由甲基氨基甲酰氯制备甲萘威的研究
|
摘要
本文研究了由甲基氨基甲酰氯(MCC)制备甲基异氰酸酯(MIC)后,再由MIC制备甲萘威的非四氯化碳过程。文中主要选用了甲苯、氯仿、四氯乙烯三种溶剂来替代四氯化碳。同时在MCC制备MIC的工段引入了有机碱作为除去HCl的缚酸剂;文中主要介绍了三乙胺、N-甲基咪唑(MIM)、N-丁基咪唑(BIM)三种缚酸剂。实验中首先研究了缚酸剂与HCl反应生成的有机碱盐酸盐与MIC溶液的分离,实验证明甲苯、四氯乙烯作为反应溶剂时,采用压滤的分离方法;氯仿作为反应溶剂时采用蒸馏的分离方法。
分离方法确定后,研究了影响甲萘威产率的各个影响因素;对于MCC分解为MIC的反应,主要研究了有机碱的滴加速度、有机碱的用量、MCC的分解温度、溶剂的用量、有机碱的种类等因素对甲萘威产率的影响;对于MIC溶液与1-萘酚的反应,主要研究了该反应的最佳反应时间,反应中1-萘酚的用量对甲萘威产率的影响。通过对以上影响因素的研究确定了甲萘威的最佳反应条件:甲苯为溶剂时,MCC:甲苯=1:6(m/m),有机碱:甲苯=1:1(m/m),1-萘酚:MCC:有机碱=1:1:0.98(mol/mol/mol),有机碱的滴加速度在6滴/分钟,MCC分解温度为50℃,MIC的甲苯溶液与1-萘酚的反应温度为108℃,反应时间为2小时;氯仿为溶剂时,MCC:氯仿=1:5(m/m),有机碱:氯仿=1:1(m/m),1-萘酚:MCC:有机碱=1:1:0.98(mol/mol/mol),控制有机碱的滴加速度在6滴/分钟,MCC分解温度为50℃,MIC的氯仿溶液与1-萘酚的反应温度为58℃,反应时间为4小时。在上述最优反应条件下,不论溶剂为甲苯或者氯仿,三乙胺和BIM作为缚酸剂时,甲萘威收率相近,都明显的高于MIM为缚酸剂;在缚酸剂一定时,氯仿为溶剂时甲萘威收率要明显的比甲苯为溶剂时高。
文章最后研究了以BIM为缚酸剂时,对BASIL工艺的应用,并且还考察了BIM的回收再利用。以NaOH回收BIM时,BIM溶液中水含量升高导致甲萘威的收率降低,可以采用热分解的方法回收BIM。
This thesis is focused on the preparation of methyl isocyanate (MIC) by methyl carbamyl chloride (MCC) and the preparation of Carbaryl by MIC. During these two processes carbon tetrachloride was not used as solvent. Fistly, three solvents including toluene, chloroform, and tetrachloroethylene were selected to substitute carbon tetrachloride. Meanwhile three kinds of organic alkalies including triethylamine, N- methyl imidazole, N- butyl imidazole were selected to react with hydrochloric acid, which is produced during the process of decomposing MCC to prepare MIC.
When the organic alkali reacted with hydrochloric acid, it will be neutralized to muriate. The method of separing MIC from the muriate was studied fistly. For the solvents of toluene and tetrachloroethylene, pressurized filtration method of separation was used, while for chloroform solvent, the distillation method of separation was used.
After the separation method was determined, influence factors of preparing carbaryl by MCC were investigated experimentally. These influencing factos included the droping speed of organic alkali, the amount of organic alkali, the temperature of the decomposition of MCC, the amount of solvent, the sort of organic alkali and so on.
Through the study on the influencing factors, the optimum condition had been determined. When toluene is used as solvent, the optimum condition was as follows:
MCC:toluene=1:6(mass ratio, m/m); organic alkali:toluene =1:1(m/m); 1-naphthol:MCC:organic alkali=1:1:0.98(mol/mol/mol); The decomposition temperature of MCC was set to 50℃; The synthesis temperature of carbaryl with MIC and 1- naphthol was 108℃and the reaction time was 2 hours.
When chloroform is used as solvent, the optimum condition was as follows:
MCC:toluene =1:5(m/m); organic alkali:toluene =1:1(m/m); 1- naphthol: MCC:organic alkali =1:1:0.98(mol/mol/mol); The decomposing temperature of MCC was set to 50℃; The synthesis temperature of carbaryl with MIC and 1- naphthol was 58℃and the reaction time was 4 hours.
Under the optimum condition, no matter the solvent was toluene or chloroform, the yield of carbaryl was the highest when the organic alkali was N- butyl imidazole. The yield of carbaryl was the lowest when the organic alkali was N- methyl imidazole. When the organic alkali was triethylamine, the yield of carbaryl was close to N- butyl imidazole. For a specified alkali, the yield of carbaryl in chloroform solvent was obviously higher than that in toluene solvent.
When the organic alkali was N- butyl imidazole, the BASIL process could be applied in the reaction of decomposing MCC to prepare MIC. The used N- butyl imidazole can be reclaimed using sodium hydroxide, however, the water content in the recycled N-butyl imidazole is relatively high, which may reduce the yield of carbaryl. Pyrolytic process could be used to recover N- butyl imidazole from its hydrochloric salt via decomposing at high temjperature.
分离方法确定后,研究了影响甲萘威产率的各个影响因素;对于MCC分解为MIC的反应,主要研究了有机碱的滴加速度、有机碱的用量、MCC的分解温度、溶剂的用量、有机碱的种类等因素对甲萘威产率的影响;对于MIC溶液与1-萘酚的反应,主要研究了该反应的最佳反应时间,反应中1-萘酚的用量对甲萘威产率的影响。通过对以上影响因素的研究确定了甲萘威的最佳反应条件:甲苯为溶剂时,MCC:甲苯=1:6(m/m),有机碱:甲苯=1:1(m/m),1-萘酚:MCC:有机碱=1:1:0.98(mol/mol/mol),有机碱的滴加速度在6滴/分钟,MCC分解温度为50℃,MIC的甲苯溶液与1-萘酚的反应温度为108℃,反应时间为2小时;氯仿为溶剂时,MCC:氯仿=1:5(m/m),有机碱:氯仿=1:1(m/m),1-萘酚:MCC:有机碱=1:1:0.98(mol/mol/mol),控制有机碱的滴加速度在6滴/分钟,MCC分解温度为50℃,MIC的氯仿溶液与1-萘酚的反应温度为58℃,反应时间为4小时。在上述最优反应条件下,不论溶剂为甲苯或者氯仿,三乙胺和BIM作为缚酸剂时,甲萘威收率相近,都明显的高于MIM为缚酸剂;在缚酸剂一定时,氯仿为溶剂时甲萘威收率要明显的比甲苯为溶剂时高。
文章最后研究了以BIM为缚酸剂时,对BASIL工艺的应用,并且还考察了BIM的回收再利用。以NaOH回收BIM时,BIM溶液中水含量升高导致甲萘威的收率降低,可以采用热分解的方法回收BIM。
This thesis is focused on the preparation of methyl isocyanate (MIC) by methyl carbamyl chloride (MCC) and the preparation of Carbaryl by MIC. During these two processes carbon tetrachloride was not used as solvent. Fistly, three solvents including toluene, chloroform, and tetrachloroethylene were selected to substitute carbon tetrachloride. Meanwhile three kinds of organic alkalies including triethylamine, N- methyl imidazole, N- butyl imidazole were selected to react with hydrochloric acid, which is produced during the process of decomposing MCC to prepare MIC.
When the organic alkali reacted with hydrochloric acid, it will be neutralized to muriate. The method of separing MIC from the muriate was studied fistly. For the solvents of toluene and tetrachloroethylene, pressurized filtration method of separation was used, while for chloroform solvent, the distillation method of separation was used.
After the separation method was determined, influence factors of preparing carbaryl by MCC were investigated experimentally. These influencing factos included the droping speed of organic alkali, the amount of organic alkali, the temperature of the decomposition of MCC, the amount of solvent, the sort of organic alkali and so on.
Through the study on the influencing factors, the optimum condition had been determined. When toluene is used as solvent, the optimum condition was as follows:
MCC:toluene=1:6(mass ratio, m/m); organic alkali:toluene =1:1(m/m); 1-naphthol:MCC:organic alkali=1:1:0.98(mol/mol/mol); The decomposition temperature of MCC was set to 50℃; The synthesis temperature of carbaryl with MIC and 1- naphthol was 108℃and the reaction time was 2 hours.
When chloroform is used as solvent, the optimum condition was as follows:
MCC:toluene =1:5(m/m); organic alkali:toluene =1:1(m/m); 1- naphthol: MCC:organic alkali =1:1:0.98(mol/mol/mol); The decomposing temperature of MCC was set to 50℃; The synthesis temperature of carbaryl with MIC and 1- naphthol was 58℃and the reaction time was 4 hours.
Under the optimum condition, no matter the solvent was toluene or chloroform, the yield of carbaryl was the highest when the organic alkali was N- butyl imidazole. The yield of carbaryl was the lowest when the organic alkali was N- methyl imidazole. When the organic alkali was triethylamine, the yield of carbaryl was close to N- butyl imidazole. For a specified alkali, the yield of carbaryl in chloroform solvent was obviously higher than that in toluene solvent.
When the organic alkali was N- butyl imidazole, the BASIL process could be applied in the reaction of decomposing MCC to prepare MIC. The used N- butyl imidazole can be reclaimed using sodium hydroxide, however, the water content in the recycled N-butyl imidazole is relatively high, which may reduce the yield of carbaryl. Pyrolytic process could be used to recover N- butyl imidazole from its hydrochloric salt via decomposing at high temjperature.
引文
[1]李春喜,汪文川,杨礼荣,等.四氯化碳过程助剂及其替代技术的应用与发展现状[J].氯碱工业,2000,12(12):25-28
[2]秦伟程.四氯化碳处理路在何方[J].中国石油和化工(业界观察),2004,(7):66-68
[3]张霓,卢贵武,李春喜,等.四氯化碳催化加氢制氯仿的实验研究[J].北京化工大学学报,2004,31(2):18-35
[4]王美嫒,蒋卓良,王辉.高纯甲萘威原药生产装置的财务可行性分析[J].化工设计,2004,14(3):44-46
[5]赵季芝.光气化产品的开发和应用[J].氯碱工业,1997,12:35-38
[6]钟立.异氰酸酯的合成与应用[J].化工进展,2000,4:50-52
[7]MraJ,simek P,Chvalova D,Nohova H,Smigolova P.Studies on the methyl isocyanate adducts with globin[J].Chemico-Biological Interactions,2004,148:1-10
[8]陆再林.甲基异氰酸酯的检测与防护[J].China Academic Journal Electronic Publishing House,1994-2006,18-19
[9]徐立.甲基异氰酸酯眼部损伤一例报告[J].眼外伤职业眼病杂志,1990,2:105
[10]张维凡.农药生产安全[J].化工劳动保护,2001,22(8):301-303
[11]贺季堂.化学危险品的储存和管理[J].有机氟工业,2001,1:37-41
[12]徐尚成,俞幼芬.博帕尔事故中甲基异氰酸酯的化学研究[J].农药,1988,1:17-19
[13]郭登银,李育珍,王建龙.绿色化学在异氰酸醋合成中的应用[J].中国胶粘剂,2007,16(4):53-56
[14]曾宪泽.N-甲氨基甲酰氯的合成[J].湖南化工,1995,25:13-15
[15]齐家炎,程尚武,高德喜,蔡道荣.甲基异氰酸酯生产中副产物生成量研究[J].湖北化工,2001,3:42-43
[16]张建宇.甲基异氰酸酯生产中替换四氯化碳项目实施计划[J].海利贵溪化工农药有限公司,2002,1-19
[17]陆连康,姚可植,袁国峰.我国氯化橡胶生产现状及发展趋势的探讨[R].宁波:中国涂料工业协会涂料涂装分会,2006
[18]张东生.中国:世界异氰酸酯业的热点[J].中国化工信息,2005,12:13-15
[19]于燕,米镇涛,李家玲,张香文.异氰酸酯的绿色新工艺[J].化工进展,2001,7:18-21
[20]山西省化工研究所.聚氨醋弹性体手册[M].北京:北京化学工业出版社,2001.625-630
[21]任天瑞,汪永生,李梢鸽.异氰酸酯的非光气工艺[J].化学通报,2003,66:1-7
[22]国家医药管理局上海医药设计院.化工工艺设计手册(上)[M].北京化学工业出版社, 1996
[23]Gehlawat J K.Bhopal disaster—a personal experience[J].Journal of Loss Prevention in the Process Industries,2005,18:261-263
[24]李吉文.国外非光气法合成异氰酸酯的方法[J].聚氨酯工业,1991,1:15-18
[25]江琦,赵军.绿色化工过程中的碳酸二甲酯[J].广东化工,2001,1:1-4
[26]肖翠玲,王艳花,董树生.21世纪的绿色基础化学原料碳酸二甲脂[J].化工进展,2000,19:40-42
[27]张礼和.化学科学进展[M].北京:北京化学工业出版社,2005.149-152
[28]钱伯章.绿色精细化工的新进展[J].精细化工原料及中间体,2005,11:8-13
[29]马一呜.绿色化学—光气的替代品[J].化工之友,2006,9:50-51
[30]邓友全.离子液体介质与材料研究进展[J].成果与应用,2005,20(4):299
[31]McGhee W,Riley D.Replacement of phosgene with carbon-dioxide;Synthesis of alkyl carbonates[J].Org.Chem.,1995(60):6205-6207
[32]McGhee.Isocynates from primary amines and carbon dioxide;Dehydration of carbamate anion[J].Chem.Commun,1994:957
[33]Michaell J H,Dilek S,Patricia S E,et al.A mit-sunobu-based procedure for the preparation of alkyl and hindered aryl isocynates from primary amines and carbon dioxide under mild conditions[J].Tetrahedron Letters,1999:363-366
[34]McGhee W D,Waldman T E.Process for preparing isocynates[P].US,WO 9518098.1995-07-06
[35]Riley D P,McGhee W D.Preparation of urethane and carbonate products[P].US,5055577.1991-10-08
[36]Riley D P,McGhee W D.Preparation of urethane and carbonate products[P].US,5200547.1993-04-06
[37]McGhee W D,Parnas B L,Riley D P,et al.Preparation of urethane and carbonate products[P].US,5223638.1993-06-29
[38]McGhee W D,Sterm M K,Waldman T E.Process for preparing isocynate and carbamate ester products[P].US,5223010.1993-08-03
[39]宋启煌.精细化工—绿色生产工艺[M].广州:广东科技出版社,2006.29-31
[40]马特洛可(美).绿色化学导论[M].北京:中国石化出版社,2005.27-39
[41]杨可珊,傅小云.异氰酸酯及其发展概述[J].煤化工,2002(4):12-14
[42]韦林声.甲基异氰酸酯三种生产方法简评[J].湖南化工,1992(1):7
[43]闵恩泽,吴魏.绿色化学与化工[M].北京:化学工业出版社,2001.22-23
[44]朱良天.精细化工产品手册[M].北京:化学工业出版社,2004
[45]张玉奎,张维冰,邹汉法.分析化学手册(第二版),[M].北京:化学工业出版社,2000
[46]张晓彤,云自厚.液相色谱检测方法[M].北京:化学工业出版社,2000
[47]厉墨宝.农药新品种[M].江苏:科学技术出版社,1989
[48]那晓琳,张畅,陈文华.高效液相色谱测定水源水中西维因[J].中国卫生检验杂志,1995,5(2):77-78
[49]苏宇亮,胡克武.固相萃取—高效色谱法测定水中甲萘威[J].现代科学仪器,2005,104(6):71-72
[50]胡玉玲,钟伟健,李攻科.固相微萃取—高效色谱法联用分析环境水样中的氨基甲酸酯农药[J].中山大学学报(自然科学版),2004,43(6):124-127
[51]张裕平,李向军,袁悼斌.毛细管电泳法分析西维因等农药[J].色谱,2002,20(4):341-344
[52]高玲,杨元,王炼,等.气相色谱—质谱法同时测定水中7种氨基甲酸酯类杀虫剂[J].中国卫生检验杂志,2005,15(6):713-714
[53]Maria P M,Serge C,Jordi G G,et al.Validation of two immunoassay methods for environ-mental monitoring of carbaryl and 1-naphthol in ground water samples[J].Analytica Chimica Acta,1995,311(3):319-329
[54]中国农业科学植物保护研究所,农牧渔业部农药检定所,商业部农业生产资料局合编.农药分析(第三版)[M].北京:化学工业出版社,1988.245-247
[55]Garcia Sanchez F,Navas Diaz A,Torijas M C.Selective determination of carbaryl and benomyl by fluorescence polarization[J].Analytica Chimica Acta,2000(414):25-32
[56]王忠东,王玉田,关晓晶.对几种氨基甲酸酯类农药的荧光特性研究[J].分析测试技术与仪器,2004,10(4):214-217
[57]王玉田,刘蕊.监测氨基甲酸酯类农药的光纤荧光光谱仪的研究[J].传感技术学报,2003,9(3):318-324
[58]陈九墨,黄路,李霓.高效液相色谱法测定甲萘威及其游离酚[J].湖南化工,1998,28(6):44-46
[59]朱晓慧,薛维家.甲萘威原药高效液相色谱分析方法[J].农药科学与管理,2007,28(10):8-10
[60]苏宇亮,吴杰,方黎.直接进样高效液相色谱法测定水中甲萘威[J].现代科学仪器,2007(5):125-127
[61]方新红,吴艳芬.高效液相色谱法测定水中甲萘威[J].西南给排水,2007,29(5):43-44
[62]陈明.高纯度甲萘威的合成与生产[J].江西化工,2001(4):48-51
[63]王以燕.卫生杀虫剂现状与登记政策[J].农药,2001,40(2):35-38
[64]沈继军,李德荣.绿色化学原料碳酸二甲酯在农药合成中的应用[J].化工中间体,2006,(4):7-8
[65]钱旭红,高建宝,焦家俊,徐玉芳.有机化学[M].北京:化学工业出版社,1999.195-214
[66]梁红玉,宫红,姜恒,等.离子液体催化邻二甲苯与二氯乙烷的烷基化反应性能[J].辽宁化工,2002,31(2):47-49
[2]秦伟程.四氯化碳处理路在何方[J].中国石油和化工(业界观察),2004,(7):66-68
[3]张霓,卢贵武,李春喜,等.四氯化碳催化加氢制氯仿的实验研究[J].北京化工大学学报,2004,31(2):18-35
[4]王美嫒,蒋卓良,王辉.高纯甲萘威原药生产装置的财务可行性分析[J].化工设计,2004,14(3):44-46
[5]赵季芝.光气化产品的开发和应用[J].氯碱工业,1997,12:35-38
[6]钟立.异氰酸酯的合成与应用[J].化工进展,2000,4:50-52
[7]MraJ,simek P,Chvalova D,Nohova H,Smigolova P.Studies on the methyl isocyanate adducts with globin[J].Chemico-Biological Interactions,2004,148:1-10
[8]陆再林.甲基异氰酸酯的检测与防护[J].China Academic Journal Electronic Publishing House,1994-2006,18-19
[9]徐立.甲基异氰酸酯眼部损伤一例报告[J].眼外伤职业眼病杂志,1990,2:105
[10]张维凡.农药生产安全[J].化工劳动保护,2001,22(8):301-303
[11]贺季堂.化学危险品的储存和管理[J].有机氟工业,2001,1:37-41
[12]徐尚成,俞幼芬.博帕尔事故中甲基异氰酸酯的化学研究[J].农药,1988,1:17-19
[13]郭登银,李育珍,王建龙.绿色化学在异氰酸醋合成中的应用[J].中国胶粘剂,2007,16(4):53-56
[14]曾宪泽.N-甲氨基甲酰氯的合成[J].湖南化工,1995,25:13-15
[15]齐家炎,程尚武,高德喜,蔡道荣.甲基异氰酸酯生产中副产物生成量研究[J].湖北化工,2001,3:42-43
[16]张建宇.甲基异氰酸酯生产中替换四氯化碳项目实施计划[J].海利贵溪化工农药有限公司,2002,1-19
[17]陆连康,姚可植,袁国峰.我国氯化橡胶生产现状及发展趋势的探讨[R].宁波:中国涂料工业协会涂料涂装分会,2006
[18]张东生.中国:世界异氰酸酯业的热点[J].中国化工信息,2005,12:13-15
[19]于燕,米镇涛,李家玲,张香文.异氰酸酯的绿色新工艺[J].化工进展,2001,7:18-21
[20]山西省化工研究所.聚氨醋弹性体手册[M].北京:北京化学工业出版社,2001.625-630
[21]任天瑞,汪永生,李梢鸽.异氰酸酯的非光气工艺[J].化学通报,2003,66:1-7
[22]国家医药管理局上海医药设计院.化工工艺设计手册(上)[M].北京化学工业出版社, 1996
[23]Gehlawat J K.Bhopal disaster—a personal experience[J].Journal of Loss Prevention in the Process Industries,2005,18:261-263
[24]李吉文.国外非光气法合成异氰酸酯的方法[J].聚氨酯工业,1991,1:15-18
[25]江琦,赵军.绿色化工过程中的碳酸二甲酯[J].广东化工,2001,1:1-4
[26]肖翠玲,王艳花,董树生.21世纪的绿色基础化学原料碳酸二甲脂[J].化工进展,2000,19:40-42
[27]张礼和.化学科学进展[M].北京:北京化学工业出版社,2005.149-152
[28]钱伯章.绿色精细化工的新进展[J].精细化工原料及中间体,2005,11:8-13
[29]马一呜.绿色化学—光气的替代品[J].化工之友,2006,9:50-51
[30]邓友全.离子液体介质与材料研究进展[J].成果与应用,2005,20(4):299
[31]McGhee W,Riley D.Replacement of phosgene with carbon-dioxide;Synthesis of alkyl carbonates[J].Org.Chem.,1995(60):6205-6207
[32]McGhee.Isocynates from primary amines and carbon dioxide;Dehydration of carbamate anion[J].Chem.Commun,1994:957
[33]Michaell J H,Dilek S,Patricia S E,et al.A mit-sunobu-based procedure for the preparation of alkyl and hindered aryl isocynates from primary amines and carbon dioxide under mild conditions[J].Tetrahedron Letters,1999:363-366
[34]McGhee W D,Waldman T E.Process for preparing isocynates[P].US,WO 9518098.1995-07-06
[35]Riley D P,McGhee W D.Preparation of urethane and carbonate products[P].US,5055577.1991-10-08
[36]Riley D P,McGhee W D.Preparation of urethane and carbonate products[P].US,5200547.1993-04-06
[37]McGhee W D,Parnas B L,Riley D P,et al.Preparation of urethane and carbonate products[P].US,5223638.1993-06-29
[38]McGhee W D,Sterm M K,Waldman T E.Process for preparing isocynate and carbamate ester products[P].US,5223010.1993-08-03
[39]宋启煌.精细化工—绿色生产工艺[M].广州:广东科技出版社,2006.29-31
[40]马特洛可(美).绿色化学导论[M].北京:中国石化出版社,2005.27-39
[41]杨可珊,傅小云.异氰酸酯及其发展概述[J].煤化工,2002(4):12-14
[42]韦林声.甲基异氰酸酯三种生产方法简评[J].湖南化工,1992(1):7
[43]闵恩泽,吴魏.绿色化学与化工[M].北京:化学工业出版社,2001.22-23
[44]朱良天.精细化工产品手册[M].北京:化学工业出版社,2004
[45]张玉奎,张维冰,邹汉法.分析化学手册(第二版),[M].北京:化学工业出版社,2000
[46]张晓彤,云自厚.液相色谱检测方法[M].北京:化学工业出版社,2000
[47]厉墨宝.农药新品种[M].江苏:科学技术出版社,1989
[48]那晓琳,张畅,陈文华.高效液相色谱测定水源水中西维因[J].中国卫生检验杂志,1995,5(2):77-78
[49]苏宇亮,胡克武.固相萃取—高效色谱法测定水中甲萘威[J].现代科学仪器,2005,104(6):71-72
[50]胡玉玲,钟伟健,李攻科.固相微萃取—高效色谱法联用分析环境水样中的氨基甲酸酯农药[J].中山大学学报(自然科学版),2004,43(6):124-127
[51]张裕平,李向军,袁悼斌.毛细管电泳法分析西维因等农药[J].色谱,2002,20(4):341-344
[52]高玲,杨元,王炼,等.气相色谱—质谱法同时测定水中7种氨基甲酸酯类杀虫剂[J].中国卫生检验杂志,2005,15(6):713-714
[53]Maria P M,Serge C,Jordi G G,et al.Validation of two immunoassay methods for environ-mental monitoring of carbaryl and 1-naphthol in ground water samples[J].Analytica Chimica Acta,1995,311(3):319-329
[54]中国农业科学植物保护研究所,农牧渔业部农药检定所,商业部农业生产资料局合编.农药分析(第三版)[M].北京:化学工业出版社,1988.245-247
[55]Garcia Sanchez F,Navas Diaz A,Torijas M C.Selective determination of carbaryl and benomyl by fluorescence polarization[J].Analytica Chimica Acta,2000(414):25-32
[56]王忠东,王玉田,关晓晶.对几种氨基甲酸酯类农药的荧光特性研究[J].分析测试技术与仪器,2004,10(4):214-217
[57]王玉田,刘蕊.监测氨基甲酸酯类农药的光纤荧光光谱仪的研究[J].传感技术学报,2003,9(3):318-324
[58]陈九墨,黄路,李霓.高效液相色谱法测定甲萘威及其游离酚[J].湖南化工,1998,28(6):44-46
[59]朱晓慧,薛维家.甲萘威原药高效液相色谱分析方法[J].农药科学与管理,2007,28(10):8-10
[60]苏宇亮,吴杰,方黎.直接进样高效液相色谱法测定水中甲萘威[J].现代科学仪器,2007(5):125-127
[61]方新红,吴艳芬.高效液相色谱法测定水中甲萘威[J].西南给排水,2007,29(5):43-44
[62]陈明.高纯度甲萘威的合成与生产[J].江西化工,2001(4):48-51
[63]王以燕.卫生杀虫剂现状与登记政策[J].农药,2001,40(2):35-38
[64]沈继军,李德荣.绿色化学原料碳酸二甲酯在农药合成中的应用[J].化工中间体,2006,(4):7-8
[65]钱旭红,高建宝,焦家俊,徐玉芳.有机化学[M].北京:化学工业出版社,1999.195-214
[66]梁红玉,宫红,姜恒,等.离子液体催化邻二甲苯与二氯乙烷的烷基化反应性能[J].辽宁化工,2002,31(2):47-49