CN102802410B - 包含农药和支化壬基胺的烷氧基化物的组合物 - Google Patents
包含农药和支化壬基胺的烷氧基化物的组合物 Download PDFInfo
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- CN102802410B CN102802410B CN201180014277.4A CN201180014277A CN102802410B CN 102802410 B CN102802410 B CN 102802410B CN 201180014277 A CN201180014277 A CN 201180014277A CN 102802410 B CN102802410 B CN 102802410B
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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
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- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
- C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
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Abstract
本发明涉及一种包含农药和烷氧基化物的组合物。此外,本发明涉及烷氧基化物、其制备方法以及其在包含农药的喷雾混合物中作为辅助剂的用途。此外,本发明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,其中使该组合物作用于相应害虫、其栖息地或待防止相应害虫的植物、土壤和/或不希望的植物和/或有用植物和/或其环境。此外,本发明涉及包含该组合物的种子。
Description
本发明涉及一种包含农药和烷氧基化物的组合物。此外,本发明涉及烷氧基化物、其制备方法以及其在包含农药的喷雾混合物中作为辅助剂的用途。此外,本发明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,其中使该组合物作用于相应害虫、其环境或待防止相应害虫的植物、土壤和/或不希望的植物和/或农作物和/或其环境。此外,本发明涉及包含该组合物的种子。本发明包括优选特征与其他优选特征的组合。
烷氧基化物及其在农业化学配制剂中作为辅助剂的用途通常是已知的:
WO 2009/004044公开了一种除草组合物,其包含苯氧基酸除草剂和作为辅助剂的烷氧基化烷基胺。
US 5,668,085公开了一种除草组合物,其包含草甘膦(glyphosate)和表面活性剂的水溶液。该表面活性剂可以是烷氧基化烷基胺,其中烷基包含8-22个碳原子。
WO 2007/97614公开了除草试剂,其包含除草剂和例如可以为烷氧基化烷基胺的表面活性剂。
DE 102005037971公开了包含脂肪醇烷氧基化物和含烷氧基的叔胺的组合物。该混合物可以在农业化学配制剂中用作活性提高剂。
烷氧基化烷基胺,尤其是市售乙氧基化牛脂脂肪胺(POEA),具有重要的毒性(如刺激皮肤和眼睛)和生态毒性(如对水生生物如藻类和水蚤的高生态毒性)。因此,例如通常作为润湿剂存在于 除草剂中的POEA(CAS No.61791-26-2)被认为对水生生物较具毒性(Tsui和Chu,Chemosphere 2003,52,1189-1197)。
因此,本发明的目的是找到一种充分适合除草剂如草甘膦且同时具有较低毒性(尤其是对水生生物的毒性较低)的辅助剂。此外,该辅助剂应使可使得农药的配制剂储存稳定。可使得农药的配制剂储存稳定。
该目的由一种包含农药和烷氧基化物的组合物解决,其中该烷氧基化物为胺烷氧基化物(A):
或胺烷氧基化物(A)的季化衍生物(AQ):
其中
R1为支化的脂族烷基C9H19,
R2、R3和R7相互独立地为亚乙基、亚丙基、亚丁基或这些的混合物,
R4为H、-OH、-OR6、-[R7-O]p-R5、C1-C6烷基和氧阴离子,
R5为H、C1-C6烷基、C2-C6链烯基、C2-C6炔基、-SO3Ra、-P(O)ORbORc、-CH2CO2Rd或-C(O)Re,
R6为C1-C6烷基、C2-C6链烯基或C2-C6炔基,
Ra和Rd相互独立地为H、无机或有机阳离子,
Rb和Rc相互独立地为H、无机或有机阳离子、C1-C6烷基、C2-C6链烯基或C2-C6炔基,
Re为C1-C22烷基、C2-C22链烯基、C2-C22炔基、C6-C22芳基、C7-C22烷基芳基,
n、m和p相互独立地为1-30的值,以及
A-为可农用阴离子,或者若R3为氧阴离子,则A-不存在。
优选本发明组合物包含农药和烷氧基化物,其中烷氧基化物为胺烷氧基化物(A)。
基团R1为支化脂族烷基C9H19。R1的实例尤其是2-甲基辛基、2-乙基庚基、2-丙基己基、3-甲基-2-丙基戊基、2-甲基-2-乙基己基或2,3-二甲基庚基。优选R1包括多个不同的支化脂族C9H19烷基。
R1的平均支化度在大多数情况下为1.01-2.5,优选1.05-1.8,尤其优选1.1-1.5,非常尤其优选1.2-1.3。
就此而言,术语“支化度”原则上以已知方式定义为醇分子中的甲基数减去1。平均支化度为样品的所有分子的支化度的统计平均。换言之,所用基团R1可以呈不同烷基C9H19的混合物形式。因此,用作该合成的原料的醇R1-OH可以呈不同醇的混合物形式。
平均支化度可通过1H NMR光谱法按如下测定:为此,首先将醇R1-OH的样品用三氯乙酰基异氰酸酯(TAI)衍生。在该方法中,将醇转化成氨基甲酸酯。酯化伯醇的信号位于δ=4.7-4.0ppm,酯化仲醇(若存在)的那些信号位于约5ppm,并且该样品中存在的水与TAI反应得到氨基甲酸。所有甲基、亚甲基和次甲基质子在2.4-0.4ppm范围内。<1ppm的信号归属于甲基。平均支化度(iso指数)可以由如此得到的光谱按如下计算:
iso指数=((F(CH3)/3)/(F(CH2-OH)/2))-1,
其中F(CH3)表示对应于甲基质子的信号面积且F(CH2-OH)表示CH2-OH基团中亚甲基质子的信号面积。
优选n具有1-20,尤其优选1-15的值。优选m具有1-20,尤其优选1-15的值。优选p具有1-30,尤其优选1-20的值。n、m和o的值通常为平均值,因为它们大多数情况下在用烷氧基化物烷氧基化时产生。因此,n、m和o不仅可以为整数,而且还可以为整数之间的所有值。
优选在胺烷氧基化物(A)的情况下n和m的总和为2-40,而在其季化衍生物(AQ)的情况下n、m和p的总和为3-80。
在胺烷氧基化物(A)的情况下,n和m的总和尤其优选为3-30,具体为5-25。在另一尤其优选的实施方案中,n和m的总和为6-9,尤其是6.5-8.5,尤其是6.9-7.9。在另一尤其优选的实施方案中,n和m的总和为11-40,尤其是12-30,特别是13.5-25。在另一尤其优选的实施方案中,n和m的总和为8-13,尤其是9-11。
在胺烷氧基化物(A)的季化衍生物(AQ)的情况下,n、m和p的总和尤其优选为3-40,具体为5-25。在尤其优选的实施方案中,n、m和p的总和为8-13,尤其是9-11。
R2、R3和R7优选相互独立地为亚乙基、亚乙基和亚丙基、亚乙基和亚丁基或亚乙基、亚丙基和亚丁基。在另一优选实施方案中,R2、R3和R7为亚丙基。在另一优选实施方案中,R2、R3和R7为亚丁基。尤其优选R2、R3和R7相互独立地为亚乙基或亚乙基和亚丙基。非常尤其优选R2、R3和R7为亚乙基。
若R2、R3或R7包括亚丁基,则后者可以作为正亚丁基、异亚丁基或2,3-亚丁基存在,其中优选正亚丁基和异亚丁基,最优选正亚丁基。
R2、R3和R7可以相互独立地为亚乙基、亚丙基或亚丁基的混合物。就此而言,例如基团R2、R3和R7中的一个或所有可以在各烷氧基化物链中包含这些基团的混合物。该类混合物可以以任何所需顺序相互连接,例如无规或嵌段(如一个亚乙基嵌段和一个亚丙基嵌段)连接。在每种情况下整个烷氧基化物链中的一个或多个基团R2、R3和R7还可以由不同亚烷基构成。例如,R2和R3可以由亚乙基构成且R7可以由亚丙基构成。
R4优选为H、OH、C1-C4烷基和氧阴离子,尤其优选H、甲基、丁基或氧阴离子。在具体优选的实施方案中,R4为甲基。在另一具体优选的实施方案中,R4为氧阴离子。在另一具体优选的实施方案中,R4为H。
R5优选为H或C1-C6烷基,尤其优选H或甲基,尤其是H。
R6优选为C1-C6烷基,如甲基。
Ra和Rd相互独立地为H,或可以带有一个或多个正电荷的无机或有机阳离子。无机阳离子的实例是铵阳离子、Na+、K+、Mg2+、Ca2+或Zn2+。有机阳离子的实例是甲基铵、二甲基铵、三甲基铵、四甲基铵、(2-羟基乙基)铵、二(2-羟基乙基)铵、三(2-羟基乙基)铵、四(2-羟基乙基)铵。优选Ra和Rd相互独立地为H或无机阳离子。若存在无机或有机阳离子,则由相应官能基团(如-SO3 -、-P(O)O-O-或-CH2CO2 -)在R6上形成缔合阴离子基团。
Rb和Rc优选相互独立地为H、无机或有机阳离子。合适的无机或有机阳离子是在Ra下提到的那些。
在另一实施方案中,在季衍生物(AQ)的情况下基团Ra、Rb、Rc和Rd可以相互独立地为有机阳离子,该阳离子基团为AQ本身的季氮阳离子。此时,AQ因此可以形成两性离子,其中阴离子基团由相应官能基团(如 -SO3 -、-P(O)O-O-或-CH2CO2 -)在AQ的R6上形成,而阳离子基团由AQ的季氮形成。在AQ的该两性离子形式中,任选存在可农用阴离子A-。
Re优选为C1-C12烷基、C1-C12芳基或C1-C12烷基芳基,尤其优选C1-C6烷基。
A-为可农用阴离子,正如它们通常为熟练技术人员已知的那样。优选A-为卤离子(如氯离子或溴离子)、磷酸根、硫酸根或阴离子性农药。丙酸根、乙酸根或甲酸根也适合作为A-。尤其优选A-为阴离子性农药,如草甘膦阴离子或草铵膦(glufosinate)阴离子。如果R4为氧阴离子,则存在胺氧化物。此时不存在其他阴离子如A-。
在胺烷氧基化物(A)的情况下,优选R2和R3相互独立地为亚乙基,亚乙基和亚丙基,亚乙基和亚丁基,或亚乙基、亚丙基和亚丁基,并且n和m的总和为2-60,优选2-40,尤其优选3-30,尤其是5-25。在另一优选实施方案中,R2和R3为亚乙基,亚乙基和亚丙基,亚乙基和亚丁基,或亚乙基、亚丙基和亚丁基,并且n和m的总和为6-9,尤其是6.5-8.5,特别是6.9-7.9。在另一优选实施方案中,R2和R3为亚乙基,亚乙基和亚丙基,亚乙基和亚丁基,或亚乙基、亚丙基和亚丁基,并且n和m的总和为11-40,尤其是12-30,特别是13.5-25。在尤其优选的实施方案中,R1和R2为亚乙基,亚乙基和亚丙基,亚乙基和亚丁基,或者亚乙基、亚丙基和亚丁基,并且n和m的总和为6-14,尤其是8-12,特别是9-11。
在胺烷氧基化物(A)的情况下,尤其优选R2和R3为亚乙基且n和m的总和为2-60,优选2-40,尤其优选3-30,尤其是5-25。在另一尤其优选的实施方案中,R2和R3为亚乙基且n和m的总和为6-9,尤其是6.5-8.5,特别是6.9-7.9。在另一尤其优选的实施方案中,R2和R3为亚乙基且n和m的总和为11-40,尤其是12-30,特别是13.5-25。
化合物(A)和(AQ)可以以立体异构体的混合物或分离的立体异构体存在。互变异构体和内铵盐同样由结构(A)和(AQ)包括。
本发明组合物在大多数情况下包含0.1-90重量%,优选1-50重量%,尤其是3-30重量%烷氧基化物。
术语农药是指至少一种选自杀真菌剂、杀虫剂、杀线虫剂、除草剂、 安全剂、杀软体动物剂、杀鼠剂和/或生长调节剂的活性物质。优选的农药是杀真菌剂、杀虫剂、除草剂和生长调节剂。尤其优选的农药是除草剂和生长调节剂。也可以使用两种或更多种上述类别的农药的混合物。熟练技术人员熟知该类农药,它们例如可以在Pesticide Manual,第14版(2006),The British Crop Protection Council,London中找到。合适的农药是:A)嗜球果伞素类:
腈嘧菌酯(azoxystrobin)、醚菌胺(dimoxystrobin)、丁香菌酯(coumoxystrobin)、甲香菌酯(coumethoxystrobin)、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、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)、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(N-(2-(1,3-二甲基丁基)苯基)-1,3-二甲基-5-氟-1H-吡唑-4-甲酰胺)、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-(3',4',5'-三氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、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、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(zoxamid);
-其他羧酰胺类:氯环丙酰胺(carpropamid)、双氯氰菌胺(diclocymet)、双炔酰菌胺(mandiproamid)、土霉素(oxytetracyclin)、硅噻菌胺(silthiofarm)、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)、抑霉唑硫酸盐(imazalil sulfate)、稻瘟酯(pefurazoate)、丙氯灵(prochloraz)、氟菌唑(triflumizole);
-苯并咪唑类:苯菌灵(benomyl)、多菌灵(carbendazim)、麦穗宁(fuberidazoles)、涕必灵(thiabendazole);
-其他:噻唑菌胺(ethaboxam)、氯唑灵(etridiazole)、土菌消(hymexazole)、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)含氮杂环化合物
-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(famoxadon)、咪唑菌酮(fenamidon)、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)、amisulbrom、敌菌灵(anilazin)、灭瘟素(blasticidin-S)、敌菌丹(captafol)、克菌丹(captan)、灭螨蜢(quinomethionate)、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、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、5-乙基-6-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺;
E)氨基甲酸酯和二硫代氨基甲酸酯
-硫代-和二硫代氨基甲酸酯:福美铁(ferbam)、代森锰锌(mancozeb)、代森锰(maneb)、威百亩(metam)、磺菌威(methasulfocarb)、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:乙霉威(diethofencarb)、苯噻菌胺(benthiavalicarb)、异丙 菌胺(iprovalicarb)、百维灵(propamocarb)、霜霉威盐酸盐(propamocarbhydrochloride)、valiphenal、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)其他杀真菌剂
-胍类: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(kasugamycin hydrochloride hydrate)、多氧霉素(polyoxins)、链霉素(streptomycin)、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(tecnazene);
-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(pentachlorphenol)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:亚磷酸及其盐,波尔多液(Bordeaux混合物),铜盐如乙酸铜、氢氧化铜、王铜(copper oxychloride)、碱式硫酸铜,硫;
-防治真菌的生物产品、植物强化产品:枯草芽孢杆菌(Bacillus subtilis)菌株NRRL No.B-21661(例如来自AgraQuest,Inc.,USA.的产品 MAX和 ASO),短小芽孢 杆菌(Bacillus pumilus)菌株NRRL No.B-30087(例如来自AgraQuest,Inc.,USA的 和 Plus),奥德曼细基格孢(Ulocladium oudemansii)(例如来自新西兰BotriZen Ltd.的BOTRY-ZEN),脱乙酰壳多糖(例如来自新西兰BotriZen Ltd.的ARMOUR-ZEN)。
-其他:联苯、拌棉醇(bronopol)、环氟菌胺(cyflufenamid)、清菌脲(cymoxanil)、二苯胺、苯菌酮(metrafenon)、米多霉素(mildiomycin)、喹啉铜(oxine-copper)、调环酸钙(prohexadione-calcium)、螺 茂胺(spiroxamine)、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、N-甲基-(1,2,3,4-四氢萘-1-基)-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-甲酸酯、N-甲基-(R)-(1,2,3,4-四氢萘-1-基)-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-甲酸酯、乙酸6-叔丁基-8-氟-2,3-二甲基喹啉-4-基酯、甲氧基乙酸6-叔丁基-8-氟-2,3-二甲基喹啉-4-基酯、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(ancymidole)、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(inabend)、吲哚-3-乙酸、抑芽丹(maleic hydrazide)、氟草磺(mefluidide)、助壮素阳离子(mepiquat)(助壮素 (mepiquat chloride))、环戊唑菌(metconazole)、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(prohydroj asmone)、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(napropamid)、萘丙胺(naproanilid)、烯草胺(pethoxamid)、丙草胺(pretilachlor)、扑草胺(propachlor)、噻醚草胺(thenylchlor);
-氨基酸类似物:双丙氨酰膦(bilanafos)、草甘膦、草铵膦、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);
-氨基甲酸酯类和硫代氨基甲酸酯类: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(acifuorfen)、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)、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(ametryne)、莠去津(atrazine)、草净津(cyanazine)、戊草津(dimethametryne)、乙嗪草酮(ethiozine)、六嗪同(hexazinone)、苯嗪草(metamitron)、赛克津(metribuzine)、扑草净(prometryne)、西玛津(simazine)、特丁津(terbuthylazine)、去草净(terbutryne)、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(orthosulfamuron)、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(pyriftalide)、肟啶草(pyriminobac-methyl)、pyrimisulfan、嘧硫苯甲酸(pyrithiobac)、pyroxasulfon、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)、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)、cyprosulfamid、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)、四唑酰草胺(fentrazamide)、氟烯草酸(flumiclorac-pentyl)、氟 嗪酮(flumioxazin)、胺草唑(flupoxam)、氟咯草酮(fluorochloridon)、呋草酮(flurtamon)、茚草酮(indanofan)、异恶草 胺(isoxaben)、异 氟草(isoxaflutol)、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(oxadiazone)、氯 嗪草(oxaziclomefon)、戊 唑草(pentoxazone)、唑啉草酯(pinoxaden)、双唑草腈(pyraclonil)、吡草醚(pyraflufen-ethyl)、pyrasulfotol、苄草唑(pyrazoxyfen)、吡唑特(pyrazolynate)、灭藻醌(quinoclamin)、嘧啶肟草醚(saflufenacil)、磺草酮(sulcotrione)、磺胺草唑(sulfentrazone)、特草定(terbacil)、tefuryltrione、tembotrione、thiencarbazone、topramezone、4-羟基-3-[2-(2-甲氧基乙氧基甲基)-6-三氟甲基吡啶-3-羰基]双环[3.2.1]辛-3-烯-2-酮、(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: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(dimethoat)、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(clofentazin);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(spirotetramate);
-烟碱受体激动剂/拮抗剂: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:硫丹(endosulfan)、乙虫清(ethiprole)、锐劲特(fipronil)、氟吡唑虫(vaniliprole)、pyrafluprole、pyriprole、N-5-氨基-1-(2,6-二氯-4-甲基苯基)-4-亚磺酰氨酰基(sulflnamoyl)-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);
-线粒体电子传输链抑制剂(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(hydramethylnone);
-分离剂: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);
-昆虫蜕皮抑制剂:灭蝇胺(cryomazin);
-‘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(metaflumizon);
-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(pymetrozin)、硫、硫环杀(thiocyclam)、氟虫酰胺(flubendiamid)、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pyrifluq uinazone。
优选农药包括至少一种具有至少一个H-酸性基团(如羧酸基团、膦酸基团、次膦酸基团)或其阴离子盐(例如单-、二-或三盐)的农药。具有H-酸性基团的农药的这些阴离子盐也适合作为基团A-中的阴离子性农药。优选的具有H-酸性基团的农药是具有H-酸性基团的除草剂。具有H-酸性基团的除草剂实例是氨基酸类似物(如草甘膦或草铵膦)或咪唑啉酮类(如咪草酯、咪草啶酸、甲基咪草烟、灭草烟、灭草喹、咪草烟)。尤其优选的具有H-酸性基团的农药是草甘膦和草铵膦。在另一优选实施方案中,具有H-酸性基团的农药是咪唑啉酮类。
尤其优选该农药包括具有H-酸性基团的农药和另一农药。在另一实施方案中,该农药包括至少两种具有H-酸性基团的农药以及任选其他农药(如至少一种杀真菌剂、除草剂、杀虫剂和/或安全剂,优选杀真菌剂和/或除草剂)的混合物。
在另一优选实施方案中,该农药包括草甘膦(例如作为游离盐、钠盐、倍半钠盐、钾盐、二钾盐、铵盐、二铵盐、二甲基铵盐、三甲基锍盐(trimesium salt)或异丙基胺盐)或草铵膦(例如作为铵盐)。尤其优选该农药包括草甘膦(例如作为钾盐、铵盐、异丙基胺盐)。尤其优选该农药包括草甘膦或草铵膦以及额外还有其他农药。在另一优选实施方案中,该农药包括草甘膦或草铵膦以及额外还有其他农药(如至少一种杀真菌剂、除草剂、杀虫剂和/或安全剂,优选杀真菌剂和/或除草剂)。
此外,本发明组合物还可以包含常用于农业化学配制剂的辅助剂,辅助剂的选择取决于特定使用形式、配制剂类型或活性物质。合适辅助剂的实例是溶剂、固体载体、表面活性物质(如表面活性剂、增溶剂、保护性胶体、润湿剂和增粘剂),有机和无机增稠剂,杀菌剂,防冻剂,消泡剂,任选还有着色剂和粘合剂(例如用于种子处理)或用于诱饵配制剂的常规辅助剂(例如引诱剂、进食剂、苦味物质)。
合适的溶剂是水或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,例如石蜡、四氢化萘、烷基化萘及其衍生物、烷基化苯及其衍生物,醇类如甲醇、乙醇、丙醇、丁醇和环己醇,二醇类,酮类如环己酮、γ-丁内酯, 二甲基脂肪酸酰胺,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。原则上还可以使用溶剂混合物以及上述溶剂与水的混合物。
固体载体为矿土如硅石、硅胶、硅酸盐、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、硫酸钙和硫酸镁、氧化镁;磨碎的合成材料;肥料如硫酸铵、磷酸铵、硝酸铵、脲类;以及植物产品如谷粉、树皮粉、木粉和坚果壳粉,纤维素粉或其他固体载体。
合适的表面活性物质(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(N 类型,德国BASF)及脂肪酸的碱金属、碱土金属和铵盐,烷基-和烷基芳基磺酸盐,烷基醚硫酸盐,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物,萘或萘磺酸与苯酚和甲醛的缩合物,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或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( 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),聚乙烯亚胺( 类型,德国BASF),聚乙烯吡咯烷酮及其共聚物。
本发明组合物可以包含0.1-40重量%,优选1-30重量%,尤其是2-20重量%表面活性物质,其中不考虑烷氧基化物(A)和(AQ)的量。
合适的增稠剂是赋予配制剂以改性的流动性能,即静止状态下的高粘度和搅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。该类增稠剂可市购,例如Xanthan Gum( CP Kelco,USA), 23(法国Rhodia)或 (R.T.Vanderbilt,USA)或 (Engelhard Corp.,NJ,USA)。该配制剂中增稠剂的含量取决于该增稠剂的效力。熟练人员将选择使得达到所需配制剂粘度的含量。该含量在大多数情况下为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以及还有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,有机氟化合物以及这些的混合物。
本发明组合物优选可以以农业化学配制剂形式存在。该类配制剂的实例及其制备为:
i)水溶性浓缩物(SL,LS):使用90重量份水或水溶性溶剂溶解10重量份活性物质。或者加入润湿剂或其他辅助剂。活性物质在用水稀释时溶解。这得到活性物质含量为10重量%的组合物。
ii)分散性浓缩物(DC):将20重量份活性物质溶于70重量份环己酮中并加入10重量份分散剂如聚乙烯吡咯烷酮。用水稀释得到分散体。活性物质含量为20重量%。
iii)可乳化浓缩物(EC):将15重量份活性物质溶于75重量份二甲苯中并加入十二烷基苯磺酸钙和蓖麻油乙氧基化物(在每种情况下5重量份)。
用水稀释得到乳液。该组合物的活性物质含量为15重量%。
iv)乳液(EW,EO,ES):将25重量份活性物质溶于35重量份二甲苯中并加入十二烷基苯磺酸钙和蓖麻油乙氧基化物(在每种情况下5重量份)。使用乳化机(例如Ultraturrax)将该混合物引入30重量份水中并制成均相乳液。用水稀释得到乳液。该组合物的活性物质含量为25重量%。
v)悬浮液(SC,OD,FS):在搅拌的球磨机中将20重量份活性物质粉碎并加入10重量份分散剂和润湿剂以及70重量份水或有机溶剂,得到细碎活性物质悬浮液。用水稀释得到稳定的活性物质悬浮液。该组合物中的活性物质含量为20重量%。
vi)水分散性颗粒和水溶性颗粒(WG,SG):将50重量份活性物质细碎研磨并加入50重量份分散剂和润湿剂,借助工业装置(例如挤出机、喷雾塔、流化床)将其制成水分散性或水溶性颗粒。用水稀释得到稳定的活 性物质分散体或溶液。该组合物的活性物质含量为50重量%。
vii)水分散性粉末和水溶性粉末(WP,SP,SS,WS):将75重量份活性物质在转子-定子磨机中研磨并加入25重量份分散剂、润湿剂以及还有硅胶。用水稀释得到稳定的活性物质分散体或溶液。该组合物的活性物质含量为75重量%。
viii)凝胶(GF):在球磨机中研磨20重量份活性物质、10重量份分散剂、1重量份胶凝剂和70重量份水或有机溶剂而得到精细悬浮液。用水稀释得到活性物质含量为20重量%的稳定悬浮液。
ix)粉剂(DP,DS):将5重量份活性物质细碎研磨并与95重量份细碎高岭土充分混合。这得到活性物质含量为5重量%的粉剂。
x)颗粒(GR,FG,GG,MG):将0.5重量份活性物质细碎研磨并结合99.5重量份载体。用于此目的的常见方法是挤出、喷雾干燥或流化床方法。这得到活性物质含量为0.5重量%的直接施用颗粒。
xi)ULV溶液(UL):将10重量份活性物质溶于90重量份有机溶剂如二甲苯中。这得到活性物质含量为10重量%的直接施用组合物。
该组合物通常包含0.01-95重量%,优选0.1-90重量%农药。
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。这里将该配制剂用水和/或缓冲剂稀释至所需使用浓度,任选加入其他辅助剂,从而得到即用喷雾混合物(已知为桶混物)。每公顷农业利用区通常施用50-500升,优选100-400升即用喷雾混合物。在特殊情况下,也可以超过这些量(例如果树栽培)或在这些量之下(例如飞机施用)。即用制剂中的活性物质浓度可以在相当大的范围内变化。它们通常为0.0001-10%,优选0.01-1%。
在紧临使用前可以向活性物质或包含它们的制剂中,任选也向桶混物中加入各种类型的油、润湿剂、降低漂移的试剂、粘着剂、铺展剂、辅助剂、肥料、植物强化产品、痕量元素、除草剂、杀菌剂、杀真菌剂和/或杀虫剂。这些产品可以以1:100-100:1,优选1:10-10:1的重量比混入本发明组合物中。就此而言合适的辅助剂尤其是有机改性的聚硅氧烷,例如Break Thru S 醇烷氧基化物,例如 245、 MBA 1303、 LF 300和 ON 30;EO/PO嵌段聚合物,例如 RPE 2035和 B;醇乙氧基化物,例如 XP 80;以及磺基琥珀酸二辛酯钠,例如 RA。
取决于所需效果的性质,活性物质的施用率在用于植物保护时为0.001-2.0kg活性物质/ha,优选0.005-2kg活性物质/ha,尤其优选0.05-0.9kg活性物质/ha,尤其是0.1-0.75kg活性物质/ha。
此外,本发明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相应害虫、其环境或待防止相应害虫的植物、土壤和/或不希望的植物和/或农作物和/或其环境。
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、醋栗或鹅莓;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、南瓜或柿子椒;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。基因修饰植物是其遗传材料以在自然条件下不通过杂交、突变或自然重组(即遗传材料的重构)进行的方式修饰的植物。在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,例如通过糖基化或结合聚合物如异戊二烯化、乙酰化或法呢基化残 基或PEG残基。
可以提到的实例是通过植物育种和重组措施而耐受某些类别的除草剂的植物,这些除草剂如羟基苯基丙酮酸二加氧酶(HPPD)抑制剂,乙酰乳酸合成酶(ALS)抑制剂,例如磺酰脲类(EP-A 257993,US 5,013,659)或咪唑啉酮类(例如US 6,222,100,WO 01/82685,WO 00/26390,WO 97/41218,WO 98/02526,WO 98/02527,WO 04/106529,WO 05/20673,WO 03/14357,WO 03/13225,WO 03/14356,WO 04/16073),烯醇丙酮酰莽草酸3-磷酸合成酶(EPSPS)抑制剂,例如草甘膦(例如参见WO 92/00377),谷氨酰胺合成酶(GS)抑制剂,例如草铵膦(例如参见EP-A 242236,EP-A 242246)或oxynil除草剂(例如参见US 5,559,024)。例如育种和诱变产生特征在于耐受咪唑啉酮类如咪草啶酸的 油菜(德国BASF SE)。借助重组方法,产生耐受草甘膦或草铵膦的农作物如大豆、棉花、玉米、甜菜和油菜,它们可以以商标名 (耐受草甘膦,Monsanto,U.S.A.)和Liberty (耐受草铵膦,德国Bayer CropScience)得到。
还包括借助重组措施产生一种或多种毒素如芽孢杆菌属(Bacillus)细菌菌株的那些的植物。由该类基因修饰植物产生的毒素例如包括芽孢杆菌属,尤其是苏云金芽孢杆菌(B.thuringiensis)的杀虫蛋白如内毒素Cry1Ab、Cry1Ac、Cry1F、Cry1Fa2、Cry2Ab、Cry3A、Cry3Bb1、Cry9c、Cry34Ab1或Cry35Ab1;或无性杀虫蛋白(VIP),例如VIP1、VIP2、VIP3或VIP3A;线虫定居细菌的杀虫蛋白,例如发光杆菌属(Photorhabdus)或致病杆菌属(Xenorhabdus);动物有机体的毒素如黄蜂、蜘蛛或蝎子毒素;真菌毒素,例如来自链霉菌属(Streptomycetes);植物凝集素,例如来自豌豆或大麦;凝集素,蛋白酶抑制剂,例如胰蛋白酶抑制剂,丝氨酸蛋白酶抑制剂,patatin,半胱氨酸蛋白酶抑制剂或木瓜蛋白酶抑制剂,核糖体失活蛋白(RIP),例如蓖麻蛋白、玉米-RIP、相思豆毒蛋白、丝瓜籽蛋白、皂草素或异株腹泻毒蛋白(bryodin);类固醇代谢酶,例如3-羟基类固醇氧化酶、蜕皮甾类-IDP糖基转移酶、胆固醇氧化酶、蜕皮激素抑制剂或HMG-CoA还原酶;离子通道阻断剂,例如钠通道或钙通道抑制剂;保幼激素酯酶;利尿激素受体(helicokinin受体);茋合成酶,联苄合成酶,壳多糖酶和葡 聚糖酶。在植物中,这些毒素还可以作为前毒素、杂合蛋白或截短的或其他方面改性的蛋白产生。杂合蛋白的特征在于不同蛋白域的新型组合(例如参见WO 2002/015701)。该类毒素或产生这些毒素的基因修饰植物的其他实例公开于EP-A 374753、WO 93/07278、WO 95/34656、EP-A 427529、EP-A 451878、WO 03/18810和WO 03/52073中。产生这些基因修饰植物的方法对熟练技术人员是已知的且例如公开于上述出版物中。许多上述毒素赋予产生它们的植物以对所有分类学上为节肢动物的害虫,尤其是甲虫(鞘翅目(Coeleropta))、双翅目昆虫(双翅目(Diptera))和蝴蝶(鳞翅目(Lepidoptera))以及线虫(线虫纲(Nematoda))的耐受性。对杀虫毒素产生一个或多个基因编码的基因修饰植物例如描述于上述出版物中且在一些情况下可市购,例如 (产生毒素Cry1Ab的玉米栽培品种), Plus(产生毒素Cry1Ab和Cry3Bb1的玉米栽培品种), (产生毒素Cry9c的玉米栽培品种), RW(产生毒素Cry34Ab1、Cry35Ab1和酶膦丝菌素-N-乙酰转移酶[PAT]的玉米栽培品种); 33B(产生毒素Cry1Ac的棉花栽培品种), I(产生毒素Cry1Ac的棉花栽培品种), II(产生毒素Cry1Ac和Cry2Ab2的棉花栽培品种); (产生VIP毒素的棉花栽培品种); (产生毒素Cry3A的土豆栽培品种); Bt11(例如 CB)和法国Syngenta Seeds SAS的Bt176(产生毒素Cry1Ab和PAT酶的玉米栽培品种),法国Syngenta Seeds SAS的MIR604(产生毒素Cry3A的修饰译本的玉米栽培品种,参见WO 03/018810),比利时Monsanto Europe S.A.的MON 863(产生毒素Cry3Bb1的玉米栽培品种),比利时Monsanto Europe S.A.的IPC 531(产生毒素Cry1Ac的修饰译本的棉花栽培品种)和比利时Pioneer Overseas Corporation的1507(产生毒素Cry1F和PAT酶的玉米栽培品种)。
还包括借助重组措施产生一种或多种对细菌、病毒或真菌病原体的耐受性或抵抗能力增强的蛋白质的植物,例如所谓的与发病机理相关的蛋白(PR蛋白,参见EP-A 0392225),抗性蛋白(例如产生两种针对来自野生墨西哥土豆Solanum bulbocastanum的致病疫霉(Phytophthora infestans)的 抗性基因的土豆栽培栽培品种)或T4溶菌酶(例如通过产生该蛋白而耐受细菌如Erwinia amylvora的土豆栽培品种)。
还包括借助重组方法,例如通过提高潜在产量(例如生物质、谷粒产量、淀粉含量、油含量或蛋白质含量),对干旱、盐或其他极限环境因素的耐受性或对害虫以及真菌、细菌和病毒病原体的耐受性而改善生产量的植物。
还包括尤其为了改善人类或动物营养而借助重组方法修饰其成分的植物,例如产生促进健康的长链ω-3脂肪酸或单不饱和ω-9脂肪酸的油料植物(例如 油菜,加拿大DOW Agro Sciences)。
本发明还涉及包含本发明组合物的种子(如种子或其他植物繁殖材料)。植物繁殖材料可以在播种时或者甚至播种之前或者在移栽时或者甚至移栽之前预防性地用本发明组合物处理。为了处理种子,通常使用水溶性浓缩物(LS),悬浮液(FS),粉剂(DS),水分散性和水溶性粉末(WS,SS),乳液(ES),可乳化浓缩物(EC)和凝胶(GF)。这些组合物可以以未稀释形式或者优选以稀释形式施用于繁殖材料,尤其是种子。此时可以将所述组合物稀释2-10倍,从而使0.01-60重量%,优选0.1-40重量%活性物质存在于用于种子包衣的组合物中。施用可以在播种之前或之中进行。植物繁殖材料的处理,尤其是种子的处理对熟练人员而言是已知的且通过植物繁殖材料的撒粉、包衣、造粒、浸渍或浸泡而进行,优选通过造粒、包衣和撒粉或犁沟处理而进行处理,从而例如防止种子过早萌发。优选将悬浮液用于种子处理。该类组合物通常包含1-800g/l活性物质,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。
此外,本发明涉及烷氧基化物,其中该烷氧基化物为胺烷氧基化物(A):
其中
R1为支化的脂族烷基C9H19,
R2、R3和R7相互独立地为亚乙基、亚丙基、亚丁基或这些的混合物,
R4为H、-OH、-OR6、-[R7-O]p-R5、C1-C6烷基和氧阴离子,
R5为H、C1-C6烷基、C2-C6链烯基、C2-C6炔基、-SO3Ra、
-P(O)ORbORc、-CH2CO2Rd或-C(O)Re,
R6为C1-C6烷基、C2-C6链烯基或C2-C6炔基,
Ra和Rd相互独立地为H、无机或有机阳离子,
Rb和Rc相互独立地为H、无机或有机阳离子、C1-C6烷基、C2-C6链烯基或C2-C6炔基,
Re为C1-C22烷基、C6-C22芳基、C7-C22烷基芳基,
n、m和p相互独立地为1-30的值,和
A-为可农用阴离子,或者若R3为氧阴离子,则A-不存在。
其他优选实施方案如上所述。
此外,本发明涉及烷氧基化物,其中该烷氧基化物为胺烷氧基化物(A)的季化衍生物(AQ):
其中
R1为支化的脂族烷基C9H19,
R2、R3和R7相互独立地为亚乙基、亚丙基、亚丁基或这些的混合物,
R4为H、-OH、-OR6、-[R7-O]p-R5、C1-C6烷基和氧阴离子,
R5为H、C1-C6烷基、C2-C6链烯基、C2-C6炔基、-SO3Ra、 -P(O)ORbORc、-CH2CO2Rd或-C(O)Re,
R6为C1-C6烷基、C2-C6链烯基或C2-C6炔基,
Ra和Rd相互独立地为H、无机或有机阳离子,
Rb和Rc相互独立地为H、无机或有机阳离子、C1-C6烷基、C2-C6链烯基或C2-C6炔基,
Re为C1-C22烷基、C6-C22芳基、C7-C22烷基芳基,
n、m和p相互独立地为1-30的值,和
A-为可农用阴离子,或者若R3为氧阴离子,则A-不存在。
A-在这里优选为卤离子(如氯离子或溴离子)、磷酸根、硫酸根或无机农药。A-尤其优选为无机农药,如草甘膦阴离子或草铵膦阴离子。其他优选的实施方案如上所述。
此外,本发明涉及制备胺烷氧基化物(A)或胺烷氧基化物(A)的季化衍生物(AQ)的方法,包括用氧化乙烯、氧化丙烯、氧化丁烯或这些的混合物烷氧基化胺R1-NH2。
此外,本发明涉及胺R1-NH2。它是制备胺烷氧基化物(A)或胺烷氧基化物(A)的季化衍生物(AQ)的重要中间体。R1的优选实施方案如上所述。胺R1-NH2可以通过使氨与醇R1-OH反应而制备。合适的催化剂和反应条件如US 5,808,158所述。
醇R1-OH通常是已知的(例如CAS No.27458-94-2)且可市购,例如以Isononanol INA购自Evonik Oxeno GmbH,以Isononanol购自OXEACorporation,或以Nonanol N购自BASF SE。异壬醇含量通常为至少70重量%,优选至少95重量%,尤其是至少99重量%。
醇R1-OH原则上可以通过任何方法合成,只要它们在每种情况下具有所述支化度。
R1-OH可以优选由包含丁烯的烃混合物开始制备,例如如WO2000/63151所述:
a)在第一步中将丁烯二聚而得到异构辛烯的混合物。
b)然后将a)的辛烯混合物加氢甲酰化而得到C9醛。
c)使b)的醛得到异壬醇。
该合成的详情通常对熟练技术人员是已知的,例如参见WO 2000/63151[步骤a)见第6页第2行至第8页第7行;步骤b)见第8页第9行至第9页第30行;步骤c)参见第9页第32行至第10页第16行]。特别合适的醇R1-OH可以如WO 2000/63151实施例1,工艺步骤1和2(第13页第35行至第14页第33行)所述制备。
烷氧基化可以由强碱,例如碱金属氢氧化物和碱土金属氢氧化物,布朗斯台德酸或路易斯酸,如AlCl3、BF3催化。可以将催化剂如水滑石或DMC用于具有窄分布的醇烷氧基化物。烷氧基化优选在约80-250°C,优选约100-220°C的温度下进行。压力优选为环境压力至600巴。需要的话,氧化烯可以包含惰性气体混合物,例如约5-60%的惰性气体混合物。
胺烷氧基化物(A)的季化衍生物(AQ)可以通过季化胺烷氧基化物(A)而 在另一反应步骤中制备。为了将基团R4引入胺烷氧基化物(A)中,例如可以使后者与烷基化试剂如甲基氯、硫酸二甲酯或丁基氯反应。为了将一个氧阴离子引入胺烷氧基化物(A)中,可以将后者氧化,例如通过使氨基与过氧化氢、过酸(如间氯过苯甲酸或过乙酸)或过氧单硫酸反应。
其中R4=H的季化衍生物(AQ)可以通过简单质子化具有结构(A)的起始化合物而制备。其中R4=OH的季化衍生物(AQ)可以通过简单质子化其中R4=氧阴离子的起始化合物(AQ)而制备。适合质子化的酸是有机酸(例如C1-C20羧酸,尤其是苯甲酸)或无机酸(例如盐酸、磷酸或硫酸)。同样合适的其他物质是H-酸性农药如草甘膦酸或草甘膦单盐。质子化可以在分开的合成中进行,从而可以分离季化衍生物(AQ)。还可以通过将起始化合物与一种或多种酸在组合物中或在喷雾混合物中混合而进行质子化。
本发明还涉及如上所定义的胺烷氧基化物(A)或胺烷氧基化物(A)的季化衍生物(AQ)在包含农药的喷雾混合物中作为助剂的用途。助剂优选为提高活性的助剂。该提高活性的助剂也称为辅助剂。与农药在没有辅助剂存在下的活性相比,它们提高或促进农药的活性。
本发明的优点是配制剂和喷雾混合物的高稳定性,在喷雾施用的情况下很少有风引起的漂移,该配制剂在被处理植物表面上的良好粘附,农药在该配制剂中的溶解性增加,农药向植物的渗透增加以及因此更快速和提高的活性。重要的优点是新烷氧基化物的低毒性,尤其是低水生毒性。另一优点是这些烷氧化物的简单处理,因为例如当将它们掺入配制剂中时不会发生凝胶形成。另一优点是对农作物的低毒性,即低植物毒性效果。另一优点是支化壬醇以工业规模可得(全世界的年产能为几十万(!)吨),因为也为增塑剂前体且可以由廉价的C4原料得到。
下列实施例说明本发明而不施加任何限制。
实施例
实施例1:由C
9
醇制备支化C
9
胺
所用C9醇为Nonanol N,其可以由BASF SE市购(饱和、异构伯壬基醇的混合物,CAS 248-471-3,沸程195-203°C(DIN 51751),折射率1.4353,在20°C下的动态粘度12.95mPas(DIN 51562),比重0.8335g/ml(DIN 53217))。
将C9醇(1450g)和醇胺化催化剂(描述于EP 696572A1中;基于C17醇为4.8重量%)引入高压釜中并将该高压釜用氮气和氢气吹洗。然后加入2500g氨并在搅拌下温热。在在235°C和280巴的H2压力下反应10小时之后,将所得C9胺过滤并在旋转蒸发器上除去水(水含量小于0.1重量%)。
实施例2:用5、7、10个EO单元烷氧基化支化C
9
胺
首先用23.1g水处理715g(5mol)实施例1的C9胺。将该混合物用氮气吹洗,然后在100°C下在12小时内计量加入440g(10mol)氧化乙烯(EO),其中计量加料由重量控制。然后继续在100°C下搅拌6小时。然后使该混合物在90°C和真空下脱水2小时。这得到1164g的产量(=理论值的101%),胺值为239mg KOH/g(理论上为243mg KOH/g)。在第二步中将2.3g浓度为50%的KOH加入300g(1.3mol)该前体中并将该混合物在90°C和真空下脱水2小时。在用氮气吹洗之后,在120°C下在6小时内计量加入286g(6.5mol)氧化乙烯,其中计量加料由重量控制。然后继续在120°C下搅拌6小时。将该产物在真空中脱气并用几滴乙酸中和。这得到产量为592g(理论值的101%)的低粘度无色液体(下文为“异-C9-7EO”;胺值为119mg KOH/g(理论上为124mg KOH/g)。
由实施例1的胺开始,也类似于异-C9-7EO的制备制备异-C9-5EO(即用总共5个EO基团乙氧基化)和异-C9-10EO(即用总共10个EO基团乙氧基化)。
实施例3—在模型植物冬小麦或大豆上的草甘膦SL
为了进行温室试验,将冬小麦或大豆以1-2cm的播种深度播种或盆栽于壤质砂中。一旦植株达到10-25cm的高度(即播种之后大约10-21天),就将喷雾混合物施用于喷雾箱中的植株。
将包含溶于水中的草甘膦异丙基铵和实施例2的胺烷氧基化物的浓缩配制剂用软化水稀释并以375l/ha的水施用重量(140g或280g草甘膦/ha以及在每种情况下300g胺烷氧基化物/ha)施用。将 T-150(“C16/18胺-15EO”,由德国Clariant市购)用作对比,其为被15个氧化乙烯烷氧基化的脂族C16/18胺。在为3-4周的该试验期中温度为 18-35°C。在此期间,测试植物受到最佳灌溉,其中养分供应由灌溉水提供。
除草活性通过与未处理的对照植株对比地对被处理植株打分而评价(表1-3)。评价标准为0%至100%活性。100%活性是指至少地面上植物部分完全死亡。相反,0%活性是指在被处理植株和未处理植株之间没有观察到不同。表1和2中的结果证实活性物质的活性因加入胺烷氧基化物而提高。
表1:冬小麦栽培品种Cubus
a)对比试验,不按本发明。
表2:大豆栽培品种Oxford
a)对比试验,不按本发明。
Claims (19)
1.一种包含农药和烷氧基化物的组合物,其中所述烷氧基化物为胺烷氧基化物(A):
或胺烷氧基化物(A)的季化衍生物(AQ)
其中
R1为支化的脂族烷基C9H19,
R2、R3和R7相互独立地为亚乙基、亚丙基、亚丁基或这些的混合物,
R4为H、-OH、-OR6、-[R7-O]p-R5、C1-C6烷基和氧阴离子,
R5为H、C1-C6烷基、C2-C6链烯基、C2-C6炔基、-SO3Ra、-P(O)ORbORc、-CH2CO2Rd或-C(O)Re,
R6为C1-C6烷基、C2-C6链烯基或C2-C6炔基,
Ra和Rd相互独立地为H、无机或有机阳离子,
Rb和Rc相互独立地为H、无机或有机阳离子、C1-C6烷基、C2-C6链烯基或C2-C6炔基,
Re为C1-C22烷基、C2-C22链烯基、C2-C22炔基、C6-C22芳基、C7-C22烷基芳基,
n、m和p相互独立地为1-30的值,和
A-为可农用阴离子,或者若R3为氧阴离子,则A-不存在,
其中所述农药为具有至少一个H-酸性基团或其阴离子盐的农药。
2.根据权利要求1的组合物,其中R2、R3和R7相互独立地为亚乙基、亚乙基和亚丙基、亚乙基和亚丁基或亚乙基、亚丙基和亚丁基。
3.根据权利要求1的组合物,其中A-为卤离子、磷酸根、硫酸根或阴离子性农药。
4.根据权利要求2的组合物,其中A-为卤离子、磷酸根、硫酸根或阴离子性农药。
5.根据权利要求1-4中任一项的组合物,其中R4为H。
6.根据权利要求1-4中任一项的组合物,其中在胺烷氧基化物(A)中n和m的总和为2-40且在其季化衍生物(AQ)中n、m和p的总和为3-80。
7.根据权利要求5的组合物,其中在胺烷氧基化物(A)中n和m的总和为2-40且在其季化衍生物(AQ)中n、m和p的总和为3-80。
8.根据权利要求1-4中任一项的组合物,其中R1的平均支化度为1.01-2.5并且其中所述支化度定义为分子中的甲基数减去1。
9.根据权利要求7的组合物,其中R1的平均支化度为1.01-2.5并且其中所述支化度定义为分子中的甲基数减去1。
10.根据权利要求1-4中任一项的组合物,其中所述农药包括草甘膦或草铵膦。
11.根据权利要求9的组合物,其中所述农药包括草甘膦或草铵膦。
12.根据权利要求1-4中任一项的组合物,其中所述农药包括草甘膦或草铵膦以及额外还有其他农药。
13.根据权利要求11的组合物,其中所述农药包括草甘膦或草铵膦以及额外还有其他农药。
14.一种根据权利要求1-5中任一项的胺烷氧基化物(A),其中n和m的总和为3-30。
15.一种根据权利要求1-5中任一项的胺烷氧基化物(A)的季化衍生物(AQ),其中n、m和p的总和为3-80。
16.一种制备根据权利要求14的胺烷氧基化物(A)或根据权利要求15的胺烷氧基化物(A)的季化衍生物(AQ)的方法,包括用氧化乙烯、氧化丙烯、氧化丁烯或这些的混合物烷氧基化胺R1-NH2,其中R1如权利要求1中所定义。
17.一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,其中使根据权利要求1-13中任一项的组合物作用于相应害虫、其环境或待防止相应害虫的植物、土壤和/或不希望的植物和/或农作物和/或其环境。
18.一种通过将根据权利要求1-13中任一项的组合物施用于种子而处理种子的方法。
19.根据权利要求1-9中任一项的胺烷氧基化物(A)或胺烷氧基化物(A)的季化衍生物(AQ)在包含农药的喷雾混合物中作为辅助剂的用途,其中所述农药为具有至少一个H-酸性基团或其阴离子盐的农药。
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JP5881623B2 (ja) | 2016-03-09 |
EP2547200A2 (de) | 2013-01-23 |
EP2547200B1 (de) | 2015-02-25 |
BR112012023244A2 (pt) | 2015-09-15 |
BR112012023244B1 (pt) | 2018-02-14 |
JP2013522265A (ja) | 2013-06-13 |
WO2011113786A2 (de) | 2011-09-22 |
CN102802410A (zh) | 2012-11-28 |
KR20130051927A (ko) | 2013-05-21 |
WO2011113786A3 (de) | 2012-01-19 |
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