磺化聚苯醚质子交换膜的制备与性能研究

以氯磺酸为磺化剂制备了一系列不同磺化度的磺化聚苯醚(SPPO)膜,通过热重-红外联用分析、差示扫描量热分析、含水率测试、力学性能和电导率测试,探讨了SPPO膜作为质子交换膜用于燃料电池的可能性。结果表明,SPPO存在3个阶段的失重,分别归属于吸收的水分、磺酸基团及主链的降解,磺化之后热稳定性虽有所下降,但主链的降解温度基本保持不变,玻璃化转变温度明显升高;SPPO的含水率随着磺化度和温度的增加而增加;膜的拉伸强度则随着磺化度的增加而降低,且膜在湿态时的强度较干态时的要低,但与商业化的Nafion 112膜相比仍具有较高的强度;磺化度为40.1%的SPPO膜在室温下的电导率为1.16×10-2S/cm,与Nafion 112膜为同一数量级。     

羟乙基纤维素/甲基咪唑硫酸氢盐共混质子交换膜的制备与表征

质子交换膜是氢燃料电池的重要组成部分之一。本文将甲基咪唑硫酸氢盐质子化离子液体与羟乙基纤维素共混,通过溶液浇铸法制备了均匀透明的质子交换膜。交流阻抗测试表明,共混膜的传导率随着离子液体比例的增加而增大,70%(wt)时传导率达到2.9×10~(-3) s/cm。质子传导率随使用温度的变化基本服从Arrhenius定律,表明质子主要通过跳跃机理实现传导,传导活化能随着离子液体比例的增加而降低。     

聚丙烯腈/聚砜共混膜的制备及其结构表征

采用粘度法和红外光谱法研究聚丙烯腈(PAN)/聚砜(PS)的相容性,研究聚合物组成,共混物浓度,添加剂,凝胶浴等对PAN/PS共混膜的水通量和截留率的影响.采用扫描电镜分析PAN/PS共混膜的显微结构.结果表明:PAN/PS共混膜与PAN膜具有相似的化学稳定性,但较PAN膜具有更好的分离和透过特性.     

多孔有机笼在聚丙烯腈纳米纤维表面固载及其复合质子交换膜

质子交换膜（PEM）是质子交换膜燃料电池的核心部件,需具备选择性地快速传递质子的特性。多孔有机笼具有高比表面积、良好的化学稳定性和高吸水特性以及三维连通的质子传递路径,可提升PEM的质子传导性能。本文将多孔有机笼（CC3）原位固载到聚丙烯腈（PAN）纳米纤维表面,与Nafion复合制备了CC3/PAN-Nafion复合质子交换膜,对其结构和性能进行了研究,结果表明：CC3的固载改变了纤维的微观形貌,增加了纤维直径,使纳米纤维比表面积从9.57m²/g增加到113.6m²/g;将CC3/PAN引入复合膜显著提升了CC3/PAN-Nafion的热稳定性、吸水性、阻醇性以及质子传导性能,其中CC3/PAN-Nafion12在100%RH,80℃时质子传导率可达0.165S/cm,较Nafion膜提升了一倍。     

PAN/PVC共混膜的制备及性能研究

以N,N-二甲基乙酰胺（DMAC）为溶剂,制备了不同质量百分比的聚丙烯腈（PAN）和聚氯乙烯（PVC）共混溶液,并采用异相成膜法制备PAN/PVC共混薄膜,研究了共混膜中PAN与PVC的共混比例对其相转变行为的影响因素.结果发现当PAN为分散相时,共混膜相分布均匀,PAN相尺寸较小且相边缘较模糊;而当PAN为连续相时,共混膜出现明显空洞,PAN/PVC发生明显相分离,两者几乎不相容.在此基础上,作者还研究了相容剂聚乙二醇（PEG）对PAN/PVC共混物相容性的影响,结果表明,加入PEG后的共混物较未加PEG的共混物相容性有明显改善.     

PTAM/PAN共混膜的抗静电性能研究

采用甲基丙烯酸氨基乙酯的均聚物(PTAM)与聚丙烯腈(PAN)共混,以硫氰酸钠溶液为凝固浴制备PTAM/PAN共混膜。探讨了PTAM含量、凝固时间以及凝固浴温度对共混膜抗静电性能的影响。结果表明:当共混膜中PTAM质量分数为7%、凝固时间为65 min、凝固浴温度为6℃时,PTAM/PAN共混膜体积电阻率降低到109Ω.cm。     

燃料电池用聚乙烯基质子交换膜研究进展

简介了燃料电池的重要性及质子交换膜在燃料电池中的核心地位.简述了目前燃料电池用质子交换膜研究中,设计具有成本低、加工性好、燃料选择性好等优点的质子交换膜替代全氟磺酸膜的发展趋势,分析了聚乙烯基质子交换膜的优势,介绍了近年来聚乙烯基质子交换膜的制备方法和基本性能,指出可通过聚乙烯与磺化聚合物共混、设计合成磺化聚乙烯以及聚...     

SPEEK/B-SPEEK共混质子交换膜的制备及其性能

聚醚醚酮进行磺化,得到了磺化聚醚醚酮(SPEEK),再先后与氯化亚砜和对甲苯磺酰胺反应,制备侧链含磺酰亚胺基的聚醚醚酮(B-SPEEK)。将SPEEK和B-SPEEK以不同的比例共混制备质子交换膜,研究了共混膜的结构、质子交换容量、吸水率、电导率、力学性能和热性能等。结果表明:SPEEK与B-SPEEK按质量比为1.0∶1.0制备的共混膜具有较好的力学性能(拉伸强度25.3 MPa,断裂伸长率45.1%)和最高的电导率(在80℃的条件下,电导率为0.227 S/cm),是一类非常有潜力的质子交换膜。     

PVA/PAN共混膜渗透汽化分离醋酸-水溶液的研究

对自制聚乙烯醇(PVA)/聚丙烯腈(PAN)共混膜渗透汽化分离低浓度醋酸-水溶液体系的性能进行了研究。分别考察了操作温度、下游表压以及醋酸浓度对PVA/PAN共混膜渗透蒸发分离性能影响。结果表明,随着操作温度增大和醋酸浓度及下游压力的减小,膜的渗透通量增加,分离因子减小。在操作温度323 K、下游表压8 mm Hg的条件下,采用膜厚为45μm的PVA/PAN共混膜对90wt.%的醋酸-水体系进行渗透汽化分离,其渗透通量和分离因子分别达到3746 g·m-2·h-1和3.75。     

燃料电池用磺化芳香类聚合物膜研究进展

质子交换膜作为燃料电池的核心部件,受到广大学者和研究人员的关注.本文综述了近几年科学家们通过化学交联、物理共混、无机掺杂、酸碱复合以及接枝侧链等方法对磺化芳香类聚合物质子交换膜的改性研究,并对磺化芳香类聚合物膜燃料电池发展前景进行了展望.     

Preparation of high‐flux ultrafiltration membranes by blending strongly charged polymer

Three kinds of high‐flux ultrafiltration membranes were fabricated by blending strongly charged polymer [sulfonated poly(phenylene oxide) (SPPO)] with neutral polymer [cellulose acetate (CA), polyethersulfone (PES), or polyvinylidene fluoride (PVDF)]. After blending with SPPO, the pure water flux of CA‐SPPO, PES‐SPPO, and PVDF‐SPPO membrane increase by 3, 76, and 30 times at a transmembrane pressure of 100 kPa. Compared with the unblended membranes, the pore radius of CA‐SPPO, PES‐SPPO, and PVDF‐SPPO membrane increased from 31.9 to 33.2 nm, 26.1 to 28.6 nm, and 19.8 to 25.7 nm, respectively. The addition of strongly charged polymer decreased the thermodynamic stability of casting solutions, promoting the phase inversion process and resulting in highly porous structure. The charged groups and hydrophilicity of the polymer facilitate the formation of an additive concentration gradient (more additive in the active layer), endowing the blend membrane with better hydrophilicity and greater wettability gradient. The high porosity, good hydrophilicity, and larger wettability gradient enable the high permeation of blend membranes. This work shows how the strongly charged polymer affects the formation and performance of blend membrane, which will be useful for designing high‐performance membrane. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44570.     

Performance evaluation of polyvinylchloride/polyacrylonitrile ultrafiltration blend membrane

Polyvinylchloride (PVC) membranes were modified by blending with polyacrylonitrile (PAN) as a second polymer. The miscibility of PVC/PAN blend was examined using an incompressible regular solution (CRS) model in no need to make a membrane. The results showed that the PVC/PAN blend was immiscible for all compositions at a temperature range of ?25 to 225 °C. Furthermore, the prediction of the phase behavior of a PVC/PAN/DMF ternary system showed that the blend of two polymers was highly incompatible even in their common DMF solvent. However, this incompatibility led to a remarkable increase in the porosity of the blend membrane and pure water flux compared to those for pure PVC membrane. The pure water flux of the PVC membrane (37.9 ± 1.5 L/m² h) increased about 41 and 76% by adding 10 and 20 wt% PAN, respectively. The blend membranes also showed an enhanced flux recovery ratio (FRR) compared to a pure PVC membrane, although the PVC membrane rejection for Bovine serum albumin (BSA) was decreased after blending with PAN. The PVC/PAN (90/10) blend membrane was subjected to hydrolysis with NaOH alkaline solution at three different concentrations and contact times to further enhance its performance. The membrane, which was hydrolyzed with a 0.5 mol/L NaOH solution for 0.5 h, showed a highest pure water flux of 75.6 ± 7.2 L/m² h due to its increased hydrophilicity. This membrane also revealed an improved FRR and better thermal and mechanical properties compared to an unmodified membrane.     

共混法制备酸性可染聚丙烯腈纤维

用含有碱性基团的丙烯酸氨基酯(TAM)与丙烯腈(AN)单体共聚,其共聚物与聚丙烯腈(PAN)共混,经湿法纺丝制备酸性染料可染PAN共混纤维。结果表明,AN／TAM共聚物与PAN有良好的相容性。随着TAM含量的增加,PAN共混纤维结晶度下降,力学性能下降。纤维中TAM质量分数5％较好,PAN共混纤维酸性染料上染率大于80％。     

Ion‐exchange membranes prepared by blending sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) with polybenzimidazole

New ion‐exchange acid/base‐blend (SPPO/PBI) membranes were prepared by mixing N,N‐dimethylacetamide (DMA) solutions of sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SPPO) in the ammonium form and of polybenzimidazole (PBI), casting the solution as a thin film, evaporating the solvent, and treating the membrane with aqueous hydrochloric acid. The resulting membranes were found insoluble in DMA. The preliminary tests of the membranes were carried out in an H₂/O₂ fuel cell at room temperature. Their performance in the fuel cell increased with the increase in the concentration of SPPO sulfonic acid groups in the blend, but the membranes formed with the highly sulfonated SPPO alone or predominanting, which swelled excessively in water, did not give reproducible results, and their performance was usually inferior to that of the membranes having an optimum ratio of both components. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1118–1127, 2002     

Miscibility and crystallization behavior of the solution‐blended sulfonated poly(phenylene oxide)/ poly(styrene‐co‐4‐vinyl pyridine) blend

The miscibility and crystallization behavior of the solution‐blended lightly sulfonated poly(phenylene oxide) (SPPO)/poly(styrene‐co‐4‐vinylpyridine) (PSVP) blend were investigated by conventional and modulated differential scanning calorimetry (MDSC). It was found that the original blend film is actually composed of a crystalline SPPO phase and a noncrystalline compatible SPPO–PSVP phase. The original phase‐segregated structure will evolve to a noncrystalline homogenous structure by subsequent high temperature annealing. The resulting good miscibility was attributed to two aspects: one is that the SPPO crystalline structure could be destroyed as annealing temperature is high enough; the other is that the acid–base interaction between the sulfonic group of SPPO and the pyridine ring of PSVP could promote mixing of different components effectively. And such acid–base interaction was demonstrated by ¹C NMR spectra. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2843–2848, 2001     

制取聚苯胺-聚乙烯醇导电共混膜的条件研究

用共混浇铸法制备PAN-PVA共混膜,探讨了制膜液中PAN与PVA的质量比、成膜干燥温度和制膜液浓度对共混膜性能的影响,测定了膜的拉伸断裂强度和断裂伸长率。结果表明,制取电导率高、力学性能较好的适合作电磁屏蔽材料的PAN-PVA共混膜的条件为:制膜液内PVA的质量百分数为40%,成膜干燥温度为80℃,制膜液浓度为17.0 mg/mL。     

Preparation of antimicrobial polyacrylonitrile fibers: Blending with polyacrylonitrile-co-3-allyl-5,5-dimethylhydantoin

Summary Polyacrylonitrile-co-3-allyl-5,5-dimethylhydantoin (Cop7-1) was prepared by a free radical polymerization process. The copolymer was blended with polyacrylonitrile (PAN) in a NaSCN aqueous solution, and the mixture was employed as a spinning solution. Rheological behavior of the spinning solution was studied. The PAN/Cop7-1 blend fibers were prepared through a two-stage wet spinning process. Tensile strengths of the blend fibers were lightly lower, but breaking elongations were higher than regular PAN fibers. Moisture regain and antistatic properties of the blend fibers were improved, while the thermal stability of the blend fibers decreased slightly. However, after treatment with 1% regular chlorine bleach, the blend fibers showed good antibacterial ability.     

大豆蛋白/聚丙烯腈共混纤维结构性能研究

研究了以二甲基亚砜为溶剂,经湿法纺丝所制备的大豆蛋白/聚丙烯腈共混纤维的结构性能。红外光谱分析表明:共混纤维主要组成为聚丙烯腈和大豆蛋白质;扫描电镜观察发现:纤维的表面有凸起颗粒及较深的沟槽;共混纤维的断裂强度略有降低,断裂伸长率基本不变;纤维的表面接触角及回潮率的测试表明:共混纤维的吸湿性得到提高。     

Novel,positively charged membrane from a blending,crosslinking, and coagulation procedure

A novel, positively charged membrane was prepared through a blending, crosslinking, and coagulation procedure in which poly(N,N‐dimethylaminoethyl methacrylate) (PDM) and polyacrylonitrile (PAN) were used as the functional and substrate component, respectively. Because 1,4‐dibromobutane (DBT) was used as the crosslinker and quaternizing agent, PDM was crosslinked and quaternized simultaneously. The effects of PDM content, polymer concentration, and additive dosage of the casting solution on the membrane performances are discussed in detail, and differences between the PAN membrane, PDM/PAN blend membrane, and crosslinked PDM/PAN blend membrane are also discussed. We also studied the adsorption behaviors of the membranes to a positively charged dye and a negatively charged dye. Environmental scanning electron microscopy observation showed that the resulting positively charged membrane from such a blending, crosslinking, and coagulation procedure possessed a unique and uniform structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1847–1854, 2005     

PAN／PS共混中空纤维超滤膜研究

本文将聚丙烯腈（ＰＡＮ）和聚砜（ＰＳ）材料共混，采用二甲基甲酰胺（ＤＭＦ）作溶剂，以干－湿纺丝工艺制备中空纤维超滤膜，研究了二种膜材料和溶剂的热力学性质，确定合适的共混体系，并相同共混比下共混物浓度对中空纤维超滤膜性能影响。以磷酸三乙酯（ＴＥＰ）和冰醋酸作为添加剂，分别观测其不同含量膜性能变化规律。认为磷酸三乙酯作用添加剂有一定的优越性。提高铸膜液温度，有助于增强ＰＡＮ－ＰＳ－ＤＭＦ所组成部分互溶