【作者】 李培国；

【导师】 吕秀阳；

【作者基本信息】 浙江大学 ， 化学工程， 2003， 硕士

【摘要】 3，5，6-三氯吡啶-2-醇钠(简称三氯吡啶醇钠)是一种重要的化工原料和性能优良的螯合浮选剂，更是合成多种农药的重要中间体，特别是用于生产广谱有机磷杀虫杀螨剂毒死蜱。 三氯吡啶醇钠的合成路线按起始原料分主要有吡啶法、三氯乙酰氯法、三氯乙酸苯酯法和丙烯酸法，其中以三氯乙酰氯和丙烯腈为原料，氯化亚铜为催化剂是该产品合成的主要路线。国内外均有关于这一路线合成工艺条件研究的论文和专利发表。从文献报道来看，该路线合成三氯吡啶醇钠的收率多在50～70％之间。 浙江新安化工集团股份有限公司已有一套1000吨／年的毒死蜱生产装置，采用以三氯乙酰氯和丙烯腈为原料的常压一锅法生产三氯吡啶醇钠，但其收率一直较低(平均在56％以下)，迫切需要提高收率以降低最终产品毒死蜱的生产成本，提高其品质和增强市场竞争能力。 从结构上看，以三氯乙酰氯和丙烯腈为原料合成三氯吡啶醇钠包括加成、环化和芳构化三个反应过程。其中以加成反应最为关键，它不仅是最慢的过程，其收率的多少也决定了目的产品三氯吡啶醇钠含量的高低，是整个过程的关键步骤。 本文首先对各步反应的历程进行了研究，把握各步反应的一般特性和规律，重点分析其决定作用的关键过程；其次考察了反应温度、压力、时间，催化剂的种类和助催化剂的选择，溶剂和助溶剂的选择以及各原料之间的配比等因素对三氯吡啶醇钠合成收率和含量的影响。确定了最优的工艺控制指标，并创新性的提出在环化反应中增加降温过程，将丙烯腈的投料方式由一次性加入改为连续滴加或分批加入，最终使三氯吡啶醇钠的合成收率由原来的56％左右提高至65％以上。更多还原

【Abstract】 Sodium 3,5,6-trichloropyridin-2-ol is an important chemical material, chelating floating agent of choiceness performance, main intermediate for synthesizing several herbicides, fungicides, and insecticides, for example, the organic phosphorus insecticide O-O-diethyl-O-3,5,6-trichloro-2-pyridyl phosphorothioate.According to the original material, the method for producing trichloropyridinol sodium including pyridine route, acrylic acid way, benzene trichloroacetate and trichloroacetyl chloride way etc. However, trichloroacetyl chloride technology is adopt broadly at home. A great deal of thesis and patents on the synthesis technique of trichloropyridinol sodium which using trichloroacetyl chloride (TCAC) and acrylonitrile (VCN) had been published over the seas. From the literature, the yield of product is mostly 50 percent to 70 percent.Zhejiang xin’an chemical co., Ltd. has a set of lOOOt/a production devices of chlorpyrifos which using TCAC and VCN to synthesize trichloropyridinol sodium at atmospheric pressure. Whereas, the yield of trichloropyridinol sodium which is always under 56 percent. In order to reduce the producing cost and enhance competition of market of chlorpyrifos , it is essential to improve the yield of trichloropyridinol sodium.See from the structure, the’process which to synthesize trichloropyridinol sodium with TCAC and VCN including Addition, Cyclization and Aromatization. Among the three steps, Addition reaction is the crucial step in that it is not only the slowest process but also how much its yield decides stand or fall of content of trichloropyridinol sodium.The thesis mastered the general characteristic and rule, analyzing especially the crucial process that is decisively from the principle of every step at first. In the second, the paper discussed the following factors such as reaction temperature, pressure, times, the kind of catalyst or co-catalyst, and the kind of solvent or co-solvent, and proportion of all kinds of materials and so on, which is how to influence the yield and content of trichloropyridinol sodium. At last, the thesis brought forward optional control parameters of technology;’ Innovatively add a process of reducing temperature in the Cyclization. Changing the manner joining of acrylonitrile from join-one-off to titration or batch. The data of production indicate that the yield of trichloropyridinol sodium has proved over nine percent.更多还原