废弃溴代环氧树脂制备螯合材料及其对Cu2+的吸附性能

以废弃印刷电路板固体废料中的溴代环氧树脂为高分子母体材料,经酸碱预处理后先用乙二胺进行胺化改性,然后再用氯乙酸进行功能化反应,制备了一种含有氨基乙酸基团的新型螯合树脂。通过傅立叶变换红外光谱仪(FTIR)以及13C NMR对其改性前后的树脂结构进行了表征,并测定了改性前后材料对Cu2+的吸附效果,数据表明:改性制备的胺基乙酸螯合树脂对Cu2+具有良好的吸附效果。此外,通过考察氯乙酸功能化反应过程中反应温度、反应时间以及氯乙酸的用量对改性产物吸附Cu2+的性能影响,确定了改性制备该螯合树脂的最佳工艺参数。结果表明:当树脂用量与氯乙酸的用量比为1∶1时,在60℃下反应8h,改性所得的螯合树脂对Cu2+的吸附效果最佳,最大的吸附容量达到4.727mg/g。     

一种巯基胺型羧酸螯合树脂的制备及其吸附性能

以环硫氯丙烷和多乙烯多胺为原料,通过交联反应合成了巯基胺型树脂(PA树脂)。然后对PA树脂进行氯乙酸化反应,合成了巯基胺型羧酸螯合树脂(PAC树脂),并通过傅立叶变换红外光谱仪(FTIR)对其结构进行了表征。研究了PAC树脂对模拟含Cu2+电镀废水的吸附性能,探讨了树脂用量、吸附时间和pH对Cu2+吸附性能的影响。实验结果表明,在常温常压下,取25 mL浓度为10 mmol/L的废水溶液,PAC树脂吸附Cu2+的最佳用量为0.40 g/mmol Cu2+,最佳吸附时间为150 min,最佳pH为6~10,最大吸附量和最大吸附率分别达到2.53mmol/g和94.7%。PAC树脂对Cu2+的吸附过程符合Langmiur和Freundlich等温吸附方程。     

新型硫脲螯合树脂的合成及对Ag(Ⅰ)吸附性能的研究

以聚苯乙烯小白球树脂为原料,经硝化、还原、接枝等反应,合成了含有硫脲功能基的新型螯合树脂,研究了该树脂对Ag+离子的吸附性能。结果表明,在实验条件下,新树脂在含有Ag+、Cu2+、Zn2+、Fe3+等混合离子的体系中,对Ag+有良好的吸附容量和选择性,在一定条件下,能定量地解析树脂所吸附的Ag+。     

新型咪唑类螯合树脂的制备及吸附性能

以氯甲基化聚苯乙烯树脂为大分子引发剂,采用原子转移自由基聚合新技术(ATRP)合成了咪唑类螯合树脂,并对树脂进行了吸附性能研究,取得了较好的效果。研究表明:该树脂对Au(Ⅲ),Cu(Ⅱ),Ag(Ⅰ)等重金属离子具有较好的吸附性能,在T=293 K,HAc-NaAc体系中,在各自最佳pH值下,该螯合树脂对Au(Ⅲ),Cu(Ⅱ),Ag(Ⅰ)的静态饱和吸附量分别为0.71,0.32,0.30 mmol/g。吸附模型可以用Langmuir等温吸附来描述,树脂具有良好的再生能力。     

聚苯乙烯硫代氨基脲螯合树脂的制备及其对重金属离子的吸附性能研究

以苯乙烯为单体采用分散聚合法合成聚苯乙烯微球,1,4-二氯甲氧基丁烷与聚苯乙烯反应得到氯甲基化聚苯乙烯,用氯甲基化聚苯乙烯与硫代氨基脲反应得到的聚苯乙烯硫代氨基脲螯合树脂。采用红外光谱法、扫描电镜、X射线光电子能谱对其结构及元素组成进行分析。考察了聚苯乙烯硫代氨基脲螯合树脂对Ag+、Cu2+、Pb2+和Cr3+重金属离子的吸附性能。聚苯乙烯硫代氨基脲螯合树脂对Ag+、Cu2+、Pb2+和Cr3+的吸附容量分别为16.38 mg/g、15.25 mg/g、13.69 mg/g和13.12 mg/g。     

含吡咯基聚醚螯合树脂的合成

制备了以聚环氧氯丙烷为主链、侧链末端含吡咯配位基的2种螯合树脂,产物的化学结构经红外光谱和核磁共振氢谱确认.静态最大吸附实验结果表明:该类树脂对Cu2+和Hg2+均有较高的吸附容量(大于1.0 mmol/g),而对Mg2+和Zn2+的吸附容量则较低(小于0.5 mmol/g).吸附动力学研究表明:吸附过程为液膜扩散控制,对Cu2+(pH4)和Hg2+(pH4)的吸附平衡时间分别约为2.5 h和4.0 h.此外,2种树脂在吸附性能上的差异反映出它们化学结构的差异.     

苯并咪唑螯合树脂的性能与结构表征

研究以环氧聚合物为基质的苯并咪唑螯合树脂的结构性能以及配位机制.已合成含有BBPAH的新型螯合树脂,测定其在pH 0～6.0的缓冲溶液中对Cu2、Ni2+、Zn2+、Cd2+和Co2+的配位容量.实验结果表明,在pH0～2.0条件下对Cu2+、Zn2+、Cb2+的配位容量分别为0.84、1.65、0.84 mmol/g,显示出很高的配位选择性.对络合Cu2+树脂进行了EPR表征和配位场的研究,初步证明为四面体配位结构.同时对苯并咪唑螯合树脂在强酸条件下吸附金属离子的机制进行了探讨.     

Mannich反应制备氨基树脂及由其制备的螯合树脂的吸附性能

以乙酰化聚苯乙烯微球为原料经Mannich反应制备了氮含量达13 7mmol/g的氨基树脂,再由该氨基树脂制备了氨基羧酸型和氨基膦酸型螯合树脂,测试了两种螯合树脂对Cu2+、Zn2+、Ni2+的吸附性能。体系中乙酰基会发生多取代反应。将螯合Cu2+、Zn2+、Ni2+离子的树脂吸附牛血清白蛋白第五组分(BSA-V),结果表明氨基羧酸型树脂对BSA-V的吸附性能优于氨基膦酸型树脂。     

一种高吸水树脂对电镀废水中铜离子的吸附研究

以废弃聚乙烯(PE)塑料与具有亲水性基团的丙烯酸(AA)及其盐接枝共聚合成一种高吸水性树脂,并将所得高吸水树脂用于溶液中Cu2+的吸附。通过分光光度法研究了树脂去除水溶液中Cu2+的情况,考察了起始pH、树脂用量、金属离子起始浓度和吸附时间对金属离子去除率的影响。结果表明,该树脂对Cu2+具有较强的吸附性能。树脂初期吸附速率大,吸附达到平衡时的接触时间为30 min。当溶液pH为7.0,Cu2+初始浓度为25 mg/L,树脂用量在8 g/L时,树脂对Cu2+的去除率可达95.0%以上。     

新型偕胺肟基螯合树脂对Ni(Ⅱ)和Cu(Ⅱ)吸附性能研究

用表面引发原子转移自由基聚合(SI-ATRP)将丙烯腈(AN)接枝到氯甲基化聚苯乙烯树脂(PS-CH2Cl)表面,再由羟胺和腈基的胺肟转换反应得到偕胺肟基螯合树脂(PAO-g-PS)。采用红外和扫描电镜对树脂进行了表征,并研究了树脂对Ni(Ⅱ)和Cu(Ⅱ)的吸附性能。结果表明,树脂对Ni(Ⅱ)和Cu(Ⅱ)吸附容量分别达到1.58、1.01mmol/g,经过10次吸附-解吸循环试验,树脂的吸附容量无显著变化,表明树脂具有优异的吸附性能以及良好的重复使用性。     

不同形貌PSt/PGMA双面粒子的制备和表征

溶剂挥发法制备出单分散PSt/PGMA双面粒子,用扫描电镜(SEM)、光学显微镜、红外光谱仪(FTIR)、EDS能谱仪等对其进行了表征。通过控制PSt和PGMA两种聚合物的相对分子质量(简称分子量,以下同),得到具有双面形态的雪人状、橡子状、汉堡状PSt/PGMA复合微球。选取w(十二烷基磺酸钠)=0.25%水溶液作为乳化剂制备PSt/PGMA双面粒子,依靠荧光染色分析和EDS能谱分析,得出两种聚合物相分离过程不完全,确定出了PSt/PGMA双面粒子的组成,较大半球主要为PGMA,较小半球主要为PSt。     

PGMA／Al2O3填充环氧树脂灌封材料性能的研究

采用“Grafting from”的方法,制备了接枝微粒聚甲基丙烯酸缩水甘油酯／Al2O3（PGMA／Al2O3）。研究了PGMA/Al2O3及固化剂用量对环氧灌封材料的性能影响。利用扫描电镜观察了PGMA/Al2O3填充的环氧灌封材料的冲击断面的形貌。结果表明,对氧化铝粒子进行接枝改性后,复合粒子在环氧树脂灌封中得到良好的分散、增韧效果明显优于未改性的Al2O3,且在用量较少时就可明显提高环氧灌封材料的冲击强度。     

PGMA/(Al)_2O_3制备及其对环氧树脂体系性能的影响

将带有环氧基的功能性单体甲基丙烯酸缩水甘油酯(GMA)接枝聚合在微米级氧化铝颗粒表面,制备了接枝微粒PGMA/(Al)_2O_3。考察了各种因素对接枝率的影响;利用红外光谱、扫描电镜表征了PGMA/(Al)_2O_3;并通过扫描电镜观察了PGMA/(Al)_2O_3在环氧树脂中的分散情况,初步研究了PGMA/(Al)_2O_3对环氧树脂体系的增强增韧性能。结果表明:表面引发自由基聚合反应可以成功制备复合粒子PGMA/(Al)_2O3,其接枝率随引发剂浓度和氧化铝与GMA质量比的增大先增大后减小;将PGMA/(Al)_2O_3填充到环氧密封材料中后,氧化铝颗粒在环氧树脂中分散良好,其复合材料的韧性明显高于未改性Al2O3填充的复合材料。     

Preparation of iminodiacetic acid-type composite chelating material IDAA-PGMA/SiO2 and preliminary studies on adsorption behavior of heavy metal ions and rare earth ions

A kind of iminodiacetic acid (IDAA)-type composite chelating materials was prepared by first graft polymerization and subsequent polymer reaction. Monomer glycidyl methacrylate (GMA) was grafted on micron-sized silica gel particles in the manner of “graft through” in a solution polymerization system, resulting in the grafted particles poly(glycidyl methacrylate) (PGMA)/silicon dioxide (SiO₂). Subsequently, the ring-opening reaction of the epoxy groups of the grafted PGMA was carried out with IDAA as reaction reagent, resulting in the bonding of IDAA groups onto PGMA/SiO₂ and obtaining the composite chelating material IDAA-PGMA/SiO₂ particles. The effects of the main factors on the graft polymerization of GMA and the bonding reaction of IDAA were examined emphatically, and the adsorption behavior of IDAA-PGMA/SiO₂ particles toward several kinds of heavy metal ions and rare earth ions was preliminarily explored. The experiments results show that: (a) to obtain the grafted particles PGMA/SiO₂ with high grafting degree, in the graft polymerization step, the reaction temperature and the used amount of initiator should be controlled. The suitable temperature is 70°C and the appropriate used amount of initiator is 1.4 % of the monomer mass. Under the optimal conditions, the grafted degree of PGMA can reach 17.50 g/100 g. (b) It is feasible to introducing of IDAA groups onto PGMA/SiO₂ particles via ring-opening reaction of epoxy groups of the grafted PGMA under alkaline conditions, and the bonding rate of IDAA group can get up to 70% based on epoxy groups of the grafted PGMA. (c)The composite chelating material IDAA-PGMA/SiO₂ possesses very strong chelating adsorption ability for heavy metal ions, and especially toward Pb²⁺ ion, the adsorption capacity can reach 24 g/100 g. (d) The adsorption ability of IDAA-PGMA/SiO₂ for rare earth ions is weaker than that for heavy metal ions. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of monodisperse nonporous crosslinked poly(glycidyl methacrylate) particles with metal affinity ligands for protein adsorption

Monodisperse nonporous crosslinked poly(glycidyl methacrylate) (PGMA) particles with immobilized metal affinity ligands were prepared for selective recovery of proteins. The PGMA particles, with an average size of 2.2 µm, were prepared by a simple dispersion polymerization of glycidyl methacrylate (GMA) and ethylene glycol dimethacrylate (EGDMA). The particles were characterized by scanning electron microscopy (SEM) and Fourier‐transform infrared spectroscopy (FTIR). The epoxy groups of the particles were modified with the metal chelating agent iminodiacetic acid (IDA), which forms metal–IDA chelates at the active sites. After charging with copper ions, the particles were used to recover a model protein, bovine hemoglobin (BHb), in a batchwise manner. The particles had the adsorption capacity of 218.7 mg g⁻¹ with little nonspecific adsorption. The adsorption behavior could be described with the Langmuir equation. The effect of pH on the adsorption was also studied. Regeneration of the metal‐chelated particles was easily performed with 50 mmol L⁻¹ ethylenediaminetetraacetic acid (EDTA), followed by washing with water and reloading with Cu²⁺. The particles could be very useful as an affinity separation adsorbent. Copyright © 2005 Society of Chemical Industry     

Thermal stabilization of poly(3‐hydroxybutyrate) by poly(glycidyl methacrylate)

Poly(3‐hydroxybutyrate) (PHB)/poly(glycidyl methacrylate) (PGMA) blends with the PGMA content up to 30 wt % were prepared by a solution‐precipitation procedure. The thermal decomposition of PHB/PGMA blends was studied by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and differential thermal analysis (DTA). The thermograms of PHB/PGMA blends contained a two‐step degradation process, while that of pure PHB sample exhibited only one‐step degradation process. This degradation behavior of PHB/PGMA blends, which have a higher thermal stability as measured by maximum decomposition temperature or residual weight after isothermal degradation for 1 h, is probably due to crosslinking reactions of the epoxide groups in the PGMA component with the carboxyl chain ends of PHB fragments during the degradation process, and the occurrence of such reactions can be assigned to the exothermic peaks in their DTA thermograms. An isothermal study of these blends at 200–250°C for 1 h indicated that the residual weight was directly correlated with the amount of epoxide groups in the PHB/PGMA blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2945–2952, 2002; DOI 10.1002/app.10318     

Preparation and characterization of imidazole‐functionalized microspheres

The preparation of imidazole‐functionalized latex microspheres by a two‐stage emulsion copolymerization process and their characterization are reported on. Emulsifier‐free emulsion copolymerization of styrene (St) and 1‐vinyl imidazole (VIMZ) exhibited bimodal particle size distributions caused by secondary homogeneous nucleation process. However, secondary nucleation can be avoided by using cetyltrimethylammonium bromide (CTAB) as a stabilizer at a concentration below its cmc (critical micelle concentration). This would result in the formation of monodisperse latex particles. The final particle size diameter depended on the concentration of CTAB as well as the amount of VIMZ. To control the amount of the functional imidazole groups on the latex particle surfaces, independent of the latex diameters, without secondary nucleation of particles, the seeded emulsion copolymerization of styrene and VIMZ was explored as a second‐stage polymerization at different concentrations and ratios of monomers in the presence of the previously prepared monodisperse poly(styrene‐co‐1‐vinyl imidazole) seed latex particles. The concentration of imidazole functional groups on the surface of the latex particles could also be varied through the rearrangement of hydrophilic imidazole groups by varying the second‐stage monomer addition process such as the utilization of monomer‐swollen seed particles or a shot addition of monomers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 120:5753–5762, 2006     

Swelling of poly(glycidyl methacrylate) gel particles by organic solvents

Fine particles of poly(glycidyl methacrylate) (PGMA) were prepared by suspension polymerization and crosslinked via the ring-opening reaction of the epoxide group with formic acid. A fraction of the spherical gel particles averaging about 70°m in diameter was examined under an optical microscope with its swelling behavior in a number of solvents. Equilibrium degrees of swelling were established with accuracy to show that this polymer gel has rather unusual affinities for solvents: (i) It is swollen (and, without the crosslinks, soluble in most cases) in many types of solvents, (ii) it cannot be represented by a single value of solubility parameter, and (iii) it is not swollen at all in water nor in aliphatic alcohols, in spite of the presence of hydroxy groups in the chain.     

铈盐引发高吸附量氨基化PGMA高分子微球合成及去除废水中Cr(VI)(英文)

A novel polyglycidylmethacrylate(PGMA) microspheres with high adsorption capacity of Cr(VI) was prepared by cerium(IV) initiated graft polymerization of tentacle-type polymer chains with amino group on polymer microspheres with hydroxyl groups.The micron-sized PGMA microspheres were prepared by a dispersion polym-erization method and subsequently modified by ring-opening reaction to introduce functional hydroxyl groups.The polymer microspheres were characterized by scanning electron microscopy(SEM) and Fourier transform infrared spectroscopy(FTIR).The results indicated that the polymer microspheres had an average diameter of 5 μm with uniform size distribution.The free amino group content was determined to be 5.13 mmol?g?1 for g-PGMA-NH2 mi-crospheres by potentiometric and conductometric titration methods.The Cr(VI) adsorption results indicated that the graft polymerization of tentacle-type polymer chains on the polymer microspheres could produce adsorbents with high adsorption capacity(500 mg?g?1).The polymer microspheres with grafted tentacle polymer chains have poten-tial application in large-scale removal of Cr(VI) in aqueous solution.     

Studies on preparation of PGMA/Al2O3 and its effect on impact strength of epoxy resin

In this article, two kinds of methods for grafting polyglycidyl methacrylate (PGMA) onto Al₂O₃ surface by the radical polymerization initiated by peroxide groups and double bond groups, respectively, were investigated. In the first method, peroxide groups, as initiators, were immobilized onto the Al₂O₃ surface. Then, GMA was polymerized on Al₂O₃ under the radicals decomposed by peroxide groups, and PGMA was grafted onto Al₂O₃. But in the second method, 3‐methacryloylpropyl trimethoxysilane was chemically bonded onto the Al₂O₃ surfaces firstly to introduce double bonds. Secondly, the copolymerizations between the immobilized double bonds and the monomer GMA were performed, homopolymerizations of GMA followed, and finally PGMA was grafted to the Al₂O₃ surfaces. The effects of grafting methods on grafting degree were examined mainly. At the same time, the effects of different grafting conditions on the grafting degree were researched. Furthermore, the effect of the grafted particles PGMA/Al₂O₃ on impact strength of the epoxy composites was studied. It was found that the grafting degree achieved by the first method was much higher than that by the second, and the grafting degree can reach about 54%. Moreover, the impact strength of epoxy composites containing PGMA/Al₂O₃ particles were improved largely, and which increased with the grafting degree. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009