高聚物辐射接枝的发展及应用

综述高聚物辐射接枝的分类和基本原理，讨论接枝体系主要的影响因素和一些提高接枝率的方法，以及介绍近年的研究成果，包括一些新型添加剂和目前辐射接枝高聚物的应用。进而讨论高分子材料辐射接枝方法研究发展方向和应用，并认为这种方法在高聚物改性方面具有广阔的应用前景。     

预辐射接枝法制备FEP-g-PSSA/AA膜

采用γ射线预辐射接枝方法制备了FEP—g—PSSA／AA膜，反应制得的接枝膜是一种含氟磺酸型质子交换膜。系统研究了影响接枝反应的阻聚剂用量、膜的厚度、单体摩尔比及总摩尔浓度变化等因素。结果表明，丙烯酸（Acrylic acid，AA）与苯乙烯磺酸钠（Sodium styrene sulfonate，SSS）对全氟乙丙烯（Polytetranuoroethyleneco-hexanuoropropylene，FEP）的接枝率几乎不受膜厚度变化的影响，而且全氟乙丙烯（FEP）辐照后放置三个月再进行接枝反应，接枝率也几乎没有变化。     

用辐射接枝法对HDPE膜进行功能化改性

利用预辐射接枝技术,在聚乙烯膜上接枝苯乙烯磺酸钠（ＳＳＳ）、苯乙烯三甲基氯化铵（ＶＢＴＡＣ）等具有离子交换性能的单体,研制出具有抗菌性能的离子交换膜,并且使得原先增水性的基膜转变为亲水性较好的膜。通过实验,掌握了膜的接枝工艺,并对膜接枝过程、结构特征、经性能有较多的了解。从各个角度对膜的亲水性能作了定量研究,提出了水合数与表面自由能的计算方法。对几种膜的抗菌性能进行了评价。确定了ＶＢＴＡＣ膜作为抗     

辐射接枝制备电池隔膜研究现状

电池隔膜的制备方法有许多种，其中聚合物膜辐射引发接枝功能型单体是电池隔膜制备的重要手段之一。通过辐射接枝不同的单体，可以赋予聚合物薄膜特定的电化学和物理化学等性能，使其符合不同种类电池对隔膜的技术要求。本工作详细介绍了辐射接枝法制备电池隔膜的研究和应用状况。     

聚丙烯辐射接枝硅烷的制备及表征

采用γ射线固相辐射接枝方法,在聚丙烯粉末表面接枝乙烯基三甲氧基硅烷制备PP—g—Si。研究了不同吸收剂量对聚丙烯接枝率的影响,发现加入第二单体苯乙烯可以提高其接枝率到4．2％。吸收剂量的提高可显著提高硅烷在聚丙烯上的接枝量,使得接枝聚丙烯水解后物理交联凝胶含量增加。由于γ射线辐射会引起聚丙烯分子链断裂,经固相辐射接枝聚丙烯的熔体流动速率会变大。利用DSC研究了产物PP—g—Si的熔点随辐射吸收剂量的变化,同时以XRD研究了PP-g—Si的结晶形态。     

聚四氟乙烯膜辐射接枝反应条件的研究

采用了共辐射接枝技术，在室温下将苯乙烯接枝到聚四氟乙烯薄膜上，合成了辐射接枝膜。研究了溶剂种类、单体浓度、辐射剂量以及剂量率等因素对接枝反应的影响。结果表明，单体浓度和辐射剂量率是反应的主要影响因素，两者对接枝反应速率的影响指数分别为1．2和0．4。     

辐射法制备含氟磺酸型质子交换膜

含氟磺酸型质子交换膜是一类具有高热稳定性、化学稳定性及良好机械性能的离子交换膜，具有极其广阔的应用前景。采用辐射法制备了一种含氟磺酸型质子交换膜，分别测试了该膜的抗拉强度、面电阻、吸碱率等物理化学性能，通过扫描电镜观察了其表面形貌并对其在质子交换膜燃料电池中的应用进行了初步研究。     

Observation of H/D isotope effects on polymer electrolyte membrane fuel cell operations

The hydrogen isotope effects upon operation of a polymer electrolyte membrane fuel cell have been observed. The deuterium concentration in the exhaust hydrogen gas from the cell was found lower than that of the hydrogen gas fed to the cell, which indicated that the heavier isotope of hydrogen was preferentially oxidized at the anode. The overall hydrogen isotopic separation factor between the oxidized and non-oxidized hydrogen ranged from 3.46 to 3.99 and increased with decreasing flow rate of the feed gas or increasing rate of hydrogen utilization.     

Radiolytic preparation of ETFE and PFA based anion exchange membranes for alkaline fuel cell

In this study, a versatile monomer, vinylbenzyl chloride (VBC) was radiolytically grafted onto a partially fluorinated ETFE and perfluorinated polymer PFA films. The VBC grafted films were treated with trimethylamine to prepare the alkaline anion exchange membranes (AAEMs). No significant differences in the ion exchange capacities and water uptakes were observed between the ETFE and PFA based AAEMs with similar degree of grafting (DOG). However, the distribution patterns of the graft chains over the cross-section of the ETFE and PFA based AAEMs were found to be quite different; the even distribution was observed from the ETFE based AAEMs while the uneven distribution was observed from the PFA based AAEMs. It was also found that the PFA based AAEMs have the higher ionic conductivity and chemical stability, compared to the ETFE based AAEMs.     

Preparation of composite polymer electrolytes by electron beam-induced grafting: Proton- and lithium ion-conducting membranes

Two classes of composite polymer electrolyte membranes, one conducting lithium ions (Li⁺) and the other conducting protons (H⁺) were prepared using simultaneous electron beam-induced grafting. Porous poly(vinylidene fluoride) (PVDF) films were impregnated with styrene and subjected to electron beam (EB) irradiation to obtain polystyrene (PS) filled PVDF precursor films that were subsequently treated with either chlorosulfonic acid/1,1,2,2-tetrachloroethane mixture to obtain H⁺-conducting composite membranes or LiPH₆/EC/DEC liquid electrolyte to obtain Li⁺-conducting composite membranes. The properties of the obtained membranes were evaluated using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and AC impedance measurements. The obtained membranes were found to achieve grafting content up to 46% with superior Li⁺-conductivity of 1.91 × 10⁻³ S/cm and H⁺-conductivity of 5.95 × 10⁻² S/cm. The results of this work show that simultaneous radiation-induced grafting with EB is a promising method to prepare high quality ion-conducting membranes for possible use in fuel cells and lithium batteries.     

聚合物表面辐射接枝改性研究进展

辐射接枝是聚合物表面改性的重要方法之一。本工作讨论了接枝单体和基材的性质、溶剂、酸、阻聚剂以及其它添加剂对聚合物辐射接枝反应的影响,介绍了利用光学显微镜、扫描电子显微镜原子力显微镜、凝胶色谱、X射线光电子能谱、拉曼光谱、红外光谱等所取得的接枝条件对接枝层的形态结构及接枝链长短研究结果。对近年来出现的能精确控制接枝链分子量和结构的活性聚合方法也作了简单介绍。     

Radiation synthesis and characteristics of PTFE-g-PSSA ion exchange membrane applied in vanadium redox battery

Radiation-induced grafting of styrene onto polytetrafluoroethylene （PTFE） membranes was studied by a simultaneous irradiation technique. Grafting was carded out using γ-radiation from a ^60Co source at room temperature. Effects of absorbed dose, atmosphere, dose rate, and the concentration of initial monomer on the degree of grafting （DOG） were investigated and the most appropriate grafting condition was obtained. Subsequently, sulphonation of the grafted PTFE membrane （PTFE-g-PS） was carded out and a series of ion exchange membranes （PTFE-g-PSSA） was prepared. Further characterizations of FTIR, TGA, and SEM testified that grafting and sulphonation of the membranes were successfully processed; moreover, grafting of styrene not only occurred in the surface of PTFE membrane, but also in the micropores of the membrane. Ion exchange capacity （IEC） and conductivity were found increase with the grafting yield. The results suggest that at a low dose, such as 17 kGy, the ion exchange membrane （IEM） which will be suitable for vanadium redox battery （VRB） use can be obtained.     

碳纳米管/聚丙烯酰胺复合水凝胶的制备及性能

通过活度2.072×1015 Bq、剂量率2 k Gy·h-1的钴-60进行辐照接枝和辐照交联两步法制备了碳纳米管复合水凝胶。使用傅里叶红外光谱(Fourier Transform Infrared spectroscopy,FTIR)、热释重分析(Thermal gravimetric analysis,TGA)、透射电子显微镜(Transmission electron microscope,TEM)、X射线衍射(X-ray diffraction,XRD)、BET比表面积(Brunauer-Emmett-Teller Specific Surface Area)等方法对样品进行了表征。结果显示,改性后的碳纳米管(Carbon nanotubes,G-CNTs)的管壁出现了明显的链段,其傅里叶红外光谱在1 452 cm-1和1 726 cm-1处多了两个吸收峰;碳纳米管复合水凝胶的BET值(30 m2·g-1)比聚丙烯酰胺水凝胶的(12 m2·g-1)提高了一倍多。实验结果表明丙烯酸被成功接枝到CNTs的管壁上。G-CNTs在凝胶中均匀分散,并提高了复合水凝胶的比表面积和机械强度。     

Solid polymer electrolyte water electrolysis systems for hydrogen production based on our newly developed membranes, Part I: Analysis of voltage–current characteristics

A new solid polymer electrolyte water electrolysis system was constructed using an original proton exchange membrane (PEM). The highly proton-conductive PEM was prepared by the γ-ray-induced post-grafting of styrene into a crosslinked-polytetrafluoroethylene (PTFE) film and subsequent sulfonation. The water vapor to be electrolyzed was controlled at a constant relative humidity and introduced into the cell at different temperatures up to 80 °C. As the cell voltage was increased, the current became higher; the maximum current was 50 mA/cm² at 2.5 V at a temperature of 80 °C, corresponding to a hydrogen production rate of 0.38 mL/min cm² in the normal state (25 °C, 1 atm). The voltage–current characteristics were analyzed with a theoretical model based on Butler–Volmer kinetics for electrodes and transport resistance through the PEM. This analysis revealed that the anode exchange current density and interfacial resistance determined the electrolysis performance.     

辐射引发悬浮聚合制备香草醛分子印迹聚合物

为提高香草醛的提取和使用价值,以香草醛为模板分子,甲基丙烯酸(MAA)为功能单体,二甲基丙烯酸乙二醇酯(EDMA)为交联剂,采用紫外辐照引发悬浮聚合制备了香草醛分子印迹聚合物(Molecularly imprinted polymer,MIP)微球。利用扫描电镜、等温吸附实验、特异性吸附实验等考察了聚合物的形貌及粒径大小、吸附分离等性能。结果表明,辐照引发悬浮聚合制备的印迹聚合物具有较均匀的粒径分布和良好的等温吸附性能,并且表现出良好的特异吸附性能,MIP对于香草醛及邻香草醛的分离因子为2。     

PVDF-g-N-IPAAm温敏膜的辐射合成及性能研究

用γ共辐射接枝的方法，将N-异丙基丙烯酰胺（N-isopropylacrylamide，N-IPAAm）接枝到聚偏氟乙烯（Poly vinylidene fluoride，PVDF）微孔膜上。通过扫描电子显微镜（Scanning electron microscopy，SEM）、傅立叶转换红外光谱（Fourier transform infrared，FT-IR）和X光电子能谱（X-ray photoelectron spectroscopy，XPS）技术对微孔膜的接枝情况进行了表征，并同时通过接触角、电导和水通量测试研究了接枝微孔膜的表面改性、渗水性能和温敏性能。结果表明，通过共辐射接枝方法成功将N-IPAAm接枝到了PVDF微孔膜的表面及孔内，由此改善了微孔膜的亲水性，并使其具有明显温度敏感性能，即在低临界溶解温度（Lower cridcal soludon temperature，LCST）上下其微孔膜的水通量发生显著变化。