本文選題：氫氰酸　切入點：甲基亞磷酸二乙酯　出處：《河北大學(xué)》2017年碩士論文

【摘要】：草銨膦是由聯(lián)邦德國Hoechst化學(xué)公司首先開發(fā)的一種有機磷除草劑。其除草作用機理是通過作物的葉片吸收后,經(jīng)過內(nèi)吸作用,然后再由葉片的基部逐漸向端部進行轉(zhuǎn)移。草銨膦對未出土的幼牙和種子無害,且容易降解,因此成為在國內(nèi)和國外都非常受歡迎的一種除草劑。目前國內(nèi)生產(chǎn)草銨膦的主要工藝路線是以亞磷酸三乙酯為原料,與三氯化磷生成一氯亞磷酸二乙酯、再經(jīng)與格氏試劑反應(yīng)生成關(guān)鍵的中間體甲基亞磷酸二乙酯。然后甲基亞磷酸二乙酯經(jīng)過縮醛反應(yīng)、解縮反應(yīng)、解縮產(chǎn)物與氰化鈉和氯化銨進行strecker反應(yīng)、氰基水解反應(yīng)和氨化反應(yīng)等復(fù)雜的反應(yīng)步驟和產(chǎn)品提純步驟最終生成草銨膦成品。此工藝雖然成熟,但存在兩個問題:第一,縮醛必須經(jīng)過解縮后才能進行strecker反應(yīng),解縮后產(chǎn)物須進行精餾,合成和操作步驟長,操作繁瑣,增加了生產(chǎn)成本。第二,strecker反應(yīng)中氰化鈉的使用,導(dǎo)致副產(chǎn)氯化鈉和氯化銨混鹽,給企業(yè)額外增加了環(huán)保壓力。本文研究的甲基亞磷酸二乙酯為原料制備草銨膦的工藝,是一種生產(chǎn)成本低,對環(huán)境友好的路線,因此本課題的開展對草銨膦的合成方法有很強的指導(dǎo)意義。本文研究了甲基亞磷酸二乙酯為原料制備草銨膦的工藝。重點對草銨膦收率起到關(guān)鍵影響的縮酯反應(yīng)進行了研究,通過大量實驗研究最終確定了較優(yōu)的工藝,減少了解縮反應(yīng)步驟及膦醛精餾操作,大大縮短了反應(yīng)時間,提高了生產(chǎn)效率和降低了生產(chǎn)成本;采用氫氰酸為原料替代氰化鈉進行strecker反應(yīng),避免了副產(chǎn)氯化鈉和氯化銨混合鹽問題,通過對副產(chǎn)氯化銨進行處理,實現(xiàn)了循環(huán)利用,徹底解決了環(huán)保副產(chǎn)鹽的問題,通過正交試驗設(shè)計最終確定了氫氰酸為原料進行strecker反應(yīng)制備氨基腈的工藝條件;對氨基腈制備草銨膦步驟進行了一定的探討,通過鹽酸鹽精制和氨化反應(yīng)終點的嚴(yán)格控制,最終得到了98%以上的高品質(zhì)的草銨膦,收率為85%左右。
[Abstract]:Ammonium phosphine is an organophosphorus herbicide first developed by Hoechst Chemical Company of Germany.The mechanism of herbicidal action is that it is absorbed through the leaves of the crop, and then transferred gradually from the base of the leaf to the end.Phosphine oxalate is a very popular herbicide at home and abroad because it is harmless to unexcavated young teeth and seeds and easy to degrade.At present, the main process of producing ammonium phosphine in China is to produce diethyl monochlorite from triethyl phosphite and phosphorus trichloride, and then react with Grignard reagent to form the key intermediate methyl diethyl phosphite.Then diethyl methylene phosphite was synthesized by acetal reaction, decompression reaction, strecker reaction with sodium cyanide and ammonium chloride, hydrolysis of cyanide and ammoniation reaction, and purification steps of the product to form the finished product of ammonium oxalate and phosphine.The use of sodium cyanide in the second strecker reaction led to the by-product of sodium chloride and ammonium chloride mixed salt, which increased the pressure of environmental protection.The process of preparing ammonium phosphine from diethyl methyl phosphite in this paper is a low cost and environmentally friendly route. Therefore, the development of this topic has a strong guiding significance for the synthesis of ammonium phosphine.In this paper, the preparation of ammonium phosphate from diethyl methyl phosphite was studied.The esterification reaction which has a key effect on the yield of ammonium phosphine was studied in this paper. Through a large number of experimental studies, the optimum process was determined, and the steps of the shrinkage reaction and the rectification operation of phosphonaldehyde were reduced, and the reaction time was greatly shortened.The production efficiency was improved and the production cost was reduced, the strecker reaction was carried out by using hydrocyanic acid as the raw material instead of sodium cyanide, the problem of mixed salt of by-product sodium chloride and ammonium chloride was avoided, and the by-product ammonium chloride was treated to realize recycling.The problem of producing salt by environmental protection was solved thoroughly, and the process conditions for the preparation of aminonitrile by strecker reaction of hydrocyanic acid as raw material were determined by orthogonal design, and the steps of preparing ammonium phosphine from aminonitrile were discussed.Through the strict control of the end point of the reaction of hydrochloric acid and ammoniation, more than 98% high quality ammonium phosphine was obtained, and the yield was about 85%.
【學(xué)位授予單位】：河北大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ457.29

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