Blends with Polybenzimidazole PBI

Recently it has been discovered that polyaryletherketoneketone (PEKK) forms miscible blends with PBI [22]. Patents have also been filed on blends of PBI, PAEK and PEI [23]. 

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Chung TS, Guo WE, Liu Y. Enhanced matri-mid membranes for pervaporation by homogenous blends with polybenzimidazole (PBI). J Membr Sci 2006 271(1-2) 221-31. 

Attractive blends for PEMs with high proton conductivity have been made from sulfonated PES, PSU, polyetherketone (PEK), PEEK or poly(2,6-dimethyl 1,4-phenylene ether) (PPE) blended with polybenzimidazole (PBI) or polyetherimide (PEI). To preserve the desired PEM performance, the blends are often crosslinked by radiation, chemical reaction of ionic interactions. For long-term PEM applications it is important that membranes resistance to mechanical, chemical and thermal degradation is maximized. Accelerated aging tests should follow several membrane functionalities, for example conductivity, membrane integrity and permeability. The tests should also identify a possible cross-correlation of effects, namely stress on thermal and/or chemical degradation. 

PAr with polybenzimidazole (PBI) miscible blends Chen etaL, 1990... 

Membrane prepared by blending sulfonated polybenzimidazole (PBI) with Nafion polymer showed a conductivity of 0.032 S cm The methanol permeability of the composite membrane was found to be 0.82 x 10 cm s as compared to Nafion, which is around 2.21 x 10 cm s [22]. Addressing the problem of methanol permeation, a composite membrane of Nafion with polyvinyl alcohol (PVA) for direct methanol fuel cell has been reported. It is concluded that at the weight ratio of 1 1 in PVA and Nafion, the thin film-coated Nafion membrane exhibited low methanol crossover, and the membrane protonic conductivity could be improved by the sulfonation treatment [23]. Recently, Zaidi et al. [24] prepared composite membranes of PFSA ionomer with boron phosphate and showed the conductivity of 6.2 X 10-2 S cm-i at 120°C. 

Chen DH, Chen YP, Arnold CA, Hedrick JC, Graybeal JD, McGrath JE (1989) Compatible blends of segmented polyimide siloxane copolymers with engineering thermoplastics I polybenzimidazole (PBI). 34th International SAMPE Symposium 1247... 

To prepare new and inexpensive membranes, various trials have been made 196 sulfonated aromatic polyether membrane such as polyether ketones (PEEK),197 sulfonated polysulfone198 and membranes from sulfonated polyphenylene sulfide,199 phosphoric acid-doped polybenzimidazole, (PBI),200 polybenzimidazole having sulfonic acid groups,201 polybenzimidazole with phosphonic acid groups,202 a blend membrane of polybenzimidazole and sulfonated polysulfone,203 sulfonated phosphazene polymer.204... 

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]. 

In the following, those publications dealing with synthesis and characterization of intermediate-T blend membranes from PBI basic polymers and sulfonated or phosphonated polymers utilized as acidic macromolecular cross-linkers in the blends are discussed. In Fig. 4.4, those polybenzimidazoles along... 

In contrast to the Nafion-FEP system, in which the immiscibility of the polymer components is clearly shown in Fig. 14.8, greater compatibility of Nafion and polybenzimidazole (PBI) was expected due to acid-base interactions between imidazole nitrogens and sulfonic acid protons. PBI should function in such a system as a crosslinker (see Fig. 14.15), producing a reduction in membrane swelling and permeability by methanol. Although the idea of examining acid-base membrane blends in fuel cells is not new [9,11-13,30], little work has been carried out with Nafion. 

Blends of sulfonated PS and sulfonated PPO have been described in several papers as offering a combination of high proton conductivity and low methanol permeability [104, 105]. Optimum conductivity was obtained with a 50/50 blend of the sulfonated polymers, with each having an identical ion exchange capacity [104]. The miscibility of the PS/PPO system appeared to be maintained with the blend of the sulfonated polymers. Polybenzimidazole (PBI) and polysulfone (PSF) are immiscible however, sulfonated PSF is miscible with PBI and showed utility in phosphoric acid based fuel cells operated upto200°C[106]. PEMs comprised of Nafion and a vinylidene fluoride-hexafluoropropylene copolymer blend were evaluated... 

Arrieta et al. [47] conducted hydrolytic and photochemical aging studies for a Kevlar-Polybenzimidazole (PBI) blend in yam form. UV irradiation was conducted at X, = 340 nm and four different temperatures (50, 60, 70 and 80 °C) between 4 and 31 days. The PBI stracture is given in Fig. 5 [47] (reproduced with kind permission from Elsevier—License no. 3890161358622). 

Perfluorinated sulfonic acid polymers, such as Nafion membranes, were the most commonly used materials in practical systems for their high proton conductivity and extremely high oxidative stability. However, due to the poor dimensional stability, low mechanical properties of Nafion at high humidity and high temperature, and high cost, an essential need for cost-effective and reinforced substitutes with improved performance arises [193-195]. Nafion blended with the second component could not only reduce the cost, but also improve the mechanical properties and the dimensional stability. Recently, the reinforced composite membranes based on semi-interpenetrating polymer network (semi-IPN) structures of Nafion , polyimidazole (PI) [196-198], polybenzimidazole (PBI) [199], and poly(vinyIidene fluoride) (PVDF) [200] were reported. As shown in Fig. 2.35, the composite membranes with... 

In a follow-up study, combinations of three different polybenzimidazoles with the partially sulfonated ionomer M were investigated comparatively in terms of their stabilities to identify which S2/PBI combinations showed the best stabilities [49]. As polybenzimidazoles, Bl, B2, and have been used in this study. All blend membranes contained 70 wt% of the polybenzimidazole and 30 wt% of M. The blend membranes have been characterized in terms of oxidative stability by immersion in Fenton s Reagent for up to 120 h and subsequent... 

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