CN104768373B - 改善水溶性除草剂盐的相容性的组合物和方法 - Google Patents
改善水溶性除草剂盐的相容性的组合物和方法 Download PDFInfo
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- CN104768373B CN104768373B CN201380057253.6A CN201380057253A CN104768373B CN 104768373 B CN104768373 B CN 104768373B CN 201380057253 A CN201380057253 A CN 201380057253A CN 104768373 B CN104768373 B CN 104768373B
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- 239000000203 mixture Substances 0.000 title claims abstract description 95
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- 238000000034 method Methods 0.000 title claims abstract description 49
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- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000005562 Glyphosate Substances 0.000 claims abstract description 50
- 229940097068 glyphosate Drugs 0.000 claims abstract description 50
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 92
- -1 ethyl alcohol Amine Chemical class 0.000 claims description 54
- 239000012141 concentrate Substances 0.000 claims description 51
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- 150000001767 cationic compounds Chemical class 0.000 claims description 26
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- 238000006116 polymerization reaction Methods 0.000 claims description 6
- WNTGYJSOUMFZEP-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)propanoic acid Chemical compound OC(=O)C(C)OC1=CC=C(Cl)C=C1C WNTGYJSOUMFZEP-UHFFFAOYSA-N 0.000 claims description 5
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- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 18
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- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims 6
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- CJKRXEBLWJVYJD-UHFFFAOYSA-N N,N'-diethylethylenediamine Chemical compound CCNCCNCC CJKRXEBLWJVYJD-UHFFFAOYSA-N 0.000 claims 4
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- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 claims 2
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- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 14
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- 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
- A01N25/22—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 containing ingredients stabilising the active ingredients
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- A—HUMAN NECESSITIES
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- 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
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- 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
- A01N25/02—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 containing liquids as carriers, diluents or solvents
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- A—HUMAN NECESSITIES
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- 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
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- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
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- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
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- A01N2300/00—Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
Landscapes
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- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
提供了通过添加表面活性增容剂来改善除草剂水溶液的相容性的方法和组合物,所述除草剂水溶液包含芳氧基链烷酸的水溶性盐、吡啶氧基链烷酸的水溶性盐、和草甘膦的水溶性盐中的至少一种。
Description
背景技术
杀虫的和植物生长调节的化学品的含水浓缩物制剂在全世界广泛用于农业、工业、娱乐和住宅区域。这些浓缩物的活性成分常常包含酸官能团例如羧酸或膦酸,更常见的是它们的水溶性盐的形式。含水浓缩物本质上是活性成分在水中的相对高浓度的溶液,在通过喷雾或其它方法施用之前往往需要在水中稀释。通常,在施用前,将含水浓缩物在体积为其自身体积的约10至约500倍的水中稀释。
在现今的农用化学品市场,随着对改善的生产力的需求持续增加,越来越常见的是在喷雾罐中将多于一种配制的产品合并,以便实现对产品的控制、功效、和递送效率的最佳范围。但是,当这样做时,当喷雾罐混合物或溶液的各组分在化学或物理性质上相互影响以产生下述不利影响时,可能发生产品之间的喷雾罐不相容性,所述不利影响是对喷雾罐混合物的稳定性、均质性、或其它性质的不利影响,这将会降低喷雾施用的产品的效力。喷雾罐混合物或溶液的不相容性可通过以下现象在物理上得到证明:形成结晶析出物,表面泡沫,油滴,凝胶,过量的固体物质的泡沫或结块,这可导致堵塞喷嘴或筛。
相容的含水杀虫剂混合物或溶液定义为下述那些混合物或溶液,当通过将一种或多种杀虫剂产品和/或其它常用的成分组合或混合而形成时,得到具有极少或没有固体析出物或相分离的均匀液体,且保留它们完整的生物学功效。
发明内容
描述了通过向除草剂水溶液中添加一种或多种表面活性增容剂来改善除草剂水溶液的相容性的方法,所述除草剂水溶液包含芳氧基链烷酸的水溶性盐、吡啶氧基链烷酸的水溶性盐、或草甘膦(glyphosate)的水溶性盐中的至少一种。
此外,也提供了具有改善的相容性的除草剂水溶液,所述除草剂水溶液包含芳氧基链烷酸的水溶性盐、吡啶氧基链烷酸的水溶性盐、或草甘膦的水溶性盐中的至少一种,以及一种或多种表面活性增容剂。
另外,也提供了干燥除草剂组合物,其包括2,4-D的水溶性盐和/或草甘膦的水溶性盐,以及一种或多种表面活性增容剂。
具体实施方式
提供了除草剂水溶液以及产生这种溶液的方法,所述除草剂水溶液包含芳氧基链烷酸的水溶性盐、吡啶氧基链烷酸的水溶性盐、和草甘膦的水溶性盐中的至少一种,以及一种或多种表面活性增容剂。本申请描述的除草剂水溶液具有改善的相容性,与之前已知的除草剂水溶液相比,之前已知的除草剂水溶液包含芳氧基链烷酸的水溶性盐、吡啶氧基链烷酸的水溶性盐、和/或草甘膦的水溶性盐,但是不包含本申请所述的表面活性增容剂。本申请所述的表面活性增容剂通过抑制形成固体或相分离而保持所述溶液均质。当无机或有机铵阳离子存在时,这些表面活性增容剂特别有用,可在无需升高溶液的pH的情况下提供增容作用。
包含芳氧基链烷酸的水溶性盐例如2,4-D的盐的水溶液可能具有相容性问题,导致在下述条件下形成析出的固体,在所述条件中酸等价物(ae)浓度为约0.3wt%或更高,pH为约6.5或更低,且存在足够浓度的无机阳离子例如K+,Na+,Ca2+,Mg2+,NH4 +,Fe2+,Fe3+等。由这些2,4-D盐溶液形成析出固体所必需的精确条件也将取决于所用的水的温度以及硬度以及实际组成以及组分在溶液中的浓度。例如,由施用率为800g ae/公顷的-6除草剂(Dow AgroSciences LLC,Indianapolis,IN;2,4-D二甲基铵盐溶液,其pH值为约7)和施用率为840g ae/公顷的Roundup除草剂(Monsanto,St.Louis,MO;草甘膦钾盐溶液,其pH值为约4.7)的浓缩物制成且喷雾体积为约47升/公顷的喷雾罐混合物的pH值将为约5,该混合物将不相容,且导致显著形成固体。
将硫酸铵添加到包含草甘膦的除草剂含水喷雾混合物中以改善除草剂性能的常用实践也可以导致相容性问题。例如,如果除草剂例如2,4-D二甲基铵(DMA)存在于已经向其中添加了硫酸铵的包含草甘膦的喷雾混合物,则只要pH和2,4-D浓度在刚刚描述的范围内,就可发生固体的结晶。
提供了改善除草剂水溶液的相容性的方法和组合物,所述除草剂水溶液包括芳氧基链烷酸的水溶性盐、吡啶氧基链烷酸的水溶性盐、和草甘膦的水溶性盐中的至少一种,且进一步包括一种或多种表面活性增容剂。用于本申请所述除草剂水溶液的表面活性增容剂包括,例如,1)聚乙烯基吡咯烷酮及其共聚物或接枝聚合物;2)聚乙烯醇及其共聚物或接枝聚合物;3)与聚环氧乙烷侧链接枝的聚甲基丙烯酸酯;4)与聚环氧乙烷侧链接枝的聚丙烯酸酯;5)聚合的两性分散剂;6)环氧乙烷-环氧丙烷嵌段共聚物;7)合成胶乳;8)磺化木质素(也称为木质素磺酸盐);以及任何本申请所述表面活性增容剂的混合物。表面活性增容剂的形式可以为盐,例如,有机胺盐或包含无机阳离子的盐。有机胺盐的实例包括有机铵盐。存在于这样的盐中的有机铵阳离子的实例包括单甲基铵、异丙基铵、丁基铵、二甲基铵、二乙基铵、三乙基铵、单乙醇铵、二乙醇铵、二甲基乙基铵、二乙基乙醇铵、三乙醇铵、三异丙醇铵、四甲基铵、四乙基铵、和N,N,N-三甲基乙醇铵(胆碱),或其混合物。有用的无机阳离子的实例包括,例如,铵,钠,钾,镁,和钙。表面活性增容剂的形式可以为盐到部分为其酸形式,例如,部分具有氢阳离子而非有机胺或其它阳离子。表面活性增容剂可以包括与聚合物连接的一个或多个羧酸、磺酸、或膦酸基团,这些酸基团可以按盐形式存在。
本申请使用的术语共聚物是指通过使两种或更多种不同的单体单元按无规或嵌段排列聚合形成的链状高分子。本申请使用的术语接枝聚合物是指通过单种单体的聚合形成的链状高分子,其进一步与具有不同化学性质的一种或多种链状分子反应(接枝)以在链状聚合物主链结构上按无规或规则排列形成侧链或分支。这样的接枝聚合物可以包括链状聚合物主链中的烯键式不饱和羧酸单体单元。
适用于本申请所述方法和组合物的表面活性增容剂包括,聚乙烯基吡咯烷酮(例如15,30,60,90),与烷基链接枝的聚乙烯基吡咯烷酮(例如AL-10,AL-25,AL-22,AL30),乙烯基吡咯烷酮-乙酸乙烯基酯共聚物(例如,VA3,VA6,VA5,VA7),和乙烯基吡咯烷酮-苯乙烯嵌段共聚物例如ST,所述产品购自International Specialty Products,Ashland(Wayne,NJ)的部门;聚乙烯醇、其共聚物、及其衍生物,例如M05/290和M05/190,其购自Celanese(Dallas,TX);与聚环氧乙烷侧链接枝的聚甲基丙烯酸酯聚合物例如4913和聚合的两性分散剂例如4915,它们都购自Croda(Edison,NJ);和环氧乙烷-环氧丙烷嵌段共聚物例如F-68和304,其购自BASF(Florham Park,NJ)。
适用于本申请所述方法和组合物的合成胶乳包括丙烯酸类胶乳,苯乙烯-丁二烯胶乳,丙烯腈-丁二烯-苯乙烯胶乳,聚乙酸乙烯基酯胶乳,和乙烯基-丙烯酸类胶乳,其中UCARTM Latex 162和ENCORTM 162胶乳是实例且购自Arkema,Inc.(King of Prussia,PA)。
用于本申请所述方法和组合物的表面活性增容剂也包括磺化木质素,也称为木质素磺酸盐,它们是在用于制备造纸业中的脱木素纸浆的硫酸盐或亚硫酸盐工艺中产生的副产物。适宜的木质素磺酸盐包括但不限于,Borresperse NA,Borresperse CA,UltrazineNA,Ultrazine CA,Norlig A,Norlig TSD,Ufoxane 3A,Ufoxane 2和Marasperse AG,其全部购自Borregaard Lignotech USA(Rothschild,WI)。这些木质素磺酸盐特别适当的实例包括F、H、O、和T,以及83A、85A、907、和910,其全部购自MeadWestvaco(Charleston,SC),以及一种或多种木质素磺酸盐与萘磺酸钠的组合例如DD-6,也购自MeadWestvaco。本申请所述的磺化木质素也可以包括一种或多种选自但不限于氢、铵、钠、和钙的无机碱阳离子,以及一种或多种选自但不限于单甲基铵、异丙基铵、丁基铵、二甲基铵、二乙基铵、三乙基铵、单乙醇铵、二乙醇铵、二甲基乙基铵、二乙基乙醇铵、三乙醇铵、三异丙醇铵、四甲基铵、四乙基铵、和N,N,N-三甲基乙醇铵(胆碱)的有机铵阳离子。
本申请所述的芳氧基链烷酸的水溶性盐包括,例如,2,4-D((2,4-二氯苯氧基)乙酸),2,4-DB,2,4-滴丙酸(dichlorprop),2甲4氯丙酸(mecoprop),MCPA,和MCPB。本申请所述的吡啶氧基链烷酸包括,例如,三氯吡氧乙酸(triclopyr)和氯氟吡氧乙酸(fluroxypyr)。芳氧基链烷酸和吡啶氧基链烷酸的水溶性盐包括包含有机铵阳离子的那些,例如,单甲基铵、异丙基铵、丁基铵、二甲基铵、二乙基铵、三乙基铵、单乙醇铵、二乙醇铵、二甲基乙基铵、二乙基乙醇铵、三乙醇铵、三异丙醇铵、四甲基铵、四乙基铵、和N,N,N-三甲基乙醇铵(胆碱),或其混合物。包含芳氧基链烷酸或吡啶氧基链烷酸的水溶性盐的水溶液可以包括除草喷雾溶液或除草剂浓缩物。
本申请所述用于改善除草剂水溶液相容性的方法和组合物也可以适用于下述水溶液,所述水溶液包含芳基羧酸和/或杂芳基羧酸除草剂例如氯氨基吡啶酸(aminopyralid),二氯吡啶酸(clopyralid),麦草畏(dicamba),氨氯吡啶酸(picloram)等的水溶性盐。
本申请所述的草甘膦的水溶性盐包括其中阳离子选自以下阳离子的那些盐:钾,钠,和铵,以及有机铵例如异丙基铵,二甲基铵,三乙基铵,单乙醇铵,二乙醇铵,三乙醇铵,胆碱等,和三甲基锍阳离子,及其混合物。
本申请所述的无机阳离子是下述那些,当其以可测的量或浓度存在时可导致芳氧基链烷酸、吡啶氧基链烷酸、芳基羧酸、和/或杂芳基羧酸(任选包含草甘膦)的水溶性盐的水溶液变得不相容并形成固体。这些无机阳离子包括,例如,碱金属阳离子,例如钠和钾;碱土金属阳离子,例如钙和镁;过渡金属阳离子,例如锰,铜,锌和铁;和铵。包含2,4-D和草甘膦的水溶性盐的水溶液在pH水平低于约pH 6.5时在可测浓度的无机阳离子存在下往往较不相容,与这样的溶液在较高pH水平时相比。
本申请所用术语无机阳离子的可测浓度是指无机阳离子在除草剂水溶液中的存在浓度,所述除草剂水溶液包含芳氧基链烷酸的可溶性盐、吡啶氧基链烷酸的可溶性盐、芳基羧酸的可溶性盐、杂芳基羧酸的可溶性盐、和草甘膦中的至少一种,该浓度将会导致固体从该溶液中析出,如果所有对溶液不相容性必要的其它条件都存在,例如除草羧酸盐的组成和在溶液中的浓度,以及水的温度、硬度、和pH。例如,下述浓度将是不相容的,在室温草甘膦钾在水溶液中基于酸等价物(ae)为约0.8重量百分比(wt%)或更高,该水溶液基于ae包含大于约0.8wt%的2,4-D DMA且用硬度为342份每百万份(ppm)的水制成且最终pH为约5。除了本申请讨论的其它因素之外,这样的除草剂溶液的相容性还将取决于无机阳离子在溶液中存在的总浓度和实际组成。
可向本申请所述除草剂水溶液提供无机阳离子的成分可以包括但不限于,包含以下物质的产品或水溶液:肥料,微量营养物,硬水,共配制成分等,以及包含无机阳离子例如钾、钠、和铵的草甘膦的水溶性盐。
肥料任选包含在本申请所述的方法和组合物中并且可以分散或溶解于水中并且可以包含足够量的无机阳离子例如铵和钾以致于当与包含芳氧基链烷酸、吡啶氧基链烷酸、芳基羧酸、杂芳基羧酸、和草甘膦中至少一种的水溶性盐的水溶液混合时引起不相容问题。可任选包括在本申请所述方法和组合物中的肥料的量为小于或等于30%,小于或等于28%,小于或等于26%,小于或等于24%,小于或等于22%,小于或等于20%,小于或等于18%,小于或等于16%,小于或等于14%,小于或等于13%,小于或等于12%,小于或等于11%,小于或等于10%,小于或等于9%,小于或等于8%,小于或等于7%,小于或等于6%,小于或等于5%,小于或等于4.5%,小于或等于4%,小于或等于3.5%,小于或等于3%,小于或等于2.5%,小于或等于2%,小于或等于1.5%,或小于或等于1%。肥料可以包括但不限于,硫酸铵(AMS),磷酸铵,硝酸铵,硝酸铵和脲的溶液(其在本领域通常称为28%N或32%N或UAN),硫代硫酸铵,硝酸钾,磷酸钾,氯化钾,碳酸钾等,及其混合物。除了它们的肥料性质之外,AMS和UAN通常与草甘膦除草剂处理物一起用作喷雾辅料或水调理剂,从而改善生物学功效。因此,通常将AMS与草甘膦混合,本申请所述的方法和组合物可以用于改善相容性,当这些溶液与下述除草剂水溶液组合时,所述除草剂水溶液包含芳氧基链烷酸的水溶性盐、吡啶氧基链烷酸的水溶性盐、芳基羧酸的水溶性盐和/或杂芳基羧酸的水溶性盐。
微量营养物可以包括仅需极小量但对植物生长和健康必要的一种或多种养分,其尤其可以包含一种或多种无机阳离子,例如,锰、铜、铁、钼、和锌的阳离子。可以将这样的微量营养物添加到除草剂喷雾水溶液中,以经济地递送于作物植物,所述喷雾水溶液包含芳氧基链烷酸的水溶性盐、吡啶氧基链烷酸的水溶性盐、芳基羧酸的水溶性盐、杂芳基羧酸的水溶性盐、和/或草甘膦的水溶性盐。如果如本申请所述这些溶液的不相容条件存在,则可能发生这些除草剂喷雾水溶液的相容性问题。
可在本申请所述除草剂水溶液中、特别是在浓缩物和预混合浓缩物中引起不相容性的有机铵阳离子包括单甲基铵、异丙基铵、丁基铵、二甲基铵、二乙基铵、三乙基铵、单乙醇铵、二乙醇铵、二甲基乙基铵、二乙基乙醇铵、三乙醇铵、三异丙醇铵、四甲基铵、四乙基铵、和N,N,N-三甲基乙醇铵(胆碱),或其混合物。
共配制成分包括包含无机阳离子的那些产品或成分并且可以选自以下的一种或多种:辅料,防沫剂,抗菌剂,缓冲剂,腐蚀抑制剂,消泡剂,沉积试剂,分散剂,染料,防冻剂,中和剂,渗透助剂,掩蔽剂,喷雾漂移控制剂,铺展剂,稳定剂,粘着剂,悬浮助剂,粘度调节添加剂,润湿剂等。
本申请所述的表面活性增容剂可以用于改善喷雾罐混合物、浓缩物、或预混合浓缩物中除草剂水溶液的相容性,所述除草剂水溶液包含芳氧基链烷酸的水溶性盐、吡啶氧基链烷酸的水溶性盐、芳基羧酸的水溶性盐、杂芳基羧酸的水溶性盐、和/或草甘膦的水溶性盐。在含水喷雾罐混合物中,相对于具有改善的相容性的除草剂喷雾水溶液,本申请所述的表面活性增容剂可以占约0.01至约5wt%,约0.01至约4wt%,约0.01至约3wt%,约0.01至约2wt%,约0.01至约1wt%,约0.05至约2wt%,约0.05至约1wt%,约0.05至约0.5wt%,约0.1至约0.4wt%,约0.15至约0.3wt%,或约0.15至约0.25wt%。在含水浓缩物和含水预混合浓缩物中,相对于具有改善的相容性的除草剂水溶液,本申请所述的表面活性增容剂可以占约0.05至约10wt%,约0.05至约8wt%,约0.05至约6wt%,约0.1至约5wt%,约0.2至约5wt%,约0.3至约5wt%,约0.4至约5wt%,约0.5至约5wt%,约0.5至约4wt%,约0.5至约3wt%,约1至约3wt%,或约1.5至约2.5wt%。
在一些情况下,本申请所述的表面活性增容剂可以包含下述无机离子,该无机离子会增加已经存在于本申请所述除草剂水溶液中的无机离子的浓度,并且可以在这样的溶液中引起不相容问题。在这些情况中,选择的表面活性增容剂应该能够使得在添加了表面活性增容剂之后使包含无机离子浓度升高的这种溶液增容。或者,可以使用不包含无机阳离子的表面活性增容剂例如其中磺酸基团为酸形式或有机铵盐形式的木质素磺酸盐或不包含可形成盐的化学官能团的表面活性增容剂。这种不包含无机阳离子的表面活性增容剂可以特别用于在环境温度条件和低于环境温度的条件改善除草剂含水浓缩物和预混合浓缩物的储存稳定性。
不希望受理论限制,认为本申请所述的表面活性增容剂可通过防止或抑制固体的结晶或析出来改善除草剂水溶液的相容性,所述除草剂水溶液包含芳氧基链烷酸的水溶性盐、吡啶氧基链烷酸的水溶性盐、芳基羧酸的水溶性盐、杂芳基羧酸的水溶性盐和草甘膦的水溶性盐中的至少一种,具有适当浓度的一种或多种无机阳离子,且pH小于约6.5。表面活性增容剂在防止形成这些固体方面的有关效力可以如下评估:在滴定分析过程中测量固体的结晶起始pH(on-set pH of crystallization)(OSPOC)。特定组合物的OSPOC可以如下测量,例如,用强酸例如硫酸滴定无机阳离子的芳氧基链烷酸或吡啶氧基链烷酸盐(例如,2,4-D的钾盐)的溶液,直到在特定的pH值固体或晶体开始形成(OSPOC)。使用任何特定的本申请所述表面活性增容剂观察到的OSPOC越低,其可越好地防止在本申请所述除草剂水溶液中结晶,因此可越好地改善本申请所述除草剂水溶液的相容性。
或者,本申请所述表面活性增容剂在改善本申请所述除草剂水溶液相容性方面的有关效力可通过测量可以通过测量罐混合物溶液中无机阳离子的芳氧基链烷酸盐、吡啶氧基链烷酸盐、芳基羧酸盐、或杂芳基羧酸盐(例如,2,4-D的钾盐)的临界结晶浓度(CCC)确定。特定组合物的CCC可以如下测量:制备组合物的饱和或过饱和溶液或混合物,然后测量溶液中剩余的特定除草剂羧酸的浓度。使用特定表面活性增容剂观察到的CCC越高,其在防止在本申请所述除草剂水溶液中结晶方面可表现得越好,由此在改善本申请所述除草剂水溶液的相容性方面可表现得越好。
可使用本申请所述的表面活性增容剂增容的本申请所述除草剂水溶液包括浓缩物、预混合浓缩物、和喷雾溶液,所述喷雾溶液通过将这样的浓缩物或预混合浓缩物稀释或通过将喷雾溶液的多种组分罐混合来制备。含水的除草剂浓缩物或预混合浓缩物可以包括:相对于总组合物,使用约0.05至10wt%、0.05至8wt%、0.05至6wt%、0.1至5wt%、0.2至5wt%、0.3至5wt%、0.4至5wt%、0.5至5wt%、0.5至4wt%、0.5至3wt%、1至3wt%、或1.5至2.5wt%的一种或多种本申请所述表面活性增容剂和基于酸等价物为约20至约60wt%的以下物质中的至少一种,即,芳氧基链烷酸(例如2,4-D)的水溶性盐、吡啶氧基链烷酸(例如三氯吡氧乙酸)的水溶性盐、芳基羧酸(例如麦草畏)的水溶性盐、杂芳基羧酸(例如氯氨基吡啶酸)的水溶性盐和草甘膦的水溶性盐、或包含这些盐的一种或多种的预混合物。具有改善相容性的含水除草剂浓缩物或预混合浓缩物优选为下述溶液,该溶液包含溶解或分散在浓缩物中的表面活性增容剂,当将该浓缩物用产品或溶液且在本申请所述常容易引起不相容性的条件在水中稀释时,则形成具有改善的相容性的除草剂喷雾溶液。具有改善的相容性的除草剂喷雾溶液也可以通过将喷雾溶液的单个组分在使用点罐混合来制备。这样的喷雾溶液也可以与产品或溶液在本申请所述常容易引起不相容性的条件组合或用产品或溶液在本申请所述常容易引起不相容性的条件稀释,从而形成具有改善的相容性的除草剂喷雾溶液。
在包含2,4-D的可溶性盐、草甘膦的可溶性盐、和无机阳离子的含水喷雾溶液中,使用本申请所述的表面活性增容剂在低于约6.5的pH水平可得到具有改善的相容性的溶液。另外,改善的相容性可以在低于约pH 5.5提供。此外,改善的相容性可以在低于约pH 5提供。
包含草甘膦和2,4-D的水溶性盐的相容性含水喷雾溶液可以如下制备:将草甘膦和2,4-D的盐的水溶性浓缩物添加到包含一种或多种所述表面活性增容剂的水溶液中。可以将其它共配制成分例如水溶性或水可分散的成分任选添加到喷雾溶液中,所述成分包括但不限于,分散剂,润湿剂,喷雾漂移减少剂,肥料,和防沫剂。
使用本申请所述方法在pH低于约6.5改善喷雾溶液相容性的实例包括(其中所述溶液包含草甘膦和2,4-D的水溶性盐,和无机阳离子):
a)制备在水中的溶液,相对于最终喷雾溶液,所述溶液包含约0.01至约5wt%的表面活性增容剂,例如O;
b)将2,4-D DMA的含水浓缩物添加到在a)中制备的溶液,从而得到下述溶液,所述溶液相对于最终的喷雾溶液包含约0.3至约5wt%的2,4-D,基于酸等价物(ae);
c)将Roundup除草剂的含水浓缩物(包含草甘膦钾盐的含水浓缩物)(Monsanto,St.Louis,MO)添加到在b)中制备的溶液,从而得到下述溶液,所述溶液相对于最终的喷雾溶液包含约0.3至约5wt%的草甘膦,基于酸等价物(ae),其中最终pH小于约6.5;
d)将硫酸铵(AMS)的水溶液添加到在c)中制备的溶液,从而得到相容性溶液,所述相容性溶液相对于最终的喷雾溶液包含约1至约5wt%的AMS;和
e)任选地,将其它惰性的共配制成分添加到在d)中制备的溶液。
在进一步的实例中,增容的除草剂含水喷雾溶液可以通过稀释一种或多种含水除草剂浓缩物或通过将喷雾溶液的各组分罐混合来制备。这样的喷雾溶液相对于总的喷雾溶液可以包含约0.01至约5wt%、约0.05至约2wt%、或约0.05至约0.5wt%的一种或多种本申请所述表面活性增容剂,各自约0.3至约10wt%或约0.3至约5wt%的2,4-D的水溶性盐和草甘膦的水溶性盐的每一种,和任选的任何另外成分例如肥料。
在进一步的实例中,增容的除草剂含水浓缩物可以包含下述物质的一种或多种:本申请所述的表面活性增容剂,和2,4-D的水溶性盐或草甘膦的水溶性盐,或包含2,4-D和草甘膦的水溶性盐的预混合物。浓缩物相对于总组合物可以包含约0.05至约10wt%、约0.1至约5wt%、或约0.5至约5wt%的一种或多种表面活性增容剂,和基于酸等价物约20至约60wt%的2,4-D的水溶性盐和草甘膦的水溶性盐中的至少一种。如本申请所述,增容的含水除草剂浓缩物是下述溶液,其包含溶解或分散在浓缩物中的表面活性增容剂,当将该浓缩物用产品或溶液且在本申请所述常容易引起不相容性的条件在水中稀释时,则形成具有改善的相容性的除草剂喷雾溶液。
在制备本申请所述相容性含水除草剂浓缩物的典型方法中,将一种或多种表面活性增容剂、2,4-D和草甘膦中至少一种的水溶性盐、和任选的任何另外成分在水中混合在一起,得到含水浓缩物。添加成分的顺序和混合条件可以由本领域技术人员确定。
本申请所述的方法和组合物也包括干燥的除草剂组合物,所述组合物包括2,4-D的水溶性盐和/或草甘膦的水溶性盐,以及一种或多种上述表面活性增容剂。干燥的除草剂组合物可以包括约0.05至约10wt%、约0.05至约8wt%、约0.05至约6wt%、约0.1至约5wt%、约0.2至约5wt%、约0.3至约5wt%、约0.4至约5wt%、约0.5至约10wt%、约0.5至约5wt%、约0.5至约4wt%、约0.5至约3wt%、约1至约3wt%、或约1.5至约2.5wt%的一种或多种表面活性增容剂,和基于酸等价物约20至约80wt%的2,4-D的水溶性盐或草甘膦的水溶性盐、或2,4-D和草甘膦的水溶性盐的混合物。本申请所述的干燥的除草剂组合物在用产品或溶液并且处于常容易引起本申请所述的不相容性的条件在水中溶解时可形成具有改善的相容性的除草剂喷雾溶液。
在制备干燥除草剂组合物的典型方法中,将一种或多种表面活性增容剂、2,4-D和草甘膦中至少一种的水溶性盐、和任选的任何另外成分在水中混合在一起,得到含水浓缩物。添加成分的顺序和使用的混合条件可以容易地由本领域技术人员确定。然后可以通过移除水使含水浓缩物浓缩然后干燥,得到干燥除草剂组合物,所述组合物也可以通过将本申请所述的各成分干燥共混来制备。可以将干燥组合物添加到包含产品或溶液且处于本申请所述常容易引起不相容性的条件的含水喷雾溶液中,从而形成具有改善的相容性的除草剂喷雾溶液。正如公知,可以根据农业实践在使用点将浓缩或干燥的制剂在水中稀释或溶解,达约10至约500倍稀释。
本申请所述的方法和组合物可以用于防治不期望的植物生长。在这样的用途中,将除草有效量的具有改善相容性的含水喷雾溶液施用于土壤或目标植物叶片的区域,从而杀死不期望的杂草植物或提供对不期望的杂草植物的适当防治。
用于典型农业应用的本申请所述方法和组合物中使用的活性成分的有效量通常取决于,例如,植物的类型,植物的生长阶段,环境条件的严苛程度,待防治的杂草和施用条件。通常,使需要防治的杂草植物与含水除草喷雾溶液接触,所述喷雾溶液包含约0.01至约10wt%、优选约0.1至约5wt%的除草剂活性成分,基于酸等价物,相对于总的含水喷雾溶液。接触可以按任何有效的方式进行。例如,可以用作为在载体例如水中的溶液的活性成分喷洒植物的任何暴露部分例如叶子或茎。
本申请所述的方法和组合物特别适用于防治作物中的杂草,所述作物对包含在喷雾溶液中的除草剂是天然耐受的,或者已经通过基因处理或通过变异和选择而对包含在喷雾溶液中的除草剂具有耐受性或抗性。例如,可以处理玉米、小麦、稻子、大豆、甜菜、棉花、低芥酸菜子、和其它作物,已经将它们处理成对草甘膦具有耐受性或抗性,并且它们是对2,4-D天然耐受或具有抗性或者已经将它们基因处理成对2,4-D具有耐受性或抗性。本发明的含水除草喷雾溶液也可有效防治已经对草甘膦变得具有抗性的很多杂草,例如,加拿大乍蓬(horseweed)(小蓬草(Conyza Canadensis),ERICA)。
本申请所述的方法和组合物可以任选地另外包含一种或多种表面活性剂。表面活性剂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的盐,例如月桂基硫酸二乙醇铵;烷基芳基磺酸盐,例如十二烷基苯磺酸钙;烷基酚和/或芳基烷基酚-环氧烷烃加成产物,例如壬基酚乙氧基化物;醇-环氧烷烃加成产物,例如十三烷基醇乙氧基化物;皂,例如硬脂酸钠;烷基萘-磺酸盐,例如二丁基萘磺酸钠;磺基琥珀酸盐的二烷基酯,例如二(2-乙基己基)磺基琥珀酸钠;山梨糖醇酯,例如油酸山梨糖醇酯;季胺,例如月桂基三甲基氯化铵;乙氧基化的胺,例如牛油胺乙氧基化物;甜菜碱表面活性剂,例如椰油酰胺丙基甜菜碱;脂肪酸的聚乙二醇酯,例如聚乙二醇硬脂酸酯;磷酸一烷基酯和磷酸二烷基酯的盐;及其混合物。待使用的这些表面活性剂的量和组合可容易由本领域技术人员确定。正如以上针对表面活性增容剂所讨论,可能有利的是,避免使用包含可影响结晶的含量的无机离子(例如,Na+,K+,或NH4 +)的表面活性剂,以便于保持所述组合物的物理稳定性。
除了以上陈述的具体方法和组合物之外,本申请所述的方法和组合物也可以包括含有一种或多种另外的相容性成分的组合物。这些另外的成分可以包括,例如,一种或多种杀虫剂或其它成分,其可以溶解或分散在组合物中并且可以选***螨剂,灭藻剂,拒食素,杀鸟剂,杀菌剂,驱鸟剂,化学绝育剂,脱叶剂,干燥剂,消毒剂,杀真菌剂,除草剂安全剂,除草剂,昆虫引诱剂,杀昆虫剂,驱虫剂,驱哺乳动物剂,交配干扰剂,杀软体动物剂,植物激活剂(plant activator),植物大小和结构的调节剂(modifiers of plant size andstructure),杀啮齿动物剂(rodenticide),信息素(semiochemicals),协同剂,和杀病毒剂。同样,任何其它提供功能用途的另外成分可以包含在这些组合物中,例如,防沫剂,杀菌剂,缓冲剂,腐蚀抑制剂,分散剂,染料,香料,防冻剂,中和剂,着嗅剂(odorants),渗透助剂,掩蔽剂,喷雾漂移控制剂,铺展剂,稳定剂,粘着剂,粘度调节添加剂等。
以下实施例用于说明本申请所述组合物和方法的各个方面,不应该认为其限制权利要求的范围。
实施例
实施例1.降低2,4-D钾与本申请所述表面活性增容剂(SAC)的水溶液的结晶起始 pH(OSPOC)
当pH通过添加0.2N硫酸水溶液而缓慢降低时,确定3wt%(基于酸等价物)2,4-D钾(2,4-D K)连同和不连同添加的SAC的水溶液的100mL样品的结晶起始pH(OSPOC;当结晶开始时溶液的pH)。如表1所示,添加相对于总溶液为0.2wt%的SAC到2,4-D K的水溶液中可显著降低含2,4-D的溶液的OSPOC,与其中不使用SAC的对照实施例相比。
表1.通过OSPOC测量的在低pH使用表面活性增容剂(SAC)抑制2,4-D钾盐从水溶液中结晶
产品购自International Specialty Products,Ashland(Wayne,NJ)的部门;产品购自Celanese(Dallas,TX);AtloxTM和MetasperseTM产品购自Croda Inc.(Edison,NJ);和产品购自MeadWestvaco Corp.(Charleston,SC);UCARTM 162胶乳购自Arkema,Inc.(King of Prussia,PA);和产品购自BASF(Florham Park,NJ)。
实施例2.测定2,4-D的盐在草甘膦与添加的表面活性增容剂(SAC)的水溶液中的 临界结晶浓度(CCC)
2,4-D组合物的CCC使用以下方法测量。制备喷雾混合物,其包含2,4-D、草甘膦、无机离子、和表面活性增容剂,在观察到结晶的各种过饱和的2,4-D浓度。将在每种混合物中形成的晶体分离、干燥、和称重。将从每种混合物中分离的晶体的量/重量相对于初始混合物中2,4-D wt%AE浓度作图,得到线性函数。CCC通过测量晶体重量相对于2,4-D wt%AE浓度的外推线性函数的X轴截距来测定。例如,以下过程用于测定在表2中显示的CCC值:
1.在100ml离心管中添加适当量的342ppm硬度的水和2,4-D含水浓缩物制剂,例如DMA盐连同或不连同内在1-2%w/w SAC,并混合,直到得到均匀溶液。
2.添加作为罐混合物添加剂的SAC,如果其未作为内在成分包含在步骤1中的2,4-D含水浓缩物中。
3.将适当量的草甘膦含水浓缩物制剂例如在Roundup中发现的草甘膦K盐添加到离心管中并通过倒置来混合。
4.任选地将其它罐混合物成分例如硫酸铵(AMS)添加到离心管中。
5.使样品在环境温度平衡24小时,然后将结晶析出物过滤,收集,干燥,和称重。
6.添加一定量的2,4-D和草甘膦盐以达到2,4-D和草甘膦按1:1比率的所需的AE浓度,水的量计算为达到100ml的最终混合物体积所需的平衡成分。
7.通常,一系列混合物按照以上步骤在过饱和浓度制备,所述浓度为,例如,基于酸等价物(AE),1.8%、2.4%、和3.0%的每种除草剂盐。将收集的结晶析出物的重量相对于混合物中2,4-D的相应AE浓度作图。然后可以将临界结晶浓度(CCC)如下测定为发生结晶前的最大%2,4-D AE浓度:将晶体析出物重量相对于2,4-D%AE浓度的线性函数外推至横轴上晶体析出物重量变为0的位置。
表2.测定2,4-D的盐在包含草甘膦的盐与添加的表面活性增容剂(SAC)的含水组合物中的临界结晶浓度(CCC)
1使用的2,4-D盐是未掩蔽的二甲基铵盐,提供为4(包含456g ae/L的2,4-D二甲基铵盐的含水浓缩物)或6(包含678g ae/L的2,4-D二甲基铵盐的含水浓缩物),都购自Dow AgroSciences LLC,Indianapolis,IN;和2,4-D DMEA(包含456g ae/L 2,4-D二甲基乙醇铵盐的含水浓缩物)。
2Roundup是包含540g ae/L草甘膦钾盐的含水浓缩物(MonsantoCompany,St.Louis,MO)。
产品购自MeadWestvaco Corp.(Charleston,SC)。
实施例3.制备包含表面活性增容剂(SAC)的2,4-D胆碱盐的相容性含水浓缩物并 将其在包含草甘膦盐和硫酸铵(AMS)的喷雾溶液中稀释
制备表3中所示的喷雾溶液的典型过程包括以下步骤:
1.将适当量的硬度为342ppm的水添加到100ml离心管中,然后添加适当量的2,4-D含水浓缩物制剂例如2,4-D胆碱盐,并混合,直到得到均匀溶液。
2.将SAC引入到以上喷雾混合物中,或从含有内在SAC的2,4-D浓缩物制剂中引入,或者通过直接添加SAC或其浓缩物溶液到混合物中而引入。
3.将适当量的草甘膦含水浓缩物制剂例如草甘膦K盐添加到离心管中并通过倒置来混合。
4.任选地将其它罐混合成分例如AMS添加到离心管中。
5.添加一定量的2,4-D和草甘膦盐以达到2,4-D和草甘膦按1:1重量比的所需的AE浓度,水的量计算为达到100ml的最终混合物体积所需的平衡成分。例如,对于840gae/ha使用率,15gal/ac、10gal/ac、和5gal/ac喷雾体积将分别对应于罐混合物中约0.6%、0.9%、和1.8%的2,4-D和草甘膦的AE。
6.在环境温度平衡24小时之后检测由此制备的喷雾溶液是否存在晶体或析出物。
表3.评价通过在各种条件在存在或不存在SAC的情况下将456g ae/l的2,4-D二甲基铵盐的含水浓缩物与540g ae/l草甘膦钾盐的含水浓缩物混合制备的喷雾溶液的相容性
1使用的2,4-D盐是未掩蔽的二甲基铵盐,提供为-4(包含456g ae/L的2,4-D二甲基铵盐的含水浓缩物),购自Dow AgroSciences LLC(Indianapolis,IN)。
2Roundup是包含540g ae/L草甘膦钾盐的含水浓缩物,购自MonsantoCompany(St.Louis,MO)。
产品购自MeadWestvaco Corp.(Charleston,SC)。
本发明的范围不受本申请所公开的实施方式的限制,本申请所公开的实施方式意在说明本发明的几个方面,功能等价的任何实施方式也包括在本发明的范围内。除本申请所示和描述那些之外,工艺、方法、和组合物的各种变型也落入所附权利要求的范围内。此外,尽管以上实施方式中仅特别讨论了本申请所公开的工艺和方法步骤以及组合物的某些代表性组合,但是组合物组分以及工艺和方法步骤的其它组合对于本领域技术人员而言也是显而易见的,因此也落入所附权利要求的范围内。因此,组分或步骤的组合可以在本申请明确提及;但是,即使没有明确陈述也包括组分和步骤的其它组合。本申请使用的术语包括及其派生词与术语包含及其派生词可同义使用,并且为开放式的非限制性术语。
Claims (28)
1.改善除草剂水溶液的相容性的方法,所述除草剂水溶液包括:(a)芳氧基链烷酸的水溶性盐或吡啶氧基链烷酸的水溶性盐中的至少一种;和(b)草甘膦的水溶性盐,所述方法包括向所述除草剂水溶液中添加一种或多种表面活性增容剂,其中所述表面活性增容剂为与聚环氧乙烷侧链接枝的聚丙烯酸酯或聚甲基丙烯酸酯,聚合的两性分散剂,磺化木质素,或其混合物。
2.权利要求1的方法,其中所述芳氧基链烷酸是2,4-D,2,4-DB,2,4-滴丙酸(dichlorprop),2甲4氯丙酸(mecoprop),MCPA,或MCPB。
3.权利要求1的方法,其中所述吡啶氧基链烷酸是三氯吡氧乙酸(triclopyr)或氯氟吡氧乙酸(fluroxypyr)。
4.权利要求2的方法,其中所述吡啶氧基链烷酸是三氯吡氧乙酸(triclopyr)或氯氟吡氧乙酸(fluroxypyr)。
5.权利要求1-4中任一项的方法,其进一步包含一种或多种选自NH4 +、Na+、K+、Ca2+、Mg2+、Fe2+、Fe3+、Cu2+、Mn2+、和Zn2+的无机阳离子,或一种或多种选自单甲基胺、异丙基胺、丁基胺、二甲基胺、二乙基胺、三乙基胺、单乙醇胺、二乙醇胺、二甲基乙基胺、二乙基乙醇胺、三乙醇胺、三异丙醇胺、四甲基胺、四乙基胺、和N,N,N-三甲基乙醇胺(胆碱)的有机胺阳离子,或其混合物。
6.权利要求1-4中任一项的方法,其中所述除草剂水溶液是浓缩物或预混合浓缩物。
7.权利要求6的方法,其中所述除草剂水溶液是包含2,4-D和草甘膦的水溶性盐的浓缩物。
8.权利要求1-4中任一项的方法,其中所述除草剂水溶液是喷雾溶液。
9.权利要求1的方法,其中所述表面活性增容剂的形式为盐。
10.权利要求1的方法,其中所述表面活性增容剂的形式为酸。
11.权利要求9的方法,其中所述盐是有机胺盐或包含无机阳离子的盐。
12.权利要求11的方法,其中所述有机胺盐包含选自以下的阳离子:单甲基胺、异丙基胺、丁基胺、二甲基胺、二乙基胺、三乙基胺、单乙醇胺、二乙醇胺、二甲基乙基胺、二乙基乙醇胺、三乙醇胺、三异丙醇胺、四甲基胺、四乙基胺、和N,N,N-三甲基乙醇胺(胆碱),或其混合物。
13.具有改善的相容性的除草剂水溶液,其包括:(a)芳氧基链烷酸的水溶性盐或吡啶氧基链烷酸的水溶性盐中的至少一种;(b)草甘膦的水溶性盐;和(c)一种或多种表面活性增容剂,其中所述表面活性增容剂为与聚环氧乙烷侧链接枝的聚丙烯酸酯或聚甲基丙烯酸酯,聚合的两性分散剂,磺化木质素,或其混合物。
14.权利要求13的除草剂水溶液,其中所述芳氧基链烷酸是以下的至少一种:2,4-D,2,4-DB,2,4-滴丙酸,2甲4氯丙酸,MCPA,和MCPB。
15.权利要求13的除草剂水溶液,其中所述吡啶氧基链烷酸是三氯吡氧乙酸或氯氟吡氧乙酸。
16.权利要求14的除草剂水溶液,其中所述吡啶氧基链烷酸是三氯吡氧乙酸或氯氟吡氧乙酸。
17.权利要求13-16中任一项的除草剂水溶液,其进一步包含一种或多种选自NH4 +、Na+、K+、Ca2+、Mg2+、Fe2+、Fe3+、Cu2+、Mn2+、和Zn2+的无机阳离子,或一种或多种选自单甲基胺、异丙基胺、丁基胺、二甲基胺、二乙基胺、三乙基胺、单乙醇胺、二乙醇胺、二甲基乙基胺、二乙基乙醇胺、三乙醇胺、三异丙醇胺、四甲基胺、四乙基胺、和N,N,N-三甲基乙醇胺(胆碱)的有机铵阳离子,或其混合物。
18.权利要求13-16中任一项的除草剂水溶液,其中所述除草剂水溶液是浓缩物或预混合浓缩物。
19.权利要求13-16中任一项的除草剂水溶液,其中所述除草剂水溶液是包含2,4-D和草甘膦的水溶性盐的浓缩物。
20.权利要求13-16中任一项的除草剂水溶液,其中所述除草剂水溶液是喷雾溶液。
21.权利要求13的除草剂水溶液,其中所述表面活性增容剂的形式为盐。
22.权利要求21的除草剂水溶液,其中所述盐是有机胺盐或包含无机阳离子的盐。
23.权利要求22的除草剂水溶液,其中所述有机胺盐包含选自以下的阳离子:单甲基胺、异丙基胺、丁基胺、二甲基胺、二乙基胺、三乙基胺、单乙醇胺、二乙醇胺、二甲基乙基胺、二乙基乙醇胺、三乙醇胺、三异丙醇胺、四甲基胺、四乙基胺、和N,N,N-三甲基乙醇胺(胆碱),或其混合物。
24.干燥除草剂组合物,其包含:(a)2,4-D的水溶性盐;(b)草甘膦的水溶性盐;和(c)一种或多种表面活性增容剂,其中所述表面活性增容剂为与聚环氧乙烷侧链接枝的聚丙烯酸酯或聚甲基丙烯酸酯,聚合的两性分散剂,磺化木质素,或其混合物。
25.权利要求24的干燥除草剂组合物,其进一步包含一种或多种选自NH4 +、Na+、K+、Ca2+、Mg2+、Fe2+、Fe3+、Cu2+、Mn2+、和Zn2+的无机阳离子,或一种或多种选自单甲基胺、异丙基胺、丁基胺、二甲基胺、二乙基胺、三乙基胺、单乙醇胺、二乙醇胺、二甲基乙基胺、二乙基乙醇胺、三乙醇胺、三异丙醇胺、四甲基胺、四乙基胺、和N,N,N-三甲基乙醇胺(胆碱)的有机胺阳离子,或其混合物。
26.权利要求24的干燥除草剂组合物,其中所述表面活性增容剂的形式为盐。
27.权利要求26的干燥除草剂组合物,其中所述盐是有机胺盐或包含无机阳离子的盐。
28.权利要求27的干燥除草剂组合物,其中所述有机胺盐包含选自以下的阳离子:单甲基胺、异丙基胺、丁基胺、二甲基胺、二乙基胺、三乙基胺、单乙醇胺、二乙醇胺、二甲基乙基胺、二乙基乙醇胺、三乙醇胺、三异丙醇胺、四甲基胺、四乙基胺、和N,N,N-三甲基乙醇胺(胆碱),或其混合物。
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