聚醚醚酮／聚醚砜共混物的研究

采用熔融共混技术制备聚醚醚酮/聚醚砜共混物,研究了共混物的性能。在K_2CO_3和Na_2CO_3等比混合盐存在下,在二苯砜溶剂中4,4′-二氟苯酮与对苯二酚熔融缩聚,然后加入用二苯砜熔融的聚醚砜即得到共混物。研究发现两者有较好的相容性,共混物力学性能相当于两者的加和值,与聚醚醚酮相比,共混物Tg提高了50～75℃,压片温度降低了约100℃,结晶度随聚醚醚酮含量增加而增大,表明改性后的聚醚醚酮加工性有了明显改进。     

磺化聚醚醚酮共混膜的制备及其特性的研究

通过溶液共混的方法,以磺化聚醚醚酮(SPEEK)和聚醚砜(PES)为原料,N,N-二甲基甲酰胺(DMF)为溶剂,制备了一系列不同比例的SPEEK与PES的共混膜,并研究了膜的组成对膜的吸水率、电导率、甲醇渗透系数的影响,与目前所使用的Nafion117膜相比,这种共混膜既可以提高阻醇性能,同时又具有一定的电导率。     

磺化聚醚砜/聚醚砜共混膜的制备及膜催化酯化反应动力学研究

以聚醚砜(PES)为基体,磺化聚醚砜(SPES)为催化活性成分,通过溶剂挥发法制备SPES/PES共混膜,用于酸化油(酸值153 mg KOH/g)酯化反应制备生物柴油,并研究了SPES/PES共混型催化膜酯化反应动力学。结果表明,在不同反应温度(45,55,65,75℃),不同的催化剂用量(0.68%,1.35%和2.70%)以及醇油质量比(1∶1,2∶1,5∶1,8∶1和10∶1)条件下,通过反应动力学计算出相应的反应速率以及反应级数。随着催化剂用量和醇油质量比的增加,反应速率逐渐增加,反应级数也增大,平均反应级数为n=2.2,而指前因子和活化能逐渐减小,说明由反应控制逐渐转为混合控制和反应控制。建立了SPES/PES共混型催化膜酯化反应动力学模型。得到实验值与理论值吻合程度较高(误差在±5%左右),验证了动力学模型的正确性。     

磺化聚醚砜/聚醚砜共混膜的制备及膜催化酯化反应动力学研究

以聚醚砜(PES)为基体,磺化聚醚砜(SPES)为催化活性成分,通过溶剂挥发法制备SPES/PES共混膜,用于酸化油(酸值153 mg KOH/g)酯化反应制备生物柴油,并研究了SPES/PES共混型催化膜酯化反应动力学。结果表明,在不同反应温度(45,55,65,75℃),不同的催化剂用量(0.68%,1.35%和2.70%)以及醇油质量比(1∶1,2∶1,5∶1,8∶1和10∶1)条件下,通过反应动力学计算出相应的反应速率以及反应级数。随着催化剂用量和醇油质量比的增加,反应速率逐渐增加,反应级数也增大,平均反应级数为n=2.2,而指前因子和活化能逐渐减小,说明由反应控制逐渐转为混合控制和反应控制。建立了SPES/PES共混型催化膜酯化反应动力学模型。得到实验值与理论值吻合程度较高(误差在±5%左右),验证了动力学模型的正确性。     

磺化聚醚砜/聚醚砜共混膜催化酯化反应性能研究

制备了磺化聚醚砜SPES膜和3种磺化度的SPES/PES共混膜用于催化酯化酸化油制备生物柴油。考察了磺化度、催化膜用量、酸化油和甲醇质量比、反应时间对酯化反应的影响。结果表明,单独使用SPES催化膜较脆,而SPES/PES共混膜机械强度较好,其中磺化度20.3%SPES/PES膜的重复使用性能最好。SPES/PES共混膜催化酯化酸化油制备生物柴油的最佳反应条件为:磺化度20.3%的SPES/PES共混膜为催化剂,催化膜用量1.66%,醇油质量比为1∶1,反应温度65℃,反应时间6 h,此时酸化油转化率为97.44%。     

磺化聚砜/聚醚砜纳滤膜的制备及性能表征

采用相转化法制备了磺化聚砜(SPSF)/聚醚砜(PES)共混新型纳滤膜,并研究了SPSF/PES共混质量比、水解的苯乙烯–马来酸酐共聚物(H–PSMA)的添加量、铸膜液预蒸发时间和温度对膜的脱盐率及水通量的影响。结果表明,当SPSF/PES共混质量比为4∶6,添加剂H–PSMA的质量分数为2%,铸膜液预蒸发时间为3 min,预蒸发温度为70℃时,在操作压力为0.5 MPa,料液温度为25℃下,SPSF/PES共混膜对2 g/L的Na_2SO_4盐溶液脱盐率为56.77%,水通量为24.45 L/(m~2·h)。     

聚醚砜和磺化聚醚砜膜结构及性能研究

采用电镜和孔径分布测定仪对自制聚醚砜( PES)和磺化聚醚砜(SPES)膜进行表征,根据Darcy-Poiseuille定律研究PES膜和SPES膜过滤牛血清蛋白液(BSA)阻力分布情况.结果表明,PES膜孔径为0.22～0.27 μm,初始纯水通量为642 L·m-2·h-1,过滤质量浓度为1 g·L-1的BSA溶液时平衡通量为30.4～31.9 L·m-2· h-1; SPES膜孔径为5.2～11.1 nm,初始纯水通量为8.1 L·m-2·h-1,质量浓度为1 g·L-1的BSA时平衡通量为3.4～6.9 L· m-2·h-1.过滤时PES膜阻力主要集中在吸附和堵孔阻力,2者相加为总阻力的91.1％;而SPES膜阻力主要集中在膜本身的阻力,为总阻力的41.8％,其次为堵孔阻力,占总阻力的38.3％.经清洗后,PES膜的纯水通量可以恢复到82％,而SPES膜可以恢复到494％.     

聚醚砜和磺化聚砜共混超滤膜的研究

本文主要叙述聚醚砜(PES)和磺化聚砜(S-PSF)共混之后膜性能的改善,得出共混膜要比单组分膜性能优良。并且,在加入致孔添加剂丙酮和聚乙二醇(PEG)后,膜性能得到进一步改善。     

磺化聚醚砜超滤膜的制备研究

本文研究了磺化聚醚砜的制备和膜性能的测试 ,通过选择适当的配方研制性能稳定的较小孔径的超滤膜。该膜在 0 .2Mpa操作压力下对聚乙二醇 1 0 0 0 0的截留率大于 95 % ,水通量为 5 5L/m2 H ,通过扫描电镜观察膜的断面结构 ,结果表明 :PES膜断面形态属于典型的非对称指状孔结构 ,SPES膜断面形态是海绵层结构     

DMFCs用磺化聚醚醚酮/磺化酚酞型聚醚砜共混质子交换膜

A sulfonated poly(ether ether ketone) (SPEEK) membrane with fairly high degree of sulfonation (DS) swells excessively and even dissolves at high temperature. To solve these problems, sulfonated phenolphthalein poly(ether sulfone) (SPES-C, DS 53.7%) is blended with the SPEEK matrix (DS 55.1%, 61.7%) to prepare SPEEK/SPES-C blend membrane. The decrease in swelling degree and methanol permeability of the membrane is dose-dependent. Pure SPEEK (DS 61.7%) membrane dissolves completely in water at 70ºC, whereas the swelling degree of the SPEEK (DS 61.7%)/SPES-C (40%, by mass) membrane is 29.7% at 80ºC. From room temperature to 80ºC, the methanol permeability of all SPEEK (DS 55.1%)/SPES-C blend membranes is about one order of magnitude lower than that of Nafion®115. At higher temperature, the addition of SPES-C polymer increases the dimensional stability and greater proton conductivity can be achieved. The SPEEK (DS 55.1%)/SPES-C (40%, by mass) membrane can withstand temperatures up to 150ºC. The proton conductivity of SPEEK (DS 55.1%)/SPES-C (30%, by mass) membrane approaches 0.16 S•cm－1, matching that of Nafion115 at 140ºC and 100% RH, while pure SPEEK (DS 55.1%) membrane dissolves at 90ºC. The SPEEK/SPES-C blend membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.     

Preparation and characterization of poly(vinylidene fluoride)/sulfonated poly(phthalazinone ether sulfone ketone) blends for proton exchange membrane

Poly(vinylidene fluoride)/sulfonated poly(phthalazinone ether sulfone ketone) (PVdF/SPPESK) blend membranes are successfully prepared by solution blending method for novel proton exchange membrane (PEM). PVdF crystallinity, FTIR‐ATR spectroscopy, thermal stability, morphology, water uptake, dimension stability, and proton conductivity are investigated on PVdF/SPPESK blends with different PVdF contents. XRD and DSC analysis reveal that the PVdF crystallinity in the blends depends on PVdF content. The FTIR‐ATR spectra indicate that SPPESK remains proton‐conducting function in the blends due to the intactness of ? SO₃H group. Thermal analysis results show a very high thermal stability (T_d1 = 246–261°C) of the blends. PVdF crystallinity and morphology study demonstrate that with lower PVdF content, PVdF are very compatible with SPPESK. Also, with lower PVdF content, PVdF/SPPESK blends possess high water uptake, e.g., P/S 10/90 and P/S 15/85 have water uptake of 135 and 99% at 95°C, respectively. The blend membranes also have good dimension stability because the swelling ratios are at a fairly low level (e.g., 8–22%, 80°C). PVdF/SPPESK blends with low PVdF content exhibit very high proton conductivity, e.g., at 80°C, P/S 15/85 and P/S 10/90 reach 2.6 × 10^?2 and 3.6 × 10^?2 S cm^?1, respectively, which are close to or even higher than that (3.4 × 10^?2 S cm^?1) of Nafion115 under the same test condition. All above properties indicate that the PVdF/SPPESK blend membranes (particularly, with 10–20% of PVdF content) are very promising for use in PEM field. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

DMFCs用SPEEK/SiOx-S复合质子交换膜

A sulfonated poly(ether ether ketone) (SPEEK) membrane with a fairly high degree of sulfonation (DS) can swell excessively and even dissolve at high temperature. To solve these problems, insolvable functionalized silica powder with sulfonic acid groups (SiOx-S) was added into the SPEEK matrix (DS 55.1%) to prepare SPEEK/ SiOx-S composite membranes. The decrease in both the swelling degree and the methanol permeability of the membranes was a dose-dependent result of addition of the SiOx-S powder. Pure SPEEK membrane swelled 52.6% at 80°C, whereas the SPEEK/SiOx-S (15%, by mass) membrane swelled only 27.3% at the same temperature. From room temperature to 80℃, all SPEEK/SPEEK/SiOx-S composite membranes had methanol permeability of about one order of magnitude lower than that of Nafion115. Compared with pure SPEEK membranes, the addition of the SiOx-S powder not only leads to higher proton conductivity, but also increases the dimensional stability at higher temperatures, and greater proton conductivity can be achieved at higher temperature. The SPEEK/SiOx-S (20%, by mass) membrane could withstand temperature up to 145°C, at which in 100% relative humidity (RH) its proton conductivity exceeded slightly that of Nafion115 membrane and reached 0.17 S•cm－1, while pure SPEEK mem-brane dissolved at 90°C. The SPEEK/SiOx-S composite membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.     

Sulfonated poly(ether ether ketone)/zirconium tricarboxybutylphosphonate composite proton-exchange membranes for direct methanol fuel cells

Sulfonated poly(ether ether ketone) (SPEEK) is a very promising alternative membrane material for direct methanol fuel cells. However, with a fairly high degree of sulfonation (DS), SPEEK membranes can swell excessively and even dissolve at high temperature. This restricts membranes from working above a high tolerable temperature to get high proton conductivity. To deal with this contradictory situation, insolvable zirconium tricarboxybutylphosphonate (Zr(PBTC)) powder was employed to make a composite with SPEEK polymer in an attempt to improve temperature tolerance of the membranes. SPEEK/Zr(PBTC) composite membranes were obtained by casting a homogeneous mixture of Zr(PBTC) and SPEEK in N,N-dimethylacetamide on a glass plate and then evaporating the solvent at 60°C. Many characteristics were investigated, including thermal stability, liquid uptake, methanol permeability and proton conductivity. Results showed significant improvement not only in temperature tolerance, but also in methanol resistance of the SPEEK/Zr(PBTC) composite membranes. The membranes containing 30 wt-% ∼ 40 wt-% of Zr(PBTC) had their methanol permeability around 10⁻⁷ cm²·s⁻¹ at room temperature to 80°C, which was one order of magnitude lower than that of Nafion?115. High proton conductivity of the composite membranes, however, could also be achieved from higher temperature applied. At 100% relative humidity, above 90°C the conductivity of the composite membrane containing 40 wt-% of Zr(PBTC) exceeded that of the Nafion?115 membrane and even reached a high value of 0.36 S·cm⁻¹ at 160°C. Improved applicable temperature and high conductivity of the compositemembrane indicated its promising application inDMFC operations at high temperature. __________ Translated from Acta Polymerica Sinica, 2007, (4): 337–342 [译自:高分子学报]     

直接甲醇燃料电池用三羧基丁烷膦酸锆/磺化杂萘联苯聚醚酮复合质子交换膜

用高磺化度的磺化杂萘联苯聚醚酮（SPPEK）制备DMFC质子交换膜时,膜的机械强度会因过度溶胀而下降。通过在SPPEK（DS=61%）中掺杂1,2,4-三羧基丁烷-2-膦酸锆(Zr(PBTC)),我们制备出 Zr(PBTC)/SPPEK复合质子交换膜。实验表明, Zr(PBTC)的掺杂能有效降低膜的吸水量（溶胀）,并能减小膜的甲醇透过系数。80℃时,30wt.%Zr(PBTC) /SPPEK复合膜的吸水量与SPPEK膜比降低了30％。室温下复合膜的甲醇透过系数在10－7 cm2.s-1数量级上,比Nafion 115膜低一个数量级以上。液体甲醇溶液进料的DMFC单电池测试表明,30wt.%Zr(PBTC) /SPPEK复合膜的电池性能优于SPPEK的电池性能。     

磷钨酸/二氧化硅/磺化聚醚醚酮复合膜的制备、表征与性能

以二氧化硅和磷钨酸改性磺化聚醚醚酮制得一种新型磺化聚醚醚酮复合膜。复合膜中杂多酸仍然保持着Keggin型PW12O430-阴离子的特征结构,二氧化硅和磷钨酸以无定形状态均匀分散于复合膜中。磷钨酸/二氧化硅/磺化聚醚醚酮复合膜的阻醇性能优于Nafion115;质子导电性能随着温度的提高有所增加。复合膜在磷钨酸中具有良好的稳定性。     

Proton exchange membranes based on modified sulfonated poly(ether ether ketone) membranes with chemically in situ polymerized polypyrrole

Sulfonated poly(ether ether ketone) (SPEEK) membranes were modified with chemically in situ polymerized polypyrrole (PPy). The effects of temperature and methanol concentration on the solution uptake and the swelling ratio of SPEEK/PPy membranes were investigated. The solution uptake and the swelling ratio of the membranes decreased upon the incorporation of PPy. When the methanol concentration increased, both the solution uptake and the swelling ratio increased to a maximum, and then decreased. FT-IR, XRD, DSC and TGA were used to characterize the modified membranes. The methanol permeability of modified SPEEK membranes decreased upon the incorporation of PPy, and higher selectivity values were found for SPEEK/PPy membranes in comparison with pure SPEEK and Nafion^® 117 membranes.     

Synthesis and characterization of sulfonated poly(phthalazinone ether sulfone ketone) for ultrafiltration and nanofiltration membranes

Modification of poly(phthalazinone ether sulfone ketone) (PPESK) by sulfonation with concentrated or fuming sulfuric acid as sulfonation agents was carried out to prepare membrane materials with increased hydrophilicity and potentially increased fouling resistance. Sulfonated PPESK (SPPESK) copolymers, with a degree of sulfonation ranging from 10–300%, were prepared and characterized. Factors affecting the sulfonation reaction were studied, and reaction conditions for the preparation of SPPESK with different degrees of sulfonation were determined. Compared with the properties of PPESK, the hydrophilicity of SPPESK was increased, as shown by a reduced contact angle with water. The glass transition temperature was increased from 278°C (PPESK) to a maximum of 323°C for the highly sulfonated derivative, due to the strong polarity of  SO₃H and hydrogen bonding. Ultrafiltration membranes prepared with PPESK and SPPESK were compared. For a SPPESK asymmetric membrane, the PEG12000 rejection was 98% and the water flux was 876 kg · m⁻² · h⁻¹. SPPESK/PPESK composite nanofiltration membranes were also prepared and were shown to have short‐term operational stability up to 120°C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1685–1692, 2001     

PWA/silica doped sulfonated poly(ether sulfone) composite membranes for direct methanol fuel cells

A novel sulfonated poly(ether sulfone) (SPES)/phosphotungstic acid (PWA)/silica composite membranes for direct methanol fuel cells (DMFCs) application were prepared. The structure and performance of the obtained membranes were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), water uptake, proton conductivity, and methanol permeability. Compared to a pure SPES membrane, PWA and SiO₂ doped membranes had a higher thermal stability and glass transition temperature (T_g) as revealed by TGA‐FTIR and DSC. The morphology of the composite membranes indicated that SiO₂ and PWA were uniformly distributed throughout the SPES matrix. Proper PWA and silica loadings in the composite membranes showed high proton conductivity and sufficient methanol permeability. The selectivity (the ratio of proton conductivity to methanol permeability) of the SPES‐P‐S 15% composite membrane was almost five times than that of Nafion 112 membrane. This excellent selectivity of SPES/PWA/silica composite membranes indicate a potential feasibility as a promising electrolyte for DMFC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

磺化聚醚醚酮的性能与应用

聚醚醚酮(PEEK)是一种性能优异的工程塑料。笔者简单地介绍了聚醚醚酮的特性,对近年来磺化聚醚醚酮的制备、SPEEK的性能及应用做了比较全面的归纳,并对磺化聚醚醚酮未来的发展前景进行了展望。