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首页> 外文期刊>Journal of Applied Polymer Science >The Limiting Value of ZDMC Formation: New Insight into the Reaction of ZnO and TMTD
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The Limiting Value of ZDMC Formation: New Insight into the Reaction of ZnO and TMTD

机译：ZDMC形成的极限值：ZnO和TMTD反应的新见解

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摘要

The reaction of ZnO and tetramethylthiuram disulfide (TMTD) was reinvestigated in detail. Under conditions where evaporation fo volatiles is possible, TMTD and an excess of ZnO are found to produce bis(dimethyldithiocarbamato)zinc(II) (ZDMC) in limiting amount close to 60 mol %, irrespective of the ratio between ZnO and TMTD. This result points to the operatof more than one route toward ZDMC. When ZnO and TMTD are reacted in closed vessels in inert atmosphere, a nucleophilic reaction of ZnO with TMTD was confirmed by GC-mass spectroscopy (MS) detection of COS and NMR observation of tetramethylthiourea (TMTU). This toute is found to account for about 70 mol % of the total amount of ZDMC formed. A previously unrecognized redox reaction between ZnO, sulfur, and TMTD, furnishing ZnSO_4 and ZDMC, is responsible for approximately 15 mol % of the amount of ZDMC. Other products that were detected are CO_2, CS_2, and tetramethylurea, whereas ZnSO_3, ZnS, and dioxygen were absent. Based on the latter observation, the operation of a mechanism constituting radical reduction of water by TMTD, yielding dioxygen, was excluded.
机译：ZnO和四甲基秋兰姆二硫化物（TMTD）的反应进行了详细的研究。在可能挥发挥发物的条件下，发现TDTD和过量的ZnO会以接近60 mol％的限制量生成双（二甲基二硫代氨基甲酸酯）锌（II）（ZDMC），而与ZnO和TMTD的比例无关。这一结果指向了运营商通往ZDMC的不止一条路线。当ZnO和TMTD在惰性气氛下在密闭容器中反应时，通过COS的GC-质谱（MS）检测和四甲基硫脲（TMTU）的NMR观察证实了ZnO与TMTD的亲核反应。发现该吹塑占形成的ZDMC总量的约70mol％。 ZnO，硫和TMTD之间先前无法识别的氧化还原反应提供了ZnSO_4和ZDMC，约占ZDMC量的15摩尔％。检测到的其他产物是CO_2，CS_2和四甲基脲，而没有ZnSO_3，ZnS和双氧。基于后者的观察结果，排除了通过TMTD自由基还原水而产生双氧的机理。

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