3, 3'-二乙基-1, 1'-一缩二乙二醇二羰基双硫脲的合成、表征与性能

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摘 要：以一缩二乙二醇双氯甲酸酯与硫氰酸钾为原料，以N, N-二甲基苯胺为催化剂，经相转移催化反应，合成一缩二乙二醇二羰基双异硫氰酸酯中间体；该中间体再与乙胺发生加成反应，合成了一种未见报道的3,3'-二乙基-1,1'-一缩二乙二醇二羰基双硫脲(DEOECTU)。经元素分析、红外光谱和核磁共振氢谱分析，证实所合成的化合物即为目标产物。DEOECTU与金属离子的作用结果表明：在实验条件下，DEOECTU与Zn²⁺、Pb²⁺、Fe³⁺或Fe²⁺的之间可能不存在化学作用，而与Cu²⁺之间存在化学作用，其可通过分子中的S和N原子与Cu²⁺作用而生成螯合环。吸附实验结果表明：DEOECTU能以化学作用方式吸附在黄铜矿表面，其在黄铜矿表面的吸附量远远高于在黄铁矿、闪锌矿和方铅矿表面的吸附量。纯矿物浮选实验进一步表明，DEOECTU对黄铜矿具有优良的捕收能力，而对黄铁矿、闪锌矿和方铅矿的捕收能力弱。

关键词：二乙氧羰基双硫脲；合成；金属离子；吸附；浮选

Synthesis, characterization and properties of 3,3'-diethyl-1,1'-oxydiethylenedicarbonylbis(thiourea)

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Abstract:The synthesis and characterization of novel thiourea compounds containing two alkoxycarbonyl and two thiourea groups were reported. Using oxydiethylene bis(chloroformate) and KSCN as reactants, N,N-dimethylaniline as catalyst, an oxydiethylenedicarbonyl bis(isothiocyanate) intermediate was synthesized by a phase transfer catalytic reaction. Then, through a nucleophilic addition reaction, this intermediate reacts with ethylamine to produce 3,3'-diethyl-1,1'-oxydiethylenedicarbonyl bis(thiourea) (DEOECTU). The compound DEOECTU was characterized by UV-visible spectra, elemental analysis, infrared spectra and ¹H NMR. The results of the interation of DEOECTU with metal ions indicate that DEOECTU can react with Cu²⁺ in solution to form a chelated complex through bonding of its S and N atoms with Cu atom, but no reaction of DEOECTU with Zn²⁺, Pb²⁺, Fe³⁺ or Fe²⁺ is observed under the experimental conditions. The results of adsorption measurement demonstrate that DEOECTU can be chemically adsorbed on chalcopyrite surface, and the adsorption amount of DEOECTU on chalcopyrite surfaces is further greater than on pyrite, sphalerite or galena surfaces. The flotation results of pure minerals were further confirmed that DEOECTU exhibits superior collecting power to chalcopyrite and good selectivity against pyrite, sphalerite and galena.

Key words:diethoxycarbonybis(thiourea), synthesis; metal ion; adsorption; flotation