CN1316880A - 草甘膦制剂 - Google Patents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
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- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
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Abstract
一种优选包含以草甘膦酸表示的大于400g/l草甘膦的储藏稳定的高浓度的草甘膦浓水制剂,其中包含草甘膦钾盐,烷基苷表面活性剂和烷氧基化烷基胺表面活性剂,其中烷基苷和烷氧基化烷基胺优选的总浓度为约160至300g/l,烷基苷与烷氧基化烷基胺的优选比例为每1重量份烷氧基化烷基胺对大约1重量份烷基苷至每1重量份烷氧基化烷基胺对大约5重量份烷基苷。
Description
本发明涉及草甘膦制剂,特别是涉及高浓度草甘膦的浓水制剂。
N-膦酰甲基甘氨酸(本文中称其通用名草甘膦)是通常以其盐形式使用的已知除草剂。为了满足各种商业需要,可将草甘膦配制成多种液体和固体组合物。本发明涉及需要在使用前稀释的液体浓制剂。已有许多此类液体浓制剂在市场上销售,但从增强商业竞争力和环境的原因考虑,与市售产品相比,还需要提高在水制剂中草甘膦的浓度。很明显,高浓度的浓水制剂使给定剂量的草甘膦处于较小的液体体积中,得到的明显优点是降低运输、储藏和处理的费用,减少并更方便地处理容器。
在商业实践中已知需要使用一种或多种表面活性剂提高草甘膦的活性,许多有效表面活性剂单剂或混合表面活性剂体系在文献中是已知的。在稀释草甘膦浓水制剂的同时可以将所需的表面活性剂体系单独地加入桶混制剂中,因此浓制剂中可以省略掉表面活性剂体系并在桶混合时单独加入。可是,很明显的是,在桶混阶段加入单独的组分,在除草剂喷雾前需要另外的加料步骤,这需要使用者对混合的体积进行准确的测量以保证在最终产品中正确的配合比。因此这就需要高浓度草甘膦浓制剂,其中表面活性剂体系的有效比例已经在组合物中确定。在实际中限制含有表面活性剂的有效高浓度草甘膦浓制剂的因素是上述浓制剂在长期储藏时对销售使用可能遇到的极端环境温度的物理稳定性。对高浓度的制剂加入有效水平的常规表面活性剂体系是非常困难的,例如对含有浓度大于以草甘膦酸计的400或450g/l的草甘膦盐的制剂就是如此。
在高浓度体系中使草甘膦盐和表面活性剂结合还存在的问题是粘度问题。如果组合物太粘不能从容器中方便地到出或从容器中很快地洗出残留物,那么,在实际中低体积、高浓度组合物的优点或多或少受到影响。如果产品是批量大规模地供给使用者时,这就特别重要了。
许多草甘膦盐在文献中公开,但广泛商业化使用的仅是含有三甲基锍和异丙胺盐的液体浓制剂。在一些固体制剂中使用的是铵盐或钠盐。我们现在发现草甘膦钾盐特别好地适合于提供高浓度草甘膦浓水制剂,因为其容易溶于水中形成相对高密度的溶液(大约1.45g/cc)。可是广泛的研究显示常规表面活性剂体系非常难于加入有效水平的表面活性剂以提供含有草甘膦盐,如钾盐的物理稳定的高浓度组合物。
本发明在此提供了含有草甘膦钾盐、烷基苷表面活性剂和烷氧基化的烷基胺表面活性剂的高浓度草甘膦浓水制剂。
在本文中使用的术语“高浓度”草甘膦浓水制剂是表示其中草甘膦的浓度大于400g/l,更优选大于440g/l以草甘膦酸计的浓制剂。在此应当说明的是,除非另外指明,本文中给出的草甘膦的各种浓度都是草甘膦酸的重量百分比,即便草甘膦是以盐存在。通常在实践中草甘膦浓度的上限是根据粘度确定的。如下述讨论的,如果浓度超过500g/l,需要加入粘度调节剂,浓度超过550g/l的制剂对使用常规设备的有效商业用途来讲就太粘了。本发明组合物中草甘膦的浓度为大约440g/l至540g/l是特别有利的。
在浓水制剂中烷基苷和烷氧基化烷基胺表面活性剂体系的优选总含量为大约160g/l至300g/l,例如大约200g/l至270g/l。如果需要可使用其它非烷基苷和烷氧基化烷基胺表面活性剂,当使用上限浓度的烷基苷和烷氧基化烷基胺时,上述其它表面活性剂对制剂的稳定性存在有害作用。
在表面活性剂体系中烷基苷与烷氧基化烷基胺的比例优选为每1重量份烷氧基化的烷基胺对大约1重量份烷基苷至每1重量份烷氧基化烷基胺对大约5重量份烷基苷。特别优选的比例为每1重量份烷氧基化烷基胺对大约1.5或更优选2重量份烷基苷至每1重量份烷氧基化烷基胺对大约4重量份烷基苷。
虽然本发明的范围不受任何特定的理论限制且表面活性剂活性的作用方式是非常复杂的,但是可以确认的是烷基苷和烷氧基化烷基胺作用的总机理不同并能够一起作用从而对不丧失制剂物理稳定性的高浓度制剂一起提供最大的助剂效果和最佳的固定容积。具体可确认的是烷基苷的作用是非常被动地大量留在叶表面,调节喷雾溶液在干燥时的物理性质确保有效吸收。一个存在的现象是在这种作用方式中,如果烷基苷加入量的增加超过特定的最佳范围,活性的增加不再与烷基苷的加入量成比例。进一步加入烷基苷只能得到相对小的效果。另一方面可确认烷氧基化烷基胺以较活性的机理发挥作用,其中烷氧基化烷基胺渗透入叶角质层并通过促进活性成分向植物系统中渗透增强生物活性。
因此,虽然可以在高浓度草甘膦钾制剂中加入相对高浓度的烷基苷,但是生物活性的增加将小于最佳值,且同时所得溶液的粘度将变得很高(这是不希望的)。另一方面烷氧基化烷基胺在高浓度的草甘膦浓制剂中具有相对低的相容性临界值。但是我们发现我们要求保护的草甘膦组合物组合了尽可能高浓度的钾盐与最佳“被动”提高活性的烷基苷和“渗透”提高的相对低水平的烷氧基化烷基胺,它们组成一个完整的相容性的系统。这样,与迄今证明对上述高浓度组合物可能的表面活性剂总量相比而言,要求保护的高浓度草甘膦组合物含有高得多浓度的表面活性剂总量,结果同许多有低得多的草甘膦浓度的市售制剂相比具有极好的生物活性。如本文下述更详细讨论的,适当选择烷氧基化烷基胺才能保证使用的浓制剂的粘度处于在商业上可接受的限制范围内。
在本发明中使用的烷基苷是通过烷基醇与葡萄糖或其它单-或二-或聚多糖反应获得的。在本文中使用的术语“烷基苷”包括烷基单苷和烷基多苷。在本发明中优选使用的烷基苷是通过葡萄糖与直链或支链烷基醇或烷基醇混合物反应制备的烷基苷,烷基醇例如含有7至18,优选7至16个碳原子,例如8至10个碳原子烷基醇的混合物,或含有8个碳原子的单一支链醇。在分子中每个烷基的糖基的数目可以变化,且可以是烷基单-或二-或多葡萄糖或糖衍生物。市售的烷基多苷通常含有每个烷基具有平均糖基数的衍生物混合物。因此烷基苷具有通式(Ⅰ)其中n为聚合度,且典型的在1至3,例如1至2范围内,和R5为具有4至18碳原子的支链或直链烷基,或具有在给定范围内平均值的烷基的混合物。典型的烷基苷是商品名为AL2042(Imperial ChemicalIndustries PLC)和AGRIMUL PG2067(Henkel Corp)的产品,其中n为平均数1.7和R5为辛基(45%)和癸基(55%)的混合物,商品名为AGRIMUL PG2069(Henkel Corp)的产品,其中n为平均数1.6和R5为壬基(20%),癸基(40%)和十一烷基(40%)的混合物,和2-乙基-1-己基苷其中R5为2-乙基-1-己基,其衍生于单一支链醇(2-乙基-1-己醇),聚合度(n)为1至2,例如1.5至1.9,如大约1.75。
在烷氧基化烷基胺中适合的烷基含有8至22碳原子(如果存在的是烷基混合物则平均8至22碳原子)且可以是线性或支链的。特别优选的烷基含有10至20个碳原子。优选烷氧基化烷基胺的具体实例是烷氧基化的椰子胺、牛油脂肪胺、油胺和硬酯胺。典型的上述烷氧基化烷基胺表面活性剂的平均烷氧化度为1至15。适合的烷氧基包括乙氧基、丙氧基或其混合物。特别优选乙氧基。因此适合的烷氧基化烷基胺为乙氧基化或丙氧基化或乙氧基化和丙氧基化混合的C8至C22烷基胺,烷氧化度为1至大约15。
虽然在本发明组合物中可以使用的烷氧基化烷基胺的平均烷氧化度(或更具体的是乙氧基化度)在市售产品的范围内,例如1至大约15,但我们发现具有高乙氧基化度的乙氧基化烷基胺比低乙氧基化度的烷基胺与高浓度组合物的相容性低。因此优选平均烷氧化度(或更具体的是乙氧基化度)为2至12。可是我们还发现具有大约为2的低烷氧化度(或更具体的是乙氧基化度)的烷氧基化烷基胺趋向于增加组合物的粘度。因此特别优选平均烷氧化度(或更具体的是乙氧基化度)为4至12。特别适合的烷氧基化烷基胺的实例是具有平均乙氧基化度大约为5的乙氧基化烷基胺,例如平均乙氧基化度大约为5的乙氧基化椰子胺。
如果组合物的粘度高,例如如果草甘膦钾的浓度靠近上限,可以适当地加入粘度调节剂。适合的粘度调节剂包括丙二醇。在实际中对含有烷基苷的制剂,一般需加入防泡剂。许多种防泡剂都是现有技术中已知的,市售的防泡剂在非常低的浓度下使用(例如少于5g/l),因此不会对组合物的加入产生主要影响。
如果需要可加入其它常规的添加剂如湿润剂(humectants)、增效剂(如无机铵盐)、防冻剂、润湿剂(wetters)、或其它表面活性剂,但是通常优选不再加入上述物质,特另是在上述物质以相当量存在时。类似的,如果需要可加入其它水溶性除草剂或其它如杀真菌剂和杀虫剂的农用化学品,但本发明主要涉及其中活性成分仅为草甘膦的组合物。
在稀释使用时,本发明组合物对很多种包括单子叶和双子叶的杂草具有活性。本组合物适合直接使用到不需要的植物上(苗后施用)。
这样,本发明的另一方面提供了严重损害或杀死不需要植物的方法,其中包含稀释本发明浓组合物,并将除草有效量的所述稀释组合物使用到植物上。
本发明组合物的使用剂量将根据多种因素确定,例如包括被抑制植物生长的种类和化合物是否使用于叶面或根部吸收。可是一般来讲,适用剂量为每公顷0.001至20公斤,同时优选每公顷0.025至10公斤。
通过下述实施例例示了本发明,除非另外指明,其中所有份数和百分比均以重量计。
实施例1-15
在下述实施例中,组合物的制备是通过将草甘膦酸(见表中PMG酸)溶于足量的50%氢氧化钾溶液中中和酸并形成钾盐。这样例如当PMG酸的浓度为450g/l,相应的50%氢氧化钾溶液的比例为334g/l。按注明的比例(g/l)加入其它成分,并加入一定比例的水补足体积。
所有的制剂在54℃贮藏4周和在-10℃储藏2周评价物理稳定性。在下述表1至4中制剂稳定性用“A”表示,说明在此试验后保持物理稳定性。制剂稳定性用“B”表示,说明在室温下保持物理稳定性,但在54℃储藏4周试验中出现相分离。
在表1至4中使用的烷基苷(APG)为AGRIMUL PG2067,其组合物已经在前给出。
ETHOMEEN C15(ETHOMEEN是Akzo Nobel的商标)是平均乙氧基化度为5的乙氧基化椰子胺。
ETHOMEEN C12是平均乙氧基化度为2的乙氧基化椰子胺。
ETHOMEEN T15是平均乙氧基化度为5的乙氧基化牛油脂脂胺。
ETHOMEEN T25是平均乙氧基化度为15的乙氧基化牛油脂肪胺。
ETHOMEEN S22是平均乙氧基化度为12的豆油胺(soyamine)。
表1
表2
表3
表4
实施例号 | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
PMG-酸(g/l) | 540 | 500 | 450 | 450 | 450 | 450 | 450 |
烷基葡糖苷(g/l) | 214 | 172.2 | 229 | 197 | 161 | 160 | 157 |
“Ethomeen”C15(g/l) | 50 | 46.3 | 50 | 50 | 75 | 75 | 100 |
防泡剂(g/l) | 0.7 | 1.3 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 |
稳定性 | A | A | A | A | A | A | A |
实施例号 | 8 | 9 | 10 | 11 |
PMG-酸(g/l) | 540 | 450 | 450 | 450 |
烷基葡糖甘(g/l) | 186 | 197 | 161 | 126 |
“Ethomeen”T15(g/l) | 50 | 50 | 75 | 100 |
防泡剂(g/l) | 0.7 | 0.7 | 0.7 | 0.7 |
稳定性 | A | A | A | A |
实施例号 | 12 |
PMG-酸(g/l) | 450 |
烷基葡糖苷(g/l) | 197 |
“Ethomeen”C15(g/l) | 10 |
“Ethomeen”S22(g/l) | 40 |
防泡剂(g/l) | 0.7 |
稳定剂 | A |
实施例号 | 13 |
PMG-酸(g/l) | 450 |
烷基葡糖苷(g/l) | 197 |
“Ethomeen”C15(g/l) | 10 |
“Ethomeen”T25(g/l) | 40 |
防泡剂(g/l) | 0.7 |
稳定剂 | B |
实施例号 | 14 |
PMG-酸(g/l) | 450 |
烷基葡糖苷(g/l) | 229 |
“Ethomeen”C12(g/l) | 50 |
防泡剂(g/l) | 0.7 |
稳定性 | A |
实施例号 | 15 |
PMG-酸(g/l) | 540 |
烷基葡糖苷 | 186 |
“Ethomeen”C15(g/l) | 50 |
防泡剂(g/l) | 1.3 |
丙二醇 | 25 |
稳定性 | A |
实施例12和13例示了平均氧化乙烯含量为10.6的乙氧基化烷基胺(10份“Ethomeen”C15和40份“Ethomeen”S22)配制的制剂的物理稳定性是令人满意的,但比平均氧化乙烯含量为13的乙氧基化烷基胺(10份“Ethomeen”C15和40份“Ethomeen”T25)制剂的最佳物理稳定性差。
在实施例15中含有540g/l草甘膦酸制剂的粘度通过加入丙二醇而降低。
实施例16和17
采用实施例1至15的方法,只是使用聚合度水平为大约1.75的2-乙基-1-己基苷的烷基苷。制备具有表5中所示组合物的制剂,发现至少在-10℃至40℃下是稳定的。
表5
实施例号 | 16 |
PMG-酸(g/l) | 450 |
2-乙基己基葡糖苷(g/l) | 197 |
“Ethomeen”C15(g/l) | 50 |
实施例号 | 17 |
PMG-酸(g/l) | 500 |
2-乙基己基葡糖苷(g/l) | 172.2 |
“Ethomeen”C15(g/l) | 46.3 |
Claims (12)
1.一种高浓度草甘膦浓水制剂,其中包含草甘膦钾盐,烷基苷表面活性剂和烷氧基化烷基胺表面活性剂。
2.根据权利要求1的草甘膦浓制剂,其中草甘膦的浓度以草甘膦酸含量计大于400g/l。
3.根据权利要求2的草甘膦浓制剂,其中草甘膦的浓度以草甘膦酸含量计为440g/l至540g/l。
4.根据上述任一权利要求的草甘膦浓制剂,其中烷基苷和烷氧基化烷基胺表面活性剂体系的总含量为160至300g/l。
5.根据权利要求4的草甘膦浓制剂,其中在表面活性剂体系中烷基苷与烷氧基化烷基胺的比例为每1重量份烷氧基化烷基胺对1重量份烷基苷至每1重量份烷氧基化烷基胺对大约5重量份烷基苷。
6.根据权利要求5的草甘膦浓制剂,其中在表面活性剂体系中烷基苷与烷氧基化烷基胺的比例为每1重量份烷氧基化烷基胺对2重量份烷基苷至每1重量份烷氧基化烷基胺对大约4重量份烷基苷。
8.根据权利要求7的草甘膦浓制剂,其中R5为2-乙基-1-己基,n为1至2。
9.根据上述任一权利要求的草甘膦浓制剂,其中烷氧基化烷基胺为乙氧基化或丙氧基化或乙氧基化和丙氧基化混合的C8至22烷基胺,其烷基化度为1至大约15。
10.根据权利要求9的草甘膦浓制剂,其中烷氧基化度为4至12。
11.根据权利要求1的草甘膦浓制剂,其中草甘膦钾的浓度以草甘膦酸计大于400g/l,在浓水制剂中烷基苷和烷氧基化烷基胺表面活性剂体系的总浓度为约160至300g/l,且烷基苷与烷氧基化烷基胺的比例为大约每1重量份烷氧基化烷基胺对1重量份烷基苷至每1重量份烷氧基化烷基胺对大约5重量份烷基苷。
12.一种严重损害或杀死不需要植物的方法,其包含稀释根据上述任一权利要求的浓组合物,并将除草有效量的上述稀释组合物使用到植物上。
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CN102143685B (zh) * | 2008-07-03 | 2015-05-27 | 孟山都技术公司 | 作为除草剂辅助剂的衍生化糖表面活性剂和醚胺氧化物表面活性剂的组合 |
CN104872125A (zh) * | 2008-07-03 | 2015-09-02 | 孟山都技术公司 | 作为除草剂辅助剂的衍生化糖表面活性剂和醚胺氧化物表面活性剂的组合 |
CN106879623A (zh) * | 2008-08-19 | 2017-06-23 | 阿克佐诺贝尔股份有限公司 | 增稠草甘膦配制剂 |
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