季铵化改性PSA的结构与性能研究

通过氯甲基化反应,制得了氯甲基化聚芳砜酰胺(CMPSA),并研究了聚芳砜酰胺(PSA)氯甲基化反应的影响因素。用流延法制成CMPSA膜,将CMPSA膜通过季铵化反应、离子交换制得了季铵化聚芳砜酰胺(QAPSA)阴离子交换膜。利用FT-IR和1H-NMR对其进行结构表征。并测定了QAPSA膜的离子交换容量(IEC)、离子电导率、吸水率和溶胀度。结果表明,QAPSA阴离子交换膜在室温下离子电导率为1.025×10-2S/cm,且具有良好的尺寸稳定性。     

抗污染超滤膜的研制

本文研制了氯甲基化／季铵化聚砜与聚偏氟乙烯共混超滤膜用于阴极电泳漆超滤系统。首先优化了氯甲基化／季铵化聚砜超滤膜的制备工艺，在此基础上，用聚偏氟乙烯部分代替氯甲基化聚砜制备共混超滤膜。结果表明：氯甲基化／季铵化聚砜与聚偏氟乙烯共混超滤膜不仅具有优良的分离性能，而且改善了膜的抗污染性。     

季铵型交联聚芳醚砜薄膜的制备及其性能研究

以甲基丙烯酸二甲氨基乙酯(DMAEMA)为铵化试剂,合成了含有双键的季铵型聚芳醚砜共聚物,通过流延技术,在热处理条件下挥发溶剂并交联,制备了季铵型交联聚芳醚砜(cPAES-N)薄膜。论文研究了聚芳醚砜的基本结构、交联情况、热稳定性和不同温度下的吸水溶胀情况。研究发现,交联聚芳醚砜薄膜可在流延溶剂中稳定存在,而且其热稳定性优于非交联聚芳醚砜(PAES-N);交联聚芳醚砜薄膜的吸水率与溶胀率均低于非交联聚芳醚砜薄膜,尺寸稳定性良好。     

聚醚砜的功能化改性及其性能

聚醚砜(PES)是一种带有苯环的高分子材料,比较容易进行功能改性。以1,4-二氯甲氧基丁烷为氯甲基化试剂,N-甲基咪唑为季铵化试剂,对PES进行季铵化改性,使其成为一种表面带有电荷的功能材料。采用红外光谱和核磁氢谱分析表征了PES的氯甲基化和季铵化程度,并测试了样品Zeta电位、静电荷、离子交换量和接触角等性能。结果表明,季铵化聚醚砜膜的离子交换量、静电荷和Zeta电位值皆与季铵化程度呈正相关关系,季铵化改性可以明显提高聚醚砜的亲水性。     

季铵化聚醚砜氢氧根离子交换膜的制备及研究

以氯甲基辛基醚(CMOE)为氯甲基化试剂,成功制备了不同取代度的氯甲基化聚醚砜(CMPES),使用三甲胺水溶液将CMPES膜季铵化,制备出季铵化聚醚砜氢氧根离子(QAPESOH)交换膜。对膜的离子交换容量、吸水率、溶胀度以及离子传导率进行测试,结果表明,当QAPESOH膜的氯甲基化程度(DC)在23%～51%时,即使温度升高到60℃,膜都具有良好的吸水率和适当的溶胀度。特别是DC为51%的膜,其氢氧根传导率在20℃时可以达到15.6mS/cm,并且具有良好的机械稳定性,说明QAPESOH膜在氢氧根离子交换膜燃料电池方面有很好的应用前景。     

正交实验法优化氯甲基化聚砜／聚砜共混膜的季铵化条件

将氯甲基化聚砜(CMPSF)/聚砜(PSF)共混膜浸于三甲胺溶液中制得季铵化聚砜(QMPSF)/聚砜(PSF)膜.采用正交实验考察了季铵化反应条件如季铵化温度、季铵化时间、三甲胺浓度等对QMPSF/PSF膜性能的影响,优化了季铵化条件,制得了性能较佳的季铵化QMPSF/PSF膜.研究结果表明,在0.2MPa压力下.制备的季铵化QMPSF/PSF膜的水通量为31.35 L/(m2·h),对相对分子质量为31 000～50 000的聚乙烯醇溶液的截留率为89.6%.     

PPESK中空纤维疏水膜膜蒸馏法脱除水中氯酚

采用表面涂覆改性的方法制得新型的改性聚芳醚砜酮（PPESK）中空纤维疏水膜，并用真空膜蒸馏法（VMO）进行了水溶液中2,4，6-三氯酚的去除试验。分别考察了氯酚水溶液以及两种合氯酚废水中氯酚的去除效果，研究了料液进口温度（0～30℃）、真空侧压力（0．03～0．08MPa）对脱除率及脱除因子的影响。     

平板式共混超滤膜的研究

本文报道了聚砜酰胺，聚砜酰胺／磺化聚芳醚砜，聚偏二氟乙烯／磺化聚芳醚砜平板超滤膜的制备工作，所得膜截留分子量分别为３００００－７００００，１０００－２００００，１０００００。并并对北京醋进行了澄清过滤试验，工业试验结果表明，用ＰＶＤＦ／ＳＰＥＳ－Ｃ超滤膜，２０ｍ＾２平板超滤机上醋产量为６００－８００Ｌ／ｍ＾２．ｈ，产量稳定，清洗容易，满足生产需要。     

磺化聚醚酮复合纳滤膜的制备

以含酞侧基聚芳醚酮（PEK—C）超滤膜为底膜,以磺化聚芳醚酮（SPEK—C）为复合膜涂层的功能材料制备了复合纳滤膜,研究了制备条件,包括SPEK—C含量、磺化度、固化温度和时间对复合纳滤膜性能的影响,还考察了该复合纳滤膜对不同无机盐的分离性能以及耐热性能。     

高浓度含盐含酸有机废水预处理及膜清洗初试

以聚合氯化铝（PAC）为絮凝剂,结合杂萘联苯聚芳醚砜酮（PPESK）超滤膜技术处理高浓度含盐含酸有机废水,考察了絮凝剂最佳投药量,同时研究超滤膜的清洗恢复情况,主要考察了水力清洗以及不同化学清洗剂和清洗时间的影响下,膜通量的恢复情况,从而确定了最佳的膜清洗方法。结果表明：PAC最佳投加量为100mg／L,废水絮凝效果最好,COD及SS去除率分别达到30％、90％。EDTA碱液反洗有很好的再生效果,渗透通量恢复率高至98．3％。     

Preparation and characterization of chloromethylated/quaternized poly(phthalazinone ether sulfone ketone) for positively charged nanofiltration membranes

Chloromethylated poly(phthalazinone ether sulfone ketone) (CMPPESK) as a novel membrane material was successfully prepared from poly(phthalazinone ether sulfone ketone), with concentrated sulfuric acid as the solvent and catalyst, and chloromethyl octyl ether with lower toxicity as the chloromethylated regent. The effects of the reaction conditions on the preparation of CMPPESKs with different degrees of chloromethylation were examined. The quantity of chloromethyl groups per repeated unit (DCM) of CMPPESK was determined by the method of analysis of the chlorine element, and structures were characterized by ¹H‐NMR spectroscopy. The introduction of chloromethyl groups into the polymer chains led to a decrease in the decomposition temperature. With increasing DCM, the initial degradation temperature declined. CMPPESK had good solubility and was soluble in N‐methyl‐2‐pyrrolidone (NMP), N,N‐dimethylacetamide (DMAc), and chloroform. However, quaternized poly(phthalazinone ether sulfone ketone) (QAPPESK) had excellent solvent resistance, was only partly soluble in sulfuric acid (98%), and was swollen in N,N‐dimethylformamide. QAPPESK nanofiltration (NF) membranes had about 90% rejection for MgCl₂, and the performance of the NF membrane prepared with DMAc as the solvent was superior to that of the NF membrane prepared with NMP as the solvent. In addition, the rejection to the different salt solutions followed the following sequence: MgCl₂ > MgSO₄ > NaCl > Na₂SO₄. Furthermore, the thermotolerance of the QAPPESK NF membrane was examined, and the results show that when the solution temperature rose from 11 to 90°C, the water flux increased more than threefold with stable salt rejection. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation,morphologies, and properties of positively charged quaternized poly(phthalazinone ether sulfone ketone) nanofiltration membranes

Positively charged quaternized poly(phthalazinone ether sulfone ketone) (QAPPESK) nanofiltration (NF) membranes were prepared from chloromethylated poly(phthalazinone ether sulfone ketone) by the dye/wet phase inversion method with N‐methyl‐2‐pyrrolidone (NMP) and N,N‐dimethylacetamide (DMAc) as solvents. The effects of the ratio of NMP to DMAc, the evaporation time, the evaporation temperature, and the coagulation temperature on membrane performance were evaluated by the orthogonal design method. The results showed that the optimal preparation conditions were an NMP/DMAc ratio of 2/8, an evaporation time of 5 min at 70°C, and a coagulation temperature lower than 5°C. The effects of the additive type and concentration on the QAPPESK NF membrane cross‐section morphology and performance were investigated in detail. Furthermore, QAPPESK NF membranes exhibited good thermal stability with stable membrane performance for 120 h at 60°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

聚芳醚砜酮复合膜浓缩回收环丁砜初探

以含二氮杂萘酮结构聚芳醚砜酮(PPESK)为基膜、均苯三甲酰氯为有机相单体、哌嗪与间苯二胺为水相单体通过界面聚合工艺制备了复合膜,研究了不同操作条件下复合膜对环丁砜水溶液的分离浓缩效果,考察了复合膜运行的稳定性与2次浓缩效果.结果表明,在50℃,1.8MPa下聚芳酰胺聚芳醚砜酮复合膜2次浓缩质量浓度10g·L~(-1)的环丁砜溶液,混合浓缩液环丁砜的质量浓度在28～36 g·L~(-1),透过液环丁砜的质量浓度为0.2 g·L~(-1),且13周静态及24 h连续分离操作性能稳定.     

Synthesis of amphiphilic poly(phthalazinone ether sulfone ketone)‐graft‐poly(ethylene glycol) graft copolymers via Williamson etherification

Amphiphilic graft copolymers consisting of poly(phthalazinone ether sulfone ketone) (PPESK) backbones and poly(ethylene glycol) (PEG) side chains were synthesized via reaction of chloromethylated PPESK (CMPPESK) with a sodium alkoxide of methoxyl PEG (PEG‐ ONa). The reactive precursor, CMPPESK, was prepared by the chloromethylation of PPESK with chloromethylether (CME) using concentrated H₂SO₄ as reaction medium. FTIR spectroscopy, ¹H‐NMR and Solid‐state ¹³C CP‐MAS NMR analysis confirmed the covalent linking of PEG with PPESK backbones. The PEG content in the graft copolymers from ¹H‐NMR analysis varied from 21.0 to 37.2 wt %, which was approximately in agreement with that calculated from TGA tests. The graft products have good solubility in many aprotic polar solvents and can be slightly swelled by water and ethanol, but water insoluble. Contact angle measurements revealed that the hydrophilicity of PPESK was significantly improved by the introduction of PEG graft chains, indicating the graft copolymer is a potential hydrophilic additive for PPESK membranes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007.     

Comparison of the water uptake and swelling between sulfonated poly(phthalazinone ether ketone ketone)s and sulfonated poly(arylene ether ketone ketone)s

Summary Sulfonated poly(phthalazinone ether ketone ketone)s (sPPEKK) and sulfonated poly(arylene ether ketone ketone sulfone)s (sPAEKK) were successfully synthesized by direct polycondensation. The water uptake and swelling of sPPEKK are much less compared with those of sPAEKK, especially in high temperature, which result from the powerful intermolecular hydrogen bonds of sPAEKK, confirmed by variable temperature IR spectra. The maximum operation temperature of proton exchange membranes made of sPPEKK is higher than 80 °C, improving the property of resistance to swelling.     

PPESK／PS共混物流变性能的研究

以溶液共沉淀的方法制备了含二氮杂萘联本结构的聚芳醚砜酮（PPESK）。聚苯乙烯（PS）共混物，用毛细管流变仪测定了共混物的流为性能。结果表明，在本实验条件下，PPESK／PS共混物熔体属假塑性非牛顿汉体，其熔体粘度随PS含量的增加、温度的升高、剪切速率的增大而下降。PS的加入有利于改善PPESK的熔融加工流动性。     

Synthesis of novel poly(phthalazinone ether sulfone ketone)s and improvement of their melt flow properties

A series of novel poly(phthalazinone ether sulfone ketone)s was synthesized from bis(4-fluorophenyl) ketone, bis(4-chlorophenyl)sulfone, and 4-(4-hydroxybenzyl)-2,3-phthalazin-1-one through nucleophilic substitution polycondensation. The synthesized polymers exhibited surprisingly high glass transition temperatures and had excellent thermooxidative properties. The melt viscosities of these synthesized polymers are generally too high to be processed by common processing methods because of their very high glass transition temperatures and amorphous microstructure. An attempt was made to reduce their melt viscosities by solution blending the synthesized polymer with two kinds of oligomers: low molecular weight poly(phthalazinone ether sulfone ketone) and commercial poly(ether sulfone). The results proved that the addition of the oligomers to the polymers led to a marked decrease in melt viscosities. Furthermore, no obvious changes were observed in the thermal and mechanical properties of these blends after oligomer additions. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1425–1432, 1997     

Synthesis of sulfonated poly(phthalazinone ether sulfone)s by direct polymerization

Sulfonated poly(phthalazinone ether sulfone)s with high molecular weight were directly prepared by polycondensation of 4-(4-hydroxyphenyl) phthalazinone with various ratios of disodium 5.5′-sulfonylbis(2-fluoro-benzenesulfonate) to 4-fluorophenyl sulfone. The resulting ionomers with high IEC showed low swelling. The low swelling originates from intermolecular hydrogen bonds, which is confirmed by variable temperature IR spectroscopy. The membranes show very good perspectives in PEMFC applications.     

无机杂化倍半硅氧烷／磺化杂萘联苯聚醚酮质子导电复合膜

通过磺化反应制备了一系列不同磺化程度的磺化杂萘联苯聚醚酮（SPPEK）,采用共混法将无机杂化倍半硅氧烷（POSS）掺杂到IEC值为1．60的SPPEK中,通过溶液浇铸制得复合膜。对SPPEK／POSS复合膜进行了FTIR、TGA分析和SEM表观形貌观察。研究了SPPEK／POSS复合膜的吸水性、溶胀度和质子导电性,并与Nation 117进行对比。随着POSS的加入,复合膜的吸水性、溶胀度和氧化稳定性提高。SPPEK／POSS复合膜的室温电导率达到0．75×10^-2S·cm^-1,接近Nafion 117膜相同条件下的电导率（1．08×10^-2S·cm^-1）。随着温度升高,SPPEK／POSS复合膜的电导率逐渐增大。采用不同测试方法分别对复合膜的膜平面方向和厚度方向上的电导率进行了测试,表明在两个方向上的电导率相差较大,SPPEK／POSS复合膜室温下膜平面方向上的电导率达到2．1×10^-2S·cm^-1。