茚虫威及其混剂悬浮悬乳体系的构建与触变性研究
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摘要
目前,我国农药新剂型以水基性剂型和可分散粒剂为发展重点,其中水基性剂型用水代替有机溶剂作分散介质,较乳油和可湿性粉剂等传统剂型具有利于节约资源、降低成本、保护环境的优点,因而具有广阔的发展前景。农药悬浮剂是现代农药中十分重要的农药剂型,具有较好的生物活性,但是由于农药悬浮体系成分复杂,往往出现制剂经时物理稳定性不佳的现象,如分层、析水、絮凝等问题。基于此,本文作者于2007年6月～2009年5月以新型杀虫剂茚虫威为对象,研究了茚虫威及其茚虫威-毒死蜱混配的悬浮悬乳体系及触变性,探索了茚虫威10%悬浮剂和茚虫威-毒死蜱25%悬乳剂的分析方法,评价了茚虫威-毒死蜱25%悬乳剂的联合作用,并取得了一些阶段性的研究成果。根据研究内容,全文共分为六个部分。
第一部分为文献综述。简单评述了农药悬浮/悬乳剂体系的研究概述以及目前存在的共性技术关键问题,通过茚虫威及毒死蜱物化性质的介绍,提出了该文的研究背景及其意义。
第二部分研究了茚虫威10%悬浮剂体系的构建及其触交性能。采用流点法和正交试验方法筛选了茚虫威悬浮体系中表面活性剂的种类和用量,当润湿分散剂D-425、农乳1602、NS-500LQ和粘度调节剂XG的添加量为3%、1%、1%和0.10%的水平时,茚虫威悬浮体系的各项质量检测指标基本符合要求;在此基础上继续研究膨润土、酸性膨润土、碱性膨润土、硅藻土、凹凸棒土以及硅酸镁铝等矿物质在悬浮液中构成触变体系的可能性与优劣性,发现膨润土和硅酸镁铝在体系添加1%～3%和3%时,可以与悬浮液构成触变性体系,并对触变体系的触变性与可复性具有主要影响;筛选了不同防冻剂对悬浮液的防冻效果,发现防冻剂对体系分散性有一定的影响;探索了茚虫威10%悬浮剂的配方,确定了二个优惠配方组成:①茚虫威10%、D-425 3%、农乳1602 1%、NS-500LQ 1%、膨润土1～3%、乙二醇3%、黄原胶XG 0.2%及余量水补足;②茚虫威10%、D-425 3%、农乳1602 1%、NS-500LQ1%、硅酸镁铝3%、乙二醇3%、黄原胶XG 0.1%及余量水补足。
第三部分研究了茚虫威-毒死蜱25%悬乳体系的构建。通过毒死蜱水乳剂配方的优化,加工制得了稳定性良好的毒死蜱30%水乳剂,并将其与茚虫威悬浮剂混配,通过不同混配比例与混合工艺的研究,发现当茚虫威:毒死蜱(m:m)=1:4～1:5时,将茚虫威置于毒死蜱水乳剂分散相中进行砂磨3h,可以制得稳定性良好的茚虫威-毒死蜱25%悬乳剂,配方组成为茚虫威4%、毒死蜱21%、D-425 3%、农乳1602 5%、NS-500LQ 1%、PNP 10 5%、助溶剂1%、乙二醇5%、硅酸镁铝3%、黄原胶XG0.1%、CMC 0.1%、余量水。
第四部分研究了茚虫威单剂和茚虫威-毒死蜱混剂的检测方法。通过色谱条件的探索,建立了茚虫威10%悬浮剂和茚虫威-毒死蜱25%悬乳剂的高效液相色谱分析方法,所建立的方法准确快速、重现性好、灵敏度高,适合于产品质量检测与分析。
第五部分评价了茚虫威-毒死蜱混剂对小菜蛾的联合作用。采用生测技术测定了茚虫威、毒死蜱及其混配组合对小菜蛾的毒力,结果发现茚虫威与毒死蜱混配对小菜蛾具有明显的增效作用,其共毒系数为128.24。
第六部分是结论与建议。该部分对全文研究结果进行了总结,阐述了该研究的特色及其创新点,提出了今后有待于进一步研究的问题。
At present,new formulation of pesticides has been foscued on water-based formulation and water dispensible granulate in China.Due to the facts that water was used as the dispensible medium to take place of organic solvents in the water-based formulation,the water-based formulation should show a wide development prospect with its saved resource,reduced cost and friendly-environment compared to emulsifiable concentrate and wettable powder.Suspension concentrate(SC) is one of the most important formulations in modern pesticides with the advantages of good biological activities and clean producing processes.However,the phenomenons such as bleeding, thickening,sedimentation and flocculation have appeared during the storage of the SC formulation because of its complex suspension system of pesticides.Therefore,From June of 2007 to May of 2009,the construction and thixotropy of indoxacarb suspension concentrate and its mixture with chlorpyrifos suspoemulsion(SE)system have been studied,analysis of indoxacarb 10%SC and indoxacarb-chlorpyrifos 25%SE has been investigated,and joint action of indoxacarb and chlorpyrifos against the diamondback moth Plutella xylostella.The some progresses have been made through the work.The results were divided into six parts according to the research contents.
The first part was literature review.Current development and key technologies of suspension or suspoemulsion systems of pesticides were briefly reviewed,and the research background and its significance of the project were put forward through introduction of physiochemical properties of indoxacarb and chlorpyrifos.
The second part was a study on contruction and thixotropy of indoxacarb 10%SC., the proper surfactants and their dosages in the suspension system were selected using the flowing point test and orthogonal design,the parameters of indoxacarb 10%SC met the specifications for the pesticide SC when the dosages of D425,1602,NS-500LQ and XG was 3%,1%,1%and 0.10%,respectively.On the basis of this result,the possibility and consequence of building thixotropic suspension system added with the minerals such as bentonite,acid bentonite,alkaline bentonite,diatomite,attapulgite,and magnalium silicate have been studied.The bentonite and magnalium silicate could form thixotropic suspension system when the dosages were 1%～3%and 3%,respectively,which affected the thixotropy and reversibility of the system.It was found that the antifreezing agents could affect the dispensability by the selection of the antifreezing agents on the antifreezing effect of the system.The suspension system of indoxacarb 10%SC was built as follow:the amount of the SC components indoxacarb,D425,1602,NS-500LQ,XG, bentonite,ethanediol and water was 10%,3%,1%,1%,0.10%,1%～3%,3%and the rest, respectively,or indoxacarb,D425,1602,NS-500LQ,XG,magnalium silicate ethanediol and water was 10%,3%,1%,1%,0.10%,3%,3%and the rest,respectively.
The third part was a study on construction of indoxacarb-chlorpyrifos 25% suspoemulsion system.The chlorpyrifos 30%emulsion oil in water(EW) formulation with good stability was prepared through optimization of the existing formulation,and mixed with indoxacarb10%SC to give the chlorpyrifos-indoxacarb 25%SE using the formulation process technology.When the mass ratio of indoxacarb and chlorpyrifos was 1:4～1:5,mixture of indoxacarb10%SC into chlorpyrifos 30%EW was sand-grounded for 3h to get the chlorpyrifos-indoxacarb 25%SE with excellent stability.The amount of components in the chlorpyrifos-indoxacarb 25%SE formulation was as follow: indoxacarb,chlorpyrifos,D425,1602,NS-500LQ,PNP10,cosolvent,ethanediol, magnalium silicate,XG,CMC and water was 4%,21%,3%,1%,1%,5%,1%,5%,3%, 0.10%,1%and the rest,respectively.
The fourth part was determination of the active ingredients in the indoxacarb 10%SC and chlorpyrifos-indoxacarb 25%SE formulation.A quantitative high performance liquid chromatography method of the active ingredient indoxacarb and chlorpyrifos in the formulation 10%SC and the formulation 25%SE was developed, respectively,through the selection of chromatography conditions.The method was fast, sensitive,reproducible and practical for the quality control and analysis of the manufacture of the product.
The fifth part was joint action of indoxacarb and chlorpyrifos against the diamondback moth in the laboratory.Toxicity of binary mixture of indoxacarb and chlorpyrifos againstdiamond back moth was tested using bioassay technique,the result showed the indoxacarb and chlorpyrifoshad an obvious syngergism against the third instar larva of diamondback moth,and its cotoxicity coeffienct(CTC) was 128.24.
The last part was conclusions and suggestions.Conclusions were summaried based on the whole results,the characteristics and novel findings were described,and some caveats were put forward to be further done in the future.
第一部分为文献综述。简单评述了农药悬浮/悬乳剂体系的研究概述以及目前存在的共性技术关键问题,通过茚虫威及毒死蜱物化性质的介绍,提出了该文的研究背景及其意义。
第二部分研究了茚虫威10%悬浮剂体系的构建及其触交性能。采用流点法和正交试验方法筛选了茚虫威悬浮体系中表面活性剂的种类和用量,当润湿分散剂D-425、农乳1602、NS-500LQ和粘度调节剂XG的添加量为3%、1%、1%和0.10%的水平时,茚虫威悬浮体系的各项质量检测指标基本符合要求;在此基础上继续研究膨润土、酸性膨润土、碱性膨润土、硅藻土、凹凸棒土以及硅酸镁铝等矿物质在悬浮液中构成触变体系的可能性与优劣性,发现膨润土和硅酸镁铝在体系添加1%～3%和3%时,可以与悬浮液构成触变性体系,并对触变体系的触变性与可复性具有主要影响;筛选了不同防冻剂对悬浮液的防冻效果,发现防冻剂对体系分散性有一定的影响;探索了茚虫威10%悬浮剂的配方,确定了二个优惠配方组成:①茚虫威10%、D-425 3%、农乳1602 1%、NS-500LQ 1%、膨润土1～3%、乙二醇3%、黄原胶XG 0.2%及余量水补足;②茚虫威10%、D-425 3%、农乳1602 1%、NS-500LQ1%、硅酸镁铝3%、乙二醇3%、黄原胶XG 0.1%及余量水补足。
第三部分研究了茚虫威-毒死蜱25%悬乳体系的构建。通过毒死蜱水乳剂配方的优化,加工制得了稳定性良好的毒死蜱30%水乳剂,并将其与茚虫威悬浮剂混配,通过不同混配比例与混合工艺的研究,发现当茚虫威:毒死蜱(m:m)=1:4～1:5时,将茚虫威置于毒死蜱水乳剂分散相中进行砂磨3h,可以制得稳定性良好的茚虫威-毒死蜱25%悬乳剂,配方组成为茚虫威4%、毒死蜱21%、D-425 3%、农乳1602 5%、NS-500LQ 1%、PNP 10 5%、助溶剂1%、乙二醇5%、硅酸镁铝3%、黄原胶XG0.1%、CMC 0.1%、余量水。
第四部分研究了茚虫威单剂和茚虫威-毒死蜱混剂的检测方法。通过色谱条件的探索,建立了茚虫威10%悬浮剂和茚虫威-毒死蜱25%悬乳剂的高效液相色谱分析方法,所建立的方法准确快速、重现性好、灵敏度高,适合于产品质量检测与分析。
第五部分评价了茚虫威-毒死蜱混剂对小菜蛾的联合作用。采用生测技术测定了茚虫威、毒死蜱及其混配组合对小菜蛾的毒力,结果发现茚虫威与毒死蜱混配对小菜蛾具有明显的增效作用,其共毒系数为128.24。
第六部分是结论与建议。该部分对全文研究结果进行了总结,阐述了该研究的特色及其创新点,提出了今后有待于进一步研究的问题。
At present,new formulation of pesticides has been foscued on water-based formulation and water dispensible granulate in China.Due to the facts that water was used as the dispensible medium to take place of organic solvents in the water-based formulation,the water-based formulation should show a wide development prospect with its saved resource,reduced cost and friendly-environment compared to emulsifiable concentrate and wettable powder.Suspension concentrate(SC) is one of the most important formulations in modern pesticides with the advantages of good biological activities and clean producing processes.However,the phenomenons such as bleeding, thickening,sedimentation and flocculation have appeared during the storage of the SC formulation because of its complex suspension system of pesticides.Therefore,From June of 2007 to May of 2009,the construction and thixotropy of indoxacarb suspension concentrate and its mixture with chlorpyrifos suspoemulsion(SE)system have been studied,analysis of indoxacarb 10%SC and indoxacarb-chlorpyrifos 25%SE has been investigated,and joint action of indoxacarb and chlorpyrifos against the diamondback moth Plutella xylostella.The some progresses have been made through the work.The results were divided into six parts according to the research contents.
The first part was literature review.Current development and key technologies of suspension or suspoemulsion systems of pesticides were briefly reviewed,and the research background and its significance of the project were put forward through introduction of physiochemical properties of indoxacarb and chlorpyrifos.
The second part was a study on contruction and thixotropy of indoxacarb 10%SC., the proper surfactants and their dosages in the suspension system were selected using the flowing point test and orthogonal design,the parameters of indoxacarb 10%SC met the specifications for the pesticide SC when the dosages of D425,1602,NS-500LQ and XG was 3%,1%,1%and 0.10%,respectively.On the basis of this result,the possibility and consequence of building thixotropic suspension system added with the minerals such as bentonite,acid bentonite,alkaline bentonite,diatomite,attapulgite,and magnalium silicate have been studied.The bentonite and magnalium silicate could form thixotropic suspension system when the dosages were 1%～3%and 3%,respectively,which affected the thixotropy and reversibility of the system.It was found that the antifreezing agents could affect the dispensability by the selection of the antifreezing agents on the antifreezing effect of the system.The suspension system of indoxacarb 10%SC was built as follow:the amount of the SC components indoxacarb,D425,1602,NS-500LQ,XG, bentonite,ethanediol and water was 10%,3%,1%,1%,0.10%,1%～3%,3%and the rest, respectively,or indoxacarb,D425,1602,NS-500LQ,XG,magnalium silicate ethanediol and water was 10%,3%,1%,1%,0.10%,3%,3%and the rest,respectively.
The third part was a study on construction of indoxacarb-chlorpyrifos 25% suspoemulsion system.The chlorpyrifos 30%emulsion oil in water(EW) formulation with good stability was prepared through optimization of the existing formulation,and mixed with indoxacarb10%SC to give the chlorpyrifos-indoxacarb 25%SE using the formulation process technology.When the mass ratio of indoxacarb and chlorpyrifos was 1:4～1:5,mixture of indoxacarb10%SC into chlorpyrifos 30%EW was sand-grounded for 3h to get the chlorpyrifos-indoxacarb 25%SE with excellent stability.The amount of components in the chlorpyrifos-indoxacarb 25%SE formulation was as follow: indoxacarb,chlorpyrifos,D425,1602,NS-500LQ,PNP10,cosolvent,ethanediol, magnalium silicate,XG,CMC and water was 4%,21%,3%,1%,1%,5%,1%,5%,3%, 0.10%,1%and the rest,respectively.
The fourth part was determination of the active ingredients in the indoxacarb 10%SC and chlorpyrifos-indoxacarb 25%SE formulation.A quantitative high performance liquid chromatography method of the active ingredient indoxacarb and chlorpyrifos in the formulation 10%SC and the formulation 25%SE was developed, respectively,through the selection of chromatography conditions.The method was fast, sensitive,reproducible and practical for the quality control and analysis of the manufacture of the product.
The fifth part was joint action of indoxacarb and chlorpyrifos against the diamondback moth in the laboratory.Toxicity of binary mixture of indoxacarb and chlorpyrifos againstdiamond back moth was tested using bioassay technique,the result showed the indoxacarb and chlorpyrifoshad an obvious syngergism against the third instar larva of diamondback moth,and its cotoxicity coeffienct(CTC) was 128.24.
The last part was conclusions and suggestions.Conclusions were summaried based on the whole results,the characteristics and novel findings were described,and some caveats were put forward to be further done in the future.
引文
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