CN102821601B - 共聚物在提高农药活性中的用途 - Google Patents
共聚物在提高农药活性中的用途 Download PDFInfo
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- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
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- AMHNZOICSMBGDH-UHFFFAOYSA-L zineb Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 description 1
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- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/04—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aldehyde or keto groups, or thio analogues thereof, directly attached to an aromatic ring system, e.g. acetophenone; Derivatives thereof, e.g. acetals
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- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
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- A01N43/647—Triazoles; Hydrogenated triazoles
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Abstract
公开了通过自由基聚合包含N-乙烯基内酰胺、乙烯基酯和聚醚的单体混合物得到的接枝共聚物在提高农药活性中的用途。还公开了一种包含农药和通过单体混合物的自由基聚合得到的接枝共聚物的组合物,其中该单体混合物包含i)30-80重量%N-乙烯基吡咯烷酮、N-乙烯基己内酰胺或其混合物,ii)10-50重量%乙酸乙烯酯和iii)10-50重量%聚醚。进一步公开了一种通过混合该农药和该接枝共聚物而制备所述组合物的方法以及一种防治植物病原性真菌和/或不希望的植物生长和/或不希望的昆虫或螨虫侵袭和/或调节植物生长的方法。
Description
本发明涉及可以通过自由基聚合包含N-乙烯基内酰胺、乙烯基酯和聚醚的单体混合物得到的接枝共聚物在提高农药活性中的用途。本发明还涉及一种包含农药和可通过单体混合物的自由基聚合得到的接枝共聚物的组合物,其中该单体混合物包含i)30-80重量%N-乙烯基吡咯烷酮、N-乙烯基内酰胺或其混合物,ii)10-50重量%乙酸乙烯酯和iii)10-50重量%聚醚。进一步涉及一种通过混合该农药和该接枝共聚物而制备所述组合物的方法以及一种防治植物病原性真菌和/或不希望的植物生长和/或不希望的昆虫或螨虫侵袭和/或调节植物生长的方法。优选实施方案与其他优选实施方案的组合处于本发明范围内。
除了优化活性成分性能外,开发有效试剂对于活性成分的工业生产和应用特别重要。通过正确配制活性成分,必须在性能之间找到最佳平衡,其中一些性能相互冲突,如生物学活性、毒理性、潜在环境影响和成本。此外,该配制在决定组合物的储存期限和用户友好性方面为决定性因素。
活性成分被植物有效吸收对于农业化学组合物的活性特别重要。若该吸收经由叶子,则其构成复杂的转移过程,其中活性物质,例如除草剂必须首先渗透叶子的蜡状表皮,然后经由表皮扩散进入下面的组织,达到实际作用位置。
通常已知的农业实践是将某些助剂加入配制剂中以改善后者的活性。有利地,这允许配制剂中活性成分的量降低,同时维持相同的活性,从而能够使成本最小化并且合适的话能够在现有法规内操作。在单独的情况下,这也允许拓宽活性成分的作用谱,因为在没有添加剂下仅能以不令人满意的程度用特定活性成分对其进行处理的植物现在由于加入某些辅助剂而能够进行该类处理。此外,在不利环境条件下的性能在单独的情况下可以通过合适的配制剂提高。当然,也可以避免各种活性成分在一种配制剂中的不相容性。该类辅助剂有时也称为助剂。
表面活性类型的助剂以许多方式用于农业化学目的。它们可以分成阴离子、阳离子、非离子或两性组的物质。基于石油产品的油传统上用作活化助剂。近来也使用种子提取物、天然油及其衍生物,例如来自大豆、向日葵和椰子。
可通过N-乙烯基内酰胺、乙酸乙烯酯和聚醚的自由基聚合而得到的共聚物是已知的:
WO2007/051743公开了通过自由基聚合N-乙烯基内酰胺、乙酸乙烯酯和聚醚而得到的共聚物作为水不溶性化合物如农业化学活性成分用加溶剂的用途。
WO2007/051742公开了一种在聚氧化烯存在下接枝聚合乙烯基酯和N-乙烯基内酰胺的方法。所得接枝聚合物用于抑制气体水化物以及在液体洗涤剂中用作添加剂和用作颜料分散剂。
已知助剂所具有的问题是它们通常例如通过使粘度或粒度增加而降低该配制剂,尤其是悬浮液配制剂的稳定性。许多已知的助剂具有高植物毒性,因此不建议将它们用于处理葡萄藤、水果和蔬菜。还存在对农夫的皮肤具有不利影响或者太昂贵而难以以工业规模合成的助剂。本发明的目的是克服这些上述问题。
该目的通过可以通过自由基聚合包含N-乙烯基内酰胺、乙烯基酯和聚醚的单体混合物得到的接枝共聚物在提高农药活性中的用途实现。
提高农药活性涉及提高该农药的农药活性。该活性相对于在其他方面相当的条件下不存在该聚合物时的农药活性提高。因此,该接枝聚合物也可以称为助剂,或具有助剂效果的接枝聚合物。
接枝聚合物是一类众所周知的聚合物结构,它们通常包含与聚合物侧链连接的聚合物主链。该接枝共聚物可以通过自由基聚合该单体混合物而得到(优选通过自由基聚合该单体混合物而得到)。得到接枝共聚物的单体混合物的该类自由基聚合如下所述是众所周知的。
合适乙烯基酯的实例包括具有1-20个,尤其是1-6个碳原子的饱和羧酸的乙烯基酯。实例是乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、己酸乙烯酯和/或辛酸乙烯酯。优选使用乙酸乙烯酯和丙酸乙烯酯。特别优选使用乙酸乙烯酯。按照本发明可以使用单独一种乙烯基酯或者使用两种或更多种乙烯基酯的混合物。
合适的N-乙烯基内酰胺是在内酰胺环中具有4-13个碳原子的N-乙烯基内酰胺。实例是N-乙烯基-2-吡咯烷酮、N-乙烯基己内酰胺、N-乙烯基戊内酰胺、N-乙烯基月桂内酰胺、N-乙烯基-2-哌啶酮、N-乙烯基-2-吡啶酮、N-乙烯基-3-甲基-2-吡咯烷酮、N-乙烯基-4-甲基-2-吡咯烷酮和/或N-乙烯基-5-甲基-2-吡咯烷酮。优选使用N-乙烯基-2-吡咯烷酮、N-乙烯基己内酰胺和/或N-乙烯基-2-哌啶酮。更优选的N-乙烯基内酰胺是N-乙烯基吡咯烷酮或N-乙烯基己内酰胺或其混合物。特别优选N-乙烯基己内酰胺。按照本发明可以使用单独一种N-乙烯基内酰胺或两种或更多种N-乙烯基内酰胺的混合物。
合适且优选的聚醚为聚亚烷基二醇。聚亚烷基二醇可以具有的分子量为1000-100000D[道尔顿],优选1500-35000D,特别优选1500-10000D。分子量基于如DIN 53240所述测量的OH值测定。
聚乙二醇是合适且特别优选的聚亚烷基二醇。聚丙二醇、聚四氢呋喃或由2-乙基环氧乙烷或2,3-二甲基环氧乙烷得到的聚丁二醇也是合适的。
合适的聚醚还有由氧化乙烯、氧化丙烯和氧化丁烯得到的聚亚烷基二醇的无规或嵌段共聚物,例如聚乙二醇-聚丙二醇嵌段共聚物。嵌段共聚物可以呈AB或ABA类型。
聚亚烷基二醇可以由羟基封端或者在一个或两个OH端基上烷基化。合适的烷基是支化或未支化的C1-C22烷基,优选C1-C18烷基,例如甲基、乙基、正丁基、异丁基、戊基、己基、辛基、壬基、癸基、十二烷基、十三烷基或十八烷基。优选聚亚烷基二醇由羟基封端。
该单体混合物可以包含额外的共聚单体。
合适的额外共聚单体实例是乙烯基羧酰胺,如N-乙烯基甲酰胺、N-乙烯基-N-甲基甲酰胺、N-乙烯基乙酰胺、N-乙烯基-N-甲基乙酰胺、N-乙烯基-N-甲基丙酰胺和N-乙烯基丙酰胺。优选使用N-乙烯基甲酰胺和/或N-乙烯基-N-甲基乙酰胺。共聚的N-乙烯基甲酰胺和/或N-乙烯基-N-甲基乙酰胺单体单元可以部分或完全水解。
合适的其他额外共聚单体还有具有3-6个碳原子的单烯属不饱和单羧酸和二羧酸或其酸酐,如丙烯酸、甲基丙烯酸、巴豆酸、马来酸或酸酐、富马酸、衣康酸或酸酐以及柠康酸或酸酐。
其他合适的额外共聚单体是上述单烯属不饱和C3-C6羧酸的酰胺、酯和腈,例如酰胺类—丙烯酰胺,甲基丙烯酰胺,还有具有1-6个碳原子的烷基的N-烷基-和N,N-二烷基酰胺,如N-甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N-甲基甲基丙烯酰胺、N,N-二甲基甲基丙烯酰胺、N-乙基丙烯酰胺、N-丙基丙烯酰胺、叔丁基丙烯酰胺和叔丁基甲基丙烯酰胺,还有碱性(甲基)丙烯酰胺,如2-N,N-二甲基氨基乙基丙烯酰胺、2-N,N-二甲基氨基乙基甲基丙烯酰胺、2-N,N-二乙基氨基乙基丙烯酰胺、2-N,N-二乙基氨基乙基甲基丙烯酰胺、3-N,N-二甲基氨基丙基丙烯酰胺、3-N,N-二乙基氨基丙基丙烯酰胺、3-N,N-二甲基氨基丙基甲基丙烯酰胺和3-N,N-二乙基氨基丙基甲基丙烯酰胺。
其他合适的额外共聚单体是单烯属不饱和羧酸与C1-C6醇的酯,如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯和甲基丙烯酸乙酯,或与二醇或聚二醇的酯,其中在每种情况下在二醇和聚二醇中仅一个OH基团被烯属不饱和羧酸酯化,如丙烯酸羟乙基酯、甲基丙烯酸羟乙基酯、丙烯酸羟丙基酯、丙烯酸羟丁基酯、甲基丙烯酸羟丙基酯、甲基丙烯酸羟丁基酯,还有分子量为200-10000的聚亚烷基二醇的(甲基)丙烯酸单酯。进一步合适的是上述烯属不饱和羧酸与吡咯烷酮衍生物的酯,如丙烯酸2-(N-吡咯烷酮)乙基酯或甲基丙烯酸2-(N-吡咯烷酮)乙基酯,以及上述烯属不饱和羧酸与氨基醇的酯,如丙烯酸2-N,N-二甲基氨基乙基酯、甲基丙烯酸2-N,N-二甲基氨基乙基酯、丙烯酸2-N,N-二乙基氨基乙基酯、甲基丙烯酸2-N,N-二乙基氨基乙基酯、丙烯酸3-N,N-二甲基氨基丙基酯、甲基丙烯酸3-N,N-二甲基氨基丙基酯、丙烯酸3-N,N-二乙基氨基丙基酯、甲基丙烯酸3-N,N-二乙基氨基丙基酯、丙烯酸4-N,N-二甲基氨基丁基酯、丙烯酸4-N,N-二乙基氨基丁基酯、丙烯酸5-N,N-二甲基氨基戊基酯、甲基丙烯酸二甲基氨基新戊基酯和丙烯酸6-N,N-二甲基氨基己基酯。该碱性(甲基)丙烯酸酯和(甲基)丙烯酰胺以游离碱形式、与无机酸如盐酸、硫酸和硝酸的盐形式或者以季化形式使用。合适季化剂的实例包括硫酸二甲酯、甲基氯、乙基氯、苄基氯或硫酸二乙酯。
上述烯属不饱和羧酸的腈实例是丙烯腈和甲基丙烯腈。
额外适合作为额外的共聚单体的是N-乙烯基咪唑类以及取代的N-乙烯基咪唑类,如N-乙烯基-2-甲基咪唑、N-乙烯基-4-甲基咪唑、N-乙烯基-5-甲基咪唑和N-乙烯基-2-乙基咪唑、N-乙烯基咪唑啉类,如N-乙烯基咪唑啉、N-乙烯基-2-甲基咪唑啉和N-乙烯基-2-乙基咪唑啉,还有N-乙烯基咪唑啉酮类,如N-乙烯基-2-咪唑啉酮和N-乙烯基-4-甲基-2-咪唑啉酮。N-乙烯基咪唑类,N-乙烯基咪唑啉类以及N-乙烯基咪唑啉酮类不仅以游离碱形式使用,而且以用无机酸中和的形式或季化形式使用,其中季化优选使用硫酸二甲酯、硫酸二乙酯、苄基氯、甲基氯或乙基氯。
最后,适合作为额外共聚单体的单体包括包含磺基的那些,如乙烯基磺酸、烯丙基磺酸、甲代烯丙基磺酸、苯乙烯磺酸、丙烯酸3-磺基丙基酯、甲基丙烯酸3-磺基丙基酯和2-丙烯酰胺基-2-甲基丙烷磺酸。含有酸基的化合物可以以游离酸形式、铵盐或碱金属和碱土金属盐形式用于接枝聚合。
额外的共聚单体还可以是具有交联作用的单体,如亚甲基二丙烯酰胺,丙烯酸和甲基丙烯酸与多元醇的酯,实例是乙二醇二丙烯酸酯、甘油三丙烯酸酯、乙二醇二甲基丙烯酸酯和甘油三甲基丙烯酸酯,还有被丙烯酸或甲基丙烯酸至少双重酯化的多元醇如季戊四醇和葡萄糖。其他合适的交联剂是二乙烯基苯、二乙烯基二烷、N,N-二乙烯基-2-咪唑啉酮、季戊四醇三烯丙基醚和五烯丙基蔗糖。优选的交联单体c)是水溶性单体,如二醇二丙烯酸酯或分子量(数均)为300-10000的聚乙二醇的二醇二丙烯酸酯。
在额外共聚单体中,优选使用N-乙烯基咪唑、丙烯酸、甲基丙烯酸、甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N-甲基甲基丙烯酰胺、叔丁基丙烯酰胺、叔丁基甲基丙烯酰胺、二甲基氨基乙基甲基丙烯酰胺、丙烯酸羟乙基酯、丙烯酸2-(N-吡咯烷酮)乙基酯、甲基丙烯酸2-(N-吡咯烷酮)乙基酯和2-丙烯酰胺基-2-甲基丙烷磺酸。然而,按照本发明有利的是不使用单体c)。
根据本发明的一个实施方案,合适的接枝共聚物可以由包含如下单体的单体混合物得到:
i)30-80重量%N-乙烯基内酰胺,
ii)10-50重量%乙烯基酯,和
iii)10-50重量%聚醚。
优选的接枝共聚物可以由如下单体得到:
i)30-70重量%N-乙烯基内酰胺,
ii)15-35重量%乙烯基酯,和
iii)15-35重量%聚醚,
特别优选的接枝共聚物由如下单体得到:
i)40-60重量%N-乙烯基内酰胺,
ii)15-35重量%乙烯基酯,和
iii)15-30重量%聚醚。
组分i)、ii)、iii)以及任选额外的共聚单体的量在该单体混合物中通常加起来为100%。优选组分i)、ii)和iii)在该单体混合物中加起来为100%。在本发明的另一实施方案中,优选的聚合物包含10-35重量%聚醚。应理解的是还可以使用两种或更多种额外共聚单体的混合物。
制备接枝共聚物的通用方法本身是已知的(例如由WO 2007/051743已知)。该制备通过自由基聚合,优选溶液聚合在非水有机溶剂中或者在混合的非水/含水溶剂中进行。该聚合优选在60-100°C的温度下进行。合适的非水有机溶剂例如为醇类,如甲醇、乙醇、正丙醇和异丙醇,以及二醇如乙二醇和甘油。其他合适的溶剂是酯类,如乙酸乙酯、乙酸丙酯、乙酸异丙酯、乙酸异丁酯或乙酸丁酯。
使用自由基引发剂来引发该聚合。所用引发剂或引发剂混合物的量基于所用单体为0.01-10重量%,优选0.3-5重量%。取决于所用溶剂的性质,有机和无机过氧化物均合适,如过硫酸钠,或偶氮引发剂如偶氮二异丁腈、偶氮二(2-酰胺基丙烷)二盐酸盐或2,2’-偶氮二(2-甲基丁腈)。过氧化物引发剂的实例是过氧化二苯甲酰、过氧化二乙酰、过氧化琥珀酰、过新戊酸叔丁酯、过乙基己酸叔丁酯、过新癸酸叔丁酯、过马来酸叔丁酯、二(叔丁基过氧)环己烷、碳酸叔丁基过氧异丙基酯、过乙酸叔丁基酯、2,2-二(叔丁基过氧)丁烷、过氧化二枯基、过氧化二叔戊基、过氧化二叔丁基、氢过氧化对烷、氢过氧化蒎烷、氢过氧化枯烯、氢过氧化叔丁基、过氧化氢以及所述引发剂的混合物。所述引发剂还可以与氧化还原组分如抗坏血酸组合使用。特别合适的引发剂是过新癸酸叔丁酯、过新戊酸叔丁酯或过乙基己酸叔丁酯。
自由基聚合合适的话可以在乳化剂、合适的话其他保护性胶体、合适的话分子量调节剂、合适的话缓冲剂体系存在下并且合适的话随后使用碱或酸调节pH而进行。
合适的分子量调节剂是巯基化合物如烷基硫醇,例如正十二烷基硫醇、叔十二烷基硫醇、巯基乙酸及其酯,巯基链烷醇如巯基乙醇。其他合适的调节剂例如在DE 197 12 247 A1第4页中提到。分子量调节剂的必要量基于待聚合的(共聚)单体量为0-5重量%。若使用调节剂,则用量尤其为0.05-2重量%,特别优选0.1-1.5重量%。然而,非常特别优选在不存在调节剂下的聚合。
合适的话还可以使用乳化剂,例如HLB通常为3-13的离子性或非离子性表面活性剂。对于HLB的定义,参考W.C.Griffin的出版物,J.Soc.Cosmetic Chem.,第5卷,249(1954)。基于聚合物的表面活性剂的量可以为0-10重量%,优选0-5重量%。
单体或单体混合物或单体的乳液与通常存在于溶液中的引发剂一起在聚合温度下引入搅拌的反应器中(分批方法)或者合适的话连续或在多个接连的步骤中计量加入聚合反应器中(进料方法)。在进料方法中在实际聚合开始之前除了溶剂(以使反应混合物的搅拌成为可能)之外通常还向反应器中加入部分量,少有的情况是聚合所需全部量的原料如乳化剂、保护性胶体、单体、调节剂等或部分量的进料(通常是单体进料或乳液进料和引发剂进料)。
聚合既可以在大气压力下进行也可以在密闭反应器中在升高的压力下进行。此时可以在反应过程中设定的压力下聚合,或者可以通过注入气体或抽空而调节压力。压力还可以通过将反应器部分减压至冷凝器而控制。
用于聚合的非水溶剂随后可以通过蒸汽蒸馏除去并置换为水。这通常导致非水溶剂首先尽可能纯地蒸出,然后通过送入蒸汽而被水完全置换。
在聚合之后,可以使用通常已知的方法来降低残留单体。该类方法的实例是在聚合结束之后进一步加入引发剂,通过加入酸水解乙烯基内酰胺单体,用固相如离子交换剂处理聚合物溶液,供入良好共聚的单体,膜滤和其他常规方法。
所得聚合物水分散体或水溶液的固体含量通常为10-70重量%,优选15-60重量%,特别优选15-40重量%。
聚合物分散体或溶液可以通过各种干燥方法如喷雾干燥、流化喷雾干燥、转鼓干燥、桨叶干燥、带式干燥或冷冻干燥转化成粉末形式或转化成颗粒。可行的是在喷雾干燥过程中加入添加剂如胶体二氧化硅或疏水改性的胶体二氧化硅。该共聚物以水分散体或水溶液得到,或者在除去水分之后以极易自由流动的水分散性或水溶性粉末得到。
该聚合物通常具有的Fikentscher K值在1重量%乙醇溶液中测量为10-60,优选20-50,更优选25-40。
该聚合物可以具有30-12°C,优选50-80°C的玻璃化转变温度。
分子量Mw由凝胶渗透色谱法测量通常为10000-1000000g/mol,优选30000-500000g/mol,更优选60000-300000g/mol。
本发明共聚物可以与其一起使用的下列活性物质用来说明可能的组合,但不限制它们:
A)嗜球果伞素类:
-腈嘧菌酯(azoxystrobin)、丁香菌酯(coumoxystrobin)、甲香菌酯(coumethoxystrobin)、醚菌胺(dimoxystrobin)、烯肟菌酯(enestroburin)、氟嘧菌酯(fluoxastrobin)、亚胺菌(kresoxim-methyl)、叉氨苯酰胺(metominostrobin)、肟醚菌胺(orysastrobin)、啶氧菌酯(picoxystrobin)、唑菌胺酯(pyraclostrobin)、pyrametostrobin、pyraoxystrobin、pyribencarb、肟菌酯(trifloxystrobin)、2-[2-(2,5-二甲基苯氧基甲基)苯基)-3-甲氧基丙烯酸甲酯和2-(2-(3-(2,6-二氯苯基)-1-甲基亚烯丙基氨基氧甲基)苯基)-2-甲氧亚氨基-N-甲基乙酰胺;
B)羧酰胺类:
-羧酰苯胺类:苯霜灵(benalaxyl)、精苯霜灵(benalaxyl-M)、麦锈灵(benodanil)、bixafen、啶酰菌胺(boscalid)、萎锈灵(carboxin)、呋菌胺(fenfuram)、环酰菌胺(fenhexamid)、氟酰胺(flutolanil)、氟唑菌酰胺(fluxapyroxad)、呋吡唑灵(furametpyr)、isopyrazam、异噻菌胺(isotianil)、kiralaxyl、丙氧灭绣胺(mepronil)、甲霜灵(metalaxyl)、精甲霜灵(metalaxyl-M)(mefenoxam)、甲呋酰胺(ofurace)、霜灵(oxadixyl)、氧化萎锈灵(oxycarboxin)、penflufen、吡噻菌胺(penthiopyrad)、sedaxane、叶枯酞(tecloftalam)、溴氟唑菌(thifluzamide)、噻酰菌胺(tiadinil)、2-氨基-4-甲基噻唑-5-甲酰苯胺、N-(4'-三氟甲硫基联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺和N-(2-(1,3,3-三甲基丁基)苯基)-1,3-二甲基-5-氟-1H-吡唑-4-甲酰胺;
-羧酸吗啉化物:烯酰吗啉(dimethomorph)、氟吗啉(flumorph)、丁吡吗啉(pyrimorph);
-苯甲酰胺类:氟联苯菌(flumetover)、氟吡菌胺(fluopicolide)、氟吡菌酰胺(fluopyram)、苯酰菌胺(zoxamide);
-其他羧酰胺类:氯环丙酰胺(carpropamid)、双氯氰菌胺(dicyclomet)、双炔酰菌胺(mandiproamid)、土霉素(oxytetracyclin)、硅噻菌胺(silthiofarm)和N-(6-甲氧基吡啶-3-基)环丙烷甲酰胺;
C)唑类:
-三唑类:戊环唑(azaconazole)、双苯三唑醇(bitertanol)、糠菌唑(bromuconazole)、环唑醇(cyproconazole)、醚唑(difenoconazole)、烯唑醇(diniconazole)、烯唑醇M(diniconazole-M)、氧唑菌(epoxiconazole)、腈苯唑(fenbuconazole)、喹唑菌酮(fluquinconazole)、氟硅唑(flusilazole)、粉唑醇(flutriafol)、己唑醇(hexaconazole)、酰胺唑(imibenconazole)、环戊唑醇(ipconazole)、环戊唑菌(metconazole)、腈菌唑(myclobutanil)、oxpoconazole、多效唑(paclobutrazole)、戊菌唑(penconazole)、丙环唑(propiconazole)、丙硫菌唑(prothioconazole)、硅氟唑(simeconazole)、戊唑醇(tebuconazole)、氟醚唑(tetraconazole)、三唑酮(triadimefon)、唑菌醇(triadimenol)、戊叉唑菌(triticonazole)、烯效唑(uniconazole);
-咪唑类:氰霜唑(cyazofamid)、抑霉唑(imazalil)、稻瘟酯(pefurazoate)、丙氯灵(prochloraz)、氟菌唑(triflumizol);
-苯并咪唑类:苯菌灵(benomyl)、多菌灵(carbendazim)、麦穗宁(fuberidazole)、涕必灵(thiabendazole);
-其他:噻唑菌胺(ethaboxam)、氯唑灵(etridiazole)、土菌消(hymexazole)和2-(4-氯苯基)-N-[4-(3,4-二甲氧基苯基)异唑-5-基]-2-丙-2-炔氧基乙酰胺;
D)杂环化合物
-吡啶类:氟啶胺(fluazinam)、啶斑肟(pyrifenox)、3-[5-(4-氯苯基)-2,3-二甲基异唑烷-3-基]吡啶、3-[5-(4-甲基苯基)-2,3-二甲基异唑烷-3-基]吡啶;
-嘧啶类:磺嘧菌灵(bupirimate)、环丙嘧啶(cyprodinil)、二氟林(diflumetorim)、异嘧菌醇(fenarimol)、嘧菌腙(ferimzone)、嘧菌胺(mepanipyrim)、氯草定(nitrapyrin)、氟苯嘧啶醇(nuarimol)、二甲嘧菌胺(pyrimethanil);
-哌嗪类:嗪氨灵(triforine);
-吡咯类:氟菌(fludioxonil)、拌种咯(fenpiclonil);
-吗啉类:4-十二烷基-2,6-二甲基吗啉(aldimorph)、吗菌灵(dodemorph)、吗菌灵乙酸酯(dodemorph-acetate)、丁苯吗啉(fenpropimorph)、克啉菌(tridemorph);
-哌啶类:苯锈啶(fenpropidin);
-二羧酰亚胺类:氟菌安(fluorimid)、异丙定(iprodione)、杀菌利(procymidone)、烯菌酮(vinclozolin);
-非芳族5员杂环:唑酮菌(famoxadone)、咪唑菌酮(fenamidone)、flutianil、异噻菌酮(octhilinone)、噻菌灵(probenazole)、5-氨基-2-异丙基-3-氧代-4-邻甲苯基-2,3-二氢吡唑-1-硫代甲酸S-烯丙基酯;
-其他:噻二唑素(acibenzolar-S-methyl)、唑嘧菌胺(ametoctradin)、amisulbrom、敌菌灵(anilazin)、灭瘟素(blasticidin-S)、敌菌丹(captafol)、克菌丹(captan)、灭螨蜢(chinomethionat)、棉隆(dazomet)、咪菌威(debacarb)、哒菌清(diclomezine)、野燕枯(difenzoquat)、野燕枯甲基硫酸酯(difenzoquat-methylsulfate)、氰菌胺(fenoxanil)、灭菌丹(folpet)、恶喹酸(oxolinic acid)、粉病灵(piperalin)、丙氧喹啉(proquinazid)、咯喹酮(pyroquilon)、喹氧灵(quinoxyfen)、唑菌嗪(triazoxide)、三环唑(tricyclazole)、2-丁氧基-6-碘-3-丙基苯并吡喃-4-酮、5-氯-1-(4,6-二甲氧基嘧啶-2-基)-2-甲基-1H-苯并咪唑和5-氯-7-(4-甲基哌啶-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶;
E)氨基甲酸酯类
-硫代-和二硫代氨基甲酸酯类:福美铁(ferbam)、代森锰锌(mancozeb)、代森锰(maneb)、威百亩(metam)、磺菌威(methasulphocarb)、代森联(metiram)、甲基代森锌(propineb)、福美双(thiram)、代森锌(zineb)、福美锌(ziram);
-氨基甲酸酯类:苯噻菌胺(benthiavalicarb)、乙霉威(diethofencarb)、异丙菌胺(iprovalicarb)、百维灵(propamocarb)、霜霉威盐酸盐(propamocarb hydrochlorid)、valiphenal和N-(1-(1-(4-氰基苯基)乙磺酰基)丁-2-基)氨基甲酸4-氟苯基酯;
F)其他活性物质
-胍类:胍、多果定(dodine)、多果定游离碱、双胍盐(guazatine)、双胍辛胺(guazatine-acetate)、双胍辛醋酸盐(iminoctadine)、双胍辛胺三乙酸盐(iminoctadine-triacetate)、双八胍盐(iminoctadine-tris(albesilate));
-抗生素类:春雷素(kasugamycin)、水合春雷素(kasugamycinhydrochloride-hydrate)、链霉素(streptomycin)、多氧霉素(polyoxine)、井冈霉素(validamycin A);
-硝基苯基衍生物:乐杀螨(binapacryl)、氯硝胺(dicloran)、敌螨通(dinobuton)、敌螨普(dinocap)、异丙消(nitrothal-isopropyl)、四氯硝基苯(tecnazen);
-有机金属化合物:三苯锡基盐,例如薯瘟锡(fentin-acetate)、三苯锡氯(fentin chloride)或毒菌锡(fentin hydroxide);
-含硫杂环化合物:二噻农(dithianon)、稻瘟灵(isoprothiolane);
-有机磷化合物:克瘟散(edifenphos)、藻菌磷(fosetyl)、乙磷铝(fosetyl-aluminum)、异稻瘟净(iprobenfos)、亚磷酸及其盐、定菌磷(pyrazophos)、甲基立枯磷(tolclofos-methyl);
-有机氯化合物:百菌清(chlorothalonil)、抑菌灵(dichlofluanid)、双氯酚(dichlorphen)、磺菌胺(flusulfamide)、六氯苯(hexachlorobenzene)、戊菌隆(pencycuron)、五氯酚(pentachlorphenole)及其盐、四氯苯酞(phthalide)、五氯硝基苯(quintozene)、甲基托布津(thiophanate-methyl)、对甲抑菌灵(tolylfluanid)、N-(4-氯-2-硝基苯基)-N-乙基-4-甲基苯磺酰胺;
-无机活性物质:波尔多液(Bordeaux混合物)、醋酸铜、氢氧化铜、王铜(copper oxychloride)、碱式硫酸铜,硫;
-抗真菌的生物控制剂、植物生物活化剂:白粉寄生孢(Ampelomycesquisqualis)(例如来自德国Intrachem Bio GmbH & Co.KG的AQ黄曲霉(Aspergillus flavus)(例如来自Syngenta,CH的出芽短梗霉(Aureobasidium pullulans)(例如来自德国bio-ferm GmbH的短小芽孢杆菌(Bacillus pumilus)(例如来自AgraQuestInc.,USA的和Plus,NRRL Accession No.B-30087),枯草芽孢杆菌(Bacillus subtilis)(例如来自AgraQuest Inc.,USA的MAX和ASO,分离物NRRL-Nr.B-21661),解淀粉芽孢杆菌(Bacillus subtilis var.amylolique-faciens)FZB24(例如来自Novozyme Biologicals,Inc.,USA的橄榄假丝酵母(Candida oleophila)I-82(例如来自EcogenInc.,USA的Candida saitoana(例如来自Micro Flo Company,USA(BASF SE)和Arysta的(呈与溶菌酶的混合物)和脱乙酰壳多糖(例如来自新西兰BotriZen Ltd.,NZ的ARMOUR-ZEN),Clonostachys rosea f.catenulata,也称链孢粘帚霉(Gliocladium catenulatum)(例如来自芬兰Verdera的分离物J1446:盾壳霉(Coniothyrium minitans)(例如来自德国Prophyta的寄生隐丛赤壳菌(Cryphonectria parasitica)(例如来自法国CNICM的栗疫菌(Endothia parasitica)),白色隐球菌(Cryptococcusalbidus)(例如来自南非Anchor Bio-Technologies的YIELD尖孢镰刀菌(Fusarium oxysporum)(例如来自意大利S.I.A.P.A.的来自法国Natural Plant Protection的核果梅奇酵母(Metschnikowia fructicola)(例如来自以色列Agrogreen的Microdochium dimerum(例如来自法国Agrauxine的Phlebiopsis gigantea(例如来自芬兰Verdera的Pseudozymaflocculosa(例如来自加拿大Plant Products Co.Ltd.的寡雄腐霉(Pythium oligandrum)DV74(例如来自捷克共和国RemesloSSRO,Biopreparaty的Reynoutria sachlinensis(例如来自Marrone BioInnovations,USA的黄蓝状菌(Talaromyces flavus)V117b(例如来自德国Prophyta的棘孢木霉(Trichoderma asperellum)SKT-1(例如来自日本Kumiai ChemicalIndustry Co.,Ltd.的深绿木霉(T.atroviride)LC52(例如来自Agrimm Technologies Ltd,NZ的哈茨木霉(T.harzianum)T-22(例如来自Firma BioWorks Inc.,USA的哈茨木霉(T.harzianum)TH 35(例如来自以色列Mycontrol Ltd.的哈茨木霉(T.harzianum)T-39(例如来自以色列Mycontrol Ltd.和以色列Makhteshim Ltd.的和TRICHODERMA哈茨木霉(T.harzianum)和绿色木霉(T.viride)(例如来自Agrimm Technologies Ltd,NZ的TRICHOPEL),哈茨木霉(T.harzianum)ICC012和绿色木霉(T.viride)ICC080(例如来自意大利Isagro Ricerca的WP),多孔木霉(T.polysporum)和哈茨木霉(T.harzianum)(例如来自瑞典BINAB Bio-Innovation AB的钩木霉(T.stromaticum)(例如来自巴西C.E.P.L.A.C.的绿木霉(T.virens)GL-21(例如来自Certis LLC,USA的绿色木霉(T.viride)(例如来自印度Ecosense Labs.(India)Pvt.Ltd.的来自印度T.Stanes & Co.Ltd.的绿色木霉(T.viride)TV1(例如来自意大利Agribiotec srl的绿色木霉(T.viride)TV1),奥德曼细基格孢(Ulocladium oudemansii)HRU3(例如来自Botry-Zen Ltd,NZ的
-其他:联苯、拌棉醇(bronopol)、环氟菌胺(cyflufenamid)、清菌脲(cymoxanil)、二苯胺、苯菌酮(metrafenone)、pyriofenone、米多霉素(mildiomycin)、喹啉铜(oxin-copper)、调环酸钙(prohexadione-calcium)、螺茂胺(spiroxamine)、tebufloquin、对甲抑菌灵、N-(环丙基甲氧亚氨基-(6-二氟甲氧基-2,3-二氟苯基)甲基)-2-苯基乙酰胺、N'-(4-(4-氯-3-三氟甲基苯氧基)-2,5-二甲基苯基)-N-乙基-N-甲基甲脒、N'-(4-(4-氟-3-三氟甲基苯氧基)-2,5-二甲基苯基)-N-乙基-N-甲基甲脒、N'-(2-甲基-5-三氟甲基-4-(3-三甲基硅烷基丙氧基)苯基)-N-乙基-N-甲基甲脒、N'-(5-二氟甲基-2-甲基-4-(3-三甲基硅烷基丙氧基)苯基)-N-乙基-N-甲基甲脒、2-{1-[2-(5-甲基-3-三氟甲基吡唑-1-基)乙酰基]哌啶-4-基}噻唑-4-甲酸甲基-(1,2,3,4-四氢萘-1-基)酰胺、2-{1-[2-(5-甲基-3-三氟甲基吡唑-1-基)乙酰基]哌啶-4-基}噻唑-4-甲酸甲基-(R)-(1,2,3,4-四氢萘-1-基)酰胺、甲氧基乙酸6-叔丁基-8-氟-2,3-二甲基喹啉-4-基酯和N-甲基-2-{1-[2-(5-甲基-3-三氟甲基-1H-吡唑-1-基)乙酰基]哌啶-4-基}-N-[(1R)-1,2,3,4-四氢萘-1-基)-4-噻唑甲酰胺;
G)生长调节剂
脱落酸(abscisic acid)、先甲草胺(amidochlor)、嘧啶醇(ancymidol)、苄胺基嘌呤(6-benzylaminopurine)、油菜素内酯(brassinolide)、地乐胺(butralin)、矮壮素阳离子(chlormequat)(矮壮素(chlormequat chloride))、氯化胆碱(choline chloride)、环丙酸酰胺(cyclanilide)、丁酰肼(daminozide)、敌草克(dikegulac)、噻节因(dimethipin)、2,6-二甲基吡啶(2,6-dimethylpuridine)、乙烯利(ethephon)、抑芽敏(flumetralin)、呋嘧醇(flurprimidol)、达草氟(fluthiacet)、调吡脲(forchlorfenuron)、九二O(gibberellic acid)、抗倒胺(inabenfide)、吲哚-3-乙酸、抑芽丹(maleichydrazide)、氟草磺(mefluidide)、助壮素阳离子(mepiquat)(助壮素(mepiquat chloride))、萘乙酸、N-6-苄基腺嘌呤、多效唑、调环酸(prohexadione)(调环酸钙)、茉莉酸丙酯(prohydrojasmone)、赛二唑素(thidiazuron)、抑芽唑(triapenthenol)、脱叶磷(tributylphosphorotrithioate)、2,3,5-三碘苯甲酸、抗倒酯(trinexapac-ethyl)和烯效唑;
H)除草剂
-乙酰胺类:乙草胺(acetochlor)、甲草胺(alachlor)、丁草胺(butachlor)、克草胺(dimethachlor)、噻吩草胺(dimethenamid)、氟噻草胺(flufenacet)、苯噻草胺(mefenacet)、异丙甲草胺(metolachlor)、吡草胺(metazachlor)、草萘胺(napropamide)、萘丙胺(naproanilide)、烯草胺(pethoxamid)、丙草胺(pretilachlor)、扑草胺(propachlor)、噻醚草胺(thenylchlor);
-氨基酸衍生物:双丙氨酰膦(bilanafos)、草甘膦(glyphosate)、草铵膦(glufosinate)、草硫膦(sulfosate);
-芳氧基苯氧基丙酸酯类:炔草酯(clodinafop)、氰氟草酯(cyhalofop-butyl)、唑禾草灵(fenoxaprop)、吡氟禾草灵(fluazifop)、吡氟氯禾灵(haloxyfop)、恶唑酰草胺(metamifop)、喔草酯(propaquizafop)、喹禾灵(quizalofop)、喹禾灵(四氢糠基酯)(quizalofop-p-tefuryl);
-联吡啶类:敌草快阳离子(diquat)、对草快阳离子(paraquat);
-(硫代)氨基甲酸酯类:黄草灵(asulam)、苏达灭(butylate)、长杀草(carbetamide)、异苯敌草(desmedipham)、哌草丹(dimepiperate)、扑草灭(eptam)(EPTC)、禾草畏(esprocarb)、草达灭(molinate)、坪草丹(orbencarb)、苯敌草(phenmedipham)、苄草丹(prosulfocarb)、稗草畏(pyributicarb)、杀草丹(thiobencarb)、野麦畏(triallate);
-环己二酮类:丁氧环酮(butroxydim)、烯草酮(clethodim)、噻草酮(cycloxydim)、环苯草酮(profoxydim)、稀禾定(sethoxydim)、醌肟草(tepraloxydim)、肟草酮(tralkoxydim);
-二硝基苯胺类:氟草胺(benfluralin)、丁氟消草(ethalfluralin)、黄草消(oryzalin)、胺硝草(pendimethalin)、氨基丙氟灵(prodiamine)、氟乐灵(trifluralin);
-二苯基醚类:氟锁草醚(acifluorfen)、苯草醚(aclonifen)、治草醚(bifenox)、氯甲草(diclofop)、氯氟草醚(ethoxyfen)、氟黄胺草醚(fomesafen)、乳氟禾草灵(lactofen)、乙氧氟草醚(oyfluorfen);
-羟基苄腈类:溴苯腈(bromoxynil)、敌草腈(dichlobenil)、碘苯腈(ioxynil);
-咪唑啉酮类:咪草酯(imazamethabenz)、咪草啶酸(imazamox)、甲基咪草烟(imazapic)、灭草烟(imazapyr)、灭草喹(imazaquin)、咪草烟(imazethapyr);
-苯氧基乙酸类:稗草胺(clomeprop)、2,4-二氯苯氧基乙酸(2,4-D)、2,4-DB、2,4-滴丙酸(dichlorprop)、MCPA、2甲4氯乙硫酯(MCPA-thioethyl)、MCPB、2甲4氯丙酸(mecoprop);
-吡嗪类:杀草敏(chloridazon)、氟哒嗪草酯(flufenpyr-ethyl)、达草氟、达草灭(norflurazon)、达草止(pyridate);
-吡啶类:氨草啶(aminopyralid)、二氯皮考啉酸(clopyralid)、吡氟草胺(diflufenican)、氟硫草定(dithiopyr)、氟草同(fluridone)、氟草烟(fluroxypyr)、毒莠定(picloram)、氟吡酰草胺(picolinafen)、噻氟啶草(thiazopyr);
-磺酰脲类:磺氨黄隆(amidosulfuron)、四唑黄隆(azimsulfuron)、苄嘧黄隆(bensulfuron)、氯嘧黄隆(chlorimuron-ethyl)、绿黄隆(chlorsulfuron)、醚黄隆(cinosulfuron)、环丙黄隆(cyclosulfamuron)、乙氧嘧黄隆(ethoxysulfuron)、啶嘧黄隆(flazasulfuron)、氟吡磺隆(flucetosulfuron)、氟啶黄隆(flupyrsulfuron)、酰胺磺隆(foramsulfuron)、吡氯黄隆(halosulfuron)、啶咪黄隆(imazosulfuron)、甲基碘磺隆(iodosulfuron)、甲磺胺磺隆(mesosulfuron)、双醚氯吡嘧磺隆(metazosulfuron)、甲黄隆(metsulfuron-methyl)、烟嘧黄隆(nicosulfuron)、环丙氧黄隆(oxasulfuron)、氟嘧黄隆(primisulfuron)、氟丙黄隆(prosulfuron)、吡嘧黄隆(pyrazosulfuron)、玉嘧黄隆(rimsulfuron)、嘧黄隆(sulfometuron)、乙黄黄隆(sulfosulfuron)、噻黄隆(thifensulfuron)、醚苯黄隆(triasulfuron)、苯黄隆(tribenuron)、三氟啶磺隆(trifloxysulfuron)、氟胺磺隆(triflusulfuron)、三氟甲磺隆(tritosulfuron)、1-((2-氯-6-丙基咪唑并[1,2-b]哒嗪-3-基)磺酰基)-3-(4,6-二甲氧基嘧啶-2-基)脲;
-三嗪类:莠灭净(ametryn)、莠去津(atrazine)、草净津(cyanazine)、戊草津(dimethametryn)、乙嗪草酮(ethiozin)、六嗪同(hexazinone)、苯嗪草(metamitron)、赛克津(metribuzin)、扑草净(prometryn)、西玛津(simazine)、特丁津(terbuthylazine)、去草净(terbutryn)、苯氧丙胺津(triaziflam);
-脲类:绿麦隆(chlorotoluron)、香草隆(daimuron)、敌草隆(diuron)、伏草隆(fluometuron)、异丙隆(isoproturon)、利谷隆(linuron)、噻唑隆(methabenzthiazuron)、丁唑隆(tebuthiuron);
-其他乙酰乳酸合成酶抑制剂:双草醚钠盐(bispyribac-sodium)、氯酯磺草胺(cloransulam-methyl)、唑嘧磺胺(diclosulam)、双氟磺草胺(florasulam)、氟酮磺隆(flucarbazone)、氟唑啶草(flumetsulam)、唑草磺胺(metosulam)、嘧苯胺磺隆(ortho-sulfamuron)、五氟磺草胺(penoxsulam)、丙氧基卡巴腙(propoxycarbazone)、丙酯草醚(pyribambenz-propyl)、嘧苯草肟(pyribenzoxim)、环酯草醚(pyriftalid)、肟啶草(pyriminobac-methyl)、pyrimisulfan、嘧硫苯甲酸(pyrithiobac)、pyroxasulfone、甲氧磺草胺(pyroxsulam);
-其他:胺唑草酮(amicarbazone)、三唑胺(aminotriazole)、莎稗磷(anilofos)、beflubutamid、草除灵(benazolin)、bencarbazone、benfluresate、吡草酮(benzofenap)、噻草平(bentazone)、苯并双环酮(benzobicyclon)、bicyclopyrone、除草定(bromacil)、溴丁酰草胺(bromobutide)、氟丙嘧草酯(butafenacil)、草胺磷(butamifos)、胺草唑(cafenstrole)、氟酮唑草(carfentrazone)、吲哚酮草酯(cinidon-ethyl)、敌草索(chlorthal)、环庚草醚(cinmethylin)、异恶草酮(clomazone)、苄草隆(cumyluron)、cyprosulfamide、麦草畏(dicamba)、苯敌快(difenzoquat)、二氟吡隆(diflufenzopyr)、稗内脐蠕孢菌(Drechslera monoceras)、敌草腈(endothal)、乙呋草黄(ethofumesate)、乙苯酰草(etobenzanid)、fenoxasulfone、四唑酰草胺(fentrazamide)、氟烯草酸(flumiclorac-pentyl)、氟嗪酮(flumioxazin)、胺草唑(flupoxam)、氟咯草酮(fluorochloridone)、呋草酮(flurtamone)、茚草酮(indanofan)、异恶草胺(isoxaben)、异氟草(isoxaflutole)、环草定(lenacil)、敌稗(propanil)、拿草特(propyzamide)、二氯喹啉酸(quinclorac)、喹草酸(quinmerac)、硝草酮(mesotrione)、甲胂酸(methylarsonic acid)、抑草生(naptalam)、炔丙唑草(oxadiargyl)、恶草灵(oxadiazon)、氯嗪草(oxaziclomefone)、戊唑草(pentoxazone)、唑啉草酯(pinoxaden)、双唑草腈(pyraclonil)、吡草醚(pyraflufen-ethyl)、pyrasulfotole、苄草唑(pyrazoxyfen)、吡唑特(pyrazolynate)、灭藻醌(quinoclamine)、嘧啶肟草醚(saflufenacil)、磺草酮(sulcotrione)、磺胺草唑(sulfentrazone)、特草定(terbacil)、tefuryltrione、tembotrione、thiencarbazone、topramezone、(3-[2-氯-4-氟-5-(3-甲基-2,6-二氧代-4-三氟甲基-3,6-二氢-2H-嘧啶-1-基)苯氧基]吡啶-2-基氧基)乙酸乙酯、6-氨基-5-氯-2-环丙基嘧啶-4-甲酸甲酯、6-氯-3-(2-环丙基-6-甲基苯氧基)哒嗪-4-醇、4-氨基-3-氯-6-(4-氯苯基)-5-氟吡啶-2-甲酸、4-氨基-3-氯-6-(4-氯-2-氟-3-甲氧基苯基)吡啶-2-甲酸甲酯和4-氨基-3-氯-6-(4-氯-3-二甲基氨基-2-氟苯基)吡啶-2-甲酸甲酯;
I)杀虫剂:
-有机(硫代)磷酸酯类:高灭磷(acephate)、唑啶磷(azamethiphos)、谷硫磷(azinphos-methyl)、毒死蜱(chlorpyrifos)、甲基毒死蜱(chlorpyrifos-methyl)、毒虫畏(chlorfenvinphos)、二嗪农(diazinon)、敌敌畏(dichlorvos)、百治磷(dicrotophos)、乐果(dimethoate)、乙拌磷(disulfoton)、乙硫磷(ethion)、杀螟松(fenitrothion)、倍硫磷(fenthion)、异唑磷(isoxathion)、马拉硫磷(malathion)、甲胺磷(methamidophos)、杀扑磷(methidathion)、甲基对硫磷(methyl-parathion)、速灭磷(mevinphos)、久效磷(monocrotophos)、砜吸磷(oxydemeton-methyl)、对氧磷(paraoxon)、一六零五(parathion)、稻丰散(phenthoate)、伏杀硫磷(phosalone)、亚胺硫磷(phosmet)、磷胺(phosphamidon)、甲拌磷(phorate)、辛硫磷(phoxim)、虫螨磷(pirimiphos-methyl)、丙溴磷(profenofos)、丙硫磷(prothiofos)、田乐磷(sulprophos)、杀虫威(tetrachlorvinphos)、特丁磷(terbufos)、三唑磷(triazophos)、敌百虫(trichlorfon);
-氨基甲酸酯类:棉铃威(alanycarb)、涕灭威(aldicarb)、虫威(bendiocarb)、丙硫克百威(benfuracarb)、甲萘威(carbaryl)、虫螨威(carbofuran)、丁硫克百威(carbosulfan)、双氧威(fenoxycarb)、呋线威(furathiocarb)、灭虫威(methiocarb)、灭多虫(methomyl)、甲氨叉威(oxamyl)、抗蚜威(pirimicarb)、残杀威(propoxur)、硫双威(thiodicarb)、唑蚜威(triazamate);
-合成除虫菊酯类:丙烯除虫菊(allethrin)、氟氯菊酯(bifenthrin)、氟氯氰菊酯(cyfluthrin)、(RS)氯氟氰菊酯(cyhalothrin)、苯醚氰菊酯(cyphenothrin)、氯氰菊酯(cypermethrin)、甲体氯氰菊酯(alpha-cypermethrin)、乙体氯氰菊酯(beta-cypermethrin)、己体氯氰菊酯(zeta-cypermethrin)、溴氰菊酯(deltamethrin)、高氰戊菊酯(esfenvalerate)、醚菊酯(etofenprox)、甲氰菊酯(fenpropathrin)、杀灭菊酯(fenvalerate)、咪炔菊酯(imiprothrin)、氯氟氰菊酯(lambda-cyhalothrin)、氯菊酯(permethrin)、炔酮菊酯(prallethrin)、除虫菊(pyrethrin)I和II、灭虫菊(resmethrin)、灭虫硅醚(silafluofen)、氟胺氰菊酯(tau-fluvalinate)、七氟菊酯(tefluthrin)、胺菊酯(tetramethrin)、四溴菊酯(tralomethrin)、四氟菊酯(transfluthrin)、丙氟菊酯(profluthrin)、四氟甲醚菊酯(dimefluthrin);
-昆虫生长抑制剂:a)几丁质合成抑制剂:苯甲酰脲类:定虫隆(chlorfluazuron)、灭蝇胺(cyramazin)、氟脲杀(diflubenzuron)、氟螨脲(flucycloxuron)、氟虫脲(flufenoxuron)、氟铃脲(hexaflumuron)、氟丙氧脲(lufenuron)、双苯氟脲(novaluron)、伏虫隆(teflubenzuron)、杀虫隆(triflumuron);噻嗪酮(buprofezin)、茂醚(diofenolan)、噻螨酮(hexythiazox)、特苯唑(etoxazole)、四螨嗪(clofentazine);b)蜕皮激素拮抗剂:特丁苯酰肼(halofenozide)、甲氧苯酰肼(methoxyfenozide)、双苯酰肼(tebufenozide)、艾扎丁(azadirachtin);c)保幼激素类似物:蚊蝇醚(pyriproxyfen)、蒙五一五(methoprene)、双氧威;d)类脂生物合成抑制剂:螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)、螺虫乙酯(spirotetramat);
-烟碱受体激动剂/拮抗剂化合物:噻虫胺(clothianidin)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)、噻虫嗪(thiamethoxam)、硝胺烯啶(nitenpyram)、吡虫清(acetamiprid)、噻虫啉(thiacloprid)、1-(2-氯噻唑-5-基甲基)-2-硝酰亚氨基(nitrimino)-3,5-二甲基-[1,3,5]三嗪烷(triazinane);
-GABA拮抗剂化合物:硫丹(endosulfan)、乙虫清(ethiprole)、锐劲特(fipronil)、氟吡唑虫(vaniliprole)、pyrafluprole、pyriprole、5-氨基-1-(2,6-二氯-4-甲基苯基)-4-亚磺酰氨酰基(sulfinamoyl)-1H-吡唑-3-硫代甲酰胺;
-大环内酯杀虫剂:齐墩螨素(abamectin)、甲氨基阿维菌素(emamectin)、米尔螨素(milbemectin)、lepimectin、艾克敌105(spinosad)、乙基多杀菌素(spinetoram);
-线粒体电子传输抑制剂(METI)I杀螨剂:喹螨醚(fenazaquin)、哒螨酮(pyridaben)、吡螨胺(tebufenpyrad)、唑虫酰胺(tolfenpyrad)、嘧虫胺(flufenerim);
-METI II和III物质:灭螨醌(acequinocyl)、fluacyprim、灭蚁腙(hydramethylnon);
-解偶联剂:氟唑虫清(chlorfenapyr);
-氧化磷酸化抑制剂:三环锡(cyhexatin)、杀螨硫隆(diafenthiuron)、杀螨锡(fenbutatin oxide)、克螨特(propargite);
-昆虫蜕皮干扰剂化合物:灭蝇胺(cryomazine);
-混合功能氧化酶抑制剂:增效醚(piperonyl butoxide);
-钠通道阻断剂:二唑虫(indoxacarb)、氰氟虫胺(metaflumizone);
-其他:benclothiaz、联苯肼酯(bifenazate)、杀螟丹(cartap)、氟啶虫酰胺(flonicamid)、啶虫丙醚(pyridalyl)、拒嗪酮(pymetrozine)、硫、硫环杀(thiocyclam)、氟虫酰胺(flubendiamide)、氯虫酰胺(chlorantraniliprole)、cyazypyr(HGW86)、cyenopyrafen、吡氟硫磷(flupyrazofos)、丁氟螨酯(cyflumetofen)、amidoflumet、imicyafos、双三氟虫脲(bistrifluron)和pyrifluquinazon。
该农药优选具有至少30°C,更优选至少50°C,尤其是至少70°C的熔点。
该农药在20°C下在水中优选具有小于10g/l,更优选小于1g/l,甚至更优选小于0.5g/l,最优选小于0.1g/l的溶解度。
该农药可以以任何形式存在,例如以液体或固体存在。优选该农药以溶解或分散(例如悬浮或乳化)形式存在。
该接枝聚合物的量基于该农药的重量通常为5-1000重量%,优选10-500重量%,更优选20-100重量%。
本发明共聚物和组合物在各种栽培植物,如禾谷类,例如小麦、黑麦、大麦、小黑麦、燕麦或稻;甜菜,例如糖用甜菜或饲料甜菜;水果,如仁果、核果或浆果,例如苹果、梨、李、桃、杏仁、樱桃、草莓、悬钩子、黑莓或鹅莓;豆科植物,例如扁豆、豌豆、苜蓿或大豆;油料植物,例如油菜、芥菜、橄榄、向日葵、椰子、可可豆、蓖麻油植物、油棕、花生或大豆;葫芦科植物,例如南瓜、黄瓜或甜瓜;纤维植物,例如棉花、亚麻、大麻或黄麻;柑桔类水果,例如橙子、柠檬、葡萄柚或橘;蔬菜,例如菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、西红柿、土豆、葫芦或柿子椒;月桂类植物,例如鳄梨、肉桂或樟脑;能量和原料植物,例如玉米、大豆、油菜、甘蔗或油棕;玉米;烟草;坚果;咖啡;茶;香蕉;葡萄藤(食用葡萄和酿酒用葡萄);啤酒花;草坪;甜叶菊(也称Stevia);天然橡胶植物或观赏和森林植物,例如花卉、灌木、阔叶树或常绿树,以及植物繁殖材料如种子和这些植物的作物材料上特别重要。
优选的栽培植物是水果,如仁果、核果或浆果,例如苹果、梨、李、桃、杏仁、樱桃、草莓、悬钩子、黑莓或鹅莓;葫芦科植物,例如南瓜、黄瓜或甜瓜;柑桔类水果,例如橙子、柠檬、葡萄柚或橘;蔬菜,例如菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、西红柿、土豆、葫芦或柿子椒;月桂类植物,例如鳄梨、肉桂或樟脑;坚果;咖啡;茶;香蕉;葡萄藤(食用葡萄和酿酒用葡萄);啤酒花;观赏和森林植物,如花卉、灌木、阔叶树或常绿树,例如针叶树。最优选葡萄藤、水果和蔬菜。
术语“植物繁殖材料”应理解为表示植物的所有繁殖部分如种子,以及可以用于繁殖植物的无性植物材料如插条和块茎(例如土豆)。这包括种子、根、果实、块茎、球茎、地下茎、嫩枝、芽和其他植物部分,包括在萌发后或出苗后由土壤移植的秧苗和幼苗。这些幼苗可以在移栽之前通过浸渍或浇灌以完全或部分处理而保护。
术语“栽培植物”应理解为包括已经通过育种、诱变或基因工程修饰的植物,包括但不限于上市销售或正在开发的农业生物技术产品。基因修饰植物是其基因材料通过使用在自然条件下不易通过杂交、突变或自然重组得到的重组DNA技术修饰的植物。通常将一个或多个基因整合到基因修饰植物的基因材料中以改善植物的某些性能。这类基因修饰还包括但不限于蛋白质、寡肽或多肽的靶向翻译后修饰,例如通过糖基化或聚合物加成如异戊二烯化、乙酰化或法呢基化结构部分或PEG结构部分。
本发明进一步涉及一种包含农药和可以通过包含如下单体的单体混合物自由基聚合而得到的接枝共聚物的组合物:
i)30-80重量%N-乙烯基吡咯烷酮、N-乙烯基内酰胺或其混合物,
ii)10-50重量%乙酸乙烯酯,和
iii)10-50重量%聚醚。
组分i)、ii)、iii)以及任选额外的共聚单体的量在该单体混合物中通常加起来为100%。优选组分i)、ii)和iii)在该单体混合物中加起来为100%。该接枝共聚物和该农药的优选实施方案如上所述。
本发明进一步涉及一种通过将该农药和该接枝共聚物混合而制备本发明组合物的方法。各组分的混合可以通过常规设备在任何温度下,例如在室温下实现。优选的混合方法是用于制备农业化学组合物的那些。
本发明进一步涉及一种防治植物病原性真菌和/或不希望的植物生长和/或不希望的昆虫或螨虫侵袭和/或调节植物生长的方法,其中使本发明组合物作用于特定害虫、其栖息地或要防止所述特定害虫的植物、土壤和/或不希望的植物和/或有用植物和/或其生长地。
本发明接枝共聚物和/或组合物可以转化成常规类型的农业化学组合物,例如溶液、乳液、悬浮液、粉剂、粉末、糊和颗粒。组合物类型取决于特定的意欲目的;在每种情况下应确保本发明化合物精细和均匀地分布。组合物类型实例是悬浮液(SC,OD,FS),可乳化浓缩物(EC),乳液(EW,EO,ES),糊,锭剂,可湿性粉末或粉剂(WP,SP,SS,WS,DP,DS)或可以呈水溶性或可湿性的颗粒(GR,FG,GG,MG),以及用于处理植物繁殖材料如种子的凝胶配制剂(GF)。组合物类型(例如SC,OD,FS,EC,WG,SG,WP,SP,SS,WS,GF)通常以稀释形式使用。组合物类型如DP,DS,GR,FG,GG和MG通常以未稀释形式使用。优选本发明组合物为悬浮液。
该农药可以以任何形式存在于该农业化学组合物中,例如以液体或固体。优选该农药以在溶剂中的溶解形式或者以分散(例如悬浮或乳化)形式存在于含水农业化学组合物中。更优选该农药悬浮于含水农业化学组合物中。
该农业化学组合物还可以包含常用于农业化学组合物的辅助剂。所用辅助剂分别取决于特定施用形式和活性物质。合适辅助剂的实例是溶剂、固体载体、分散剂或乳化剂(如其他加溶剂、保护性胶体、表面活性剂和粘附剂),有机和无机增稠剂,杀菌剂,防冻剂,消泡剂,合适的话还有着色剂和增粘剂或粘合剂(例如用于种子处理配制剂)。
合适的溶剂是水,有机溶剂如中到高沸点的矿物油馏分如煤油或柴油,此外还有煤焦油和植物或动物来源的油,脂族、环状和芳族烃类,例如甲苯、二甲苯、石蜡、四氢化萘、烷基化萘或其衍生物,醇类如甲醇、乙醇、丙醇、丁醇和环己醇,二醇类,酮类如环己酮和γ-丁内酯,脂肪酸二甲基酰胺,脂肪酸和脂肪酸酯以及强极性溶剂,例如胺类如N-甲基吡咯烷酮。
固体载体为矿土如硅酸盐、硅胶、滑石、高岭土、石灰石、石灰、白垩、红玄武土、黄土、粘土、白云石、硅藻土、硫酸钙、硫酸镁、氧化镁;磨碎的合成材料;肥料如硫酸铵、磷酸铵、硝酸铵、脲类;以及植物来源的产品如谷粉、树皮粉、木粉和坚果壳粉,纤维素粉和其他固体载体。
合适的表面活性剂(辅助剂、润湿剂、增粘剂、分散剂或乳化剂)是芳族磺酸如木素磺酸类型,挪威Borregaard)、苯酚磺酸、萘磺酸类型,Akzo Nobel,USA)和二丁基萘磺酸(类型,德国BASF)及脂肪酸的碱金属、碱土金属和铵盐,烷基磺酸盐,烷基芳基磺酸盐,烷基硫酸盐,月桂基醚硫酸盐,脂肪醇硫酸盐,以及硫酸化十六-、十七-和十八烷醇化物,硫酸化脂肪醇乙二醇醚,此外还有萘或萘磺酸与苯酚和甲醛的缩合物,聚氧乙烯辛基苯基醚,乙氧基化异辛基酚、辛基酚或壬基酚,烷基苯基聚乙二醇醚,三丁基苯基聚乙二醇醚,三硬脂基苯基聚乙二醇醚,烷基芳基聚醚醇,醇和脂肪醇/氧化乙烯缩合物,乙氧基化蓖麻油,聚氧乙烯烷基醚,乙氧基化聚氧丙烯,月桂醇聚乙二醇醚缩醛,山梨醇酯,木素亚硫酸盐废液,以及蛋白质,变性蛋白,多糖(例如甲基纤维素),疏水改性淀粉,聚乙烯醇类型,瑞士Clariant),聚羧酸盐类型,德国BASF),聚烷氧基化物,聚乙烯胺类型,德国BASF),聚乙烯吡咯烷酮及其共聚物。
增稠剂(即赋予组合物以改性的流动性,即静止条件下的高粘度和搅动过程中的低粘度的化合物)实例是多糖以及有机和无机粘土,如黄原胶CP Kelco,USA),23(法国Rhodia),(R.T.Vanderbilt,USA)或(Engelhard Corp.,NJ,USA)。
可以加入杀菌剂来保存和稳定该组合物。合适杀菌剂的实例是基于双氯酚和苄醇半缩甲醛的那些(ICI的或Thor Chemie的RS以及Rohm & Haas的MK)以及异噻唑啉酮衍生物如烷基异噻唑啉酮类和苯并异噻唑啉酮类(Thor Chemie的MBS)。
合适防冻剂的实例是乙二醇、丙二醇、尿素和甘油。消泡剂的实例是聚硅氧烷乳液(例如SRE,德国Wacker或法国Rhodia),长链醇,脂肪酸,脂肪酸盐,有机氟化合物及其混合物。增粘剂或粘合剂的实例是聚乙烯吡咯烷酮、聚乙酸乙烯酯、聚乙烯醇和纤维素醚日本Shin-Etsu)。
农业化学组合物通常包含0.01-95重量%,优选0.1-90重量%,最优选0.5-90重量%活性物质(例如农药)。活性物质以90-100%,优选95-100%的纯度(根据NMR光谱)使用。
本发明接枝共聚物或组合物可以直接使用或者以其组合物形式,例如以可直接喷雾溶液、粉末、悬浮液、分散体、乳液、油分散体、糊、可撒粉产品、撒播用材料或颗粒形式借助喷雾、雾化、撒粉、铺展、刷涂、浸渍或浇灌来使用。施用形式完全取决于意欲的目的;在任何情况下意欲确保本发明活性物质的最佳可能分布。
含水施用形式可通过加入水由乳液浓缩物、糊或可湿性粉末(可喷雾粉末、油分散体)制备。为制备乳液、糊或油分散体,可借助润湿剂、增粘剂、分散剂或乳化剂将该物质直接或溶于油或溶剂中后在水中均化。或者可以制备由活性物质、润湿剂、增粘剂、分散剂或乳化剂以及合适的话溶剂或油组成的浓缩物且该浓缩物适于用水稀释。
即用制剂中的活性物质浓度可在较宽范围内变化。它们通常为0.0001-10重量%,优选0.01-1重量%活性物质。当用于植物保护中时,活性物质的施用量取决于所需效果的种类为0.001-2kg/ha,优选0.005-2kg/ha,更优选0.05-0.9kg/ha,尤其是0.1-0.75kg/ha。
各种类型的油、润湿剂、助剂、除草剂、杀菌剂、其他杀真菌剂和/或农药可加入活性物质或包含它们的组合物中,合适的话恰在紧临使用前加入(桶混合)。这些试剂通常可以与本发明组合物以1:100-100:1,优选1:10-10:1的重量比混合。
可以使用的助剂尤其是有机改性的聚硅氧烷如Break Thru S醇烷氧基化物如AtplusAtplus MBAPlurafac LF和Lutensol ONEO/PO嵌段聚合物,例如Pluronic RPE和Genapol醇乙氧基化物如Lutensol XP以及磺基琥珀酸二辛酯钠如Leophen
可以将该共聚物和该农药单独或者已经部分或完全相互混合而制备本发明组合物。还可以将它们作为结合组合物如多组分成套包装来包装和进一步使用。在本发明的一个实施方案中,成套包装可以包含一种或多种(包括所有)可以用于制备本发明农业化学组合物的组分。例如成套包装可以包含一种或多种农药和共聚物。一种或多种组分可已相互组合或预配制。在其中超过两种组分提供在成套包装中的那些实施方案中,各组分可以相互组合并直接包装在单独容器如罐、瓶、桶、袋、囊或箱中。在其他实施方案中,成套包装的两种或更多种组分可以分开包装,即不预配制。成套包装可以直接包含一个或多个分开的容器如罐、瓶、桶、袋、囊或箱,其中各容器包含农业化学组合物的单独组分。在两种形式中,成套包装的某一组分可以与其他组分分开或一起或者作为本发明结合组合物的一种组分用于制备本发明组合物。
用户通常将本发明组合物用于前剂量装置、小背包喷雾器、喷雾罐或喷雾飞机。此时将该农业化学组合物用水和/或缓冲剂配制至所需施用浓度,其中合适的话可以加入其他助剂,从而得到即用喷雾液或本发明农业化学组合物。每公顷农业利用区通常施用50-500升,优选100-400升即用喷雾液。根据一个实施方案,用户可以自己在喷雾罐中混合本发明组合物的各组分,例如成套包装的各部分或二元或三元混合物的各部分并且合适的话可以加入其他助剂(桶混合)。在另一实施方案中,用户可以在喷雾罐中混合本发明组合物的各组分或部分预混的组分。
本发明的优点例如是本发明组合物具有优异的稳定性(例如就粒度、粘度而言)。接枝共聚物提高了农药的农药活性。该辅助效果在不降低该组合物的稳定性下实现。该接枝共聚物具有非常低的植物毒性,这对于处理蔬菜和水果尤其重要。该类接枝共聚物易于处理并且在与皮肤接触时没有不利影响,例如对于处理该农业化学配制剂的农夫而言。该接枝共聚物可以容易地以工业规模低成本生产。此外,该接枝聚合物提高了农药在植物表面上的保留。
本发明由下列实施例进一步说明,但不限于此。
实施例1—活性物质在植物上的保留
制备含有300g/l氟唑菌酰胺、分散剂、消泡剂、黄原胶增稠剂、杀菌剂和1,2-丙二醇防冻剂的含水悬浮浓缩物(称为“SC Blank”)。任选加入接枝聚合物A。接枝聚合物A根据WO 2007051746由13重量%聚乙二醇(平均分子量由羟值计算为6000g/mol)、57重量%N-乙烯基己内酰胺和30重量%乙酸乙烯酯制备,K值为35。
为了测量含水喷雾液的保留,将该悬浮浓缩物用水和荧光示踪剂(荧光素)稀释以制备可喷雾桶混物。所述桶混物以200l/ha的施用率经由喷嘴组(喷嘴类型:扇形雾锥(空气进入),ID 12002,Lechler)在1.4m/s下的速度下使用3.4巴的压力和喷杆(1m,3个喷嘴;喷嘴距离50cm)施用。将该桶混物施用于处于生长阶段BBCH 12的小麦(栽培品种Melon)。在施用之后,收集植物叶子并用限定量的洗涤溶液(0.1mol/l NaOH)洗涤。使用荧光计测量与保留在叶子上的活性物量成正比的荧光强度。各试验重复4次并在表1中给出平均值。数据表明在植物上的保留由于聚合物添加剂A而与没有该添加剂的配制剂相比或者与水相比增加。
表1:在植物上的保留
1)对比,非本发明。2)桶混物中的浓度。
实施例2—在葫芦上提高的效力
制备含有120g/l醚唑(杀真菌剂,在20°C下的水溶性为3.3mg/L)、300g/l苯菌酮(杀真菌剂,在20°C下的水溶性为0.49mg/L)、任选50g/l接枝聚合物A(见实施例1)和常规助剂(如1,2-丙二醇、抗菌剂、消泡剂、增稠剂)的含水悬浮浓缩物(“SC1”)。在西班牙以大田试验对被单丝壳白粉菌(Sphaerotheca fuliginea)侵染的葫芦测试农药活性。在140g农药/ha(500L水/ha;3次施用,间隔7天)的使用率下将植物用SC1处理。侵染百分数(施用后7天)总结于表2中。数据表明具有本发明接枝聚合物的组合物与没有接枝聚合物的对照相比具有更高农药活性。
表2:
用如下组合物处理 | %侵染 |
未处理对照 | 65 |
SC1,不含接枝聚合物A | 13 |
SC1,含接枝聚合物A | 8 |
实施例3—在葡萄上提高的效力
使用实施例2的含水悬浮浓缩物(“SC1”)。在西班牙以大田试验对被葡萄钩丝壳(Erysiphe necator)侵染的葡萄测试农药活性。在84g农药/ha(500L水/ha;5次施用,间隔14天)的使用率下将植物用SC1处理。对簇群的侵染百分数(施用后14天)总结于表3中。数据表明具有本发明接枝聚合物的组合物与没有接枝聚合物的对照相比具有更高农药活性。
表3:
用如下组合物处理 | %侵染 |
未处理对照 | 85 |
SC1,不含接枝聚合物A | 22 |
SC1,含接枝聚合物A | 0.8 |
实施例4—在葡萄上提高的效力
如实施例3所述在西班牙在另一位置以大田试验对被葡萄钩丝壳(Erysiphe necator)侵染的葡萄测试农药活性。在280g农药/ha(500L水/ha;6次施用,间隔14天)的使用率下将植物用SC1处理。对簇群的侵染百分数(施用后14天)总结于表4中。数据表明具有本发明接枝聚合物的组合物与没有接枝聚合物的对照相比具有更高农药活性。
表4:
用如下组合物处理 | %侵染 |
未处理对照 | 100 |
SC1,不含接枝聚合物A | 2.7 |
SC1,含接枝聚合物A | 1.0 |
Claims (13)
1.可以通过自由基聚合包含N-乙烯基内酰胺、乙烯基酯和聚醚的单体混合物而得到的接枝共聚物在提高农药活性中的用途,其中所述农药悬浮于含水农业化学组合物中,
其中所述接枝共聚物由包含如下单体的单体混合物得到:
i)30-80重量%N-乙烯基吡咯烷酮、N-乙烯基己内酰胺或其混合物,
ii)10-50重量%乙酸乙烯酯,和
iii)10-50重量%聚醚。
2.根据权利要求1的用途,其中所述接枝共聚物由包含如下单体的单体混合物得到:
i)30-70重量%N-乙烯基吡咯烷酮、N-乙烯基己内酰胺或其混合物,
ii)15-35重量%乙酸乙烯酯,和
iii)10-35重量%聚乙二醇。
3.根据权利要求1的用途,其中所述聚醚为聚乙二醇。
4.根据权利要求1-3中任一项的用途,其中所述接枝聚合物的量基于所述农药的重量通常为10-500重量%。
5.根据权利要求1-3中任一项的用途,其中所述农药在20℃下在水中的溶解度小于10g/l。
6.根据权利要求4的用途,其中所述农药在20℃下在水中的溶解度小于10g/l。
7.根据权利要求1-3中任一项的用途,其中所述农药为苯菌酮或醚唑。
8.根据权利要求6的用途,其中所述农药为苯菌酮或醚唑。
9.一种含水农业化学组合物,包含悬浮于所述含水组合物中的农药和可以通过自由基聚合包含如下单体的单体混合物而得到的接枝共聚物的组合物:
i)30-80重量%N-乙烯基吡咯烷酮、N-乙烯基己内酰胺或其混合物,
ii)10-50重量%乙酸乙烯酯,和
iii)10-50重量%聚醚,
其中所述农药为苯菌酮或醚唑,所述组合物为悬浮液。
10.根据权利要求9的组合物,其中所述混合物包含:
i)30-70重量%N-乙烯基吡咯烷酮、N-乙烯基己内酰胺或其混合物,
ii)15-35重量%乙酸乙烯酯,和
iii)10-35重量%聚乙二醇。
11.根据权利要求9或10的组合物,其中所述接枝聚合物的量基于所述农药的重量为10-500重量%。
12.一种通过将所述农药和所述接枝共聚物混合而制备如权利要求9-11中任一项所定义的组合物的方法。
13.一种防治植物病原性真菌和/或不希望的植物生长和/或不希望的昆虫或螨虫侵袭和/或调节植物生长的方法,其中使权利要求9-11中任一项所定义的组合物作用于特定害虫、其栖息地或要防止所述特定害虫的植物、土壤和/或不希望的植物和/或有用植物和/或其生长地。
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DE19712247A1 (de) | 1997-03-24 | 1998-10-01 | Basf Ag | Wässrige Copolymerisatdispersionen aus wasserlöslichen Monomeren mit N-Vinylgruppen und hydrophoben Monomeren |
DE10042815A1 (de) * | 2000-08-30 | 2002-03-14 | Basf Ag | Verwendung von gepfropften Polyalkylenoxiden als Vergrauungsinhibitoren beim Waschen |
GB0021786D0 (en) * | 2000-09-05 | 2000-10-18 | Zeneca Ltd | Fungicidal formulations |
DK1742531T4 (en) * | 2004-04-26 | 2017-12-11 | Basf Se | Use of aqueous fungicidal preparations to control harmful microorganisms |
BRPI0609170A2 (pt) * | 2005-03-10 | 2010-11-16 | Basf Ag | processos para produzir dispersões poliméricas aquosas contendo pesticida, e para combater microrganismos nocivos e/ou para regular o crescimento de plantas e/ou para combater o crescimento de plantas indesejáveis e/ou para combater a infestação de insetos ou acarìdeos indesejáveis e/ou para combater fungos fitopatogênicos e /ou para tratar sementes, dispersão aquosa, formulação agroquìmica, uso das dispersões, e, semente |
DE102005052262B4 (de) | 2005-11-02 | 2007-10-25 | Siemens Ag | Verfahren zur Auswahl einer S-CSCF-Einheit innerhalb eines IMS basierten Dienstekommunikationssystems |
DE102005053064A1 (de) | 2005-11-04 | 2007-05-16 | Basf Ag | Verfahren zur Herstellung von Pfropfpolymerisaten |
EP2173781A1 (de) * | 2007-07-26 | 2010-04-14 | Basf Se | Verfahren zur herstellung von durch pfropfpolymerisation in lösung erhaltenen copolymeren auf basis von polyethern in fester form |
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CN101299994A (zh) * | 2005-11-04 | 2008-11-05 | 巴斯夫欧洲公司 | 共聚物作为微水溶性化合物的加溶剂的用途 |
CN101541170A (zh) * | 2006-11-13 | 2009-09-23 | 巴斯夫欧洲公司 | 基于乙烯基内酰胺和乙酸乙烯酯的嵌段共聚物作为增溶剂的用途 |
WO2009103760A2 (en) * | 2008-02-21 | 2009-08-27 | Basf Se | Coated inert granules |
EP2158922A1 (de) * | 2008-08-28 | 2010-03-03 | Basf Se | Verfahren zur Trocknung von als Solubilisatoren für in Wasser schwerlösliche Verbindungen geeigneten Copolymeren auf Basis von Polyethern |
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EP2552197A4 (en) | 2013-09-25 |
KR20130027014A (ko) | 2013-03-14 |
IL221934A (en) | 2017-09-28 |
WO2011121477A1 (en) | 2011-10-06 |
BR112012024638B1 (pt) | 2018-01-16 |
BR112012024638A2 (pt) | 2015-09-15 |
JP2013523713A (ja) | 2013-06-17 |
EP2552197B1 (en) | 2014-11-26 |
CA2793687C (en) | 2018-03-13 |
AU2011234110B2 (en) | 2013-11-07 |
RU2558542C2 (ru) | 2015-08-10 |
JP5882298B2 (ja) | 2016-03-09 |
RU2012145937A (ru) | 2014-05-10 |
AU2011234110A1 (en) | 2012-10-18 |
EP2552197A1 (en) | 2013-02-06 |
CN102821601A (zh) | 2012-12-12 |
UA108752C2 (ru) | 2015-06-10 |
CA2793687A1 (en) | 2011-10-06 |
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