高分子分离膜材料及其研究进展

膜材料是膜研究的主要内容,从理论与应用两个角度对高分子分离膜材料进行阐述,先从分离膜的分离机制、分离性能及类别展开介绍,总结各类常见的高分子分离膜材料的性能特点及适用性,针对近年来高分子分离膜材料的合成和制备、改性与应用等研究成果进行概述,通过分析并总结分离膜材料的结构与性能之间的关系,对未来开发新型高分子分离膜材料作出展望。     

煤系高岭土微波合成NaA分子筛膜及其性能与表征

主要对高岭土微波合成NaA分子筛膜及其性能进行了研究.从铝源和晶化时间等方面研究了对煤系高岭土微波合成NaA分子筛膜的影响,并比较了水热合成NaA分子筛膜和微波合成NaA分子筛膜性能.通过实验发现,以高岭土为原料制备的NaA分子筛膜经微波合成,其乙醇脱水渗透汽化中分离因数超过10 000;NaA分子筛膜的微波合成在晶化时间分别为15、20和25min时,其渗透汽化通量由2.44kg/(m2.h)降低为0.92kg/(m2.h),分离因数由2 945增大为11 846,其中NaA分子筛膜在晶化时间为20min时,其分离因数和渗透通量分别为10 359和1.13kg/(m2.h);同时在相同配方条件下,水热合成的NaA分子筛膜和微波加热合成的NaA分子筛膜相比,反应时间由4h降低为20min,而分离因数由5 231增加到10 360.     

MFI型分子筛膜的制备及气体渗透性能研究

采用原位水热合成和无模板剂二次生长合成的方法在α-Al2O3基膜上合成了MFI型分子筛膜,并用XRD,SEM和气体渗透实验等方法进行表征,结果表明合成在α-Al2O3基膜的物质为MFI型分子筛.对于水热合成的分子筛膜,氢/异丁烷的理想分离系数在298 K和473 K时分别为97和52;对于二次生长合成的分子筛膜,氢/异丁烷的理想分离系数在298 K和473 K时分别为497和370,远大于它们Knudsen扩散5.34的比值.表明气体是通过MFI型分子筛的孔道透过.水热合成分子筛膜的正/异丁烷理想分离系数在298 K和473 K时分别为22和13;二次生长分子筛膜的正/异丁烷理想分离系数在298 K和473 K时分别为77和70,气体分离数据表明,两种分子筛膜对气体分离是由分子筛分占主导,同时分子筛膜没有裂缺.     

聚偏氟乙烯微孔膜的表面功能化研究进展

介绍了聚偏氟乙烯(PVDF)微孔膜的表面功能化的研究进展,包括合成分子印迹膜、环境敏感性分离膜和分离膜上蛋白和酶的固定化.     

MFI型分子筛膜的制备及气体渗透特性

采用原位水热合成和无模板剂二次生长合成的方法,在α-Al2O3基膜上合成了MFI型分子筛膜,用XRD,SEM和气体渗透实验等方法进行表征,表明合成在α-Al2O3基膜的物质为MFI型分子筛.原位合成的分子筛膜,氢/异丁烷的理想分离系数在298K和473K时分别为97和52;二次生长合成的分子筛膜,氢/异丁烷的理想分离系数在298K和473K时分别为497和370,远大于它们Knudsen扩散5.34的比值,表明气体是通过MFI型分子筛的孔道透过.SF6分子动力学直径大于分子筛膜孔径,H2/SF6分离因子远大于Knudsen扩散值,几乎不透过分子筛膜.原位合成分子筛膜的正/异丁烷理想分离系数在298K和473K时分别为24和17;二次生长分子筛膜的正/异丁烷理想分离系数在298K和473K时分别为77和74.气体渗透分离实验结果表明,两种分子筛膜对气体分离是由分子筛分占主导,分子筛膜完整没有缺陷.     

新型聚酰亚胺渗透汽化膜

合成了三种新型聚酰亚胺,并制成渗透汽化膜用以分离乙醇-水、异丙醇-水混合物。结果表明,三种聚酰亚胺均具有较高的分离系数,在分子主链中含有—Si—(CH_3)_2—链节的聚酰亚胺膜,其透过速率高于、分离系数低于其它两种聚酰亚胺,并从聚合物分子结构的观点讨论了其原因。     

导电聚合物复合透膜的研究进展

导电聚合物复合透膜具有良好的力学性能和独特的电化学性质,是一类新型的分离膜,已在膜分离技术、分子水平上的识别与控制等领域显示出了广阔的应用前景．本文介绍了导电透膜的合成制备方法、形态结构和分离机理,并对导电聚合物复合透膜的性能与结构研究进展以及在液体分离、气体分离方面的应用研究进行了综述．     

聚酰亚胺气体分离膜

介绍了一种新型的气体分离膜材料－－聚酰亚胺，对其发展历史，合成，制膜及气体分离的应用研究了作评术，从四个方面讨论了聚酰亚胺膜的气体透过机理。并与普通膜材料进行了比较，指出了该膜材料的广阔发展前景。     

四通道中空纤维NaA分子筛内膜的制备与表征

采用错流真空抽吸涂晶与动态水热合成的方法在四通道陶瓷中空纤维载体的内表面制备出高性能的NaA分子筛膜, 并用于75℃下90wt%乙醇/水混合物渗透汽化脱水分离, 系统考察了晶种液流速、涂晶时间与合成温度对NaA分子筛膜形貌与分离性能的影响。结果表明, 当晶种液流速为100 mL/h、涂晶时间为5 s时制备的NaA分子筛膜致密均匀; 晶种液流速过慢或者涂晶时间过长会导致膜厚增加同时也会在膜表面产生缺陷。当膜在100℃下水热合成两次, 制备的NaA分子筛膜分离性能最佳, 此时膜的分离因子为1585, 通量高达8.8 kg/(m²•h)。当合成温度过低时, 膜的晶化程度较低, 膜表面出现缺陷; 当合成温度过高时, 膜晶体生长速率过快, 交互生长程度较差, 膜的断面产生缺陷, 导致膜分离性能较低。     

陶瓷中空纤维内表面动态水热合成NaA分子筛膜及其表征

采用动态水热法在氧化铝陶瓷中空纤维内表面原位合成了NaA分子筛膜。利用X射线衍射仪(XRD)、场发射扫描电子显微镜(FE-SEM)表征了分子筛膜的物相及微观形貌,通过渗透汽化测试考察了膜的乙醇/水分离性能,研究了合成工艺参数对成膜过程及膜质量的影响。结果表明,动态下合成的分子筛膜,晶体交联紧致,膜层薄且连续性好,厚度约4μm;提高动态速度有利于降低载体内外合成液的温差和浓度差,缩短晶化时间。在温度343K下,分离质量分数90%的乙醇/水体系,膜的渗透通量和分离因子可达1.03kg/(m2·h)和3 781,对乙醇/水表现出良好的分离效果和可重复性。     

分离膜表面接枝制备刺激响应性膜研究进展

刺激响应性分离膜的制备及研究是近年来的热点,其在生物传感器、选择性分离、药物可控释放等领域具有广阔的应用前景。文中综述了等离子处理引发接枝,紫外光引发接枝,化学热引发接枝和可控活性接枝等四种主要的接枝方法在高分子分离膜表面的接枝改性研究进展,主要围绕具有刺激响应性功能的分离膜的制备研究进行介绍,对存在的问题进行了讨论,并阐述了刺激响应性分离膜的发展方向。     

新型界面聚合法制备高性能聚酰胺反渗透膜

目的 为减缓界面聚合反应速率,使聚合过程可控,以制备结构和性能稳定的反渗透膜.方法 提出一种新的含缓冲层的自由界面聚合工艺(Buffer Layer Free Interfacial Polymerization,BLIP)来实现聚合速率的控制,研究单体浓度和反应时间对BLIP膜结构和性能的影响,选用硫酸钠(Na2SO4)和氯化钠(NaCl)测试BLIP膜的脱盐性和耐氯性.结果 当间苯二甲胺(m-xylylenediamine,m-XDA)与均苯三甲酰氯(trimesoyl chloride,TMC)质量分数分别为0.6％,0.3％时,BLIP膜对硫酸钠(Na2SO4)和氯化钠(NaCl)的脱盐率最佳,分别为92.55％,83.99％,水通量分别为8.30,9.15 L/(m2·h).当膜在活性氯浓度为l g/L的NaClO溶液中浸泡12h后,Na2SO4和NaCl的脱盐率均保持在72％以上.结论 添加缓冲层提高了TMC在油相的分散均匀性,减缓了界面聚合速率,显著提高了BLIP膜的性能.文中提出了一种新颖、节能、简单的反渗透膜制备工艺,为促进界面聚合工艺的发展提供了新的思路.     

Plasma-polymerized alkaline anion-exchange membrane: Synthesis and structure characterization

After-glow discharge plasma polymerization was developed for alkaline anion-exchange membranes synthesis using vinylbenzyl chloride as monomer. X-ray photoelectron spectroscopy and attenuated total reflection Fourier transform infrared spectroscopy were used to characterize the chemical structure properties of plasma-polymerized membranes. Ion-exchange capacities of quaternized poly(vinylbenzyl chloride) (QPVBC) membranes were measured to evaluate their capability of hydroxyl ion transport. A mechanism of plasma polymerization using VBC as monomer that accounts for the competitive effects of free radicals polymerization and plasma ablation in the plasma polymerization process was proposed. Our results indicate that plasma discharge power influences the contents of functional groups and the structure of the plasma polymer membranes, which attribute to the coactions of polymerization and ablation. The properties of uniform morphology, good adhesion to the substrate, high thermal stability and satisfying anion conduction level suggest the potential application of QPVBC membrane deposited at discharge power of 20 W in alkaline direct methanol fuel cells.     

ATRP-based synthesis and characterization of light-responsive coatings for transdermal delivery systems

Abstract

The grafting of poly(hydroxyethylmethacrylate) on polymeric porous membranes via atom transfer radical polymerization (ATRP) and subsequent modification with a photo-responsive spiropyran derivative is described. This method leads to photo-responsive membranes with desirable properties such as light-controlled permeability changes, exceptional photo-stability and repeatability of the photo-responsive switching. Conventional track etched polyester membranes were first treated with plasma polymer coating introducing anchoring groups, which allowed the attachment of ATRP-initiator molecules on the membrane surface. Surface initiated ARGET–ATRP of hydroxyethylmethacrylate (where ARGET stands for activator regenerated by electron transfer) leads to a membrane covered with a polymer layer, whereas the controlled polymerization procedure allows good control over the thickness of the polymer layer in respect to the polymerization conditions. Therefore, the final permeability of the membranes could be tailored by choice of pore diameter of the initial membranes, applied monomer concentration or polymerization time. Moreover a remarkable switch in permeability (more than 1000%) upon irradiation with UV-light could be achieved. These properties enable possible applications in the field of transdermal drug delivery, filtration, or sensing.     

ATRP-based synthesis and characterization of light-responsive coatings for transdermal delivery systems

The grafting of poly(hydroxyethylmethacrylate) on polymeric porous membranes via atom transfer radical polymerization (ATRP) and subsequent modification with a photo-responsive spiropyran derivative is described. This method leads to photo-responsive membranes with desirable properties such as light-controlled permeability changes, exceptional photo-stability and repeatability of the photo-responsive switching. Conventional track etched polyester membranes were first treated with plasma polymer coating introducing anchoring groups, which allowed the attachment of ATRP-initiator molecules on the membrane surface. Surface initiated ARGET–ATRP of hydroxyethylmethacrylate (where ARGET stands for activator regenerated by electron transfer) leads to a membrane covered with a polymer layer, whereas the controlled polymerization procedure allows good control over the thickness of the polymer layer in respect to the polymerization conditions. Therefore, the final permeability of the membranes could be tailored by choice of pore diameter of the initial membranes, applied monomer concentration or polymerization time. Moreover a remarkable switch in permeability (more than 1000%) upon irradiation with UV-light could be achieved. These properties enable possible applications in the field of transdermal drug delivery, filtration, or sensing.     

表面光接枝技术及其在分离膜中的应用

与其它方法相比,膜分离因具有分离效率高、操作过程简单、能耗低、没有环境污染等特点而成为各个行业不可缺少的技术．随着科学技术的进步及分离膜应用范围的拓宽,对分离膜的性能要求越来越高;一些不单以分离为目的的膜技术的出现,则要求有与之相适应的功能性分离膜,所有这些问题都急需解决．将表面光接枝方法引入到分离膜技术中,改善传统膜的性能,制备新型功能性复合分离膜,已成为一个具有很大希望的领域．     

不同接枝率对PVDF-g-PNIPAAm温敏膜性能影响研究

以聚偏氟乙烯(PVDF)为基材,分别采用直接引发原子转移自由基聚合(ATRP)和碱处理后自由基聚合的方法接枝N-异丙基丙烯酰胺(NIPAAm),合成出不同接枝率的PVDF-g-PNIPAAm共聚物,然后用相转化法制备出PVDF-g-PNIPAAm共聚温敏膜.用核磁共振(1H NMR)和X射线光电子能谱(XPS)分别对共...     

Preparation of gas separation membranes by plasma polymerization with fluoro compounds

Plasma polymerization coatings were applied for the preparation of gas separation membranes. Mainly fluoro compounds were used as coating materials. The membranes showed good separation characteristics with high flux for gaseous systems. The plasma polymerization composite parameter given by W/FM plays an important role in obtaining excellent separation characteristics. The correlation between the conversion rate DR/FM, where DR is the deposition rate of plasma polymer, and W/FM is useful to consider the plasma polymer character under the different plasma polymerization conditions (discharge power W and monomer flow rate F). The proper conditions for membrane preparation lie in the intermediate region between the region in which the monomer flow rate is deficient and that in which the discharge power is deficient. Furthermore, the plasma polymerization coatings with the higher molecular weight monomer gave the higher separation characteristics. Plasma polymer composite membranes in this study showed superiority for the molecular sieve type of separation over the solution-diffusion type of separation.     

聚醚砜超滤膜的亲水化改性研究进展

聚醚砜(PES)超滤膜的疏水性导致在处理水的过程中驱动力高、易污染,需要亲水化改性．调研了PES超滤膜的亲水化改性方法：物理共混、化学共聚、表面物理吸附、表面化学处理、表面接枝等．围绕亲水化综述了PES超滤膜亲水改性的研究进展．