CN106068076B - 作为作物保护用助剂的醇烷氧基化物的碳酸酯 - Google Patents
作为作物保护用助剂的醇烷氧基化物的碳酸酯 Download PDFInfo
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- CN106068076B CN106068076B CN201580012688.8A CN201580012688A CN106068076B CN 106068076 B CN106068076 B CN 106068076B CN 201580012688 A CN201580012688 A CN 201580012688A CN 106068076 B CN106068076 B CN 106068076B
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- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- A—HUMAN NECESSITIES
- 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
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/02—Acyclic compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
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Abstract
本发明涉及一种包含农药和如下所定义的式(I)的烷氧基化物的农业化学组合物。本发明进一步涉及所述烷氧基化物。本发明进一步涉及一种通过使该烷氧基化物和该农药接触而制备所述组合物的方法。最后,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,其中使所述组合物作用于相应有害物、其环境或待保护以防相应有害物的农作物、土壤和/或不希望的植物和/或农作物和/或其环境;以及含有所述组合物的种子。
Description
本发明涉及一种包含农药和如下所定义的式(I)的烷氧基化物的农业化学组合物。本发明进一步涉及所述烷氧基化物。本发明进一步涉及一种通过使该烷氧基化物和该农药接触而制备所述组合物的方法。最后,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,其中使所述组合物作用于相应有害物、其环境或待保护以防相应有害物的农作物、土壤和/或不希望的植物和/或农作物和/或其环境;以及含有所述组合物的种子。在这里下文所提到的本发明的优选实施方案必须理解为相互独立地活着相互组合地是优选的。
助剂是重要的农业配制剂辅助剂且帮助改善该配制剂的稳定性和该农药的效力。确定具有改进性能的新助剂仍是挑战。
本发明的目的是要克服现有技术的问题。该目的由一种包含农药和式(I)的烷氧基化物的组合物解决:
R1–[AO1]n–O–C(O)–O–[AO2]m–R2 (I)
其中
R1和R2独立地为C6-C32烃基,
AO1和AO2独立地为C2-C6亚烷氧基,以及
n和m独立地为2-100的值。
在另一形式中,该目的由式(I)的烷氧基化物解决。
术语农业化学组合物通常是指一种适合工业施用于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/或调节植物生长的组合物,其中使该组合物作用于相应有害物、其环境或待保护以防相应有害物的农作物、土壤和/或不希望的植物和/或农作物和/或其环境。农业化学组合物的工业施用通常经受各种特定法规限制和特定注册方法。专家充分知晓其他组合物如祛臭或药物制剂以及化妆品通常不适合工业施用于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,其中使该组合物作用于相应有害物、其环境或待保护以防相应有害物的农作物、土壤和/或不希望的植物和/或农作物和/或其环境。
R1和R2通常独立地为一价C6-C32脂族烃基,优选线性或支化的饱和或不饱和C8-C20烷基。更优选R1和R2独立地为线性或支化的饱和C10-C18烷基。不同烃基的混合物也是可能的,例如不同链长的混合物和/或饱和和不饱和烃的混合物。在一种形式中,R1和R2相同。在另一形式中,R1和R2不同。
R1或R2的典型实例是线性或支化的癸基、十一烷基、十二烷基、十三烷基、十六烷基、十七烷基和十八烷基,或上述残基的混合物。在另一形式中,R1或R2的实例选自支化C13烷基。在另一形式中,R1或R2的实例选自线性C12-C18烷基。在另一形式中,R1或R2的实例选自支化C10烷基,如2-丙基庚基。在另一形式中,R1和R2独立地为支化的C10烷基。在尤其优选的形式中,R1和R2为2-丙基庚基。
AO1和AO2通常独立地为饱和或不饱和的线性或支化C2-C6亚烷氧基。不同C2-C6亚烷氧基的混合物也是可能的(例如AO1和AO2各自独立地为亚乙氧基和C3-C6亚烷氧基的混合物,其中优选亚乙氧基和亚丙氧基的混合物)。AO1或AO2的实例独立地为亚乙氧基、亚丙氧基、亚丁氧基或其混合物。AO1或AO2更优选独立地为亚乙氧基或亚乙氧基和亚丙氧基的混合物。AO1和AO2尤其为亚乙氧基。
指数n和m通常独立地为2-100,优选2.2-50,更优选2.5-20,尤其是3-13的任何值。
n与m之比通常为10/1-1/10,优选3/1-1/3,更优选2/1-1/2,尤其是1.5/1-1/1.5。
在另一形式中,该烷氧基化物具有式(I),其中R1和R2独立地为线性或支化的饱和或不饱和C8-C20烷基,AO1和AO2独立地为亚乙氧基或亚乙氧基和亚丙氧基且n和m独立地为2-50。
在另一形式中,该烷氧基化物具有式(I),其中R1和R2独立地为线性或支化的饱和或不饱和C8-C20烷基,AO1和AO2为亚乙氧基且n和m独立地为2.5-20。
在另一形式中,该烷氧基化物具有式(I),其中R1和R2为2-丙基庚基,AO1和AO2独立地为亚乙氧基或亚乙氧基和亚丙氧基且n和m独立地为2-30。
在另一形式中,该烷氧基化物具有式(I),其中R1和R2独立地为线性C12-C18烷基,AO1和AO2独立地为亚乙氧基或亚乙氧基和亚丙氧基且n和m独立地为2-30。
在另一形式中,该烷氧基化物具有式(I),其中R1和R2独立地为支化的C13烷基,AO1和AO2独立地为亚乙氧基或亚乙氧基和亚丙氧基且n和m独立地为2-30。
在一种形式中,该烷氧基化物具有式(I),其中AO1和AO2为亚乙氧基。该形式对应于式(II)的烷氧基化物:
R1–[O–CH2-CH2]n–O–C(O)–O–[CH2–CH2–O]m–R2 (II),
其中R1、R2、n和m具有如上所定义的含义和优选含义。
式(I)和(II)的烷氧基化物可以通过使碳酸二烷基酯(例如碳酸二乙酯或碳酸二甲酯,其中优选后者)与烷基烷氧基化物反应而制备。合适的烷基烷氧基化物为式(III)的那些:
R1–[AO1]n–O–H (III)
其中R1、AO1和n具有上述含义。该反应可以通过碱性催化剂如甲醇钠催化。反应温度通常为15-250℃。可以使用各种措施如真空来除去副产物(例如来自碳酸二乙酯的乙醇)。反应产物可以进一步提纯而得到的式(I)或(II)的烷氧基化物。在优选形式中,可以将含有式(I)或(II)的烷氧基化物的反应产物以没有进一步提纯的工业质量使用。工业质量的反应产物可以包含至多40重量%,优选至多25重量%,更优选至多15重量%的原料或副产物。
该组合物可以含有至少0.1重量%,优选至少1重量%式(I)的烷氧基化物。本发明组合物可以作为农业化学组合物类型存在且包含1-80重量%,优选2-50重量%,尤其是5-30重量%式(I)的烷氧基化物。
术语农药是指至少一种选***真菌剂、杀虫剂、杀线虫剂、除草剂、安全剂、生物农药和/或生长调节剂的活性物质。优选的农药为杀真菌剂、杀虫剂、除草剂和生长调节剂。尤其优选农药为杀真菌剂。也可使用两种或更多种上述类别的农药的混合物。技术人员所熟知该类农药,它们例如可以在Pesticide Manual,第16版(2013),The British CropProtection Council,London中找到。合适的杀虫剂为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、拟除虫菊酯类、新烟碱类、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杀螨剂以及诸如如下的杀虫剂:氯化苦(chloropicrin)、拒嗪酮(pymetrozin)、氟啶虫酰胺(flonicamid)、四螨嗪(clofentezin)、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)、嘧螨酯(fluacrypyrim)、鱼藤酮(rotenone)或其衍生物。合适的杀真菌剂为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、芳族烃、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、羧酸二酰胺类、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***类、噻唑羧酰胺类、硫代氨基甲酸酯类、托布津类(thiophanates)、噻吩羧酰胺类、甲苯甲酰胺类、三苯基锡化合物、三嗪类、***类。合适的除草剂为如下类别的除草剂: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、氯代羧酸类、环己烷二酮类、二硝基苯胺类、二硝基苯酚类、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、氧乙酰胺类、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***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、***类、***啉酮类、***羧酰胺类、***并嘧啶类、三酮类、尿嘧啶类、脲类。
优选该农药在20℃下以至多10g/l,优选至多1g/l,尤其至多0.5g/l可溶于水中。
本发明组合物可以以包含农药、式(I)的烷氧基化物和任选地助剂的农业化学配制剂形式存在。农业化学配制剂通常包含农药有效量的农药。术语“有效量”表示足以防治栽培植物上或周围或在材料保护中的有害物且不对被处理植物产生显著损害的量的组合物或化合物I。该量可以在宽范围内变化且取决于各种因素,如待防治的真菌品种、被处理的栽培植物或材料、气候条件和所用具体农药。
合适的农业化学组合物的常规类型例如为溶液、乳液、悬浮液、粉剂、粉末、糊、颗粒、模压品、胶囊及其混合物。配制剂类型的实例为悬浮液(例如SC、OD、FS),可乳化浓缩物(例如EC),可分散浓缩物(DC),乳液(例如EW、EO、ES、ME),胶囊(例如CS、ZC),糊,锭剂,可湿性粉末或粉剂(例如WP、SP、WS、DP、DS),模压品(例如BR、TB、DT),颗粒(例如WG、SG、GR、FG、GG、MG),杀虫制品(例如LN)以及处理植物繁殖材料如种子的凝胶配制剂(例如GF)。这些和其他配制剂类型在“Catalogue of pesticide formulation types and internationalcoding system”,Technical Monograph,第2期,第6版,2008年5月,CropLifeInternational中有定义。
农业化学配制剂通常以已知方式制备,例如如Mollet和Grubemann,Formulationtechnology,Wiley VCH,Weinheim,2001;或Knowles,New developments in cropprotection product formulation,Agrow Reports DS243,T&F Informa,London,2005所述。
合适助剂的实例为溶剂,液体载体,固体载体或填料,表面活性剂,分散剂,乳化剂,润湿剂,其他辅助剂,加溶剂,渗透促进剂,保护性胶体,粘附剂,增稠剂,保湿剂,驱除剂,引诱剂,进食刺激剂,相容剂,杀菌剂,防冻剂,消泡剂,着色剂,增粘剂和粘合剂。
合适的溶剂和液体载体为水和有机溶剂,如中到高沸点的矿物油馏分,例如煤油、柴油;植物或动物来源的油;脂族、环状和芳族烃,例如甲苯、石蜡、四氢萘、烷基化萘;醇,如乙醇、丙醇、丁醇、苄醇、环己醇;二醇;DMSO;酮,例如环己酮;酯,例如乳酸酯、碳酸酯、脂肪酸酯、γ-丁内酯;脂肪酸;膦酸酯;胺;酰胺,例如N-甲基吡咯烷酮,脂肪酸二甲基酰胺;及其混合物。
合适的固体载体或填料为矿土,例如硅酸盐、硅胶、滑石、高岭土、石灰石、石灰、白垩、粘土、白云石、硅藻土、膨润土、硫酸钙、硫酸镁、氧化镁;多糖粉末,例如纤维素、淀粉;肥料,例如硫酸铵、磷酸铵、硝酸铵、脲类;植物来源的产品,例如谷粉、树皮粉、木粉和坚果壳粉,及其混合物。
合适的表面活性剂为表面活性化合物,如阴离子、阳离子、非离子和两性表面活性剂,嵌段聚合物,聚电解质,及其混合物。该类表面活性剂可用作乳化剂、分散剂、加溶剂、润湿剂、渗透促进剂、保护性胶体或辅助剂。表面活性剂的实例列于McCutcheon’s,第1卷:Emulsifiers&Detergents,McCutcheon’s Directories,Glen Rock,USA,2008(国际版或北美版)中。
合适的阴离子表面活性剂为磺酸、硫酸、磷酸、羧酸的碱金属、碱土金属或铵盐及其混合物。磺酸盐的实例为烷基芳基磺酸盐、二苯基磺酸盐、α-烯烃磺酸盐、木素磺酸盐、脂肪酸和油的磺酸酯盐、乙氧基化烷基酚的磺酸盐、烷氧基化芳基酚的磺酸盐、缩合萘的磺酸盐、十二烷基-和十三烷基苯的磺酸盐、萘和烷基萘的磺酸盐、磺基琥珀酸盐或磺基琥珀酰胺酸盐。硫酸盐的实例为脂肪酸和油的硫酸酯盐、乙氧基化烷基酚的硫酸盐、醇的硫酸酯盐、乙氧基化醇的硫酸酯盐或脂肪酸酯的硫酸盐。磷酸盐的实例是磷酸酯盐。羧酸盐的实例是烷基羧酸盐以及羧化醇或烷基酚乙氧基化物。
合适的非离子表面活性剂为烷氧基化物表面活性剂,N-取代的脂肪酸酰胺,胺氧化物,酯,糖基表面活性剂,聚合物表面活性剂及其混合物。烷氧基化物表面活性剂的实例为诸如已经被1-50当量烷氧基化的醇、烷基酚、胺、酰胺、芳基酚、脂肪酸或脂肪酸酯的化合物。可将氧化乙烯和/或氧化丙烯用于烷氧基化,优选氧化乙烯。N-取代的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。酯的实例为脂肪酸酯,甘油酯或甘油单酯。糖基表面活性剂的实例为脱水山梨醇、乙氧基化脱水山梨醇、蔗糖和葡萄糖酯或烷基聚葡糖苷。聚合物表面活性剂的实例为乙烯基吡咯烷酮、乙烯醇或乙酸乙烯酯的均聚物或共聚物。
合适的阳离子表面活性剂为季型表面活性剂,例如具有1或2个疏水性基团的季铵化合物,或长链伯胺的盐。合适的两性表面活性剂为烷基甜菜碱和咪唑啉类。合适的嵌段聚合物为包含聚氧乙烯和聚氧丙烯的嵌段的A-B或A-B-A型嵌段聚合物,或包含链烷醇、聚氧乙烯和聚氧丙烯的A-B-C型嵌段聚合物。合适的聚电解质为聚酸或聚碱。聚酸的实例为聚丙烯酸的碱金属盐或聚酸梳状聚合物。聚碱的实例为聚乙烯基胺或聚乙烯胺。
合适的其他辅助剂为本身具有可忽略的农药活性或者本身甚至没有农药活性且改善农药对目标的生物学性能的化合物。实例为表面活性剂,矿物油或植物油以及其他助剂。其他实例由Knowles,Adjuvants and additives,Agrow Reports DS256,T&F InformaUK,2006,第5章列出。
合适的增稠剂为多糖(例如黄原胶、羧甲基纤维素)、无机粘土(有机改性或未改性的)、聚羧酸盐和硅酸盐。
合适的杀菌剂为拌棉醇(bronopol)和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。
合适的防冻剂为乙二醇、丙二醇、尿素和甘油。
合适的消泡剂为聚硅氧烷、长链醇和脂肪酸盐。
合适的着色剂(例如着红色、蓝色或绿色)为低水溶性颜料和水溶性染料。实例为无机着色剂(例如氧化铁、氧化钛、六氰合铁酸铁)和有机着色剂(例如茜素着色剂、偶氮着色剂和酞菁着色剂)。
合适的增粘剂或粘合剂为聚乙烯吡咯烷酮、聚乙酸乙烯酯、聚乙烯醇、聚丙烯酸酯、生物蜡或合成蜡以及纤维素醚。
配制剂类型及其制剂的实例为:
i)水溶性浓缩物(SL,LS)
将10-60重量%农药和5-15重量%润湿剂(例如醇烷氧基化物)溶于加至100重量%的水和/或水溶性溶剂(例如醇)中。活性物质在用水稀释时溶解。ii)分散性浓缩物(DC)
将5-25重量%农药和1-10重量%分散剂(例如聚乙烯吡咯烷酮)溶于加至100重量%的有机溶剂(例如环己酮)中。用水稀释得到分散体。
iii)可乳化浓缩物(EC)
将15-70重量%农药和5-10重量%乳化剂(例如十二烷基苯磺酸钙和蓖麻油乙氧基化物)溶于加至100重量%的水不溶性有机溶剂(例如芳族烃)中。用水稀释得到乳液。
iv)乳液(EW,EO,ES)
将5-40重量%农药和1-10重量%乳化剂(例如十二烷基苯磺酸钙和蓖麻油乙氧基化物)溶于20-40重量%水不溶性有机溶剂(例如芳族烃)中。借助乳化机将该混合物引入加至100重量%的水中并制成均一乳液。用水稀释得到乳液。
v)悬浮液(SC,OD,FS)
在搅拌的球磨机中将20-60重量%农药在加入2-10重量%分散剂和润湿剂(例如木素磺酸钠和醇乙氧基化物)、0.1-2重量%增稠剂(例如黄原胶)和加至100重量%的水下粉碎,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。对于FS类型组合物加入至多40重量%粘合剂(例如聚乙烯醇)。
vi)水分散性颗粒和水溶性颗粒(WG,SG)
在加入加至100重量%的分散剂和润湿剂(例如木素磺酸钠和醇乙氧基化物)下精细研磨50-80重量%农药并借助工业装置(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。
vii)水分散性粉末和水溶性粉末(WP,SP,WS)
将50-80重量%农药在加入1-5重量%分散剂(例如木素磺酸钠)、1-3重量%润湿剂(例如醇乙氧基化物)和加至100重量%的固体载体(例如硅胶)下在转子-定子磨机中研磨。用水稀释得到稳定的活性物质分散体或溶液。
viii)凝胶(GW,GF)
在搅拌的球磨机中在加入3-10重量%分散剂(例如木素磺酸钠)、1-5重量%增稠剂(例如羧甲基纤维素)和加至100重量%的水下粉碎5-25重量%农药,得到活性物质的精细悬浮液。用水稀释得到稳定的活性物质悬浮液。
iv)微乳液(ME)
将5-20重量%农药加入5-30重量%有机溶剂混合物(例如脂肪酸二甲基酰胺和环己酮)、10-25重量%表面活性剂混合物(例如醇乙氧基化物和芳基酚乙氧基化物)和加至100重量%的水中。将该混合物搅拌1小时以自发产生热力学稳定的微乳液。
iv)微胶囊(CS)
将包含5-50重量%农药、0-40重量%水不溶性有机溶剂(例如芳族烃)、2-15重量%丙烯酸系单体(例如甲基丙烯酸甲酯、甲基丙烯酸和二-或三丙烯酸酯)的油相分散到保护性胶体(例如聚乙烯醇)的水溶液中。由自由基引发剂引发的自由基聚合导致形成聚(甲基)丙烯酸酯微胶囊。或者将包含5-50重量%农药、0-40重量%水不溶性有机溶剂(例如芳族烃)和异氰酸酯单体(例如二苯基甲烷-4,4’-二异氰酸酯)的油相分散到保护性胶体(例如聚乙烯醇)的水溶液中。加入多胺(例如六亚甲基二胺)导致形成聚脲微胶囊。单体量为1-10重量%。重量%涉及整个CS组合物。
ix)可撒粉粉末(DP,DS)
将1-10重量%农药细碎研磨并与加至100重量%的固体载体(例如细碎高岭土)充分混合。
x)颗粒(GR,FG)
将0.5-30重量%农药细碎研磨并结合加至100重量%的固体载体(例如硅酸盐)。通过挤出、喷雾干燥或流化床实现造粒。
xi)超低容量液体(UL)
将1-50重量%农药溶于加至100重量%的有机溶剂(例如芳族烃)中。
配制剂类型i)-xi)可任选包含其他助剂,例如0.1-1重量%杀菌剂,5-15重量%防冻剂,0.1-1重量%消泡剂和0.1-1重量%着色剂。优选的组合物类型为悬浮浓缩物。
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0.5-75重量%的活性物质(即农药)。活性物质以90-100%,优选95-100%的纯度(根据NMR光谱)使用。
为了处理植物繁殖材料,尤其是种子,通常使用水溶性浓缩物(LS)、悬浮乳液(SE)、可流动浓缩物(FS)、干处理用粉末(DS)、淤浆处理用水分散性粉末(WS)、水溶性粉末(SS)、乳液(ES)、可乳化浓缩物(EC)和凝胶(GF)。所述组合物在稀释2-10倍后在即用制剂中给出0.01-60重量%,优选0.1-40重量%的活性物质浓度。施用可在播种之前或期间进行。农药及其组合物分别在植物繁殖材料,尤其是种子上的施用或处理方法包括繁殖材料的拌种、包衣、造粒、撒粉、浸泡和犁沟内施用方法。优选通过不诱发萌发的方法,例如通过拌种、造粒、包衣和撒粉将农药或其组合物分别施用于植物繁殖材料上。
当用于植物保护中时,活性物质的施用量取决于所需的效果类型为0.001-2kg/ha,优选为0.005-2kg/ha,更优选为0.05-0.9kg/ha,特别为0.1-0.75kg/ha。
在植物繁殖材料如种子例如通过撒粉、包衣或浸透种子的处理中,通常要求活性物质的量为0.1-1000g/100kg,优选为1-1000g/100kg,更优选为1-100g/100kg,最优选为5-100g/100kg植物繁殖材料(优选种子)。
当用于保护材料或储存产品中时,活性物质的施用量取决于施用区域的类型和所需的效果。在材料保护中常用的施用量为0.001g-2kg,优选为0.005g-1kg活性物质/立方米被处理材料。
可向活性物质或包含它们的组合物中作为预混物加入或者合适的话在紧临使用前加入(桶混合)各种类型的油、润湿剂、辅助剂、肥料或微量营养素和其他农药(例如除草剂、杀虫剂、杀真菌剂、生长调节剂、安全剂)。这些试剂可以以1:100-100:1,优选1:10-10:1的重量比与本发明组合物混合。
式(I)的烷氧基化物在即用制剂(例如桶混物)中的浓度在大多数情况下为0.01-50g/l,优选0.08-10g/l,尤其是0.5-8g/l。
水在即用制剂(例如桶混物)中的浓度在大多数情况下为至少60重量%,优选至少75重量%,尤其是至少90重量%。
桶混物通常为含水液体,其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袭和/或调节植物生长的方法中易于施用(例如通过喷雾)。
用户通常从预剂量装置、背包式喷雾器、喷雾罐、喷雾飞机或灌溉***施用本发明组合物。通常将该农业化学组合物用水、缓冲剂和/或其他助剂配制至所需的施用浓度,由此得到即用喷雾液或本发明的农业化学组合物。每公顷农业利用区通常施用20-2000升,优选50-400升即用喷雾液。
根据一个实施方案,用户可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。
在另一实施方案中,用户可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,例如包含农药和辅助剂的组分,并且合适的话可以加入其他助剂和添加剂。在另一实施方案中,可以联合(例如在桶混合后)或依次施用本发明组合物的各组分或部分预混的组分,例如包含农药和/或辅助剂的组分。
此外,本发明涉及一种通过使式(I)的助剂和农药接触,例如通过混合制备本发明组合物的方法。该接触可以在5-95℃下进行。因此,可制得桶混物或农业化学组合物。
此外,本发明涉及一种式(I)的烷氧基化物:
R1–[AO1]n–O–C(O)–O–[AO2]m–R2 (I)
其中
R1和R2独立地为C6-C32烃基,
AO1和AO2独立地为C2-C6亚烷氧基,以及
n和m独立地为2-100的值。
R1、R2、AO1、AO2、n和m的其他形式或优选形式如上所定义。
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,其中使包含农药和本发明式(I)的烷氧基化物的组合物作用于相应有害物、其环境或待保护以防相应有害物的农作物、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,其中使包含农药和本发明式(I)的助剂的组合物作用于相应有害物、其环境或待保护以防相应有害物的农作物、土壤和/或不希望的植物和/或农作物和/或其环境。
合适农作物的实例为禾谷类,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/笋瓜、黄瓜或甜瓜;纤维作物,例如棉花、亚麻、***或黄麻;柑桔类水果,例如橙、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/笋瓜或柿子椒;月桂类植物,例如鳄梨、肉桂或樟脑;能源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);橡胶植物和森林植物,例如花卉、灌木、落叶树和针叶树;以及繁殖材料,例如种子以及这些植物的收获产物。
术语“农作物”还包括已通过育种、诱变或重组方法修饰的那些植物,包括市场销售或开发方法中的生物技术农业产品。基因修饰植物是其遗传物质以无法在自然条件下由杂交、诱变或自然重组(即遗传物质的重组)产生的方式修饰的植物。此处,通常将一个或多个基因整合到所述植物的遗传物质中以改善所述植物的性能。这类重组修饰还包括蛋白质、寡肽或多肽的翻译后修饰,例如通过糖基化或粘结聚合物如异戊二烯化、乙酰化或法呢基化残基或PEG残基。
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)。在播种时或甚至在播种之前或者在移植时或甚至移植之前,可用本发明组合物对植物繁殖材料进行预防性处理。为了处理种子,人们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)。可将这些组合物以未经稀释形式或优选以稀释形式施用至繁殖材料,尤其是种子上。此时,可将所述组合物稀释2-10倍,以使得拌种用组合物中存在0.01-60重量%,优选0.1-40重量%的活性物质。施用可在播种之前或期间进行。植物繁殖材料,尤其是种子的处理是本领域技术人员所已知的,且通过植物繁殖材料的撒粉、包衣、造粒、浸泡或浸渍而进行,其中处理优选通过造粒、包衣和撒粉或犁沟内处理而进行,从而例如防止种子不适时的早期萌发。优选使用悬浮液处理种子。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着色剂和溶剂,优选为水。
本发明进一步涉及本发明式(I)的烷氧基化物在改善农药效力中的用途。与没有式(I)的烷氧基化物的农药的相同用途相比通常改善效力。
本发明的优点是配制剂和喷雾混合物的稳定性高、喷雾施用情况下风引起的漂移性很低、配制剂在所处理植物表面上的粘着性良好、农药在配制剂中的溶解性提高、农药在植物中的吸收提高或农药的更迅速或提高的活性(例如甚至在低剂量率下)。其他优点是烷氧基化物的高可生物降解性;烷氧基化物的低毒性,烷氧基化物降低含水组合物的表面张力的能力或在植物表面上的铺展提高;对农作物的有害作用低,即低植物毒性作用。
下列实施例阐述本发明,但不施加任何限制。
实施例
醇烷氧基化物A:乙氧基化的(9个EO单元)C12-C18脂肪醇。
醇烷氧基化物B:乙氧基化的(3个EO单元)饱和i-C13醇,布氏粘度为约50mPas(23℃,60rpm)。
醇烷氧基化物C:乙氧基化的(5个EO单元)饱和i-C13醇,布氏粘度为约85mPas(23℃,60rpm)。
醇烷氧基化物D:乙氧基化的(7个EO单元)饱和i-C13醇,布氏粘度为约100mPas(23℃,60rpm)。
醇烷氧基化物E:乙氧基化的(10个EO单元)饱和i-C13醇,布氏粘度为约30mPas(60℃,60rpm)。
醇烷氧基化物F:乙氧基化的(12个EO单元)饱和i-C13醇,布氏粘度为约40mPas(60℃,60rpm)。
醇烷氧基化物G:乙氧基化的(3个EO单元)C12-C18脂肪醇,倾点<13℃。
醇烷氧基化物H:乙氧基化的(5个EO单元)C12-C18脂肪醇,固化温度约12℃。
醇烷氧基化物I:乙氧基化的(7个EO单元)C12-C18脂肪醇,固化温度约15℃。
醇烷氧基化物J:乙氧基化的(3个EO单元)2-丙基庚醇,HLB约9。
醇烷氧基化物K:乙氧基化的(4个EO单元)2-丙基庚醇,HLB约10.5。
醇烷氧基化物L:乙氧基化的(6个EO单元)2-丙基庚醇,HLB约12.5。
实施例1-15—制备烷氧基化物
将199.5g醇烷氧基化物A(0.33mol)和碳酸二乙酯或碳酸二甲酯(0.23mol)与0.59g甲醇钠(30%,在甲醇中)混合并在搅拌下加热至80℃。升温至140℃并蒸除所得乙醇。当不再蒸除乙醇时,施加1巴的真空以除去其他挥发性组分。最后将该组合物冷却至室温并过滤。以黄色产物得到175g产物。相应地使醇烷氧基化物B-L与碳酸二乙酯反应而制备本发明式(I)的烷氧基化物(表1,“原料”栏表示醇烷氧基化物A-L。
表1:产物特征(SZ表示总酸值;VZ表示皂化值;OHZ表示羟值)。
实施例16—提高的生物学活性
在温室中在小麦(“Kanzler”品种)上评价生物学活性,将小麦在两叶阶段用小麦柄锈菌(Puccinia triticina)侵染并在高湿度下孵化3天。将植株用包含50ppm(10g/ha)氧唑菌(epoxiconazole)和100ppm(20g/ha)来自实施例1-15的相应助剂样品的组合物喷雾(喷雾体积200l/ha)。在对比例中没有加入助剂。将植株在20-24℃和60-90%相对湿度下进一步栽培10天。最后肉眼检测侵染叶面积(脓疱)的百分数。各数值基于三次重复测量。结果总结于表2中。为了对比,测试用于制备实施例4的产物的原料醇烷氧基化物G。
表2:
来自如下实施例的样品 | 侵染的叶面积 |
–<sup>a)b)</sup> | 75 |
醇烷氧基化物G<sup>a)</sup> | 11 |
4 | 8 |
a)对比例。b)无助剂
实施例17—提高的生物学活性
生物学活性如实施例16所述在温室中以2.5g/ha农药的降低剂量率评价。结果总结于表3中。为了对比,测试用于制备实施例4的产物的原料醇烷氧基化物G。
表3:
来自如下实施例的样品 | 侵染的叶面积 |
–<sup>a)</sup> | 75 |
醇烷氧基化物G<sup>a)</sup> | 33 |
4 | 24 |
a)对比例,无助剂
实施例18—表面张力
使用1g/l来自实施例1-15的样品在去离子水中的溶液或分散体进行物理测量。静态或平衡表面张力为配制剂在喷雾液中界面活性的特征性值。在临界胶束浓度(CMC)以下,静态表面张力取决于表面活性成分在配制剂中的浓度,而在CMC以上,静态表面张力保持不变。测量使用工艺过程张力计Kruess K 100以威廉米平板法进行。在测量期间,将垂直悬挂铂板的底部线用要分析的液体润湿。测量将板拉入液体中的力且可将该力转化为液体的表面张力(mN/m)。将40mL制得的喷雾液装填到设备中的特氟隆槽中并检测表面张力。在0.1mN/m内匹配5个连续测量点后计算静态表面张力。结果总结于表4中。
表4:
来自如下实施例的样品 | 基于醇烷氧基化物 | 表面张力[mN/m] |
6 | I | 30 |
5 | H | 33 |
4 | G | 29 |
9 | L | 29 |
8 | K | 28 |
7 | J | 28 |
3 | D | 30 |
2 | C | 29 |
1 | B | 28 |
实施例19—提高的吸收率
将小麦植株(普通小麦(Triticum aestivum)品种Melon)在温室中栽培6周至到发育阶段BBCH 39。将植株转移至自动实验室轨道喷雾器且将其根据下列参数用125g/ha氧唑菌、125g/ha氟唑菌酰胺(fluxapyroxad)和250g/ha相应助剂喷雾:
水量:200l/ha
喷嘴类型:空气注射器,ID 120 02(德国Lechler)
速度:1.4m/s
压力:3.33巴
在喷雾之后,将植株再次在温室中在环境条件下栽培。在8天后,切取10-15个被处理叶子的样品并称重。
将叶子切成小片,转移至玻璃瓶并用50%在软化水中的甲醇作为洗涤介质洗涤5分钟。然后将洗涤介质与叶子分离。将叶子再次用洗涤介质洗涤5分钟。将两种洗涤介质合并并稀释以分析。
最后,将叶子转移至含有提取介质(75%甲醇、20%水和5%HCl)的小瓶中并使用Polytron PT 6100分散装置(Kinematica,CH)均化2分钟。将10ml提取液以4000rpm离心5分钟。将2ml上清液用2ml NaOH(0.2mol/L)和5ml环己烷处理并搅拌30分钟,随后离心。将1ml环己烷相转移至玻璃瓶中并干燥(德国Liebisch N2蒸发器)。将残余物加溶于甲醇/水50:50并通过HPLC-MS/MS分析。
使用装备有电喷射离子化源的与Applied Biosystems API 3000三重四极质谱仪联用的Agilent 1100系列HPLC。质谱仪以MS/MS正型离子模式与多反应监测(MRM)使用在优化条件下每个分析物两个转变操作。此外,未喷雾的植物以相同方式处理以观察其是否被污染。未喷雾的植物添加有标准活性成分以测定在洗涤和提取步骤过程中的活性成分回收。根据回收率,校正测得的样品值。结果总结于表5中。
为了对比,测试用于制备实施例4的产物的原料醇烷氧基化物G。为了另外对比,测试用于制备实施例5的产物的原料醇烷氧基化物H。
数据表明在使用本发明助剂时,氧唑菌和氟唑菌酰胺的吸收率提高。表5:吸收率
如下实施例的样品 | 氧唑菌吸收率[%] | 氟唑菌酰胺吸收率[%] |
–<sup>a),b)</sup> | 8 | 4 |
醇烷氧基化物G<sup>a)</sup> | 36 | 23 |
4 | 62 | 38 |
醇烷氧基化物H<sup>a)</sup> | 35 | 21 |
5 | 56 | 39 |
a)对比例。b)无任何助剂
实施例20—提高的生物学活性
在温室中在小麦(“Kanzler”品种)上评价生物学活性,将小麦在两叶阶段用小麦柄锈菌侵染并在高湿度下温育3天。将植株用包含50ppm(10g/ha)氧唑菌和100ppm(20g/ha)相应助剂样品的组合物(“10g/ha剂量率”一栏)喷雾(喷雾体积200l/ha)。作为替换,测试50g/ha氧唑菌和100g/ha助剂的剂量率(“50g/ha剂量率”一栏)。在对比例中没有加入助剂。将植株在20-24℃和60-90%相对湿度下进一步栽培10天。最后肉眼检测侵染叶面积(脓疱)的百分数。各数值基于三次重复测量。结果总结于表6中。
表6:
a)对比例,无助剂。
Claims (24)
1.一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,其中使包含杀真菌剂、杀虫剂、杀线虫剂、除草剂、安全剂、生物农药和/或生长调节剂和式(I)的烷氧基化物的农业化学组合物作用于相应有害物、其环境或待保护以防相应有害物的农作物、土壤和/或不希望的植物和/或农作物和/或其环境:
R1–[AO1]n–O–C(O)–O–[AO2]m–R2 (I)
其中
R1和 R2独立地为线性或支化的饱和或不饱和C8-C20烷基,
AO1和AO2独立地为C2-C6亚烷氧基,以及
n和m独立地为2-100的值。。
2.根据权利要求1的方法,其中n和m独立地为2.5-20的值。
3.根据权利要求1的方法,其中AO1和AO2独立地为亚乙氧基或亚乙氧基和亚丙氧基的混合物。
4.根据权利要求2的方法,其中AO1和AO2独立地为亚乙氧基或亚乙氧基和亚丙氧基的混合物。
5.根据权利要求1的方法,其中R1和R2独立地为线性或支化的饱和C10-C18烷基。
6.根据权利要求2的方法,其中R1和R2独立地为线性或支化的饱和C10-C18烷基。
7.根据权利要求3的方法,其中R1和R2独立地为线性或支化的饱和C10-C18烷基。
8.根据权利要求1-7中任一项的方法,其中所述杀真菌剂、杀虫剂、杀线虫剂、除草剂、安全剂、生物农药和/或生长调节剂与式(I)的烷氧基化物的重量比为4:1-1:10。
9.根据权利要求8的方法,其中所述杀真菌剂、杀虫剂、杀线虫剂、除草剂、安全剂、生物农药和/或生长调节剂与式(I)的烷氧基化物的重量比为2:1-1:4。
10.根据权利要求1-7中任一项的方法,其中n与m之比为3/1-1/3。
11.根据权利要求10的方法,其中n与m之比为3/1-1/3。
12.根据权利要求1的方法,其中R1和R2独立地为线性或支化的饱和或不饱和C8-C20烷基,AO1和AO2独立地为亚乙氧基或亚乙氧基和亚丙氧基且n和m独立地为2-50。
13.根据权利要求8的方法,其中R1和R2独立地为线性或支化的饱和或不饱和C8-C20烷基,AO1和AO2独立地为亚乙氧基或亚乙氧基和亚丙氧基且n和m独立地为2-50。
14.根据权利要求10的方法,其中R1和R2独立地为线性或支化的饱和或不饱和C8-C20烷基,AO1和AO2独立地为亚乙氧基或亚乙氧基和亚丙氧基且n和m独立地为2-50。
15.根据权利要求1的方法,其中所述烷氧基化物具有式(II):
R1–[O–CH2-CH2]n–O–C(O)–O–[CH2–CH2–O]m–R2 (II)
其中R1、R2、n和m如权利要求1所定义。
16.根据权利要求1的方法,其中R1和R2独立地为线性或支化的饱和或不饱和C8-C20烷基,AO1和AO2为亚乙氧基且n和m独立地为2.5-20。
17.根据权利要求8的方法,其中R1和R2独立地为线性或支化的饱和或不饱和C8-C20烷基,AO1和AO2为亚乙氧基且n和m独立地为2.5-20。
18.根据权利要求10的方法,其中R1和R2独立地为线性或支化的饱和或不饱和C8-C20烷基,AO1和AO2为亚乙氧基且n和m独立地为2.5-20。
19.根据权利要求1的方法,其中所述农业化学组合物包含杀真菌剂和式(I)的烷氧基化物。
20.根据权利要求1-7中任一项的方法,其中所述杀真菌剂、杀虫剂、杀线虫剂、除草剂、安全剂、生物农药和生长调节剂在20°C下以至多10g/l可溶于水中。
21.根据权利要求1-7中任一项的方法,其中所述杀真菌剂选自氧唑菌、氟唑菌酰胺及其混合物。
22.一种通过将所述杀真菌剂、杀虫剂、杀线虫剂、除草剂、安全剂、生物农药和/或生长调节剂与式(I)的烷氧基化物接触而制备如权利要求1-21中任一项所定义的农业化学组合物的方法。
23.一种处理种子的方法,其包括使用如权利要求1-21中任一项所定义的农业化学组合物。
24.如权利要求1-21中任一项所定义的式(I)的烷氧基化物在改善杀真菌剂、杀虫剂、杀线虫剂、除草剂、安全剂、生物农药和/或生长调节剂效力中的用途。
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