Atom transfer radical polymerization (ATRP): A versatile and forceful tool for functional membranes

The progress in atom transfer radical polymerization (ATRP) provides an effective means for the design and preparation of functional membranes. Polymeric membranes with different macromolecular architectures applied in fuel cells, including block and graft copolymers are conveniently prepared via ATRP. Moreover, ATRP has also been widely used to introduce functionality onto the membrane surface to enhance its use in specific applications, such as antifouling, stimuli-responsive, adsorption function and pervaporation. In this review, the recent design and synthesis of advanced functional membranes via the ATRP technique are discussed in detail and their especial advantages are highlighted by selected examples extract the principles for preparation or modification of membranes using the ATRP methodology.     

新型特种工程塑料聚芳醚砜酮和聚芳醚砜热分解动力学及寿命预测

采用逐步聚合方法制备了新型特种工程塑料含二氮杂萘酮结构的聚芳醚砜酮［PPESK(1/1)］和聚芳醚砜(PPES).利用热失重(TGA)分析仪,氮气氛围中,多重加热扫描速率下的不定温法对PPESK(1/1)及PPES进行热分解动力学研究.根据Satava法得出,聚合物PPESK(1/1)分解反应机理为随机成核和随后生长,反应级数n=1;而聚合物PPES的热分解反应机理为相界面反应模式,反应级数n＝2.同时采用经典动力学方程Friedman、Kissinger-Akahira-Sunose(KAS)及Ozawa方程计算了热分解动力学参数(E_a,lnZ).重点考察升温速率、不同酮/砜比对PPESK（1/1）热稳定性影响,并且根据得到的动力学参数推测其在高温使用条件下的使用寿命及对热分解反应过程中“动力学补偿效应”（KCE）进行分析.     

聚醚砜酮基炭膜的制备及其气体分离性能

采用浸渍涂膜法,以商用聚醚砜酮(PPESK)为前驱体制备了管式复合炭膜,考察了涂膜次数、改性剂及其加入量对所制备炭膜的气体分离性能的影响.结果表明,随着涂膜次数增多,气体分子的渗透速率逐渐减小而选择性呈增大趋势;加入改性剂后的复合炭膜渗透速率和分离系数均有不同程度的提高,表明改性剂不仅改善了涂膜液与支撑体之间的复合效果、减少涂膜次数,同时也促进了气体渗透速率的提高.利用扫描电镜对复合炭膜的微观形貌进行观测,可以看出,复合炭膜由支撑体和分离膜层2部分组成.膜表面很致密均匀,无明显缺陷,分离层薄而均一,厚度在5μm左右,且与支撑体结合紧密.     

Performance control of asymmetric poly(phthalazinone ether sulfone ketone) ultrafiltration membrane using gelation

We studied the influence of the gelation conditions on the formation kinetics of the polyphthalazine ether sulfone ketone (PPESK) membrane via wet phase inversion process experimentally and theoretically. Membrane formation and its morphology were first observed with an online optical microscope - CCD camera system. The resulting membranes prepared under various gelation conditions were then characterized by the gelation parameter, optical microscope, and SEM. Lastly, the relationship between the final membrane structure/permeation properties and the gelation parameter was discussed extensively. The results showed that both the gelation rate and the membrane flux increased dramatically as the gelation temperature increased. Moreover, the membrane structures became loose, and the porosity of membrane increased. Different non-solvent could change the solubility parameter between the polymer and the non-solvent, and thus the gelation rate greatly. With the increasing number of carbons in non-solvent, the gelation rate became slow, and the membrane gradually changed from a finger structure into a sponge structure. Adding NMP into the non-solvent changed the difference in the chemical potential and the solubility parameter between the polymer solution and the non-solvent, which in turn changed the gelation rate of polymer solution greatly. With the increasing concentration of NMP in non-solvent, the gelation rate became very slow and sponge structures formed with the non-solvent system of 80% NMP. A novel conclusion could be made that we could control the flux and reject of membrane just by changing the mean diffusion coefficient of skin, D, and the diffusion coefficient of skin, D1, in the process of membrane formation. This work was presented at 13 ^th YABEC symposium held at Seoul, Korea, October 20–22, 2007.     

Mechanical and morphological properties of epoxy resins modified by poly(phthalazinone ether sulfone ketone)

A series of blends have been prepared by adding a novel thermoplastic poly(phthalazinone ether sulfone ketone) (PPESK) in varying proportions to diglycidyl ether of bisphenol A epoxy resin (DGEBA) cured with p‐diaminodiphenylsulfone (DDS). All the blends showed two‐phase structures characterized by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Addition of the PPESK resulted in great enhancement of glass transition temperatures (T_g) both in the epoxy‐rich phase and in the PPESK‐rich phase by reason of the special structure of PPESK. There was moderate increase in the fracture toughness as estimated by impact strength. Fracture mechanisms such as crack deflection and branches, ductile microcracks, ductile tearing of the thermoplastic, and local plastic deformation of the matrix were responsible for the increase in the fracture toughness of the blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

甲酰胺对PES及PPESK相转化非对称膜结构与性能的影响

采用凝胶相转化法,以聚醚砜(PES)、杂萘联苯聚芳醚砜酮(PPESK)为膜材料,N,N-二甲基乙酰胺(DMAc)、N-甲基吡咯烷酮(NMP)为溶剂,通过改变铸膜液中非溶剂添加剂甲酰胺的含量,在平板刮膜机上制备了一系列超滤膜。考察了甲酰胺对铸膜液黏度、膜结构和性能的影响,对PES/DMAc和PPESK/NMP铸膜液体系中甲酰胺的作用规律进行了研究。     

NaX分子筛填充PDMS膜对丙烯／丙烷分离性能的研究

采用了对丙烯／丙烷有吸附选择性的NaX型分子筛填充PDMS,通过真空涂敷法涂敷至PPESK／PEI中空纤维基膜上,制备了NaX／PDMS中空纤维复合膜。研究了固化温度、固化时间、涂敷时间（抽真空时间）、NaX填充含量对丙烯／丙烷分离性能的影响。实验结果表明,室温下,在固化温度80℃,固化时间80min,涂敷时间6min,NaX填充含量30％时,复合膜对丙烯,丙烷的分离性能最佳,分离系数达到2．68。为丙烯／丙烷的分离提供了一种新的可能性,开辟了一条研制高性能丙烯／丙烷分离有机膜的新途径。     

Porous honeycomb films prepared from poly (phthalazionone ether sulfone ketone) (PPESK) by self‐organization method

Preparation of honeycomb‐patterned films from Poly (phthalazionone ether sulfone ketone) (PPESK), one of the thermally stable polymers, in a humid atmosphere was reported in this article. The mechanism of forming honeycomb structure was discussed. Some influences, such as the effect of PPESK concentration and the atmosphere humidity were tested. Furthermore, the thermal stability of honeycomb‐patterned films was also investigated, and it was shown that the honeycomb structures could be stable existed at 300°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

工艺参数对静电纺PPESK微纳米纤维膜性能的影响

通过溶液静电纺丝法制备了聚芳醚砜酮(PPESK)微纳米纤维膜,借助于扫描电子显微镜和拉伸试验机分别对纤维膜的形貌和力学性能进行了表征,用正交试验对微纳米纤维膜的制备工艺参数进行了优化。结果表明,在给定条件下,对纤维直径影响由大到小的工艺参数依次为:溶液浓度给料速度纺丝电压。纤维直径最小的工艺条件为:溶液浓度19%,纺丝电压10 k V,给料速度为0.04 mm/min。对纤维膜拉伸强度影响由大到小的工艺参数依次为:给料速度纺丝电压溶液浓度。纤维拉伸强度最大的工艺条件为:溶液浓度24%,纺丝电压14 k V,给料速度0.04 mm/min。     

连续纤维增强PPESK树脂基复合材料的界面性能

用SEM观察了复合材料的微观断面结构,用横向拉伸强度和层间剪切强度表征玻璃纤维(GF)、T700碳纤维(CF)、芳纶纤维(F-12)增强PPESK树脂基复合材料的界面性能,研究了界面性能对三种复合材料耐湿热性能的影响.结果表明,T700/PPESK和F-12/PPESK复合材料的界面粘接性能均优于GF/PPESK复合体系.三种纤维复合材料的破坏机理不同:玻璃纤维发生纤维与树脂的界面脱粘破坏,碳纤维复合材料在破坏时,树脂与纤维并没有完全脱粘,破坏发生在树脂内;而芳纶纤维复合材料的破坏总伴随着纤维本身横向的撕裂破坏.三种复合材料体系均具有较低的吸湿率和良好的耐湿热性能,T700/PPESK复合材料在湿热条件下的性能保持率最高.