CN104472488B - 一种含氟啶虫酰胺和氯氟氰虫酰胺的杀虫组合物 - Google Patents
一种含氟啶虫酰胺和氯氟氰虫酰胺的杀虫组合物 Download PDFInfo
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- CN104472488B CN104472488B CN201410705379.6A CN201410705379A CN104472488B CN 104472488 B CN104472488 B CN 104472488B CN 201410705379 A CN201410705379 A CN 201410705379A CN 104472488 B CN104472488 B CN 104472488B
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- insecticidal composition
- flonicamid
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Abstract
本发明公开了一种含有二种活性成分的杀虫组合物，第一种活性成分为氟啶虫酰胺，第二种活性成分为氯氟氰虫酰胺，两者之间的质量配比为1～50:20～1。本发明提供的杀虫组合物适合用于防治同翅目和鳞翅目害虫。
Description
技术领域
本发明属于农药领域，具体涉及一种杀虫组合物。
背景技术
农业害虫的抗性问题是一个全球性的问题。随着害虫化学防治的的延续、农药使用量的增加以及不科学使用农药，害虫抗性日益严重，产生抗性的害虫种类不断增多。特别是对农业生产为害严重的鳞翅目类害虫，其抗性程度较高、抗性发展速度相对较快。同时随着高强度农药的使用，以致农产品农药残留超标、环境污染和农民用药成本增加，不利于农业可持续发展。
现有技术中，已有的农药例如氟啶虫酰胺等，其单独使用时用药成本较高，不仅在一定程度上限制了其推广应用，而且长期单独使用容易造成害虫抗性程度不断增加。不同农药品种的混配，是防治农业抗性害虫的常见方法。通过农药配方筛选，筛选出合理的配方，可有效提高实际防治效果，减少用药量，降低成本，延缓害虫抗药性的产生，延长药剂的使用寿命，是害虫综合治理的重要手段。
因此，研究开发高效、低毒、环保的杀虫组合物及杀虫剂对农业可持续发展具有积极意义。
发明内容
本发明要解决的技术问题可提供一种高效、低毒且持效期长的杀虫组合物，能够用于防治鳞翅目类害虫，有利于害虫的综合治理。
为解决上述问题，本发明所采用的技术方案是：
一种杀虫组合物，含有二种活性成分，第一种活性成分为氟啶虫酰胺，第二种活性成分为氯氟氰虫酰胺，所述第一种活性成分与第二种活性成分的质量配比为1～50:20～1。
本发明提供的杀虫组合物中，上述氟啶虫酰胺(flonicamid)是一种新型低毒吡啶酰胺类昆虫生长调节剂，具有触杀和胃毒作用及很好的神经毒剂和快速拒食作用，对黄瓜、苹果蚜虫有较好的防治效果。蚜虫等刺吸式口器害虫取食吸入带有氟啶虫酰胺的植物汁液后，会被迅速阻止吸汁，1小时之内完全没有排泄物出现，最终因饥饿而死亡。本发明提供的杀虫组合物中，上述3－氯－N1－(2－甲基－4－七氟异丙基苯基)－N2－(1－甲基－1－氰基乙基)邻苯二甲酰胺(以下简称“ZJ4042”)，又称为“氯氟氰虫酰胺”，是浙江省化工研究院自行研制的新型杀虫剂，结构式如下(I)所示：
该化合物的杀虫活性与近期开发的氟虫双酰胺的基本相当。氟虫双酰胺，英文通用名(flubendiamide)由日本农药株式会社研发，化学名称为3-碘-N-(2-甲磺酞基-1,1-二甲基乙烷基-N-{4-「1,2,2,2-四氟-1-(三氟甲基)乙基-o-甲苯基}邻苯二酰胺，分子式为：C23H22F7N2O4，属新型邻苯二甲酰胺类杀虫剂，激活兰尼碱受体细胞内钙释放通道，导致贮存钙离子的失控性释放，是目前为数不多的作用于昆虫细胞兰尼碱(Ryanodine)受体的化合物。对鳞翅目害虫有广谱防效，与现有杀虫剂无交互抗性产生，非常适宜于现有杀虫剂产生抗性的害虫的防治。
作为优选的方式，上述第一种活性成分与第二种活性成分的质量配比优选为1～10:10～1，并进一步优选为1～5:5～1。
本发明还提供了一种杀虫剂，以重量计含有5～90％上述杀虫组合物,其余为农业上可接受的载体和助剂。作为优选的实施方式，所述杀虫剂中，含有以重量计5～40％的杀虫组合物。
本发明所述的载体可以是固体或液体，通常用于配制杀虫剂组合物的任何载体均能使用。
合适的固体载体包括：矿物类，植物类，合成填料类和无机盐类。其中矿物类包括硅酸盐类，碳酸盐类，硫酸盐类和氧化物类。硅酸盐类例如高岭土，海泡石，珍珠陶土，蒙脱土，云母，蛭石，叶蜡石，滑石。碳酸盐类例如：碳酸钙，白云石。硫酸盐类如硫酸铵，硫酸钠，硫酸钙。氧化物类如生石灰，镁石灰，硅藻土。植物类例如：柑橘渣，玉米棒芯，谷壳粉，稻壳，大豆秸粉，烟草粉，胡桃壳，锯木粉。合成填料类如沉淀碳酸钙水合物，沉淀碳酸钙，白炭黑。无机盐类例如氯化钾，氯化钠。
液体载体包括水和有机溶剂。当有效成分为悬乳剂时，有机溶剂起到增溶和防冻作用。合适的有机溶剂包括芳烃，例如苯、二甲苯、甲苯、烷基苯、烷基萘和氯代芳烃；氯代脂肪烃，例如氯乙烯、三氯甲烷、二氯甲烷、氯仿、四氯化碳和多氯乙烷；脂肪烃，例如石油馏分、环己烷、轻质矿物油和石蜡。醇类例如甲醇，乙醇，异丙醇、丁醇、异丁醇，乙二醇、丙二醇、丙三醇、脂肪醇等；醚类例如甲基乙二醇醚，乙基乙二醇醚，石油醚。酮类例如丙酮、甲乙酮、甲基异丁基酮、环己酮以及异氟尔酮、N-甲基-吡咯烷酮；特种溶剂还有二甲基甲酰胺，二甲基亚砜，聚乙二醇，已腈；植物油及甲基化植物油。上述有机溶剂既可以单独使用，也可以混合使用，还可以与水一起混合使用。
本发明所述助剂可以根据需要包括表面活性剂、消泡剂、增稠剂、助悬剂和防冻剂中的一种或几种，还可以根据需要包括本行业常用的其他助剂。
表面活性剂可以是乳化剂、分散剂、稳定剂或湿润剂；可以是离子型的或非离子型的。合适的表面活性剂包括：聚丙烯酸和木质素磺酸的钠盐和钙盐；分子中含有至少12个碳原子的脂肪酸或脂肪胺与环氧乙烷和/环氧丙烷的缩聚产物；甘油、十二烷醇-1、十四烷醇-1、山梨醇、蔗糖或季戊四醇的脂肪酸酯；及它们与环氧乙烷和/或环氧丙烷的缩聚产物；它们的缩聚产物的硫酸盐或磺酸盐；在分子中至少含有10个碳原子的硫酸或磺酸的碱金属或碱土金属盐，较佳的为钠盐，如十二烷基硫酸钠、仲烷基硫酸钠、磺化蓖麻油的钠盐、烷芳基磺酸钠和十二烷基苯磺酸钠；环氧乙烷的聚合物、环氧乙烷和环氧丙烷的共聚物。
乳化剂包括非离子型乳化剂和阴离子型乳化剂。非离子型乳化剂优选壬基酚聚氧乙烯醚，脂肪醇聚氧乙烯醚，苯乙烯基苯基聚氧乙烯醚，烷基酚甲醛树脂聚氧乙烯醚，端羟基聚氧乙烯聚氧丙烯醚，苯乙烯基苯酚甲醛树脂聚氧乙烯聚氧丙烯醚，蓖麻油聚氧乙烯醚。阴离子型乳化剂主要包括十二烷基苯磺酸钙，三苯乙基酚聚氧乙醚磷酸酯胺盐，壬基酚聚氧乙烯醚磷酸酯胺盐，蓖麻油聚氧乙烯醚磷酸酯胺盐。
本发明所述的分散剂包括：丙烯酸均聚物钠盐，马来酸二钠盐，萘磺酸甲醛缩合物钠盐，松香嵌段聚氧乙烯醚聚氧丙烯醚磺酸盐，端羟基聚氧乙烯聚氧丙烯醚嵌段共聚物，三苯乙基酚聚氧乙烯醚磷酸酯，脂肪醇聚氧乙烯醚磷酸，对羟苯基木质素磺酸钠盐中的一种或几种。
本发明所述的湿润剂包括：脂肪醇聚氧乙烯醚，萘磺酸盐，十二烷基硫酸钠，烷基酚树脂聚氧乙烯醚硫酸盐中的一种或两种以上组合。
本发明所述的增稠剂包括黄原胶，硅酸镁铝，海藻酸钠，羧甲基纤维素钠，阿拉伯胶，明胶，聚乙烯醇中的一种或几种。本发明所述的消泡剂优选为：泡敌、硅酮类、C8～10脂肪醇、C10～20饱和脂肪酸类及酰胺等。
本发明所述杀虫剂可以按照本领域通用的方法配制成乳油、油悬剂、悬浮剂、可湿性粉剂或水分散粒剂。
本发明提供的杀虫组合物和杀虫剂特别适合用于防治同翅目害虫和/或鳞翅目害虫，尤其适合防治蔬菜、水稻或棉花中的同翅目害虫和/或鳞翅目害虫，所述同翅目害虫为蚜虫，所述鳞翅目害虫为甜菜夜蛾、小菜蛾、稻纵卷叶螟或棉铃虫。
本发明所述的杀虫组合物相比现有技术具有如下优势：
(1)组合物中二种药剂复配在一定配比范围内表现出优良的增效作用，混合后的组合物的杀虫效果较其单剂有明显的提高，而且具有速效性好和持效性长的特点；
(2)利用两种活性组分对害虫不同的作用方式、不同的作用机理进行合理地混配，既延长了农药使用寿命，又延缓害虫抗药性的产生；
(3)降低了使用剂量，减少农民用药成本。
具体实施方式
下面的实施例为用来说明本发明的几个具体实施方式，但并不将本发明局限于这些具体实施方式。本领域技术人员应该认识到，本发明涵盖了权利要求书范围内所可能包括的所有备选方案、改进方案和等效方案。
下述实施例中材料配方选择可因地制宜，对结果无实质性的影响。在这些实施例中，除另有说明外，所有百分比均为重量百分比。
下述实施例中，参照杀虫剂农药室内生物测定试验准则(农业行业标准NY/T1154.7-2006)和创制农药生物活性评价SOP(杀虫剂卷)，采用浸渍法。
联合作用采用下述方法进行计算：
理论混用毒力指数(TTI)＝A的毒力指数×A在混用中的含量(％)
+B的毒力指数×B在混用中的含量(％)
共毒系数若大于120，表明有增效作用；若小于80，表明为拮抗作用；若大于80小于120，表明为相加作用。
实施例1：ZJ4042与氟啶虫酰胺混配
表1、ZJ4042与氟啶虫酰胺对蚜虫Aphis medicagini联合增效作用
| 配方 | LC50(mg/L) | 实测毒力指数 | 理论毒力指数 | 共毒系数 |
| 氟啶虫酰胺 | 1.67 | 1949.70 | ||
| ZJ4042 | 32.56 | 100.00 | ||
| 氟啶虫酰胺:ZJ4042＝50:1 | 1.02 | 3192.16 | 1913.43 | 166.83 |
| 氟啶虫酰胺:ZJ4042＝20:1 | 1.22 | 2668.85 | 1861.62 | 143.36 |
| 氟啶虫酰胺:ZJ4042＝1:1 | 1.89 | 1722.75 | 1024.85 | 168.10 |
| 氟啶虫酰胺:ZJ4042＝1:10 | 7.01 | 464.48 | 268.15 | 173.21 |
| 氟啶虫酰胺:ZJ4042＝1:20 | 10.56 | 308.33 | 188.08 | 163.94 |
表2、ZJ4042与氟啶虫酰胺对稻纵卷叶螟Cnaphalocrocis medinalis联合增效作用
| 配方 | LC50(mg/L) | 实测毒力指数 | 理论毒力指数 | 共毒系数 |
| 氟啶虫酰胺 | 31.29 | 4.12 | ||
| ZJ4042 | 1.29 | 100.00 | ||
| 氟啶虫酰胺:ZJ4042＝50:1 | 15.26 | 8.45 | 6.00 | 140.83 |
| 氟啶虫酰胺:ZJ4042＝20:1 | 10.31 | 12.51 | 8.69 | 144.01 |
| 氟啶虫酰胺:ZJ4042＝1:1 | 1.68 | 76.79 | 52.06 | 147.49 |
| 氟啶虫酰胺:ZJ4042＝1:10 | 0.91 | 141.76 | 91.28 | 155.29 |
| 氟啶虫酰胺:ZJ4042＝1:20 | 0.89 | 144.94 | 95.43 | 151.88 |
从试验结果表1和2可以看出，氟啶虫酰胺和ZJ4042的组合物在1～50:20～1(按重量比)的范围内，共毒系数均大于120，对蚜虫和水稻稻纵卷叶螟均表现为增效作用。氟啶虫酰胺和ZJ4042混配具有合理性和可行性。
实施例2：20％氟啶虫酰胺·ZJ4042悬浮剂
按氟啶虫酰胺18％、ZJ40422％、乳化剂1601#(苯乙烯基苯酚聚氧乙烯聚氧丙烯醚)10％、分散剂SOPA-2704％、膨润土2％、黄原胶0.1％、有机硅消泡剂0.4％、丙三醇5％、余量为去离子水的配方，将各组分进行预先粉碎，再加入砂磨机中研磨，经高剪切混合后调配后制得20％氟啶虫酰胺·ZJ4042悬浮剂。
将制得的20％氟啶虫酰胺·ZJ4042悬浮剂应用于甘蓝小菜蛾防治。20％氟啶虫酰胺·ZJ4042悬浮剂按10克/亩于甘蓝小菜蛾幼虫发生盛期兑水均匀喷雾，在药后3天和7天的防效分别为93.8％和97.8％。按同样方法施药，对照单剂20％氟啶虫酰胺悬浮剂(施药量为30克/亩)和20％ZJ4042悬浮剂(施药量为10克/亩)，在药后3天的防效分别为60.5％和87.4％、药后7天的防效分别为65.1％和84.8％。氟啶虫酰胺和ZJ4042混配后增效作用明显，防效优于单剂。
实施例3：40％氟啶虫酰胺·ZJ4042水分散性粒剂
按氟啶虫酰胺35％、ZJ40425％、十二烷基硫酸钠6％、聚羧酸酸盐4％、氯化钠8％、聚乙二醇3％、余量为高岭土的配方，将各组分进行干法粉碎、造粒、干燥、筛分后制得40％氟啶虫酰胺·ZJ4042水分散性粒剂。
将制得的40％氟啶虫酰胺·ZJ4042水分散性粒剂应用于蚜虫防治。40％氟啶虫酰胺·ZJ4042水分散性粒剂按10克/亩于蚜虫发生高峰期兑水均匀喷雾，在药后3天和7天防效分别为95.9％和93.7％。按同样方法施药，对照单剂20％氟啶虫酰胺悬浮剂(施药量为30克/亩)和20％ZJ4042悬浮剂(施药量为10克/亩)，在药后3天的防效分别为79.7％和55.3％、药后7天的防效分别为81.5％和57.3％。氟啶虫酰胺和ZJ4042混配后增效作用明显，防效优于单剂，速效性和持效性也好于单剂，且用药量比单剂降低。
实施例4：70％氟啶虫酰胺·ZJ4042水分散性粒剂
按氟啶虫酰胺55％、ZJ404215％、十二烷基硫酸钠6％、聚羧酸酸盐4％、氯化钠8％、聚乙二醇3％、余量为高岭土的配方，将各组分进行干法粉碎、造粒、干燥、筛分后制得70％氟啶虫酰胺·ZJ4042水分散性粒剂。
将制得的70％氟啶虫酰胺·ZJ4042水分散性粒剂应用于稻纵卷叶螟防治。70％氟啶虫酰胺·ZJ4042水分散性粒剂按10克/亩于稻纵卷叶螟低龄幼虫盛发期兑水均匀喷雾，在药后7天和14天防效分别为93.1％和94.7％。按同样方法施药，对照单剂20％氟啶虫酰胺悬浮剂(施药量为30克/亩)和20％ZJ4042悬浮剂(施药量为10克/亩)，在药后7天的防效分别为52.2％和85.5％、药后14天的防效分别为53.6％和87.8％。氟啶虫酰胺和ZJ4042混配后增效作用明显，防效优于单剂，速效性和持效性也好于单剂。
实施例5：40％氟啶虫酰胺·ZJ4042可湿性粉剂
按氟啶虫酰胺35％、ZJ40425％、十二烷基硫酸钠6％、聚羧酸酸盐4％、氯化钠8％、聚乙二醇3％、余量为高岭土的配方，将各组分进行干法粉碎、造粒、干燥、筛分后制得40％氟啶虫酰胺·ZJ4042可湿性粉剂。
将制得的40％氟啶虫酰胺·ZJ4042可湿性粉剂应用于稻纵卷叶螟防治。40％氟啶虫酰胺·ZJ4042可湿性粉剂按10克/亩于稻纵卷叶螟低龄幼虫发生高峰期兑水均匀喷雾，在药后7天和14天的防效分别为95.7％和96.6％。按同样方法施药，对照单剂20％氟啶虫酰胺悬浮剂(施药量为30克/亩)和20％ZJ4042悬浮剂(施药量为10克/亩)，在药后7天的防效分别为51.2％和83.7％、药后14天的防效分别为53.6％和82.9％。氟啶虫酰胺和ZJ4042混配后增效作用明显，防效优于单剂，速效性和持效性也好于单剂。
实施例6：20％氟啶虫酰胺·ZJ4042油悬剂
按氟啶虫酰胺15％、ZJ40425％、蓖麻油聚氧乙烯醚13％、三苯乙烯基苯酚聚氧乙烯醚磷酸酯3％、有机膨润土1％、油酸甲酯补至100％的配方，将各组分混合均匀，砂磨至一定粒径后即得20％氟啶虫酰胺·ZJ4042油悬剂。
将制得的20％氟啶虫酰胺·ZJ4042油悬剂应用于棉铃虫防治。20％氟啶虫酰胺·ZJ4042油悬剂按10克/亩于棉铃虫幼虫发生盛期兑水均匀喷雾，在药后3天和7天防效分别为92.7％和93.3％。按同样方法施药，对照单剂20％氟啶虫酰胺悬浮剂(施药量为30克/亩)和20％ZJ4042悬浮剂(施药量为10克/亩)，在药后3天的防效分别为46.4％和82.7％、药后7天的防效为49.7％和85.2％。氟啶虫酰胺和ZJ4042混配后增效作用明显，防效优于单剂。
实施例7：20％氟啶虫酰胺·ZJ4042乳油
按氟啶虫酰胺15％、ZJ40425％、十二烷基苯磺酸钙6％、三苯乙基酚聚氧乙烯醚6％、NMP8％、余量为二甲苯的配方，将各组分混合搅拌均匀后即得20％氟啶虫酰胺·ZJ4042乳油。
将制得的20％氟啶虫酰胺·ZJ4042乳油应用于甜菜夜蛾防治。20％氟啶虫酰胺·ZJ4042乳油按10克/亩于甜菜夜蛾幼虫发生盛期兑水均匀喷雾，在药后3天和7天防效分别为96.7％和98.7％。按同样方法施药，对照单剂20％氟啶虫酰胺悬浮剂(施药量为30克/亩)和20％ZJ4042悬浮剂(施药量为10克/亩)，在药后3天的防效分别为55.4％和82.3％、药后7天的防效为57.2％和86.7％。氟啶虫酰胺和ZJ4042混配后增效作用明显，防效优于单剂。
Claims (9)
1.一种杀虫组合物，其特征在于所述杀虫组合物含有二种活性成分，第一种活性成分为氟啶虫酰胺，第二种活性成分为氯氟氰虫酰胺，所述第一种活性成分与第二种活性成分的质量配比为1～50:20～1。
2.按照权利要求1所述的杀虫组合物，其特征在于所述第一种活性成分与第二种活性成分的质量配比为1～10:10～1。
3.按照权利要求2所述的杀虫组合物，其特征在于所述第一种活性成分与第二种活性成分的质量配比为1～5:5～1。
4.按照权利要求1所述的杀虫组合物的应用，其特征在于所述杀虫组合物被配制成杀虫剂，所述杀虫剂中含有以重量计5～90％的杀虫组合物，其余为农业上可接受的载体和助剂。
5.按照权利要求4所述的杀虫组合物的应用，其特征在于所述杀虫剂中含有以重量计5～40％的杀虫组合物。
6.按照权利要求4所述的杀虫组合物的应用，其特征在于所述杀虫剂被配制成乳油、油悬剂、悬浮剂、可湿性粉剂或水分散粒剂。
7.按照权利要求1所述的杀虫组合物的应用，其特征在于所述杀虫组合物被用于防治同翅目害虫和/或鳞翅目害虫。
8.按照权利要求7所述的杀虫组合物的应用，其特征在于所述同翅目害虫为蚜虫，所述鳞翅目害虫为甜菜夜蛾、小菜蛾、稻纵卷叶螟或棉铃虫。
9.按照权利要求7所述的杀虫组合物的应用，其特征在于所述杀虫组合物被用于防治蔬菜、水稻或棉花中的同翅目害虫和/或鳞翅目害虫。
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