Synthesis and Characterization of Proton-conducting Polymer Electrolytes Based on Acrylonitrile-Styrene Sulfonic Acid Copolymer/Layered Double Hydroxides Nanocomposltes

Acrylonitrile-sodium styrene sulfonate copolymer/layered double hydroxides nanocomposites were prepared by in situ aqueous precipitation copolymerization of acrylonitrile （AN） and sodium styrene sulfonate （SSS） in the presence of 4-vinylbenzene sulfonate intercalated layered double hydroxides （MgA1-VBS LDHs） and transferred to acrylonitrile-styrene sulfonic acid （AN-SSA） copolymer/LDHs nanocomposites as a proton-conducting polymer electrolyte. MgA1-VBS LDHs were prepared by a coprecipitation method, and the structure and composition of MgAl-VBS LDHs were determined by X-ray diffraction （XRD）, infrared spectroscopy, and elemental analysis. X-ray diffraction result of AN-SSS copolymer/LDHs nanocomposites indicated that the LDHs layers were well dispersed in the AN-SSS copolymer matrix. All the AN-SSS copolymer/LDHs nanocomposites showed significant enhancement of the decomposition temperatures compared with the pristine AN-SSS copolymer, as identified by the thermogravimetric analysis. The methanol crossover was decreased and the proton conductivity was highly enhanced for the AN-SSA copolymer/LDHs nanocomposite electrolyte systems. In the case of the nanocomposite electrolyte containing 2% （by mass） LDHs, the proton conductivity of 2.60×10^- 3 S·m^-1 was achieved for the polymer electrolyte.

Thermal Emulsion Polymerization without any Conventional Initiators and Emulsifiers

Stable poly（styrene-co-sodium styrene sulfonate） （P（St-NaSS） nanoparticles with broader size distribution were synthesized by thermal emulsion polymerization without any conventional initiators and emulsifiers. The obtained polymer nanoparticles have higher potential, and the particle sizes have broad distribution. The stability of polymer particles originated from the addition of small amounts of ionic comonomer, NaSS, which can act as an emulsifier in somewhat. The monomer conversion could reach up to about 28 wt% in 48 h, and did not increase by further polymerization when higher polymerization temperature （120℃） was employed. This polymerization system may be give some further understand for mechanism of emulsion polymerization.

RADIATION GRAFTED POLY(VINYLIDENE FLUORIDE)-GRAFT-POLYSTYRENE SULFONIC ACID MEMBRANES FOR FUEL CELLS:STRUCTURE-PROPERTY RELATIONSHIPS

Structure-property relationships for poly（vinylidene fluoride）-graft-polystyrene sulfonic acid （PVDF-g-PSSA） fuel cell membranes prepared by a single step method involving radiation-induced grafting of sodium styrene sulfonate （SSS） onto electron beam （EB） irradiated poly（vinylidene fluoride） （PVDF） films were established. The physico-chemical properties of the membranes such as ion exchange capacity, water swelling and proton conductivity were correlated with the degree of grafting （G, %） and the structural changes taking place in the membrane matrix during the preparation procedure. The variation in the crystallinity and the thermal stability of membranes was studied by differential scanning calorimetry （DSC） and thermogravimetric analysis （TGA）, respectively. The membranes were found to undergo substantial structural changes in forms of ionic sites increase, hydrophilicity enhancement, hydrophobicity reduction and crystallinity decrease with the variation in G （%） and the preparation method. The structural and thermal properties of the obtained membranes were also compared with their counterparts prepared by a conventional two-steps method i.e. radiation induced grafting of styrene onto EB irradiated PVDF films followed by sulfonation. The PVDF-g-PSSA membranes obtained by a single-step method were found to have superior properties compared to those obtained by the conventional two-steps method.