CN114071996A - 天然油和其衍生物在农业制剂中的用途 - Google Patents
天然油和其衍生物在农业制剂中的用途 Download PDFInfo
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- CN114071996A CN114071996A CN202080033453.8A CN202080033453A CN114071996A CN 114071996 A CN114071996 A CN 114071996A CN 202080033453 A CN202080033453 A CN 202080033453A CN 114071996 A CN114071996 A CN 114071996A
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- Prior art keywords
- solvent
- oil
- agricultural formulation
- ester
- formulation
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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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
-
- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- 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
-
- 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
- A01N25/30—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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
一种农业制剂,其包含:活性组分,所述活性组分包含农药、杀真菌剂、除草剂或其组合;天然油溶剂;和非离子表面活性剂。
Description
相关申请的交叉引用
本申请要求2019年5月3日提交的美国临时申请第62/842,605号和2019年11月26日提交的美国临时申请第62/940,432号的权益,所述美国临时申请以全文引用的方式并入本文中。
技术领域
在各种实施例中,本公开大体上涉及天然油在可乳化浓缩物制剂中的用途,所述天然油例如蒸馏松油、松油脂肪酸酯、大豆油脂肪酸酯、脱氢松香酯、松香酸、松香酯、松香油、多萜、植物油、坚果油、籽油脂肪酸、棕榈油、椰子油等,或其组合。
背景技术
液体可喷雾制剂,例如杀虫剂制剂,通常配制成可乳化浓缩物(EC)。由于水溶性低,例如拟除虫菊酯(pyrethroid)的农药的常规EC制剂包括大于50重量百分数(wt%)的溶剂,特别是挥发性有机化合物(VOC),例如石油衍生的芳香族和脂肪族溶剂。这些溶剂可能对施用者造成健康和安全问题,造成环境/监管问题,并可能导致作物中轻微至严重的植物毒性。因此,需要不含石油衍生的芳香族和脂肪族溶剂的农业制剂。
因此,期望具有其中挥发性有机化合物被最大限度地减少或消除的农业制剂,从而提供更环保且更安全的制剂。
发明内容
本发明描述可乳化浓缩物制剂,例如农业制剂和其使用方法。令人惊讶且出乎意料地发现,可以制备可乳化浓缩物制剂,例如农业制剂,其导致溶质的稳定分散,同时最大限度地减少或消除挥发性有机化合物。
因此,在一个方面,本公开提供了一种可乳化浓缩物制剂,其包含待分散的活性组分、天然油溶剂和非离子表面活性剂。在某些实施例中,本公开提供一种农业制剂,其包含活性组分、天然油溶剂和非离子表面活性剂,所述活性组分包含农药、杀真菌剂、除草剂或其组合。在某些实施例中,本公开提供一种农业制剂,其进一步包含绿色共溶剂。
在其它方面,本公开提供制备如本文所述的可乳化浓缩物制剂的方法和使用所述制剂的方法。例如,在某些实施例中,本公开提供了一种使用如本文所述的可乳化浓缩物制剂的方法,其包含以下步骤:提供包括有效量的活性组分,例如农药、杀真菌剂、除草剂或其组合的可乳化浓缩物制剂,以及施用可乳化浓缩物制剂。在某些实施例中,方法包含将可乳化浓缩物制剂施用或施加于土壤或植物或生物体(例如昆虫或害虫)的表面,其中所述可乳化浓缩物制剂实现保护土壤或植物免受昆虫或害虫侵害,或实现至少一部分(例如大量)昆虫或害虫的死亡,或防止来自所述昆虫或害虫的损害。
前述一般实用领域仅为了举例而给出,并且不希望对本公开的范围和所附权利要求书构成限制。根据本发明的权利要求书、说明书和实例,本领域的普通技术人员将了解与本发明的组合物、方法和过程相关的额外目标和优点。例如,本发明的各个方面和实施例可以众多组合利用,所有这些组合都由本说明书明确地加以考虑。这些额外优点目标和实施例明确地包括在本发明的范围内。本文用于阐明本发明的背景并且在特定情况下提供关于实践的另外细节的出版物和其它材料以引用方式并入。
具体实施方式
本文公开了用于使用例如天然气的催化部分氧化(CPO)以生产合成气和任选地随后由其合成甲醇的系统和方法。本文公开的系统和方法通过使用水煤气变换(WGS)和二氧化碳(CO2)去除来调节CPO反应器流出物的组成,并利用热集成来提高能效。现在将在下文中更全面地描述本公开,但是未示出本公开的所有实施例。虽然已经结合示例性实施例描述了本公开,但是本领域的技术人员将会理解,在不脱离本公开的范围的情况下,可以进行各种改变并且可以用等同物替换其要素。另外,在不脱离本公开的实质范围的情况下,可以进行许多修改,以使特定结构或材料适应于本公开的教导内容。
在提供值的范围的情况下,应当理解,所述范围的上限和下限之间的每个中间值以及所述范围中的任何其它所述或中间值都包含在本发明中。这些较小范围的上限和下限可以独立地包括在更小范围内并且也涵盖于本发明内,从属于所述范围内的任何具体排除限值。在所述范围包括一个或两个限值的情况下,本发明中还包括排除所包括的那些限值中的任两个的范围。
下述术语用于描述本发明。在本文中未具体定义一个术语的情况下,那个术语是所属领域的一般技术人员在其用于描述本发明的上下文中应用那个术语时作为领域公认的含义给出。
如本文和所附权利要求中使用的冠词“一个”和“一种”在本文中用于指冠词的一个或多于一个(即,至少一个)语法对象,除非上下文另有明确说明。例如,“要素”意指一个要素或多于一个要素。
如本文在说明书和权利要求中所用,短语“和/或”应理解为意指如此结合的要素中的“任一者或两者”,即在某些情况下结合地存在且在其它情况下分离地存在的要素。用“和/或”列出的多个要素应该以相同的方式加以解释,即,如此结合的“一个或多个”要素。除了由“和/或”子句具体鉴定的要素之外,可以任选地存在其它要素,无论与具体鉴定的那些要素相关还是不相关。因此,作为非限制性示例,对“A和/或B”的引用在结合诸如“包含”等开放式语言使用时在一个实施例中可仅指A(可任选地包括除B以外的元素);在另一实施例中,仅指B(任选地包括除A以外的元素);在又一实施例中,指A和B(任选地包括其它元素);等等。
如本文在说明书和权利要求中使用的,“或”应该理解为具有与如上定义的“和/或”相同的含义。例如,当分开列表中的项目时,“或”或“和/或”应该解释为包含性的,即包含至少一个,但也包括许多要素或要素列表的多于一个,以及任选地,另外未列出的项目。只有明确指出相反的术语,例如“仅一个”或“恰好一个”,或者,当在权利要求中使用时,“由……组成”指许多要素或要素列表的恰好一个要素。一般而言,当之前为排他性术语例如“任一”、“之一”、“仅一个”或“恰好一个”时,如本文使用的,术语“或”应该仅解释为指示排他性替代物(即“一个或另一个但不是两者”)。
在权利要求以及上文说明书中,所有过渡短语、例如“包含”、“包括”、“携带”、“具有”、“含有”、“涉及”、“持有”、“组成”等等应理解为开放式的,即,意指包括但不限于。仅过渡短语“由……组成”和“基本上由……组成”应该分别为闭合式或半闭合式过渡短语,如10美国专利局专利审查程序手册(United States Patent Office Manual of PatentExamining Procedures)第2111.03节中所述。
如本文在说明书和权利要求中使用的,提及一个或多个要素的列表,短语“至少一个”应该理解为意指选自要素列表中的任何一个或多个要素的至少一个要素,但不一定包括要素列表中具体列出的每个和每一个要素中的至少一个,并且不排除要素列表中的任何要素组合。所述定义还允许除了在短语“至少一个”所指的要素列表内具体鉴定的要素之外,可以任选地存在无论与具体鉴定的那些要素相关还是不相关的要素。因此,作为非限制性实例,在一个实施例中,“A和B中的至少一个”(或等同地,“A或B中的至少一个”,或等同地,“A和/或B中的至少一个”)可以指至少一个,任选地包括多于一个A,不存在B(和任选地包括除B以外的要素);在另一个实施例中,指至少一个、任选地包括多于一个B,不存在A(和任选地包括除A以外的元素);在又一实施例中,指至少一个、任选地包括多于一个A,和至少一个B、任选地包括多于一个B(和任选地包括其它元素);等等。还应该理解,除非清楚地相反指示,在本文要求保护的包括多于一个步骤或动作的任何方法中,所述方法的步骤或动作的次序不一定限于其中叙述所述方法的步骤或动作的次序。
示例性方面和实施例
令人惊讶且出乎意料地发现,包括作为溶剂的天然油以及非阴离子表面活性剂的农业制剂是稳定的,并且在几周内和在不同温度下保持溶解状态。有利的是,此类制剂可以最大限度地减少或消除农业制剂对VOC和半挥发性有机化合物(SVOC)的需要。所公开的制剂的另一优点是硬水稳定性。在一些区域中,富含矿物质,例如钙和镁的水被称为“硬水”。由于潜在的环境和降水问题,水硬度给配方设计师和农民带来了巨大的挑战。所公开的制剂可以最大限度地减少或消除这些问题。实际上,在所公开的制剂中,当与可商购的制剂,例如具有烃溶剂的联苯菊酯EC制剂(BIFEN XTS,可从ADAMA获得)相比,一些实施例具有改善的乳液稳定性。
如上所述,含有有机溶剂的先前常规液体农业制剂存在众所周知的缺点,包括对敏感植物的损害风险,并且成为VOC和SVOC排放源。有机溶剂通常用于常规制剂中,因为农药不溶于水,但可溶于有机溶剂。因此,需要最大限度地减少或消除对有机溶剂的需要的农业制剂。
因此,在一个方面,本说明书提供包含以下者的农业制剂:活性组分,所述活性组分包括农药、杀真菌剂、除草剂或其组合;天然油溶剂和非离子表面活性剂。
在本文所述的任何方面或实施例中,当存在时,农药可以是本领域已知的任何农药。农药可以是氨基甲酸酯,如加保利(carbaryl)或灭虫威(methiocarb);有机磷酸酯,如欧杀松(acephate)、陶斯松(chlorpyrifos)、马拉松(malathion)或亚胺硫磷(phosmet);苯基吡唑,如氟虫腈(fipronil);拟除虫菊酯,如联苯菊酯、赛扶宁(cyfluthrin)、甲氰菊酯、福化利(fluvalinate)、λ-赛洛宁(cyhalothrin)或氯菊酯;植物,如除虫菊酯;新烟碱,如啶虫脒(acetamiprid)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)或噻虫嗪(thiamethoxam);丁烯酸内酯,如氟吡呋喃酮(flupyradifurone);多杀菌素,如赐诺杀(spinosad);糖苷,如阿巴汀(abamectin);阿维菌素,如甲苯甲酸氨基阿维菌素或密灭汀(milbemectin);保幼激素模拟物,如s-烯虫炔酯(s-Kinoprene)或苯氧威(fenoxycarb);吡啶-昆虫生长调节剂,如百利普芬(pyriproxyfen);吡啶甲亚胺,如吡蚜酮(pymetrozine)或吡氟喹腙(pyrifluquinazon);四嗪,如克芬螨(clofentezine);噻唑烷酮,如噻螨酮(hexythiazox);2,4-二苯基噁唑啉衍生物,如依杀螨(etoxazole);生物杀虫剂,如苏云金杆菌库斯塔克亚种(bacillus thuringiensis kurstaki)或苏云金杆菌以色列亚种(bacillus thuringiensis israelensis);有机锡杀螨剂,如苯丁锡-氧化物;吡咯,如克凡派(chlorfenapyr);苯甲酰脲-昆虫生长调节剂,如除虫脲(diflubenzuron)或诺伐隆(novaluron);布芬净(buprofezin),如布芬净;赛灭净(cyromazine)-昆虫生长调节剂,如赛灭净;二酰基肼,如虫酰肼(tebufenozide)、甲氧虫酰肼;三氟甲基氨基腙,如爱美松(hydramethylnon);肼基甲酸酯,如毕芬载(bifenazate);萘醌衍生物,如亚醌螨(acequinocyl);METI杀螨剂和杀虫剂,如哒螨灵(pyridaben)、芬普螨(fenpyroximate)、唑虫酰胺(tolfenpyrad)、芬杀螨(fenazaquin);缩氨基脲,如氰氟虫腙(metaflumizone);季酮酸,如螺甲螨酯(spiromesifen);特拉姆酸,如螺虫乙酯(spirotetramat);β-酮腈,如丁氟螨酯(cyflumetofen);邻氨基苯甲酸二酰胺,如氰虫酰胺(cyantraniliprole);吡啶甲酰胺,如氟尼胺(flonicamid);生物杀虫剂昆虫生长调节剂,如印楝素(azadirachtin);啶虫丙醚(pyridalyl),如啶虫丙醚;生物杀虫剂,如球孢白僵菌(beauveria bassiana)、玫烟色棒束孢(isaria fumosorosea)Apopka菌株97(ATCC20874)、夜蛾斯氏线虫(steinernemafelitae)、小卷蛾斯氏线虫(steinernema carpocapsae);油,如植物油、澄清疏水性印度楝树油提取物、矿物油或石油;皂,如脂肪酸的钾盐;除虫菊酯和油,如除虫菊酯和菜籽油;除虫菊酯,如除虫菊酯和胡椒基丁醚;有机磷酸酯和拟除虫菊酯,如陶斯松和赛扶宁;拟除虫菊酯和新烟碱,如赛扶宁和吡虫啉;糖苷和肼基甲酸酯,如阿巴汀和毕芬载。在优选实施例中,农药是拟除虫菊酯。示例性拟除虫菊酯包括联苯菊酯、二甲戊乐灵(pendimethalin)、氯菊酯、苄呋菊脂(resmethrin)、丙烯菊酯(allethrin)、赛灭宁(cypermethrin)、第灭宁(deltamethrin)和聚醚菊酯(sumithrin)。在某些实施例中,农药是印度楝树油。
在本文所述的任何方面或实施例中,当存在时,杀真菌剂可以是本领域已知的任何杀真菌剂。杀真菌剂可包括例如嘧菌酯(azoxystrobin)、吡氟菌酯(bifujunzhi)、甲香菌酯(甲香菌酯)、丁香菌酯(coumoxystrobin);二莫西史卓宾(dimoxystrobin)、依尼菌胺(enestroburin)、烯肟菌酯(enoxastrobin)、烯肟菌胺(fenaminstrobin)、菌螨酯(fenoxystrobin)、氟菌螨酯(flufenoxystrobin)、氟嘧菌酯(fluoxastrobin)、甲香菌酯(jiaxiangjunzhi)、克收欣(kresoxim-methyl)、甲氧基丙烯酸酯类(mandestrobin)、苯氧菌胺(metominostrobin)、肟醚菌胺(orysastrobin)、啶氧菌酯(picoxystrobin)、百克敏(pyraclostrobin)、唑胺菌酯(pyrametostrobin)、唑菌酯(pyraoxystrobin)、氯啶菌酯(triclopyricarb)、三氟敏(trifloxystrobin)、2-[2-(2,5-二甲基苯基氧基甲基)苯基]-3-甲氧基丙烯酸甲酯、吡菌苯威(pyribencarb)、氯啶菌酯(triclopyricarb/chlorodincarb)、唑酮菌(famoxadon)、咪唑菌酮(fenamidon)、赛座灭(cyazofamid)、吲唑磺菌胺(amisulbrom)、麦锈灵(benodanil)、必杀吩(bixafen)、白克列(boscalid)、萎锈灵(carboxin)、甲呋酰胺(fenfuram)、氟吡胺(fluopyram)、氟酰胺(flutolanil)、氟唑菌酰胺(fluxapyroxad)、福拉比(furametpyr)、异吡瑞沙(isopyrazam)、灭普宁(mepronil)、萎锈散(oxycarboxin)、氟幼脲(penflufen)、吡噻菌胺(penthiopyrad)、氟唑环菌胺(sedaxane)、叶枯酞(tecloftalam)、噻氟菌胺(thifluzamide)、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、N-[9-(二氯亚甲基)-1,2,3,4-四氢-1,4-甲烷萘-烯-5-基]-3-(二氟甲基)-1-甲基-H-吡唑-4-甲酰胺、二氟林(diflumetorim)、百螨克(binapacryl)、大脱螨(dinobuton)、白粉克(dinocap)、消螨多(meptyl-dinocap)、扶吉胺(fluazinam)、嘧菌腙(ferimzone)、辛唑嘧菌胺(ametoctradin)、硫硅菌胺(silthiofam)、氧环唑(azaconazole)、联苯三唑醇(bitertanol)、糠菌唑(bromuconazole)、环克座(cyproconazole)、待克利(difenoconazole)、烯唑醇(diniconazole)、烯唑醇-M(diniconazole-M)、依普座(epoxiconazole);腈苯唑(fenbuconazole)、氟喹唑(fluquinconazole)、护硅得(flusilazole)、粉唑醇(flutriafol)、己唑醇(hexaconazole)、亚胺唑(imibenconazole)、种菌唑(ipconazole)、灭特座(metconazole)、迈克尼(myclobutanil)、噁咪唑(oxpoconazole)、巴克素(paclobutrazole)、平克座(penconazole)、普克利(propiconazole)、丙硫菌唑(prothioconazole)、硅氟唑(simeconazole)、戊唑醇(tebuconazole)、四克利(tetraconazole)、三泰芬(triadimefon)、三泰隆(triadimenol)、灭菌唑(triticonazole)、烯效唑(uniconazole)、抑霉唑(imazalil)、稻瘟酯(pefurazoate)、咪酰胺(prochloraz)、三氟咪唑(triflumizole)、嘧啶(pyrimidines)、芬瑞莫(fenarimol)、尼瑞莫(nuarimol)、啶斑肟(pyrifenox)、嗪氨灵(triforine)、阿迪吗啉(aldimorph)、吗菌灵(dodemorph)、乙酸吗菌灵、丁苯吗啉(fenpropimorph)、克啉菌(tridemorph)、苯锈啶(fenpropidin)、粉病灵(piperalin)、螺恶茂胺(spiroxamine)、环酰菌胺(fenhexamid)、本达乐(benalaxyl)、本达乐-M、克拉昔(kiralaxyl);灭达乐(metalaxyl)、灭达乐-M(右灭达乐(mefenoxam))、呋酰胺(ofurace);欧杀斯(oxadixyl)、杀纹宁(hymexazole)、辛噻酮(octhilinone)、欧索林酸(oxolinicacid)、布瑞莫(bupirimate)、苯菌灵(benomyl)、贝芬替(carbendazim)、麦穗灵(fuberidazole)、噻苯达唑(thiabendazole)、多保净(thiophanate)、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、乙霉威(diethofencarb)、噻唑菌胺(ethaboxam)、宾克隆(pencycuron)、氟辟高立(fluopicolid)、苯酰菌胺(zoxainid)、苯菌酮(metrafenon)、哌芬酮(pyriofenon)、嘧菌环胺(cyprodinil)、嘧菌胺(mepanipyrim)、嘧霉胺(pyrimethanil)、氟酰亚胺(fluoroimide)、依普同(iprodione)、腐霉利(procymidone)、农利灵拌种咯(vinclozolin fenpiclonil)、氟二恶尼(fludioxonil)、喹氧灵(quinoxyfen)、护粒松(edifenphos)、异稻瘟净(iprobenfos)、白粉松(pyrazophos)、稻瘟灵(isoprothiolane)、氯硝胺(dicloran)、五氯硝基苯(quintozene)、四氯硝基苯(tecnazene)、立枯磷(tolclofos-methyl)、联苯、地茂散(chloroneb)、依得利(etridiazole)、达灭芬(dimethomorph)、氟吗啉(flumorph)、双炔酰菌胺(mandipropamid)、丁吡吗啉(pyrimorph)、苯噻菌胺(benthiavalicarb)、丙森锌(iprovalicarb)、霜霉灭(valifenalate)和N-(1-(1-(4-氰基苯基)乙烷磺酰基)丁-2-基)氨基甲酸4-氟苯酯、霜霉威(propamocarb)、霜霉威盐酸盐、福美铁(ferbam)、代森锰锌(mancozeb)、代森锰(maneb)、代森联(metiram)、甲基锌乃浦(propineb)、福美双(thiram)、代森锌(zineb)、福美锌(ziram)、敌菌灵(anilazine)、四氯异苯腈(chlorothalonil)、四氯丹(captafol)、盖普丹(captan)、灭菌丹(folpet)、益发灵(dichlofluanid)、二氯酚(dichlorophen)、氟硫灭(flusulfamide)、六氯苯(hexachlorobenzene)、五氯苯酚(pentachlorophenol)、四氯苯酞(phthalid)、甲基益发灵(tolylfluanid)、N-(4-氯-2-硝基苯基)-N-乙基-4-甲基苯磺酰胺、胍、腈硫醌(dithianon)、维利微素(validamycin)、保粒霉素B(polyoxin B)、咯喹酮(pyroquilon)、三赛唑(tricyclazole)、加普胺(carpropamid)、双环维林(dicyclomet)、氰菌胺(fenoxanil)或其组合。
在本文所述的任何方面或实施例中,当存在时,所述除草剂可以是本领域已知的任何除草剂,例如乙草胺(acetochlor)、三氟羧草醚(acifluorfen)、禾草灭(alloxydim)、酰嘧磺隆(amidosulfuron)、氯氨吡啶酸(aminopyralid)、莠去津(atrazine)、氟丁酰草胺(beflubutamid)、双草醚(bispyribac)、氟丙嘧草酯(butafenacil)、唑草胺(cafenstrole)、唑草酮(carfentrazone)、氯嘧磺隆(chlorimuron)、绿麦隆(chlorotoluron)、吲哚酮草酯(cinidon)-乙基、克草同(clethodim)、炔草酸(clodinafop)、异噁草酮(clomazone)、氯丙氧定(cloproxydim)、毕克草(clopyralid)、氯酯磺草胺(cloransulam)、氰草津(cyanazine)、环磺隆(cyclosulfamuron)、环杀草(cycloxydim)、氰氟草酯(cyhalofop)、杀草隆(daimuron)、汰克草(dicamba)、禾草灵(diclofop)、双氯磺草胺(diclosulam)、吡氟草胺(diflufenican)、二甲噻草胺(dimethenamid)、敌草快(diquat)、氟硫草定(dithiopyr)、敌草隆(diuron)、乙丁烯氟灵(ethalfluralin)、噁唑禾草灵(fenoxaprop)、嘧啶磺隆(flazasulfuron)、双氟磺草胺(florasulam)、吡氟禾草灵(fluazifop)、氟酮磺隆(flucarbazone)、氟噻草胺(flufenacet)、氟芬尼康(flufenican)、氟哒嗪草酯(flufenpyr)、唑嘧磺草胺(flumetsulam)、氟胺草酯(flumiclorac)、丙炔氟草胺(flumioxazin)、氟草定(fluroxypyr)、氟噻草酯(fluthiacet)、氟磺胺草醚(fomesafen)、甲酰嘧磺隆(foramsulfuron)、草铵膦(glufosinate)、草甘膦(glyphosate)、卤索芬(halosafen)、氯吡嘧磺隆(halosulfuron)、合氯氟(haloxyfop)、咪草酸(imazamethabenz)、甲氧咪草烟(imazamox)、甲基咪草烟(imazapic)、灭草烟(imazapyr)、灭草喹(imazaquin)、咪草烟(imazethapyr)、唑吡嘧磺隆(imazosulfuron)、碘甲磺隆(iodosulfuron)、碘苯腈(ioxynil)、异噁草胺(isoxaben)、异噁唑草酮(isoxaflutole)、乳氟禾草灵(lactofen)、利谷隆(linuron)、苯噻酰草胺(mefenacet)、氟磺酰草胺(mefluidide)、甲基二磺隆(mesosulfuron)、甲基磺草酮(mesotrione)、噁唑酰草胺(metamifop)、吡草胺(metazachlor)、磺草唑胺(metosulam)、赛克津(metribuzin)、MSMA、敌草胺(napropamide)、烟嘧磺隆(nicosulfuron)、达草灭(norflurazon)、氨磺乐灵(oryzalin)、噁草酮(oxadiazon)、乙氧氟草醚(oxyfluorfen)、巴拉割(paraquat)、克草猛(pebulate)、二甲戊乐灵(pendimethalin)、平速烂(penoxsulam)、毕克烂(picloram)、氟吡草胺(picolinafen)、唑啉草酯(pinoxaden)、氟嘧磺隆(primisulfuron)、环苯草酮(profoxydim)、敌稗(propanil)、吡草醚(pyraflufen)、吡嘧磺隆(pyrazosulfuron)、嘧啶肟草醚(pyribenzoxim)、嘧草醚(pyriminobac)、嘧硫草醚(pyrithiobac)、吡咯磺隆(pyroxasulfone)、嘧氧磺胺(pyroxsulam)、二氯喹啉酸(quinclorac)、喹草酸(quinmerac)、快伏草(quizalofop)、砜嘧磺隆(rimsulfuron)、稀禾定(sethoxydim)、西玛津(simazine)、磺草酮(sulcotrione)、甲磺草胺(sulfentrazone)、甲嘧磺隆(sulfometuron)、特呋喃隆(tefuryltrione)、环磺酮(tembotrione)、吡喃草酮(tepraloxydim)、特草定(terbacil)、噻草啶(thiazopyr)、噻苯隆(thidiazuron)、噻酮磺隆(thiencarbazone)、噻吩磺隆(thifensulfuron)、禾草丹(thiobencarb)、苯吡唑草酮(topramezone)、肟草酮(tralkoxydim)、醚苯磺隆(triasulfuron)、苯磺隆(tribenuron)、绿草定(triclopyr)、三氟啶磺隆(trifloxysulfuron)、氟乐灵(trifluralin)、氟胺磺隆(triflusulfuron)、三氟甲磺隆(tritosulfuron)或其组合。
农业制剂可包含活性组分,其量在以下范围内:约1至约50wt%、约1至约45wt%、约1至约40wt%、约1至约35wt%、约1至约30wt%、约1至约25wt%、约1至约20wt%、约1至约15wt%、约1至约10wt%、约1至约5wt%、约5至约50wt%、约5至约45wt%、约5至约40wt%、约5至约35wt%、约5至约30wt%、约5至约25wt%、约10至约50wt%、约10至约45wt%、约10至约40wt%、约10至约35wt%、约10至约30wt%、约10至约25wt%、约15至约50wt%、约15至约45wt%、约15至约40wt%、约15至约30wt%、或约15至约25wt%。在一些实施例中,活性组分可以农业制剂的总重量的约5wt%、约6wt%、约7wt%、约8wt%、约9wt%、约10wt%、约11wt%、约12wt%、约13wt%、约14wt%、约15wt%、约16wt%、约17wt%、约18wt%、约19wt%、约20wt%、约21wt%、约22wt%、约23wt%、约24wt%、约25wt%、约26wt%、约27wt%、约28wt%、约29wt%、约30wt%、约31wt%、约32wt%、约33wt%、约34wt%、约35wt%、约36wt%、约37wt%、约38wt%、约39wt%、约40wt%、约41wt%、约42wt%、约43wt%、约44wt%、约45wt%、约46wt%、约47wt%、约48wt%、约49wt%或约50wt%存在。
农业制剂包括天然油溶剂。天然油和其衍生物已用作农业制剂中的佐剂,如蒸馏松油(DTO)、松油脂肪酸(TOFA)、大豆油脂肪酸(SOFA)、棕榈油、椰子油等。然而,天然油尚未用作常规制剂中的溶剂。因此,令人惊讶且出乎意料的是包括天然油作为溶剂并且最大限度地减少或消除常规有机溶剂的使用的农业制剂将提供合适的制剂。在一些实施例中,制剂不包括添加的有机溶剂。
天然油溶剂可以是松油脂肪酸的酯、大豆油脂肪酸的C1-C5酯、松香油、松香C1-C3酯、蒸馏松油、氢化松香的C1-C3、植物油、红花油、芝麻油、菜籽油、橄榄油、多萜或其组合。天然油溶剂可以是松油脂肪酸的C1-C3酯、大豆油脂肪酸的C1-C5酯、松香油、松香C1-C3酯、多萜、氢化树脂的C1-C3甲酯、蒸馏松油或其组合。示例性TOFA酯包括甲酯,例如可从INGEVITY获得的POLYFAC TE-110;丁酯,例如可从INGEVITY获得的JONREZ FE-110;或季戊四醇(PE)酯,例如可从INGEVITY获得的POLYFAC TE-319。示例性大豆油脂肪酸的酯包括大豆油脂肪酸的甲酯,例如可从AGP获得的SOYGOLD。示例性松香酯包括松香甲酯。氢化松香的合适的C1-C3酯包括氢化松香的甲酯(100%松香),其以HERCOLYN D的形式获得,可从PINOVA获得。
在某些实施例中,具有较高松香含量的天然油溶剂可提供比具有较低松香含量的天然油溶剂更稳定的制剂。天然油溶剂的松香含量可为大于约30%、大于约35%、大于约40%、大于约45%、大于约50%、约30至约90%、约40至约80%、或约50至约75%。
在一些实施例中,具有较低松香含量的天然油溶剂可提供粘度比具有较高松香含量的制剂低的制剂,从而提供易用性和应用性。松香含量可为小于约50%、小于约45%、小于约40%、小于约35%、小于约30%、小于约25%、小于约20%、约5至约50%、约10至约50%、约5至约45%、约10至约45%、约5至约40%、约10至约40%、约5至约35%、约10至约35%、约5至约30%、约10至约30%、约5至约20%、或约10至约20%。
以农业制剂的总重量计,天然油溶剂以约20至约80wt%、约20至约70wt%、约20至约60wt%、约20至约50wt%、约20至约40wt%、约20至约30wt%、25至约80wt%、约25至约70wt%、约25至约60wt%、约25至约50wt%、约25至约40wt%、30至约80wt%、约30至约70wt%、约30至约60wt%、约30至约50wt%、约30至约40wt%、40至约80wt%、约40至约70wt%、或约40至约60wt%存在。
尽管期望最大限度地减少或消除所公开的农业制剂中的有机溶剂,但取决于活性组分负载和天然溶剂组成(例如,蒸馏松油的松香含量),制剂可变得高度粘稠,这可能降低制剂的流动性和实际适用性。可以添加有机溶剂以降低农业制剂的粘度。如本文所用,术语“有机溶剂”是不同于天然油溶剂的溶剂,因此从“有机溶剂”的含义中排除天然油。有机溶剂的非限制性实例包括:二醇,如乙二醇、丙二醇、单丙二醇、己二醇;卤代烃,如二氯甲烷和二氯乙烷;极性非质子溶剂,如乙腈、N-甲基吡咯烷酮(NMP)和N-乙基吡咯烷酮(NEP)、N-辛基吡咯烷酮、二甲基乙酰胺(DMA)、二甲基甲酰胺(DMF)、二甲亚砜(DMSO)、单甲基乙酰胺、六甲基磷酸三酰胺(HMPT);醚,如四氢呋喃(THF)和二甲醚;脂肪族烃,如石蜡和矿物油;芳香族烃,如烷基苯,例如二甲苯、苯基二甲苯基乙烷、烷基萘;以及γ-丁内酯、环己酮和二甲基咪唑烷酮。在一些实施例中,有机溶剂包括C11-C16环状和芳香族烃,其可以TITOMATICND200(EXXON)的形式商购获得。以农业制剂的总重量计,有机溶剂可以如下范围内的量存在:约1至约50wt%、约5至约50wt%、约5至约45wt%、约5至约40wt%、约5至约35wt%、约5至约30wt%、约5至约25wt%、约5至约20wt%、约5至约15wt%、约5至约10wt%、小于约10wt%、或小于约5wt%。
然而,如上文所论述,有机溶剂遭受众所周知的缺点,包括对敏感植物的损害风险,并且充当VOC和SVOC排放源。因此,期望最大限度地减少存在于农业制剂中的有机溶剂的量。有利地,本发明人已发现天然油溶剂与绿色共溶剂的组合可提供其中有机溶剂的量被最大限度地减少或消除的制剂。如本文所用,术语“绿色共溶剂”是指不同于天然油溶剂和有机溶剂的溶剂。绿色共溶剂可包括酮溶剂、醇溶剂、有机酸溶剂、乙酸酯溶剂、乳酸酯溶剂、乙酰丙酸酯溶剂或其组合。在一些实施例中,绿色共溶剂包括C3-C8酮溶剂、C1-C6醇溶剂、C2-C10羧酸溶剂、C3-C8乙酸酯溶剂、C4-C8乳酸酯溶剂、C6-C10乙酰丙酸酯溶剂或其组合。绿色共溶剂可包括丙酮、甲基乙基酮、甲基异丁基酮、甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、叔丁醇、乙酸、乙酸乙酯、乙酸异丙酯、乙酸丙酯、乙酸丁酯、乙酸异丁酯、乙酸叔丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸异丙酯、乳酸丁酯、乳酸异丁酯、乳酸叔丁酯、乙酰丙酸甲酯、乙酰丙酸乙酯、乙酰丙酸丙酯、乙酰丙酸异丙酯、乙酰丙酸丁酯、乙酰丙酸异丁酯、乙酰丙酸叔丁酯、或其组合。
天然油溶剂和绿色共溶剂的混合物可存在于制剂中。以农业制剂的总重量计,绿色共溶剂可以约20至约80wt%、约20至约70wt%、约20至约60wt%、约20至约50wt%、约20至约40wt%、约20至约30wt%、25至约80wt%、约25至约70wt%、约25至约60wt%、约25至约50wt%、约25至约40wt%、30至约80wt%、约30至约70wt%、约30至约60wt%、约30至约50wt%、约30至约40wt%、40至约80wt%、约40至约70wt%、或约40至约60wt%存在。
当存在绿色共溶剂时,天然油溶剂的重量与绿色共溶剂的重量的比率可以是约10:1至约1:10,或约4:1至约1:4、约3:1至约1:3、约6:4至约4:6、约2:1至约1:2、或约1:1。
农业制剂包括非离子表面活性剂。表面活性剂是两亲性的,具有对水具有极少吸引力的结构基团(疏水性基团)连同对水具有强吸引力的基团(亲水性基团)。不同类别的表面活性剂所共同的是,疏水性基团可以是长链烃。亲水性基团区分不同类别的表面活性剂:阳离子、阴离子、非离子和两性。阴离子表面活性剂的亲水性基团可以是磺酸酯、硫酸酯或羧酸酯基团,例如直链烷基苯磺酸酯(LAS)。非离子表面活性剂可以是本领域已知的任何非离子表面活性剂。可使用非离子表面活性剂的混合物。在一些实施例中,非离子表面活性剂可以是环氧乙烷-共-环氧丙烷、乙氧基化蓖麻油、聚山梨醇酯、壬基酚乙氧基化物、乙氧基化蒸馏松油或其组合。以组合物的总重量计,非离子表面活性剂以约5至约40wt%、约5至约30wt%、约5至约20wt%、约10至约30wt%、约10至约25wt%、或约10至约20wt%存在。
农业制剂可进一步包含额外表面活性剂,所述额外表面活性剂包含阳离子表面活性剂、阴离子表面活性剂、两性表面活性剂或其组合。在某些实施例中,除了非离子表面活性剂之外,农业制剂还包括阴离子表面活性剂。在示例性实施例中,阴离子表面活性剂是直链烷基苯磺酸酯。当存在时,以农业制剂的总重量计,非离子表面活性剂和额外表面活性剂的总wt%为约5至约40wt%、约5至约30wt%、约5至约20wt%、约10至约30wt%、约10至约25wt%、或约10至约20wt%。
合适的额外表面活性剂的实例包括但不限于:酰胺基胺表面活性剂;咪唑啉;非离子表面活性剂;季铵表面活性剂;三胺;四胺;五胺;酰胺化松油衍生物,例如脂肪酸或松香等,以及其衍生物。适用于本公开中的离子表面活性剂包括两性表面活性剂、阳离子表面活性剂和其组合。
如本文所用,术语“两性表面活性剂”包括单两性表面活性剂和多两性表面活性剂两者。适用于本公开的两性表面活性剂包括但不限于以下:C-12至C-24(优选C-16至C-18)脂肪酸、松香酸和其组合,经丙烯酸、马来酸酐、富马酸和/或其它亲烯体和亲二烯体修饰且进一步与以下各者反应:聚乙烯多胺、C-12至C-24烷基酰胺丙基卤化物甲酸甲酯甜菜碱锂、C-12至C-24烷基酰胺丙基卤化物甲酸甲酯甜菜碱钠、C-12至C-24烷基酰胺丙基卤化物甲酸甲酯甜菜碱钾、C-12至C-24烷基酰胺丙基卤化物磷酸甜菜碱锂、C-12至C-24烷基酰胺丙基卤化物磷酸甜菜碱钠、C-12至C-24烷基酰胺丙基卤化物磷酸甜菜碱钾、C-12至C-24烷基酰胺丙基卤化物硫酸甜菜碱锂、C-12至C-24烷基酰胺丙基卤化物硫酸甜菜碱钠、C-12至C-24烷基酰胺丙基卤化物硫酸甜菜碱钾。除非上下文另外指示,否则术语“两性表面活性剂”包括上述化合物和其衍生物。
本文所述的组合物中适用的阴离子表面活性剂包括但不限于石油磺酸盐,如α-烯烃磺酸盐或硫酸盐、皂型乳化剂,通常为高级(例如C6-C32)脂肪酸(例如月桂酸、肉豆蔻酸、棕榈酸、油酸、蓖麻油酸和亚油酸)的碱金属盐,或可从动物或植物油获得的酸的混合物。阴离子表面活性剂的其它实例描述于美国专利第4,282,037号中,其描述以引用的方式并入本文中。可包括于本文所述的组合物中的额外阴离子表面活性剂包括例如饱和或不饱和高级(C6-C32)脂肪酸的水溶性钾盐、高级醇的硫酸酯的钠盐、烷基苯磺酸钠、琥珀酸二烷基酯磺酸的钠盐和烷基二苯基醚磺酸的钠盐。其中,优选的是烷基苯磺酸钠、月桂基硫酸钠、聚氧乙烯烷基(或烷基苯基)醚磺酸盐等。优选的表面活性剂是阴离子乳化剂,如木素酸盐-表面活性剂混合物(Indulin SA-L,MWV,Charleston Heights,S.C.)。除非上下文另有说明,否则术语“阴离子表面活性剂”包括上述化合物和其衍生物。
适用于本文所述的组合物的阳离子表面活性剂包括但不限于以下:衍生自C-12至C-24脂肪酸的脂肪咪唑啉、衍生自以下各者的脂肪酰亚胺基胺:C-12至C-24(优选C-16至C-18)脂肪酸、松香酸和其组合,经马来酸酐、富马酸和/或其它亲烯体和亲二烯体修饰且进一步与聚亚烷基多胺反应;衍生自以下各者的脂肪酰胺基胺:C-12至C-24(优选C-16至C-18)脂肪酸、松香酸和其组合,经丙烯酸、马来酸酐、富马酸和/或其它亲烯体和亲二烯体修饰且进一步与聚亚烷基多胺反应;饱和C-12至C-24烷基单胺、不饱和C-12至C-24烷基单胺、饱和C-12至C-24烷基聚丙烯多胺;不饱和C-12至C-24烷基聚丙烯多胺;饱和C-12至C-24烷基单胺,其通过与环氧乙烷和/或环氧丙烯反应改性,得到聚氧乙烯衍生物;不饱和C-12至C-24烷基单胺,其通过与环氧乙烷和/或环氧丙烯反应改性,得到聚氧乙烯衍生物;饱和C-12至C-24烷基聚丙烯多胺,其通过与环氧乙烷和/或环氧丙烯反应改性,得到聚氧乙烯衍生物;不饱和C-12至C-24烷基聚丙烯多胺,其通过与环氧乙烷和/或环氧丙烯反应改性,得到聚氧乙烯衍生物;饱和C-12至C-24烷基芳基单胺、不饱和C-12至C-24烷基芳基单胺;饱和C-12至C-24烷基芳基聚丙烯多胺、不饱和C-12至C-24烷基芳基聚丙烯多胺;C-12至C-24季铵;C-12至C-24烷基醚胺;C-12至C-24烷基醚多胺;C-12至C-24烷基聚丙烯多胺N-氧化物;单宁的胺衍生物、酚醛树脂的胺衍生物;木质素的胺衍生物、胺改性的聚丙烯酸酯;和其组合。在某些实施例中,阳离子表面活性剂是选自由以下组成的组的成员:饱和C-12至C-24烷基单胺、不饱和C-12至C-24烷基单胺、饱和C-12至C-24烷基聚丙烯多胺、不饱和C-12至C-24烷基聚丙烯多胺和其组合。在某些实施例中,阳离子表面活性剂是选自由饱和和不饱和C-12至C-24烷基单胺组成的组的至少一个成员与选自由饱和和不饱和C-12至C-24烷基聚丙烯多胺组成的组的至少一个成员的掺合物。除非上下文另外指示,否则术语“阳离子表面活性剂”包括上述化合物和其衍生物。
农业制剂可包含至多约15wt%联苯菊酯;约65至约80wt%包含天然油溶剂的溶剂,其中所述天然油溶剂是松油脂肪酸的酯、大豆油脂肪酸的C1-C5酯、松香油、松香C1-C3酯、蒸馏松油、氢化松香的C1-C3、植物油、红花油、芝麻油、菜籽油、橄榄油、多萜或其组合;以及约5至约20wt%的非离子表面活性剂。
农业制剂可包含约15至约30wt%联苯菊酯;约50至约80wt%包含天然油溶剂的溶剂,其中所述天然油溶剂是以蒸馏松油的总重量计包含至少50wt%松香的蒸馏松油、松油脂肪酸的C1-C3酯、大豆油脂肪酸的C1-C5酯、松香油、多萜、松香C1-C3酯、氢化松香的甲酯或其组合;以及约5至约20wt%的非离子表面活性剂。
农业制剂可包括至多约45wt%的活性组分;约20至约60wt%的天然油溶剂,其中所述天然油溶剂是松油脂肪酸、蒸馏松油、植物油、红花油、芝麻油、菜籽油、橄榄油或其组合;以及约5至约30wt%的绿色共溶剂,其中所述绿色共溶剂是乳酸正丁酯。
农业制剂通常包括活性和惰性成分。活性组分包括农药、杀真菌剂、除草剂或其组合。惰性成分有助于将活性组分递送至目标害虫,并增强农药的效用。本公开的农业制剂可包括适用于农业制剂的任何惰性成分,如表面活性剂、分散剂、湿润剂;不同于天然油溶剂、有机溶剂和绿色共溶剂的溶剂;乳化剂、消泡剂、稳定剂、抗微生物剂、抗冻剂、颜料、着色剂、缓冲剂等。
制备农业制剂的方法包含将农药、杀真菌剂、除草剂或其组合与天然油溶剂混合。在一些实施例中,在加热或不加热的情况下在天然油溶剂中搅拌溶解活性组分以形成均匀溶液。在某些实施例中,可添加有机溶剂、绿色共溶剂或其组合。
有利地,本文公开的农业制剂的VOC和SVOC含量被最大限度地减少。如本文所用,“VOC”是指沸点为至多约200℃的有机化合物。如本文所用,“SVOC”是指沸点为约200℃至约400℃的有机化合物。天然油溶剂的VOC含量可小于约1%。天然油溶剂的SVOC含量可小于约1%。天然油溶剂的VOC和SVOC含量的总和可小于约5%、小于约4%、小于约3%、小于约2%、或小于约1%。
本公开的农业制剂可以是本领域已知的任何液体可喷雾制剂。在一些实施例中,农业制剂是可乳化浓缩物。在其它实施例中,农业制剂是油分散体(OD)。在其它实施例中,农业制剂是悬乳液(SE)。
使用测量制剂的“黄度”的加德纳(Gardner)色标来定量农业制剂的颜色。加德纳颜色是指根据方法ASTM D1544-04(2010)使用分光光度计测量的纯颜色。所公开的农业制剂可具有至多约9.0、约1.0至约8.0、约1.0至约7.0、约1.0至约6.0、约1.0至5.0、约1.0至约4.5、约1.0至约4.0、约1.0至约3.5、约1.0至约3.3、约1.0至约2.0、约1.5至约4.0、约1.5至约3.5、约1.5至约3.0、约1.5至约2.5、或自1.5至约2.0的加德纳颜色(纯)。
在一些实施例中,制剂在25℃下的粘度为约10至约500厘泊(cP)、约10至约400cP、约10至约300cP、约10至约250cP、约10至约200cP、约10至约150cP、约10至约100cP、约10至约50cP、约10至约25cP、或约10至约20cP。
农业制剂使用动态光散射(DLS)粒度分析仪测量的乳液液滴尺寸(D50)可在以下范围内:约1至约50微米(μm)、约1至约40μm、约1至约30μm、约1至约20μm、约1至约10μm或约1至约5μm。
通过在去离子(DI)水中制备1%乳液,使乳液静置30分钟,并观察相是否分离或是否发生乳油化来确定农业制剂可能具有良好的乳液稳定性。
使用Wilhelmy板式张力计测量的农业制剂的表面张力可以在约30至约40毫牛顿/米(mN/m)的范围内。
根据ASTM方法STP1579(“评估新涂布器-粘着剂佐剂的粘附(Evaluating theadhesion of new spreader-sticker adjuvants)”)确定的农业制剂的抗雨性可在约10至约80%、约10至约70%、约10至约60%、约10至约50%、约10至约40%、约10至约30%、或约10至约20%的范围内。
在其它方面,本公开提供制备如本文所述的可乳化浓缩物制剂的方法和使用所述制剂的方法。例如,在某些实施例中,本公开提供一种使用如本文所述的可乳化浓缩物制剂的方法,其包含以下步骤:提供包括有效量的试剂,例如农药的可乳化浓缩物制剂,以及施用可乳化浓缩物制剂。在某些实施例中,方法包含将可乳化浓缩物制剂施用或施加于土壤或植物或生物体(例如昆虫或害虫)的表面,其中所述可乳化浓缩物制剂实现保护土壤或植物免受昆虫或害虫侵害,或实现至少一部分(例如大量)昆虫或害虫的死亡,或防止来自所述昆虫或害虫的损害。
以下实例进一步说明本公开,所述实例是非限制性的。
实例
实例中使用的材料在表1中列出。
表1.
加德纳颜色是使用ColorQuest XT分光光度计(HunterLab)使用ASTM D1544-04(2010)测量的,无需稀释(纯)。
抗雨性是根据ASTM方法STP1579“评估新涂布器-粘着剂佐剂的粘附”测定的。
粘度是使用TA流变仪测定的,在20℃下以25s-1剪切率、2cm、2度锥形几何形状进行测试。
乳液液滴尺寸(D50)是使用动态光散射(DLS)粒度分析仪测量的。
乳液稳定性是如下确定的:通过在DI水中制备1%乳液,使乳液静置30分钟,观察相是否分离或是否发生乳油化。良好乳液稳定性意味着不发生相分离或乳油化。
用pH计测量每种制剂的pH。
如下地测量质量损失百分比。在室温下将开口的20ml小瓶中的约12g制剂置于通风柜中。2天后,称取小瓶的重量以确定质量损失。高质量损失%与VOC相关。
使用Wilhelmy板式张力计测量表面张力。
老化测试,室温(RT):使每种制剂在室温下带封闭盖静置2周。
老化测试,54℃:使每种制剂在54℃烘箱中带封闭盖静置2周。
冻融测试:将制剂在-10℃下冷却16h,然后使其在25℃下静置8h。此过程执行四次。
实例的细节被设想为所述方法和组合物的其它实施例。因此,如本文所阐述的细节在此作为替代实施例并入到详细描述中。
表2.
*CEx8是一种包括25.1%联苯菊酯和74.9%惰性成分的商业产品(可以Bifen XTS的形式获自ADAMA)。
实例1-7显示在25%联苯菊酯负载和10%非离子表面活性剂下,所有制剂在54℃下2周之后均稳定。然而,在室温下另外两周之后,对于实例1、3、5和6观察到晶体生长,而对于实例2、4和7未观察到晶体生长。在实例1、3、5和6中,溶剂为DTO并且芳香族ND200不存在。在未观测到晶体生长的制剂中,实例2和4包括一部分溶剂作为有机溶剂。在实例1-7中,实例7(SOFA的甲酯)是唯一没有观察到晶体生长且不含有机溶剂的制剂。
观察到具有较高松香含量的溶剂减少晶体的形成(未示出)。例如,在25%联苯菊酯负载下,具有低松香含量DTO溶剂(DTO-1和DTO-2)或中等松香含量DTO溶剂(DTO-3、DDTO-4DTO-5、NS-6)的所选非离子表面活性剂(NS-1和NS-2)的制剂(数据未示出)不产生稳定的制剂。使用中等松香含量DTO溶剂(DTO-4,28%松香含量),测试各种非离子表面活性剂(NS-1至NS-5)以及非离子和阴离子表面活性剂(NS-2和AS-1)的组合的影响(数据未显示),以查看表面活性剂的选择是否将改善稳定性。在所有情况下,均观察到晶体形成。
表3.
对于实例8-18,所有制剂在最初以及在四个冻融循环之后是稳定的。这显示,在25%联苯菊酯负载和10%非离子表面活性剂下,所述TOFA甲酯(实例8)、SOFA甲酯(实例9)、松香甲酯(实例10)、松香甲酯和TOFA甲酯的50:50混合物(实例11)、松香油(实例12-13)、氢化松香的甲酯(实例17)和多萜(实例18)均提供稳定性与仅含有机溶剂的制剂(比较实例14-15)相当的制剂。如实例12-13和比较实例14-15中所示,松香油和芳香族ND200似乎对不同的非离子表面活性剂耐受。如实例16中所示,当蒸馏松油的松香含量为50重量%或更多时,可获得稳定制剂。这与表2(实例1、3、5和6)中获得的结果形成对比。
表4.
尽管最初稳定,但在四个冻融循环之后,对于实例19-22观察到晶体形成(表4)。在25%联苯菊酯负载下,TOFA丁酯(实例20)和TOFAPE酯(实例21)未能产生不同于TOFA甲酯(实施例8)的稳定制剂。使用TOFA甲酯或SOFA甲酯作为溶剂的制剂的储存性能可取决于表面活性剂的选择,如表4所示。在实例19中,TOFA甲酯和非离子表面活性剂(NS-1)在四个冻融循环后导致晶体形成,而TOFA甲酯和非离子表面活性剂(NS-2)产生稳定制剂(实例8)。类似地,SOFA甲酯和非离子表面活性剂(NS-1)(实例22)在四个冻融循环后导致晶体形成,而SOFA甲酯和非离子表面活性剂(NS-2)产生稳定制剂(实例9)。
这些初步实验表明,适用于25重量%联苯菊酯制剂的溶剂包括TOFA-甲酯、SOFA-甲酯、松香油、芳香族ND200、DTO(50重量%松香)、多萜、松香甲酯、氢化松香的甲酯或其组合。
使用气相色谱-火焰电离检测器(GC-FID)分析天然油溶剂和有机溶剂两者的VOC和SVOC含量。使用的GC-FID参数在表5中列出。分析结果在表6中列出。
表5.
表6.
如表6中所示,蒸馏松油和SOFA甲酯含有小于1%的VOC,而有机溶剂具有高含量的VOC和/或SVOC。
实例23-24
表7.
组分 | 单位 | E23 | E24 |
戊唑醇 | wt% | 25 | 10 |
嘧菌酯 | wt% | 5.6 | |
咪酰胺 | wt% | 20 | |
GS-1 | wt% | 13 | 21.6 |
DTO-1 | wt% | 32.4 | |
DTO-4 | wt% | 52 | |
Surfom 360 | wt% | 10 | 10 |
表7示出了使用绿色共溶剂与天然油溶剂的组合的示例性制剂。实例23包括DTO-4(具有28%松香含量)和乳酸丁酯(GS-1)的混合物中的25wt%负载。实例24包括活性组分(戊唑醇、嘧菌酯和咪酰胺)在DTO-1(具有1%松香含量)和乳酸丁酯(GS-1)的混合物中的35.6wt%负载。有利地,实例23-24的制剂通过使用作为天然溶剂的蒸馏松油和作为绿色共溶剂的乳酸正丁酯的混合物而消除了非所需有机溶剂的使用。
示例性实施例
在一个方面,本公开提供了一种可乳化浓缩物制剂,其包含活性组分、天然油溶剂和非离子表面活性剂。在本文所述的任何方面或实施例中,活性组分包含农药、杀真菌剂、除草剂或其组合。在本文所述的任何方面或实施例中,制剂包含有效量的活性组分。在本文所述的任何方面或实施例中,制剂包含天然油溶剂。
在本文所述的任何方面或实施例中,溶剂具有至多约1wt%的挥发性有机物含量。在本文所述的任何方面或实施例中,当存在时,所述农药是拟除虫菊酯。在本文所述的任何方面或实施例中,当存在时,所述农药是联苯菊酯。
在本文所述的任何方面或实施例中,天然油溶剂是松油脂肪酸的酯、大豆油脂肪酸的C1-C5酯、松香油、松香C1-C3酯、蒸馏松油、氢化松香的C1-C3、植物油、红花油、芝麻油、菜籽油、橄榄油、多萜或其组合。
在本文所述的任何方面或实施例中,天然油溶剂是松油脂肪酸的C1-C3酯、大豆油脂肪酸的C1-C5酯、松香油、松香C1-C3酯、多萜、氢化树脂的C1-C3甲酯、蒸馏松油或其组合。
在本文所述的任何方面或实施例中,制剂进一步包含有机溶剂。
在本文所述的任何方面或实施例中,制剂进一步包含不同于天然油溶剂以及当存在时,不同于有机溶剂的绿色共溶剂,其中所述绿色共溶剂包含C3-C8酮溶剂、C1-C6醇溶剂、C3-C8乙酸酯溶剂、C4-C8乳酸酯溶剂、C6-C10乙酰丙酸酯溶剂或其组合。
在本文所述的任何方面或实施例中,当存在时,所述绿色共溶剂包含丙酮、甲基乙基酮、甲基异丁基酮、甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、叔丁醇、乙酸乙酯、乙酸异丙酯、乙酸丙酯、乙酸丁酯、乙酸异丁酯、乙酸叔丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸异丙酯、乳酸丁酯、乳酸异丁酯、乳酸叔丁酯、乙酰丙酸甲酯、乙酰丙酸乙酯、乙酰丙酸丙酯、乙酰丙酸异丙酯、乙酰丙酸丁酯、乙酰丙酸异丁酯、乙酰丙酸叔丁酯、或其组合。
在本文所述的任何方面或实施例中,非离子表面活性剂是环氧乙烷-共-环氧丙烷、乙氧基化蓖麻油、聚山梨醇酯、壬基酚乙氧基化物、乙氧基化蒸馏松油或其组合。在本文所述的任何方面或实施例中,不存在有机溶剂。在本文所述的任何方面或实施例中,制剂进一步包含额外表面活性剂。
在本文所述的任何方面或实施例中,活性组分是农药,并且占制剂的总重量的至多25wt%。在本文所述的任何方面或实施例中,天然油溶剂包含蒸馏松油,其包含以蒸馏松油的总重量计至少50wt%的松香。
在本文所述的任何方面或实施例中,制剂包含至多约15wt%的联苯菊酯;约65至约80wt%的天然油溶剂,其中所述天然油溶剂是松油脂肪酸的酯、大豆油脂肪酸的C1-C5酯、松香油、松香C1-C3酯、蒸馏松油、氢化松香的C1-C3、植物油、红花油、芝麻油、菜籽油、橄榄油、多萜或其组合;以及约5至约20wt%的非离子表面活性剂。
在本文所述的任何方面或实施例中,制剂包含约15至约30wt%的联苯菊酯;约50至约80wt%的天然油溶剂,其中所述天然油溶剂是以蒸馏松油的总重量计包含至少50wt%松香的蒸馏松油、松油脂肪酸的C1-C3酯、大豆油脂肪酸的C1-C5酯、松香油、多萜、松香C1-C3酯、氢化松香的甲酯或其组合;以及约5至约20wt%的非离子表面活性剂。
在本文所述的任何方面或实施例中,制剂进一步包含水(与100重量%的差值)。
在一个方面,本公开提供了一种制备农业制剂的方法,其包含混合活性成分、天然油溶剂和非离子表面活性剂;任选地绿色共溶剂;和任选地有机溶剂;以及溶解所述混合物以形成均匀溶液。
Claims (20)
1.一种农业制剂,其包含:
活性组分,其包含农药、杀真菌剂、除草剂或其组合;
天然油溶剂;以及
非离子表面活性剂。
2.根据权利要求1所述的农业制剂,其中所述天然油溶剂具有至多约1重量%的挥发性有机物含量。
3.根据权利要求1所述的农业制剂,其中所述农药存在并且包含联苯菊酯(bifenthrin)。
4.根据权利要求1所述的农业制剂,其进一步包含有机溶剂,所述有机溶剂包含极性非质子溶剂、脂肪族烃、芳香族烃或其组合。
5.根据权利要求1所述的农业制剂,其进一步包含不同于所述天然油溶剂以及当存在时,不同于所述有机溶剂的绿色共溶剂,其中所述绿色共溶剂包含酮溶剂、醇溶剂、有机酸溶剂、乙酸酯溶剂、乳酸酯溶剂、乙酰丙酸酯溶剂或其组合。
6.根据权利要求1所述的农业制剂,其中所述绿色共溶剂包含C3-C8酮溶剂、C1-C6醇溶剂、C2-C10羧酸、C3-C8乙酸酯溶剂、C4-C8乳酸酯溶剂、C6-C10乙酰丙酸酯溶剂或其组合。
7.根据权利要求1所述的农业制剂,其中所述绿色共溶剂包含丙酮、甲基乙基酮、甲基异丁基酮、甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、叔丁醇、乙酸、乙酸乙酯、乙酸异丙酯、乙酸丙酯、乙酸丁酯、乙酸异丁酯、乙酸叔丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸异丙酯、乳酸丁酯、乳酸异丁酯、乳酸叔丁酯、乙酰丙酸甲酯、乙酰丙酸乙酯、乙酰丙酸丙酯、乙酰丙酸异丙酯、乙酰丙酸丁酯、乙酰丙酸异丁酯、乙酰丙酸叔丁酯、或其组合。
8.根据权利要求1所述的农业制剂,其中所述天然油溶剂是松油脂肪酸的酯、大豆油脂肪酸的C1-C5酯、松香油、松香C1-C3酯、蒸馏松油、氢化松香的C1-C3、植物油、红花油、芝麻油、菜籽油、橄榄油、多萜或其组合。
9.根据权利要求1所述的农业制剂,其中所述天然油溶剂是松油脂肪酸的C1-C3酯、大豆油脂肪酸的C1-C5酯、松香油、松香C1-C3酯、多萜、氢化树脂的C1-C3甲酯、蒸馏松油或其组合。
10.根据权利要求1所述的农业制剂,其中所述非离子表面活性剂是环氧乙烷-共-环氧丙烷、乙氧基化蓖麻油、聚山梨醇酯、壬基酚乙氧基化物、乙氧基化蒸馏松油或其组合。
11.根据权利要求1所述的农业制剂,其中有机溶剂不存在。
12.根据权利要求1所述的农业制剂,其进一步包含额外表面活性剂。
13.根据权利要求1所述的农业制剂,其中所述活性组分是占所述制剂的总重量的至多约25wt%的农药。
14.根据权利要求1所述的农业制剂,其中所述天然油溶剂包含蒸馏松油,其包含以所述蒸馏松油的总重量计至少约50wt%的松香。
15.根据权利要求1所述的农业制剂,其包含
至多约45wt%的所述活性组分;
约20至约60wt%的所述天然油溶剂,其包含松油脂肪酸、蒸馏松油、植物油、红花油、芝麻油、菜籽油、橄榄油或其组合;以及
约5至约30wt%的包含乳酸丁酯的所述绿色共溶剂。
16.根据权利要求1所述的农业制剂,其包含
至多约15wt%作为所述活性组分的联苯菊酯;
约65至约80wt%包含天然油溶剂的溶剂,其中所述天然油溶剂是松油脂肪酸的酯、大豆油脂肪酸的C1-C5酯、松香油、松香C1-C3酯、蒸馏松油、氢化松香的C1-C3、植物油、红花油、芝麻油、菜籽油、橄榄油、多萜或其组合;以及
约5至约20wt%的非离子表面活性剂。
17.根据权利要求1所述的农业制剂,其包含
约15至约30wt%的联苯菊酯;
约50至约80wt%包含天然油溶剂的溶剂,其中所述天然油溶剂是以所述蒸馏松油的总重量计包含至少50wt%松香的蒸馏松油、松油脂肪酸的C1-C3酯、大豆油脂肪酸的C1-C5酯、松香油、多萜、松香C1-C3酯、氢化松香的甲酯或其组合;以及
约5至约20wt%的非离子表面活性剂。
18.根据权利要求14所述的农业制剂,其进一步包含有机溶剂。
19.根据权利要求1所述的农业制剂,其进一步包含水。
20.一种制备根据权利要求1所述的农业制剂的方法,其包含:
混合所述活性组分、所述天然油溶剂、所述非离子表面活性剂、任选地绿色共溶剂;和任选地有机溶剂;以及
溶解所述混合物以形成均匀溶液。
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US62/940,432 | 2019-11-26 | ||
PCT/US2020/027047 WO2020226825A1 (en) | 2019-05-03 | 2020-04-07 | Use of natural oils and their derivatives in agricultural formulations |
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BR112021022034A2 (pt) | 2021-12-28 |
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