CN101548675B - 一种除草剂组合物 - Google Patents
一种除草剂组合物 Download PDFInfo
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- CN101548675B CN101548675B CN2008101032108A CN200810103210A CN101548675B CN 101548675 B CN101548675 B CN 101548675B CN 2008101032108 A CN2008101032108 A CN 2008101032108A CN 200810103210 A CN200810103210 A CN 200810103210A CN 101548675 B CN101548675 B CN 101548675B
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- penoxsuam
- weedicide
- weed
- rice
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Abstract
本发明属于农用除草剂技术领域，涉及一种以喹草烯和五氟磺草胺为有效成分组成二元组合物，其活性组分的重量份数的比例为1∶10至10∶1；该组合物中活性组分重量百分含量为1～99％。可以采用通用方法制成粉剂、悬浮剂、乳油、油悬剂、水乳剂、微乳剂等多种农药制剂。本发明的除草剂组合物对水稻安全，以最少的用药量，最低的用药成本，可以有效地防治稻田禾本科杂草和阔叶杂草，其最佳使用时期在水稻2～3叶期。该除草剂组合物配制方法简单，施用方便，是目前国内外农田一次性防除禾本科及阔叶杂草的理想除草剂。
Description
技术领域
本发明属于农用除草剂技术领域，涉及一种二元复配稻田用除草剂组合物。
背景技术
水稻不仅是我国的最主要粮食作物，也是世界主要粮食作物之一。我国水稻种植面积大约5亿亩，居粮食作物首位，我国所有稻区的稻田，历来都有大量杂草发生，水稻田除草剂的使用比例很大。由于多年来化学除草剂的使用，我国的杂草群发生了变化，例如千金子由于比水稻更适合“干干湿湿”的轻型栽培模式，导致其在稻田的发生面积逐年扩大，危害日益加重。
目前市场上各种稻田除草剂中，只有氰氟草酯能够较为有效地防除3叶期以后的千金子，且安全性好，但因使用成本太高而难以为广大农民接受。这样就迫切需要开发一种对千金子防除效果好，又能同时防除禾本科及阔叶杂草，且对后茬作物安全的除草药剂。
中国专利申请CN1626526A中首次公开了具有除草活性的化合物2-(2-(4-(6-氯喹喔啉-2基氧)苯氧)丙酰氧基)-3-甲基丁-3-烯酸乙酯(通用名：喹草烯)，结构式如下：
该化合物可有效地防除水稻田多种杂草，特别是对千金子防效更优，其作用方式与反应速度与氰氟草酯相近且成本较低，但安全性较之稍差。
2-(2，2-二氟乙氧)-N-(5，8-二甲氧〔1，2，4〕三唑-〔1，5-C〕嘧啶-2-基)-6-三氟甲基-苯磺胺(通用名：五氟磺草胺)系美国道化学公司最新研制的稻田茎叶处理除草剂，是目前水稻上唯一的既可以防治禾本科杂草，又可以防除阔叶杂草和莎草科杂草且对水稻生产安全性好的除草剂，但该药剂对千金子无效。
因此，目前尚缺乏一种对千金子等禾本科及阔叶杂草均有较好防除效果、对水稻安全性高且使用成本经济的除草药剂。
发明内容
本发明的目的在于：利用喹草烯和五氟磺草胺各自的特点，开发出一种既能防除水稻田禾本科杂草如稗草和千金子等、又能防除阔叶杂草，并且安全性高、使用成本经济的复配组合物，从而克服单独使用上述除草剂所存在的弊端，为农业生产提供一种理想的稻田用除草剂组合物。
喹草烯与五氟磺草胺比较最大的优点在于对千金子的防除效果好和成本相对较低，但其对水稻的安全性幅度比较窄。
为了实现本发明的目的，本发明在保证满意的杂草防除效果的前提下考虑到喹草烯与五氟磺草胺的除草活性、用药成本和对作物的安全性这三个主要因素进行组合物活性组分配比的研究。
组合物效果的评价方法如下：先求出各单剂和混剂的ED50或ED90值，再以其中的某个单剂为标准药剂计算各单剂及混剂的毒力指数(标准药剂的毒力指数为100)，最后计算共毒系数。计算公式为：
混剂的理论毒力指数＝A的毒力指数×A在混剂中的比例(％)+B的毒力指数×B在混剂中的比例(％)+C的毒力指数×C在混剂中的比例(％)+......
对于混用后的联合作用类型的判断，我国目前较为通用的判断标准为共毒系数接近100(在80～120之间)时为相加作用，明显小于80时为拮抗作用，明显大于100(120以上)时为增效作用。
实例结果表明，本发明的除草剂组合物，对水稻田禾本科杂草防治效果理想，应用Sun&Johnson法(孙云沛法即共毒系数法)评价混用后的联合作用，结果表明二者混用在一定比例范围内具有增效作用或者相加作用，同时对水稻安全。因此确定了本发明的技术方案如下：
本发明除草剂组合物中，活性组分为喹草烯和五氟磺草胺。组合物中活性组分喹草烯与五氟磺草胺之间的重量比为1∶10到10∶1，优选的比例为1∶4到2∶1。
本发明组合物中活性组分的含量取决于单独使用时的施用量，但也取决于一种化合物与另一种化合物的混配比例以及增效作用程度。通常组合物中活性组分的重量百分含量为总重量的1～99％，较佳的为5％至85％。活性组分含量的最佳范围依组合物的制剂类型而有所不同。通常，固体制剂中活性组分含量按重量计为5～85％；液体制剂中活性组分含量按重量计为1～70％；悬浮液制剂中活性组分含量按重量计为5～60％。
本发明的组合物由使用者在使用前经稀释或直接兑水喷雾使用。其配制可由通常的加工方法制备，即将活性物质与液体载体或固体载体混合后，加入一种或几种表面活性剂如乳化剂、分散剂、稳定剂、湿润剂、粘合剂或消泡剂等经加工配制而成。因此本发明的组合物中含有至少一种载体和至少一种表面活性剂。
适合制备本发明的除草剂组合物的液体载体包括水、芳烃、氯代芳烃、氯代脂族烃、脂族烃，特别适用的是极性溶剂，如醇类以及它们的醚和酯。此外还有植物油和甲基溶纤维。同时，不同液体的混合物也是适用的。
适合制备本发明的除草剂组合物的固体载体是通常用于配制除草剂的任何载体。例如硅藻土、硅酸铝镁、活性白土、高岭土、粘土、石膏、膨润土、白碳黑、轻质碳酸钙、石灰石、六甲撑二胺、苯并呋喃树脂、苯乙烯聚合物和共聚物、玉米淀粉和可溶性淀粉等。
适合制备本发明的除草剂组合物的乳化剂可为阴离子型或非离子型乳化剂，例如烷基酚聚氧乙烯基醚、烷基芳基聚氧乙烯聚氧丙烯基醚、烷基酚聚氧乙烯聚氧丙烯基醚、苄基酚聚氧乙烯基醚、聚氧乙烯脂肪酸脂、聚氧乙烯脂肪醇醚、聚氧乙烯脂肪胺等。例如农乳500#、农乳600#、农乳700#、农乳OX-635、农乳OX-662、农乳OX-690、农乳OX-2511、农乳OX-8653C、农乳MOA-3、农乳OP-10、农乳2201、农乳CS-7、农乳507#、宁乳36#、农乳0201B、农乳0203B、农乳0203C等。
适合制备本发明的除草剂组合物的分散剂可以为烷基萘磺酸盐、烷酰胺基牛磺酸盐、双(烷基)萘磺酸盐甲醛缩合物、萘酚磺酸甲醛缩合物钠盐、烷基酚聚氧乙烯基磷酸盐、烷基酚聚氧乙烯基醚甲醛缩合物硫酸盐、烷基酚聚氧乙烯磷酸酯、烷基酚聚氧乙烯醚、蓖麻油环氧乙烷加成物、环氧乙烷-环氧丙烷嵌段共聚物、烷基酚聚氧乙烯醚甲醛缩合物、烷基酚聚氧乙烯聚氧丙烯醚和甲基纤维素等。例如木质素磺酸钠、木质素磺酸钙、烷基萘磺酸甲醛缩合物、甲基萘磺酸钠甲醛缩合物、萘磺酸甲醛缩合物、亚甲基萘磺酸钠、油酸甲基氨基乙基磺酸钠、烷基-二乙二醇醚-磺酸钠、N-甲基-油酰基-牛磺酸钠、环氧聚醚、对叔丁基醚、二丁基萘磺酸甲醛缩合物和六偏磷酸钠等。
适合制备本发明的除草剂组合物的湿润剂可以为月桂醇硫酸钠、十二烷基硫酸钠、十二烷基磺酸钠、烷基苯磺酸钠、烷基萘磺酸钠、失水山梨醇脂肪酸酯聚氧乙烯基醚等。
适合制备本发明的除草剂组合物的粘合剂可以是天然的或合成的，例如黄原胶、明胶、阿拉伯树胶、聚乙烯吡咯烷酮、硅酸镁铝、聚乙烯醇、酚醛树脂、虫胶、羧甲基纤维素、甲基纤维素和海藻酸钠等。消泡剂可以是泡敌、硅酮类、C8～10脂肪醇、C10～20饱和脂肪酸类(如癸酸)及酰胺等。
此外，本发明的组合物中还可以含有着色剂，例如无机颜料氧化铁、氧化钛或普鲁士兰；有机染料阿利札林、偶氮染料、金属酞菁或三苯甲烷染料等。
本发明的组合物可以按普通的方法施用，即可茎叶喷雾处理，施用量随视杂草叶龄而变化，杂草较大时应用较大的剂量，杂草较小时可应用较低的剂量，施用适期为作物苗后杂草基本出齐时进行茎叶喷雾处理。其持效期通常与组合物中单剂的含量有关，也与外界因素相关。
本发明的除草剂组合物，可用于防治水稻田中的禾本科及阔叶杂草，如稗草、千金子及鸭舌草等，且在一定的配比范围内具有令人满意的增效作用。与单用五氟磺草胺相比不但农用成本降低了，而且扩大了杀草谱。一次施药即能控制作物整个生长期内的杂草，不仅除草效果显著，而且对环境友好，对下茬作物无影响，对环境的污染小，对人、畜、鸟类及有益生物安全，有利于保护生态平衡；该组合物中各单剂的作用机理不同，不存在交互抗性的问题，所以组合物的应用可以延缓耐药性或抗药性杂草的发生与发展，有助于延长药剂的使用时间。与单用喹草烯相比，本发明的除草剂组合物显著提高了药剂对水稻的安全性。因此，是目前防治效果理想的二元复配除草剂品种。
具体实施方式
以下具体实例用于详细说明本发明，但本发明绝非仅限于这些例子。所有制剂的配比中百分数均以重量计。活性组分喹草烯由沈阳化工研究院提供，原药含量95％；五氟磺草胺采用美国道化学公司的产品，2.5％油悬浮剂，商品名：稻杰。
配方实例
实例1.10％喹草烯·五氟磺草胺乳油
按配方要求，依次加入7.5％喹草烯、2.5％五氟磺草胺、8％农乳2201、3.5％农乳600#，6％甲醇，二甲苯补足至100％，搅拌均匀，即可制得透明状10％喹草烯·五氟磺草胺乳油。
实例2.20％喹草烯·五氟磺草胺油悬剂
按配方要求，依次将10％喹草烯、10％五氟磺草胺、6％木质素磺酸钠、0.3％白碳黑、0.1％黄原胶、4％乙二醇、大豆油补足至100％，加入到混合罐中，经过高速剪切机粗粉碎、匀化，然后转移到砂磨釜中进行砂磨，直到固体颗粒粒径合格后，过滤，即可制成20％油悬剂。
实例3.10％喹草烯·五氟磺草胺水乳剂
在高速剪切混合釜中，按配方量依次加入2％五氟磺草胺、8％喹草烯、0.8％聚乙烯醇、10.5％烷基芳基甲醛树脂聚氧乙烯醚、8.5％农乳507#、0.6％十四烷醇、15％二甲基甲酰胺、5％丙二醇、水补足至100％，经过乳化、匀化，即可制得10％喹草烯·五氟磺草胺水乳剂。
实例4.40％喹草烯·五氟磺草胺可湿性粉剂
按配方要求，将32％喹草烯、8％五氟磺草胺、1.5％十二烷基硫酸钠、2％对叔丁基醚、8％木质素磺酸钠、30％白碳黑、轻质碳酸钙补足至100％的物料充分混合，经超细粉碎机粉碎后，即得到40％喹草烯·五氟磺草胺可湿性粉剂。
实例5.20％喹草烯·五氟磺草胺悬浮剂
按配方要求，将5％喹草烯、15％五氟磺草胺、2.5％甲基萘磺酸钠甲醛缩合物、1％膨润土、3％农乳1601、4％丙三醇、水补足至100％，依次加入混合罐中，先经过高剪切进行粗粉碎、匀化，然后抽入到砂磨机中进行细磨，粒度分布仪检测砂磨物料的粒度，当粒径达到标准要求后，过滤，即可得到20％喹草烯·五氟磺草胺悬浮剂。
实例6.10％喹草烯·五氟磺草胺水乳剂
按配方要求，将8％喹草烯、2％五氟磺草胺、20％环己酮、8％环己醇、2.6％三苯乙烯基酚聚氧乙烯(n20)醚磷酸化三乙醇胺盐、17.4％十二烷基磺酸镁、5％二甲基甲酰胺、5％宁乳36#加到混合罐中，搅拌，使溶解成均匀油相。在高速搅拌下，将5％乙二醇及补足至100％的水的混合物加入到上述油相中，使其形成分散性良好的水乳剂。
生测实例
实例7.组合物在温室的除草效果
处理方法：在温室内采用盆栽的方法测定组合物的制剂及各单剂对禾本科及阔叶杂草的防除效果。试验方法：试验采用温室盆栽法，在一次性纸杯中播种定量的水稻和杂草种子，待杂草出土后1.5～2叶期时进行间苗，每个纸杯选留5～10株长势较为一致的杂草植株进行培养，并定期浇灌N、P、K复合肥的水溶液。用电子天平称取定量的喹草烯和五氟磺草胺，分别加水稀释至所需的母液浓度，用母液配制二者的不同混用比例的药液，按试验设计剂量用移液枪量取即可，待水稻3叶期、禾本科杂草3叶期、阔叶杂草2～4片真叶期时用履带式作物喷雾机进行茎叶喷雾处理，处理后置于操作大厅，待药液自然风干后放于温室内正常管理，观察杂草对供试药剂的反应，处理后20天称量各处理杂草地上部分鲜重，计算鲜重防效；处理后30天调查供试药剂对水稻的安全性。
组合物效果的评价：应用Sun&Johnson法(孙云沛法即共毒系数法)评价混用后的联合作用。
试验结果见表1～表4。
表1.喹草烯与五氟磺草胺不同混用配比对杂草的防除效果
表2.喹草烯与五氟磺草胺不同混用配比对水稻的安全性
表3.喹草烯与五氟磺草胺不同混用配比对水稻的选择性指数
| 供试药剂 | 对水稻的ED10值 | 对杂草的平均ED90值 | 选择性指数 |
| 喹草烯 | 81.4 | 31.2* | 2.61 |
| 五氟磺草胺 | 97.5 | 26.4 | 3.69 |
| 喹草烯∶五氟磺草胺1∶4 | 90.8 | 25.5 | 3.56 |
| 喹草烯∶五氟磺草胺1∶2 | 89.8 | 28.2 | 3.18 |
| 喹草烯∶五氟磺草胺1∶1 | 97.5 | 34.8 | 2.80 |
| 喹草烯∶五氟磺草胺2∶1 | 119.7 | 47.5 | 2.52 |
| 喹草烯∶五氟磺草胺4∶1 | 129.9 | 66.1 | 1.97** |
注：1)作物的选择性指数计算公式为
2)表3中数据是由表1、表2中数据应用DPS2000数据处理系统(唐启义，冯明光.实用统计分析及其DPS数据处理系统[M].北京：科学出版社，2002.188-201)计算得到的。
3)表中*为喹草烯对稗草的ED90值，因为喹草烯是禾本科杂草除草剂，所以用对禾本科杂草的ED90值计算选择性指数。
4)表中**的数值偏低是由于此配比下对阔叶杂草的ED90值大，导致平均ED90值偏大所致。
试验结果表明，本发明的除草剂组合物，对禾本科杂草-稗草和阔叶杂草-苘麻均有较好的防除效果，应用孙云沛法计算不同混用配比的共毒系数，结果表明二者混用后对稗草属于相加或略有增效作用，对苘麻属于相加作用。
本发明的除草剂组合物，对禾本科杂草和阔叶杂草均有较好的防除效果，扩大了杀草谱，达到了一次性施药防除全田杂草的目的，同时提高了药剂对水稻的安全性。
Claims (4)
1.一种除草剂组合物，其特征在于：活性成分为喹草烯和五氟磺草胺；组合物中活性组分喹草烯与五氟磺草胺之间的重量比为1∶4至4∶1。
2.根据权利要求1中任意一项所述的除草剂组合物，其特征在于：组合物中活性组分的重量百分含量为1～99％。
3.根据权利要求1中任意一项所述的除草剂组合物，其特征在于：组合物中含有至少一种载体和至少一种表面活性剂。
4.根据权利要求1所述的除草剂组合物防除水稻田中发生的禾本科及阔叶杂草的用途。
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