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Synthesis of Poly(3-(4-Ethoxysulfonylphenoxy)-2

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Synthesis of Poly(3-(4-Ethoxysulfonylphenoxy)-2 Polymer Journal (2015) 47, 287–293 & 2015 The Society of Polymer Science, Japan (SPSJ) All rights reserved 0032-3896/15 www.nature.com/pj ORIGINAL ARTICLE Synthesis of poly(3-(4-ethoxysulfonylphenoxy)- 2-methylpropyl)silsesquioxane and its application as a proton-conducting membrane Satoru Tsukada, Akira Tomobe, Yoshimoto Abe and Takahiro Gunji A polysilsesquioxane-based organic-inorganic hybrid membrane was prepared and applied as a proton-conducting membrane for fuel cells. poly(STES-ran-MTES), a random copolymer of ethyl 4-(2-methyl-3-triethoxysilylpropoxy)benzenesulfonate (STES) and triethoxy(methyl)silane (MTES) was synthesized by hydrolysis and condensation in the presence of hydrochloric acid under a nitrogen stream. The molecular weight was 7500–7600 g mol − 1, and the percentage of hydrolyzed ethoxysulfonyl group was 32–50%. A poly(STES-ran-MTES) membrane was prepared by heating for several days, which showed thermal resistivity up to 200 °C and proton conductivity of 2.0 × 10 − 5 to 1.1 × 10 − 3 Scm− 1 at room temperature. By contrast, a membrane of a block copolymer, poly(SPES-block-PMS), showed proton conductivity of 2.5 × 10 − 3 Scm− 1. The proton conductivity of the poly(3-(4-ethoxysulfonylphenoxy)-2-methylpropyl)silsesquioxane (SPES) membrane increased from 2.7 × 10 − 3 Scm− 1 at 25 °C to 1.0x10 − 2 Scm− 1 at 110 °C. The proton conductivity of the SPES membrane increased from 2.7 × 10 − 3 Scm− 1 at relative humidity (RH) = 25–30% to 2.0 × 10 − 3 Scm− 1 at RH = 60% and 1.4 × 10 − 1 Scm− 1 at RH = 90%. The mixture of SPES and poly(vinyl alcohol), poly(ethylene oxide) or polyoctahedralpolysilsesquioxane showed proton conductivities of 2.7 × 10 − 3, 1.5 × 10 − 3 and 2.5 × 10 − 3 Scm− 1, respectively, at 25 °C and RH = 25–30%. The open-circuit voltage of the SPES membrane was 0.92 V. Polymer Journal (2015) 47, 287–293; doi:10.1038/pj.2014.112; published online 10 December 2014 INTRODUCTION energy conversion and avoid carbon monoxide poisoning of the Fuel cells, which generate power using hydrogen and oxygen gases, catalysts, polymer electrolyte fuel cells that can operate in the medium have been a focus of recent interest because of their potential to temperature range (150 °C) are strongly desired. resolve both energy and environmental problems because they Alternatively, polysilsesquioxane, with the typical chemical formula produce very little pollution and efficiently generate power. In (RSiO3/2)n, is useful as a framework in organic-inorganic polymer particular, polymer electrolyte fuel cells, which are fuel cells that hybrid materials because of its high heat resistivity, good mechanical utilize a proton-conductive membrane as an electrolyte, are expected properties, high durability and the ease with which functional groups to have considerable potential because polymer electrolyte fuel cells can be introduced in the side chain.10,11 Thus far, a proton-conductive can generate power at low temperature with high energy density. membrane utilizing a siloxane bond as a main chain with high heat Therefore, polymer electrolyte fuel cells can be miniaturized to make resistance has been utilized: polysilsesquioxanes having an acid group them suitable for home use, portable devices or car batteries, all of in the side chain were prepared using the sol-gel method12–19 or which can have reduced power-generation efficiencies because of the polysilsesquioxanes having an ammonium group were mixed with low heat resistance of the electrolyte membranes.1–3 acid.20,21 The membrane showed high proton conductivity (approxi- The most commonly used proton-conductive membranes are mately 10 − 2–10 − 3 Scm− 1). based on perfluorosulfonic acid polymers such as Nafion.4–6 These In our previous work, the membrane formation was performed membranes have demonstrated good electrochemical performance by poly(3-(4-ethoxysulfonylphenoxy)- 2-methylpropyl)silsesquioxane and good stability. However, at low water content, the continuity of a (SPES).22 First, 3-(4-ethoxysulfonylphenoxy)-2-methylpropyl(triethoxy) hydrated proton-conductive pathway in the membrane is lost, silane (STES) was synthesized by a four-step reaction, and polysilses- resulting in decreased proton conductivity. In addition, Nafion suffers quioxane was obtained by hydrolytic polycondensation. A membrane from poor conductivity above 90 °C because of glass transformation, was prepared by heating the polysilsesquioxane at 80 °C for 4 days. although operation at a higher temperature can increase the catalytic The membrane showed proton conductivity of 10 − 3 Scm− 1 at room activity and energy conversion.7–9 Therefore, to efficiently improve the temperature and low humidity. However, SPES has a low degree of Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science, Noda, Chiba, Japan Correspondence: Professor T Gunji, Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan. E-mail: [email protected] Received 9 August 2014; revised 30 September 2014; accepted 10 October 2014; published online 10 December 2014 Poly(3-(4-ethoxysulfonylphenoxy)-2-methylpropyl)silsesquioxane synthesis and application S Tsukada et al 288 SO3Et SO3R SO3R hydrolytic block copolymer polycondensation O O O CH3 Si O Si O Si(OEt)3 Si O O O n O m n x STES SPES (R=Et or H) Poly(SPES-block-PMS) hybridization (R=Et or H) random copolymer SO3R O SO3R OH n n PVA PEG + O H H O O H OSi Si Si O SiO H Si O O O CH3 O O OSi O Si O n H O H Si O Si O Si O Si SPES (R=Et or H) H O m O n H T H Poly(STES-ran-MTES) 8 (R=Et or H) Scheme 1 Aschematicfigure for the preparation of SPES-based polymers and composites. condensation and low molecular weight; therefore, the SPES mem- Synthesis of poly(SPES-block-PMS) brane showed low mechanical resistance. SPES (2.00 g, 5 mmol), polymethylsilsesquioxane (PMS, 0.48 g, 5 mmol) and In this work, the synthesis and membrane preparation of poly ethanol were charged into a 100 ml four-necked flask. After the solution was − (STES-ran-MTES) and poly(SPES-block-PMS), or the preparation of cooled for 10 min in an ice bath, water and 6 mol l 1 hydrochloric acid were H added in the molar ratio of HCl/Si = 0.105 and stirred for 10 min. After SPES/organic polymer hybrid membranes and SPES/T8 hybrid membranes, were investigated according to Scheme 1 to improve removal from the ice bath, the solution was stirred for 10 min at room temperature. The flask was then heated at 80 °C for 4 h with stirring to provide their mechanical properties. In addition, thermal analysis, water poly(SPES-block-PMS) as a highly viscous liquid. uptake and proton conductivity of the membrane were investigated, and the open-circuit voltage was measured. Synthesis of SPES SPES was obtained by the hydrolytic polycondensation of STES. EXPERIMENTAL PROCEDURE The molecular weight, viscosity and sulfonation percentage increased as the Reagents molar ratio of water increased. To investigate the proton conductivity of STES was synthesized from 4-hydroxybenzenesulfuric acid by a four-step different sulfonation ratios, SPES with sulfonation rates of 7% and 61% were = reaction as described in the literature.22 synthesized from H2O/Si 3.0 and 10.0, respectively. Ethanol, 6 mol l − 1 hydrochloric acid, tetrahydrofuran, poly(vinyl alcohol) (PVA; polymerization degree approximately 500), and polyethylene glycol Preparation of poly(STES-ran-MTES) and poly(SPES-block-PMS) (PEG; average molecular weight 180–220) (Wako Pure Chemical Industries, membranes Tokyo, Japan, reagent grade) were used as received. A 20wt% solution of polymer in THF was mixed into a 50 mmϕ polytetra- MTES (Shin-Etsu Chemical Industry, Tokyo, Japan) was used as received. fluoroethylene Petri dish and heated at 80 °C for several days. Pt/C (Pt 40 wt%), carbon paper and a gasket (Toyo Corporation, Tokyo, Japan) were used as received. Preparation of SPES/organic polymer hybrid membrane A 20wt% solution of SPES in THF and a 1wt% hot liquid solution of PVA or = ϕ Synthesis of poly(STES-ran-MTES) PEG were poured (SPES:PVA or PEG 1:0.01; weight ratio) into a 50 mm fl STES (2.10 g, 5 mmol), MTES and ethanol were charged into a 100 ml four- polytetra uoroethylene dish and heated at 80 °C for 1 day. necked flask. After the solution was cooled for 10 min in an ice bath, water and − 1 = H 6moll hydrochloric acid were added in the molar ratio of HCl/Si 0.105 Preparation of SPES/T8 hybrid membrane H H and stirred for 10 min. After removal from the ice bath, the solution was stirred A 20wt% solution of SPES and T8 (SPES:T8 = 1:0.01; weight ratio) in THF for 10 min at room temperature. The flask was then heated at 80 °C for 4 h with was mixed and poured into a 50 mmϕ polytetrafluoroethylene dish and heated stirring to provide poly(STES-ran-MTES) as a highly viscous liquid. at 80 °C for 3 days. Polymer Journal Poly(3-(4-ethoxysulfonylphenoxy)-2-methylpropyl)silsesquioxane synthesis and application S Tsukada et al 289 Table 1 Results of the synthesis of poly(STES-ran-MTES)a Molar ratio Molecular weightb c Run STES:MTES H2O/Si Mw Mw/Mn Percentage of sulfonation (%) State 12:11.018001.2 — Viscous liquid 2 2.0 5400 1.4 11 Viscous liquid 3 3.0 7000 1.6 23 Viscous liquid 4 4.0 7600 1.5 32 Viscous liquid 51:11.022001.5 — Viscous liquid 6 2.0 5000 1.5 33 Viscous liquid 7 3.0 7600 1.7 43 Viscous liquid 8 3.5 7100 1.7 50 Viscous liquid 94.0—— — Gel 10 1:2 1.0 1800 1.3 11 Viscous liquid 11 2.0 7500 2.5 34 Viscous liquid 12 2.5 5500 1.3 — White powder 13 3.0 4000 1.3 — White powder Abbreviations: MTES, methyltriethoxysilane; STES, ethyl 4-(2-methyl-3-triethoxysilylpropoxy)benzenesulfonate.
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