秋兰姆是一类重要的多硫化物，主要应用于医药、农业和橡胶助剂行业，其传统合成方法存在过氧化程度高，废水化学需氧量（COD）值高，副产大量废盐等问题，亟待发展绿色、高效的新合成技术。电化学有机合成方法是实现秋兰姆类化合物绿色合成的重要途径，具有氧化电位可控、无需引入无机阴离子、反应条件温和等优势，其反应装备与工艺的构建是发展秋兰姆类化合物电化学合成技术的关键核心。论文工作针对秋兰姆类化合物电化学合成装备在低欧姆阻抗、高电极比表面积、高氧化产物选择性方面的技术需求，构建了电极间距仅为0.3mm的电化学微通道反应平台，发展了以甲苯和二硫代氨基甲酸钠（NaR2DTC）水溶液混合物为原料的电化学反应体系，系统考察了电流、电压、流量、反应物浓度、相比等关键因素对秋兰姆收率、反应法拉第效率等参数的影响规律。研究结果表明：在反应电压为2-2.5V且使用金属铂作为阳极的情况下，无过氧化反应发生，四甲基秋兰姆二硫化物的收率达42%，四乙基秋兰姆二硫化物的收率达70%，四正丁基秋兰姆二硫化物的收率达88%，四苄基秋兰姆二硫化物的收率达86%，反应的法拉第效率为85%-100%，证明了电化学微反应过程良好的反应选择性。以镀有FTO的透明玻璃电极作为阳极，构建了可视化的电化学微通道反应装置，系统考察了电压、流量和相比等因素对于微通道内复杂多相流型的影响，揭示了电解气泡的形成与聚并对反应速率和产物溶解的关键作用，分析了反应电流衰减的机制，明确了8%-15%气含率和1.5×10-2 m/s以上液相流速是获得高电流密度的相对优化条件。 以电化学微反应装置和规律研究为基础，提出产物水相溶液循环的绿色反应工艺，利用反应产物中氢氧化钠与仲胺和二硫化碳反应制备了电化学反应原料NaR2DTC水溶液，反应转化率达99%以上，三次溶液循环实验证明该工艺的响应电流、产物收率和法拉第效率稳定，反应的原子经济性接近100%。发展了微颗粒填充床反应器，强化了二甲基二硫代氨基甲酸钠（NaMe2DTC）、二乙基二硫代氨基甲酸钠（NaEt2DTC）、二正丁基二硫代氨基甲酸钠（NaBu2DTC）的合成反应，反应时间不足3 min，保障了循环反应工艺的实施。
Thiuram disulfides are important polysulfides which are mainly used in pharmaceutical, agricultural and rubber vulcanization fields. The conventional synthesis method of thiuram disulfides has some technological difficulties including peroxidation of reactant, high chemical oxygen demand (COD) of wastewater, and the generation of waste salts. It is urgent to develop green and efficient synthesis methods for thiuram disulfides synthesis. Controllable and mild electrochemical organic synthesis is an effective way to achieve the green synthesis of thiuram compounds without inorganic anions. The establishment of reaction equipment and process is the key of thiuram disulfides electrosynthesis.An electrochemical microreaction platform with a channel thickness of 0.3 mm was constructed in order to decrease ohmic impedance, increase electrode specific surface area and achieve high product selectivity. Based on the electrochemical microreactor, a multiphasic reaction system with toluene and sodium dithiocarbamate (NaR2DTC) aqueous solution was developed. The influences of the applied current, voltage, flow rate, reactant concentration and phase ratio on yield and Faraday efficiency were analyzed carefully. The results show that with the voltage of 2-2.5 V and the use of platinum anode, there was no peroxide reaction. The yield of tetramethylthiuram disulfide reached 42%, the yield of tetraethylthiuram disulfide reached 70%, the yield of tetrabutylthiuram disulfide reached 88% and the yield of tetrabenzylthiuram disulfide reached 86%. The Faraday efficiencies of the reaction above were in the range of 85% - 100%, which proved the good selectivity of the electrochemical microreaction process.A visualization electrochemical microreactor was constructed with a transparent glass anode coated with FTO material. The effects of applied voltage, flow rate, and phase ratio on the complex multiphase flow pattern in the microchannel were systematically investigated. The significant effects of bubble coalescence and slug flow on the reaction rate and product dissolution were revealed. Based on the experiments, the mechanism of reaction current attenuation was analyzed. As a result, a gas holdup ranging from 8% to 15% and a liquid phase velocity above 1.5×10-2 m/s were determined as the relatively optimal condition to obtain a high current density. Based on the study of electrochemical microreaction devices and laws, a green reaction process of product aqueous solution circulation was proposed. The aqueous solution of NaR2DTC was prepared by the reaction between secondary amines and CS2 in the NaOH solution generated during electrolysis with a conversion of over 99%. The response currents, product yields and Faraday efficiencies in the three cycles were both stable. Besides, the atomic economy of the reaction is close to 100%. To enhance the reaction rate of sodium dimethyldithiocarbamate (NaMe2DTC), sodium diethyldithiocarbamate (NaEt2DTC) and sodium dibutyldithiocarmate (NaBu2DTC), a microparticle packed bed reactor was developed. The reaction time was less than 3 minutes in the packed bed reactor, which ensured the implementation of the cyclic reaction process.
