辐射接枝制备离子交换膜

一、引言通常离子交换膜是指有离子交换基团的高分子聚合物薄膜。不论异相膜或均相膜按照离子交换基团引入的不同途径,它的合成路线可分两类:一类是先合成带有离子交换基团的单体然后通过聚合反应或缩合反应聚合成高分子;另一类是先将单体聚合成高分子聚合物然后通过高分予化学反应引入离子交换基团。将各种带高子交换基团的单体辐射接枝于各种聚合物薄膜或粉末以制备均相离子交换膜的方法属于后一类。辐射接枝是在高分子薄膜上引发高     

无光敏剂光引发亲水性单体在嵌段聚醚氨酯膜上接枝聚合的研究

<正> 嵌段聚醚氨酯(SPEU)是一类应用广泛的医用高分子材料。用亲水性单体进行表面接枝改性,已有不少研究,接枝聚合方法有铈盐引发、辐射引发以及光敏引发等。 本文研究一种新的接枝方法,不加光敏剂,用紫外光照射,直接引发亲水性单体接枝于SPEU膜上、接枝的单体有丙烯酰胺(AAM)与N,N-二甲基丙烯酰胺(DMAA),从接枝前后膜的性能变化可以证实接枝反应的发生。文中研究了反应条件与单体结构对接枝率的影响,并通过模型化合物,对接枝部位进行了研究。     

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.     

聚四氟乙烯强酸性阳离子交换纤维的制备研究

采用共辐射引发将苯乙烯接枝到聚四氟乙烯(PTFE)纤维上,然后磺化制备出强酸性和超强酸性离子交换纤维,接枝率随苯乙烯单体浓度和辐射剂量增加而提高,随辐射剂量率的增加而降低,当接枝率为20%左右时,PTFE-co-St-SO3H离子交换纤维的Hammett酸度函数低于-11.99,呈现出超强酸性。     

植物纤维素辐射接枝改性研究与应用

本文报道了天然高分子材料——植物纤维素辐射接枝改性研究的现状与前景。讨论了纤维素分子结构与辐射稳定性。纤维素辐射接枝共聚的优点、基本方法、接枝机理、添加剂效应等。评述了纤维素辐射接枝产物在改善其抗皱、防水(吸水)防霉、染色、离子交换等性能以及实际应用的可行性和前景。     

等离子体引发聚丙烯接技苯乙烯共聚物的合成及性能

将等离子体接枝技术用于聚丙烯接枝苯乙烯共聚物的合成．ＦＴ ＩＲ、ＳＥＭ及ＸＰＳ证明所得产物为接枝共聚物．研究了不同等离子体处理体系压强、处理功率，反应瓶不同直径、体积，不同接枝聚合反应时间、温度对接枝率的影响．利用接枝共聚物制备了硫酸钠型离子交换膜，并对其电性能进行了初步探讨．     

苯乙烯/马来酸酐和苯乙烯/甲基丙烯酸二甲氨基乙酯二元体系在聚四氟乙烯多孔膜上的γ辐射接枝

在氮气的氛围下用γ辐照的方法在聚四氟乙烯多孔膜上接枝苯乙烯 马来酸酐、苯乙烯 甲基丙烯酸二甲氨基乙酯二元单体 .并且研究了剂量、剂量率、溶液中单体的浓度和二元单体的摩尔比等条件对接枝率的影响 .探讨了两种单体的竞聚率对接枝率、接枝膜的组成及性能的影响 .结果表明 ,苯乙烯 马来酸酐二元体系对接枝率有协同效应 ,苯乙烯 甲基丙烯酸二甲氨基乙脂二元体系对接枝率表现为加合效应 .制备的二元接枝的聚四氟乙烯多孔膜可以进一步磺化来制备用于质子交换膜燃料电池的质子交换膜 .     

《功能高分子材料》

全书共分17章，结合功能高分子材料的结构与性能、制备方法及应用领域，对离子交换树脂，吸附树脂，离子交换纤维和活性碳纤维，高分子膜分离材料，高分子色谱固定相，高分子试剂，高分子负载催化剂，导电高分子材料，电效发光聚合物材料，非线性光学高分子材料，液晶高分子材料，感光高分子材料，医用高分子材料，环境敏感高分子材料，高分子电解质，高分子染料，淀粉，纤维素衍生物高分子等进行了详细论述。[第一段]     

聚合物反应加工过程中的原位合金化

用反应加工方法将具有不同性能的高分子材料通过共价键或离子键组装在一起,制备具有各共混组分优良性能的新型高分子合金材料,是当前高分子材料科学发展较快的领域之一.本文分别就聚合物/聚合物共混体系和聚合物/可聚合性单体共混体系原位合金化问题进行了讨论,简要概括了国内外该领域研究取得的最新成果.     

氨基氮杂环荧光分子改性苯乙烯马来酸酐共聚物的研究

荧光高分子材料 ,由于其独特光学性质 ,成为功能高分子研究热点[1～ 3 ] .一般而言 ,荧光聚合物的合成有两种方法 ,一是首先合成荧光单体 ,然后与其他适宜单体聚合 ,得到荧光聚合物 ,然而荧光单体结构复杂 ,提纯困难 ,难以获得高分子量、成膜性能好的聚合物[4] ;另一种方法是通过官能团的反应 ,用荧光物质对聚合物进行化学改性来制备[5,6] .苯乙烯 马来酸酐共聚物 (ＳＭＡ)是一类成本低廉 ,性能良好的商品化聚合物材料 ,主链中含有具有反应性能的酸酐基团 ,这就使通过化学改性制备荧光聚合物成为可能 .本文通过 2 氨基苯并咪唑 ( 1 ) ,4 …     

Heterogeneous ion-exchange membranes

The field of heterogeneous ion exchange membranes is reviewed briefly. Specific advantages and disadvantages of heterogeneous ion exchange membranes are discussed compared with those of homogeneous ion exchange membranes. p]The development of heterogeneous ion exchange membranes is presented in historical perspective. The electrochemistry of ion-selective membranes began with Ostwald in 1890. After the classical work of Michaelis (1925) with collodion membranes, the first fully synthetic ion exchange membranes were prepared by Zhukov (1933) and Wassenegger (1940), based on sulfonated phenol—formaldehyde resins. These initial membranes, which were of the homogeneous type found no practical uses. The era of commercially useful ion exchange membranes began with the work of Wyllie (1948), Juda (1950), Bodamer (1953) and their collaborators who prepared heterogeneous ion exchange membranes by embedding ion exchange particles into polymer matrices. p]Methods for making heterogeneous ion exchange membranes include compression-molding of polymer powders, compounding on hot rolls, latex or solvent blending in situ generation of either the matrix or the ion exchange material. Microheterogeneous ion exchange membranes can be made from block and graft copolymers, interpolymers snake-cage resins, similar techniques and materials. p]Even though the first commercial ion exchange membranes were heterogeneous, the interest in this type of membranes subsided later. As polymer science progressed, speciality monomers and polymers were being made which opened the way to the preparation of quite sophisticated homogeneous ion exchange membranes of satisfactory mechanical strength. However, the possibilities of heterogeneous ion exchange membranes are by no means exhausted and this field may warrant further exploration, applying modern methods and materials and thus progressing beyond the relatively crude heterogeneous ion exchange membranes of the pioneer times.     

Preparation and basic characterization of heterogeneous weak acid cation exchange membrane

The goal of this article is focused on the preparation and the basic characterization of heterogeneous weak acid cation exchange membranes. The six weak cation exchange resins were chosen for the preparation of the membranes. The strong acid cation exchange membrane was prepared for the comparison of properties and preparation parameters. Heterogeneous membranes were prepared in the several steps. The last operations were the extrusion and hydraulic hot-pressing. The torque and pressure in the extrusion head were observed while the extrusion of heterogeneous membranes. According to the type of the ion exchange resin, parameters varied greatly. The strong acid cation exchange membrane and weak acid cation exchange membranes with carboxylic groups had the lowest values of the torque and pressure while the homogenization and extrusion. All membranes were characterized. Electrochemical (permselectivity, ion exchange capacity, resistance), physical (relative water content, swelling in the different solutions), and mechanical properties were measured. Properties varied distinctly according to the type of the ion exchange resins. Swelling dimensional changes of ion exchange membranes in sodium hydroxide and water were bigger than changes in hydrochloric acid. Ion exchange capacity of membranes related with ion exchange capacity of used ion exchange resins. Weak acid cation exchange membranes with carboxylic functional groups compared to the strong membrane had the best specific and areal resistance.     

A Study of Concentration Polarization on Ion Exchange Membrane Electrodialysis

The concentration polarization phenomena in ion exchange membrane electrodialysis have been studied with single exchange membrane cell. The limiting current densities of Asahi ion-permselective membranes CK-1 and CK-2, Selemion ion-exchange membranes CMV, AMV, DMV and ASV have been measured with Ag-AgCl reversible electrode in various electrolyte solutions under 25°C and constant flow rate. In sodium chloride solution, the cation exchange membrane is easier to occur concentration polarization than the anion exchange membrane. The limiting current density increases as the concentration of solution increases for the same kind of ion exchange membrane. The experimental limiting current densities of Selemion CMV and AMV in NaCl, KCl, MgCl₂, CaCl₂, BaCl₂, Na₂SO₄, NaOH and HCl aqueous solutions are measured. The results show that the limiting current density increases as the ion mobility and diffusivity increase, and is affected by the transference number of ion. For the mixture of electrolyte solution, there are linear relationship between limiting current density and equivalent fraction of electrolytes.     

Transport properties of highly ordered heterogeneous ion-exchange membranes

Model "ordered" heterogeneous ion exchange membranes are made with ion exchange particles heaving ion exchange capacity in the range 3 to 2.5 meq/gr (dry basis) and diameters ranging from 37 to 7 microm and 2 component room-temperature vulcanizing silicon rubber as a polymeric matrix, by applying an electric field normal to the membrane surface during preparation. These membranes were shown to have an improved ionic conductivity compared with "nonordered" membranes based on the same ion exchange content (for instance, at 10% resin content "nonordered" membranes show <10(-5) mS/cm while "ordered" membranes have conductivity of 1 mS/cm). The transport properties of ordered membranes were compared with those of nonordered membranes, through the current-voltage characteristics. Limiting currents measured for the ordered membranes were significantly higher than those of the nonordered membranes with the same resin concentration. In addition, higher limiting currents were observed in ordered membranes as the resin particles became smaller. Energy dispersion spectrometry analyses revealed that the concentration of cation exchange groups on the membrane surface was higher for ordered membrane as compared to that of nonordered membranes. This implies that the local current density for the conducting domains at the surface of the nonordered membranes is higher, leading to higher concentration polarization and, eventually, to lower average limiting current densities. The effect of ordering the particles on the membrane conductivity and transport properties was studied, and the advantages of the ordered membranes are discussed.     

Radiation grafted poly(vinylidene fluoride)-graft-polystyrene sulfonic acid membranes for fuel cells: Structure-property relationships

<正>Structure-property relationships for poly(vinylidene fluoride)-graft-polystyrene sulfonic acid(PVDF-g-PSSA) fuel cell membranes prepared by a single step method involving radiation-induced grafting of sodium styrene sulfonate(SSS) onto electron beam(EB) irradiated poly(vinylidene fluoride)(PVDF) films were established.The physico-chemical properties of the membranes such as ion exchange capacity,water swelling and proton conductivity were correlated with the degree of grafting(G,%) and the structural changes taking place in the membrane matrix during the preparation procedure. The variation in the crystallinity and the thermal stability of membranes was studied by differential scanning calorimetry (DSC) and thermogravimetric analysis(TGA),respectively.The membranes were found to undergo substantial structural changes in forms of ionic sites increase,hydrophilicity enhancement,hydrophobicity reduction and crystallinity decrease with the variation in G(%) and the preparation method.The structural and thermal properties of the obtained membranes were also compared with their counterparts prepared by a conventional two-steps method i.e.radiation induced grafting of styrene onto EB irradiated PVDF films followed by sulfonation.The PVDF-g-PSSA membranes obtained by a single-step method were found to have superior properties compared to those obtained by the conventional two-steps method.     

离子交换膜的渗透汽化

本文介绍了离子交换膜的渗透汽化研究工作。从离子交换膜的吸附溶解性、离子特性等几个方面论述了渗透汽化过程的分高性能及可能的传递机理。     

Swelling behavior of nafion and radiation-grafted cation exchange membranes

The swelling properties of Nafion and six radiation-grafted cation exchange membranes in various solvents were investigated. It was found that the swelling of the membranes was strongly related to the type of ion exchange group and was not influenced by the perfluorinated nature of the polymer. Membranes with sulfonic acid groups exhibited two swelling peaks: a distinct peak at about 17 Hb and a second peak at about 10 Hb. These peaks were attributed to the ionic groups and the organic material of the membrane, respectively. On the other hand, there was no distinct swelling for membranes with carboxylic acid groups, but extensive swelling in water was observed when the membrane was neutralized. Finally, the electrochemical application of this membrane is discussed.     

Polymers with Tethered Anionic and Cationic Groups as Membranes for Fuel Cells

Ionic clustering, water binding, and ion conductivity were studied in polymers functionalized with sulfonic acid and quaternary ammonium hydroxide groups. Small-angle x-ray scattering showed that no clustering occurred in the quaternary ammonium containing anion exchange membranes, while evidence of ionic clusters was present in both sulfonated poly(phenylene) and in Nafion, a poly(perfluorosulfonic acid). Interestingly, the water self-diffusion coefficients of the anion exchange membranes were generally greater than those observed for the sulfonated poly- (phenylene)s, and moreover, the water self diffusion coefficients in anion exchange membranes were not a strong function of diffusion time. The water binding behavior lead to increased normalized conductivity in anion exchange membranes as compared to proton exchange membranes at the highest ion exchange capacities.     

Controlled porosity monolithic material as permselective ion exchange membranes

Ion exchange membranes (IEMs) are used in a variety of analytical devices, including suppressors, eluent generators and other components used in ion chromatography. Such membranes are flexible and undergo substantial dimensional changes on hydration. Presently the push to miniaturization continues; a resurgent interest in open tubular ion chromatography requires microscale adaptation of these components. Incorporating IEMs in microscale devices is difficult. Although both macroporous and microporous ion exchange materials have been made for use as chromatographic packing, ion exchange material used as membranes are porous only on a molecular scale. Because such pores have vicinal ion exchange sites, ions of the same charge sign as those of the fixed sites are excluded from the IEMs. Monolithic polymers, including ion exchangers derived therefrom, are presently extensively used. When used in a separation column, such a monolithic structure contains an extensively connected porous network. We show here that by controlling the amount of porogen added during the synthesis of monolithic polymers derived from ethylene dimethacrylate – glycidyl methacrylate, which are converted to an anion exchanger by treatment with trimethylamine, it is possible to obtain rigid ion exchange polymers that behave like IEMs and allow only one charge type of ions to pass through, i.e., are permselective. We demonstrate successful open tubular cation chromatography suppressor performance.     

Modification of properties of ion-exchange membranes. IV. Change of transport properties of cation-exchange membranes by various polyelectrolytes

A change in electrodialytic transport properties of various cation exchange membranes was observed after the membranes had been adsorbed or ion-exchanged with various cationic polyelectrolytes. Transport properties measured in this report were the relative transport number of calcium ion to sodium ion P^Ca_Na, the current efficiency of cations, and the electric resistance of the membrane during the electrodialysis. Weakly basic and strongly basic cationic polyelectrolytes of various molecular weights were used. Though P^Ca_Na of any cation exchange membrane decreased by the adsorption or ion exchange of any cationic polyelectrolyte, the degree of the decrease in P^Ca_Na changed with species and molecular weight of polyelectrolytes and species of cation-exchange membranes. Weakly basic polyelectrolytes and low molecular weight, strongly basic polyelectrolytes were effective in producing a marked decrease in P^Na_Ca of any cation exchange membrane. The effect of strongly basic polyelectrolytes of high molecular weight on P^Ca_Na was weak in most cases. However, if it was possible to make the polyelectrolyte adhere to the surface of the membrane to form a compact coiled structure, any cationic polyelectrolyte was effective in producing a remarkable decrease in P^Ca_Na of any cation-exchange membrane.