农药新剂型微乳粒剂及其微乳液形成与稳定机理
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摘要
本论文分别以三唑磷、氯氰菊酯、阿维菌素为代表性农药,研究油溶性的液态原药、低熔点及高熔点固态原药配制成一种稀释后能形成微乳液的新型固体剂型——微乳粒剂(MEG)的可行性。以三唑磷MEG为对象,研究微乳粒剂兑水稀释后微乳液的形成及稳定机制。
通过测试溶解度、溶解速度及吸油率,筛选出苯甲酸钠、乳糖、甘露醇、硫酸镁、水溶性淀粉5个载体,采用混料均匀设计U11(105)优化得到混合载体C12,吸油率为56.2g/100g；比表面积及孔隙参数测试表明,影响载体吸油率的主要因子为BET表面积、总孔面积、BJH解吸附累积孔表面积、BJH解吸附累积孔容积、总孔容积。
按U10(1O8)配制30%三唑磷微乳剂(ME)(不含有机溶剂)来筛选可用于配制MEG的表面活性剂(SAA)。根据Xi的标准回归系数(SRC)筛选得到602#+EL40+JM6140(SAA-6EJ),以甘露醇或硫酸镁与柠檬酸复配后作为载体可以配制得到10%三唑磷MEG (10%SAA-6EJ),D5o最小为40.64nm;15%三唑磷MEG(8%SAA-6EJ)的D5o为75.49nm。根据Xi及XiXj的SRC筛选得到500#+602#(SAA-56),用乳糖或甘露醇或水溶性淀粉作为载体或分别与柠檬酸复配后作为载体,均可配制得到10%三唑磷MEG；15%三唑磷MEG(8%SAA-56)的D5o为54.2nm。根据XiXj的SRC筛选得至(?)FS7PG+602#(SAA-F6)、HASS7+602#(SAA-H6),以硫酸镁或C12为载体可配制得到10%三唑磷MEG(10%SAA-F6),以乳糖、甘露醇、水溶性淀粉、硫酸镁或C12作为载体可配制得到10%三唑磷MEG (10%SAA-H6),15%三唑磷MEG (10%SAA-H6)的D5o为63.69nm。试验发现,对于同一个乳状液,D5o的变化与透明度或透射率的变化呈负相关；不同乳状液间对比时,离心稳定性更高的乳状液其D5o不一定更小；纳米乳液在RCF100g下离心5min亦可保持稳定,且纳米乳液与微乳液之间的临界相对离心力会随乳化体系的改变而改变。
采用熔融共混法,按U6(63)配制10%氯氰菊酯MEG (10%SAA),应用偏最小二乘回归(PLSR)对FS7PG、500“、EL60间比例进行优化后所配制10%氯氰菊酯MEG的Dso为51.45nm。根据SRC筛选得到FS7PG+EL60,比例法试验表明,两者在1/9-10/0配比范围内均能配制出10%氯氰菊酯MEG,其中以9/1时Dso最小,为59.91nn。采用10%氯氰菊酯MEG的配方,可以成功配制三氟氯氰菊酯10%MEG、氟氯菊酯10%及5%MEG、顺式氯氰菊酯10%MEG。
按L9(34)配制2%阿维菌素ME,以透明温度区域为因变量,对TSP16、JM6180、 HASS7间比例进行优化后配制2%阿维菌素MEG (10%SAA),载体为苯甲酸钠、硫酸镁、乳糖的混合物,D5o为79.54nm。以苯甲酸钠为载体,按U11(114)配制2%阿维菌素MEG(10%SAA),以D5o为因变量,用PLSR对602#、NP10P、AEC903、NP10间比例进行优化后所配制2%阿维菌素MEG的Dso为12.13m；根据SRC对SAA筛选得到602#+NP10P+NP10、602#+NP10、NP10P+NP10,根据优化后的配比配制所得2%阿维菌素MEG(10%SAA)的Dso分别为44.31nm、14.22nm、14.04nm。采用2%阿维菌素MEG的配方可成功配制2%伊维菌素MEG、2%甲氨基阿维菌素苯甲酸盐MEG。
微乳粒剂的配制采用旋转括壁式挤压造粒或沸腾造粒。各个微乳粒剂的理化性能满足实际使用的要求。提出了微乳粒剂产品登记所需的质量指标,并建立了乳化时间测试方法——机械搅拌法。
对粘虫的生物测定结果表明,15%三唑磷MEG的生物活性要优于10%三唑磷MEG、15%三唑磷ME、15%三唑磷EC,后3个药剂之间无显著差异。10%氯氰菊酯MEG的生物活性与10%氯氰菊酯ME、10%氯氰菊酯EC之间无显著差异,但要显著优于10%氯氰菊酯EG。阿维菌素配制成微乳粒剂、微乳粉剂后,在生物活性上与微乳剂无显著差异,但要显著好于乳油。毒力回归方程斜率对比表明剂型的变化不会影响靶标生物对农药的敏感性程度。
以三唑磷MEG为研究对象,采用动态或静态光散射技术研究水硬度、自来水、水温、载体对微乳液形成的影响,初步分析微乳粒剂微乳液的形成机理。以SAA-56或SAA-6EJ为乳化剂时,水硬度≤1368mg/L时不影响微乳液的形成,水硬度的升高可促使前者的粒径缓慢减小,水硬度≤684mg/L时可促使后者形成粒径更小的微乳液；以SAA-H6为乳化剂时,水硬度的升高可促进微乳液的形成,并可促使形成粒径显著减小的微乳液。以SAA-6EJ、SAA-H6或SAA-56为乳化剂时,自来水对形成微乳液的影响分别为促使形成粒径更小的微乳液、促进微乳液的形成、阻止微乳液的形成。温度过高可能会阻止微乳液的形成,以SAA-H6、SAA-56为乳化剂时,分别在≥40℃、≥50℃时无法形成微乳液。以SAA-6EJ为乳化剂时,乳糖、甘露醇、水溶性淀粉、苯甲酸钠、硫酸镁的溶解过程均会阻止微乳液的形成；柠檬酸的溶解过程则可以促进微乳液的形成,并且柠檬酸用量的升高可促使形成粒径更小的微乳液。以SAA-56或SAA-H6为乳化剂时,甘露醇、乳糖、水溶性淀粉、硫酸镁的溶解过程不影响微乳液的形成,但苯甲酸钠的溶解过程会阻止微乳液的形成。
采用近红外多重光散射技术研究乳液稳定机理。各个三唑磷MEG稀释后形成的微乳液,在70min内,液滴的迁移速率均为0,但D5o或保持不变,或增大,或减小,载体是造成这种变化的主要因素。以碳水化合物或无机盐为载体的微乳粒剂的乳状液,随着时间的推移,前者的D5o会逐渐增大,而后者的Dso会逐渐减小。与制剂中未含柠檬酸时相比,若柠檬酸的加入使乳状液的初始粒径增大,则会升高D5o的增大速率；若使初始粒径减小,则会降低Dso增大或减小的速率。另外,Zeta电位对微乳粒剂乳状液D5o的变化无影响。
研究结果表明,常温下呈液态或熔点较低的农药原药可以配制成微乳粒剂,且无需使用有机溶剂；高熔点农药原药通过添加合适的有机溶剂也可以配制成微乳粒剂。RCF100g下离心5min后体系是否保持稳定可作为判别是否有可能是微乳液的依据,但不能认为此条件下稳定的透明或半透明乳状液就是微乳液。SRC在农药制剂配方筛选中可作为一种非常有效的筛选依据。Ca2+、Mg2+及自来水中的离子会影响乳滴形成前及界面重新平衡后的界面张力,最终影响微乳液的形成及粒径大小。SAA烷基及乙氧基链长上的差异会导致微乳粒剂能形成微乳液的温度范围不一样。载体溶解时的吸热及放热过程会阻止或促进微乳液的形成。静电斥力不是微乳粒剂乳状液的稳定机理。微乳粒剂的生物活性不低于微乳剂。微乳粒剂是一种新型、高效的环境友好型剂型,具有较好的应用前景。
The feasibility to formulate oil-soluble pesticide technical material (TC) into a novel solid formulation, micro-emulsifiable granule (MEG) was studied. The test pesticides were triazophos, cypermethrin and abamectin to represent oil-soluble pesticide TC, including liquid TC, low melting point TC and high melting point TC, respectively. Triazophos MEG as object of study, the mechanisms of micro emulsion formation and emulsion stability were researched.
By testing the solubility, dissolution rate and oil absorption rate, sodium benzoate, lactose, mannitol, magnesium sulfate and water soluble starch were selected as carriers of MEG. And a mixture, C12was obtained by uniform design of experiments with mixtures U11(105). The oil absorption rate of C12was56.2g oil per100g carrier. Specific surface area and pore size parameters test showed the parameters which had significantly influence on carrier's oil absorption rate were BET surface area, total area in pores, BJH desorption cumulative surface area of pores, BJH desorption cumulative volume of pores and total volume in pores.
According to U10(108), triazophos300ME (not containing organic solvent) were prepared in order to screen surface active agent (SAA) used for the preparation of MEG. A mixture SAA of non-ionic surfactants,602#+EL40+JM6140(named SAA-6EJ), was screened out by standard regression coefficient (SRC) of Xi. Triazohpos100MEG which contains10%SAA-6EJ was successfully formulated when using mannitol or MgSO4conjoined citric acid as carrier, and its minimum value of D5o was40.64nm. D50of triazohpos150MEG containing8%SAA-6EJ was75.49nm. A mixture SAA of anionic surfactant and non-ionic surfactant,500#+602#(named SAA-56), was screened out by SRC of Xi and XiXj. Triazophos100MEG containing SAA-56was successfully formulated when the carrier was a mixture of lactose or mannitol or water soluble starch and citric acid. D50of triazohpos150MEG containing8%SAA-6EJ was54.2nm. Triazophos300micro-emulsifiable gel (MGL) was formulated using the mixture SAA of anionic surfactant and non-ionic surfactant, FS7PG+602#(named SAA-F6) or HASS7+602#(named SAA-H6), which screened out by SRC of XiXj And triazophos100MEG could be successfully formulated using SAA-F6, if the carrier was MgSO4or C12. Triazophos100MEG also could be successfully prepared using SAA-H6, when the carrier was the one of lactose, mannitol, water soluble starch, MgSO4, or C12. D50of triazophos150MEG containing10%SAA-H6was63.69nm. They were discovered in experiments. First, in same emulsion, the change of D50negatively correlated with the change of transparency or transmission. Second, although the D50of one emulsion was smaller than another emulsion, its centrifugal stability might not higher than that of another. Third, Nano emulsion could maintain stability after centrifuge5min under relative centrifugal force (RCF)100g, and the critical RCF between nano emulsion and micro emulsion would change along with the change of emulsifier system.
According to U8(63), cypermethrin100MEG containing10%SAA were prepared by melt-blending process. The optimum combination of FS7PG,500#and EL60, optimized by Partial Least Squares Regression (PLSR), was used as emulsifier of cypermethrin100MEG, and the value of D50was51.45nm. Two surfactants, FS7PG and EL60, were screened out by SRC. The test results of proportional method were showed cypermethrin100MEG could be successfully formulated using FS7PG and EL60as emulsifiers when the ratio of FS7PG/EL60between1/9and10/0, and the least value of D50was59.91nm when the ratio was9/1. Lambda-cyhalothrin100MEG, bifenthrin100MEG, bifenthrin50MEG and alpha-cypermethrin100MEG could be successfully formulated using the recipes of cypermethrin100MEG.
According to L9(34), abamectin20ME were prepared. And the optimum combination (named SAA-TJH) of TSP16, JM6180, and HASS7was obtained when the independent variable was transparency temperature section of ME. When the carrier was the mixture of benzoate, MgSO4and lactose, D50of abamectin20MEG containing10%SAA-TJH was79.54nm. According to U11(114), abamectin20MEG were prepared using benzoate as carrier, and the proportion of602#, NP10-P, AEC903and NP-10was optimized by PLSR. When the optimum combination was used as emulsifier of abamectin20MEG, D50was12.13nm. There were three combinations,602#+NP10P+NP10,602#+NP10and NP10P+NP10, screened out by SRC. Using their optimized proportion, D50of abamectin20MEG (10%SAA) was44.31nm,14.22nm, and14.04nm, respectively. Ivermectin MEG and emamectin benzoate MEG could be successfully formulated using the recipes of abamectin20MEG.
The formulation process of MEG was rotary extruding granulation or fluidized granulation. The physical and chemical properties of MEG preparations meet the requirements of application. In the thesis, the test items and corresponding values for product registration quality requirements were proposed, and mechanical stirring method as the test method of emulsified time, one of test items, was established.
The bioassay test results of armyworm (Leucania separata) showed that the bioactivity of triazophos150MEG was higher than that of triazophos100MEG, triazophos150ME and triazophos150EC, and there were no significant differences of bioactivity among later3preparations. There were no significant differences of bioactivity among cypermethrin100MEG, cypermethrin100ME, cypermethrin100EC, but they were significantly better than of cypermethrin100EG. If abamectin was formulated as MEG or micro-emulsifiable powder, its bioactivity was no significant difference with that of ME, but significantly better than that of EC. And it was found that the formulation would not affect the biological sensitivity level of target organism to pesticide active ingredient by comparing the slopes of toxicity regression equations.
Triazophos MEG was selected as the research object. The effect of water hardness, tap water, water temperature and carrier on the micro emulsion formation after MEG diluted using dynamic light scattering technique and static light scattering technique, and the formation mechanism was preliminary analyzed. If water hardness was less than or equal to1368mg/L, the formation of micro emulsion would not be affected when MEG's emulsifier was SAA-56or SAA-6EJ, and the rise of water hardness could make former's droplet diameter decreased slowly, the latter could form micro emulsion with smaller droplet diameter if water hardness was not greater than684mg/L. Water hardness could promote the formation of micro emulsion if emulsifier was SAA-H6, and droplet diameter decreased rapidly following the rise of water hardness. The effect of tap water on micro emulsion formation was to promote forming a micro emulsion with smaller droplet size, or promote the formation of micro emulsion, or prevent the formation of micro emulsion, when the emulsifier was SAA-6EJ, SAA-H6and SAA-56, respectively. If the water temperature was too high, the micro emulsion formation might be prevented. When MEG's emulsifier was SAA-H6or SAA-56, the formation of micro emulsion would be prevented if the water temperature was not lower than40℃and50℃, respectively. When the emulsifier of MEG was nonionic mixture surfactants, SAA-6EJ, the carrier's dissolution process could prevent the formation of micro emulsion if the MEG's carrier was lactose, mannitol, water soluble starch, benzoate and MgSO4, respectively; but the dissolution process of citric acid could promote the formation of micro emulsion, and it could form a micro-emulsion with more smaller droplet size following the rise of citric acid dosage. When MEG's emulsifier was a mixture of anionic and nonionic surfactants, like SAA-56and SAA-H6, the dissolution process of lactose, mannitol, water soluble starch and MgSO4would not prevent the formation of micro emulsion, but the dissolution process of benzoate could prevent the micro emulsion formation.
The technique, near-infrared multiple light scattering, was introduced to study mechanism of MEG's emulsion stability. Within70min, the migration velocity of droplet was zero, and D50might unchanged, or increased or decreased following time, and the carrier was the major factor contributing to this change. D50would gradually increase as time goes by if the carrier was carbohydrates. But if the carrier was inorganic salts, D50would gradually decrease as time goes by. Compared with MEG that no contain citric acid, if the initial droplet size increased because citric acid as one of carriers, the rising rate of D50would be increased by citric acid; but if the initial droplet size decreased because citric acid as one of carriers, the change rate of D50, including rising rate and decreasing rate, would be reduced by citric acid. Moreover, the Zeta potential had no obviously affect to the change of D50.
The research results show that pesticide TC, including liquid TC and low melting point TC, can be formulated as micro-emlsifiable granule with no organic solvent; and high melting point TC also can be formulated into micro-emulsifiable granule by adding suitable organic solvent. The fact that transparent or translucent emulsion remains steady after5min centrifugation at RCF100g can be regard as a necessity for determining that the emulsion is a microemulsion. In spite of that the stability is not adequate to ensure the emulsion is microemulsion. Standard regression coefficient can be used as a very effective filter of pesticide formulation recipe screen. Ca2+, Mg2+and ions in tap water can affect the interfacial tension before the droplet formation and after interfacial rebalance, and finally make effects on the formation of micro emulsion and droplet size. The chain length difference of alkyl and ethoxy group between different surfactants can cause the different temperature range that MEG's dilution can form micro emulsion. The endothermic and exothermic processes of carrier's dissolution can prevent or promote the formation of micro emulsion. The electrostatic repulsion is not emulsion stability mechanism of micro-emulsifiable granule. And the bioactivity of micro-emulsifiable granule will not lower than that of microemulsion. Micro-emulsifiable granule is a high effective and environment friendly pesticide formulation, and good application prospect.
通过测试溶解度、溶解速度及吸油率,筛选出苯甲酸钠、乳糖、甘露醇、硫酸镁、水溶性淀粉5个载体,采用混料均匀设计U11(105)优化得到混合载体C12,吸油率为56.2g/100g；比表面积及孔隙参数测试表明,影响载体吸油率的主要因子为BET表面积、总孔面积、BJH解吸附累积孔表面积、BJH解吸附累积孔容积、总孔容积。
按U10(1O8)配制30%三唑磷微乳剂(ME)(不含有机溶剂)来筛选可用于配制MEG的表面活性剂(SAA)。根据Xi的标准回归系数(SRC)筛选得到602#+EL40+JM6140(SAA-6EJ),以甘露醇或硫酸镁与柠檬酸复配后作为载体可以配制得到10%三唑磷MEG (10%SAA-6EJ),D5o最小为40.64nm;15%三唑磷MEG(8%SAA-6EJ)的D5o为75.49nm。根据Xi及XiXj的SRC筛选得到500#+602#(SAA-56),用乳糖或甘露醇或水溶性淀粉作为载体或分别与柠檬酸复配后作为载体,均可配制得到10%三唑磷MEG；15%三唑磷MEG(8%SAA-56)的D5o为54.2nm。根据XiXj的SRC筛选得至(?)FS7PG+602#(SAA-F6)、HASS7+602#(SAA-H6),以硫酸镁或C12为载体可配制得到10%三唑磷MEG(10%SAA-F6),以乳糖、甘露醇、水溶性淀粉、硫酸镁或C12作为载体可配制得到10%三唑磷MEG (10%SAA-H6),15%三唑磷MEG (10%SAA-H6)的D5o为63.69nm。试验发现,对于同一个乳状液,D5o的变化与透明度或透射率的变化呈负相关；不同乳状液间对比时,离心稳定性更高的乳状液其D5o不一定更小；纳米乳液在RCF100g下离心5min亦可保持稳定,且纳米乳液与微乳液之间的临界相对离心力会随乳化体系的改变而改变。
采用熔融共混法,按U6(63)配制10%氯氰菊酯MEG (10%SAA),应用偏最小二乘回归(PLSR)对FS7PG、500“、EL60间比例进行优化后所配制10%氯氰菊酯MEG的Dso为51.45nm。根据SRC筛选得到FS7PG+EL60,比例法试验表明,两者在1/9-10/0配比范围内均能配制出10%氯氰菊酯MEG,其中以9/1时Dso最小,为59.91nn。采用10%氯氰菊酯MEG的配方,可以成功配制三氟氯氰菊酯10%MEG、氟氯菊酯10%及5%MEG、顺式氯氰菊酯10%MEG。
按L9(34)配制2%阿维菌素ME,以透明温度区域为因变量,对TSP16、JM6180、 HASS7间比例进行优化后配制2%阿维菌素MEG (10%SAA),载体为苯甲酸钠、硫酸镁、乳糖的混合物,D5o为79.54nm。以苯甲酸钠为载体,按U11(114)配制2%阿维菌素MEG(10%SAA),以D5o为因变量,用PLSR对602#、NP10P、AEC903、NP10间比例进行优化后所配制2%阿维菌素MEG的Dso为12.13m；根据SRC对SAA筛选得到602#+NP10P+NP10、602#+NP10、NP10P+NP10,根据优化后的配比配制所得2%阿维菌素MEG(10%SAA)的Dso分别为44.31nm、14.22nm、14.04nm。采用2%阿维菌素MEG的配方可成功配制2%伊维菌素MEG、2%甲氨基阿维菌素苯甲酸盐MEG。
微乳粒剂的配制采用旋转括壁式挤压造粒或沸腾造粒。各个微乳粒剂的理化性能满足实际使用的要求。提出了微乳粒剂产品登记所需的质量指标,并建立了乳化时间测试方法——机械搅拌法。
对粘虫的生物测定结果表明,15%三唑磷MEG的生物活性要优于10%三唑磷MEG、15%三唑磷ME、15%三唑磷EC,后3个药剂之间无显著差异。10%氯氰菊酯MEG的生物活性与10%氯氰菊酯ME、10%氯氰菊酯EC之间无显著差异,但要显著优于10%氯氰菊酯EG。阿维菌素配制成微乳粒剂、微乳粉剂后,在生物活性上与微乳剂无显著差异,但要显著好于乳油。毒力回归方程斜率对比表明剂型的变化不会影响靶标生物对农药的敏感性程度。
以三唑磷MEG为研究对象,采用动态或静态光散射技术研究水硬度、自来水、水温、载体对微乳液形成的影响,初步分析微乳粒剂微乳液的形成机理。以SAA-56或SAA-6EJ为乳化剂时,水硬度≤1368mg/L时不影响微乳液的形成,水硬度的升高可促使前者的粒径缓慢减小,水硬度≤684mg/L时可促使后者形成粒径更小的微乳液；以SAA-H6为乳化剂时,水硬度的升高可促进微乳液的形成,并可促使形成粒径显著减小的微乳液。以SAA-6EJ、SAA-H6或SAA-56为乳化剂时,自来水对形成微乳液的影响分别为促使形成粒径更小的微乳液、促进微乳液的形成、阻止微乳液的形成。温度过高可能会阻止微乳液的形成,以SAA-H6、SAA-56为乳化剂时,分别在≥40℃、≥50℃时无法形成微乳液。以SAA-6EJ为乳化剂时,乳糖、甘露醇、水溶性淀粉、苯甲酸钠、硫酸镁的溶解过程均会阻止微乳液的形成；柠檬酸的溶解过程则可以促进微乳液的形成,并且柠檬酸用量的升高可促使形成粒径更小的微乳液。以SAA-56或SAA-H6为乳化剂时,甘露醇、乳糖、水溶性淀粉、硫酸镁的溶解过程不影响微乳液的形成,但苯甲酸钠的溶解过程会阻止微乳液的形成。
采用近红外多重光散射技术研究乳液稳定机理。各个三唑磷MEG稀释后形成的微乳液,在70min内,液滴的迁移速率均为0,但D5o或保持不变,或增大,或减小,载体是造成这种变化的主要因素。以碳水化合物或无机盐为载体的微乳粒剂的乳状液,随着时间的推移,前者的D5o会逐渐增大,而后者的Dso会逐渐减小。与制剂中未含柠檬酸时相比,若柠檬酸的加入使乳状液的初始粒径增大,则会升高D5o的增大速率；若使初始粒径减小,则会降低Dso增大或减小的速率。另外,Zeta电位对微乳粒剂乳状液D5o的变化无影响。
研究结果表明,常温下呈液态或熔点较低的农药原药可以配制成微乳粒剂,且无需使用有机溶剂；高熔点农药原药通过添加合适的有机溶剂也可以配制成微乳粒剂。RCF100g下离心5min后体系是否保持稳定可作为判别是否有可能是微乳液的依据,但不能认为此条件下稳定的透明或半透明乳状液就是微乳液。SRC在农药制剂配方筛选中可作为一种非常有效的筛选依据。Ca2+、Mg2+及自来水中的离子会影响乳滴形成前及界面重新平衡后的界面张力,最终影响微乳液的形成及粒径大小。SAA烷基及乙氧基链长上的差异会导致微乳粒剂能形成微乳液的温度范围不一样。载体溶解时的吸热及放热过程会阻止或促进微乳液的形成。静电斥力不是微乳粒剂乳状液的稳定机理。微乳粒剂的生物活性不低于微乳剂。微乳粒剂是一种新型、高效的环境友好型剂型,具有较好的应用前景。
The feasibility to formulate oil-soluble pesticide technical material (TC) into a novel solid formulation, micro-emulsifiable granule (MEG) was studied. The test pesticides were triazophos, cypermethrin and abamectin to represent oil-soluble pesticide TC, including liquid TC, low melting point TC and high melting point TC, respectively. Triazophos MEG as object of study, the mechanisms of micro emulsion formation and emulsion stability were researched.
By testing the solubility, dissolution rate and oil absorption rate, sodium benzoate, lactose, mannitol, magnesium sulfate and water soluble starch were selected as carriers of MEG. And a mixture, C12was obtained by uniform design of experiments with mixtures U11(105). The oil absorption rate of C12was56.2g oil per100g carrier. Specific surface area and pore size parameters test showed the parameters which had significantly influence on carrier's oil absorption rate were BET surface area, total area in pores, BJH desorption cumulative surface area of pores, BJH desorption cumulative volume of pores and total volume in pores.
According to U10(108), triazophos300ME (not containing organic solvent) were prepared in order to screen surface active agent (SAA) used for the preparation of MEG. A mixture SAA of non-ionic surfactants,602#+EL40+JM6140(named SAA-6EJ), was screened out by standard regression coefficient (SRC) of Xi. Triazohpos100MEG which contains10%SAA-6EJ was successfully formulated when using mannitol or MgSO4conjoined citric acid as carrier, and its minimum value of D5o was40.64nm. D50of triazohpos150MEG containing8%SAA-6EJ was75.49nm. A mixture SAA of anionic surfactant and non-ionic surfactant,500#+602#(named SAA-56), was screened out by SRC of Xi and XiXj. Triazophos100MEG containing SAA-56was successfully formulated when the carrier was a mixture of lactose or mannitol or water soluble starch and citric acid. D50of triazohpos150MEG containing8%SAA-6EJ was54.2nm. Triazophos300micro-emulsifiable gel (MGL) was formulated using the mixture SAA of anionic surfactant and non-ionic surfactant, FS7PG+602#(named SAA-F6) or HASS7+602#(named SAA-H6), which screened out by SRC of XiXj And triazophos100MEG could be successfully formulated using SAA-F6, if the carrier was MgSO4or C12. Triazophos100MEG also could be successfully prepared using SAA-H6, when the carrier was the one of lactose, mannitol, water soluble starch, MgSO4, or C12. D50of triazophos150MEG containing10%SAA-H6was63.69nm. They were discovered in experiments. First, in same emulsion, the change of D50negatively correlated with the change of transparency or transmission. Second, although the D50of one emulsion was smaller than another emulsion, its centrifugal stability might not higher than that of another. Third, Nano emulsion could maintain stability after centrifuge5min under relative centrifugal force (RCF)100g, and the critical RCF between nano emulsion and micro emulsion would change along with the change of emulsifier system.
According to U8(63), cypermethrin100MEG containing10%SAA were prepared by melt-blending process. The optimum combination of FS7PG,500#and EL60, optimized by Partial Least Squares Regression (PLSR), was used as emulsifier of cypermethrin100MEG, and the value of D50was51.45nm. Two surfactants, FS7PG and EL60, were screened out by SRC. The test results of proportional method were showed cypermethrin100MEG could be successfully formulated using FS7PG and EL60as emulsifiers when the ratio of FS7PG/EL60between1/9and10/0, and the least value of D50was59.91nm when the ratio was9/1. Lambda-cyhalothrin100MEG, bifenthrin100MEG, bifenthrin50MEG and alpha-cypermethrin100MEG could be successfully formulated using the recipes of cypermethrin100MEG.
According to L9(34), abamectin20ME were prepared. And the optimum combination (named SAA-TJH) of TSP16, JM6180, and HASS7was obtained when the independent variable was transparency temperature section of ME. When the carrier was the mixture of benzoate, MgSO4and lactose, D50of abamectin20MEG containing10%SAA-TJH was79.54nm. According to U11(114), abamectin20MEG were prepared using benzoate as carrier, and the proportion of602#, NP10-P, AEC903and NP-10was optimized by PLSR. When the optimum combination was used as emulsifier of abamectin20MEG, D50was12.13nm. There were three combinations,602#+NP10P+NP10,602#+NP10and NP10P+NP10, screened out by SRC. Using their optimized proportion, D50of abamectin20MEG (10%SAA) was44.31nm,14.22nm, and14.04nm, respectively. Ivermectin MEG and emamectin benzoate MEG could be successfully formulated using the recipes of abamectin20MEG.
The formulation process of MEG was rotary extruding granulation or fluidized granulation. The physical and chemical properties of MEG preparations meet the requirements of application. In the thesis, the test items and corresponding values for product registration quality requirements were proposed, and mechanical stirring method as the test method of emulsified time, one of test items, was established.
The bioassay test results of armyworm (Leucania separata) showed that the bioactivity of triazophos150MEG was higher than that of triazophos100MEG, triazophos150ME and triazophos150EC, and there were no significant differences of bioactivity among later3preparations. There were no significant differences of bioactivity among cypermethrin100MEG, cypermethrin100ME, cypermethrin100EC, but they were significantly better than of cypermethrin100EG. If abamectin was formulated as MEG or micro-emulsifiable powder, its bioactivity was no significant difference with that of ME, but significantly better than that of EC. And it was found that the formulation would not affect the biological sensitivity level of target organism to pesticide active ingredient by comparing the slopes of toxicity regression equations.
Triazophos MEG was selected as the research object. The effect of water hardness, tap water, water temperature and carrier on the micro emulsion formation after MEG diluted using dynamic light scattering technique and static light scattering technique, and the formation mechanism was preliminary analyzed. If water hardness was less than or equal to1368mg/L, the formation of micro emulsion would not be affected when MEG's emulsifier was SAA-56or SAA-6EJ, and the rise of water hardness could make former's droplet diameter decreased slowly, the latter could form micro emulsion with smaller droplet diameter if water hardness was not greater than684mg/L. Water hardness could promote the formation of micro emulsion if emulsifier was SAA-H6, and droplet diameter decreased rapidly following the rise of water hardness. The effect of tap water on micro emulsion formation was to promote forming a micro emulsion with smaller droplet size, or promote the formation of micro emulsion, or prevent the formation of micro emulsion, when the emulsifier was SAA-6EJ, SAA-H6and SAA-56, respectively. If the water temperature was too high, the micro emulsion formation might be prevented. When MEG's emulsifier was SAA-H6or SAA-56, the formation of micro emulsion would be prevented if the water temperature was not lower than40℃and50℃, respectively. When the emulsifier of MEG was nonionic mixture surfactants, SAA-6EJ, the carrier's dissolution process could prevent the formation of micro emulsion if the MEG's carrier was lactose, mannitol, water soluble starch, benzoate and MgSO4, respectively; but the dissolution process of citric acid could promote the formation of micro emulsion, and it could form a micro-emulsion with more smaller droplet size following the rise of citric acid dosage. When MEG's emulsifier was a mixture of anionic and nonionic surfactants, like SAA-56and SAA-H6, the dissolution process of lactose, mannitol, water soluble starch and MgSO4would not prevent the formation of micro emulsion, but the dissolution process of benzoate could prevent the micro emulsion formation.
The technique, near-infrared multiple light scattering, was introduced to study mechanism of MEG's emulsion stability. Within70min, the migration velocity of droplet was zero, and D50might unchanged, or increased or decreased following time, and the carrier was the major factor contributing to this change. D50would gradually increase as time goes by if the carrier was carbohydrates. But if the carrier was inorganic salts, D50would gradually decrease as time goes by. Compared with MEG that no contain citric acid, if the initial droplet size increased because citric acid as one of carriers, the rising rate of D50would be increased by citric acid; but if the initial droplet size decreased because citric acid as one of carriers, the change rate of D50, including rising rate and decreasing rate, would be reduced by citric acid. Moreover, the Zeta potential had no obviously affect to the change of D50.
The research results show that pesticide TC, including liquid TC and low melting point TC, can be formulated as micro-emlsifiable granule with no organic solvent; and high melting point TC also can be formulated into micro-emulsifiable granule by adding suitable organic solvent. The fact that transparent or translucent emulsion remains steady after5min centrifugation at RCF100g can be regard as a necessity for determining that the emulsion is a microemulsion. In spite of that the stability is not adequate to ensure the emulsion is microemulsion. Standard regression coefficient can be used as a very effective filter of pesticide formulation recipe screen. Ca2+, Mg2+and ions in tap water can affect the interfacial tension before the droplet formation and after interfacial rebalance, and finally make effects on the formation of micro emulsion and droplet size. The chain length difference of alkyl and ethoxy group between different surfactants can cause the different temperature range that MEG's dilution can form micro emulsion. The endothermic and exothermic processes of carrier's dissolution can prevent or promote the formation of micro emulsion. The electrostatic repulsion is not emulsion stability mechanism of micro-emulsifiable granule. And the bioactivity of micro-emulsifiable granule will not lower than that of microemulsion. Micro-emulsifiable granule is a high effective and environment friendly pesticide formulation, and good application prospect.
引文
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