Preparation of anion exchanger by amination of acrylic acid grafted polypropylene nonwoven fiber and its ion-exchange property

To develop the polymeric adsorbent that possess anionic exchangeable function, PP-g-AA-Am fibers were prepared by photoinduced grafting of acrylic acid (AA) onto polypropylene (PP) nonwoven fibers and subsequent conversion of carboxyl group in grafted AA to an amine (Am) group by reaction with diethylene triamine (DETA). The amination of grafted AA increased with increase in the degree of grafting, the reaction time and temperature of the chemical modification process. Catalytic effect of metal chlorides such as AlCl(3) and FeCl(3) on the amination of grafted AA was significant but not essential to lead the amination. FT-IR and solid (13)C NMR data indicate that amine group was introduced into PP-g-AA fiber through amide linkage between grafted AA and DETA. The anion exchange capacity of PP-g-AA-Am fiber increased with increase in the degree of amination, but reached maximum value at about 60% amination of 150% grafted AA. PP-g-AA-Am fiber showed much higher maximum capacity for PO(4)-P and a similar capacity for NO(3)-N compared to commercial anion resins. Furthermore, the PP-g-AA-Am fiber also has adsorption ability for cations because of unaminated residual carboxyl group.     

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.     

Cellulose/poly(ethylene imine) composites as efficient and reusable adsorbents for heavy metal ions

A series of Cellulose/poly-ethylene imine (PEI) composites were prepared by grafting hyperbranched PEI onto cellulose chains in alkali/urea aqueous solvent system through “one step” method. The SEM results showed that the Cellulose/PEI composite maintained porous structure. The Cellulose/PEI composites were tested as Cu(II) adsorbents through thermodynamics and kinetics study. The adsorption process followed pseudo-second-order kinetics equation. The adsorption isotherms could be described by both Langmuir and Freundlich isotherm models. The maximum adsorption amount was calculated to be 285.7 mg/g. The composites showed good stability so that they could be used in a wide range of pH and temperature. Besides, the Cu(II) loaded Cellulose/PEI composite could also be easily regenerated by dilute sulfuric acid and still keep a major adsorption capacity. Finally, the adsorption capacities of Celluloes/PEI composite towards other metal ions, such as Zn(II), Ni(II), Cr(III) and Pb(II), were also demonstrated. It will be a new high-performance and environmental friendly material for sewage disposal and metal pollution treatment with promising developmental potential.     

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.     

CO2 capture by polyethylenimine-modified fibrous adsorbent

This work focuses on developing a novel adsorbent for CO2 capture, by coating polyethylenimine (PEI) on glass fiber matrix and using epichlorohydrin (ECH) as cross-linking agent. The physicochemical properties of the fibrous adsorbent were characterized. The CO2 adsorption capacity was evaluated. Factors that affect the adsorption capacity of the fibrous adsorbent were studied. The experimental results show that this fibrous PEI adsorbent exhibits a much higher adsorption capacity for CO2 compared with another PEI fiber prepared in our previous work, which employed epoxy resin as the cross-linking agent. A CO2 adsorption capacity as high as 4.12 mmol CO2/g of adsorbent was obtained for this fibrous PEI adsorbent at 30 degrees C, equal to 13.56 mmol CO2/g of PEI, with a PEI/ECH ratio of 20:1. The adsorbent can be completely regenerated at 120 degrees C.     

Cu(II) immobilization in AAc/NIPAAm-based polymer systems synthesized using ionizing radiation

Polymer systems based on the pH-responsive monomer acrylic acid (AAc) and the thermosensitive monomer N-isopropylacrylamide (NIPAAm) were synthesized using gamma radiation. Three systems were synthesized: a comb-type hydrogel structure (grafting of NIPAAm onto crosslinked PAAc), a binary graft of both monomers onto a polypropylene (PP) film synthesized by a one-step method and a binary graft prepared by a two-step method. The binary graft systems were characterized by swelling behavior and the reversibility of water uptake. The three systems were compared with respect to their Cu(II) adsorption quantity, reversibility and time response. The binary graft system synthesized in one step exhibited the best adsorption response. The comb-type hydrogel required 150 h to reach its maximum swelling percentage, and the binary graft systems on polypropylene (PP) prepared by the one- and two-step irradiation-based methods required 10 and 30 min, respectively. The optimum pH range for Cu(II) immobilization was 5-6 in the binary graft system synthesized in one step. The maximum adsorption capacity for Cu(II) in the (PP-g-(AAc/NIPAAm)) (45% graft) was found to be 337 mg g⁻¹, and the adsorption followed the Freundlich model.     

Adsorption of cationic copolymer nanoparticles onto bamboo fiber surfaces measured by conductometric titration

Monosized nanoparticles of 57.3 nm were prepared by cationic emulsion polymerization using a polymerizable emulsifier DMHB. The adsorption of nanoparticles onto bamboo fibers was measured by conductometric titration. The results indicated that the adsorption capacity increased with increasing contact time until 120 min. The equilibrium data for nanoparticles adsorption onto bamboo fibers were well fitted to the Langmuir equation. Moreover, the monolayer adsorption capacity of nanoparticles in the concentration range (from 0.03 g/L to 0.6 g/L) studied, as calculated from Langmuir isotherm model at 25℃, was found to be 38.61 mg/g of fibers. The SEM images showed that the nanoparticles form a uniform monolayer on bamboo fiber surfaces.     

Preparation and some properties of a polyethyleneimine-agarose metal adsorbent

An adsorbent for metal ions has been prepared by reacting high molecular weight polyethyleneimine (PEI) with a crosslinked and activated agarose gel, Novarose. The synthesis variables, i.e. time, temperature, pH, PEI concentration and PEI/Novarose ratio, were optimized in order to obtain a high metal binding capacity of the adsorbent. The binding capacity for Cu(2+) is 500 micromol/ml packed adsorbent. A number of properties of the adsorbent relevant for metal ion accumulation has been investigated for Cu(2+), Ni(2+), Cd(2+) and Zn(2+). Adsorption capacities, adsorption isotherms, distribution coefficients, recoveries and relative rates of accumulation were determined. The adsorbent can be used for preconcentration and for separation of interfering alkali and alkaline earth metals in analytical applications.     

Environmentally benign preparation of bifunctional cation exchange fibers

A bifunctional cation exchange fiber was prepared by an efficient and environmentally benign method. In this method, sodium p‐styrene sulfonate (SSS) was cografted directly onto the polypropylene (PP) fiber along with acrylic acid (AA), which eliminated the sulfonation process of grafting fiber with concentrated sulfuric acid or chlorosulfonic acid in the conventional method. Effects of the grafting conditions such as reaction temperature, reaction time, pH value, and the influence of acrylic acid and metallic salt on the graft copolymer reaction were investigated. The physicochemical properties of the cation exchange fibers were characterized with diffuse reflectance infrared spectroscopy (FT‐IR), scanning electron microscopy (SEM), X‐ray diffractometer (XRD), thermal gravimetric analysis (TGA), TG‐IR analysis, and monofilament tensile properties test. The experimental results indicate that the optimal conditions of pre‐irradiation grafting are 80°C for 5 hr, and the mechanical properties and thermal stability of the product are better than those of commercial materials (Fiban.K‐1). The total static ion exchange capacity (IEC) of the cationic exchange fiber is up to 5.33 mmol/g. The maximal IEC contribution from the strong acid part is 2.47 mmol/g. This synthetic method provides a clean industrial way for the preparation of bifunctional cation exchange fibers. Copyright © 2009 John Wiley & Sons, Ltd.     

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.     

Properties and evaluation of amidoxime-based UHMWPE fibrous adsorbent for extraction of uranium from seawater

An amidoxime-based ultra-high molecular weight polyethylene (UHMWPE) fibrous adsorbent was successfully prepared by γ-irradiation-induced graft copolymerization of acrylonitrile (AN) and acrylic acid (AA), followed by amidoximation. The grafting of AN and AA on the UHMWPE fiber and the amidoximation of the grafted fiber were confirmed by Fourier transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis. The mechanical property of the original and modified UHMWPE fibers was compared by single-filament strength test. The adsorption property of the UHMWPE fibrous adsorbent was evaluated by adsorption test in uranyl nitrate solution and seawater. The surface of the modified UHMWPE fibers was covered by the grafting layer and became rough. The tensile strength of the amidoxime-based UHMWPE fibrous adsorbent was influenced by the absorbed dose and hydrochloric acid elution, but was independent of the grafting yield and amidoximation. The uranium adsorption amount of the amidoxime-based UHMWPE fibrous adsorbent after immersing in seawater for 42 days was 2.3 mg-U/g.     

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     

Sorption and permeation behaviour of metal thiocyanate complexes on cellulose acetate polymers

Various metal thiocyanate complexes in aqueous solution were sorbed on solid cellulose acetate polymers. The sorption selectivity increased in the order Zn(2+) > Fe(3+) > Cu(2+) > Co(2+) > Ni(2+). The sorption behaviour followed a Langmuir-type adsorption isotherm, and the maximum adsorption capacity was 6.1 x 10(-5) mole of complex per g of polymer under optimum conditions. The zinc species sorbed appear to be NH(4)Zn(H(2)O)(SCN)(3) or (NH(4))(2)Zn(SCN)(4) according to analysis of the sorption equilibrium. The ion-association species formed by the complex zinc anion and the ammonium ion was supposed to be sorbed (or "extracted") onto the polymer matrix. As an application of sorption of metal complexes, a new hyperfiltration process was proposed for selective separation of metal ions. Thus, a mixture of metal thiocyanate complexes was hyperfiltered through cellulose acetate membranes. Permeation of certain metal complexes was preferred, and the selectivity was found to be similar to the sorption selectivity. These findings lead to a generalized idea that hyperfiltration separation of ionic species, particularly anionic metal complexes, can be attained by using polymer membranes which selectively adsorb or extract such ionic species as ion-association complexes onto the polymer matrix.     

聚丙烯纤维预辐照接枝制备弱碱性离子交换纤维及其对链霉素的吸附

以γ-射线预辐照,在聚丙烯(PP)纤维上接枝丙烯酰胺(AAm),再经过Hofmarm降解反应制备弱碱性离子交换纤维(PP-g-YAm)交换容量达到5.47mmol/g干纤维.研究了PP-g-VAm纤维对链霉素的吸附和解吸性能.其吸附等温曲线符合Langmiur吸附等温式.静态吸附试验表明,PP-g-AAm纤维对链霉素的吸附量可以达到446.96mg/g千纤维,脱附率达到98.9%.     

载双硫腙螯合纤维制备及富集重金属离子研究

合成了一种聚苯乙烯基载双硫腙 (DzS) 螯合纤维,研究了该纤维对4种重金属离子的螯合性能,讨论了吸附酸度、吸附时间等对4种重金属吸附性能的影响,选择了适当的反应条件,得出了该螯合纤维对重金属离子吸附量及选择性大小顺序:Pd(Ⅱ)>Cu(Ⅱ)>Co(Ⅱ)>Cd(Ⅱ),指出该纤维与石墨炉原子吸收分光光度测定法结合,可成功地应用于环境检测天然水样中的重金属离子.     

铅(Ⅱ)离子印迹复合膜的制备及其性能研究

以聚丙烯微孔膜(MPPM)为支撑,采用共价表面修饰和离子印迹技术,制备了Pb(Ⅱ)离子印迹复合膜.首先通过紫外光引发丙烯酸接枝聚合,在MPPM表面引入羧基;然后基于羧基和氨基的反应,将壳聚糖共价接枝到MPPM表面;再以Pb(Ⅱ)为模板离子、环氧氯丙烷为交联剂,通过配位键作用形成离子印迹位点.制备过程通过ATR-FTIR和XPS分析得到了证实.利用扫描电子显微镜(SEM)-能量色散X射线光谱仪(EDX)对膜表面及截面的形貌及元素分布进行了分析.静态水接触角和纯水通量实验结果显示,印迹复合膜具有良好的表面亲水性和渗透性,在离子印迹聚合物接枝率为174.4μg/cm2时,水通量高达2659±58 L/(m2.h).印迹复合膜对Pb(Ⅱ)离子的吸附亲和性和渗透选择性分别通过平衡结合实验和竞争渗透实验进行评价.与非印迹复合膜相比,印迹复合膜对Pb(Ⅱ)离子展现出更强的吸附亲和性,更快的吸附速率及更好的渗透选择性,以Cu(Ⅱ)和Zn(Ⅱ)作为竞争离子,其渗透选择性因子分别为3.43和3.93.     

Effect of polyethyleneimine ion on the sorption of a reactive dye onto Leacril fabric: electrokinetic properties and surface free energy of the system

Data are presented on the kinetics, electrokinetics, and surface free energy in the process of adsorption of polyethyleneimine (PEI) as a pretreatment of Leacril, later dyed with the reactive dye Remazol Brilliant Blue R (RBBR). The electrokinetic potential of Leacril is negative, due probably to the presence of sulfonate and sulfate end-group onto Leacril fibers. The zeta potential of Leacril decreases in absolute value as a function of NaCl concentration in solution, probably because of compression of the electrical double layer. The zeta potential of Leacril as a function of the concentration of PEI in solution increases because of the adsorption of PEI ions through chemical reaction between the sulfonate end-groups of Leacril and the amine groups of PEI. The adsorption kinetics shows that an increase in the concentration of PEI, brings about an increase in the amount of RBBR adsorbed onto the fiber. This may be an indication of the chemical reaction between the reactive groups of the polyelectrolyte and dye molecules. The behavior of the surface free energy of the systems involved confirms these conclusions.     

“Surface-photografting”: new applications to synthetic fibers

“Surface-photografting” with UV-irradiation of polypropylene (PP) fiber and film and high-strength polyethylene (HSPE) yarn has been made with acrylic acid (AA) and acrylamide (AM) as monomers and benzophenone (BP), 4-chlorobenzophenone (4-BCP) and hydroxylcyclohexylacetophenone (HHA) as photoinitiators using a new continuous method. The grafting reaction occurs in a thin liquid layer on the fiber or film substrate, which is presoaked in a solution containing initiator and monomer. After irradiation with a highpressure mercury lamp, HPM 15 (2 kW) from Philips, for 5–20 sec at about 50°C the fiber and film surface is completely covered with a 2–8 nm thick layer of grafted polymer, analyzed by electron spectroscopy for chemical analysis. The grafting efficiency is 70–80%, i.e. only 20–30% of the polymer is homopolymer which can be removed by extraction. The grafted layers are so thin that they cannot be analyzed as weight increase (<0.1% of fiber weight). Absolute values for the amount of grafted AA polymer is analyzed by microtitration of the COOH groups at the fiber surface. The results agree well with the relative ESCA values. Grafting of commercial PP yarn with AA increases the adsorption of Crystal Violet dye with a factor of about 6. Grafting the same yarn with AM increases the adhesion to epoxy resin by a factor of 3–4 without affecting the mechanical properties of the fiber more than a few percent. For comparison, strips of blown PP film (5 mm wide) are modified by “surface-photografting” with AM. With increasing grafting, the contact angle for drops of distilled water decreases from 90° to 20°, indicating extensive wetting. The adhesion to epoxy resin increases from about 0.35 to 1.7 N/mm², i.e. with a factor of about 5 when the film surface is completely covered. Other comparisons are made with grafting of commercial HSPE yarn. Grafting with AA increases the adsorption of Crystal Violet dye by a factor of about 6. Grafting with AM increases the adhesion to epoxy resin from 0.25 to 1.3 N/nm², i.e. with a factor of 5. The bulk mechanical properties of the HSPE filaments are not affected by the grafting measured as tensile strength 2.7±0.1 GPa, elongation at break 4.8±0.3%, and Young's modulus 55±3 GPa, both before and after “surface-photografting”.     

接枝亲水型高分子的丝瓜络对水中重金属离子的吸附行为

采用接枝聚合的方法将亲水性聚丙烯酰胺接枝到丝瓜络上,部分水解的聚丙烯酰胺的接枝率可高达161.3%.选择典型的Cu~(2+)和Pb~(2+)体系,研究亲水型丝瓜络对水中重金属离子的吸附行为.结果表明,在单离子体系中,准二级动力学方程适于描述亲水型丝瓜络吸附动力学过程,饱和吸附量随着接枝率和pH值增加而增大,对Cu~(2+)和Pb~(2+)的最大饱和吸附量分别为647和887 mg/g.Langmuir和Freundlich等温吸附模型都适合描述等温吸附过程.8次吸附-解吸附循环实验表明,饱和吸附量基本保持恒定,同时对吸附机理进行了讨论.     

Preparation, characterization of carboxylated bamboo fibers and their adsorption for lead(II) ions in aqueous solution

The present study was conducted to develop a simple and versatile method to prepare carboxylated bamboo fibers which can be applied as potential bio-adsorbent for metal ions removal due to the high content of carboxyl groups. The chemical modification of bamboo fibers with citric acid (CA) was carried out by friendly semi-dry oven method. The resulting products with carboxyl group content between 1.99 and 4.13 mmol/g were accessible by changing ultrasonic pretreatment time, reaction temperature, reaction time and the amounts of catalyst and citric acid in order to minimize cross-linking reaction and thereby maximize carboxyl groups content. The characterization of the resulting products confirmed that carboxyl groups were successfully grafted onto surface of bamboo fibers. Moreover, the carboxylated bamboo fibers could be applied as bio-adsorbent for the removal of lead(II) ions from aqueous solution. Results showed that the adsorption capacity of Pd²⁺ could reach 127.1 mg/g for carboxylated bamboo fibers with 4.13 mmol/g carboxyl group content prepared under the ultrasonic pretreatment for 20 min at the CA/bamboo fibers weight ratio of 4.0 in the catalyst amount of 30 wt% at 120 °C for 90 min and the carboxylated bamboo fibers exhibited highly efficient regeneration with no significant loss of adsorption capacity of lead ion after five repeated adsorption/desorption cycles.