A novel aromatic block–graft copolymer of sulfonated poly(styrene–isobutylene–styrene)‐graft‐poly(vinyl phosphonic acid) (SIBS‐g‐PVPA SO3H) was synthetized for direct methanol fuel cell (DMFC) and chemical and biological protective clothing (CBPC) applications. The polystyrene (PS) blocks of SIBS were chloromethylated via a Friedel–Crafts reaction to obtain the macroinitiator SIBS‐CH2Cl. Atom transfer radical polymerization (ATRP) was performed to graft VPA to the chloromethylated groups of the macroinitiator and yield SIBS‐g‐PVPA, which was subsequently sulfonated using acetyl sulfate as the sulfonating agent. After each functionalization step, a membrane was prepared by using the solvent casting technique. The final membrane was composed of triblock SIBS as the backbone, PVPA grafts attached to the chloromethylated PS end blocks and sulfonic groups in the non‐chloromethylated PS units. A comprehensive materials characterization study (e.g., GPC, FTIR, TGA, EA) was performed to confirm proper functionalization of each material. Unique ionic interactions (i.e., crosslinking via formation of sulfonate–phosphonium complexes) arose between the phosphonic and sulfonic groups (i.e., PO3H2 and SO3H, respectively) that enhanced the water absorption capabilities, thermal and oxidative stability, and the transport properties of SIBS. The SIBS‐g‐PVPA SO3H membrane presented high Nafion® normalized selectivity and separation efficiency, indicating that this ionomer adequately functions for both applications. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1424–1435

This work discusses the effect of isopropyl phosphate (IP) on the transport properties of sulfonated poly(styrene-isobutylene-styrene) (SO 3 H SIBS) as membranes for direct methanol fuel cell (DMFC) and chemical and biological protective clothing (CBPC) applications. The properties were determined as a function of SIBS sulfonation level (i.e., 24, 34, 49, and 84 mol %) and IP loading (i.e., 1, 3, 5, 11, and 15 wt %). A comprehensive material characterization study (e.g., FTIR, TGA, AFM, and SAXS) was performed to confirm the presence of the phosphate groups in the polymer matrix, assess the thermal stability of the proton-exchange membranes (PEMs), and understand how the unique interactions between the phosphate and sulfonic groups influenced the nanostructure of SO 3 H SIBS. The transport properties, water absorption capabilities (i.e., swelling ratio, water uptake, etc.), oxidative stability, and ion-exchange capacity (IEC) were performed to evaluate the impact of IP on the properties of the resulting solvent-casted membranes. Results suggest that the morphology, thermal stability, and vapor permeability are governed by the sulfonation level, whereas the IEC, oxidative stability, water absorption capabilities, and the rest of the transport properties are dominated by the ionic content (i.e., sulfonic and phosphate groups) and their synergistic effects.

Graphene oxide (GO) and its sulfonated analog (sGO) have been incorporated into sulfonated poly(styrene‐isobutylene‐styrene) (SO3H SIBS) in order to enhance its water retention and proton conductivity, while aiming to block permeant passage through the material. The polymer nanocomposite membranes (PNMs) were tested for two applications: direct methanol fuel cell and chemical and biological protective clothing. The transport properties of the membranes were determined as a function of SIBS sulfonation level (i.e., 37, 61, and 88 mol%), filler type (i.e., GO and sGO) and filler loading (i.e., 1, 3, 5, and 10 wt%). Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) confirmed the functionalization and incorporation of the fillers into SO3H SIBS. No significant changes were observed in the thermal stability or FTIR spectra of the PNMs after addition of the fillers. Dissimilar behaviors were observed for the ion exchange capacity, water absorption capabilities and transport properties of the membranes after incorporation of the fillers. Atomic force microscopy (AFM) phase images and Fenton's test results indicate that the oxidative stability of the PNMs is associated to the interconnectivity between the hydrophilic domains of the fillers and SO3H SIBS. The PNMs presented low permeability and high proton conductivity and thus, functioned adequately for both applications. POLYM. ENG. SCI., 59:E455–E467, 2019. © 2018 Society of Plastics Engineers

Graphene oxide (GO) and its phosphonated analogue (pGO) have been incorporated into sulfonated poly(styrene-isobutylene-styrene) (SO3H SIBS) to generate membranes with enhanced water retention. The polymer nanocomposite membranes (PNMs) were prepared per SIBS sulfonation level (i.e., 38, 61, and 90 mole %), filler type (i.e., GO and pGO) and filler loading (i.e., 0.1, 0.5 and 1.0 wt.%). FT-IR and TGA confirmed the functionalization and incorporation of the fillers into SO3H SIBS. No significant changes were observed in the thermal stability or FTIR spectra of the PNMs after addition of the fillers. Dissimilar behaviors were observed for the water absorption capabilities (i.e., swelling ratio and water uptake) after incorporation of the fillers. The nanofillers enhanced the water absorption of the sulfonated polymer, possibly due to interconnections between the ionic groups. Therefore, the PNMs could not only potentially function as proton exchange membranes (PEMs) for several applications such as direct methanol fuel cells (DMFCs).

This study discusses the effect of carboxylated (COOH) and phosphonated (PO3H2) single‐walled carbon nanotubes (SWCNTs) on the transport properties of sulfonated poly(styrene‐isobutylene‐styrene) (SO3H SIBS) as polymer nanocomposite membranes (PNMs) for direct methanol fuel cell (DMFC) and chemical and biological protective clothing (CBPC) applications. The properties were determined as a function of sulfonation level of SIBS, SWCNTs functionalization and loading. A comprehensive materials characterization study was performed to understand the interactions between the nanofillers and the functionalized polymer matrix, and to determine the effect of their incorporation on the resulting nanostructure of the PNMs. Results indicate that the sulfonation level is the variable that dictates nanofiller dispersion, mechanical properties, water absorption capabilities, morphology, and oxidative stability of SO3H SIBS. Meanwhile, the nanofiller loading and functionalization influenced the transport properties. The nanofillers reduced methanol permeation. PO3H2 SWCNTs increased the proton conductivity but at a high sulfonation level (i.e., 90 mol %), the ionic interconnectivity caused a more complex morphology decreasing the transport of protons. Optimal selectivity in transport properties were found with a sulfonation level of 61 mol % and a PO3H2 SWCNTs loading of 1.0 wt. % for DMFC and 0.5 wt. % for CBPC due to changes in morphology and the unique transport mechanism of permeants through the PNMs. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2475–2495