發(fā)布時間：2018-05-27 18:35

  本文選題：聯(lián)苯肼酯 + 水解��； 參考：《西南大學(xué)》2015年碩士論文

【摘要】：水解和光解是農(nóng)藥在環(huán)境中最重要的消減途徑,對農(nóng)藥在環(huán)境中的殘留時間具有決定性作用。本研究以新型殺螨劑聯(lián)苯肼酯為研究對象,以高效液相色譜儀研究其在不同環(huán)境中的水解和光解行為,并通過液質(zhì)聯(lián)用儀分析其水解和光解產(chǎn)物,以推測其可能的水解和光解途徑,對指導(dǎo)科學(xué)合理使用聯(lián)苯肼酯,減輕該農(nóng)藥對環(huán)境的污染,以及該農(nóng)藥的風(fēng)險評估等具有重要的環(huán)境生態(tài)學(xué)意義。主要結(jié)果如下：(1)設(shè)計了9種新的聯(lián)苯肼酯的高效液相色譜檢測條件,其中以Agilent Eclipse Plus C18不銹鋼色譜柱(250 mm×4.6 mm,5μm),二級管陣列檢測器,乙腈：水=70：30為流動相,流速為0.8mL/min,進(jìn)樣體積10gL,檢測波長230nm時,LOD最低(0.01 mg.L-1),出峰時間最短,目標(biāo)峰與雜質(zhì)峰完全分離,峰形良好；(2)建立了聯(lián)苯肼酯的液質(zhì)聯(lián)用檢測方法：電噴霧離子源(ESI)；正離子模式掃描；掃描范圍：50 Da-500 Da；電噴霧電壓(IS):5500 V;氣簾氣(CUR):30.0 Psi;霧化氣(GS1):30.0 Psi;輔助氣(GS2):60.0 Psi;去溶劑溫度(TEM):550℃；碰撞氣(CAD):High；去簇電壓(DP)：25 V；碰撞室入口電壓(EP):10V；駐留時間：0.3 second;(3)研究了萃取劑和分散劑的種類和體積,以及萃取時間,鹽效應(yīng)對渦旋輔助液液微萃取方法萃取水體中聯(lián)苯肼酯效率的影響。結(jié)果表明以0.3mL二氯乙烷作為萃取劑,1mL丙酮作為分散劑,渦旋萃取lmin,不加鹽,4500rpm離心5min時,萃取效果最好,相對回收率超過89%,相對標(biāo)準(zhǔn)偏差小于5.7%：(4)聯(lián)苯肼酯的水解速率隨著初始濃度的增加而變慢；隨著溫度的升高而加快,活化能降低,活化熵的絕對值升高,說明活化能和活化熵共同驅(qū)動其水解反應(yīng)的進(jìn)行；隨著pH的升高而加快,屬于堿性水解,其降解機(jī)理可能與聯(lián)苯肼酯化學(xué)結(jié)構(gòu)中的酯鍵有關(guān)；在河水、湖水、自來水和河水滅菌四種自然水體中的水解速率,是與水體的pH值呈正相關(guān)；聯(lián)苯肼酯的水解反應(yīng)均符合一級動力學(xué)模型；(5)聯(lián)苯肼酯在不同光源中,光解速率為300W高壓汞燈15W紫外燈300W氙燈,且乙酸乙酯乙腈甲醇丙酮,與溶劑的極性無明顯的相關(guān)性；乙腈屬于沒有光敏和光猝性溶劑,因此可推斷乙酸乙酯對聯(lián)苯肼酯的光解存在光敏作用,而甲醇和丙酮對聯(lián)苯肼酯的光解具有光猝作用；(6)在15W紫外燈照射下,隨著pH的升高,光解速率越快；在不同自然水體中,光解速率為河水滅菌湖水滅菌自來水河水湖水純水,是與水體的pH值呈正相關(guān)；(7)通過液質(zhì)聯(lián)用儀,跟蹤分析聯(lián)苯肼酯的水解產(chǎn)物,獲得聯(lián)苯肼酯水解產(chǎn)物的總離子流圖和質(zhì)量分?jǐn)?shù)圖。通過定性分析,初步推測出聯(lián)苯肼酯在純水中三種水解產(chǎn)物,即C17H18N2O3、C14H12N2O3和C13H120；根據(jù)水解產(chǎn)物和化學(xué)鍵斷裂方式,初步推測出聯(lián)苯肼酯的水解途徑是：聯(lián)苯肼酯在水分子的作用下,轉(zhuǎn)化成聯(lián)苯肼酯二氮烯,二氮烯的酯鍵在OH-離子的進(jìn)攻下,發(fā)生堿性水解,使酯鍵斷裂,生成羧酸,羧酸再進(jìn)一步水解,形成分子量更小,結(jié)構(gòu)更簡單的4-甲氧基-聯(lián)苯；(8)通過液質(zhì)聯(lián)用儀,跟蹤分析聯(lián)苯肼酯的光解產(chǎn)物,獲得聯(lián)苯肼酯光解產(chǎn)物的總離子流圖和質(zhì)量分?jǐn)?shù)圖。通過定性分析,初步推測出聯(lián)苯肼酯的五種光解產(chǎn)物,即C17H18N2O3, C14H12N2O3,C12H10, C13H13NO, C13H12N2O和兩種未知結(jié)構(gòu)式的產(chǎn)物(離子碎片為217.6/239.3與242.2)；根據(jù)光解產(chǎn)物和化學(xué)鍵斷裂方式,初步推測出聯(lián)苯肼酯的光解途徑是：聯(lián)苯肼酯在紫外燈的作用下,轉(zhuǎn)化成聯(lián)苯肼酯二氮烯,二氮烯的酯鍵在溶劑中少量OH-離子的進(jìn)攻下,發(fā)生堿性水解,使酯鍵斷裂,生成羧酸；羧酸在光子的進(jìn)攻下,斷裂形成4-Methoxy-biphenyl-3-yl-diazene,再逐步光解為4-Methoxy-biphenyl-3-ylamine, biphenyl。
[Abstract]:Hydrolysis and photolysis are the most important subtractive ways of pesticides in the environment, which play a decisive role in the residual time of pesticides in the environment. In this study, the hydrolysis and photolysis of the new acaric hydrazide ester was studied by high performance liquid chromatograph, and the hydrolysis and photolysis were analyzed by a liquid chromatograph. The product, in order to speculate on the possible hydrolysis and photolysis pathway, has important environmental ecological significance for guiding scientific and rational use of hydrazine ester, reducing the pollution of the pesticide to the environment, and the risk assessment of the pesticide. The main results are as follows: (1) a high performance liquid chromatography test condition for 9 new hydrazine esters was designed, in which Agilent Eclipse Plus C18 stainless steel chromatography column (250 mm x 4.6 mm, 5 mu m), acetonitrile: water =70:30 is a mobile phase, the flow velocity is 0.8mL/min, the sample volume 10gL, the wavelength 230nm, LOD lowest (0.01 mg.L-1), the peak time is the shortest, the target peak and the impurity peak are completely separated, the peak shape is good; (2) established the hydrazine ester liquid chromatograph. Detection methods: electrospray ion source (ESI); positive ion mode scanning; scanning range: 50 Da-500 Da; electrospray voltage (IS): 5500 V; gas curtain gas (CUR): 30 Psi; atomized gas (GS1): 30 Psi; auxiliary gas (GS2): 60 Psi; desolvent temperature (TEM): 550; collision gas; collision chamber entrance voltage 10V: 10V; residing time: 0.3 second; (3) the effect of the type and volume of extractants and dispersants, and the extraction time, and the extraction time, and the effect of salt effect on the extraction of hydrazine ester in water by the vortex assisted liquid liquid microextraction. The results show that 0.3mL two chloroethane is used as an extractant, 1mL acetone is used as dispersant, vortex extraction lmin, no salt, 4500rp When m was centrifuged for 5min, the extraction effect was best, the relative recovery rate was over 89%, the relative standard deviation was less than 5.7%: (4) and the hydrolysis rate of hydrazine ester decreased with the increase of initial concentration. As the temperature increased, the activation energy decreased and the absolute value of activation entropy increased, indicating that the activation energy and the activation entropy jointly drive the hydrolysis reaction. With the increase of pH, it belongs to alkaline hydrolysis, and its degradation mechanism may be related to the ester bond in the chemical structure of hydrazine ester; the hydrolysis rate of four natural water bodies in water, lake water, tap water and river water is positively correlated with the pH value of water body; the hydrolysis reaction of hydrazide ester is in line with the first order kinetic model; (5) The photolysis rate of phenyl hydrazide in different light sources is 300W high pressure mercury lamp 15W ultraviolet lamp 300W xenon lamp, and ethyl acetate acetonitrile acetone acetone has no obvious correlation with the polarity of solvent; acetonitrile belongs to the absence of photosensitivity and light quenching solvent. Therefore, it is inferred that ethyl acetate has photosensitive effect on the photolysis of hydrazine ester, while methanol and acetone are used to biphenyl. The photolysis of hydrazide has the effect of light quenching; (6) with the increase of pH, the faster the photolysis rate increases with the increase of 15W ultraviolet lamp. In different natural waters, the photolysis rate is pure water of water and lake water, which is sterilized by river water sterilization lake water, and is positively related to the pH value of water body. (7) the hydrolysate of hydrazine ester is tracked and analyzed by the liquid chromatograph. The total ion flow diagram and mass fraction diagram of the hydrolysates of hydrazine ester were obtained. Through qualitative analysis, three kinds of hydrolysates of hydrazine ester in pure water, C17H18N2O3, C14H12N2O3 and C13H120, were preliminarily speculated. According to the hydrolysis products and chemical bond breaking ways, the hydrolysis pathway of hydrazine ester was preliminarily deduced: hydrazine ester was used in the water molecule. Under the attack of hydrazine ester two nitroalkene, the ester bond of two nitroalkene is hydrolyzed under the attack of OH- ion to break the ester bond and produce carboxylic acid, and then the carboxylic acid is further hydrolyzed to form 4- methoxy biphenyl, which has smaller molecular weight and simpler structure. (8) the photodissociation product of hydrazide ester was tracked and analyzed by liquid chromatograph, and hydrazide ester was obtained. Total ion flow diagrams and mass fraction diagrams of photolysis products. Through qualitative analysis, five kinds of photodissociation products of hydrazine ester are preliminarily deduced, namely, C17H18N2O3, C14H12N2O3, C12H10, C13H13NO, C13H12N2O and two kinds of unknown structural products (ion fragments are 217.6/239.3 and 242.2). According to the photolysis products and chemical bond breaking modes, preliminary speculates The photodissociation route of hydrazine ester is that hydrazine ester is converted into hydrazine ester of two nitroalkene under the action of ultraviolet lamp, and the ester bond of two nitroalkene is hydrolyzed under the attack of a small amount of OH- ions in the solvent, breaking the ester bond and producing the carboxylic acid; the carboxylic acid is broken to form 4-Methoxy-biphenyl-3-yl-diazene under the attack of the photon and then gradually photolysis. For 4-Methoxy-biphenyl-3-ylamine, biphenyl.
【學(xué)位授予單位】：西南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：X592

【參考文獻(xiàn)】

相關(guān)期刊論文 前2條

1 萬海濱;殺螟松、馬拉松、殺撲磷和殺滅磷在不同pH和溫度下的水解速率[J];環(huán)境科學(xué)學(xué)報;1989年04期

2 鄒雅竹;龔道新;汪傳剛;;順式氯氰菊酯在不同pH值下的光化學(xué)降解[J];湖南農(nóng)業(yè)大學(xué)學(xué)報(自然科學(xué)版);2006年03期

相關(guān)碩士學(xué)位論文 前3條

1 徐玉紅;農(nóng)藥米滿的水解作用研究[D];廣東工業(yè)大學(xué);2004年

2 程燕;丙草胺在水體中的光化學(xué)降解研究[D];安徽農(nóng)業(yè)大學(xué);2004年

3 熊雅琴;雙草醚鈉鹽的水解動力學(xué)及影響因素研究[D];湖南農(nóng)業(yè)大學(xué);2006年

，

本文編號：1943318