含氮聚醚型螯合树脂的合成及吸附性能

通过接枝反应制备了一系列以聚环氧氟丙烷为主链,侧链末端含吡咯配位基的HPnCP（n=6．4,2）螯合树脂。各步产物的化学结构经IR和^1H NMR检测得以确认。静态吸附实验及等温吸附实验结果表明：该类树脂对Cu（Ⅱ）和Hg（Ⅱ）有着较好的吸附性能（大于1．0mmol／g）;对Co（Ⅱ）和Cd（Ⅱ）达到饱和吸附时的平衡浓度约为（0．06～0．07）mol／L;HP4CP对Co（Ⅱ）和Cd（Ⅱ）以及HP2CP对Co（Ⅱ）的等温吸附既可用Langmuir方程描述也可用Freundlich方程描述;但HP2CP时Cd（Ⅱ）的等温吸附不符合Langmuir方程,只可用Freundlich方程描述。     

含氦聚醚型螯合树脂的合成及吸附性能

通过接枝反应制备了一系列以粜环氧氯丙烷为主链,侧链末端含吡略配位基的HPnCP(n=6,4,2)螯整合树脂,各步产物的化学结构经IR和1H NMR检洲得以确认,静态吸附实验及等温吸附实验结果表明:该类树脂对Cu(Ⅱ)和Hg(Ⅱ)有着较好的吸附性能(大于1.0mmol/g),对Co(Ⅱ)和Cd(Ⅱ)达到饱和吸附时的平衡浓度约为(0.06～0.07)mol/L; HP4CP对Co(Ⅱ)和Cd(Ⅱ)以及HP2CP对co(Ⅱ)的等温吸附既可用Langmuir方程描述也可用Freundlich方程描述;但HP2CP对Cd(Ⅱ)的等温吸附不符合Langmuir方程.只可用Freundlich方程描述.     

蛇笼型螯合树脂的合成及性能研究

以羧甲基纤维素为蛇,二乙烯三胺－甘油环氧树脂体系为笼,合成了一种新型弱酸弱碱型蛇笼树脂,并研究其在不同溶剂中的溶胀性能及对Ｃｕ＾２、Ｐｂ＾２＋、Ｎｉ＾２＋、Ｚｎ＾２＋的吸附量、吸附动力学、等温吸附过程等静态吸附性能。     

Synthesis and characterization of some new chelating amphoteric ion-exchange resins

Some new chelating amphoteric ion exchange resins have been synthesized by condensing catechol, 8-hydroxyquinoline, hydroquinone, salicyclic acid, sulfosalicyclic acid, 3-hydroxy-2-naphthoic acid, p-hydroxybenzoic acid, β-resorcylic acid, and anthranilic acid with epichlorohydrin employing diethylenetriamine as a cross linking agent in a nonaqueous medium, toluene. These resins are characterized by their physicochemical properties such as moisture retention ability, true density, apparent density, void fraction, concentration of ionogenic groups, volume capacity, total ion exchange capacity, copper exchange capacity, rate of ion exchange, pH titration curves, apparent pK_a and pK_b values, isoionic point values, oxidative degradation, thermal stability, the effect of temperature of equilibration on the capacity of the resin, swelling behavior in various solvents, and absorption specificity towards certain bivalent metal cations in ammonium acetate–dimethylformamide media.     

Preparation and adsorption properties of chelating resins from thiosemicarbazide and formaldehyde

A novel chelating resin was synthesized in just one step under mild synthetic conditions. The synthesis was carried out through the copolymerization of thiosemicarbazide and formaldehyde in an aqueous solution. The adsorption properties for some noble metal ions were investigated. The results showed that the resin had high adsorption selectivity for Au(III) and Ag(I). The adsorption capacities for the two metal ions reached up to 7.3 and 11.8 mmol/g, respectively. The adsorption rate for the two metal ions in a dilute solution was 99.9%. The adsorption fit first‐order kinetics, and an isothermal adsorption study indicated that it corresponded to Langmuir monomolecular layer adsorption. The change in the bonding energy during the chelating process was investigated with X‐ray photoelectron spectroscopy. The study revealed that nitrogen and sulfur atoms of the resins were electron donors and metal ions were electron acceptors in the process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Studies on syntheses and properties of chelating resins based on chitosan

Chelating resins have some good adsorption properties for some metal ions, especially for several noble metal ions. Thus to retrieve rare metals using chelating resins is always an interesting project for chemistry researchers. In this study we synthesized a series of chelating resins based on chitosan and investigated adsorbing capacities, adsorption rates, and adsorption selectivities for Ag(I), Au(III), Pd(II), Pt(IV), Cu(II), Hg(II), and Zn(II). The results indicate that the resins have remarkable adsorbing capacities and adsorption rates for four noble metal ions and Hg(II). For instance, one of the resins adsorbs Au(III) and the adsorbing capacity is up to 7.11 mmol/g. However, the adsorbing capacities of the resins for Cu(II) and Zn(II) are much less than for the noble metal ions. Finally, x-ray photoelectron spectroscopy studies of a chelating resin and its metal chelates were made. The result reveals that the basis of the chelations is a chemical process. © 1996 John Wiley & Sons, Inc.     

Synthesis of chelating resins with iminodiacetic acid and its wastewater treatment application

The chelating resins have high potential applications for the selective removal and recovery of metal ions from industrial waste solutions. The hydrophilic acrylate monomer with the iminodiacetic acid chelating group was prepared from glycidyl methacrylate and iminodiacetic acid at 60°C. The microbeads, prepared from acrylate monomer with the iminodiacetic acid chelating group, were employed by inversion suspension polymerization. In the pH range of 2–6, a reasonably good equilibrium sorption capacity is maintained for Cr³⁺ (ca. 2.7 mmol/g) and Cu²⁺ (ca. 1.8 mmol/g) in the chelating resins. The adsorption of Cd²⁺ and Pb²⁺ on microbeads is clearly affected by the pH of the solution, such that these ions' adsorption capacity increased with the pH of the aqueous solution. The adsorption of Cd²⁺ (ca. 1.25–1.87 mmol/g) and Pb²⁺ (ca. 0.99–1.89 mmol/g) showed a maximum at approximately pH = 5 and 6, respectively. The adsorption isotherms of Cr³⁺ and Cu²⁺ adsorbed on microbeads were following the Langmuir isotherm, but the adsorption behavior of Cd²⁺ and Pb²⁺ were not. The concentration of alkaline earth–metal cations on the range of 0–200 ppm had no influence on metal ions adsorbed capacity of chelating resins. Additionally, NTA (nitrilotriacetic acid) had no significant influence on metal ion adsorption by chelating resins. Furthermore, phenol pollutant can be adsorbed effectively by metal ions chelated microbeads; therefore, the microbeads were useful not only in recovering metal ions but also in the treating phenol pollutants in wastewater. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1353–1362, 2002; DOI 10.1002/app.10243     

Synthesis and characterization of amide linkage-incorporated polyethyleneimine-based chelating resins and studies of the crosslink density and surface properties on metal ion uptake

The chelating resins incorporating amide linkages were synthesized in open reaction vessels (OV) by polycondensing different proportions, viz., 1 : 1, 1 : 1.3, and 1.3 : 1 of polyethyleneimine (PEI) and diethylenetriaminepentaacetic acid (DTPA), respectively, at 145–155°C, and at varying curing times (15 h and 22 h). For the proportion 1 : 1, the synthesis was performed in a closed reaction vessel (CV) as well. The resins were characterized by FTIR, elemental, and thermogravimetric analysis, apart from sarptometric surface studies. The extent of crosslinking was evaluated by swelling measurements and the chemical stability was assessed by acid and alkali treatment. The effect of the mode of heating and curing times on the extent of crosslinking and pore structure modifications were evaluated. The influence of these factors on the capacities, the kinetics, and the break through curve trends of these resins were studied using zinc and cadmium metal ions as references. The reproducibility of the resins were ascertained by assessing the extent of change in the break through curve trends of their different batches, synthesized under identical conditions. © 1993 John Wiley & Sons, Inc.     

Synthesis and properties of silicon-containing bismaleimide resins

Two novel bismaleimide (BMI) monomers containing silicon atom in the structure, i.e., bis[4-(4-maleimidophenylcarbonyloxy)phenyl]dimethylsilane (BMI-SiE1) and bis[4-(4-maleimidophenyloxycarbonyl)phenyl]dimethylsilane (BMI-SiE2), were designed, synthesized, and polymerized with and without the use of diamine as comonomers to yield novel silicon-containing BMI resins. Both monomers obtained are readily soluble in organic solvents, such as chloroform and N, N-dimethylformamide. Differential scanning calorimetry and thermogravimetric analysis investigation of these two monomers indicated a high polymerization temperature (T_p > 240°C) and a good thermal and thermo-oxidative stability of cured BMI resins. The onset temperature for 5% weight loss was found to be above 450°C in nitrogen and above 400°C in the air. Polymerization of BMI-SiE1 and BMI-SiE2 with 4,4′-diaminodiphenylether (DPE) yielded a series of polyaspartimides that had good solubility and could be thermally cured at 250°C. TGA investigations of the cured diamine-modified BMI resins showed onset of degradation temperatures (T_ds) in the range of 344–360°C in nitrogen and 332–360°C in the air. Composites based on the cured diamine-modified BMI resins and glass cloth were prepared and characterized for their dynamic mechanical properties. All the composites showed high glass transition temperatures (e.g., >190°C) and high bending modulus in the range of 1000–2700 MPa. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and properties of unsaturated epoxyfumarate resins

Synthesis and properties of epoxyfumarate and epoxymaleate resins obtained by the addition of acidic ester of maleic acid to the commercially available resin, Epidian 5, is presented. In acidic ester preparation, n‐hexanol was used. The resins were synthesized in one‐ and two‐step procedures. In the two‐step procedure, acidic hexyl maleate was synthesized separately and then used for the addition reaction with epoxy resin. In the one‐step synthesis, acidic ester was formed during the synthesis process. Properties of the obtained resins were compared. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3077–3084, 2000     

国产螯合树脂的应用

总结了河南煤业化工集团贵州金宏化工有限责任公司树脂塔的运行状况,针对存在的问题提出了保持树脂塔处于最佳运行状态的办法.     

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     

UV固化水性聚氨酯丙烯酸酯的合成与性能

以异佛尔酮二异氰酸酯(IPDI)、聚醚二元醇(DL-1000)、二羟甲基丙酸(DMPA)和甲基丙烯酸羟乙酯(HEMA)为主要原料合成了具有感光性能的水性聚氨酯丙烯酸酯(PUA)乳液,通过红外光谱对其结构进行了表征。其与活性稀释剂二缩三丙二醇二丙烯酸酯(TPGDA)、光引发剂混合均匀得到水性紫外光(UV)固化树脂。通过涂膜性能测试,研究了各配方组分、UV固化条件等对涂膜性能的影响。结果表明:适宜的DMPA质量分数为5.5%～6.0%,NCO/OH物质的量比为1.55∶1,TPGDA质量分数为10%,光引发剂为TPO,其用量为总树脂质量的4%,光照时间为7.0 s,以其制得的PUA树脂外观、贮存稳定性和耐黄变性良好,涂膜的综合性能最佳。     

Synthesis and chelating properties of some poly(amidoxime‐hydroxamic acid) resins toward some trivalent lanthanide metal ions

The chelation properties of the addition‐type polymers poly(amidoxime‐hydroxamic acid) and poly(N‐methyl amidoxime‐N‐methyl hydroxamic acid) toward some trivalent lanthanide metal ions [La(III), Nd(III), Sm(III), Gd(III), and Tb(III)] were studied by a batch equilibration technique as a function of contact time, pH, and counterion. The effect of the crosslinker, divinylbenzene, was also studied. The selectivity and binding capacity of the resins toward various lanthanide metal ions are discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 691–696, 2005     

A spectroscopic study of Cu(II)-complexes of chelating resins containing nitrogen and sulfur atoms in the chelating groups

The structures of different Cu(II)-thiol, dithiocarbamate, methylthiourea and amino complexes have been investigated on the basis of their spectroscopic properties. The influence of the chemical structure, both the nature of the functional groups and the spacers, on the resin chelating behaviour towards Cu(II) ions in diluted solution has been evaluated. The resins are macroporous polystyrene–divinylbenzene polymer functionalized with two spacer groups, poly(ethylene glycol) and poly(ethylene imine) chains, supporting thiol, dithiocarbamate, methylthiourea and amino groups. Electron paramagnetic resonance (EPR) was employed to show the coordination of Cu(II) ions into the complexes. Cu(II)-dithiocarbamate complexes have a square planar coordination with two dithiocarbamate groups bound to the metal. The resins with methylthiourea as functional group form Cu(II)-complexes in tetragonal symmetry with four nitrogen atoms as equatorial ligands. Further, a partial reduction of Cu(II) to diamagnetic Cu(I) with formation of Cu(I)-methylthiourea complexes, where copper is S-bonded to the methylthiourea group, could be suggested. In Cu(II)-thiol complexes, Cu(II) ions are bound through sulfur bridges.     

Synthesis and properties of cationic resins derived from polyether/polyester-modified epoxy resins

Four polyether and one polyester-modified cationic resins were synthesized by reacting polyether/polyester-modified epoxy resins with 2-ethylhexanol-blocked-toluene diisocyanate (2-EH-blocked TDI) and diethanolamine and subsequently neutralizing the resins with acetic acid. Four different polyethers and one polycaprolactone diol (PCP) were used to react with epoxy resin to form polyether-modified epoxy resins (1a–d) and polyester-modified epoxy resin (1e). The extent of reaction of epoxy resin and polyether or polyester was evaluated by the change of epoxy equivalent weight and the gel permeation chromatography curve of the resulting product. Cationic resins were dissolved in suitable solvents and were mixed with deionized water to form emulsions. Some factors, such as pH value of emulsion, solvent content, and applied voltage affecting the emulsion and electrodeposition properties, were investigated. Cationic resins, prepared from PPG (#1000)-modified epoxy resins, yielded a wider pH range of stable emulsion and also yielded deposited films with a pleasing appearance. PEG (#1000)-modified cationic resins produced a higher deposition yield, but higher throwing power was obtained by deposition of the PCP (#530)-modified cationic resins.     

Synthesis and heavy metal ion adsorptivity of macroreticular chelating resins containing phosphono and carboxylic acid groups

Macroreticular copolymer beads were prepared by suspension polymerization of 4-vinylbenzyl chloride (VBC), divinylbenzene (DVB) and monomers with carboxylic ester groups like dibutyl maleate (DBM), dibutyl fumarate (DBF) and dibutyl itaconate (DBI) in the presence of toluene as diluent. The copolymer beads were phosphorylated at the chloromethylated phenyl rings with triethyl phosphite and hydrolyzed by an aqueous sodium hydroxide solution; the hydrolysis on the bead surface converted carboxylic ester/phosphonate groups into carboxylic acid/phosphono groups, respectively. The investigations on the metal ion chelation characteristics of the H-form copolymer beads revealed that they have good adsorptivity toward heavy metal ions like Pb²⁺, Cd²⁺ and Cu²⁺, and poor adsorptivity toward ions like Hg²⁺ and UO₂²⁺. The adsorptivity caused by the three carboxylic ester monomer derivatives was in the order DBM > DBI > DBF. Especially, the Na-form copolymer beads neutralized by alkali treatment were very available for the adsorption of all the metal ions under investigation.     

Phosphonitrilic chloride: 21. Synthesis of chelating polymers with cyclophosphazene thiocarbamate and the properties of chelating polymers

Chelating polymers containing copper, nickel and cobalt have been formed from cyclophosphazene thiocarbamate trimer and copper, nickel or cobalt ions. These polymers obtained from the reaction are amorphous and the values of electron conductivity are $\text{2·7 × 10}{}^{11}\text{Ω-}\text{cm}$, $\text{3·6 × 10}{}^{13}\text{Ω-}\text{cm}$ and $\text{1·5 × 10}{}^{13}\text{Ω-}\text{cm}$ for the Cu, Ni and Co polymers respectively. The Cu polymer is the most thermally stable on heating to 500°C in air.     

Synthesis and properties of cationic resins derived from aniline-modified epoxy resins and various amines

Aniline-modified epoxy resin which contains tertiary amine in the middle of the polymer chain was synthesized by the reaction of aniline and epoxy resin. The resulting aniline-modified epoxy resin and two commercial epoxy resins with different epoxy equivalent weights were reacted with 2-ethylhexanol-blocked toluene diisocyanate (2-EH-blocked TDI) to obtain thermally crosslinkable epoxy resins. These epoxy resins were subsequently reacted with various secondary amines and partially neutralized with acetic acid to give thermally crosslinkable cationic resins. The resulting cationic resins were dissolved in suitable solvents and mixed with deionized water to form emulsions. The crosslinking properties, emulsion, and electrodeposition properties of these resins were studied in some detail. The electro-deposition yields of the emulsions prepared from aniline-modified epoxy resins were higher than those of other emulsions. The crosslinked films prepared from aniline-modified epoxy resins were also glossier than those prepared from commercial epoxy resins. High deposition yield and high glossiness were the characteristic properties of the aniline-modified epoxy resins. Thermal properties were not affected by aniline-modified epoxy resins.     

Synthesis and properties of 1,3,4-oxadiazole-containing high-performance bismaleimide resins

Two novel bismaleimide (BMI) monomers containing 1,3,4-oxadiazole, i.e., 5-tert-butyl-1,3-di[5-(4-maleimidophenyl)-1,3,4-oxadiazole-2-yl]benzene (Buoxd) and 4,4′-[5-(4-maleimidophenyl)-1,3,4-oxadiazole-2-yl]diphenyldimethylsilane (Sioxd), were designed, synthesized and copolymerized with 4,4′-bismaleimidodiphenylmethane (BMDM) to yield a new series of high-performance bismaleimide resins. Both monomers obtained are readily soluble in common organic solvents, such as dichloromethane and chloroform, enabling an easy solution processing. The thermal properties of the two monomers were carefully studied by the differential scanning calorimetry (DSC), optical microscopy and thermogravimetric analysis (TGA, simultaneous DSC). The BMI resins based on a mixture of Buoxd (or Sioxd) and BMDM in a weight ratio of 10% were prepared. DSC investigations showed that the thermal curing of the BMI resins could be accomplished at a lower temperature than the thermal curing temperatures of Buoxd and Sioxd, and the thermal processing window, i.e., the temperature range between the melting transition and thermal curing process, was over 26 °C. The thermal properties and thermal mechanical properties of the resulting BMI resins were investigated by DSC, thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). No glass transition temperature was found in the range of 50–350 °C, and very good thermal stability (T_d > 490 °C in nitrogen) and high thermo-oxidative stability (T_d > 460 °C in air) were revealed. Composites composed of the above BMI resins and glass cloth were also prepared, which showed high bending modulus (>1.6 GPa) at a very high temperature (e.g., 400 °C).