Synthesis,characteristics and adsorption properties of polyphenylene sulfide based strong acid ion exchange fiber

A novel strong acid ion exchange fiber (HO₃S‐BC‐XDC‐PPS) was prepared via crosslinking and grafting copolymerization of 1,4‐bischloromenthyl benzene (XDC), benzyl chloride (BC) on polyphenylene sulfide (PPS) matrix, as well as following sulfonation reaction. The physicochemical structures and properties of the fibrous ion exchanger were characterized with Fourier transform infrared, scanning electron microscopy, thermogravimetric analysis, elementary analysis and chemical titration, respectively. Compared with the preparation of traditional polypropylene–styrene–divinylbenzene‐based ion exchange fibers, the synthesis strategy of PPS‐based strong acid ion exchange fiber avoided the complicated irradiation grafting process with ⁶⁰Co or other radiation facilities. Owing to the existing of thioether (Ar―S―Ar) and sulfoxide (―SO―) unit in fibrous matrix, a super‐equivalent adsorption phenomenon for Cu(II) ion was observed. The HO₃S‐BC‐XDC‐PPS fiber possessed high exchange capacity (≥3.0 mmol/g) and excellent thermostabilities, and the exchange capacity and desorption rate were not decreased after six adsorption desorption cycles. Copyright © 2014 John Wiley & Sons, Ltd.     

Ion exchange textiles from the finishing of PET fabrics with cyclodextrins and citric acid for the sorption of metallic cations in water

We describe a chemical method based on the use of cyclodextrins (CDs) and citric acid (CTR) as finishing chemicals for the modification of polyester fibers (PET). It was observed that the reaction between these reactants yielded a cross-linked polymer, by formation of ester functions between the polyol (CD) and the polycarboxylic acid (CTR). This polymer (called polyCTR-CD) permanently coated the PET fibers. The chemical structure of polyCTR-CD consisted of CD moieties and unreacted carboxylate groups. Theses groups resulted from the partial reaction of CTR and yielded ion exchange property to the fibers. The purpose of this paper was to set up the finishing parameters in order to obtain the best possible ion exchange capacity (IEC) of the fabrics. Firstly, we observed that the IEC did not perfectly evolve with the grafting rate (expressed in %-wt) of the fibers; As a matter of fact, we observed that a maximal IEC of 0.4–0.5 mmol/g of fabric was obtained for a compromise between the amount of polyCTR-CD fixed onto the fibers, and its cross-linking rate. In fact, the lesser the cross-linking rate, the more unreacted carboxylic groups remained on the fibers. Second, it was observed that CDs could not be replaced by starch in this process, because the later resulted to inferior IEC values than textiles grafted with CDs and CTR. Finally, the ion exchange finished fabrics were applied in the decontamination of water solutions containing Pb²⁺, Ni²⁺ and Cd²⁺. It was observed that 0.3 mmol of each cation were adsorbed per gram of fabrics.     

The Application of Polytetrafluoroethylene (PTFE) Fiber Grafted Acrylic Acid as a Cation Exchanger for Removing Cu~(12)

There are many advantages for ion exchange fibers prepared from the natural fiber, i.e. the strong hydrophilicity, the large surface area and the high speed of both adsorption and desorption for organic compounds and metal ions. It has been used widely in biochemical separation, analysis, the recovery of precious metals and the environmental protection1-2. But its application still is limited because of the poor anticorrosion property. Polytetrafluoroethylene (PTFE) possesses excellent che…     

Characterization and Studies on Grafting of Methyl Methacrylate onto PAN Fibers

The graft copolymerization of methyl methacrylate (MMA) onto commercial acrylic fibers (PAN) has been studied using Azobis(isobutyro)nitrile (AIBN) as an initiator. MMA grafting initiated by radicals formed from thermal decomposition of AIBN. In this study, the effects of monomer and initiator concentration, time and temperature reaction on the grafting yield have been investigated.

The optimum conditions for this grafting reaction were obtained with an MMA concentration of 0.7 M, an AIBN concentration of 0.0073 M, a reaction temperature of T=85°C and with a 60 min reaction time.

The fiber structure has been investigated by different experimental techniques of characterization such as Fourier transform infrared spectroscopy (FT‐IR), calorimetric analysis (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), water absorption and the physical and mechanical properties has also been investigated in this study. The thermal analysis data showed that by increasing grafting yield, little changes have occurred in fibers samples up to 13.5% of grafting yield and the thermal transitions of grafted fibers have approximately the same behavior compared with the raw fibers sample. Grafting also slightly affected the fiber morphology. The experimental data of mechanical properties clearly show that by increasing grafting yield, max extension will decrease but this change up to 13.5% grafting yield is barely noticeable. Grafting of poly MMA improved water absorption.     

γ-射线辐照接枝制备几种功能性高分子材料

概述了近几年来本研究组在高分子材料辐照接枝制备功能性高分子材料方面的研究进展.分别以丙烯酸、顺丁烯二酸、苯乙烯接枝聚四氟乙烯纤维,制备了不同酸性的聚四氟乙烯功能纤维.以N-异丙基丙烯酰胺接枝壳聚糖制备温度及pH敏感材料,获得了性能特异的新型功能性高分子材料.报道了该类新型功能高分子材料的各种特异性能,如对金属离子优异的分离、吸附和解吸性能、超强酸性和一系列潜在用途.     

Synthesis and characterization of SPE membrane based on sulfonated FEP‐g‐acrylic acid by radiation induced graft copolymerization for PEM fuel cell

A Novel solid polymer electrolyte (SPE) membrane containing both ? COOH and ? SO₃H group has been prepared by simultaneous method of radiation grafting of acrylic acid onto FEP followed by sulfonation. The presence of weakly acidic acrylic acid controls the swelling in water while ? SO₃H group provides conductivity due to its strongly ionic characteristic. FEP‐g‐acrylic acid and its sulfonated derivatives were characterized by their properties. While the mechanical properties decreased, other properties such as ion exchange capacity (IEC), water uptake and ionic conductivity increased with increase in graft content. These properties further changed on sulfonation. Acrylic acid being weakly acidic in nature, conductivity values of the grafted membrane were quite low. However, introduction of strong ? SO₃H group resulted in conductivity closer to Nafion 117. Few sulfonated membranes have been tested with respect to H₂/O₂ fuel cell performance. Short‐term fuel cell test for 100 hr gave a stable performance. These membranes are less expensive compared to Nafion. Copyright © 2004 John Wiley & Sons, Ltd.     

聚四氟乙烯纤维辐照接枝制备弱酸性离子交换剂及其对Cu~(2+)的吸附

以聚四氟乙烯纤维为基体通过6 0 Co辐射引发与丙烯酸接枝制备弱酸性阳离子交换纤维 .产物功能基含量为 3 0 6mmol g,在pH =5时该纤维达到对Cu2 + 的最大动态吸附量为 10 7 4 8mg g.使用不同浓度HCl对饱和吸附铜的接枝纤维进行洗脱 ,证实该纤维对铜离子具有优异的解吸性能     

丙烯酸改性聚醚砜中空纤维渗透汽化膜的研究

采用自由基聚合反应制备了丙烯酸接枝改性的聚醚砜中空纤维渗透汽化膜,该膜用于醇／水分离获得了良好的效果。结果表明,通过改变聚合单体的浓度可以控制膜的接枝率,并调节膜的选择性和通量。改性膜的红外光谱和电镜分析结果表明：膜的接枝反应主要发生在中空纤维膜的内表面,膜的外表面接枝程度很低。力学性能测试表明接枝后膜的拉伸强度减弱。     

Preparation and characterization of a strong basic anion exchanger by radiation-induced grafting of styrene onto poly(tetrafluoroethylene) fiber

A novel anion-exchange fiber with strong basic groups has been prepared by grafting styrene onto poly(tetrafluoroethylene) fibers via irradiation. Experiments were carried out to analyze the effects of synthesis conditions on the grafting degree and to characterize the physicochemical properties of the anion-exchange fibers. The experimental results showed that preirradiation grafting styrene onto poly(tetrafluoroethylene) fiber could significantly reduce the waste of raw material and the formation of homopolymer, although the grafting degree was relatively low. The grafting reaction could be effectively enhanced through the addition of magnesium powder into the reaction system. The optimal temperature and time for preirradiation grafting were 80 degrees C and 6 h, respectively. The experimental results also showed that the anion-exchange fibers had excellent mechanical properties and thermal stability at a temperature up to 420 degrees C. The fibers were stable in acidic, alkali, and oxidative solutions. The static ion-exchange capacity of the fibers was as high as 6.08 mmol/g. The static adsorption capacities for Cr(2)O(2-)(7) and MnO(-)(4) ions were 214.08 and 290.98 mg/g, respectively.     

弱酸型阳离子交换纤维PVF-g-AA的制备研究

采用r-射线预辐射接枝共聚的方法制备了一种弱酸型阳离子交换纤维PVF-g-AA,并研究了影响接枝共聚反应的条件。     

Preparation of Zirconia Fibers via a Simple Aqueous Sol‐Gel Method

Polycrystalline tetragonal zirconia fiber was obtained by pyrolysis of precursor fibers from citrate‐acetate‐zirconium complex solution. The viscous zirconia sol with good spinnability was prepared by aging the starting solution of ZrOCl₂ · 8H₂O (ZOC) in the presence of acetic acid (HA) and citric acid (CA). The effects of molar ratio of zirconium cation to carboxylic acid and the aging time on the formation of spinnable sol were investigated. Thermogravimetric (TG) analysis, x‐ray diffraction (XRD), infrared (IR) spectra, and scanning electron microscope (SEM) techniques were used to characterize the sintered fibers. The results show that the fibers obtained at 1400°C are crack‐free with diameter of ca. 5–10 µm.     

Cation-exchange membranes by radiation-induced graft copolymerization of monomers onto HDPE

Studies were made on preparation of the cation-exchange membranes obtained by pre-irradiation grafting of acrylic acid (AA) and sodium styrene sulfonate (SSS) onto high-density polyethylene (HDPE), and its properties such as swelling behavior and electric resistance were measured as a function of ion-exchange capacity (IEC). Thermal and chemical stability was also investigated. These properties were found to be mainly dependent on IEC. The grafted membranes possessed good electrochemical, thermal and chemical properties, and were found to be acceptable for practical use as cation-exchange membranes.     

聚合物基板表面状态对异相接枝的影响研究

研究了对于羟丙基纤维素（HPC）基板进行表面修饰时,基板表面状态的调控 对基板表面化学接枝的影响。用双官能团化合物2,4-甲苯二异氰酸酯（TDI）作为 接枝桥梁,其对位的异氰酸酯基先和基板上的羟基反应,保留的邻位异氰酸酯基进 一步再与丙烯酸的羟基反应,让接枝在基板上的活性丙烯酸分子继续和丙烯酸溶液 聚合,通过这种途径在基板表面修饰聚丙烯酸。基板制备时,由于不同介质对HPC 基板表面的不同诱导作用,导致表面组成各异,大大影响了接枝反应的效果。红外 光谱和二次离子飞行时间质谱均证明了可以用2,4-甲苯-二异氰酸酯（TDI）分子 做接枝桥梁在基板表面异相接枝上羟基并进一步接枝聚丙烯酸,从而达到修饰基板 的目的。     

Study on Dyeing Properties of Functional Acrylic Fiber

Anti‐mite acrylic fiber is a new type of functional fiber which incorporates a small amount of anti‐mite agent. Basic dye can be used in the dyeing of the functional acrylic fiber. Compared with the dyeing properties of conventional fibers, the dyeing properties of the functional acrylic fiber have new characteristics such as different dyeing temperature, time, amount of leveling agent and pH level due to the rough surface and larger size of micro‐channels in the functional fiber structure that helps basic dye molecules to diffuse into the fiber.     

含季铵基离子交换纤维的制备研究

以辐射接枝丙烯酸(AA)后的聚丙烯(PP)无纺布(PP-g-AA)为基材,采用紫外引发的方法接枝甲基丙烯酰氧乙基三甲基氯化铵(DMC),建立了一种制备阴离子交换纤维的新方法,得到了PP-g-AA-DMC纤维.研究了丙烯酸接枝率、DMC浓度、溶剂种类、光照时间,浸泡时间等因素对DMC接枝率的影响,结果表明,DMC的接枝率随着丙烯酸接枝率、DMC浓度、光照时间和纤维浸泡时间的增加而增大.接枝前后纤维的红外光谱分析表明,DMC被成功接枝在PP-g-AA基材上.吸附性能测定结果表明,纤维对水中以阴阳离子存在的金属铬均具有较好的吸附性能.     

Dual‐curable fluorinated poly(methacrylate) copolymers for optical adhesives

In pursuit of photo‐curable adhesive for optical communication, dual‐curable acrylic oligomers (AOs) having alkoxy silane group, fluorine atoms and vinyl group as a pendent group were synthesized by two‐stage reactions. The isocyanate group containing oligomers were firstly synthesized via radical polymerization of acrylic monomers, and followed by urethane reaction with 2‐hydroxy ethyl methacrylate. The dual curing behaviors, e.g. thermal and photo‐cure, were studied by using photo‐differential scanning calorimetry (DSC) and real‐time IR. An optimum adhesive formulation, based on AO (15 g), epoxy acrylate (80 g), isobonyl methacrylate (17 g) and photo‐initiator (3 g), was obtained. As the content of AO was increased in the optical adhesive formulation, refractive index decreased but transmittance increased due to the increase in fluorine content. The optical transmittance at the range of 1.3 to 1.55 μm was higher than 90%. The addition of colloidal silica with the earlier mentioned formulation was helpful in decreasing crosslinking volume shrinkage and the increasing of glass fiber adhesion. The required properties for the optical adhesive, including chemical resistance and thermal resistance, dimension stability, etc. were also investigated. Copyright © 2005 John Wiley & Sons, Ltd.     

GRAFTING ONTO WOOL V.RADIATION-INITIATED GRAFTING OF ACRYLIC ACID ONTO WOOL FIBER

This paper deals with graft copolymerization of acrylic acid (AA) onto Xinjiang fine wool.fiber in aqueous medium initiated by gamma rays. Graft copolymerization was carried out by themutual irradiation method in limited air. Percent grafting and percent efficiency have been deter-mined as a function of total dose, dose rate, concentration of monomer, wool weight and reactiontemperature. Graft copolymers are characterized with infrared (IR) spectroscopy, scanning elec-tron microscopy (SEM), and X--ray diffractometer. Properties of the grafts were studied, and compared with the virgin fiber.     

Synthesis of sulfonated aromatic poly(ether amide)s and their application to proton exchange membrane fuel cells

A series of wholly aromatic sulfonated poly(ether amide)s (SPEAs) containing a sulfonic acid group on the dicarbonyl aromatic ring were prepared via a polycondensation reaction of sulfonated terephthalic acid (STA), terephthalic acid (TA), and aromatic diamine monomers. The degree of sulfonation was readily controlled by adjusting the monomer feed ratio of STA and TA in the polymerization process, and randomly sulfonated polymers with an ion exchange capacity (IEC) of 1.0–1.8 mequiv/g were prepared using this protocol. The chemical structures of randomly sulfonated polymers were characterized using NMR and FT‐IR spectroscopies. Gel permeation chromatography analysis of SPEAs indicated the formation of high‐molecular‐weight sulfonated polymer. Tough and flexible SPEA membranes were obtained from solution of N,N‐dimethylacetamide, and thermogravimetric analysis of these membranes showed a high degree of thermal stability. Compared with previously reported sulfonated aromatic polyamides, these new SPEAs showed a significantly lower water uptake of 10–30%. In proton conductivity measurements, ODA‐SPEA‐70 (IEC = 1.80 mequiv/g), which was obtained from polycondensation of 4,4′‐oxydianiline and 70 mol % STA, showed a comparable proton conductivity (105 mS/cm) to that of Nafion 117 at 80 °C. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 485–496, 2009     

硫代酰胺基螯合纤维的合成及其吸附性能研究

以腈纶纤维(PAN)为起始原料,分别经水合肼、乙二胺、二乙烯三胺预交联后,以N,N-二甲基甲酰胺(DMF)作溶剂与硫化钠反应,合成了3种携硫代酰胺功能基可达6.8mmol/g·干纤维的螯合功能纤维。利用红外光谱、元素分析、热稳定分析、重量分析等对该螯合纤维的结构、性能等进行了表征;研究了该螯合纤维对Au3 ,Ag ,Pd2 等贵金属离子的吸附性能;考察了温度、pH、硫含量等对纤维吸附Ag 离子的影响。结果表明,纤维对Au3 ,Ag 等贵金属离子具有良好的吸附性能,对Au3 的吸附容量为800mg/g·干纤维;对Ag 离子的吸附容量可达1510mg/g·干纤维,并具有良好的吸附动力学特性,该螯合纤维可用于混合溶液中Ag(I)离子的吸附分离。     

Modification and Application of Poly(Ethylene Terephethalate) Nonwoven Fiber Using Octadecyl Acrylate and Acrylic Acid as Oil Sorbers

Three series of crosslinked octadecyl acrylate and acrylic acid copolymers were prepared through suspension copolymerization based on acrylic acid content (10, 30, 50%wt. ratio). Divinyl benzene (DVB) was used as a crosslinker with different weight ratios (1, 4 and 10%). Isopropyl alcohol or dioctyl phthalate and methyl benzoate were used as two different reaction solvents in the presence of ABIN as initiator. The prepared crosslinked copolymers were characterized by SEM, TGA and FTIR spectroscopic analyses. The prepared polymers were coated onto poly(ethylene terephethalate) nonwoven fiber (NWPET). The effect of copolymerization feed composition, crosslinker wt% and reaction media or solvent on swelling properties of crosslinked polymers were studied through the oil absorption tests in toluene and 10% of diluted crude oil with toluene. It was noticed that the maximum swelling of crosslinked copolymers was increased from 30 to 100 g/g after grafting of copolymers onto NWPET.