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。     

Studies of syntheses and adsorption properties of chelating resin from thiourea and formaldehyde

Chelating resins are useful substances in industry because of their extraordinary adsorption properties for specific metal ions. In this study, a new type of chelating resin is synthesized simply by reaction between thiourea and formaldehyde. The synthetic conditions and the structure of the product are approached and the adsorbing capacities for 11 metal ions, adsorbing rates, and selectivities investigated. The results of the experiments show that the resin has high adsorbing capacities for Ag(I): 13.1 mmol/g, and for Au(III): 6.95 mmol/g. Adsorbing rates are close to 100% in dilute solution. Isothermal adsorbing study reveals that the adsorption is monomolecular layer adsorption process. It is hopeful for the resin to be used for concentrating and retrieving Ag(I) and Au(III) ions from their dilute solutions in industry. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3127–3132, 2001     

The chelating properties of chitosan fibers

Chitosan fibers were treated with aqueous solutions of CuSO₄ and ZnSO₄ for different periods of time to prepare samples containing different levels of metal-ion contents. The effect of metal ions on the tensile properties of chitosan fibers was studied. It was found that after chelation of metal ions the chitosan fibers gained substantial increases in both dry and wet strengths. The metal ions were readily removed from the chitosan fibers by treatment with an aqueous EDTA solution. The effect of the degree of acetylation on the chelating ability of the chitosan fibers was also studied. It was found that after acetylation the chitosan fibers lost the chelating ability due to the conversion of primary amine groups to acetamide groups. © 1993 John Wiley & Sons, Inc.     

Studies on selective adsorption resins. XXI. Preparation and properties of macroreticular chelating ion exchange resins containing phosphoric acid groups

Macroreticular cation exchange resins containing phosphoric acid groups (RGP) were prepared by the reaction of glycidyl methacrylate–divinylbenzene copolymer [or poly(glycidyl methacrylate)]beads (RG) with phosphoric acid or phosphorous oxychloride, and the adsorption behavior of metal ions on the RGP was investigated. The phosphorylation of the polymer beads could be effectively carried out by treatment of the polymer beads with 85% phosphoric acid at 80°C for 3 h. The RGP obtained from glycidyl methacrylate–divinylbenzene (2 mol %) copolymer beads showed high cation exchange capacity, salt splitting capacity, and adsorption capacity for Cu²⁺, Zn²⁺, Cd²⁺, Ca²⁺, and Ag⁺. On the other hand, the RGP obtained from poly(glycidyl methacrylate)beads had high adsorption capacity for Al³⁺, Fe³⁺, and UO₂²⁺. The RGP prepared by treating the RG with phosphoric acid had a higher selective adsorption for Li⁺ than for Na⁺.     

Studies on syntheses and properties of episulfide‐type optical resins with high refractive index

A series of novel high refractive index episulfide‐type optical resins were prepared by ring‐opening copolymerization of bis(β‐epithiopropylthioethyl) sulfide (BEPTES) with episulfide derivative of diglydicyl ether of bisphenol A (ESDGEBA) and 2,4‐tolylene diisocyanate (TDI), respectively, in the presence of triethylamine as a curing catalyst. The episulfide monomers, BEPTES and ESDGEBA, were synthesized from their corresponding epoxy compounds, respectively. The cured transparent resins exhibit high refractive index (n_d > 1.63) and relatively low dispersion. The refractive index (n_d) and Abbe's number (ν_d) of the BEPTES/ESDGEBA curing system increased linearly with the weight content of BEPTES monomer in the range from 1.633 and 34.0 for the copolymer with 10 wt % of BEPTES to 1.697 and 38.1 for the homopolymer of pure BEPTES. For the BEPTES/TDI curing system, the refractive index and Abbe's number varied linearly with the molar ratio of BEPTES to TDI from 1.652 and 28.7 to 1.669 and 34.6. High glass‐transition temperatures (T_g > 130°C) of the cured BEPTES/TDI resins were observed, which indicate that the cured BEPTES/TDI resins possess a good heat resistance. The optical, physical, and thermal properties of the episulfide‐type cured optical resins were also discussed in this study. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2426–2430, 2003     

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.     

Effect of carboxymethylation on the absorption and chelating properties of chitosan fibers

Chitosan fibers were treated with chloroacetic acid to prepare partially substituted carboxymethyl chitosan fibers. Fibers with different levels of carboxymethylation were prepared by controlling the ratio between the fiber and the amount of chloroacetic acid. The absorption properties of the modified fibers for Cu(II) ions were studied at different concentrations, temperature, time, and pH. Results showed that the carboxymethylated chitosan fibers were more effective than the original chitosan fibers in removing Cu(II) ions from aqueous solutions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3110–3115, 2006     

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     

Synthesis and study of the chelating properties of 3-carboxy-4-hydroxyacetophenone-formaldehyde resins

3-Carboxy-4-hydroxyacetophenone (CHAP) was polycondensed with various proportions of formaldehyde using alcoholic alkali as catalyst. The resin samples, designated as CHAP-F, have been characterized by elemental analyses and IR spectroscopy, by estimation of their number average molecular weights (M?_n), by measurement of intrinsic viscosity, and by TGA. Polymeric metal chelates of one CHAP-F sample with Cu²⁺, Fe³⁺, Co²⁺, Ni²⁺, and UO₂²⁺ ions have been prepared and characterized. Ion-exchanging properties of one CHAP-F resin sample for Fe³⁺, Cu²⁺, and Ni²⁺ metal ions are studied by the application of the batch-equilibration method.     

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.     

S-940螯合树脂运行情况总结

总结了S-940螯合树脂在盐水精制过程中的运行情况,介绍了树脂的工作原理、物化性能以及盐水精制的效果,提出了运行中应注意的问题。     

Studies of selective adsorption resin. XXIV. Preparation and properties of macroreticular chelating resins containing both polyethylenepolyamine side chains and mercapto groups

The macroreticular chelating resins containing both polyethylenepolyamine side chains and mercapto groups were prepared by the reaction of 2,3-epithiopropyl methacrylate-divinylbenzene macroreticular copolymer beads with polyethylene-polyamine. The adsorption behavior of metal ions on the obtained resins was then investigated. The amination of the macroreticular copolymer beads could effectively be carried out by treatment of the polymer beads with polyethylenepolyamine in organic solvent (benzene, terahydrofuran) or in the absence of organic solvent at 80°C or 100°C for 60 min. It was found that the adsorption capacity of the resins for metal ions is not only affected by the ion exchange capacity of the resins but also by the porosity of the resins. Hg²⁺, Ag⁺, and Cu²⁺ were effectively adsorbed on the resins even at a pH below 3, whereas Co²⁺, Ni²⁺, and Cd²⁺ were adsorbed at a pH above 3, Mn²⁺ at a pH above 7, and Ca²⁺ at a pH above 8. These metal ions adsorbed on the resins could easily be eluted with dilute mineral acid solution or dilute mineral acid solution containing thiourea.     

Synthesis and properties of polyurethane resins based on liquefied wood

Three polyurethane resins were synthesized from liquefied wood and three diisocyanates, i.e., TDI, IPDI, and HDI. The liquefied wood was obtained by the liquefaction of benzylated wood wastes using Dibasic esters (DBE) as solvent with hydrochloric acid as catalyst for 3 h, at 80°C. The thermal stability and microphase morphology of polyurethane films were investigated by TG, DSC, WAXD, and SEM methods. The experimental results indicated that polyurethane resins from liquefied wood had higher thermal stability than traditional ones, and the special structure and the difference of chemical structure of diisocyanates resulted in the crytallinity and microphase separation of obtained polyurethanes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 351–356, 2004     

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     

螯合树脂对二次盐水精制质量的影响

分析了螯合树脂处理盐水的原理和二次盐水质量的主要影响因素,提出了树脂使用过程中的注意事项,总结了正常发挥螯合树脂性能、有效提高二次盐水质量的经验。     

壳聚糖基聚电解质复合膜的制备及性能

为了克服壳聚糖薄膜力学强度差和在体液内降解太快的缺陷, 首先用"一步法"合成了—COOH含量及疏水性可控的苹果酸与乳酸共聚物(PML), 再将共聚物与壳聚糖(CS)复合, 通过溶液浇铸-挥发的方法制备改性复合薄膜。通过红外(FT-IR)、热重分析(TGA)、力学性能测试、降解实验及体外细胞毒性实验等方法对复合膜进行分析, 研究L-苹果酸(MA)与D,L-乳酸(LA)的投料比(n_MA:n_LA)对复合膜性能的影响。结果显示:当n_MA:n_LA为1:1.5时, 该共聚物与CS的复合膜拉伸强度达到54.8MPa, 断裂伸长率为10.7%, 质量损失50%所需时间为28天, 细胞相对增殖率为98.7%。研究表明:通过共聚物与壳聚糖之间的聚电解质相互作用, 有效形成了结构均匀、性能改善的薄膜, 复合膜的柔韧性提高, 降解时间适当延长, 性能可由共聚物的投料比来调节。复合膜无细胞毒性, 生物相容性好, 作为手术后防组织粘连材料具有光明的应用前景。     

具有可见光响应混晶TiO_2光催化剂的制备及光催化性能研究

采用一步水热法制备锐钛矿/金红石TiO_2混合晶体,探讨锐钛矿相和金红石相比例对光催化降解罗丹明B的性能影响以及混晶TiO_2的光催化机理。结果表明,当金红石相的比例为20%,TiO_2混晶在紫外辐射和太阳光下,使初始浓度10 mg/L的罗丹明B完全降解的时间分别为50 min和150 min;活性物捕捉实验证明,·OH为催化体系中的关键活性物质。     

The research on syntheses and properties of novel epoxy/polymercaptan curing optical resins with high refractive indices

A novel thioether glycidyl resin bis[3-(2,3-Epoxypropylthio)phenyl]-sulfone (BEPTPhS) with high refractive index was synthesized by condensation of bis(3-mercaptophenyl)sulfone (BMPS) with epichlorohydrin. It's structure was characterized by FTIR, MS and NMR. It was the first time that trimercaptothioethylamine (TMTEA) was used as curing agent to cure epoxy resins. Optical resins possessing high refractive index were prepared by curing diglycidyl ether of bisphenol A (DGEBA) with the mixture of TMTEA and ethylendiamine (EDA) and by curing BEPTPhS/DGEBA with TMTEA. The research on the optical properties of resins of DGEBA cured by the mixtures of TMTEA and EDA indicated that these resins possess higher refractive index (n_d>1.60), lower dispersity (ν_d>34), high impact strength (IPS>30 kJ m⁻²) and higher transmittance. The n_d, ν_d and density of these resins varied linearly with the EDA content in the curing agent mixtures. The optimum ratio of the EDA content to that of TMTEA is 20:80 (molar ratio), at this ratio the cured resin has the optimum optical properties (n_d²⁰=1.61, v_d=35.4). The cured resins of BEPTPhS/TMTEA have a high refractive index (the highest is n_d=1.67). The optical, physical and thermal properties of the cured optical resins of BEPTPhS/TMTEA were discussed in this paper.