淀粉基磺酸型离子交换树脂的制备及对染料吸附性能研究

以天然淀粉（RS）、甲基丙烯磺酸钠（SMAS）与苯乙烯（ST）为原料，制备了淀粉基离子交换树脂GSR。采用IR、RAM与13CNMR光谱表征了结构。当引发剂浓度为0.056mol/L，n（过硫酸铵）：n（亚硫酸氢钠）=3：1，底物n（RS）：n（SMAS）：n（ST）=4：2：1，反应温度65℃，时间3h时，磺酸基含量达15.65%，亚甲基蓝吸附量为17.98mg/g，两者随单体添加量呈先增后降趋势。BET分析显示GSR比表面为5.078m2/g，较RS增大。GSR对酸、碱及酶耐受性增强，稳定性提高。GSR对亚甲基蓝、藏红T及孔雀石绿的吸附量较RS显著提高，且对不同染料吸附差异性减小，具有广谱性，并在不同pH下均保持良好吸附性。其对混合染料废水脱色率达85.08%，较RS提高91.03%，优于沸石与001×7树脂，经四次再生循环后脱色率不低于首次吸附的91.12%。随GSR粒径减小脱色率增加，当粒径为150~250μm时，脱色率较高，且尺寸适中，便于重复使用与回收，有利于连续化操作。     

Preparation and adsorption properties of the chelating resins containing carboxylic,sulfonic, and imidazole groups

The crosslinked poly(1‐vinylimidazole‐co‐acrylic acid), P(VIm‐co‐AA), and poly(1‐vinylimidazole‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) P(VIm‐co‐APSA) were synthesized by radical polymerization and tested as adsorbents under competitive and noncompetitive conditions for Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), and Cr(III) by batch equilibrium procedure. The resin–metal ion equilibrium was achieved before 1 h. The resin P(VIm‐co‐AA) showed a maximum retention capacity (MRC) value for Pb(II) at pH 3 and Hg(II) at pH 1 of 1.1 and 1.2 mEq/g, respectively, and the resin P(VIm‐co‐AA) showed at pH 3 the following MRC values: Hg(II) (1.5 mEq/g), Cd(II) (1.9 mEq/g), Zn(II) (2.7 mEq/g), and Cr(III) (2.8 mEq/g). The recovery of the resin was investigated at 25°C with 1 M and 4 M HNO₃ and 1 M and 4 M HClO₄. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2852–2856, 2003     

High‐retention properties for Hg(II) ions of a resin containing ammonium and pyridine groups

The metal‐ion uptake behavior of the chelating resin poly([(3‐(methacryloylamino)propyl] trimethyl ammonium chloride‐co‐4‐vinyl pyridine) has been investigated. The resin is obtained by radical copolymerization in a yield of 99.6%. The hydrophilic resin shows a high retention capacity and selectivity toward Hg(II) ions in the presence of Cu(II), Pb(II), Cd(II), Zn(II), and Cr(III) ions. A retention of Hg(II) higher than 99% is observed after 5 min. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2595–2599, 2002     

Preparation,characterization, and adsorption properties for metal ions of a novel chelating resin containing sulfoxide and diethylene glycol

A novel chelating resin containing sulfoxide and diethylene glycol, poly{4‐vinylbenzyl‐[2‐2‐(hydroxyethyl)ethoxyl]sulfoxide} (PVESO) was synthesized using chloromethylated polystyrene (PS‐Cl) as material. Its structure was characterized by elemental analysis, infrared spectra, and scanning electron microscopy (SEM). The adsorption capacities of the resin for Hg²⁺, Ag⁺, Cu²⁺, Zn²⁺, and Pb²⁺ at various pH values were determined. The maximum adsorption capacities for Hg²⁺ and Ag⁺ were 1.56 and 0.75 mmol g^?1 respectively. The resin had high selectivity for Hg²⁺ and Ag⁺ over the pH range 1.0–7.0. The adsorption capacities for Hg²⁺ and Ag⁺ under competitive condition were also determined by batch experiment method. In addition, the adsorption kinetics of the resin towards Hg²⁺ at different temperatures was also investigated. The results showed that the adsorption rate was governed by film diffusion at 20°C and 25°C, by particle diffusion at 30°C and 35°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 6054–6059, 2006     

全氟磺酸离子交换纤维的制备及性能

利用熔融纺丝技术制备全氟磺酸离子交换纤维(PSAIF)。研究了PSAIF的热性能、化学稳定性及对Cu2+的离子交换性能;考察了PSAIF对Cu2+交换性能中动态、静态离子交换情况及其再生性能。结果表明:PSAIF适宜的纺丝温度为225℃,具有较好的热稳定性和化学稳定性;对Cu2+的交换属于吸热过程,离子交换的最佳pH值为4~5,动态交换结果显示PSAIF对Cu2+有较强的动态吸附能力,吸附与解吸速率较快,再生性能良好,其吸附行为符合Langmu ir和Freumd lich方程。     

离子交换树脂对D-甘油酸的吸附热力学和动力学

D-甘油酸是一种重要的甘油衍生物,具有解酒护肝的功能。关于D-甘油酸生产方法的研究已有不少,但对其分离方法及分离机理的研究却鲜见报道。通过静态吸附实验,研究了D-甘油酸在201×7阴离子交换树脂上的等温热力学和动力学特性。结果表明,D-甘油酸在201×7阴离子交换树脂上的最大平衡吸附容量随pH的增加而降低,其吸附等温线符合Freundlich模型。在293~308 K下,吸附焓变为14.77 kJ·mol^-1,表明该吸附过程为吸热过程。升高温度有利于提高吸附速率,但对最大平衡吸附容量影响不大。同时,采用动边界模型描述D-甘油酸在该树脂上的交换行为,分别考察了料液浓度、树脂粒径和温度对交换过程的影响。交换过程的吸附速率随D-甘油酸浓度和温度的增加而增大,但随树脂粒径的增大而减小。研究表明该离子交换过程的速率控制步骤为颗粒扩散过程,交换过程的反应速率常数k₀为1.22×10^-3,反应级数a为0.631,表观活化能E_a为14.90 kJ·mol^-1,并得到了动力学总方程。     

Sorption properties of the iminodiacetate ion exchange resin,amberlite IRC‐718, toward divalent metal ions

The sorption properties of the commercially available cationic exchange resin, Amberlite IRC‐718, that has the iminodiacetic acid functionality, toward the divalent metal‐ions, Fe²⁺, Cu²⁺, Zn²⁺, and Ni²⁺ were investigated by a batch equilibration technique at 25°C as a function of contact time, metal ion concentration, mass of resin used, and pH. Results of the study revealed that the resin exhibited higher capacities and a more pronounced adsorption toward Fe²⁺ and that the metal‐ion uptake follows the order: Fe²⁺ > Cu²⁺> Zn²⁺ >Ni²⁺. The adsorption and binding capacity of the resin toward the various metal ions investigated are discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of water-soluble polymers containing sulfonic acid and amine moieties for the recovery of metal ions using ultrafiltration

Copolymers from 2-acrylamido-2-methyl-propane sulfonic acid (APSA) and N-acryloyl-N-methyl piperazine (AP) were synthesized by radical polymerization with ammonium peroxydisulfate as the initiator. The copolymerization yield ranged between 93 and 95%. The copolymers were completely water soluble, and were characterized by FTIR and NMR spectroscopy. The copolymer composition was determined from elemental analysis through the S/C ratio. The binding capacity for metal ion was studied by the LPR technique at different pH and filtration factors. The retention depended strongly on the pH and on the copolymer composition. With increasing pH and increasing content of APSA units in the copolymer, the metal ion retention increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 22–30, 2001     

聚2-丙烯酰胺-2-甲基丙磺酸高吸水性树脂等温吸附重金属离子

用溶液聚合法合成了聚2-丙烯酰胺-2-甲基丙磺酸(PAMPS)高吸水性树脂。研究了PAMPS树脂等温时Pb(NO3)2,Cu(NO3)2,Zn(NO3)2中溶液浓度、吸附时间对吸附的影响。结果表明,对Pb2+的吸附质量分数随Pb(NO3)2溶液浓度、交联剂浓度和中和度增加而增大;对不同金属离子的吸附质量分数随溶液浓度增加而增加,其吸附质量分数顺序为Pb2+Cu2+>Zn2+,Langmiur等温吸附方程能较好地拟合实验数据。吸附Pb2+的PAMPS树脂在1 mol/L HCl溶液中的解吸附比随时间延长而增加,解吸附10 min后解吸附质量分数基本达定值。     

Resins containing amino and carboxylic acid groups. Synthesis,characterization, and metal ion retention properties

The crosslinked poly[3‐(methacryloylamino)propyl]dimethyl(3‐sulfopropyl)ammonium hydroxide], P(MAPDSA), and poly[3‐(methacryloylamino)propyl]dimethyl(3‐sulfopropyl)ammonium hydroxide‐co‐acrylic acid], P(MAPDSA‐co‐AA), were synthesized by radical polymerization. The resins were completely insoluble in water. Due to the lower metal ion retention of P(MAPDSA), the metal ions investigated under competitive and noncompetitive conditions for Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), and Cr(III) ions by batch and column equilibrium procedures were carried out only for P(MAPDA‐co‐AA), particularly for Hg(II). The resin–Hg(II) ion equilibrium was achieved before 15 min. The resin showed a maximum retention capacity value for Hg(II) at pH 2 of 1.89 meq/g. The resin showed a high selectivity to Hg(II) ions. The recovery of the resin was investigated at 25°C with different concentrations of HNO₃ and HClO₄. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 525–530, 2005     

Synthesis and adsorption properties of magnetic resin microbeads with amine and mercaptan as chelating groups

Three magnetic chelating resins containing amino and mercapto groups were prepared by the suspended condensation polymerization of 2‐chloroethoxymethyl thiirane with diamines. The magnetic resins were microbeads whose diameter was in the range of 10 to 45 μm. The structure of the resins was characterized by XPS, IR, and elemental analysis. Their adsorption properties for Hg(II), Au(III), Pd(II), Pt(IV), Ag(I), Cu(II), Zn(II), and Pb(II) were investigated. The experimental results show the magnetic resins have high affinity for Hg(II) and noble metal ions. In the competitive adsorption, the resins predominantly adsorbed Hg(II) or Pd(II) in the coexistence of Cu(II), Zn(II), and Mg(II). Desorption of Pd(II) loaded on the resins was studied by using 2M hydrochloric acid solution containing 1% thiourea as desorbent. A high desorption ratio (up to 96.5%) was observed, and repeated adsorption/desorption operations showed the probability of repeated use of the magnetic resins. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1587–1592, 2001     

聚酰胺接枝纤维素的合成及对金属离子的吸附性能

以葡萄秸秆为原料提取纤维素,以环氧树脂为交联剂,将聚酰胺交联到纤维素上制得聚酰胺-葡萄纤维素吸附剂。测定聚酰胺-葡萄纤维素吸附剂对Co2+和Fe2+的吸附性能,并研究环氧树脂用量、反应温度和吸附平衡时间对吸附性能的影响。结果表明,当反应温度25℃、吸附平衡时间60 min和m(聚酰胺)∶m(葡萄纤维素)∶m(环氧树脂)=2∶1∶1.5时,制备的聚酰胺-葡萄纤维素吸附剂的吸附性能最好。聚酰胺-葡萄纤维素吸附剂对Co2+和Fe2+的吸附均在60 min后达到平衡,Fe2+和Co2+的最大吸附容量分别为22.40 mg·g-1和16.82 mg·g-1。     

Adsorption behavior of metal ions by amidoxime chelating resin

The adsorption properties of poly(acrylamidoxime) chelating resin for Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), Cr(III), and U(VI) are investigated by the batch technique. Based on the research results of the binding capacity effect of the pH value on sorption kinetic experiments, it is shown that this resin has higher binding capacity to uranyl ions, fast kinetics, and very good selectivity from binary metal ion mixtures with Cu(II) and Pb(II). The uranyl ion sorption strongly depends on the pH value of the solution. The highest value of 99% is at pH 5, but at pH 1 there is no retention. The adsorbed UO can be eluted by sulfuric acid and sodium carbonate. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1994–1999, 2000     

Synthetic resins: XV. Chelation ion exchange properties of 2,4- dinitrophenylhydrazone of resacetophenone-formaldehyde resin

A number of copolymers were synthesised by condensing the 2,4-dinitrophenylhydrazone of resacetophenone with substituted benzoic acids/ phenols and formaldehyde in the presence of sodium hydroxide or hydrochloric acid. The decomposition temperature, solubility and viscosity of the polymers have been determined. The ion-exchange properties have been studied by using a batch equilibrium method. The distribution of a number of metal ions between an aqueous solution and the resin have been measured. A wide range of pH and variable ionic strengths have been investigated.     

Preparation and adsorption properties of resins containing amine,sulfonic acid,and carboxylic acid moieties

Completely water‐insoluble resins containing amine, carboxylic acid, and sulfonic acid as ligand groups were synthesized by radical polymerization in solution. The yield was higher than 97%. The resins were characterized by FTIR spectroscopy and thermal analysis. The metal ion retention properties at different pH values were investigated by a batch method. Metal ions studied were: Cu(II), Cd(II), Zn(II), Hg(II), Pb(II), and Cr(III). The metal ion binding ability depended strongly on the pH. The retention properties were also tested under competitive conditions. Elution of the metal ion was investigated in acid medium at different concentrations. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 700–705, 2003     

Synthesis of chelate resins derived from furfural and their adsorption properties for metal ions

A series of new chelate resins were synthesized by ring‐opening polycondensation of the reaction mixture of furfural with diethanolamine, using sulfuric acid as a catalyst, and the resulting chelate resins were employed in the adsorption for metal ions Bi, In, Sn, V, Ga, Y, Ti, and Pb. The composition, structure, and properties of the resulting chelate resin were studied by means of fourier transform infrared (FTIR), electron paramagnetic resonance spectrum (EPR), and elemental analysis methods. Meanwhile, the adsorption properties of the resulting chelate resins for the above metal ions were investigated by inductively‐coupled plasma–atomic emission spectrometry (ICP‐AES) procedures. The results show that the resulting chelate resins hold the structure consisting of hydroxyl groups, amine groups, and conjugated π bonds, as well as more crosslinkages, and so they exhibit a good reactivity and chemical stability. The adsorption experiments show that the chelate resins could well adsorb V, Ga, Y, Ti, and Pb in a wider acidity range and exhibit a good adsorption selectivity. Particularly, the chelate resins could adsorb and desorb for Pb, Bi, In, V, Y, and Ti, quantitatively, in the given conditions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1620–1626, 2006     

Polymeric pseudocrown ether resins containing azacrown and azathiacrown ethers: Synthesis and adsorption for metal ions

Eight novel polymeric pseudocrown ether (PPCE) resins containing azacrown and azathiacrown ethers were prepared by chemical reactions of the precursor of 1-chloro-2,3-epoxypropane, 1-(2-chloroethoxy)-2,3-epoxypropane, 1-chloro-2,3-epithiopropane, and 1-(2-chloroethoxy)-2,3-epithiopropane with triethylolamine or diethylolamine in the presence of NaH. The maximum adsorption capacities of PPCE resins for noble metals are 4.67 mmol Au/g-resin, 2.2 mmol Pd/g-resin, 0.7 mmol Pt/g-resin, and 7.3 mmol Ag/g-resin. The structure of PPCE resins were characterized by IR spectra and element analysis. The adsorption of PPCE resins for noble metals is jointly conducted by PPCE polymer backbone and the azacrown or azathiacrown cavity. The XPS study shows that there are strong complexion interactions between PPCE and Au(III) or Pd(II). © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:931–938, 1997     

离子交换树脂去除水中硝酸盐的研究

对比研究了国内生产的5种阴离子交换树脂(D201、D301、D407、330、717)对水中NO3-的吸附解吸情况。动态吸附饱和曲线表明,717和D407对NO3-的吸附较好,饱和吸附量分别为82.8mg/mL和54.8mg/mL,其他3种树脂效果很差;717和D407对NO3-的吸附速率也相对较快。5种树脂吸附等温线与经验公式拟合的线性相关性显著,其中330树脂符合BET经验公式,另外4种树脂符合Langmuir经验公式;再生试验表明5种树脂再生率均能达到85%以上。综合研究结果认为,强碱性苯乙烯系阴离子交换树脂717和螯合树脂D407对NO3-具有较好的吸附解吸性能,可作为去除硝酸盐的选用树脂。     

Grafting of polypropylene and its potential use as metal ion adsorption resin

Polypropylene (PP) was modified by radical grafting of acrylic acid (AA) in the melt by using dicumyl peroxide (DCP) as initiator. To reach a high grafting degree (GD) without substantially modifying PP‐chain structure, a few runs were carried out by employing butyl 3‐(2‐furanyl)propenoate (BFA), which is a coagent able to preserve the molecular weight (MW) of PP macromolecules in the presence of radical grafting reagents. All the samples were extracted with selective solvents to remove unreacted chemicals and free poly(acrylic acid) (PAA), and the GD was accurately determined by using the FTIR methodology. The GD ranged from 1.51 to 4.67 mol %. High‐temperature size permeation chromatography analysis was used to evaluate MW behavior, confirming the control exerted by the presence of BFA on the degradation reactions. DSC, TGA, and SEM analyses were performed to analyze the chemical modification effects on the polymer products' thermal and morphological properties. Finally, selected samples, with a particle size distribution in the range 100–850 μm, were tested as metal ion adsorption resins. Al(III), Cr(III), Zn(II), Cd(II), Pb(II), and Hg(II) were studied, and the highest adsorption efficiency values (in percentage) were obtained for Al(III) (15–20%) and Hg(II) (25–30%). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Adsorption isotherms,kinetic, and desorption studies on removal of toxic metal ions from aqueous solutions by polymeric adsorbent

Adsorption of Cd(II), Co(II), and Ni(II) on aminopyridine modified poly(styrene‐alt‐maleic anhydride) crosslinked by 1,2‐diaminoethane as an ion exchange resin has been investigated in aqueous solution. Adsorption behavior of these metal ions on the resin was studied by varying the parameters such as pH (2–6), adsorbent dose (0–4.0 g/L), contact time (0–240 min), and metal ions concentration (20–300 mg/L). Adsorption percentage was increased by increasing each of these parameters. The isotherm models such as: Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich were used to describe adsorption equilibrium. The results showed that the best fit was achieved with the Langmuir isotherm equation, yielding maximum adsorption capacities of 81.30, 49.02, and 76.92 mg/g for Cd(II), Co(II), and Ni(II), respectively. The pseudo‐first‐order, pseudo‐second‐order, and intra‐particle diffusion kinetics equations were used for modeling of adsorption data and it was shown that pseudo‐second‐order kinetic equation could best describe the adsorption kinetics. The intra‐particle diffusion study revealed that external diffusion might be involved in this case. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41642.