CN102186340A - 用自乳化酯控制农药喷雾漂移的方法 - Google Patents

用自乳化酯控制农药喷雾漂移的方法 Download PDF

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CN102186340A
CN102186340A CN2009801416581A CN200980141658A CN102186340A CN 102186340 A CN102186340 A CN 102186340A CN 2009801416581 A CN2009801416581 A CN 2009801416581A CN 200980141658 A CN200980141658 A CN 200980141658A CN 102186340 A CN102186340 A CN 102186340A
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秦奎德
霍尔格·坦克
斯蒂芬·威尔逊
刘雷
戴维·奥斯
李梅
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Corteva Agriscience LLC
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Abstract

本发明涉及通过在待喷雾液体中结合自乳化酯来降低农用化学品施用过程中喷雾漂移的方法。

Description

用自乳化酯控制农药喷雾漂移的方法
本申请要求2008年10月31日提交的美国临时申请61/110,060的权益。
技术领域
本发明涉及通过将自乳化酯结合到待喷雾液体中来降低施用过程中农用化学品喷雾漂移的新方法。
背景技术
通过经济且有效的技术进行的农业喷雾法使用液压喷嘴，所述喷嘴内在地产生宽范围喷雾液滴大小(spray droplet size)。人们发现，这些喷雾液滴从施用的最初期望位点漂移的可能性为液滴大小的函数，其中较小的液滴具有较高的发生脱靶运动(off-target movement)的倾向。重要的研究努力(包括多次田间试验、风洞试验和随后预测性数学模型的生成)大大地提高了对喷雾液滴大小和脱靶漂移可能性之间的关系的理解。尽管其它因素例如气象学条件和喷雾吊臂的高度增大了发生漂移的可能性，但已经发现喷雾液滴大小分布是主要因素。Teske等人(Teske M.E.，Hewitt A.J.，Valcore，D.L.2004.The Role of Small Droplets in Classifying Drop Size Distributions ILASS Americas 17th Annual Conference：Arlington VA)已经报道，＜156微米(μ)的值为推动发生漂移的喷雾液滴分布粒度级(fraction)。Wolf(www.bae.ksu.edu/faculty/wolf/漂 移.htm)将＜200μ的值引用为可漂移粒度级。因此，对可能推动发生漂移的液滴大小的良好推测值为低于175μ粒度级。
脱靶运动的负面后果可能会十分显著。已经证明一些除草剂在非常低的百万分率(ppm)或者甚至十亿分率(ppb)水平时对具体的植物种类具有非常敏感的植物毒性，导致其在敏感作物周围、果园周围和住宅植被周围的受限施用。例如，加利福尼亚农药管理部门(California Dept of Pesticide Regulation)对在San Joaquin谷空中施用的含有敌稗的除草剂强制要求1/2-2英里(0.8-3.2公里)缓冲距离。
目前将高分子量水溶性聚合物加到喷雾组合物中作为容器混合物(tank mix)在一起以增大液滴大小，从而降低漂移(参见，例如WO 2008/101818A2和美国专利6,214,771B1)。然而，高分子量水溶性聚合物不能完全令人满意，因为当以相当大程度增大液滴大小所需的浓度使用时它们是昂贵的。此外，研究显示，由于泵剪切、风剪切和其它多种性能问题，商购漂移阻滞剂通常不能与多种空中施用的除草剂容器混合物一起使用，这在高速空中施用条件下更加显著。。参见Hewitt，A.J.(2003)Drift Control Adjuvants in Spray Applications：Performance and Regulatory Aspects.Proc.Third Latin American Symposium on Agricultural Adjuvants，Sao Paulo，Brazil。
发明内容
现在发现，通过将自乳化酯结合到农业喷雾混合物中可降低施用过程中的喷雾漂移。本发明涉及降低农药施用过程中喷雾漂移的方法，包括在所述农药喷雾剂中结合0.01至5％体积/体积自乳化酯或其混合物。多种因素导致喷雾漂移的降低，所述因素包括微细喷雾液滴(直径＜175μ)产生的减小和喷雾液滴体积中位直径(VMD)的增大。对于给定的喷雾设备、施用和条件，并且基于自乳化酯，大部分喷雾液滴的中位直径被增大至高于不含所述自乳化酯的喷雾组合物的中位直径。
本发明另一个实施方案为预混制剂，其包含1至90wt％农药和0.05至30wt％自乳化酯。所述预混制剂优选为溶液剂、乳剂、混悬剂、可润湿散剂或可溶散剂或水可分散颗粒制剂或水可溶颗粒制剂。
降低喷雾漂移的方法适用于任意农药或作物保护剂(包括除草剂、杀真菌剂和杀虫剂(insecticide))的施用。该方法适用的特别优选的除草剂包括氰氟草酯(cyhalofop-butyl)、氟吡禾灵(haloxyfop)、五氟磺草胺(penoxsulam)、氟唑啶草(flumetsulam)、氯酯磺草胺(cloransulam-methyl)、双氟磺草胺(florasulam)、甲氧磺草胺(pyroxsulam)、唑嘧磺胺(diclosulam)、氟草烟(fluroxypyr)、二氯吡啶酸(clopyralid)、刈草胺(acetochlor)、绿草定(triclopyr)、异噁酰草胺(isoxaben)、2，4-滴(2，4-D)、2甲4氯(MCPA)、麦草畏(dicamba)、甲胂一钠(MSMA)、乙氧氟草醚(oxyfluorfen)、黄草消(oryzalin)、氟乐灵(trifluralin)、氟草胺(benfluralin)、丁氟消草(ethalfluralin)、氯氨基吡啶酸(aminopyralid)、莠去津(atrazine)、氨氯吡啶酸(picloram)、丁唑隆(tebuthiuron)、胺硝草(pendimethalin)、敌稗(propanil)、炔苯酰草胺(propyzamide)、草甘膦(glyphosate)和草铵膦(glufosinate)。该方法适用的特别优选的杀虫剂包括有机磷酸酯类例如毒死蜱(chlorpyrifos)、MAC类例如特丁苯酰肼(halofenozide)、甲氧苯酰肼(methoxyfenozide)和双苯酰肼(tebufenozide)、合成除虫菊酯类例如γ-三氟氯氰菊酯(gamma-cyhalothrin)和溴氰菊酯(deltamethrin)和生物农药例如艾克敌(spinosad)和多虫菌素(spinetoram)。该方法适用的特别优选的杀真菌剂包括代森锰锌(mancozeb)、腈菌唑(myclobutanil)、腈苯唑(fenbuconazole)、苯酰菌胺(zoxamide)、丙环唑(propiconazole)、苯氧喹啉(quinoxyfen)和噻氟菌胺(thifluzamide)。本发明特别用于除草剂的施用，最特别的是用于在敏感作物周围经受受限施用的除草剂，例如2，4-D、麦草畏、草甘膦和草铵膦，所述敏感作物已被改良对所述除草剂耐受。
用在本发明中的自乳化酯(SEE)的特征为在可在水相中形成均匀稳定乳液的单一分子中结合了油性(疏水性)、亲水性非离子和任选阴离子官能度。与常规乳液(其中一种或多种油与一种或多种表面活性剂(乳化剂)共混)不同，对于本发明披露的乳液来说，所述添加剂不是必需的。可通过轻微至适度搅动SEE和水的混合物用这些SEE形成均匀稳定的水性乳液而不额外使用乳化剂或油。这些SEE的实例包括但不限于以下：(1)基于三聚体酸的自乳化酯，其是通过使具有C54亲脂性骨架的油酸和亚油酸与含有非离子和阴离子表面活性剂官能度的分子的酯部分聚合制备的(参见，例如美国专利5,688,750和5,707,945；以商标Priolube从Croda Uniqema，Inc购买的产品)；(2)通过用脂肪酸和二羧酸酐酯化乙氧基化三羟甲基丙烷制备的酯(参见，例如WO1990/005714)；(3)衍生自高分子量二元酸、聚氧化烯二醇和单官能脂肪族醇的酯(参见，例如美国专利3,912,642)；(4)通过乙氧基化三羟甲基丙烷与羧酸或其反应性衍生物例如酸酐反应制备的自乳化酯化合物，如美国专利5,219,479中所披露；(5)衍生自马来酸甘油三酯(来自植物或陆地动物)的琥珀酸甘油三酯油(参见，例如WO 2005/071050A1)，以商标VEG-ESTER从Lubrizol，Inc.购买的产品；(6)乙氧基化脂肪酸酯(参见，例如WO 1996/022109)；(7)如美国专利4,559,226所披露，通过醇与环氧乙烷和环氧丙烷和/或环氧丁烷反应并用链烷酸或芳族酸使所得烷氧化物封端来制备的烷氧化物酯，以商标Hetester从Bernel Chemical Company，Inc.(Alzo International，Inc.的分支机构)购买的产品；和(8)以商标Aqnique RSO和Agnique SBO从Cognis，Inc.购买的烷氧基化甘油三酯产品。
可通过以下方式将所述自乳化酯结合到农药喷雾剂中：直接在容器中与稀农药制剂混合在一起，或者在稀释至最终喷雾体积之前与农药制剂预混合在一起。按以下浓度结合所述自乳化酯：最终喷雾体积的0.01至5体积％，优选最终喷雾体积的0.05至1.0体积％，最优选为最终喷雾体积的0.05至0.2体积％。
本发明方法降低空中施用和地面施用中所述农药喷雾剂的脱靶运动。
最佳液滴大小依赖于所述组合物所被用于的应用。如果液滴过大，则通过喷雾的覆盖度较小；即，大液滴会落在某些区域，而这些区域之间的区域接受很少或没有接受到喷雾组合物。最大可接受液滴大小可能依赖于每单位面积所施用的组合物的量和喷雾覆盖度所需的均匀性。较小液滴提供更均匀覆盖度，但更倾向于在喷洒过程中漂移。如果在喷洒过程中风特别强，则优选较大液滴，而在无风天优选较小液滴。
所述喷雾液滴大小也依赖于所述喷雾设备；例如，喷嘴尺寸和构造。本领域技术人员能够很容易地调整所述组合物中表面活性剂和/或聚合物的百分比，从而针对给定的设备、应用和条件提供所需液滴大小。在任意情况下，对于给定的喷雾设备、应用和条件，并且基于所述自乳化酯，大部分喷雾液滴的中位直径被增大至高于不含所述自乳化酯的喷雾组合物的中位直径。
除了上述方法，本发明还涵盖预混制剂，其包含1至90wt％，优选5至70wt％，最优选20至60wt％农药和0.05至30wt％，优选1.0至20wt％，和最优选1.0至10wt％自乳化酯。
任选地，本发明组合物可含有表面活性剂。所述表面活性剂在性质上可以是阴离子的、阳离子的或非离子的。典型的表面活性剂包括烷基硫酸盐，如二乙醇-月桂基硫酸铵；烷基芳基磺酸盐，如十二烷基苯磺酸钙；烷基酚-烯化氧加成产物和/或芳基烷基酚-烯化氧加成产物，如壬基酚-C18乙氧基化物；醇-烯化氧加成产物，如十三烷基醇-C16乙氧基化物；皂，如硬脂酸钠；烷基萘磺酸盐，如二丁基萘磺酸钠；磺化琥珀酸盐的二烷基酯，如二(2-乙基己基)磺化琥珀酸钠；山梨糖醇酯，如山梨糖醇油酸酯；季铵，如月桂基三甲基氯化铵；乙氧基化胺，例如牛脂胺聚氧乙烯醚(tallowamine ethoxylated)；甜菜碱表面活性剂，例如椰油酰氨基二丙基甜菜碱；脂肪酸的聚乙二醇酯，如硬脂酸聚乙二醇酯；环氧乙烷和环氧丙烷的嵌段共聚物；以及磷酸单烷基酯的盐和磷酸二烷基酯的盐；以及它们的混合物。所述表面活性剂或表面活性剂的混合物在制剂中的浓度通常为2-20wt％。
除了上述制剂，本发明还涵盖与一种或多种额外相容成分组合的制剂。其它额外成分可包括但不限于一种或多种其它农药、染料和任意其它提供功能性用途的额外成分，例如稳定剂、香料、降粘剂和防冻剂(freeze-point depressant)。
所述预混制剂优选为溶液剂、乳剂、混悬剂、可润湿散剂或可溶散剂或水可分散颗粒制剂或水可溶颗粒制剂。
以下实施例说明本发明。
具体实施方式
实施例1
为了制备如表1所示的每种浓度的2，4-D制剂A至G，首先向装备有机械搅拌子的不锈钢烧杯中装入90克DMA 6 SEQUESTERED(在水溶液中含有68.8％2，4-D二甲基铵盐)。然后根据表1的组成将总共10克Priolube产品的不同组合加入其中。搅拌每种液体混合物使所述组合物匀化并得到制剂。
通过以下方式制备喷雾水溶液：将每种制剂各lmL加至99mL去离子水中，制备1％v/v稀释液。然后通过TeeJet 8002扁平扇形喷嘴以40psi(276千帕(kPa))喷洒所述喷雾溶液，通过使用Sympatec Helos粒度分级器测量液滴大小。在离所述粒度分级器的测量区6或12英寸(15.24或30.48厘米(cm))处用喷嘴的尖端进行测量。结果记录在表2(6英寸；15.24cm)和表3(12英寸；30.48cm)中。从这些结果可以看出，通过本发明喷雾组合物产生的液滴大小小于175μm的可漂移微细物被大大减少。本发明通过缩小滴径分布但不显著增加大液滴而有效减少可漂移微细液滴，从而对喷雾覆盖度和质量具有最小影响。
表1.实施例1制剂的组成
Figure BDA0000056294780000051
Figure BDA0000056294780000061
*DMA 6 SEQUESTERED，6lb(2.72千克(kg))ae/gal2，4-D-二甲基铵，DowAgroSciences，LLC的制造用途浓缩物。
表2.离喷嘴6英寸(15.24cm)处的实施例1组合物的喷雾性能。
  喷雾溶液  VMD＊，μm ＜100＊＊μm的百分比  ＜175＊＊＊μm的百分比
  DMA 6 SEQ 1％  213.00 15.99  38.72
  A 1％  223.60 14.21  35.64
  B 1％  287.44 4.36  16.24
  C 1％  281.19 4.65  17.55
  D 1％  278.43 5.27  18.76
  E 1％  267.02 6.03  21.37
  F 1％  255.07 8.52  25.99
  G 1％  238.08 10.86  30.62
*VMD-体积中位直径
**液滴大小小于100μm的喷雾体积的百分比
***液滴大小小于175μm的喷雾体积的百分比
表3.离喷嘴12英寸(30.48cm)处的实施例组合物的喷雾性能
  喷雾溶液 VMD＊，μm ＜100＊＊μm的百分比 ＜175＊＊＊μm的百分比
  DMA 6SEQ 1％ 164 20.8  53.7
  A 1％ 204 13.7  40.6
  B 1％ 251 7.2  25.9
  C 1％ 248 7.9  27.6
  D 1％ 227 10.3  33.4
  E 1％ 237 9.0  30.5
  F 1％ 231 9.8  32.4
  G 1％ 190 15.4  44.8
实施例2
按照与实施例1相同的操作以1％v/v制备喷雾溶液制剂H至N。然后向每种喷雾溶液中加入合适量的草甘膦二甲基铵盐，实现2，4-D与草甘膦的酸当量比为1∶1。将稀释液搅拌均匀得到喷雾溶液。然后将其按照与实施例1所述相同的操作和设置喷雾。结果显示在表4(在离喷嘴6英寸(15.24cm)处测量)和表5(在离喷嘴12英寸(30.48cm)处测量)中。从这些结果可以看出，与之前的实施例相比，草甘膦的加入没有显著影响喷雾分布，这说明本发明在控制所述可漂移微细物中的稳键性。
表4.离喷嘴6英寸(15.24cm)处的实施例2组合物的喷雾性能
Figure BDA0000056294780000071
表5.离喷嘴12英寸(30.48cm)处的实施例2组合物的喷雾性能
Figure BDA0000056294780000072
实施例3
为了制备如表4所示的每种浓度的除草剂制剂O至Q，首先向装备有机械搅拌子的不锈钢烧杯中装入95克除草剂制剂(DMA6 SEQ(Garlon 3A*)或Milestone**)和5g Hetester PCA(从Alzo International Inc.获得)。搅拌每种液体混合物使所述组合物匀化并得到制剂，用于随后的稀释和喷雾分析。
通过以下方式制备每种喷雾水溶液：将每种制剂各2mL加至98mL去离子水中，制备2％v/v稀释液。然后按照与实施例1所述相同的操作和设置将所述溶液喷雾，其中所述喷嘴距粒度分级器测量区12英寸(30.48cm)。结果显示在表6中，从这些结果可以看出，本发明通过缩小大小分布但不显著增加大液滴而确实有效减少可漂移微细液滴，从而对喷雾覆盖度和质量具有最小影响。
*Garlon 3A，3lb(1.36kg)ae/gal绿草定三乙胺盐，Dow AgroSciences，LLC的商品。
**Milestone，2lb(0.91kg)ae/gal氯氨基吡啶酸三异丙醇胺盐，DowAgroSciences，LLC的商品。
表6.实施例3组合物的喷雾性能.
Figure BDA0000056294780000081
实施例4
为了制备表7所示的每种除草剂制剂R至T，首先向样品罐中装入294mL去离子水，然后装入6mL商购除草剂制剂(DMA6SEQ(Clarity*)或Accord XRT II**)，从而制备所述制剂的2％v/v稀释液。然后振摇样品直到均匀。然后向各溶液中加入Veg-Ester GY-350(Lubrizol，Inc.)，加入的量等于所述稀除草剂制剂的0.1％w/w。将所述样品再次振摇直到均匀。然后按照与实施例1所述相同的操作和设置喷洒所述溶液，其中所述喷嘴距粒度分级器测量区12英寸(30.48cm)。结果如表5所示。从这些结果可以看出，本发明通过改变大小分布但不显著增加大液滴而确实有效减少可漂移微细液滴，从而对喷雾覆盖度和质量具有最小影响。
*Clarity，4lb(1.8lkg)ae/gal麦草畏二甘醇胺盐，BASF公司的商品。
**Accord XRT II，4lb(1.81kg)ae/gal草甘膦二乙胺盐，DowAgroSciences，LLC的商品。
表7.实施例4组合物的喷雾性能
实施例5
将麦草畏二甲基铵盐的1.40ml水溶液(麦草畏DMA，46.9％w/wa.e.，560.92g a.e./L)和0.649g Priolube 3952加至324ml去离子水中，手动振摇得到溶液，该溶液含有0.43％v/v麦草畏DMA和0.2％w/w Priolube 3952。以相似的方式将1.45ml麦草畏二甲基铵盐溶液和0.70g Agnique SBO-10加至335ml去离子水中，得到溶液，该溶液含有0.43％v/v麦草畏DMA和0.2％w/wAgnique SBO-10。作为对照，将1.45ml麦草畏DMA浓缩物加至336ml去离子水中，得到0.43％v/v溶液。最后，制备Clarity的0.43％v/v溶液用于对比。喷洒所得溶液并如实施例1所述测量它们的液滴大小分布，其中所述喷嘴距粒度分级器测量区12英寸(30.48cm)。结果总结在表8中。从这些结果可以看出，本发明通过改变大小分布但不显著增加大液滴而确实有效减少可漂移微细液滴，从而对喷雾覆盖度和质量具有最小影响。
表8.实施例5组合物的喷雾性能.
实施例6
向359.07g去离子水中按顺序加入：2.75g2，4-D二甲基乙醇铵盐溶液(53.6％a.e.)、0.15g Agnique SBO-10、0.38g丙二醇和3.52g草甘膦二甲基铵盐溶液(42.2％a.e.)。作为对照，如刚刚所描述的那样制备另一种样品，不同的是用额外0.15g去离子水替换Agnique SBO-10。将所得溶液简单手动振摇，然后如实施例1所述针对它们的喷雾液滴分布进行分析，其中所述喷嘴距粒度分级器测量区12英寸(30.48cm)。结果显示在表9中。
表9.实施例6组合物的喷雾性能
Figure BDA0000056294780000101

Claims (8)

1.降低农药施用过程中喷雾漂移的方法，所述方法包括在农药喷雾剂中结合0.01至5％体积/体积自乳化酯或其混合物。
2.权利要求1的方法，其中所述农药为除草剂。
3.权利要求2的方法，其中所述除草剂为2，4-D、草甘膦、绿草定、氯氨基吡啶酸、麦草畏或它们的混合物。
4.权利要求1的方法，其中所述农药为杀虫剂。
5.权利要求1的方法，其中所述农药为杀真菌剂。
6.权利要求1的方法，其中所述自乳化酯为(1)基于三聚体酸的自乳化酯，其是通过使具有C54亲脂性骨架的油酸和亚油酸与含有非离子和阴离子表面活性剂官能度的分子的酯部分聚合制备的；(2)通过用脂肪酸和二羧酸酐酯化乙氧基化三羟甲基丙烷制备的酯；(3)衍生自高分子量二元酸、聚氧化烯二醇和单官能脂肪族醇的酯；(4)通过使乙氧基化三羟甲基丙烷与羧酸或其反应性衍生物反应制备的自乳化酯化合物；(5)衍生自来自植物或陆地动物的马来酸甘油三酯的琥珀酸甘油三酯油；(6)乙氧基化脂肪酸酯；(7)通过使醇与环氧乙烷和环氧丙烷和/或环氧丁烷反应并用链烷酸或芳族酸使所得烷氧化物封端制备的烷氧化物酯；和(8)烷氧基化甘油三酯。
7.预混制剂，其包含1至90wt％农药和0.05至30wt％自乳化酯。
8.权利要求6的预混制剂，其包含20至60wt％农药和1.0至10wt％自乳化酯。
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