CN107404872A - 用作农业化学惰性成分的马来酸化的天然油衍生物 - Google Patents
用作农业化学惰性成分的马来酸化的天然油衍生物 Download PDFInfo
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- CN107404872A CN107404872A CN201680017951.7A CN201680017951A CN107404872A CN 107404872 A CN107404872 A CN 107404872A CN 201680017951 A CN201680017951 A CN 201680017951A CN 107404872 A CN107404872 A CN 107404872A
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Abstract
本公开提供助剂组合物,其包括马来酸化的天然油衍生物。助剂组合物可以掺入农业化学配制剂和施用至靶标基底以灭除、抑制或驱避病虫害。
Description
与有关申请的交叉引用
本申请要求2015年3月25日提交的U.S.临时专利申请序列号62/137,886的益处,通过援引将其全部公开并入本文。
有关联邦赞助研究或开发的声明
不适用。
发明领域
本公开涉及助剂组合物,其含有得自马来酸化的天然油与衍生物化合物的反应的产品,所述衍生物化合物包含至少一种聚氧化烯二醇、聚醚胺、亚烷基胺、烷醇胺、硫醇-封端的聚氧化烯二醇、一-烷基聚氧化烯二醇、氨、IA族金属氢氧化物、IIA族金属氢氧化物或其混合物,及其在农业化学配制剂中的用途。
发明背景
除了活性成分之外,农业化学配制剂还含有惰性成分,其使得农业化学配制剂更容易处理,更便于施用和/或更有效。可以使用许多不同类别的惰性成分,包括乳化剂,分散剂和助剂,并且能够取决于其类型而增强农业化学配制剂的浸湿,铺展,粘着,乳化,分散和/或生物学活性。
能够改善全部活性成分的效能的通用惰性成分是并不存在的。从而对惰性成分加以选择并且必须按照每种施用的具体条件定制所用的相对量。实例包括:
U.S.专利号5,495,033,其公开能够与各种除草剂一起使用的甲基化的酸化大豆皂料;
U.S.专利号5,521,144,其教导用于出苗后除草剂的助剂,包括酸化的皂料和与之组合的烷基酚乙氧基化物或醇乙氧基化物和二醇醚的共混物或阴离子表面活性剂;
U.S.专利号5,658,855,其描述将胺或氨化合物、铵盐、高HLB非离子表面活性剂和水组合以及其在农药中的用途;
U.S.专利号5,888,934,其公开用于改善耐雨水冲刷性的惰性成分,包括烷基聚糖苷和得自脂族一醇的乙氧基化的乙氧基化的醇;
U.S.专利号5,928,563,其教导助剂,含有硫酸化的烷基油酸酯、烷基聚糖苷和C6-C18烷基酯;
U.S.专利号5,942,542,其描述用于拟除虫菊酯杀昆虫剂的惰性成分,包含不饱和水平为至少40%的脂肪酸的烷基酯或二价酸的烷基酯和非离子型乳化剂;
US 2003/0104947,其公开将石油与pH调节剂和非离子表面活性剂组合,及其在农业化学配制剂中的用途;
U.S.专利号6,642,178,其教导用于喷雾载体中的助剂,包含氮肥料、改性植物油、pH调节剂和高、中和低HLB非离子表面活性剂的共混物;
WO 2004/080177,其描述微乳剂的助剂,含有烃或脂肪酸酯,烷基聚糖苷,甘油或脱水山梨糖醇酯,和水;
US 2005/0129662公开植物油作为助剂的用途;
US 2011/0201504,其公开助剂混合物,含有脂肪酸烷基酯,至少两种选自烷基聚糖苷、山梨糖醇酯和聚甘油酯的非离子表面活性剂和任选地多元醇;和
US 2013/0210630,其举例说明乙基马来酸化的大豆和亚麻籽油作为活性成分的乳化剂。
绝大多数农业化学配制剂含有多于一种惰性成分,其有助于将活性成分递送至所希望的靶标杂草、昆虫、真菌等。这些惰性成分中的某些源自不可再生的或具有易变/季节可获得性的资源。其它在环境持续存在,具有毒性生物降解产品或其它不希望的副作用。另外,每当新活性成分引入市场都需要独特的配制剂开发来将活性成分递送至田间。因此,需要开发新的、多用途的农业化学惰性成分,其是非毒性的并且受可再生资源启发或产生自可再生资源。
发明概要
本公开提供包含马来酸化的天然油衍生物的助剂组合物。马来酸化的天然油衍生物可以得自马来酸化的天然油与衍生物化合物的反应,所述衍生物化合物包含至少一种聚氧化烯二醇,聚醚胺,亚烷基胺,烷醇胺,硫醇-封端的聚氧化烯二醇,一-烷基聚氧化烯二醇,氨,IA族金属氢氧化物,IIA族金属氢氧化物或其混合物。
在又一方面中,本申请提供农业化学配制剂,用于施用至靶标基底上以引起化学或生物学效果。农业化学配制剂包含(i)农药有效量的农药或农药混合物和(ii)包含马来酸化的天然油衍生物的助剂组合物。助剂组合物在农业化学配制剂中以一定浓度存在,使得农业化学配制剂的农药效力与参比农业化学配制剂相比有所增强,所述参比农业化学配制剂不含本公开助剂组合物、但除此之外具有所述农业化学配制剂的相同成分。从而,将所述助剂组合物加入农业化学配制剂使得活性成分被用农业化学配制剂处理的靶标底物更快摄取成为可能。该增强的活性可以在用农业化学配制剂处理靶标基底当中产生下述方面的效果:在一定施用率相对更高的活性成分活性;在一定活性相对更低的施用率;和相对更高的靶标基底的活性成分摄取。
在又一方面,本公开提供灭除、抑制或驱避病虫害的方法,其包括:提供农药有效量的农药或农药混合物;提供有效量的助剂组合物;将农药或农药混合物与助剂组合物组合以形成农业化学配制剂;并且将农业化学配制剂与病虫害接触。
发明详述
本公开提供包含马来酸化的天然油衍生物的助剂组合物。助剂组合物能够在与农药或农药混合物预混之后提供至使用者。另选地,助剂组合物能够原样或在例如浓缩组合物或喷雾配制剂中提供至使用者。
令人惊讶地发现的是,本公开助剂组合物可用于农业化学配制剂中以增强活性成分在农业化学配制剂中的效力。"增强"应理解为,与不含本公开马来酸化的天然油衍生物的农业化学配制剂相比,包含本公开马来酸化的天然油衍生物的助剂组合物增加活性成分在农业化学配制剂中的效能(例如施用率相同但活性成分活性更高、效果相同但施用率更低、活性成分被靶标底物更佳地摄取,以及从而用于苗前或苗后处理、尤其是靶标底物的喷雾处理的优势)。此外,本公开的马来酸化的天然油衍生物具有表面活性剂样的结构,其中分子的油部分充当疏水部分而附着的衍生物基团充当亲水部分。从而,马来酸化的天然油衍生物是双官能的,并且在某些实施方式中,可以用于基本上不含表面活性剂的助剂组合物或农业化学配制剂中。这是出人意料的且有利的,原因是一般加入的组分数目得以大幅减少。
如本文所用,术语"助剂组合物"是组合物,其增强农药的生物活性并且其本身不具有生物活性。
术语"基本上不含",在用于指物质在配制剂中实质不存在的情况下,意指上述物质(如果存在)是作为偶然的杂质或副产物存在。换言之,该物质不影响配制剂的特性。
额外地,"农药有效量"是指在施用时减少病虫害存在或增强植物对病虫害抗性的农药的量。
另外,术语"靶标基底"是指作为农药期望目标的植物叶片下的场所,包括但不限于天然地面比如土壤、水(湖泊,池塘,湿地,沼泽,溪流,水坑等)和人工表面比如人行道;病虫害;或其组合。
"病虫害"一般地包括昆虫、螨、蜱和其它节肢动物;病原比如真菌、原生动物、细菌和病毒;蠕虫、线虫(nematodes)(线虫(roundworms)),绦虫(cestodes)(绦虫(tapeworms)),扁形动物(扁形虫),吸虫(trematodes)(吸虫(flukes))和其它蠕虫;孢子虫寄生物;蛞蝓和蜗牛;和脊椎动物比如鸟类、啮齿类动物或能够直接或间接损害任意植物或其部分或任意处理的、制备的植物产品或其它植物产品或导致其病害或损害的其它脊椎动物。
术语"包含"及其衍生词不期望排除任意额外组分、步骤或程序的存在,无论其是否在本文中公开。为了避免任何疑问,本文中通过使用术语"包含"要求保护的全部组合物可以包括任何额外的添加剂或化合物,除非有与之相反的说明。与之相对,术语"基本上由…组成"如果出现则从后续陈述的范围中排除除对可操作性不是必需的那些以外的任何其它组分、步骤或程序;而术语"由…组成"如果使用则排除并未特别界定或列出的任何组分、步骤或程序。术语"或"除非另有说明是指单独的所列成员以及其任意组合。
本文中所用的"一个"和"一种"是指一种或多于一种(也即至少一种)。举例来说,"马来酸化的天然油衍生物"意指一种马来酸化的天然油衍生物或多于一种马来酸化的天然油衍生物。
短语"在一种实施方式中"、"根据一种实施方式"等一般意指该短语之后的具体特征、结构或特性包括在至少一种本发明实施方式中,并且可以包括在多于一种的本发明实施方式中。重要地,所述短语不一定是指同一实施方式。
如果说明书描述组分或特征"可以"、"能够"、"能"或"可能"包括或具有某特性,则该具体组分或特征并非必须包括或具有该特性。
助剂组合物
本公开助剂组合物包括马来酸化的天然油衍生物。马来酸化的天然油衍生物可以得自马来酸化的天然油与衍生物化合物的反应,所述衍生物化合物包含至少一种聚氧化烯二醇,聚醚胺,亚烷基胺,烷醇胺,硫醇-封端的聚氧化烯二醇,一-烷基聚氧化烯二醇,氨,IA族金属氢氧化物,IIA族金属氢氧化物或其混合物。
在一种实施方式中,用于制备本公开的马来酸化的天然油衍生物的天然油衍生自可再生原料资源,比如天然和/或转基因(GMO)植物蔬菜种子和/或动物来源脂肪。所述植物蔬菜种子或动物来源脂肪包括油和/或脂肪,其一般由甘油三酯即与甘油连接的脂肪酸构成。例如,天然油可以在甘油三酯中具有至少约70百分比的不饱和脂肪酸,而在又一实施方式中,天然油可以具有至少85重量百分比的不饱和脂肪酸。所述不饱和脂肪酸具有在脂肪酸的脂肪部分中存在的至少一个烯丙型氢或"烯部分"。
在一种实施方式中,天然油是植物油比如但不限于蓖麻油,大豆油,橄榄油,花生油,菜籽油,玉米油,芝麻油,棉花油,油菜油,红花油,亚麻籽油,棕榈油,葡萄籽油,黑黄蒿油,南瓜油,核油,琉璃苣籽油,木胚油(wood germ oil),杏仁油,阿月浑子油,扁桃油,昆士兰果坚果油,鳄梨油,沙棘油,大麻油,榛子油,月见草油,野玫瑰油,蓟油,胡桃油,向日葵油,麻风树籽油,或其组合。额外地,还可以使用得自有机体比如藻类的天然油。动物来源的天然油的实例包括猪油,牛油,鱼油及其混合物。还可以使用植物油、从藻类获得的油和/或基于动物的油的组合。在一种实施方式中,天然油不是玉米油。
如本文描述的天然油也包括衍生自天然油或脂肪的脂肪酸或脂肪酸酯。也即,术语'天然油"也包括不饱和脂肪酸及其相应的酯。这种不饱和脂肪酸的实例包括油酸,肉豆蔻烯酸,棕榈油酸,亚油酸,α-亚麻酸,花生四烯酸,二十碳五烯酸,芥酸和二十二碳六烯酸。脂肪酸酯的实例包括通过传统转酯基化技术获得的植物油的烷基酯,比如豆油脂肪酸甲酯(大豆油甲酯),油酸甲酯(油酸甲基酯),和油菜油脂肪酸甲酯(油菜油甲基酯)。
天然油也包括脂肪酸的甘油基酯,其合成如下:将甘油与1、2或3摩尔当量的脂肪酸或脂肪酸混合物反应。这些化合物能够是单个脂肪酸或脂肪酸混合物的甘油一、二或三酯。某些实例是二油酸甘油酯,三油酸甘油酯,二硬脂酸甘油酯,和三亚油酸甘油酯。
在又一实施方式中,天然油也包括糖或糖醇的脂肪酸。所述脂肪酸描述于U.S.专利号3,600,186,通过援引将其内容并入本文。术语糖在本文中的通常含义是一般的单糖和二糖。术语糖醇也以其通常含义使用,其一般是指糖类的还原产物,其中醛或酮基已被还原为醇。这些脂肪酸酯化合物可以制备如下:将单糖、二糖或糖醇与脂肪酸反应。
适宜的单糖的实例是含有4个羟基的那些,比如木糖,阿拉伯糖,和核糖;衍生自木糖的糖醇即木糖醇也是适宜的。单糖赤藓糖是不适宜的,原因是其仅含有3个羟基;然而,衍生自赤藓糖的糖醇即赤藓糖醇含有4个羟基,从而是适宜的。适用于本文的含5个羟基的单糖尤其是葡萄糖,甘露糖,半乳糖,果糖和山梨糖。衍生自蔗糖、葡萄糖或山梨糖的糖醇例如山梨醇含有6个羟基并且也适于充当脂肪酸酯化合物的醇部分。适宜的二糖的实例是麦芽糖,乳糖和蔗糖,它们全部含有8个羟基。
在制备糖或糖醇脂肪酸时,糖或糖醇化合物比如上文鉴定的那些的至少4个羟基必须用具有约8至约22个碳原子的脂肪酸酯化。所述脂肪酸的实例是辛酸,癸酸,月桂酸,肉豆蔻酸,肉豆蔻烯酸,棕榈酸,棕榈油酸,硬脂酸,油酸,蓖麻油酸,亚油酸,亚麻酸,桐油酸,花生酸,山萮酸和芥酸。脂肪酸本身或天然脂肪和油能够充当糖或糖醇脂肪酸酯中的脂肪酸组分的来源。例如,菜籽油提供C22脂肪酸的良好来源。C16-C18脂肪酸能够由牛油,大豆油或棉籽油提供。较短链的脂肪酸能够由椰子油,棕榈核油或巴西棕油提供。玉米油,猪油,橄榄油,棕榈油,花生油,红花籽油,芝麻籽油和向日葵籽油是能够充当脂肪酸组分来源的其它天然油的实例。在脂肪酸当中,优选的那些具有约14至约18个碳原子,和最优选选自肉豆蔻酸,棕榈酸,硬脂酸,油酸和亚油酸。从而,具有高含量的这些脂肪酸的天然脂肪和油代表脂肪酸组分的优选来源,例如大豆油,橄榄油,棉籽油,玉米油,牛油和猪油。
适用于本发明的糖或糖醇脂肪酸酯能够通过本领域技术人员熟知的各种方法来制备。这些方法包括:用另一种酯比如甲基、乙基或甘油酯转酯基化,用脂肪酰氯酰化,用脂肪酸酐酰化,和用脂肪酸本身酰化。
下述是适用于本公开的含有至少4个脂肪酸酯基团的适宜糖或糖醇脂肪酸酯的实例:葡萄糖四油酸酯,葡萄糖四硬脂酸酯,葡萄糖大豆油脂肪酸四酯,甘露糖牛油脂肪酸四酯,半乳糖橄榄油脂肪酸四酯,阿拉伯糖棉籽油脂肪酸四酯,木糖四亚油酸酯,半乳糖五硬脂酸酯,山梨醇四油酸酯,山梨醇橄榄油脂肪酸六酯,木糖醇五棕榈酸酯,木糖醇基本上完全氢化的棉籽油脂肪酸四酯,蔗糖四硬脂酸酯,蔗糖五硬脂酸酯,蔗糖六油酸酯,蔗糖八油酸酯,蔗糖基本上完全氢化的大豆油脂肪酸八酯,蔗糖花生油脂肪酸八酯,赤藓糖醇橄榄油脂肪酸四酯,赤藓糖醇四油酸酯,木糖醇五油酸酯,山梨醇六油酸酯,蔗糖八油酸酯,蔗糖大豆油脂肪酸八酯及其混合物。
将天然油(或天然油的组合)与含有酸、半酯或酸酐官能的亲烯体或亲烯体/亲双烯体混合物反应以形成马来酸化的天然油。如说明书通篇和权利要求书中所用,术语"马来酸化的"、"马来酸化"等是指天然油分子的修饰,其通过将天然油与一种或多种α,β-不饱和羧酸或酸酐例如马来酸酐反应而将额外的羧酸部分(或有关的酸酐结构)引入天然油分子。α,β-不饱和羧酸或酸酐能够是生物源衍生的α,β-不饱和羧酸或酸酐。生物源衍生的α,β-不饱和羧酸或酸酐的非限制性实例包括衣康酸,衣康酸酐,乌头酸,乌头酸酐,丙烯酸,甲基丙烯酸,柠康酸,柠康酸酐,中康酸,粘康酸,戊烯二酸,甲基戊烯二酸,愈伤酸和富马酸。酸和酸酐包括任意异构体(例如对映体,非对映体,和顺式-/反式-异构体)和盐。在某些实施方式中,α,β-不饱和羧酸和酸酐能够是下述不饱和酸中的一种:马来酸酐,马来酸,富马酸,丙烯酸,甲基丙烯酸及其混合物。
在一种非限制性实例中,将马来酸酐与如下所示的植物油反应:
反应条件是本领域技术人员熟知的并且能够参见例如U.S.专利号2,188,882和2,188,887,通过援引将其内容并入本文。从而,仅出于示例,上述反应的非限制性实例可以在升高的温度进行,比如约150℃至约300℃,另选约170℃至约230℃,或另选约200℃至约220℃的温度。反应时间可以是约0.5小时至约10小时。在一种实施方式中,反应时间是约1小时至约5小时,而在又一实施方式中,是约2小时至4小时。
在马来酸化期间,在某些实施方式中天然油:亲烯体或亲烯体/亲双烯体混合物的摩尔比小于或等于1,在其它实施方式中为0.3至1.0,在甚至其它实施方式中为0.50至1.00,和在其它实施方式中为0.55至0.75和在甚至其它实施方式中为0.60至0.70。所得的过量亲烯体或亲烯体/亲双烯体混合物有助于降低未反应的天然油的量,由此限制产生渗出物的倾向。
在其它实施方式中,天然油用每摩尔天然油:至少0.02摩尔亲烯体或亲烯体/亲双烯体混合物来马来酸化。在又一实施方式中,天然油用每摩尔天然油:至少0.5摩尔亲烯体或亲烯体/亲双烯体混合物来马来酸化,而在其它实施方式中,天然油用每摩尔天然油:大于约1摩尔亲烯体或亲烯体/亲双烯体混合物来马来酸化。在其它实施方式中,天然油用每摩尔天然油:不超过2.5摩尔亲烯体或亲烯体/亲双烯体混合物来马来酸化,而在其它实施方式中,天然油用每摩尔天然油:不超过2.25摩尔亲烯体或亲烯体/亲双烯体混合物来马来酸化,而在其它实施方式中,天然油用每摩尔天然油:不超过2摩尔亲烯体/亲双烯体混合物来马来酸化。在一种实施方式中,所用亲烯体是马来酸酐。
根据一种具体实施方式,马来酸化的天然油是马来酸化的脂肪酸烷基酯或马来酸化的天然脂肪酸的合成甘油三酯。
然后将马来酸化的天然油与衍生物化合物反应以形成马来酸化的天然油衍生物,所述衍生物化合物包含至少一种聚氧化烯二醇,一-烷基聚氧化烯二醇,聚醚胺,烷醇胺,亚烷基胺,硫醇-封端的聚氧化烯二醇,氨,IA族金属氢氧化物,IIA族金属氢氧化物或其混合物。在又一实施方式中,衍生物化合物包含至少一种聚氧化烯二醇,一-烷基聚氧化烯二醇,聚醚胺,烷醇胺,亚烷基胺,硫醇-封端的聚氧化烯二醇,氨,IA族金属氢氧化物,其不是一羟基-或一氨基-封端的嵌段聚氧化烯烃。
根据一种实施方式,衍生物化合物是一-烷基聚氧化烯二醇。一-烷基聚氧化烯二醇可以是聚氧化烯二醇一醚,一般相应于式T-O-(AO)y-H,其中T是C1-C24烷基或C6-C24芳基,AO是烷氧基而y是1至200的整数。
在某些实施方式中,T含有1至18个碳原子,而在其它实施方式中,其含有4至12个碳原子。T基团的实例包括甲基,乙基,丙基,异丙基,丁基和苯基。在其它实施方式中,AO是均一的或混合的可以随机或嵌段排列的烷氧基,并且其可以包含乙氧基,丙氧基和/或丁氧基。在一种实施方式中,AO包含至少一个乙氧基。在又一实施方式中y是值为1至100的整数,在其它实施方式中y是值为2至50的整数。
在又一实施方式中,聚氧化烯二醇是通式Z[(AO)wOH]w’化合物,其中Z是具有w’个羟基的多官能醇的有机残基,其中w’是3至约8,特别是3至约6,和常常是3或4的整数,而w是约3至10或更多的整数。w’个取代基中每个的AO基团的数目可以是相同或不同的,如前文所定义。在一种实施方式中,AO基团一般是乙氧基,其还可以含有次要比例、常常小于约30摩尔百分比的丙氧基。一般地,聚氧化烯二醇包含具有不同乙氧基链长的种类的混合物。多官能醇的实例包括例如甘油,三羟甲基丙烷和其它三羟甲基烷烃衍生物,季戊四醇和二季戊四醇和三季戊四醇,甘露醇,山梨醇和其它的天然多元醇,三羟基庚烷,1,2,6-己烷三醇等。
根据其它实施方式,衍生物化合物选自聚乙二醇,聚丙二醇,聚丁二醇,聚丙二醇一丁基醚,聚乙二醇一甲基醚,聚(氧化乙烯-氧化丙烯)一乙基醚,聚(氧化丙烯-氧化丁烯)一辛基醚,聚丙二醇一甲基醚,聚丁二醇一苯基醚,聚丙二醇一甲基苯基醚,聚丙二醇一己基醚,及其混合物。
根据又一实施方式,衍生物化合物是聚醚胺。聚醚胺可以是单-,二-,三-,四-或多官能的聚醚胺。制备聚醚胺的方法是熟知的并且能够参见例如U.S.专利号3,654,370,3,832,402,4,990,476和4,992,590,通过援引将其内容并入本文。通常,聚醚胺可以制备如下:将单-、二-、三-、四-或多官能的醇或烷基苯酚用氧化烯烃比如氧化乙烯、氧化丙烯、氧化丁烯或其混合物烷氧化,以形成氧化烯烃加合物,然后在氢和氨存在下催化胺化氧化烯烃加合物以形成聚醚胺。在某些实施方式中,聚醚胺可以通过烷氧基化的胺预处理,然后胺化。
根据一种实施方式,聚醚胺是式(1)或(1a)的聚醚单胺:
其中R是氢或甲基,和
a和b独立地是约1至约150的整数;
其中Y是氢或甲基,
Z是C1-C40烷基或C1-C40烷基苯酚基团和
w是约1至约100的整数。
在又一实施方式中,聚醚胺是式(2)或(2a)的聚醚单胺:
可商购的聚醚一胺包括M-系列和XTJ-系列胺,包括但不限于M-600,M-1000,M-2005,M-2070,XTJ-435和XTJ-436胺,可得自Huntsman公司。
在又一实施方式中,聚醚胺是式(3)、(4)或(5)的聚醚二胺:
其中c是约2至约100的整数;
其中e是约2至约40的整数,和
d和f独立地是约1至约10的整数;
其中g是约2至约3的整数。
可商购的聚醚二胺包括D,ED和EDR胺,包括但不限于D-200,D-400,D-2000,D-4000,ED-600,ED-900,ED-20003,EDR-148和EDR-176胺,可得自Huntsman公司。
在又一实施方式中,亲水聚醚胺是式(6)的聚醚三胺:
其中R1是氢,甲基或乙基,
n是0或1的整数,和
h,i和j独立地是整数约1至约100。
可商购的三胺包括T-系列胺,包括但不限于T-403,T-3000和T-5000胺,可得自Huntsman公司。
在又一实施方式中,亲水聚醚胺是下式的聚醚四胺:
其中各R2独立地是氢,甲基或乙基,
R3是C1-C5烷基,和
各M独立地是约2至约50的整数。
在又一实施方式中,聚醚胺是多官能聚醚胺。本公开的多官能聚醚胺可以是聚醚二-、三或四-胺比如本文描述的那些,其中胺基氢中的至少一个用羟基替换。例如,多官能聚醚胺可以具有式(8):
其中各R4和R5独立地是氢或羟基,条件是R4中至少一个是氢而R5中至少一个是羟基。
在又一实施方式中,衍生物化合物是烷醇胺。用于本公开的烷醇胺的实例包括,但不限于,一乙醇胺,二乙醇胺,甲基乙醇胺,二异丙醇胺,乙基丙醇胺,甲基二丙醇胺,甲基二乙醇胺,乙基二乙醇胺,丙基二乙醇胺,异丙基二乙醇胺,甲基二异丙醇胺,乙基二异丙醇胺,丙基二异丙醇胺,二乙基乙醇胺,二甲基乙醇胺,二丙基乙醇胺,三乙醇胺,和前述的混合物。
在又一实施方式中,衍生物化合物是亚烷基胺。术语亚烷基胺用于指具有至少一个亚烷基胺单元或重复亚烷基胺单元的胺,例如亚乙基胺,亚丙基胺和亚丁基胺。在一种实施方式中,亚烷基胺是亚乙基胺,也即具有至少一个亚乙基胺单元或重复亚乙基胺单元的胺。亚乙基胺单元是-(C(R6)2-C(R6)2-NH-)-,其中R6是H或烷基(直链、支化或环状)基团,优选H,但如果是烷基则具有约1至约10个碳原子。亚乙基胺具有至少2个胺基团,该基团是伯胺或仲胺基团;也任选存在叔胺基团。从而,亚乙基胺包括乙二胺(EDA),二亚乙基四胺(DETA),三亚乙基乙胺(TEDA),三亚乙基四胺(TETA),四亚乙基五胺(TEPA),哌嗪(PIP),氨基乙基哌嗪(AEP),亚乙基胺混合物比如平均分子量约250-500的亚乙基胺低聚物的混合物(可商购自The Dow Chemical Company,名为亚乙基胺E-100(E-100)),及其其它混合物。在亚乙基胺具有异构体的情况下,本公开中适宜地使用一种异构体或异构体的混合物。在亚乙基胺,乙二胺,二亚乙基三胺,三亚乙基四胺,四亚乙基五胺,和亚乙基胺E-100亚乙基胺中优选的是乙二胺,二亚乙基三胺,三亚乙基四胺,和四亚乙基五胺更优选。亚丙基胺是较少运用的亚烷基胺类别,但是商业上使用的亚丙基胺实例可以是二甲基氨基丙胺(DMAPA)和氨基丙基吗啉(APM)。
在其它实施方式中,衍生物化合物是硫醇-封端的聚氧化烯二醇。硫醇-封端的聚氧化烯二醇是化合物,其中聚氧化烯二醇的至少一个羟基已被硫醇基团替换。硫醇-封端的聚氧化烯二醇的实例包括但不限于描述于U.S.专利号3,258,495和3,431,239的那些,通过援引将其内容并入本文。
在又一实施方式中,衍生物化合物是IA族金属氢氧化物或IIA族金属氢氧化物。所述化合物的实例包括但不限于氢氧化钠,氢氧化钾,氢氧化钙和氢氧化镁。
根据一种实施方式,出于示例意图,将聚氧化烯二醇与马来酸化的天然油比如上文所述的马来酸化的植物油反应,以形成下述通式结构的化合物
马来酸化的天然油与衍生物化合物的摩尔比可以是约1:20至约20:1和另选可以是约10:1独立地至约1:10。在某些实施方式中,马来酸化的天然油:衍生物化合物的摩尔比可以大于1.1:1,在其它实施方式中为1.8至10:1和甚至为2.0至7.5:1,在其它实施方式中为2.5至5:1和进一步地3.0至3.5:1。
马来酸化的天然油与衍生物化合物的反应能够不加特殊考虑地进行并且是本领域技术人员已知的。通常,其可以在约20℃至约260℃的温度范围和约1至约10atm(0.1至1MPa)的压力范围,在存在或不存在一般的基于苯酚的抗氧化剂比如2,6-二-叔丁基苯酚,2,6-二-叔丁基-4-甲基苯酚,2,5-二-叔丁基对苯二酚,聚异丁烯苯酚,维生素E(维生素E家族)等及其混合物的情况下进行。路易斯酸催化剂可以用来改善反应速率,但是一般不用催化剂。
在某些实施方式中,助剂组合物可以由马来酸化的天然油组成,而在其它实施方式中,助剂组合物可以包含马来酸化的天然油和辅剂组分。在某些实施方式中,部分或全部辅剂组分可以另选地在形成下述的农业化学配制剂期间加入。
辅剂组分的实例包括但不限于溶剂,液体载体,固体载体或填料,表面活性剂,分散剂,乳化剂,湿润剂,助剂,增溶剂,穿透增强剂,保护性胶体,粘着剂,增稠剂,保湿剂,驱避剂,吸引剂,摄食刺激剂,增容剂,杀菌剂,防冻剂,结晶抑制剂,消泡剂,着色剂,增粘剂,粘合剂,防腐剂,中和pH的无机或有机酸,澄清剂,稳定剂,肥料,比如硫酸铵、尿素或复合肥料,例如磷基、钾基和氮基复合肥料,比如P,K,N肥料,UV稳定剂及其混合物。
溶剂和液体载体能够是水和有机溶剂比如:中至高沸点的矿物油级分例如煤油、柴油;天然油比如上文描述的那些和生物柴油;脂族烃、环状烃和芳烃例如甲苯、石蜡、四氢萘、烷基化萘;醇例如乙醇、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。在一种实施方式中,溶剂是有机溶剂。
结晶抑制剂能够是聚丙烯酸及其盐,优选后者。聚丙烯酸的盐可以是铵,伯、仲或叔铵衍生物,或碱金属(例如钠、钾、锂离子)盐,其中碱金属盐比如钠盐是在实施方式中优选的。聚丙烯酸及其盐通常具有1000Da至300kDa,另选1000Da至80kDa,和尤其是1000Da至15kDa的分子量(由GPC确定,用聚苯乙烯磺酸酯校准)。结晶抑制剂通常是水可溶的,例如在20℃至少1g/l、另选地至少10g/l和尤其是至少100g/l。
固体载体或填料能够是矿质土例如硅酸盐、硅胶、滑石、高岭土、石灰石、石灰、白垩、粘土、白云石、硅藻土、斑脱土、硫酸钙、硫酸镁、氧化镁,多糖粉末例如纤维素、淀粉,植物来源产品例如禾谷类粉、树皮粉、木屑、坚果壳粉,及其混合物。
可以使用的乳化剂的实例是烷基芳基磺酸的钙盐,比如十二烷基苯磺酸钙,或非离子型乳化剂比如脂肪酸聚乙二醇酯,烷基芳基聚乙二醇醚,脂肪醇聚乙二醇醚,氧化丙烯氧化乙烯缩合物,烷基聚醚,脱水山梨糖醇酯例如脱水山梨糖醇脂肪酸酯,或聚氧乙烯脱水山梨糖醇酯例如聚氧乙烯脱水山梨糖醇脂肪酸酯。
表面活性剂是表面活性的化合物比如阴离子,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。所述表面活性剂能够用作乳化剂,分散剂,增溶剂,湿润剂,穿透增强剂或保护性胶体。表面活性剂的实例列于McCutcheon's,Vol.1:Emulsifiers&Detergents,McCutcheon's Directories,Glen Rock,USA,2008(International Ed.or North American Ed.)。
阴离子表面活性剂包括磺酸、硫酸、磷酸、羧酸的碱金属盐、碱土金属盐或铵盐,及其混合物。磺酸盐的实例是脂肪酸和油的烷基芳基磺酸盐、二苯基磺酸盐、α-烯烃磺酸盐、木质素磺酸盐、磺酸盐,乙氧基化的烷基酚的磺酸盐,烷氧基化的芳基酚的磺酸盐,稠合萘的磺酸盐,十二烷基苯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磺酸盐。硫酸盐的实例是脂肪酸和油的硫酸盐,乙氧基化的烷基酚的硫酸盐,醇的硫酸盐,乙氧基化醇的硫酸盐,或脂肪酸酯的硫酸盐。磷酸盐的实例是磷酸酯。羧酸盐的实例是烷基羧酸盐,和羧基化的醇或烷基酚乙氧基化物。
非离子表面活性剂包括烷氧基化物,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。烷氧基化物的实例是已用1至50当量烷氧基化的化合物比如醇,烷基酚,胺,酰胺,芳基酚,脂肪酸或脂肪酸酯。氧化乙烯和/或氧化丙烯可以用于烷氧基化,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(glucamides)或脂肪酸烷醇酰胺。酯的实例是脂肪酸酯,甘油酯或甘油单酯。糖基表面活性剂的实例是脱水山梨糖醇,乙氧基化的脱水山梨糖醇,蔗糖和葡萄糖酯。聚合物表面活性剂的实例是乙烯基吡咯烷酮,乙烯基醇或乙酸乙烯酯的均聚物或共聚物。
阳离子表面活性剂包括季表面活性剂例如具有一个或两个疏水基团的季铵化合物,或长链伯胺的盐。适宜的两性表面活性剂是烷基内铵盐和咪唑啉。适宜的嵌段聚合物是A-B或A-B-A类型的嵌段聚合物,包含聚氧化乙烯和聚氧化丙烯的嵌段,或A-B-C类型的嵌段聚合物,包含烷醇、聚氧化乙烯和聚氧化丙烯。适宜的聚电解质是多元酸或多元碱。多元酸的实例是聚丙烯酸或多元酸梳形聚合物的碱盐。多元碱的实例是聚乙烯基胺或聚乙烯胺。
增稠剂包括多糖(例如黄原胶,羧甲纤维素),有机粘土(有机修饰的或未修饰的),聚羧酸盐和硅酸盐。
杀菌剂包括溴硝醇和异噻唑啉酮衍生物比如烷基异噻唑啉酮和苯并异噻唑啉酮。
防冻剂包括乙二醇,丙二醇和甘油。
消泡剂包括有机硅,长链醇,和脂肪酸的盐。优选的消泡剂是有机硅,比如聚二甲基硅氧烷。
着色剂(例如红色,蓝色或绿色)包括低水溶解度的色素和水可溶的染料。实例是无机着色剂(例如氧化铁,氧化钛,六氰基高铁酸铁)和有机着色剂(例如茜素-,偶氮-和酞菁着色剂)。
增粘剂或粘合剂包括聚乙烯基吡咯烷酮,聚乙酸乙烯酯,聚乙烯醇,聚丙烯酸类,生物学或合成的蜡,和纤维素醚。
防飘剂是例如非离子聚合物,比如分子量至少20kDa、优选至少50kDa和尤其是至少100kDa的聚丙烯酰胺、聚乙二醇或瓜耳胶。防飘剂的进一步实例是卵磷脂和可自乳化的聚酯。
保湿剂一般是化合物,其吸引水和/或将水保持在助剂组合物内。实例包括甘油或糖浆剂。
如上文描述,助剂组合物增强农药的生物活性,从而助剂组合物是组合物,其中在与农药或农药混合物组合并施用至靶标底物的情况下实现至少60%,65%,70%,75%,80%或甚至至少85%,或甚至至少90%的防治。"%的防治"如本文所用是指靶标底物生长防治的任何可观察度量,其能够包括下述作用中的一种或多种:(1)灭除,(2)抑制生长、繁殖或增殖,和(3)除去、破坏或者减少病虫害的存在和活性。防治能够通过本领域已知的任何各种方法来测量。
在某些实施方式中,在将助剂组合物和农药或农药混合物施用至靶标底物之后不超过5、10、15、20、25或30天实现至少80%防治。
配制助剂组合物
为了制备本申请的助剂组合物,提供上文公开的单独组分并通过常规方法一起组合,例如通过在任意适宜器皿或容器中,优选在室温下溶解单独组分来混合。选择各组分的相对水平以提供需要的效能,使得一方面组分以足够有效的水平存在,但另一方面通过限制组分的上限避免成本过度。混合各组分的次序不是特别重要的,和一般能够按顺序加入或一次全部加入单独组分。
从而,在一种实施方式中,将马来酸化的天然油衍生物和任选辅剂组分一起组合以形成助剂组合物。根据某些实施方式,助剂组合物包括至少约10%重量,和进一步至少约50%重量,和还进一步至少约75%重量,和甚至进一步至少约90.5%重量,和还甚至进一步至少约99%重量的马来酸化的天然油衍生物,其中%重量按助剂组合物的总重量计。在又一实施方式中,助剂组合物包括小于约90%重量,和进一步小于约75%重量,和还进一步小于约45%重量和还甚至进一步小于约29.5%重量的马来酸化的天然油衍生物,其中%重量按助剂组合物的总重量计。
在又一实施方式中,助剂组合物包括(i)约0.1-99.9%重量的马来酸化的天然油衍生物和(ii)约0.1-99.9%重量的辅剂组分,其中%重量按助剂组合物的总重量计。在又一实施方式中,助剂组合物包括(i)约0.1-50%重量的马来酸化的天然油衍生物和(ii)约0.1-50%重量的辅剂组分,其中%重量按助剂共混物的总重量计。在其它实施方式中,助剂组合物包括(i)约0.1-29.9%重量的马来酸化的天然油衍生物和(ii)约70.1-99.9%重量的辅剂组分,其中%重量按助剂组合物的总重量计。
农业化学配制剂
本公开的又一目的涉及农业化学配制剂,包含农药和本公开助剂组合物(和实施方式中的辅剂组分,其中在配制助剂组合物中不包括所述辅剂组分)。农业化学配制剂可以用于处理靶标底物比如上文公开的那些,并且是指组合物的全部形式,包括浓缩物和喷雾配制剂。"喷雾配制剂"是含水农业化学配制剂,包括希望施用至靶标底物或其环境的全部组分,其形式和浓度(稀释)适于喷雾。喷雾配制剂能够制备如下:简单稀释含希望组分(除水外)的浓缩物,或混合单独的组分,或者稀释浓缩物和加入其它单独组分或组分混合物的组合。一般来说,所述最终应用混合在配制剂从其喷雾的喷雾槽或用于填充喷雾槽的存储槽中进行,并且一般所述混合和混合物称为桶混和桶混剂。"浓缩物"是农业化学配制剂,其可以是含水或非水的并且其设计用来用水稀释(或水基液体)以形成相应的喷雾配制剂和包括下述形式的所述组合物:液体形式比如溶液、乳液或分散液,和固体形式、特别是水可分散性固体形式比如颗粒或粉末。"乳油"是液体"浓缩物",包括溶液或分散液中的农药和助剂组合物,通常也包括乳化剂和/或表面活性剂,其容易地在水中稀释时乳化,一般进行不超过温和程度的搅拌。
根据本申请的农业化学配制剂可以通过常规过程制备,例如通过研磨、溶解或分散单独组分来混合,优选在室温下进行。如果存在其它配制辅助组分,则它们优选类似地在室温下掺入。通常,加入单独组分的顺序并不是决定性地重要的。从而,在一种实施方式中,上文公开的助剂组合物可以在容器中例如在不锈钢槽,钢、锡、铝罐,塑料或玻璃瓶和纸或卡纸板容器中配制。助剂组合物可以然后与农药和水和/或其它溶剂组合,和在某些实施方式中与辅剂组分组合以在临施用之前在田间形成农业化学配制剂。
本申请描述的助剂组合物并不限于与任何特别类型的农药一起使用。目前所述技术的农业化学配制剂能够包含农药或农药混合物。
在一种实施方式中,农药包括用于预防、毁坏、驱避或缓和病虫害的任何化学或生物学试剂(也即"活性成分")。从而,在一种具体实施方式中,农药是杀真菌剂,除草剂,杀昆虫剂,杀藻剂,杀软体动物剂,杀螨剂,杀鼠剂,生长调节剂或昆虫驱避剂。
根据一种实施方式,农药是杀真菌剂。杀真菌剂的实例包括但不限于:嘧菌酯,肟菌酯,醚菌酯,噁唑菌酮,苯氧菌胺和啶氧菌酯,多菌灵,噻菌灵,烯酰吗啉,乙烯菌核利,异菌脲,二硫代氨基甲酸盐/酯,抑霉唑,咪鲜胺,氟喹唑,氟环唑,粉唑醇,氧环唑,联苯三唑醇,糠菌唑,环丙唑醇,苯醚甲环唑,己唑醇,多效唑,丙环唑,戊唑醇,三唑酮,灭菌唑,丁苯吗啉,十三吗啉,苯锈啶,代森锰锌,代森联,百菌清,福美双,福美锌,敌菌丹,克菌丹,灭菌丹,氟啶胺,氟酰胺,萎锈灵,甲霜灵,乙嘧酚磺酸酯,乙嘧酚,二甲苯氧菌胺,氟嘧菌酯,肟醚菌胺,苯氧菌胺,丙硫菌唑,8-(2,6-二乙基-4-甲基-苯基)四氢吡唑并[1,2-d][1,4,5]氧杂二氮杂-7,9-二酮,2,2,-二甲基-丙酸-8-(2,6-二乙基-4-甲基-苯基)-9-氧代-1,2,4,5-四氢-9H-吡唑并-[1,2d][1,4,5]氧杂二氮杂-7-基酯和甲霜灵。
在又一实施方式中,农药是除草剂。除草剂的实例包括但不限于:吡氟禾草灵,硝磺草酮,氟磺胺草醚,三甲苯草酮,敌草胺,双甲脒,敌稗,嘧菌环胺,嘧霉胺,氯硝胺,四氯硝基苯,甲基立枯磷,麦草氟M,2,4-D,2甲4氯,2甲4氯丙酸,炔草酯,氰氟草酯,禾草灵,氟吡禾灵,精喹禾灵,吲哚-3-基乙酸,1-萘基乙酸,异噁酰草胺,牧草胺,氯酞酸二甲基,苯菌灵,呋草黄,麦草畏,敌草腈,草除灵,咪唑嗪,啶蜱脲,氟苯脲,甜菜宁,乙草胺,甲草胺,异丙甲草胺,丙草胺,噻吩草胺,禾草灭,丁苯草酮,烯草酮,环草酮(cyclodim),烯禾啶,吡喃草酮,二甲戊灵,特乐酚,甲羧除草醚,乙氧氟草醚,三氟羧草醚,乙羧氟草醚-乙酯,溴苯腈,碘苯腈,咪草酸-甲酯,咪唑烟酸,咪唑喹啉酸,咪唑乙烟酸,甲咪唑烟酸,甲氧咪草烟,丙炔氟草胺,氟烯草酸-戊酯,氨氯吡啶酸,酰嘧磺隆,氯磺隆,烟嘧磺隆,砜嘧磺隆,醚苯磺隆,野麦畏,克草敌,苄草丹,禾草敌,莠去津,西玛津,氰草津,莠灭净,扑草净,特丁津,特丁净,磺草酮,异丙隆,利谷隆,非草隆,绿麦隆,甲氧隆,N-膦酰基甲基甘氨酸及其盐(草甘膦),草铵膦酸(glufosinate),矮壮素,百草枯,敌草快,三氟啶磺隆(trifloxysulfuron),氟磺胺草醚,硝磺草酮和非草隆。
在又一实施方式中,农药是杀昆虫剂。杀昆虫剂的实例包括但不限于:阿维菌素,乙酰甲胺磷,啶虫脒,氟丙菊酯,棉铃威,涕灭威,烯丙菊酯,α-氯氰菊酯,双甲脒,磺草灵,印楝素,甲基吡噁磷,益棉磷,保棉磷,噁虫威,丙硫克百威,杀虫磺,高效氟氯氰菊酯,高效氯氰菊酯,联苯菊酯,生物烯丙菊酯,生物苄呋菊酯,双三氟虫脲,硼砂,噻嗪酮,丁酮砜威,硫线磷,甲萘威,克百威,氯苯胺灵,噻虫胺,氟氯氰菊酯,氯氟氰菊酯,氯氰菊酯,溴氰菊酯,乙霉威,除虫脲,呋虫胺,甲氨基阿维菌素,硫丹,苯氧威,倍硫磷,氰戊菊酯,氟虫腈,苄螨醚,七氯,氟蚁腙,吡虫啉,炔咪菊酯,异丙威,高效氯氟氰菊酯,甲胺磷,甲硫威,灭多威,烯啶虫胺,氧乐果,氯菊酯,抗蚜威,甲基嘧啶磷,残杀威,虫酰肼,噻虫嗪,硫双威,杀铃脲,和灭杀威。
在又一实施方式中,农药是杀藻剂。杀藻剂的实例包括但不限于:bethoxazin,二辛酸铜,硫酸铜,cybutryne,二氯萘醌,双氯酚,茵多酸,三苯锡,消石灰,代森钠,灭藻醌,quinonamid,西玛津,乙酸三苯基锡,和氢氧化三苯基锡。
在又一实施方式中,农药是杀软体动物剂。杀软体动物剂的实例包括但不限于:四聚乙醛,甲硫威和硫酸铝。
在又一实施方式中,农药是杀螨剂。杀螨剂的实例包括但不限于:抗生素杀螨剂,氨基甲酸酯杀螨剂,甲脒杀螨剂,螨生长调节剂,有机氯,氯菊酯和有机磷酸酯杀螨剂。
在又一实施方式中,农药是杀鼠剂。杀啮齿类剂的实例包括但不限于:2-异戊酰茚满-1,3-二酮,4-(喹喔啉-2-基氨基)苯磺酰胺,α-氯醇,磷化铝,anta,氧化砷,碳酸钡,双鼠脲(bisthiosemi),溴鼠灵,溴敌隆,溴鼠胺,氰化钙,氯醛糖(chloralose),氯鼠酮,胆钙化醇,氯灭鼠灵,克鼠灵,杀鼠醚,鼠立死,鼠得克,噻鼠灵,敌鼠,麦角钙化醇(ergocalciferol),氟鼠灵,氟乙酰胺,氟鼠啶,氟鼠啶盐酸盐,林丹,六六六,氰化氢,碘甲烷,林丹,磷化镁,溴甲烷,鼠特灵,毒鼠磷,膦,磷,鼠完,亚砷酸钾,灭鼠优,红海葱素(scilliroside),亚砷酸钠,氰化钠,氟乙酸钠,马钱子碱,硫酸亚铊,杀鼠灵,和磷化锌。
在又一实施方式中,农药是生长调节剂。实例包括但不限于S-诱抗素,先甲草胺(amidochlor),环丙嘧啶醇,6-苄氨基嘌呤,芸苔素内酯,仲丁灵,矮壮素(氯化矮壮素),氯化胆碱,环丙酰胺酸,丁酰肼,调呋酸,噻节因,2,6-二甲基吡啶,乙烯利,氟节胺,呋嘧醇,嗪草酸,氯吡脲,赤霉酸,抗倒胺,吲哚-3-乙酸,抑芽丹,氟磺酰草胺,mepiquat(甲哌鎓),萘乙酸,N-6-苄基腺嘌呤,多效唑,调环酸(调环酸钙),prohydrojasmon,噻苯隆,抑芽唑,三硫代磷酸三丁基酯,2,3,5-三碘苯甲酸,抗倒酯和烯效唑。
在额外的实施方式中,农药是昆虫驱避剂。昆虫驱避剂的实例包括但不限于:2-乙基-1,3-己二醇;N-辛基二环庚烯二甲酰亚胺;N,N-二乙基-M-甲苯酰胺;2,3:4,5-二(2-亚丁基)四氢-2-糠醛;异辛可部酸二正丙基酯;和2-羟基乙基-正辛基硫醚。
包括在本申请农业化学配制剂中的农药的量根据许多参数变化,比如待处理的靶标基底,待处理的面积等。通常,约5克至约4千克每公顷(g/ha)的农药施用率可以是适宜的。农业化学配制剂中助剂组合物的量可以是约0.01-99%重量,基于农业化学配制剂总重量。
本公开农业化学配制剂可以用于常规的农业方法中。例如,农药或农药的混合物和助剂组合物可以与水和/或其它溶剂和/或肥料混合,并在出苗后通过任何手段比如飞行器喷雾槽、背负式喷雾槽、畜载滴药桶、地面喷雾所用的农场设备(例如喷管式喷雾器、手动喷雾器)等施用至希望的靶标基底。
如上文所讨论,按照某些实施方式,农业化学配制剂能够是浓缩物组合物,其能够在适宜体积的水中稀释以形成喷雾配制剂(例如桶混组合物),用于向靶标底物施用。浓缩物组合物能够呈液体,固体或半固体形式。在至少一个实施方式中,其是含水浓缩物组合物。
例如,在一种实施方式中,农药在浓缩物组合物中的量能够是约1%重量至约80%重量,另选地约16%重量至约60%重量,另选地35%重量至约55%重量,基于浓缩物组合物的总重量。助剂组合物在浓缩物组合物中的量可以是约0.0001%重量至约20%重量,另选地约0.001%重量至约15%重量,或另选地约0.01%重量至约10%重量百分比,或另选地约0.1%重量至约5%重量,或甚至另选地约0.5%重量至约3%重量,基于浓缩物组合物的总重量。
浓缩物组合物能够通过使用者用水稀释以使得喷雾配制剂含有约0.01%重量至约15%重量,另选地约0.1%重量至约5%重量,另选地约0.2%重量至约2%重量的农药,基于喷雾配制剂的总重量。喷雾配制剂能够一般含有约0.0001%重量至约3%重量,另选地约0.001%重量至约1%重量,另选地约0.01%重量至约0.5%重量百分比的本公开助剂组合物。
在本公开的某些其它实施方式中,将农药和助剂组合物组合以形成"即用"(RTU)喷雾配制剂。RTU喷雾配制剂能够制备如下:使用者如上文描述稀释浓缩物组合物,或另选地能够原样提供给使用者。例如,RTU喷雾配制剂能够含有约0.5%重量至约5%重量,另选地约0.75%重量至约3%重量,另选地约1.5%重量至约2.5%重量的农药,基于RTU喷雾配制剂的总重量。RTU喷雾配制剂能够含有约0.01%重量至约2.5%重量,另选地约0.2%重量至约2%重量,另选地约0.5%重量至约1%重量的本公开助剂组合物。RTU组合物的余量能够是水。
按照又一实施方式,目前描述的技术提供灭除或抑制或驱避病虫害的方法,包括下述步骤:提供农药有效量的农药或农药混合物;提供有效量的本公开助剂组合物,将农药或农药混合物与助剂组合物组合以制备农业化学配制剂,和使农业化学配制剂和病虫害接触。
实施例
实施例1:马来酸化的天然油
在代表性实验中,将1029g大豆油加热至80℃并加入183g熔融马来酸酐(总反应的15%wt/wt)以及6g甲苯。在配有搅拌子和回流冷凝器的圆底烧瓶中将混合物加热至200℃持续5小时,然后减压除去甲苯,产生马来酸化的大豆油(MASBO-15)。进行相似实验,产生MASBO-5,MASBO-10,MASBO-20和MASBO-25,其中数字相应于反应连接至大豆油上的马来酸酐的重量百分比。类似地用不同的油合成其它衍生物,其中油是亚麻籽油(MALSO-#)或三油酸甘油酯,一种制备自甘油和油酸的合成甘油三酯(MAGTO-#)。
实施例2:胺-修饰的马来酸化的油
在代表性实验中,将MASBO-15(407.5g)加入圆底烧瓶和加热至40℃。然后,在搅拌下加入623.0g的M-1000聚醚胺。在40℃搅拌该混合物2小时,然后加入257.4g的2-丁氧基乙醇充当溶剂,提供MASBO-15A。在稀释于水中时,MASBO-15A形成微乳液。其它胺以相似方式反应,产生列于下表1的产品。
实施例3:mPEG-修饰的马来酸化的油
在代表性实验中,将MASBO-20(50.0g)加入圆底烧瓶并加热至50℃。然后,加入66.0g mPEG-650(650MW的一甲基聚乙二醇),搅拌反应,加热至80℃持续2小时。冷却后,产品是蜡状固体,其在水中缓慢分散以形成微乳液(MASBO-20A)。其它mPEGs以相似方式反应,产生列于下表1的产品。
制得的化合物和它们在稀释入WHO 342ppm水时的行为概括如下。
表1缩写: MEA=一乙醇胺,DGA=二甘醇胺,APM=氨基丙基吗啉,mPEG-#=指定分子量的甲基化聚乙二醇,PEG/PPG嵌段共聚物,2-EH=2-乙基己醇,EGBE=乙二醇丁基醚,PGBE=丙二醇丁基醚,MSO=豆油脂肪酸甲酯,
田间试验
需要田间试验来测试新助剂增加农药效力的能力。在田间试验中使用样品MASBO-10N来试验其对两种不同除草剂系统(草甘膦是Syngenta公司供给的Touchdown而麦草畏是BASF公司供给的)的辅助作用,与本领域技术人员已知的其它普通助剂比较。结果如下表2所示。
如表2所示,MASBO-10N能够增加除草剂系统的效力(相对对照)并且与许多标准助剂相比更有利。这指出的是,本公开马来酸化的天然油衍生物作为用于农药的助剂组合物具有显著效用。由于它们比较容易制备和配制,它们可以比效果类似的助剂还更有利。
表3含有又一田间试验的结果,其使用草甘膦和苯嘧磺草胺,一种普通除草剂组合(草甘膦是Syngenta公司供给的Touchdown而苯嘧磺草胺是Bayer CropScience供给的)。
在表3中,MASBO衍生物再次改善除草剂的效力并且与其它熟知的助剂类别相比更有利。这指出的是,本公开马来酸化的天然油衍生物作为用于农药的助剂组合物具有显著效用。由于它们比较容易制备和配制,它们可以比效果类似的助剂更有利。
表4显示MASBO助剂的不同变型的比较,MASBO-15B+草甘膦和苯嘧磺草胺(与表3中所用的除草剂相同)。在该实施例中不用助表面活性剂与MASBO一起配制,但效果仍然比较有利,与许多熟知助剂相同或者比其更佳。这指出的是,本公开马来酸化的天然油衍生物作为用于农药的助剂组合物具有显著效用。由于它们比较容易制备和配制,它们可以比效果类似的助剂更有利。
尽管制备和使用本发明各种实施方式已在上文详加描述,应认识到本发明提供了能够体现在各式各样的特定上下文中的许多可行的创造性概念。本文讨论的特定实施方式仅示例制备和使用本发明的特定方式,但并不界定本发明的范围。
Claims (17)
1.包含马来酸化的天然油衍生物的助剂组合物,所述马来酸化的天然油衍生物得自马来酸化的天然油与衍生物化合物的反应,所述衍生物化合物包含至少一种聚氧化烯二醇,一-烷基聚氧化烯二醇,聚醚胺,亚烷基胺,烷醇胺,硫醇-封端的聚氧化烯二醇,氨,IA族金属氢氧化物,IIA族金属氢氧化物或其混合物。
2.根据权利要求1的助剂组合物,其中马来酸化的天然油是马来酸化的植物油。
3.根据权利要求2的助剂组合物,其中马来酸化的植物油是马来酸化的大豆油。
4.根据权利要求1的助剂组合物,其中马来酸化的天然油是马来酸化的脂肪酸烷基酯。
5.根据权利要求1的助剂组合物,其中马来酸化的天然油是马来酸化的天然脂肪酸的合成甘油三酯。
6.根据权利要求1的助剂组合物,其中衍生物化合物是聚氧化烯二醇。
7.根据权利要求1的助剂组合物,其中衍生物化合物是聚醚胺。
8.根据权利要求7的助剂组合物,其中聚醚胺是聚醚单胺。
9.根据权利要求1的助剂组合物,其中所述助剂组合物还包含一种或多种辅剂组分。
10.一种助剂组合物,包含(i)约0.1-99.9%重量的马来酸化的天然油衍生物,其得自马来酸化的天然油与衍生物化合物的反应,所述衍生物化合物包含至少一种聚氧化烯二醇,一-烷基聚氧化烯二醇,聚醚胺,亚烷基胺,烷醇胺,硫醇-封端的聚氧化烯二醇或其混合物,和(ii)约0.1-99.9%重量的辅剂组分,其中%重量按助剂组合物的总重量计。
11.农业化学配制剂,包含农药或农药的混合物和根据权利要求1的助剂组合物。
12.根据权利要求11的农业化学配制剂,其中所述农药是杀真菌剂,除草剂,杀昆虫剂,杀藻剂,杀软体动物剂,杀螨剂,杀鼠剂或昆虫驱避剂。
13.根据权利要求12的农业化学配制剂,其中所述农业化学配制剂还包含一种或多种辅剂组分。
14.包含根据权利要求1的助剂共混物的容器。
15.浓缩物组合物,包含约1%重量至约80%重量的农药和约0.0001%重量至约20%重量的权利要求1的助剂组合物,其中%重量按浓缩物组合物的总重量计。
16.喷雾配制剂,包含农药,根据权利要求1的助剂组合物和水或其它溶剂。
17.用于灭除或抑制或驱避病虫害的方法,包括下述步骤:以农药有效量提供农药或农药的混合物;提供有效量的根据权利要求1的助剂组合物,将农药或农药的混合物与助剂组合物组合以制备农业化学配制剂,并且将农药配制剂与病虫害接触。
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