【作者】 葛娜；

【导师】 顾强；

【作者基本信息】 吉林大学 ， 应用化学， 2011， 硕士

【摘要】 磷酸酯是一种重要的精细化学品,且品种繁多,在增塑剂、阻燃剂、催化剂、杀虫剂、抗氧剂、消泡剂及水处理剂等方面有广泛的用途,并在国民经济中占有重要位置。本文运用了备受科学工作者青睐的相转移催化技术,以较高的收率合成了有用的磷酸酯,具有增加反应速度、反应条件更温和、操作简便、收率高、清洁、低毒等优点。以大庆新世纪精细化工有限公司生产的荧光增白剂的副产物磷酸二乙酯钠盐为原料,经纯化处理后,分别研究了磷酸二乙酯钠盐与二氯亚砜合成焦磷酸四乙酯的反应以及在相转移催化剂存在下,磷酸二乙酯钠盐与取代氯化苄、硫酸二乙酯的反应,均以较好的收率得到了目标产物。在磷酸二乙酯钠盐和二氯亚砜的反应中,通过正交试验得到合成焦磷酸四乙酯的最佳反应条件,然后在最佳条件下重复实验3次,得到满意的实验结果,同时证明了正交实验结果的可靠性。通过折射率、质谱、红外、1H NMR、31P NMR等对所合成的焦磷酸四乙酯进行了表征,并且提出了可能的反应机理。在相转移催化条件下,磷酸二乙酯钠盐分别和取代氯化苄、硫酸二乙酯反应合成了取代苄基二乙基磷酸酯和磷酸三乙酯。讨论了投料比、反应温度、催化剂种类和加入量等因素对苄基二乙基磷酸酯收率的影响,确定了最佳的反应条件,并对反应机理进行了探究。同时讨论了取代氯化苄上推、吸电子效应对取代苄基二乙基磷酸酯收率的影响,对合成的所有目标产物利用折射率(nD)、红外光谱(IR)、核磁共振氢谱(1H NMR)和质谱(MS)等进行了表征,通过紫外—可见分光光度法对磷酸三乙酯中磷的含量进行了定量分析,磷酸三乙酯的含量达到99%以上。更多还原

【Abstract】 Organic phosphate is an extremely useful important fine chemical, and including many varieties. It has a wide application in plasticizers, flame retardants, catalysts, insecticides, antioxidants, defoamers and water treatment agent. And it occupies an important position in the national economy.In this paper, useful organic phosphate products were synthesized by phase transfer catalysis method which was used by many research scholars. It has the advantages of increasing reaction rate, mild reaction conditions, simple operations, high yields, clean technology and low toxicity and so on.Sodium salt of diethyl phosphate derived from the by-product of fluorescent brightener ER in Daqing New Century Fine Chemical Co., Ltd was used as raw materials. Because of complex composition of industry wastes, it has been purified firstly. Then we studied three reactions separately, such as sodium of diethyl phosphate with thionyl chloride, in the phase transfer catalysis sodium of diethyl phosphate with substituted benzyl chlorides and diethyl sulfate. The resulting compounds of three reactions are obtained in better yield by applying this phase transfer catalysis method.In the preparing tetraethyl pyrophosphate from sodium of diethyl phosphate and thionyl chloride, the optimized reaction conditions was obtained by orthogonal experimental design, then we repeated several experiments at the optimized reaction conditions, and the results are basically stable. The synthesized product was characterized by refractive index, MS, IR,1H NMR and 31P NMR. The possibly mechanism of this reaction was explored.In phase transfer catalysis, substituted benzyl diethyl phosphates and triethyl phosphate were synthesized from sodium of diethyl phosphate and substituted benzyl chlorides, diethyl sulfate separately. The effects of the raw material molar ratio, reaction temperature, catalyst structure and amounts on the yield of the benzyl diethyl phosphates were investigated and the possibly mechanism of this reaction was explored. At the same time, the effect of electron-donating substituting groups and electron-withdrawing substituting groups on substituted benzyl diethyl phosphates has been studied. The structures of all target products generated were confirmed by refractive index, MS, IR, and ~1H NMR. Through the ultraviolet - visible spectrophotometry, the content of triethyl phosphate is measured above 99%.更多还原