CN104202975B - 包含酰胺、聚亚烷基二醇(甲基)丙烯酸酯和(甲基)丙烯酸烷基酯的共聚物的农业配制剂 - Google Patents
包含酰胺、聚亚烷基二醇(甲基)丙烯酸酯和(甲基)丙烯酸烷基酯的共聚物的农业配制剂 Download PDFInfo
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Classifications
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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
- A01N25/02—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
- 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
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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
- A01N25/02—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
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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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
- A01N25/08—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 solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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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
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Abstract
本发明提供了一种包含农药和共聚物的组合物,该共聚物以聚合形式含有酰胺(单体A)—含有N-乙烯基内酰胺、N-C1-C6烷基丙烯酰胺和N,N-二-C1-C6烷基丙烯酰胺中的至少一种;聚(C2-6亚烷基二醇)(甲基)丙烯酸酯和/或单C1-22烷基封端的聚(C2-6亚烷基二醇)(甲基)丙烯酸酯(单体B);以及(甲基)丙烯酸C1-C8烷基酯(单体C)。此外,提供了一种通过使该农药与该共聚物接触而制备所述组合物的方法;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染和/或调节植物生长的方法,其中使所述组合物作用于相应有害物、其栖息地或待防止相应有害物的植物、土壤和/或不希望的植物和/或农作物和/或其生长地上;以及一种包含所述组合物的植物繁殖材料。
Description
本发明提供了一种包含农药和共聚物的组合物,该共聚物以聚合形式含有酰胺(单体A)—含有N-乙烯基内酰胺、N-C1-C6烷基丙烯酰胺和N,N-二-C1-C6烷基丙烯酰胺中的至少一种;聚(C2-6亚烷基二醇)(甲基)丙烯酸酯和/或单C1-22烷基封端的聚(C2-6亚烷基二醇)(甲基)丙烯酸酯(单体B);以及(甲基)丙烯酸C1-C8烷基酯(单体C)。此外,提供了一种通过使该农药与该共聚物接触而制备所述组合物的方法;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染和/或调节植物生长的方法,其中使所述组合物作用于相应有害物、其栖息地或待防止相应有害物的植物、土壤和/或不希望的植物和/或农作物和/或其生长地上;以及一种包含所述组合物的植物繁殖材料。本发明包括优选特征与其他优选特征的组合。
在农业化学配制剂中稳定农药,尤其是水不溶性农药是困难的。尤其在液体配制剂中,农药倾向于结晶,尤其是在低温下结晶。还难以配制高浓度的水不溶性农药。所要求的结晶抑制剂通常仅在低浓度下可溶于配制剂中。本发明的目的是解决这些缺点。
该目的借助一种包含农药和共聚物的组合物实现,该共聚物以聚合形式含有:
含有至少一种选自N-乙烯基内酰胺、N-C1-C6烷基丙烯酰胺和N,N-二-C1-C6烷基丙烯酰胺的单体的酰胺(单体A);
聚(C2-6亚烷基二醇)(甲基)丙烯酸酯和/或单C1-22烷基封端的聚(C2-6亚烷基二醇)(甲基)丙烯酸酯(单体B);以及
C1-C8烷基(甲基)丙烯酸酯(单体C)。
酰胺(单体A)可以包括至少一种选自N-乙烯基内酰胺、N-C1-C6烷基丙烯酰胺和N,N-二-C1-C6烷基丙烯酰胺的单体。优选单体A包括N-乙烯基内酰胺和/或N-C1-C6烷基丙烯酰胺。更优选单体A包括N-乙烯基吡咯烷酮和任选N-C1-C6烷基丙烯酰胺。单体A尤其包括N-乙烯基吡咯烷酮和N-C1-C6烷基丙烯酰胺。
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-吡咯烷酮及其混合物。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、N-乙烯基己内酰胺或其混合物。特别优选N-乙烯基吡咯烷酮(“VP”)。
合适的N-C1-C6烷基丙烯酰胺是N-甲基丙烯酰胺、N-乙基丙烯酰胺、N-正丙基丙烯酰胺、N-异丙基丙烯酰胺、N-正丁基丙烯酰胺、N-叔丁基丙烯酰胺、N-正戊基丙烯酰胺、N-正己基丙烯酰胺及其混合物。优选N-C2-C5烷基丙烯酰胺,更优选N-C3-C4烷基丙烯酰胺,其中最优选N-叔丁基丙烯酰胺。
合适的N,N-二-C1-C6烷基丙烯酰胺为N,N-二甲基丙烯酰胺。
合适的单体B是聚(C2-6亚烷基二醇)(甲基)丙烯酸酯和/或单C1-22烷基封端的聚(C2-6亚烷基二醇)(甲基)丙烯酸酯,其中优选后者。优选的单体B是聚(C2-4亚烷基二醇)(甲基)丙烯酸酯和/或单C1-22烷基封端的聚(C2-4亚烷基二醇)(甲基)丙烯酸酯,其中优选后者。更优选的单体B是聚(乙二醇)(甲基)丙烯酸酯和/或单C1-22烷基封端的聚(乙二醇)(甲基)丙烯酸酯,其中优选后者。尤其优选的单体B是单C1-22烷基封端的聚(乙二醇)(甲基)丙烯酸酯。单体B通常包含2-60个,优选3-35个亚烷基二醇单元。
单C1-22烷基封端的聚(C2-6亚烷基二醇)(甲基)丙烯酸酯中的术语“烷基”通常表示线性或支化饱和烷基。这些烷基通常不含官能基团,如芳基、卤素基团或双键或叁键。
合适的(甲基)丙烯酸C1-C8烷基酯(单体C)是C1-C8链烷醇的丙烯酸酯和甲基丙烯酸酯,如丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸叔丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯及其混合物。优选的单体C是甲基丙烯酸甲酯。
该共聚物可以含有其他单体(单体D)。合适的是任何可以与单体A、B和C聚合的单体,如烯属不饱和单体。在另一形式中,该共聚物含有小于15重量%,优选小于2重量%,尤其不含包含磺酸基团的单体D,如2-丙烯酰胺基-2-甲基丙烷磺酸(AMPS)。
优选该共聚物在20℃下以10g/l,优选甚至50g/l的浓度可溶于有机溶剂(例如N,N-二甲基十二烷酰胺)。该共聚物优选以溶解形式存在于该组合物中。
该共聚物基于单体总量可以含有至少20重量%,优选至少25重量%,尤其是至少30重量%单体A。该共聚物基于单体总量可以含有至多95重量%,优选至多90重量%,尤其是至多85重量%单体A。
该共聚物基于单体总量可以含有至少1重量%,优选至少4重量%,尤其是至少8重量%单体B。该共聚物基于单体总量可以含有至多50重量%,优选至多40重量%,尤其是至多35重量%单体B。
该共聚物基于单体总量可以含有至少1重量%,优选至少5重量%,尤其是至少8重量%单体C。该共聚物基于单体总量可以含有至多50重量%,优选至多40重量%,尤其是至多35重量%单体C。
该共聚物基于单体总量可以含有至多15重量%,优选至多10重量%,尤其是至多2重量%单体D。在另一形式中,该共聚物基本不含单体D。
单体A、B、C和D的总和通常等于100%。
单体A和C的总和基于单体总量通常为至少40重量%,优选至少50重量%,尤其是至少55重量%。
该共聚物可以含有至少25重量%单体A,至少1重量%单体B,至少5重量%单体C,其中单体A和B的总和基于单体总量为至少55重量%。
该共聚物可以含有:
25-85重量%单体A,
1-40重量%单体B,
5-50重量%单体C,和
至多15重量%其他单体D,
其中单体A、B、C和D的总和等于100%。
优选该共聚物含有:
30-85重量%单体A,
5-35重量%单体B,
8-35重量%单体C,和
至多10重量%其他单体D,
其中单体A、B、C和D的总和等于100%。
在更优选的形式中,该共聚物含有:
30-85重量%单体A,其包括N-乙烯基内酰胺和N-C1-C6烷基丙烯酰胺,
5-20重量%单体B,
8-35重量%单体C,和
至多10重量%其他单体D,
其中单体A、B、C和D的总和等于100%。
在甚至更优选的形式中,该共聚物含有:
50-85重量%单体A,其包括N-乙烯基吡咯烷酮和N-C1-C6烷基丙烯酰胺,
5-15重量%单体B,
8-35重量%单体C,和
至多10重量%其他单体D,
其中单体A、B、C和D的总和等于100%。
在另一更优选形式中,该共聚物含有:
20-50重量%单体A,其包括N-乙烯基内酰胺,
5-40重量%单体B,
20-65重量%单体C,和
至多10重量%其他单体D,
其中单体A、B、C和D的总和等于100%。
在另一甚至更优选形式中,该共聚物含有:
25-45重量%单体A,其包括N-乙烯基吡咯烷酮,
5-35重量%单体B,
30-65重量%单体C,和
至多10重量%其他单体D,
其中单体A、B、C和D的总和等于100%。
共聚物通常具有1000-100000g/mol,优选2000-50000g/mol,更优选2000-30000g/mol的平均分子量Mw。平均分子量MN通常为1000-50000g/mol,优选1000-15000g/mol,更特别的是2000-8000g/mol。
单体A-D在该共聚物中的比例通常为至少85重量%,优选至少90重量%,更特别的是至少95重量%,尤其是至少98重量%。该共聚物可以任选包含自由基引发剂分子和额外的调节剂或链转移剂。
共聚物可以通过常规聚合方法,如溶液聚合而得到。共聚物优选可以通过聚合单体A、B、C和任选D而得到。该共聚物通常不是接枝聚合物。该共聚物通常为统计聚合物。
该共聚物优选可以通过单体A-D在(i)由水和至少一种沸点<140℃的有机溶剂构成的溶剂混合物中或在(ii)一种或多种纯净醇中自由基聚合而得到。可以使用典型的自由基或受控游离基聚合方法,优选自由基聚合方法,其中反应混合物包含至少一种引发剂。优选选择该溶剂混合物以使单体以及还有形成的共聚物可溶。可溶就本发明而言在这里不仅包括真溶液而且包括如此细碎以至于不产生浑浊的分散体。该聚合可以作为分批反应、以半分批程序或以连续程序进行。聚合通常在溶液中进行。
适合聚合的有机溶剂原则上包括所有沸点小于140℃的溶剂。优选的溶剂是可与水溶混并且沸点≤120℃的那些。特别优选的有机溶剂是醇、醚和腈。特别优选的醇的实例包括甲醇、乙醇、正丙醇(1-丙醇)、异丙醇(2-丙醇)、正丁醇(1-丁醇)、仲丁醇(2-丁醇)、叔丁醇(2-甲基丙-2-醇)、1-戊醇、2-戊醇、3-戊醇、2-甲基丁醇、3-甲基丁-2-醇和2,2-二甲基丙醇。尤其优选的醇是甲醇、乙醇、正丙醇(1-丙醇)和异丙醇(2-丙醇)。更特别优选异丙醇(2-丙醇)。
反应时间通常为1-48小时,优选2-24小时,更特别优选4-24小时。可以进行该反应的温度范围通常为20-200℃,优选30-120℃,更特别优选40-90℃。
作为自由基聚合的引发剂,使用典型的自由基形成物质。引发剂优选选自偶氮化合物,过氧化物或氢过氧化物。实例包括过氧化乙酰、过氧化苯甲酰、过氧化月桂酰、过氧化异丁酸叔丁酯、过氧化己酰、氢过氧化枯烯、偶氮二(异丁腈)、2,2-偶氮二(2-甲基丁腈)、2,2’-偶氮二(2-甲基丙脒)二盐酸盐和2,2’-偶氮二[2-(2-咪唑啉-2-基)丙烷]二盐酸盐。应理解的是还可以使用引发剂混合物。
无规自由基共聚物的多分散性和分子量需要的话可以通过改变引发剂/单体比,底物进料时间,尤其是与单体溶液进料时间相比引发剂溶液的进料时间,通过改变溶剂混合物的醇含量,更具体为异丙醇含量,以及通过聚合浓度而调节。若选择短引发剂进料和/或溶剂混合物中的高异丙醇含量(调节剂或链转移剂)和/或若选择低聚合浓度(高调节剂/单体比),则所得多分散性通常相对低。通过使用选自硫醇,如巯基乙醇、硫甘油或1-十二烷基硫醇的额外调节剂或链转移剂,需要的话可以实现该共聚物多分散性的进一步降低。分子量Mw和Mn以及还有多分散性借助尺寸排阻色谱法测定。可以使用的校准剂是市售聚苯乙烯或聚(氧化乙烯)校准组。
该共聚物需要的话可以分离并后处理。后处理已熟练技术人员熟知的已知方式完成,例如通过在先过滤步骤完成。这使得可以任选除去2-氨基-2-甲基丙烷磺酸副产物。需要的话,随后可以除去该溶剂。除去该溶剂的典型方法实例包括喷雾干燥、减压蒸发、冻干和在大气压力和任选升高的温度下蒸发。适合干燥的方法进一步包括在流化床干燥器中干燥。另一方案是使用可以通过该方法不经后处理而得到的共聚物溶液。
术语农药表示至少一种选自杀真菌剂、杀虫剂、杀线虫剂、除草剂、安全剂和/或生长调节剂的活性成分。优选的农药是杀真菌剂、杀虫剂、除草剂和生长调节剂。特别优选的农药是杀真菌剂。还可以使用上述类别中两种或更多种农药的混合物。熟练技术人员熟知该类农药,它们例如可以在Pesticide Manual,第15版(2009),The British CropProtection Council,London中找到。合适的杀虫剂是选自如下类别的杀虫剂:氨基甲酸酯类、有机磷酸酯类、有机氯杀虫剂、苯基吡唑类、合成除虫菊酯类、新类烟碱类、斯皮诺素类(spinosins)、阿维菌素类(avermectins)、米尔霉素类(milbemycins)、保幼激素类似物、烷基卤、有机锡化合物、沙蚕毒素类似物、苯甲酰脲类、二酰基肼类、METI杀螨剂以及杀虫剂如氯化苦(chloropicrin)、拒嗪酮(pymetrozine)、氟啶虫酰胺(flonicamide)、四螨嗪(clofentezine)、噻螨酮(hexythiazox)、特苯唑(etoxazole)、杀螨硫隆(diafenthiuron)、克螨特(propargite)、三氯杀螨砜(tetradifon)、氟唑虫清(chlorfenapyr)、二硝酚(DNOC)、噻嗪酮(buprofezine)、灭蝇胺(cyromazine)、双甲脒(amitraz)、灭蚁腙(hydramethylnon)、灭螨醌(acequinocyl)、fluacrypyrim、鱼藤酮(rotenone)或其衍生物。合适的杀真菌剂是选自如下类别的杀真菌剂:二硝基苯胺类、烯丙基胺类、苯胺基嘧啶类、抗生素类、芳族烃类、苯磺酰胺类、苯并咪唑类、苯并异噻唑类、二苯甲酮类、苯并噻二唑类、苯并三嗪类、苄基氨基甲酸酯类、氨基甲酸酯类、羧酰胺类、羧酸酰胺类、氯代腈类、氰基乙酰胺肟类、氰基咪唑类、环丙烷羧酰胺类、二羧酰亚胺类、二氢二嗪类、二硝基苯基巴豆酸酯类、二硫代氨基甲酸酯类、二硫戊环类、乙基膦酸酯类、乙基氨基噻唑羧酰胺类、胍类、羟基-(2-氨基-)嘧啶类、羟基酰替苯胺类、咪唑类、咪唑啉酮类、无机物质、异苯并呋喃酮类、甲氧基丙烯酸酯类、甲氧基氨基甲酸酯类、吗啉类、N-苯基氨基甲酸酯类、唑烷二酮类、肟基乙酸酯类、肟基乙酰胺类、肽基嘧啶核苷、苯基乙酰胺类、苯基酰胺类、苯基吡咯类、苯基脲类、膦酸酯类、硫代磷酸酯类、邻氨甲酰苯甲酸类、苯邻二甲酰亚胺类、哌嗪类、哌啶类、丙酰胺类、哒嗪酮类、吡啶类、吡啶基甲基苯甲酰胺类、嘧啶胺类、嘧啶类、嘧啶酮腙类、吡咯并喹啉酮类、喹唑啉酮类、喹啉类、醌类、磺酰胺类、氨磺酰三唑类、噻唑羧酰胺类、硫代氨基甲酸酯类、托布津类(thiophanate)、噻吩羧酰胺类、甲苯甲酰胺类、三苯基锡化合物、三嗪类和三唑类。合适的除草剂是选自如下类别的除草剂:乙酰胺类、酰胺类、芳氧基苯氧基丙酸酯类、苯甲酰胺类、苯并呋喃、苯甲酸类、苯并噻二嗪酮类、联吡啶、氨基甲酸酯类、氯代乙酰胺类、氯代羧酸、环己烷二酮类、二硝基苯胺类、二硝基苯酚、二苯基醚类、甘氨酸类、咪唑啉酮类、异唑类、异唑烷酮类、腈类、N-苯基苯邻二甲酰亚胺类、二唑类、唑烷二酮类、羟乙酰胺类、苯氧基羧酸类、苯基氨基甲酸酯类、苯基吡唑类、苯基吡唑啉类、苯基哒嗪类、次膦酸类、氨基磷酸酯类、二硫代磷酸酯类、邻氨甲酰苯甲酸酯类、吡唑类、哒嗪酮类、吡啶类、吡啶羧酸类、吡啶羧酰胺类、嘧啶二酮类、嘧啶基(硫代)苯甲酸酯类、喹啉羧酸类、缩氨基脲类、磺酰氨基羰基三唑啉酮类、磺酰脲类、四唑啉酮类、噻二唑类、硫代氨基甲酸酯类、三嗪类、三嗪酮类、三唑类、三唑啉酮类、三唑并羧酰胺、三唑并嘧啶、三酮、尿嘧啶和脲类。
优选的农药是水不溶性农药。水不溶性农药在20℃下在水中可以具有的溶解度为至多且包括10g/l。它们在水中的溶解度优选不超过1g/l,更优选不超过0.5g/l。合适水不溶性农药的实例(在20℃下在水中的溶解度在每种情况下位于括号中)是唑菌胺酯(pyraclostrobin)(1.9mg/l),氧唑菌(epoxiconazole)(7mg/l),丙氯灵(prochloraz)(34mg/l),环戊唑菌(metconazole)(30mg/l),氟唑菌酰胺(fluxapyroxad)(0.00388g/l)和/或丁苯吗啉(fenpropimorph)(4mg/l)。
该农药(例如水不溶性农药)通常具有的熔点为至少30℃,优选至少50℃,更优选至少70℃,非常优选至少100℃。
该农药(例如水不溶性农药)优选以溶解形式存在于该组合物中。这意味着该水不溶性农药中通常至少90重量%,优选至少99重量%呈溶解形式。
除了该农药外,该组合物还可以包含其他农药。该其他农药可以以溶解形式或者以固体颗粒形式(例如以悬浮液)存在。
该组合物可以包含至少一种有机溶剂,例如1、2、3或4种不同溶剂。该组合物优选包含至少两种有机溶剂。
所考虑的有机溶剂包括溶剂如中到高沸点的矿物油馏分如煤油和柴油,还有煤焦油,以及植物或动物来源的油,脂族、环状和芳族烃,例如石蜡、四氢萘、烷基化萘及其衍生物,烷基化苯及其衍生物,醇如甲醇、乙醇、丙醇、丁醇和环己醇,二醇,酮如环己酮和γ-丁内酯,二甲基脂肪酸酰胺,碳酸亚烷基酯,脂肪酸,DMSO,链烷酸烷基酯;或N-甲基吡咯烷酮。原则上还可以使用溶剂混合物。
至少一种有机溶剂可以在20℃的水中具有不超过10重量%,优选不超过8重量%,更优选不超过6重量%,尤其是不超过3重量%的溶解度。
优选的有机溶剂包含至少一种式(I)的酰胺:
R1-C(O)N(R2)2 (I)
其中R1为C5-C19烷基且R2为C1-C4烷基。优选的式(I)的酰胺是其中R1为C7-C14烷基且R2为甲基的那些。尤其优选的式(I)的酰胺是其中R1为C7-C12烷基且R2为甲基的那些。还可以使用所述酰胺的混合物。
该有机溶剂可以包含至少一种式(I)的酰胺和选自链烷酸烷基酯和烃油的另一溶剂。
合适的烃油含有脂族、脂环族和芳族烃,例如甲苯、石蜡、四氢萘、烷基化萘。还合适的是中到高沸点的矿物油馏分,例如煤油、柴油。还合适的是烷基取代的芳烃,如甲苯、二甲苯类、乙苯类和具有较长链烷基的苯类,例如C9-C10二烷基-和三烷基苯类(例如以名称100由Exxon Mobile Europe得到或以Aromatic 100由Exxon Mobile USA得到),C10-C11烷基苯(例如以名称150由Exxon Mobile Europe得到或以Aromatic150由Exxon Mobile USA得到)和烷基萘(例如以名称200由Exxon MobileEurope得到或以Aromatic 200由Exxon Mobile USA得到)。优选该烃油含有至少50重量%,更优选至少85重量%,尤其是至少95重量%脂族和/或脂环族烃。在另一优选形式中,该烃油含有至多10重量%,优选至多5重量%,尤其是至多3重量%芳族烃。在另一优选形式中,该助剂含有至多5重量%,优选至多2.5重量%,尤其是至多1.5重量%芳族烃。
合适的链烷酸烷基酯是脂肪酸酯、二酸的二酯、羟基酸的酯。优选的链烷酸烷基酯是二酸的二酯(如线性、支化或环状脂族C4-C18二酸的线性或支化二-C1-C20烷基酯)。更优选的链烷酸烷基酯是线性脂族C4-C8二酸的线性或支化二-C1-C6烷基酯,如己二酸二丁酯。
该组合物可以包含非离子表面活性剂。合适的非离子表面活性剂是选自烷氧基化物、嵌段聚合物、N-烷基化脂肪酸酰胺、胺氧化物、酯或糖基表面活性剂类别的表面活性剂。烷氧基化物的实例是诸如已经烷氧基化的醇、烷基酚、胺、酰胺、芳基酚、脂肪酸或脂肪酸酯的化合物。可以将氧化乙烯和/或氧化丙烯用于烷氧基化,优选氧化乙烯。N-烷基化脂肪酸酰胺的实例是脂肪酸葡糖酰胺或脂肪酸链烷醇酰胺。酯类的实例是脂肪酸酯、甘油酯或甘油单酯。糖基表面活性剂的实例是脱水山梨醇、乙氧基化脱水山梨醇、蔗糖酯和葡萄糖酯或烷基聚葡糖苷。合适的嵌段聚合物是包含聚氧化乙烯和聚氧化丙烯嵌段的A-B或A-B-A型嵌段聚合物或包含链烷醇、聚氧化乙烯和聚氧化丙烯的A-B-C型嵌段聚合物。优选的非离子表面活性剂是选自烷氧基化物和嵌段共聚物类别的表面活性剂,更具体为烷氧基化物。
该组合物优选包含至少20重量%,更优选至少30重量%,非常优选至少40重量%,尤其是至少50重量%有机溶剂。该组合物可以包含至多90重量%,优选至多80重量%有机溶剂。
该组合物优选包含不超过10重量%,更优选不超过8重量%,非常优选不超过5重量%,尤其不超过1重量%的水。
该组合物可以包含30-95重量%,优选40-90重量%,尤其是50-85重量%有机溶剂,该有机溶剂含有至少一种式(I)的酰胺和任选选自链烷酸烷基酯和烃油的另一溶剂。
式(I)的酰胺与选自链烷酸烷基酯和烃油的另一溶剂的重量比可以为15:1-1:2,优选10:1-1:1,尤其是7:1-1.5:1。
该组合物优选包含至少3重量%,更优选至少5重量%,非常优选至少8重量%,尤其是至少10重量%该共聚物。该组合物可以包含至多30重量%,优选至多20重量%该共聚物。
该组合物优选包含至少1重量%,更优选至少3重量%,非常优选至少5重量%农药。该组合物可以包含至多50重量%,优选至多30重量%,更优选至多20重量%农药。
该组合物优选包含至少3重量%,更优选至少6重量%,非常优选至少9重量%,尤其是至少15重量%非离子表面活性剂。该组合物可以包含至多80重量%,优选至多50重量%,更优选至多25重量%非离子表面活性剂。
该组合物优选包含:
a)至少3重量%共聚物;
b)至少20重量%有机溶剂;
c)不超过6重量%水;
d)至少1重量%农药;和
e)至少3重量%非离子表面活性剂。
该组合物更优选包含:
a)2-20重量%共聚物;
b)40-95重量%有机溶剂;
c)不超过3重量%水;
d)1-25重量%水不溶性农药;和
e)3-50重量%非离子表面活性剂。
该组合物中存在的所有组分的量通常加起来为100重量%。
共聚物与农药的重量比可以为10:1-1:10,优选5:1-1:5,更优选2:1-1:2。
该组合物通常为液体组合物,例如有机溶液。
本发明组合物可以包含配制辅助剂,此时辅助剂的选择通常由具体施用形式和/或活性成分控制。合适的配制辅助剂实例是溶剂、表面活性化合物(如表面活性剂、保护性胶体、润湿剂和粘合剂),有机和无机增稠剂,杀菌剂,任选着色剂和粘合剂(例如用于种子处理)。
所考虑的表面活性化合物(助剂、润湿剂、增粘剂、分散剂或乳化剂)包括芳族磺酸如木素磺酸(产品,挪威Borregaard)、苯酚磺酸、萘磺酸(产品,Akzo Nobel,USA)和二丁基萘磺酸(产品,德国BASF)以及脂肪酸的碱金属、碱土金属和铵盐,烷基磺酸盐和烷基芳基磺酸盐,烷基硫酸盐,月桂基醚硫酸盐和脂肪醇硫酸盐,以及硫酸化十六-、十七-和十八烷醇以及脂肪醇乙二醇醚的盐,磺化萘及其衍生物与甲醛的缩合产物,萘或萘磺酸与苯酚和甲醛的缩合产物,聚氧乙烯辛基酚醚,乙氧基化异辛基酚、辛基酚或壬基酚,烷基苯基聚乙二醇醚和三丁基苯基聚乙二醇醚,烷基芳基聚醚醇,异十三烷醇,脂肪醇/氧化乙烯缩合物,乙氧基化蓖麻油,聚氧乙烯或聚氧丙烯烷基醚,月桂醇聚乙二醇醚乙酸酯,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(产品,瑞士Clariant),聚羧酸盐(产品,德国BASF),聚烷氧基化物,聚乙烯胺(产品,德国BASF),聚乙烯亚胺(产品,德国BASF),聚乙烯吡咯烷酮及其共聚物。
合适的增稠剂是赋予配制剂以改性的流变性,即静止状态下的高粘度和运动状态下的低粘度的化合物。实例是多糖、蛋白质(如酪蛋白或明胶)、合成聚合物或无机层状矿物。这些种类的增稠剂可市购,实例是黄原胶(,CP Kelco,USA),23(法国Rhodia)或(R.T.Vanderbilt,USA)或(Engelhard Corp.,NJ,USA)。增稠剂在该配制剂中的量由该增稠剂的效力控制。熟练人员将选择一定量以获得所需粘度的配制剂。该量通常为0.01-10重量%。可以加入杀菌剂来稳定该组合物。杀菌剂的实例是基于双氯酚和苄醇半缩甲醛的那些,还有基于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的那些(Thor Chemie的MBS)。
在一个优选实施方案中,本发明组合物呈农业化学配制剂形式。该组合物优选呈可乳化浓缩物(EC)或油分散体(OD)形式。
该农业化学配制剂通常在施用之前稀释以制备所谓的桶混物。考虑用于稀释的是中到高沸点的矿物油馏分,如煤油或柴油,还有煤焦油,以及植物或动物来源的油,脂族、环状和芳族烃,例如甲苯、二甲苯、石蜡、四氢萘、烷基化萘或其衍生物,甲醇、乙醇、丙醇、丁醇、环己醇、环己酮、异佛尔酮,强极性溶剂,例如二甲亚砜、N-甲基吡咯烷酮或水。优选使用水。
该稀释组合物通常通过喷雾或成雾施用。该桶混物可以与各种类型的油、润湿剂、助剂、除草剂、杀菌剂和/或杀真菌剂在紧临施用前混合(桶混)。这些添加剂可以以以1:100-100:1,优选1:10-10:1的重量比混入本发明组合物中。桶混物中的农药浓度可以在较宽范围内变化。通常为0.0001-10%,优选0.01-1%。用于作物保护中的施用率根据所需效果的性质变化且为0.01-2.0kg活性成分/ha。
本发明进一步提供了一种通过使该共聚物、农药以及任选有机溶剂和任选非离子表面活性剂接触而制备本发明组合物的方法。各组分可以通过属于一般常识的方法,如混合、乳化或悬浮而相互接触。
本发明进一步提供了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染和/或调节植物生长的方法,其中使本发明组合物作用于相应有害物、其栖息地或要防止相应有害物的植物、土壤和/或不希望的植物和/或农作物和/或其生长地。本发明额外提供了本发明组合物在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染和/或调节植物生长中的用途,其中使该组合物作用于相应有害物、其栖息地或要防止相应有害物的植物、土壤和/或不希望的植物和/或农作物和/或其生长地。
合适农作物的实例是禾谷类,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;仁果、核果和浆果,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,例如菜豆、扁豆、豌豆、苜蓿或大豆;油料作物,例如油菜、芥菜、橄榄、向日葵、椰子、可可豆、蓖麻豆、油棕、花生或大豆;葫芦科植物,例如南瓜、黄瓜或甜瓜;纤维作物,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;蔬菜植物,例如菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、西红柿、土豆、南瓜或辣椒;月桂类植物,例如鳄梨、肉桂或樟脑;能量作物和工业原料作物,例如玉米、大豆、小麦、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;禾草,例如草坪;甜叶菊(Stevia rebaudania);橡胶植物;观赏和森林植物,例如花卉、灌木、落叶树和针叶树,以及植物繁殖材料如种子和这些植物的收获产品。
术语农作物还包括已经通过育种、诱变或重组方法修饰的那些植物,包括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已经以在自然条件下不易通过杂交、突变或自然重组(即遗传材料的重组)发生的方式修饰的植物。这里通常将一个或多个基因整合到植物的遗传材料中以改善植物的性能。这类重组修饰还包括蛋白质、寡肽或多肽的翻译后修饰,例如通过糖基化或聚合物结合如异戊二烯化或法呢基化残基或PEG残基。
本发明进一步提供了一种包含本发明组合物的植物繁殖材料,如种子。植物繁殖材料可以与播种一起或者甚至在播种之前,或者与移栽一起或者在移栽之前用本发明组合物预防性处理。这些组合物可以直接或者优选稀释后施用于繁殖材料,更具体为种子。在稀释的情况下,所述组合物可以稀释2-10倍,用于包覆的组合物从而包含0.01-60重量%,优选0.1-40重量%活性成分。施用可以在播种之前或之中进行。植物繁殖材料的处理,更具体为种子的处理对熟练技术人员而言是已知的并且通过撒粉、包衣、造粒、浸渍或浸泡植物繁殖材料而实现,其中处理优选通过造粒、包衣和撒粉或通过犁沟内处理进行,从而例如防止种子的早期萌发。为了处理种子,优选使用悬浮液。该类组合物通常包含1-800g/l活性成分,1-200g/l表面活性剂,0-200g/l防冻剂,0-400g/l粘合剂,0-200g/l着色剂以及溶剂,优选水。
本发明的优点是农药在该组合物中非常好地稳定化。它们仅非常缓慢结晶。甚至在低温下基本没有农药结晶。甚至在为了生产桶混物而用水稀释之后,农药基本没有显示出结晶。该组合物允许高浓度的共聚物,这对延缓结晶是有利的。该组合物还允许高浓度的农药。该共聚物可以几乎不含酸性基团,尤其是磺酸基团,它们倾向于降解各种农药。该组合物导致该农药的高耐雨性和/或保留。
下列实施例说明而不限制本发明。
实施例
助剂A:水溶性脂肪醇烷氧基化物,表面张力(1g/l,23℃)28-31mN/m。
助剂B:水溶性脂肪醇烷氧基化物,表面张力(1g/l,23℃)27-29mN/m。
酰胺A:N,N-二甲基C8-10脂肪酸酰胺。
表面活性剂A:非离子三芳基苯酚乙氧基化物,HLB 12-14。
表面活性剂B:阴离子烷基苯磺酸盐,40重量%,在芳族溶剂中。
烃:芳族烃的工业混合物,沸程240-300℃。
VP:N-乙烯基吡咯烷酮
tBAM:叔丁基丙烯酰胺
MMA:甲基丙烯酸甲酯
EA:丙烯酸乙酯
tBA:丙烯酸叔丁酯
MAS:甲基丙烯酸
SPEGMA:C16/18烷基封端的聚乙二醇甲基丙烯酸酯,含有25个乙二醇单元。
MPEGMA:聚乙二醇单甲基醚甲基丙烯酸酯。
制备共聚物A(34VP/6MMA/30EA/30SPEGMA)
进料1:102g N-乙烯基吡咯烷酮
90g SPEGMA
18g 甲基丙烯酸甲酯
90g 丙烯酸乙酯
400g 异丙醇
进料2:60g 异丙醇
8g 过新戊酸叔丁酯
5g 2-巯基-1,2-丙二醇
进料3:30g 异丙醇
20g 过新戊酸叔丁酯
进料4:300g N,N-二甲基十二烷酰胺
将17%进料1放入搅拌设备中并在搅拌下加热至约80℃。在80℃下加入10%进料2并预聚合。然后加入剩余的进料1和进料2。将反应混合物后聚合5小时。在加入进料3之后,将反应混合物进一步后聚合2小时。将反应混合物冷却至室温。最后加入进料4,然后除去异丙醇。得到聚合物的清澈黄色溶液。下列实施例的配制剂中浓度涉及没有N,N-二甲基十二烷酰胺溶剂的聚合物量。
制备共聚物B(40VP/20tBAM/30MMA/10SPEGMA)
进料1:694g 异丙醇
100g t-BAM
200g SPEGMA
150g MMA
10g 2-巯基乙醇
进料2:200g 乙烯基吡咯烷酮
69g 异丙醇
进料3:20g 过辛酸叔丁酯
264g 异丙醇
进料4:500g N,N-二甲基十二烷酰胺
将在异丙醇中的37%进料1、3%进料2和11%进料3引入具有回流冷凝器、内部温度计和4个分开进料装置的搅拌设备中并将该混合物在搅拌下加热至约82℃。在聚合起始之后在12小时内加入剩余的进料1,在14小时内加入剩余的进料2。当加料完成时,将该混合物在该温度下后聚合另外6小时。在加入进料4的同时蒸馏反应混合物的溶剂。
制备共聚物C(40VP/40tBAM/10MMA/10MPEGMA)
共聚物C根据共聚物B制备且含有下列单体混合物:40重量%VP,40重量%tBAM,10重量%MMA和10重量%10MPEGMA。
制备共聚物D(38VP/29MMA/20tBA/10SPEGMA/3MAS)
共聚物D根据共聚物A制备且含有下列单体混合物:38重量%VP,29重量%MMA,20重量%tBA,3重量%MAS和10重量%10SPEGMA。
制备共聚物E(38VP/29MMA/20tBAM/10SPEGMA/3MAS)
共聚物E根据共聚物A制备且含有下列单体混合物:38重量%VP,29重量%MMA,20重量%tBAM,3重量%MAS和10重量%10SPEGMA。
实施例1—啶酰菌胺(boscalid)配制剂
配制剂A-E通过混合表1中所列组分以得到该农药的可乳化浓缩物(EC)而制备。
表1:配制剂组成(全部量按重量%计)
A | B | C | D | Ea) | |
啶酰菌胺 | 8 | 8 | 8 | 8 | 8 |
N,N-二甲基十二烷酰胺 | 40 | 50 | 50 | 50 | 40 |
己二酸二丁酯 | 22 | 22 | 22 | 22 | 22 |
助剂A | 20 | 10 | 8 | 8 | 20 |
助剂B | – | – | 2 | 2 | - |
共聚物B | – | – | – | 10 | - |
共聚物C | 10 | 10 | 10 | – | - |
表面活性剂A | - | - | - | - | 8 |
表面活性剂B | - | - | - | - | 2 |
a)非本发明
实施例2—
的配制剂
配制剂A-F通过混合表2中所列组分以得到该农药的可乳化浓缩物(EC)而制备。为BASF SE对通用名苯嘧磺草胺(saflufenacil)的商标名。
表2:配制剂组成(全部量按重量%计)
a)非本发明
实施例3—氟唑菌酰胺的配制剂
配制剂A-D通过混合表3中所列组分以得到该农药的可乳化浓缩物(EC)而制备。
表3:配制剂组成(全部量按重量%计)
A | Ba) | C | Da) | |
氟唑菌酰胺 | 12 | 12 | 12 | 12 |
N,N-二甲基十二烷酰胺 | 48 | 48 | 48 | 48 |
己二酸二丁酯 | 10 | 10 | – | – |
烃 | – | – | 10 | 10 |
助剂A | 18 | 18 | 18 | 18 |
助剂B | 2 | 2 | 2 | 2 |
共聚物B | 10 | – | 10 | – |
表面活性剂A | – | 8 | – | 8 |
表面活性剂B | – | 2 | – | 2 |
a)非本发明
实施例4—氟唑菌酰胺和
醚唑(difenoconazole)的配制剂
配制剂A-D通过混合表4所列组分以得到该农药的可乳化浓缩物(EC)而制备。
表4:配制剂组成(全部量按重量%计)
a)非本发明
实施例5—氟唑菌酰胺和环戊唑菌的配制剂
配制剂A-D通过混合表5所列组分以得到该农药的可乳化浓缩物(EC)而制备。
表5:配制剂组成(全部量按重量%计)
A | Ba) | C | Da) | |
氟唑菌酰胺 | 9 | 9 | 9 | 9 |
环戊唑菌 | 9 | 9 | 9 | 9 |
N,N-二甲基十二烷酰胺 | 45 | 45 | 45 | 45 |
己二酸二丁酯 | 10 | 10 | – | – |
烃 | – | – | 10 | 10 |
助剂A | 15 | 15 | 15 | 15 |
助剂B | 2 | 2 | 2 | 2 |
共聚物B | 10 | – | 10 | – |
表面活性剂A | – | 8 | – | 8 |
表面活性剂B | – | 2 | – | 2 |
a)非本发明
实施例6—储存稳定性
将实施例1-5的EC配制剂样品在-5℃下储存7天,然后肉眼检查。
表6总结了样品是清澈(“清澈”)还是农药形成一些形式的沉淀(“沉淀”)。
表6A:储存稳定性结果
A | B | C | D | Ea) | |
实施例1 | 清澈 | 清澈 | 清澈 | 清澈 | 沉淀 |
表6B:储存稳定性结果
A | B | C | D | E | Fa) | |
实施例2 | 清澈 | 清澈 | 清澈 | 清澈 | 清澈 | 沉淀 |
表6C:储存稳定性结果
A | Ba) | C | Da) | |
实施例3 | 清澈 | 沉淀 | 清澈 | 沉淀 |
实施例4 | 清澈 | 沉淀 | 清澈 | 沉淀 |
实施例5 | 清澈 | 沉淀 | 清澈 | 沉淀 |
a)非本发明
实施例7—稀释样品在喷雾桶中的稳定性
使用下列测试来研究可乳化浓缩物在稀释至可喷雾浓度之后是否可以用于标准喷雾器而不堵塞喷雾机的过滤器或喷雾喷嘴。
测试机为具有195l桶、四活塞隔膜泵(在3巴压力下)和带有6个标准喷嘴(类型:LU90-03)的喷杆的液力喷雾器。所用喷丝头滤器是4种筛网过滤器(25、50、60和80目)、具有一体式密封的60目筛网过滤器和25目狭缝过滤器。吸滤器和压滤器各自为50目筛网过滤器。
首先对该桶填充75l水,然后填充3l可乳化浓缩物(实施例1-5)。将该混合物用活塞泵(搅拌强度:约45l/min)混合并随后对该桶填充另外75l水。在泵送循环产物混合物15分钟(搅拌强度:约45l/min)之后将喷雾溶液通过喷嘴由该桶喷出。在试验过程中该桶中的喷雾混合物温度保持恒定为5-10℃以模拟冷井水。输送试验重复3次,在各次施用之间不清洁设备。在该程序结束时对泵上游和下游的过滤器(吸滤器和压滤器)以及喷嘴中的过滤器(喷丝头滤器)检查残留物。表7总结了结果。在该表中,“堵塞”是指至少一个过滤器(吸滤器、压滤器或喷丝头滤器)显示明显结垢,引起流动降低或堵塞。在该表中的“无”是指没有发现明显结垢,且“-”是指样品没有测试。
表7A
A | B | C | D | |
实施例1 | 无 | 无 | 无 | 无 |
表7B
A | B | C | D | E | |
实施例2 | 无 | 无 | 无 | 无 | 无 |
表7C
A | Ba) | C | Da) | |
实施例3 | 无 | 堵塞 | 无 | 堵塞 |
实施例4 | 无 | 堵塞 | 无 | 堵塞 |
实施例5 | 无 | 堵塞 | 无 | 堵塞 |
a)非本发明
实施例8—氟唑菌酰胺的配制剂
配制剂A-F通过混合表8所列组分以得到该农药的可乳化浓缩物(EC)而制备。
如实施例6所述测试储存稳定性。配制剂A-F保持清澈。
如实施例7所述测试稀释样品的稳定性。配制剂A-F不显示出任何显著结垢(对应于“无”)。
表8:配制剂组成(全部量按重量%计)
A | B | C | D | E | F | |
氟唑菌酰胺 | 12 | 12 | 12 | 12 | 12 | 12 |
N,N-二甲基十二烷酰胺 | 49 | 54 | 49 | 49 | 54 | 49 |
烃 | 14 | 14 | 19 | 14 | 14 | 19 |
助剂A | 15 | 10 | 10 | 15 | 10 | 10 |
助剂B | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
共聚物D | 7.5 | 7.5 | 7.5 | - | - | - |
共聚物E | - | - | - | 7.5 | 7.5 | 7.5 |
Claims (13)
1.一种包含农药和共聚物的组合物,所述共聚物基于单体总量以聚合形式含有:
至少25重量%含有N-乙烯基内酰胺的酰胺(单体A),其中N-乙烯基内酰胺是N-乙烯基吡咯烷酮、N-乙烯基己内酰胺或其混合物;
至少1重量%单C1-22烷基封端的聚(C2-6亚烷基二醇)(甲基)丙烯酸酯(单体B);以及
至少5重量%(甲基)丙烯酸C1-C8烷基酯(单体C),其中单体C选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸叔丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯及其混合物;
其中所述共聚物与所述农药的重量比为10:1-1:10。
2.根据权利要求1的组合物,其中所述共聚物含有:
25-85重量%单体A,
1-40重量%单体B,
5-50重量%单体C,和
至多15重量%其他单体D,
其中单体A、B、C和D的总和等于100%。
3.根据权利要求1的组合物,其中单体A包括N-乙烯基吡咯烷酮和任选的N-C1-C6烷基丙烯酰胺。
4.根据权利要求2的组合物,其中单体A包括N-乙烯基吡咯烷酮和任选的N-C1-C6烷基丙烯酰胺。
5.根据权利要求1-4中任一项的组合物,其中单体B为单C1-22烷基封端的聚(乙二醇)(甲基)丙烯酸酯。
6.根据权利要求1-4中任一项的组合物,其中所述农药在水中的溶解度至多为10g/l。
7.根据权利要求1-4中任一项的组合物,含有至多10重量%水。
8.根据权利要求1-4中任一项的组合物,其中所述农药以溶解形式存在。
9.根据权利要求1-4中任一项的组合物,其中所述共聚物与所述农药的重量比为5:1-1:5。
10.根据权利要求1-4中任一项的组合物,其中所述组合物包含含有至少一种式(I)的酰胺的有机溶剂:
R1-C(O)N(R2)2 (I)
其中R1为C5-C19烷基且R2为C1-C4烷基,并且任选包含选自链烷酸烷基酯和烃油的另一溶剂。
11.根据权利要求1-4中任一项的组合物,包含:
2-20重量%共聚物;
40-95重量%有机溶剂;
不超过3重量%的水;
1-25重量%所述水不溶性农药;以及
3-50重量%非离子表面活性剂。
12.一种通过使所述农药与所述共聚物接触而制备根据权利要求1-11中任一项的组合物的方法。
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染和/或调节植物生长的方法,其中使根据权利要求1-11中任一项的组合物作用于相应有害物、其栖息地或待防止相应有害物的植物、土壤和/或不希望的植物和/或农作物和/或其生长地上。
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US201261619954P | 2012-04-04 | 2012-04-04 | |
US61/619,954 | 2012-04-04 | ||
EP12163168 | 2012-04-04 | ||
EP12163168.3 | 2012-04-04 | ||
PCT/EP2013/056060 WO2013149856A1 (en) | 2012-04-04 | 2013-03-22 | Agroformulation comprising copolymer of an amide, polyalkylene glycol (meth)acrylate, and alkyl (meth)acrylate |
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CN104202975A CN104202975A (zh) | 2014-12-10 |
CN104202975B true CN104202975B (zh) | 2016-08-24 |
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CN201380017578.1A Active CN104202975B (zh) | 2012-04-04 | 2013-03-22 | 包含酰胺、聚亚烷基二醇(甲基)丙烯酸酯和(甲基)丙烯酸烷基酯的共聚物的农业配制剂 |
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US (1) | US20150173349A1 (zh) |
EP (1) | EP2833716B1 (zh) |
JP (1) | JP6290172B2 (zh) |
CN (1) | CN104202975B (zh) |
AR (1) | AR090597A1 (zh) |
AU (1) | AU2013242909B2 (zh) |
BR (1) | BR112014024415B1 (zh) |
CA (1) | CA2868045C (zh) |
EA (1) | EA032035B1 (zh) |
ES (1) | ES2636915T3 (zh) |
HU (1) | HUE035342T2 (zh) |
PL (1) | PL2833716T3 (zh) |
WO (1) | WO2013149856A1 (zh) |
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CN104202978B (zh) | 2012-04-04 | 2016-06-22 | 巴斯夫欧洲公司 | 包含乙烯基内酰胺、n-烷基丙烯酰胺和(甲基)丙烯酸烷基酯的共聚物的农业配制剂 |
EP2838357B1 (en) | 2012-04-16 | 2017-07-19 | Basf Se | Agroformulation comprising copolymer of acrylic acid, poly(alkylene glycol) (meth)acrylate, and alkyl (meth)acrylate |
EP3104700B1 (en) | 2014-02-14 | 2018-09-26 | BASF Agro B.V. | Emulsifiable concentrate comprising pesticide, fatty amide and lactamide |
GB201805083D0 (en) * | 2018-03-28 | 2018-05-09 | Croda Int Plc | Agrochemical polymer dispersants |
CN112822943A (zh) * | 2018-09-04 | 2021-05-18 | 维乌作物保护有限公司 | 农业制剂中的结晶抑制剂 |
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WO2011003240A1 (en) * | 2009-07-10 | 2011-01-13 | Basf (China) Company Limited | Formulation comprising terpolymer and active substance, and preparation thereof |
WO2011121477A1 (en) * | 2010-03-30 | 2011-10-06 | Basf Se | Use of copolymer for increasing activity of pesticide |
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EP1569971A1 (de) * | 2002-12-02 | 2005-09-07 | Basf Aktiengesellschaft | Copolymere auf n-vinylamid-basis als adjuvans und mittel für den agrotechnischen bereich |
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2013
- 2013-03-22 BR BR112014024415-4A patent/BR112014024415B1/pt active IP Right Grant
- 2013-03-22 HU HUE13714238A patent/HUE035342T2/en unknown
- 2013-03-22 ES ES13714238.6T patent/ES2636915T3/es active Active
- 2013-03-22 CA CA2868045A patent/CA2868045C/en active Active
- 2013-03-22 JP JP2015503817A patent/JP6290172B2/ja active Active
- 2013-03-22 CN CN201380017578.1A patent/CN104202975B/zh active Active
- 2013-03-22 EP EP13714238.6A patent/EP2833716B1/en active Active
- 2013-03-22 EA EA201401079A patent/EA032035B1/ru not_active IP Right Cessation
- 2013-03-22 WO PCT/EP2013/056060 patent/WO2013149856A1/en active Application Filing
- 2013-03-22 US US14/390,458 patent/US20150173349A1/en not_active Abandoned
- 2013-03-22 PL PL13714238T patent/PL2833716T3/pl unknown
- 2013-03-22 AU AU2013242909A patent/AU2013242909B2/en active Active
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Patent Citations (5)
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US4036814A (en) * | 1974-07-04 | 1977-07-19 | Warner-Lambert Company | Lightly cross-linked hydrogel formed from N-vinyl lactam and hydrophobic acrylic ester comonomer |
WO2009040248A1 (en) * | 2007-09-27 | 2009-04-02 | Basf Se | Systemicity enhancers |
WO2010063672A2 (de) * | 2008-12-02 | 2010-06-10 | Basf Se | Verfahren zur herstellung von statistischen radikalischen copolymeren und aus diesen erhältliche wirkstoffzusammensetzungen |
WO2011003240A1 (en) * | 2009-07-10 | 2011-01-13 | Basf (China) Company Limited | Formulation comprising terpolymer and active substance, and preparation thereof |
WO2011121477A1 (en) * | 2010-03-30 | 2011-10-06 | Basf Se | Use of copolymer for increasing activity of pesticide |
Also Published As
Publication number | Publication date |
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CA2868045A1 (en) | 2013-10-10 |
PL2833716T3 (pl) | 2017-10-31 |
EP2833716B1 (en) | 2017-05-10 |
EA032035B1 (ru) | 2019-03-29 |
WO2013149856A1 (en) | 2013-10-10 |
JP2015514100A (ja) | 2015-05-18 |
BR112014024415A2 (pt) | 2017-07-25 |
ES2636915T3 (es) | 2017-10-10 |
EP2833716A1 (en) | 2015-02-11 |
JP6290172B2 (ja) | 2018-03-07 |
AR090597A1 (es) | 2014-11-26 |
EA201401079A1 (ru) | 2015-05-29 |
CA2868045C (en) | 2020-06-02 |
HUE035342T2 (en) | 2018-05-02 |
AU2013242909B2 (en) | 2016-03-03 |
US20150173349A1 (en) | 2015-06-25 |
AU2013242909A1 (en) | 2014-10-30 |
CN104202975A (zh) | 2014-12-10 |
BR112014024415B1 (pt) | 2022-06-14 |
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