羧甲基二硫代氨基甲酸酯功能化聚氯乙烯树脂的合成及对Ag~+的吸附与选择性能

以聚氯乙烯为大分子骨架,经三乙烯四胺胺化,再与二硫化碳和乙醇钠反应,得到的二硫代氨基羧酸盐改性聚氯乙烯树脂(PV-NS)进一步与氯乙酸钠反应,合成了一种同时舍N,S,O的羧甲基二硫代氨基甲酸酯改性聚氯乙烯树脂(PV-NSO).合成树脂的功能基结构经红外和元素分析确认.对合成树脂的吸附性能研究表明,合成树脂对Ag+、Hg2+、Au<'3+>、Pb2+离子的吸附容量在实验条件下分别达2.058mmol/g、1.514mmol/g,1.125mmol/g和0.415mmol/g,而对Cu2+、Cd2+、Zn2+、Ni2+、Mg2+等离子的吸附容量很小,甚至不吸附.树脂的选择性吸附表明,树脂对Ag+的吸附选择性较好,在有Hg2+、Pb2+、Cd2+、Zn2+、Cu2+或Mg2+共存时,树脂对Ag+的选择性吸附系数分别达4.74、17.33,12.98、∞、7.60和74.14.合成树脂在极性溶剂中的溶胀性能均比在非极性溶剂中好.     

新型N1-(2-呋喃烷基)-5-氟脲嘧啶的α-羟基(硫代)膦酸酯衍生物的合成

通过对N^1-(2－呋喃烷基）－5－氟脲嘧啶的氧化以及与O,O－二乙基硫代亚磷酸酯的加成反应合成了新型N^1-(2－呋喃烷基）－5－氟脲嘧啶的α-羟基（硫代）膦酸酯衍生物,进一步以间氯过氧苯甲酸氧化得到相应的α-羟基膦酸酯衍生物 。     

α-溴代丙酰氯与四氢噻唑-2-硫酮衍生物的反应及量子化学研究

α－溴代丙酰氯分别同四氢噻唑－２－硫酮及（Ｒ）－四氢噻唑－２－硫酮－４－羧酸乙酯反应得到四氢噻唑－２－α－溴代丙酰硫酯２ａ及光学活性４－乙氧羰基四氢噻唑－２－α－溴代丙酰硫酯２ｂ．用半经验的量子化学ＰＭ３方法研究了反应物和产物的电子结构和反应的焓变，得到反应物１ａ异构化的过渡态．     

含α—羰醛功能基树脂的合成及其对尿素吸附的研究.Ⅰ

本文在研究醛类化合物与尿素反应的基础上，确定含有α－羰醛基的化合物在ｐＨ７．４，３７℃下对尿素有较高的反应活性。将α－羰醛基引入到苯乙烯－二乙烯苯共聚物骨架上，合成出带有α－羰醛基的树脂。实验结果表明，含α－羰醛功能基的树脂在ｐＨ７．４，３７℃条件下与目前临床使用的氧化淀粉相比，具有更大的吸附潜力。本文还研究了吸附条件对该树脂吸附性能的影响。     

N-硫代酰基硫乙酸功能化三乙撑四胺交联PVC树脂的制备及对Hg~(2+)的吸附

以聚氯乙烯为原料依次与四乙烯五胺、CS_2和ClCH_2COONa反应合成了一种新的含N、O、S的N-硫代酰基硫乙酸功能化三乙撑四胺交联聚氯乙烯螯合树脂,树脂结构经红外分析和元素分析表征. 探讨了在不同pH值、Hg~(2+)初始浓度、吸附温度和时间等条件下合成树脂对Hg~(2+)的吸附性能. 结果表明,螯合树脂对Hg~(2+)有较快的吸附速率,pH值约为2.0时,树脂对Hg~(2+)的吸附效果最好,随温度升高吸附量逐渐增大. 温度在35 ℃、Hg~(2+)起始浓度为17.66 mmol/L时,树脂对Hg~(2+)的吸附量可达3.330 mmol/g. 树脂对Hg~(2+)的吸附符合Langmuir和Freundlich等温式. 用0.2 mol/L HNO3-10%硫脲对吸附后的树脂进行洗脱,脱附率达99.20%.     

弱酸性氨基二硫代甲酸酯功能化聚氯乙烯树脂对Hg2+的吸附与脱附性能

以聚氯乙烯为原料依次与四乙烯五胺、CS2和ClCH2COONa反应合成了一种含氮、氧、硫的弱酸性氨基二硫代甲酸酯功能化的聚氯乙烯螯合树脂,树脂的结构经红外分析和元素分析表征。探讨了在不同pH值、Hg2+初始浓度、吸附温度和时间等条件下合成树脂对Hg2+的吸附性能。结果表明,螯合树脂对Hg2+有较快的吸附速率,pH=2.0左右时树脂对Hg2+的吸附效果最好,随着温度的升高吸附量逐渐增大,35 ℃时Hg2+起始浓度为0.01766 mol/L时,树脂对Hg2+的吸附量可达3.330 mmol/g。树脂对Hg2+的吸附符合Langmuir和Freundlich等温式。用0.2 mol/L硝酸-10%硫脲对吸附后的树脂进行洗脱,脱附率达99.2%。     

邻氨基苯酚改性壳聚糖树脂的制备及吸附性能的研究

本文制备了一种邻氨基酚改性壳聚糖树脂，用红外光谱和扫描电镜表征其结构，研究了该树脂对金属离子Cu^2 、Pb^2 、Ca^2 的吸附性能。结果表明，改性壳聚糖树脂为蜂窝状多孔微球树脂，平均戏约250μm，不溶于水、酸、碱，其对金属离子的吸附在pH=4时，2h基本达到平衡，对金属离子Cu^2 、Pb^2 、Ca^2 的静态饱和吸附量分别为2.95mmol/g、1.95mmol/g、1.32mmol/g。     

一种新型亲水性胺基羧酸树脂的合成及其性能研究

以交联聚甲基丙烯酸缩水甘油酯为起始聚合物，经氨解和氯乙酸化反应，制得了一类骨架结构与聚甲基丙烯酸羟乙酯类似的亲水性胺基羰酸树脂，研究了这类树脂对Cu^2 的吸附性能，发现这类树脂对Cu^2 的吸附量可高达1.78mmol/g，且可以重复使用。     

二硫代氨基甲酸酚醛型螯合树脂的合成及其对Ag~+的吸附性能研究

以乙二醇单苯醚-甲醛负载三乙烯四胺螯合树脂(PB-TETA)为前驱体,经氨基与二硫化碳反应,得到含二硫代氨基甲酸基酚醛型螯合树脂(PB-TETA-CS2)。对所制备的新型螯合树脂进行了红外光谱和元素分析等表征,研究了树脂对Ag+、Hg2+、Cu2+、Pb2+和Ni2+等金属离子的静态饱和吸附量及树脂对Ag+的动力学及热力学吸附性能。结果表明,该树脂对Ag+的吸附量最高;pH=4时的最大吸附量为0.18mmol/g。树脂对Ag+的吸附受液膜扩散控制,等温吸附过程符合Langmuir单分子吸附模型。     

大孔吸附树脂X—5对维生素B_(12)的吸附

大孔吸附树脂X—5是一种非离子型的优良吸附剂,骨架成分是苯乙烯—二乙烯苯的交联共聚物。其比表面为550m~2/g,平均孔径为300。X—5吸附树脂对维生素B_(12)有良好的吸附及解吸性能。其吸附率高达97％,吸附量高达132mg/g(干树脂),易于洗脱,洗脱率在98％以上。     

含双亚砜及3-氨基吡啶螯合树脂的合成、表征及其吸附性能

合成了含双亚砜及3-氨基吡啶的新型螯合树脂,并进行了红外光谱、比表面积、孔径和元素分析表征。研究了不同pH下该树脂对Mn2 、Cd2 、Pb2 、Cu2 、Zn2 、Hg2 等金属离子的静态饱和吸附量以及在pH=6时该树脂对Hg2 的动力学吸附和热力学吸附。实验结果表明,该树脂对Hg2 的吸附量最大,达到0.82mmol/g,对Hg2 吸附属于液膜扩散控制。等温吸附研究表明,该树脂对Hg2 的吸附可用Langmuir方程描述。     

CMC-Na/DETA-B62型蛇笼树脂对金属离子的吸附性能

本文研究了自合成的蛇笼型螯合树脂-二乙烯三胺交联甘油环氧树脂/羰甲基纤维素体系对Cd^2 ,Pb^2 ,Fe^2 的吸附量，吸附动力学，等温吸附过程等静态吸附性能，同时研究了pH值等因素对吸附性能的影响。实验结果表明，该树脂对Cd^2 具有较强的吸附选择性，能在Cd^2 ,Pb^2 ,Fe^2 3种离子共存时选择吸附Cd^2 ，其选择性系数分别为Kcd^2 /pb^2 =3.77,Kcd^2 /Fe^2 =9.61。该树脂对上述3种离子的吸附量可分别达4.00,1.06,0.42mmol/g。该类树脂可用于含重金属离子污水的处理和金属离子的分离等方面。     

A comparison of preconcentration reagents for flow injection analysis flame atomic spectrometry

A small range of new commercially available chelating resins are compared with a resin prepared in-house in terms of their applicability for on-line preconcentration and matrix separation. The flow injection manifold was designed for rapid matrix separation and the resins were tested for the determination of Cull, ZnII, CdII, MnII and NiII. The resin based on controlled pore glass was found to be better for this rapid procedure because it did not require conditioning, although the polymer based resins had better capacities. The commercially available controlled pore glass based iminodiacetate (IDA) resin had a comparable performance to the in-house controlled pore glass 8-hydroxyquinoline (CPG-8-HQ) resin. The IDA resin had a much higher capacity than the 8-HQ, however as with all IDA based resins, some retention of Call was observed. The sample throughput was 12 h⁻¹.     

ADSORPTION BEHAVIORS OF Pt（IV） AND Pd（II） ON POLYMERIC ESTER THIOUREA RESIN

Polymeric ester thiourea resin （PDTU-I） is a new kind of chelating resin with functional atoms S, N and O, so it is an excellent adsorbent for noble metal ions. In batch testes, the adsorption capacities of PDTU-I for Pt（IV） and Pd（II） increase with the increase of contact time, temperature and initial concentration of metal ions. The adsorption data fit Boyd＇s diffusion equation of liquid film, Langmuir adsorption isotherm and Freundlich adsorption isotherm. The maximum adsorption capacities calculated by Langmuir equation are 2.54mmol/g for Pt（IV） and 4.88mmol/g for Pd（II）. According to FTIR and XPS results, functional groups of PDTU-I coordinate with noble metal ions in the adsorption process.     

PSVA螯合树脂的合成及其对金属离子的螯合性能

合成了大孔螯合树脂聚-N-亚水杨基乙烯基苯胺,研究了它对6种金属离子的螯合性能。结果表明,在pH=5时树脂对Cu²⁺的吸附容量达1.3 mmol/g干树脂。据此提出了一个用此树脂回收废水中微量铜和除去光亮镀镍溶液中微量Cu²⁺的方法,效果良好。     

Synthesis and Properties of a Chelating Resin Containing a Salicylaldimine Group

Abstract

A phenol-formaldehyde polymer, poly(salicylaldehyde 3,5-diylmethylene) was synthesized and characterized. A chelating ionexchange resin was obtained by reacting the polymer with nbutylamine. The chelation characteristics of the chelate-forming resin was studied by a batch equilibration technique. The resin showed fast rates of metal ion uptake and was found to selectively chelate Cu²⁺ and Cd²⁺ ions with capacities up to 3.56 mmol/g over a pH range of 5–8.     

新型螯合树脂研究(Ⅰ)——以聚硫醚为主链伯胺型树脂的合成及吸附性能

利用Gabriel反应以聚环硫氯丙烷为起始物合成4种新型的以聚硫醚为主链的伯胺型树脂,研究了树脂的合成条件及吸附性能.这些树脂对贵金属离子有很高的吸附容量,其中每克树脂对Au(Ⅲ)的吸附容量达到5～7mmol,对Ag⁺的为7～9mmol;而对贱金属离子吸附甚少.可望用于贵金属离子Au(Ⅲ)和Ag⁺的分离与富集.     

A column system for the selective extraction of U(VI) and Th(IV) using a new chelating sorbent

A new method has been developed using (bis-3,4-dihydroxy benzyl)p-phenylene diamine functionalized to XAD-16 (a polystyrene divinyl benzene copolymer) matrix, to preconcentrate mainly U(VI) and Th(IV) from synthetic and real samples. The developed method is free from matrix interference due to alkali and alkaline metal ions and preconcentrates the actinides with a high degree of selectivity, with consistent trace recoveries. The new chelating resin provides dramatic improvement in metal exchange rate, with half value saturation time (t_1/2) of less than 1.6 min. The developed method was superior in its metal loading capacity for U(VI) and Th(IV), with values of 0.666 and 0.664 mmol g⁻¹, respectively. Various physio-chemical properties like effect of solution pH, kinetic studies, resin loading capacity, sample breakthrough volume, matrix effects etc., on metal ion sorption to sorbent phase, were studied using both batch and column method. The new chelatogen was applied to extract U(VI) from near neutral real water samples. Preconcentration and separation of metal ions were possible through pH variation and also by varying the eluant concentration. A high preconcentration factor value of 350 with a lower limit of detection of 20 and 30 ng cm⁻³ was obtained for U(VI) and Th(IV), respectively. The practical applicability of the developed resin was examined using synthetic and real samples such as sea/well water samples. The method provides low relative standard deviation values of <3.5% for all analytical measurements, reflecting on the reproducibility and accuracy of the developed method. The new resin is quite durable with recycling time >35 cycles, without any major change in its quantitative metal uptake nature.     

Synthesis and properties of poly(hydroxamic acid) from crosslinked poly(methacrylate)

Poly(hydroxamic acid) chelating ion-exchange resin was prepared from crosslinked poly(methacrylate) beads. The starting polymer was prepared by a suspension polymerization of methacrylate and divinyl benzene. Conversion of the ester groups into the hydroxamic acid was carried out by treatment with hydroxylamine in an alkaline solution. Hydroxamic acid capacity of the product was 2.71 mmol/g. The resin exhibited high affinity towards Fe(III) and Pb ions and its capacities for Fe(III), Pb, Cu, Ni and Co ions were pH dependent. The ability of the resin to carry out the separation of Fe(III)CuCo/Ni and PbNi ions is also reported.     

酚醛基质苯并咪唑螯合树脂的合成及配位性能

通过1,4-对苯二酚二缩水甘油醚和2,2′-二苯并咪唑二乙胺反应合成四苯并咪唑单体(TBMZ),经甲醛等缩合生成酚醛聚合物为基质的苯并咪唑螯合树脂(PTBMZs)。 新型螯合树脂配基含量达2.1~3.02 mmol/g。新树脂及其单体结构经13C核磁共振谱、FT-IR红外光谱、元素分析和DSC分析确证。 测定了Cu2+、Ni2+、Zn2+、Cd2+和Co2+氯化物在pH值为1.0~6.0的缓冲溶液中的配位容量。 实验结果表明,该类螯合树脂对Cu2+有高度的选择性,KCuX≥4.3非竞争条件下,PTBMZ-1的最大配位容量为1.15 mmol/g(pH=5.0,Cu2+),PTBMZ-2的最大配位容量为0.97 mmol/g(pH=5.0,Cu2+),配基占有率分别为35.9%,33.4%。 PTBMZ-1树脂对Cu2+吸附较快,t1/2=21 min。 电子顺磁共振谱和FT-IR光谱分析结果表明,形成n(金属离子)∶n(配基)=1∶2的螯合物为主。