Phosphorylated chitosan/poly(vinyl alcohol) based proton exchange membranes modified with propylammonium nitrate ionic liquid and silica filler for fuel cell applications

In our previous work, phosphorylated chitosan was modified through polymer blending with poly(vinyl alcohol) (PVA) polymer to produce N-methylene phosphonic chitosan/poly(vinyl alcohol) (NMPC/PVA) composite membranes. The aim of this work is to further investigate the effects of a propylammonium nitrate (PAN) ionic liquid and/or silicon dioxide (SiO₂) filler on the morphology and physical properties of NMPC/PVA composite membranes. The temperature-dependent ionic conductivity of the composite membranes with various ionic liquid and filler compositions was studied by varying the loading of PAN ionic liquid and SiO₂-PAN filler in the range of 5–20 wt%. As the loading of PAN ionic liquid increased in the NMPC/PVA membrane matrix, the ionic conductivity value also increased with the highest value of 0.53 × 10^?3 S cm^?1 at 25 °C and increased to 1.54 × 10^?3 S cm^?1 at 100 °C with 20 wt% PAN. The NMPC/PVA-PAN (20 wt%) composite membrane also exhibited the highest water uptake and ion exchange capacity, with values of 60.5% and 0.60 mequiv g^?1, respectively. In addition, in the single-cell performance test, the NMPC/PVA-PAN (20 wt%) composite membrane displayed a maximum power density, which was increased by approximately 14% compared to the NMPC/PVA composite membrane with 5 wt% SiO₂-PAN. This work demonstrated that modified NMPC/PVA composite membranes with ionic liquid PAN and/or SiO₂ filler showed enhanced performance compared with unmodified NMPC/PVA composite membranes for proton exchange membrane fuel cells.     

P(DBF-VA)型柴油低温流动性改进剂的研制

针对新疆地产柴油蜡含量较高的特点,以游离基聚合法合成了富马酸双链混合酯和醋酸乙烯酯共聚物型[P(DBF-VA)]柴油低温流动改进剂,利用正交实验研究了单体配比,引发剂用量,溶剂用量,聚合温度对聚合物降冷滤效果的影响。共聚物用IR进行表征,利用XRD初步探讨了该降凝剂的降凝机理。结果表明:该剂能使吐哈—10~#、0~#柴油冷滤点降低10℃和7℃;使独山子0~#柴油冷滤点下降12℃;使石化0~#柴油冷滤点下降8℃;使克拉玛依0~#柴油的冷滤点下降8℃。     

Intramolecular crosslinking of poly(vinyl alcohol)

Poly(vinyl alcohol) is crosslinked in dilute solution (c=0.1 wt%) with glutaraldehyde. The reaction product is characterized by viscometry and gel permeation chromatography (g.p.c.). The intrinsic viscosity decreases with increasing degree of crosslinking and does not depend on temperature. G.p.c. reveals that the reaction product is not homogeneous, but consists of a mixture of particles with different sizes, possibly both intra- and intermolecularly crosslinked molecules. The intramolecularly crosslinked molecules are smaller in size than the initial polymer molecules and their size depends on the degree of crosslinking. They possess a narrow particle size distribution even if the initial polymer sample had a broad molecular weight distribution.     

医用聚氯乙烯材料的表面光接枝改性

研究了在不排氧氛围下 ,紫外光照射 ,以二苯甲酮 (BP)为光引发剂 ,甲基丙烯酸缩水甘油酯(GMA)在医用聚氯乙烯 (PVC)薄膜表面的气相接枝聚合。探讨了反应条件对接枝结果的影响 ,并用正交法指出了影响因素的显著性。用傅立叶红外 (FT- IR)、水接触角作为接枝改性结果的表征。FT- IR谱图表明 GMA已接枝到 PVC膜表面。水接触角由接枝前的 78°下降到 5 4°     

Synthesis and characterization of an interpenetrating polymer network composed of poly(methacrylic acid) and poly(vinyl alcohol)

Temperature and pH‐responsive interpenetrating polymer network (IPN) hydrogels, constructed with poly(methacrylic acid) (PMAA) and poly(vinyl alcohol) (PVA), by a sequential IPN method, were studied. The characterization of IPN hydrogels was investigated by Fourier‐transform infrared spectroscopy, differential scanning calorimetry (DSC) and swelling under various conditions. The IPN hydrogels exhibited relatively high swelling ratios, in the range 230–380 %, at 25 °C. The swelling ratios of the PMAA/PVA IPN hydrogels were pH and temperature dependent. DSC was used for the quantitative determination of the amounts of freezing and non‐freezing water. The amount of free water increased with increasing PMAA content in the IPN hydrogels. Copyright © 2004 Society of Chemical Industry     

Synthesis and Evaluation of Blends Formed by Polymeric Crown Ethers and a Fullerene-Containing Primary Ammonium Salt in Organic Thin Films

The synthesis of a series of polymers and cyclopolymers bearing crown ethers of differing structure and affinities towards primary ammonium ions is discussed. These polymers have been tested in their efficiency to form structurally homogeneous thin films when blended with an amphiphilic C₆₀ compound containing a primary ammonium ion functional group. The X-ray reflectivity characterization of the films revealed that the polymer bearing the crown ether with the least affinity for primary ammonium ions, but having the highest degree of polymerization, is the most effective in forming structurally homogeneous thin films.     

Investigation of the relationships between the chain organization and rheological properties of atactic poly(vinyl alcohol) hydrogels

The structure and rheological behavior of atactic poly(vinyl alcohol) (a-PVA) hydrogels prepared by freeze/thaw cycles were investigated as a function of polymer concentration and number of freeze/thaw cycles. The presence of phases with different mobilities was observed using ¹³C CP/MAS and DP/MAS NMR experiments. The degree of crystallinity of the a-PVA-rich phase was determined by ¹H NMR free decay experiments. Measurements of the shear storage and loss modulus were performed at a fixed frequency of 1 Hz and a strain value of 0.1%, i.e. under conditions where the deformation imposed on the gel structure is entirely reversible. Results thus obtained showed that an increase in the number of freeze/thaw cycles induces an increase in the degree of crystallinity in the polymer-rich phase together with an increase in the storage modulus. The a-PVA hydrogels became more fragile as the number of freeze/thaw cycles was increased. Moreover, both the percentage of protons in a rigid environment measured by ¹H NMR and the storage modulus values tended to a limiting value after six freeze/thaw cycles. These results show that the first five or six freeze/thaw cycles play a very important role in determining the hydrogel structure and rheological properties. A more detailed comparison of NMR and rheological data led to the conclusion that the storage modulus is mainly controlled by the a-PVA crystallinity while the hydrogen bond interactions have a much smaller contribution.     

空心微珠改性硬质聚氯乙烯复合材料的应用研究

经过改性的超细空心微珠可以作为填料加入到硬质聚氯乙烯（PVC－U）树脂中，同时改善PVC树脂的流变性、冲击性能和刚性等性能。研究结果表明，超细空心微珠加入到硬质PVC管材中，可以明显改善PVC硬管的加工流动性能，显著缩短塑化时间，降低最大扭矩。而超细空民微珠加入到硬质PVC板材时，可以提高PVC硬板的冲击性能，减小制品的收缩率，赋予PVC硬板优异的耐腐蚀性能，且产品的各项性能均符合PVC板材国家标准GB／T4454－96。     

HPVC／PP共混改性研究：Ⅲ低分子量反应性化合物作相容剂

采用低分子量反应性化合物作相容剂，即化学交联体系来改善ＨＰＶＣ／ＰＰ共混物的相容性。考察了在不同共混比下，不同化学交联体系对共混物力学性能的影响，并观察了共混物的微观形态。结果表明，采用低分子量反应性化合物作相容剂，共混物的拉伸强度提高，但冲击强度无改善。分散相尺寸减小，相间粘接得到改善。并比较了３种增容方法的效果，发现ＣＰＥ是ＨＰＶＣ／ＰＰ共混物的最佳相容剂。     

Head-to-head polymers: 33. Bromination of cis-1,4-polybutadiene to head-to-head poly(vinyl bromide)

Cis-1,4-polybutadiene (PB) in a 0.5% solution of a solvent mixture of dichloromethane and 1,2-dibromoethane or tetrahydrofuran was quantitatively brominated with elemental bromine at 0°C under careful exclusion of oxygen to head-to-head poly(vinyl bromide). Partially brominated PB has a structure of random or block sequences of butadiene units in the polymer depending on the bromination solvent but shows no stereospecificity in the CHBrCHBr-dyads. Partially brominated PB with block structure showed a microphase-separated morphology over a wide range of composition. Microphase separation is less pronounced for the more random structure of butadiene units. I.r and ¹³C n.m.r. spectroscopy of the partially brominated PB was used to follow the progress of the bromination.