辐射接枝法制备离子交换膜的研究现状

聚合物离子交换膜有多种制备方法，其中高分子材料辐射引发接枝功能性单体是一种文献中屡见报道且简单可行的方法．通过在不同聚合物基体上接枝各种类型的单体，可以改变接枝膜的电化学性能、物理化学等性能．丈中详细介绍了不同的高分子基材辐射接枝各类单体制备聚合物离子交换膜的研究现状．     

辐射接枝法制备动态超疏水棉织物及其性能研究

以棉织物为基材,利用γ-射线辐射引发甲基丙烯酸十二烷基酯(LMA)接枝聚合,使聚苯乙烯(PS)纳米微球通过接枝链以共价键固定到棉织物上,从而在棉织物表面构筑低表面能的纳米尺度粗糙结构,获得低滚动角的动态超疏水棉织物.傅里叶变换红外光谱(FTIR)分析证明通过辐射接枝,在棉织物上存在PLMA接枝链和PS纳米微球.扫描电子显微镜(SEM)表征证明了PS纳米微球的固定使得棉织物表面呈现纳米尺度的粗糙结构.接触角测试结果证明所获棉织物具有超疏水性能,且相对于仅接枝LMA的改性棉织物,PS纳米微球的固定可以显著降低水滴的滚动角,实现动态超疏水的效果.通过抗弯刚度的测量表征了改性前后棉织物的柔软度,结果表明辐射接枝方法对棉织物的柔软度改变不大,不影响穿着性能.     

辐射接枝医用水凝胶的研究Ⅰ.硅橡胶辐射接技N-乙烯基吡咯烷酮

采用填加SiO_2增强的甲基乙烯基硅橡胶混炼压片。通过~(60)Co-γ射线引发辐射硫化,利用共辐照方法,将N-乙烯基吡咯烷酮接枝到该硅橡胶上,制备了高纯度医用水凝胶。本文较系统地研究了接枝单体浓度、辐照剂量率、剂量、温度和接枝试片厚度等因素对接枝共聚反应的影响。建立了接枝速率与单体浓度、剂量率之间的动力学关系式:R_g=k[M]~(4/5)D~(1/2)。讨论了反应机制和接枝区域。     

辐射接枝技术在吸附材料制备中的应用

辐射接枝技术已成为高分子材料改性的重要方法之一.和传统化学接枝方法相比,辐射接枝技术具有操作简单,易于控制,不限制基材和单体等优点,近年来已被广泛应用于吸附材料的制备.采用辐射接枝技术制备的吸附材料,其功能团主要分布在基材表面,具有单体用量少,成本低,吸附脱附速度快,功能团利用率高,选择性好的特点.本文综述了近年来辐射接枝技术在制备选择性吸附材料方面的最新研究进展,包括对重金属、放射性核素、半金属、非金属、稀土元素、贵金属和染料等不同污染物吸附材料的合成及其应用,并对辐射接枝技术在制备吸附材料中的研究方向进行了展望.     

紫外辐射接枝法修饰聚乳酸表面及其细胞相容性

通过紫外辐射接枝在聚乳酸膜表面引入聚丙烯酸的方法使聚乳酸材料表面的亲水性和细胞相容性得到改善,研究了各种处理条件对材料表面的羧基密度、表面形态和表面接触角的影响,同时还考察了紫外辐射接枝聚丙烯酸的聚乳酸表面的成骨细胞相容性.红外光谱分析和羧基密度测定结果表明:通过紫外光引发接枝,聚丙烯酸被成功接枝到聚乳酸表面,而且接枝密度受接枝时间和聚丙烯酸质量分数的影响很大.接触角和原子力显微镜研究结果表明:接枝聚丙烯酸后的聚乳酸表面的亲水性和粗糙度明显增加,能够促进成骨细胞的生长.     

PVDF粉体60^Co-γ，射线共辐射接枝NVP

采用60^Co-γ射线共辐射接枝聚合法,将N-乙烯基-2-吡咯烷酮（NVP）接枝到聚偏氟乙烯（PVDF）粉体上,以改善其亲水性。考察了反应过程中各种因素对接枝率（FI）G）的影响,并对接枝产物进行了表征。结果表明：通过60^Co-γ射线共辐射可有效实现NVP在PVDF粉体上的接枝。当辐射吸收剂量为40kGy,阻聚剂六水合硫酸亚铁铵浓度为3mmol／L,NVP体积分数为15％,甲醇为溶剂时,rDG达到18．6％,且接枝后PVDF粉体的亲水性明显提高。     

PTFE辐射接枝对苯乙烯基三甲氧基硅烷制备质子交换膜

采用聚四氟乙烯(PTFE)膜室温下共辐射接枝单体p-苯乙烯基三甲氧基硅烷(StSi),之后经磺化和水解缩聚制备了含有亲水性的—Si—O—Si—交联结构和Si—OH基团的质子交换膜.研究了溶剂、吸收剂量、吸收剂量率以及单体浓度等参数对接枝率的影响,并对质子交换膜的离子交换容量(IEC)、吸水性、尺寸稳定性及电导率等性能进行了分析.结果表明,实验条件下接枝率随吸收剂量和单体浓度增加而增加,采用3mol·L-1的单体浓度减少均聚物;吸收剂量率为10～43Gy·min-1时,接枝率随剂量率变化不明显;以甲苯做溶剂可获得较高接枝率并保持膜的机械强度;IEC值、吸水性和电导率随接枝率增加而增大,是—SO3H、—Si—O—Si—交联结构和Si—OH基团共同作用的结果.接枝率72.5%时膜的IEC值为1.53mmol·g-1,高于Nafion117(0.89mmol·g-1),90℃吸水率为63%,尺寸稳定(优于Nafion117),质子电导率达1.5×10-2S·cm-1,获得了低于Nafion117的甲醇透过性,接枝率50.1%时甲醇透过系数0.82×10-6cm2·s-1.     

辐射接枝共聚合反应及其在有机生物医用材料制备中的应用

γ-射线辐射高分子材料表面接枝共聚合是一种绿色的、重要的有机生物材料合成制备方法. 综述了γ-射线辐射接枝共聚反应的原理、特点, 阐述了预辐射接枝共聚和共辐射接枝共聚的方法, 介绍了当前γ-射线辐射接枝共聚反应在改善有机生物医用材料的表面亲水性、生物相容性等方面的应用. 对辐射接枝共聚合制备功能药物载体研究进行了简要介绍.     

PVDF粉体^(60)Co-γ射线共辐射接枝NVP北大核心CSCD

采用60Co-γ射线共辐射接枝聚合法,将N-乙烯基-2-吡咯烷酮(NVP)接枝到聚偏氟乙烯(PVDF)粉体上,以改善其亲水性。考察了反应过程中各种因素对接枝率(rDG)的影响,并对接枝产物进行了表征。结果表明:通过60 Co-γ射线共辐射可有效实现NVP在PVDF粉体上的接枝。当辐射吸收剂量为40kGy,阻聚剂六水合硫酸亚铁铵浓度为3mmol/L,NVP体积分数为15%,甲醇为溶剂时,rDG达到18.6%,且接枝后PVDF粉体的亲水性明显提高。     

聚全氟乙丙膜电子束引发预辐射接枝AA和SSS制备阳离子交换膜的研究

利用电子束引发预辐射接枝技术,在聚全氟乙丙烯(FEP)薄膜上接枝丙烯酸(AA)和对苯乙烯磺酸钠(SSS),制备一种含羧酸基团和磺酸基团的阳离子交换膜,详细研究了反应温度、单体总浓度、pH值变化、辐照气氛及添加剂对接枝率的影响规律,明确了实验条件与接枝率的对应关系。FTIR测试证明了接枝产物是全氟乙丙烯和丙烯酸、对苯乙烯磺酸钠的接枝共聚物。     

193 nm激光引发PET表面的化学接枝

将聚对苯二甲酸乙二醇酯[Poly(ethylene terephthalate), PET]材料置于氨气气氛中, 利用激光光子同时激发材料表面及氨气形成自由基, 用激光引发反应并促进氨基在材料表面的接枝. 改性后的测试结果表明, 材料表面粗糙度没有显著变化, 但水接触角的减小表明表面化学结构发生了某种变化. 傅里叶变换红外光谱(FTIR/ATR)图谱在3352和1613 cm-1处出现了新的氨基吸收峰, 证实了表面接枝了氨基. 同时X射线光电子能谱(XPS)也证明了材料表面C—N键的存在, 其C1s结合能为285.5 eV, N1s为398.9 eV. 飞行时间二次离子质谱(Tof-SIMS)也检测到含氨基的分子碎片, 其碎片成像图显示接枝仅发生在激光辐照部位. 实验结果表明, 激光能在生物材料表面进行局部区域的选择性接枝.     

苯酰亚胺结构对PET阻燃抗熔滴及抑烟的贡献

通过本体聚合方法合成了一系列侧链含苯酰亚胺结构的聚对苯二甲酸乙二酯(PET)共聚酯.研究发现,苯酰亚胺单元的引入不仅提高了共聚酯的玻璃化转变温度(T_g)和高温成炭性,并且大大降低了共聚酯高温下的热分解速率.随着苯酰亚胺含量的增加,共聚酯表现出更高的氧指数(LOI)值和更好的阻燃抗熔滴效果.锥形量热测试结果表明,苯酰亚胺结构的引入可以有效地降低共聚酯的峰值热释放速率(p-HRR)、峰值烟释放速率(p-RSR)和总烟释放量(TSR).通过对纯PET和共聚酯燃烧测试后残炭的结构和形貌分析,发现苯酰亚胺结构有助于共聚酯形成石墨化程度更高的致密炭层,这些炭层起到隔热隔氧和抑制有机可燃烟气挥发的作用,在不引入传统阻燃剂的情况下,赋予共聚酯很好的本征阻燃性及抑烟性.     

Radiation-induced grafting of perfluorinated vinyl ether into fluorinated polymer films

We report herein the first successful grafting of perfluorinated vinyl ether monomer into base polymer films by simultaneous radiation method. 2-Bromotetrafluoroethyl trifluorovinyl ether (BrTFF) could be grafted into poly(ethylene-co-tetrafluoroethylene) (ETFE) films by γ-rays irradiation at room temperature. The grafting yield increased linearly with an increase in the dose up to 1400 kGy. The required dose for a satisfactory grafting yield, such as 20%, was as high as ca. 400 kGy probably due to low polymerization reactivity of fluorinated monomers. However, the solvent and catalyst had no positive influence for improving the grafting yield. FTIR spectra and SEM-EDS testified that BrTFF was successfully grafted into ETFE films homogeneously in the perpendicular direction. The thermal analysis of the grafted films further indicated no phase separation between poly(BrTFF) grafts and ETFE films, probably owing to high compatibility of the fluorinated grafts and base polymers.     

超临界CO2固相接枝法制备马来酸酐改性聚丙烯的分级与表征

采用不同溶剂的连续萃取法,对超临界CO2固相接枝法制备的马来酸酐改性聚丙烯(PP-g-MAH)进行分级并获得了等规度不同的级份。对所得级份用傅立叶变换红外光谱仪(FT-IR)、差示扫描量热仪(DSC)和偏光显微镜(POM)表征,结果表明:接枝率不同的级份所对应的材料性能存在明显差异,接枝反应更易发生在非晶区或结晶不完善的区域,但接枝率越高的PP-g-MAH接枝越均匀。     

低密度聚乙烯的接枝改性

低密度聚乙烯的接枝改性;低密度聚乙烯;甲基丙烯酸缩水甘油酯;非等温结晶Avrami方程     

Improving the flame retardancy of PET fabric by photo-induced grafting

Photo-induced surface grafting with glycidyl methacrylate (GMA) as monomer in association with a pad-curing treatment by using a flame retardant (FR) solution which contains 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) and sulfamic acid (H₂NSO₃H) has been used to improve the fire performance of PET fabric in this study. The effects of initiator concentration, monomer concentration and the irradiation time on the grafting percentage were investigated. The chemical structure of grafted surface of the PET fabric was characterized by an attenuated total reflection-infrared (ATR-IR) spectroscopy. The fire performance was evaluated by the LOI and the vertical flammability tests, and the results indicate that the photo grafting treatment could improve the flame retardancy and dripping resistance of PET fabric. Thermal behaviour of treated PET fabric samples was investigated by thermogravimetric (TG) and differential scanning calorimetric (DSC). The morphology of the sample char residue was also investigated by scanning electron microscope (SEM).     

Surface Modification of Polypropylene Non-Woven Fabrics by Atmospheric-Pressure Plasma Activation Followed by Acrylic Acid Grafting

Polypropylene (PP) non-woven fabrics have been activated by an atmospheric-pressure plasma treatment using surface dielectric barrier discharge in N₂ and ambient air. Subsequently, the plasma activated samples were grafted using catalyst-free water solution of acrylic acid. Surface properties of the activated and polyacrylic acid post-plasma grafted non-woven were characterised by scanning electron microscopy, Fourier transform infrared spectroscopy, electron spin resonance spectroscopy, surface energy and dyeability measurements. The grafted non-woven exhibit improved water transport and dyeing properties. The plasma activation in nitrogen plasma gas was more efficient than in air.     

Synthesis, Characterization, and Catalytic Properties of Ti, V, and Zr-HMS Prepared by Metallocene Grafting

Ti, V, and Zr-HMS molecular sieves were prepared by grafting the respective metallocene onto the pure silica HMS, XRD, N₂-physisorption, TEM, UV-Vis spectroscopy and elemental analysis were performed to characterize the samples prepared. The XRD patterns of the metal-grafted samples exhibited well-defined (100) reflections, and the intensity remained almost constant as with pure silica HMS. Surface area, hysteresis loop in N₂ adsorption isotherms and N₂ volume adsorbed decreased after metal grafting. The order of catalytic activity for 2,6-di-tert-butylphenol (2,6-DTBP) oxidation using H₂O₂ was V-HMS (91.5 % conversion) Ti-HMS(20.3 %) Zr-HMS(8.4 %). Metal leaching was detected for all the grafted samples in the reaction media; V-HMS(22 wt.%) Zr-HMS(3 wt.%) > Ti-HMS(2 wt.%). For V-HMS and Zr-HMS, further reaction after catalyst filtration indicated significant contribution to the reaction by the dissolved species.     

Influence of surface activation by plasma and nanoparticle adsorption on the morphology, thermal stability and combustion behavior of PET fabrics

Plasma surface activation at different process parameters (namely, power and etching time) has been combined with nanoparticle adsorption (i.e., a natural montmorillonite) in order to improve the thermal stability and flame retardancy of PET fabrics. Scanning electron microscopy coupled to elemental analysis has put in evidence a direct relationship between the distribution of nanoparticles on fibers and process parameters. The presence of the above nanoparticles affects the thermal stability of fabrics in air, as assessed by thermogravimetric analysis: a delay of the mass loss process has been observed for the treated samples.Combustion behavior has been investigated by cone calorimetry: plasma activated fabrics have shown a remarkable improvement in terms of time to ignition (up to 104%) and a slight reduction of the heat release rate (ca. 10%) as compared to neat PET.     

共聚法和嫁接法制备二茂铁杂化介孔材料及其催化性能

 以桥联硅氧烷 1,1'-双[(2-三乙氧基硅基) 乙基]二茂铁 (BTEF) 和正硅酸乙酯为前驱体, 以十六烷基三甲基溴化铵为结构导向剂, 采用共聚法制备了二茂铁功能化的周期介孔有机硅烷材料 (PMO-Fc). 同时以 BTEF 为修饰剂, 以甲苯为分散剂, 采用嫁接法制备了 Fc-MCM-41 杂化介孔材料. 采用 N2 物理吸附、X 射线衍射、透射电镜和红外光谱等手段对材料进行了表征, 评价了其催化苯羟化反应活性. 结果表明, PMO-Fc 具有有序的二维六方形孔道结构, 较大的比表面积和孔体积, 在苯羟化反应中表现出比 Fc-MCM-41 更高的催化活性, 苯酚的选择性和收率分别为 65.3% 和 20.2%.