-2,7-disulfonic acid. Macromolecules, 2002, 35, 6707-6713. 

A variety of polymers are used in engineering and medical applications which have relatively little impact on the environment. These are mainly high performance and relatively expensive polymers such as the silicones in rubbers, the specialised polyamides referred to above in gear wheels, polycarbonates (in office equipment), chlorinated and sulfonated rubbers, fluorinated polymers such as poly tetrafluoroethylene) Teflon ) in metal coating and the polyimides which, owing to their ladder structure, are extremely stable in high temperature apphcations. Since these polymers are high-cost durable materials, they rarely appear in the waste stream. 

The acid-base Nafion composite membranes include blends of Nafion with polypyrrole (PPy) [98-104], polybenzimidazole (PBI) [105-107], poly (propyleneoxide) (PPO) [108, 109], polyfurfuryl alcohol (PFA) [110], poly(vinyl alcohol) (PVA) [111-115], sulfonated phenol-formaldehyde (sPF) [116], polyvinylidene fluoride (PVdF) [117-122], poly(p-phenylene vinylene) (PPV) [123], poly(vinyl pyrrolidone) (PVP) [124] polyanifine (PANI) [125-128], polyethylene (PE) [129], poly(ethylene-terephtalate) [130], sulfated p-cyclodextrin (sCD) [131], sulfonated poly(ether ether ketone) (sPEEK) [132-135], sulfonated poly(aryl ether ketone) (sPAEK) [136], poly(arylene ether sulfone) (PAES) [137], poly(vinylimidazole) (PVl) [138], poly(vinyl pyridine) (PVPy) [139], poly (tetrafluoroethylene) (PTFE) [140-142], poly(fluorinated ethylene-propylene) [143], sulfonated polyhedral oligomeric silsesquioxane (sPOSS) [144], poly (3,4-ethylenedioxythiophene) (PEDT) [145, 146], polyrotaxanes (PR) [147], purple membrane [148], sulfonated polystyrene (PSSA) [149, 150], polystyrene-b-poly(ethylene-ran-butylene)-bpolystyrene (SEES) [151], poly(2-acrylamido-2-methyl-l-propanesulphonic acid-co-l,6-hexanediol propoxylate diacrylate-co-ethyl methacrylate) (AMPS) [152], and chitosan [31]. A binary PVA/chitosan [153] and a ternary Nafion composite with PVA, polyimide (PI) and 8-trimethoxy silylpropyl glycerin ether-1,3,6-pyrenetrisulfonic acid (TSPS) has also been reported [154]. 

Several non-fluorinated alternative polymers have been proposed for DAFC, mainly based on sulfonated ionomers with an aromatic or aliphatic hydrocarbon skeleton [7], Kim and Pivovar [4] have reported the number of DMFC alternative membranes papers appearing in open hterature for years 1994—2004, showing that polyarylenes, polyvinyl alcohols, grafted and block polystyrenes copolymers, and polyimides were among the most studies polymer electrolytes. In view of the dramatic increase in the number of publications since 2005 (see Fig. 6.1), the trends have changed, as shown in Table 6.1, which sununaiized the publications in open literature for the period 2005-2012, as compared to the previous period. 

Table 3.7 Comparison of Permeability and Selectivity of NTDA-Based Fluorinated Polyimides in Sulfonated and Non-Sulfonated form at 35 °C and 1 atm...

Trogadas and Ramani summarized the modification of PEM membranes, including Nafion modified by zirconium phosphates, heteropolyacids, hydrogen sulfates, metal oxides, and silica. Membranes with sulfonated non-fluorinated backbones were also described. The base polymers polysulfone, poly(ether sulfone), poly(ether ether ketone), polybenzimidazole, and polyimide. Another interesting category is acid-base polymer blend membranes. This review also paid special attention to electrode designs based on catalyst particles bound by a hydrophobic poly-tetrafluoroethylene (PTFE) structure or hydrophilic Nafion, vacuum deposition, and electrodeposition method. Issues related to the MEA were presented. In then-study on composite membranes, the effects of particle sizes, cation sizes, number of protons, etc., of HPA were correlated with the fuel cell performance. To promote stability of the PTA within the membrane matrix, the investigators have employed PTA supported on metal oxides such as silicon dioxide as additives to Nafion. 

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