Hydrocarbon-based electrode ionomer for proton exchange membrane fuel cells

The electrode ionomer is a key factor that significantly affects the catalyst layer morphology and fuel cell performance. Herein, sulfonated poly(arylene ether sulfone)-based electrode ionomers with polymers of various molecular weights and alcohol/water mixtures were prepared, and those comprising the alcohol/water mixture showed a higher performance than the ones prepared using higher boiling solvents, such as dimethylacetamide; this is owing to the formation of the uniformly dispersed ionomer catalyst layer. The relation between ionomer molecular weight for the same polymer structure and the sulfonation degree was investigated. Because the chain length of polymer varies with molecular weight and chain entanglement degree, its molecular weight affects the electrode morphology. As the ionomer covered the catalyst, the agglomerates formed were of different morphologies according to their molecular weight, which could be deduced indirectly through dynamic light scattering and scanning electron microscopy. Additionally, the fuel cell performance was confirmed in the current-voltage curve.     

Ionomer composites based on sepiolite/hydrogenated poly(styrene butadiene) block copolymer systems

Ionomeric composites based on sepiolite and hydrogenated poly(styrene butadiene) block copolymer were obtained and characterized from a microstructural and electrical point of view. Before blending, because of the high silanol group concentration in the sepiolite, the latter could be organophilized with suitable coupling agents. The resulting materials were easily processed into thin films or membranes 0.2–0.4 mm thick, their conductivity in some cases approaching 10^?1 S/cm. Their suitability for film formation and good electrical properties indicate potential applications as electrolytes in polymer fuel cells. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3512–3519, 2002     

离聚物对PET／LDPE共混物的结构与性能研究

用双螺杆挤出机反应性挤出的方法合成了低密度聚乙烯接枝马来酸镧（ＬＤＰＥ－ｇ－ＭＡＬａ）离聚物。与其它方法相比，该法具有工艺简单，易于工业化生产的特点。我们将离聚物与ＰＥＴ，ＬＤＰＥ在双螺杆挤出机上熔融共混挤出，并用注射成型机制备标准样条，对共混物力学性能进行了测试，发现离聚物有显著的增韧效果，另外，通过ＩＲ，ＤＳＣ，溶解性实验，分子量的测定等还考察了离聚物对ＰＥＴ／ＬＤＰＥ共混体系的结构影响。     

溶剂对全氟磺酸再铸膜性能的影响

将氯碱工业用过的废离子交换膜放入乙醇水溶液中，在250℃和10MPa条件下溶解4h，固液分离后，得到，浓度为7．2％的全氟磺酸离子交换树脂（PFSI）溶液。并分别利用高沸点溶剂（HBPS）——二甲基亚砜（DMSO）、乙二醇（EO）、吡硌烷酮（NMP）和二甲基甲酰胺（DMF）置换其中的低沸点溶剂，采用浇铸法制备了再铸全氟磺酸质子交换膜。通过测定再铸膜（RCM）的交换容量、电导率、抗拉强度和X射线衍射谱图等研究了浇铸温度、浇铸时间和HBPS种类等条件对RCM性能的影响。结果显示：RCM的最佳成膜温度和时间分别为140℃和2h，温度高于180℃，部分PFSI开始分解，电导率和离子交换容量有所下降，时间低于2h，HBPS不能完全从RCM中挥发，RCM的机械强度和稳定性低。HBPS的种类和加入比例影响RCM的结晶程度和晶粒大小，HBPS加入量过少，在HBPS挥发完之前，PFSI没有足够的时间结晶，稳定性差，最好的HBPS是二甲基亚砜和吡硌烷酮，RCM与Nafion112具有相近的燃料电池性能。     

离子交朕无规羧基橡胶

综述了离子交联无规羧基橡胶（羧基橡胶）的制备方法、硫化方法、硫化胶性能及其用途，指出了羧基橡胶今后的发展方向。     

Novel method for preparation of quaternary ammonium ionomer from epoxidized styrene–butadiene–styrene triblock copolymer and its use as compatibilizer for blending of styrene–butadiene–styrene and chlorosulfonated polyethylene

A novel method for the preparation of a quaternary ammonium ionomer of styrene–butadiene–styrene triblock copolymer (SBS) was developed by a ring‐opening reaction of epoxidized SBS with triethylamine hydrochloride in the presence of a phase transfer catalyst. The optimum conditions were studied. The ionomer was characterized by quantitative analysis, IR spectroscopy, and ¹H‐NMR spectroscopy. Its water absorbency, oil absorbency, dilute solution viscosity, and use as a compatibilizer for the blending of SBS and chlorosulfonated polyethylene (CSPE) were investigated. The results showed that, under optimum conditions, the epoxy groups can be completely converted to the quaternary ammonium groups. The IR spectrum did not exhibit the absorption peak for quaternary ammonium groups, whereas the ¹H‐NMR spectrum and titration method demonstrated it. With increasing ionic group content, the water absorbency of the ionomer increased whereas its oil absorbency decreased. These indicated the amphiphilic character of the SBS ionomer. The dilute solution viscosity of the ionomer in toluene/methanol (9/1) solvent increased with increasing quaternary ammonium group content. The ionomer was used as a compatibilizer for the blends of SBS and CSPE. The addition of a small amount of the ionomer to the blend enhanced the mechanical properties of the blends: 2 wt % ionomer based on the blend increased the tensile strength and ultimate elongation of the blend nearly 2 times. The blends of equal parts SBS and CSPE behaved as oil‐resistant thermoplastic elastomers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1975–1980, 2006     

Phase inversion and its effect on the properties of polyester polyurethane cationomers

Polyester polyurethane cationomers are prepared using polyester polyol of molecular weight 2000 as soft segments, N-methyl diethanolamine as chain extender, glycolic acid as quaternization agent, methyl ethyl ketone as solvent, and 4,4'-diphenylenemethylene diisocyanate (MDI) as diisocyanate. Properties of the films cast from solutions and emulsions are studied by infrared spectroscopy, dynamic mechanical analysis, thermogravimetric analysis, differential scanning calorimetry, and tensile-elongation testing. Ionization can cause phase separation and produces increased cohesion in the hard domains. The dispersion process can be divided into three stages involving a separation of hard segment aggregates due to adsorption of water on their surface, water entering into hard segment microionic lattics, and finally a rearrangement of agglomerates to form microspheres. The dispersion can disrupt the order in the hard domains and an increased phase separation.     

Poly(styrene-b-isobutylene-b-styrene) block copolymer ionomers (BCPI) and BCPI/silicate nanocomposites. 2. NaBCPI sol-gel polymerization templates

Polystyrene (PS) blocks in poly(styrene-b-isobutylene-b-styrene) (PS-PIB-PS) block copolymers were partially sulfonated and the acid groups converted to Na⁺SO₃⁻ groups to create ionomers. Then, dimethylacetamide was used to selectively swell the ionic PS domains and the swollen films were exposed to sol-gel reactive tetraethylorthosilicate solutions. (EtO)_4−xSi(OH)_x monomers then permeated films so that sol-gel reactions occurred within/around the ionic PS domains. Environmental scanning electron microscopy/energy dispersive X-ray spectroscopy investigations showed that silicate structures can be incorporated within the interior of the ionomer films. Differential scanning calorimetry studies indicated that there is no variance in the PIB block T_g with respect to ionomer formation, or with respect to silicate loading of the ionomer at low levels, which suggests that the silicate component does not reside in the PIB phase. ²³Na solid state NMR spectroscopy detected isolated Na⁺SO₃⁻ groups as well as aggregated SO₃⁻Na⁺ ion pairs for ‘as cast’ and ‘dry’ non-silicate containing ionomer samples. In a hydrated sample, almost all Na⁺ ions were solvent-separated. AFM analysis showed that phase separation exists, but that the degree of order is significantly less than that for hybrids based on the corresponding benzyltrimethylammonium ionomer. This frustrated morphology was also seen in the results of small angle X-ray scattering experiments. Given the scale of organic/inorganic heterogeneity, these hybrids are properly classified as nanocomposites.     

离聚物对热塑性聚醚酯基吸水膨胀弹性体吸水性能和力学性能的影响

以乙烯-甲基丙烯酸离子键聚合物Surlyn作为增容剂,选择交联聚丙烯酸钠(CPNa AA)作为吸水树脂,制备了热塑性聚醚酯(TPEE)基吸水膨胀弹性体(WSE),研究了CPNa AA含量对该WSE吸水性能和力学性能的影响,以及Surlyn树脂对该WSE的增容效果及力学性能和吸水性能的影响。结果表明,Surlyn能提高基体相和吸水树脂相的界面相容性和界面粘接力,减小CPNa AA在TPEE基体中的粒径,提高分散性,并减少CPNa AA从TPEE中的脱落,可同时提高该WSE的力学性能和吸水性能,并降低吸水后的质量损失。