CN102271520B - 农化助剂组合物 - Google Patents
农化助剂组合物 Download PDFInfo
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- CN102271520B CN102271520B CN200980151726.2A CN200980151726A CN102271520B CN 102271520 B CN102271520 B CN 102271520B CN 200980151726 A CN200980151726 A CN 200980151726A CN 102271520 B CN102271520 B CN 102271520B
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- agrochemical
- fungicide
- alkyl
- alkoxylated
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Abstract
本发明涉及农化助剂组合物,包括(a)烷氧基化的多元醇酯,(b)任选地烷氧基化的烷基或烯基寡糖苷,和(c)脂肪酸或它们的盐。
Description
发明领域
本发明涉及农业领域,具体涉及包含非离子表面活性剂和皂的新的助剂组合物。
发明背景
作物保护市场代表了大约220亿英镑/年的总价值。大多数杀生物剂与助剂(也称为增效剂)配制,以最大限度地实现多种功能的功效。助剂必须提供良好的润湿叶面的能力,促进杀生物剂在各种气候条件下的叶面渗透,并增强、至少不抑制杀生物剂(尤其除草剂)传导进入植物。此外,当在特殊的抗性作物上使用时,还必须不能产生植物毒性作用。
乙氧基化的植物油作为杀生物剂和植物保护配制剂的添加剂的应用为本领域所公知。描述乙氧基化的甘油三酯作为该目的的最初参考文献之一是德意志民主共和国公开出版物DD 268147A1。这方面的其他参考文献是国际专利申请WO 98/009518A1(Cognis),其公开了包含液体载体和由烷基聚葡糖苷和脂肪酸组成的乳化剂混合物的农业组合物。由两篇德国申请DE 10000320A1和DE 10018159A1(均为Cognis)已知包含特定触杀性除草剂和乙氧基化的脂肪醇或脂肪酸的组合物。欧洲专利EP 0804241B1(SEPPIC)涉及乙氧基化的脂肪酸酯和甘油三酯以及它们作为用于制备农业组合物的自乳化系统的应用。
尽管各种类型的杀生物剂和大量的添加剂如助剂、乳化剂、增溶剂等在市场上均可以得到,但仍然渴望发展增加活性成分进入所保护的植物叶片的渗透速度和增强活性成分对抗不同微生物、特别是所有真菌类型的能力的新助剂。本发明的目的是满足市场的需求。
发明描述
本发明涉及新的农用化学助剂组合物,其包含:
(a)烷氧基化的多元醇酯,
(b)任选地烷氧基化的烷基或烯基寡糖苷,
(c)脂肪酸或它们的盐。
已经观察到包含烷氧基化的多元醇酯、任选地烷氧基化的烷基或烯基寡糖苷和脂肪酸或它们的盐的混合物能够提高各种类型的杀生物剂(即杀菌剂、杀虫剂、除草剂和植物生长调节剂)的效率。虽然已知例如烷氧基化的甘油三酯能够刺激系统性杀生物剂渗透进入叶片,但现在惊奇地发现,在这些已知表面活性剂中加入糖苷和脂肪酸不仅能够总体上增加进入叶片的渗透速度,而且还允许真菌细胞壁的渗透。
烷氧基化的多元醇酯
烷氧基化的多元醇酯(组分a)为助剂组合物的主要部分。这些酯可来源于三羟甲基丙烷、季戊四醇或优选来源于甘油。根据本发明的酯包括全酯和偏酯。例如,合适的烷氧基化甘油酯包括烷氧基化的甘油单、双或三酯或它们的混合物。烷氧基化的甘油三酯-或其同义词烷氧基化的植物油-代表最优选的化合物,典型的具有下列通式(I):
其中R1、R2和R3相互独立地代表具有5-21、优选11-17个碳原子的线性或分支的、饱和或不饱和的烷基和/或羟基烷基残基;n、m和p相互独立地代表0或约1至约50的整数,优选约3至约30的整数,最优选约5至约15的整数,其中条件是三者之和(m+n+p)不为0;和AO代表乙二醇或丙二醇单元。在一个优选的实施方式中,所述的烷氧基化甘油酯来源于大豆油、菜籽油、葵花籽油或亚麻籽油,其他的植物油尽管在此没有提到,但也构成所述组分的合适基础。
多元醇酯的烷氧基化按照有机化学已知的标准流程操作。典型的,在碱性催化剂存在下,将环氧乙烷、环氧丙烷或它们的混合物添加到酯中。由于烷氧基化反应为统计学反应,反应产物呈具有不同烷氧基化程度的同系物分布。在这种情况下,应该明确的是,给定的烷氧基化程度始终代表平均值。通过选择适当的催化剂控制烷氧基化程度以得到宽或窄的同系物分布是可能的。然而,这两种类型的产物均是合适的,尽管具有较低的烷氧基化程度但较宽的同系物分布一种烷氧基化物可显示与具有较高的烷氧基化程度但窄范围同系物分布的另一种烷氧基化物类似的行为。也可以应用包含嵌段或无规则的环氧乙烷和环氧丙烷单元的混合产物。但是,最先考虑的种类是将约10mol环氧乙烷加入到大豆油、菜籽油或亚麻籽油的加合物。也可以通过HLB值定义一般的烷氧基化的多元醇酯和尤其烷氧基化的甘油酯,该HLB值可以根据下面的公式计算得到:
HLB=20[1-S/A]
其中“S”代表烷氧基化酯的皂化值(根据NFT60206),和“A”代表用于酯化反应的酸的酸值(根据NFT60204)。优选的烷氧基化的多元醇酯的HLB值在约2至约15、优选约4至约10的范围内。
烷基或烯基寡糖苷及其烷氧基化产物
可作为组分(II)用于本发明所述组合物的烷基或烯基寡糖苷(组分b1)可来源于包含5或6个碳原子的醛糖或酮糖,优选葡萄糖。因此,优选的烷基和/或烯基寡糖苷为烷基或烯基寡葡糖苷。这些材料也被称为“烷基聚糖苷”(APG)。本发明所述的烷基或烯基寡糖苷对应式(II):
R4O[G]p (II)
其中R4为具有6至22个碳原子的烷基或烯基,G是具有5个或6个碳原子的糖单元,和p为1至10的数值。通式(II)中下标p代表低聚度(DP度),即,单和寡糖苷的分布,且为1至10的数。而给定的化合物中p必须永远是一个整数,首先可以假设为1至6的值,一个确定的烷基寡糖苷的p值是通过分析计算确定的数值,其通常是分数。平均低聚度p为1.1至3.0的烷基或烯基寡糖苷是优选应用的。从应用的角度来看,平均低聚度p低于1.7、尤其在1.2和1.4之间的烷基或烯基寡糖苷是更优选的。
烷基或烯基R4可来源于包含4至22、优选8至18个碳原子的伯醇。典型的例子为丁醇,己醇,辛醇,癸醇,十一醇,月桂醇,肉豆蔻醇,鲸蜡醇,棕榈油醇(palmitoleyl alcohol),硬脂醇,异硬脂醇,油醇,反油醇,岩芹醇(petroselinyl alcohol),花生醇,二十碳烯醇,山萮醇,瓢儿菜醇和它们的工业混合物,例如通过工业脂肪酸甲酯的加氢作用或由Roelen氧化合成制备的醛的加氢作用制备。基于具有1至3低聚度(DP)的短链C8/10脂肪醇或氢化C8/18椰子油醇的烷基寡葡糖苷是优选的。
代替所述烷基或烯基寡糖苷的合适的替代品是它们的烷氧基化的产物(组分b2)。这些表面活性剂通过加入约1至约20、优选约2至约15、更优选约3至约10mol的环氧乙烷(EO)和/或环氧丙烷(PO)-嵌段或无规则-至糖苷体的自由羟基可获得。特别优选的是约2至约7mol EO和/或PO至C8/10或者C12/14的烷基寡葡糖苷的加合物。至于这些表面活性剂的制备参照EP1716163B1(Cognis),其公开了一个合适的生产工艺。
脂肪酸和它们的盐
脂肪酸和它们的盐(组分c)改善配制剂的性能和稳定性。它们典型地具有如下通式(III):
R5CO-OX (III)
其中R5CO代表具有6-22、优选12-18个碳原子的线性或分支的、饱和或不饱和的酰基,X代表氢或者碱金属。合适的例子为己酸,辛酸,癸酸,月桂酸,肉豆蔻酸,棕榈酸,十六碳烯酸,硬脂酸,油酸,亚油酸,共轭亚油酸,亚麻酸,花生四烯酸,二十碳烯酸,山萮酸、芥酸和它们的工业混合物,例如椰油脂肪酸,动物脂肪酸或优选妥尔油脂肪酸。作为酸的替代物,人们也可以应用各自的钠皂或钾皂。
助剂组合物
在一个优选的实施方式中,本发明的助剂组合物可包含:
(a)约60至约90、优选约70至约80%w/w的烷氧基化的多元醇酯,
(b)约5至约15、优选约7至约12%w/w的任选地烷氧基化的烷基或烯基寡糖苷,和
(c)约5至约15、优选约7至约12%w/w的脂肪酸或它们的盐。
条件是:上述各值任选地与水一起总计为100%w/w。
工业应用
农化组合物
本发明的另一个目的涉及农化组合物,其包含:
(a)烷氧基化的多元醇酯,
(b)任选地烷氧基化的烷基或烯基寡糖苷,
(c)脂肪酸或它们的盐,和
(d)杀生物剂。
通常,所述的包含组分(a)、(b)和(c)的农化助剂组合物配制成水溶液的形式,将相应的杀生物剂溶解于其中。根据客户的需求,将制备的浓缩液(通常包含高达40%w/w的杀生物剂)现场稀释成杀生物剂浓度约0.5至约1%w/w的即刻应用的组合物。
杀生物剂
本发明中的杀生物剂为植物保护剂,尤其是用于例如医药、农业、林业和蚊虫控制领域的能杀死不同形式的存活生物体的化学物质。另外,所谓的植物生长调节剂也被认为属于杀生物剂这个组。通常,杀生物剂分成两个亚组:
●杀有害物药,其包含杀真菌剂、除草剂、杀虫剂、杀藻剂(algicides)、杀软体动物剂(moluscicides)、杀螨剂(miticides)和杀鼠剂(rodenticides),及
●抗微生物剂,其包含杀菌剂(germicide)、抗生素、抗细菌剂、抗病毒剂、抗真菌剂、抗原生动物剂和抗寄生虫剂。
也可将杀生物剂加入其它物质(通常是液体)中来保护物质不受生物侵染和繁殖。例如,可将某些类型的季铵化合物(quats)加入池水或工业水系统中来用作杀藻剂,来保护水不受藻类的侵染和繁殖。
杀有害物药
美国环境保护局(EPA,U.S Environmental Protection Agency)将杀有害物药定义为“旨在防止、消灭、驱散或减轻任何有害生物的任何物质或物质的混合物”。杀有害物药可以是化学物质或生物制剂(例如病毒或细菌),其针对有害生物使用,所述有害生物包括与人争食、毁坏财物、传播疾病或为公害的昆虫、植物病原体、杂草、软体动物、鸟、哺乳动物、鱼、线虫(蛔虫)及微生物。在下列实例中,依照本发明,给出了适用于农化组合物的杀有害物药:
杀真菌剂:杀真菌剂是用于控制有害生物的三种主要方法之一(在此真菌的化学控制)。杀真菌剂是用于防止真菌在花园和作物中传播的化合物。杀真菌剂也用于对抗真菌感染。杀真菌剂可以是触杀性的或内吸性的(systemic)。触杀性杀真菌剂在喷雾于真菌表面时杀死真菌。内吸性杀真菌剂在真菌死亡之前必须被真菌吸收。根据本发明,合适的杀真菌剂的实例包括下列种类:(3-乙氧基丙基)溴化汞,2-甲氧基乙基氯化汞,2-苯基苯酚,8-羟基喹啉硫酸盐,8-苯汞基氧喹啉,活化酯(acibenzolar),酰基氨基酸类杀真菌剂,acypetacs,aldimorph,脂肪族含氮杀真菌剂,烯丙醇,酰胺类杀真菌剂,氨丙磷酸(ampropylfos),敌菌灵(anilazine),酰基苯胺类杀真菌剂,抗生素类杀真菌剂,芳香族杀真菌剂,金色制霉素(aureofungin),氧环唑(azaconazole),azithiram,嘧菌酯(azoxystrobin),多硫化钡,苯霜灵(benalaxyl),精苯霜灵(benalaxyl-m),麦锈灵(benodanil),苯菌灵(benomyl),醌肟腙(benquinox),bentaluron,苯噻菌胺酯(benthiavalicarb),苯扎氯铵(benzalkonium chloride),benzamacril,苯甲酰胺类杀真菌剂,benzamorf,苯甲酰苯胺类杀真菌剂,苯并咪唑类杀真菌剂,苯并咪唑前体类杀真菌剂,苯并咪唑基氨基甲酸酯类杀真菌剂,苯基异羟肟酸,苯并噻唑类杀真菌剂,bethoxazin,乐杀螨(binapacryl),联苯,联苯三唑醇(bitertanol),硫氯酚(bithionol),灭瘟素(blasticidin-S),波尔多液(bordeauxmixture),啶酰菌胺(boscalid),桥接联苯类杀真菌剂,糠菌唑(bromuconazole),乙嘧酚磺酸酯(bupirimate),burgundy混合物,丁硫啶(buthiobate),丁胺,石硫合剂(calcium polysulfide),敌菌丹(captafol),克菌丹(captan),氨基甲酸酯类杀真菌剂,吗菌威(carbamorph),苯氨酸甲酸酯类杀真菌剂,多菌灵(carbendazim),萎锈灵(carboxin),环丙酰菌胺(carpropamid),香芹酮,cheshunt混合物,灭螨猛(chinomethionat),chlobenthiazone,chloraniformethan,四氯对醌(chloranil),chlorfenazole,氯代二硝基萘(chlorodinitronaphthalene),氯苯甲醚(chloroneb),氯化苦(chloropicrin),百菌清(chlorothalonil),四氯喹喔啉(chlorquinox),乙菌利(chlozolinate),环吡酮(ciclopirox),氯咪巴唑(climbazole),克霉唑(clotrimazole),康唑类杀真菌剂,康唑类杀真菌剂(咪唑类),康唑类杀真菌剂(三唑类),乙酸铜(II),碳酸铜(II),碱性的,铜类杀真菌剂,氢氧化铜,环烷酸铜,油酸铜,王铜(copperoxychloride),硫酸铜(II),硫酸铜,碱性的,铬酸铜锌,甲酚(cresol),硫杂灵(cufraneb),cuprobam,氧化亚铜,氰霜唑(cyazofamid),cyclafuramid,环二硫代氨基甲酸酯类杀真菌剂,放线菌酮(cycloheximide),环氟苄酰胺(cyflufenamid),霜脲氰(cymoxanil),氰菌灵(cypendazole),环丙唑醇(cyproconazole),嘧菌环胺(cyprodinil),棉隆(dazomet),DBCP,咪菌威(debacarb),decafentin,脱氢乙酸,二羧酰亚胺类杀真菌剂,苯氟磺胺(dichlofluanid),二氯萘醌(dichlone),双氯酚(dichlorophen),二氯苯基,二羧酰亚胺类杀真菌剂,菌核利(dichlozoline),苄氯三唑醇(diclobutrazol),双氯氰菌胺(diclocymet),哒菌酮(diclomezine),氯硝胺(dicloran),乙霉威(diethofencarb),焦碳酸二乙酯,苯醚甲环唑(difenoconazole),氟嘧菌胺(diflumetorim),二甲嘧酚(dimethirimol),烯酰吗啉(dimethomorph),醚菌胺(dimoxystrobin),烯唑醇(diniconazole),二硝基酚类杀真菌剂,消螨通(dinobuton),二硝巴豆酸酯(dinocap),二硝酯(dinocton),硝戊酯(dinopenton),硝辛酯(dinosulfon),硝丁酯(dinoterbon),二苯胺,双吡硫翁(dipyrithione),双硫仑(disulfiram),灭菌磷(ditalimfos),二氰蒽醌(dithianon),二硫代氨基甲酸酯类杀真菌剂,dnoc,十二环吗啉(dodemorph),多地辛(dodicin),多果定(dodine),DONATODINE,肼菌酮(drazoxolon),敌瘟磷(edifenphos),氟环唑(epoxiconazole),乙环唑(etaconazole),代森硫(etem),噻唑菌胺(ethaboxam),乙嘧酚(ethirimol),乙氧喹啉(ethoxyquin),2,3-二羟基丙基硫醇乙基汞,醋酸乙基汞,溴化乙基汞,氯化乙基汞,磷酸乙基汞,土菌灵(etridiazole),唑菌酮(famoxadone),咪唑菌酮(fenamidone),敌磺钠(fenaminosulf),咪菌腈(fenapanil),氯苯嘧啶醇(fenarimol),腈苯唑(fenbuconazole),甲呋酰胺(fenfuram),环酰菌胺(fenhexamid),种衣酯(fenitropan),稻瘟酰胺(fenoxanil),拌种咯(fenpiclonil),苯锈啶(fenpropidin),丁苯吗啉(fenpropimorph),三苯锡(fentin),福美铁(ferbam),嘧菌腙(ferimzone),氟啶胺(fluazinam),咯菌腈(fludioxonil),氟酰菌胺(flumetover),氟吗啉(flumorph),氟吡菌胺(fluopicolide),氟氯菌核利(fluoroimide),三氟苯唑(fluotrimazole),氟嘧菌酯(fluoxastrobin),氟喹唑(fluquinconazole),氟硅唑(flusilazole),磺菌胺(flusulfamide),氟酰胺(flutolanil),粉唑醇(flutriafol),灭菌丹(folpet),甲醛(formaldehyde),fosetyl,麦穗宁(fuberidazole),呋霜灵(furalaxyl),呋吡菌胺(furametpyr),呋喃酰胺类杀真菌剂,呋喃甲酰苯胺类杀真菌剂,二甲呋酰胺(furcarbanil),呋菌唑(furconazole),呋醚唑(furconazole-cis),糠醛,furmecyclox,furophanate,果绿定(glyodin),灰黄霉素(griseofulvin),双胍辛乙酸盐(guazatine),丙烯酸喹啉酯(halacrinate),六氯苯(hexachlorobenzene),六氯丁二烯,六氯酚(hexachlorophene),己唑醇(hexaconazole),hexylthiofos,汞加芬(hydrargaphen),霉灵(hymexazol),抑霉唑(imazalil),亚胺唑(imibenconazole),咪唑类杀真菌剂,双胍辛胺(iminoctadine),无机杀真菌剂,无机汞类杀真菌剂,甲基碘,种菌唑(ipconazole),异稻瘟净(iprobenfos),异菌脲(iprodione),异丙菌胺(iprovalicarb),稻瘟灵(isoprothiolane),isovaledione,春雷霉素(kasugamycin),醚菌酯(kresoxim-methyl),石灰硫(limesulphur),代森锰铜(mancopper),代森锰锌(mancozeb),代森锰(maneb),邻酰胺(mebenil),mecarbinzid,嘧菌胺(mepanipyrim),灭锈胺(mepronil),氯化汞,氧化汞,氯化亚汞,汞类杀菌剂,甲霜灵(metalaxyl),精甲霜灵(metalaxyl-m),威百亩(metam),metazoxolon,叶菌唑(metconazole),磺菌威(methasulfocarb),呋菌胺(methfuroxam),溴甲烷(methyl bromide),异硫氰酸甲酯,苯甲酸甲基汞,氰胍甲汞,戊氯酚甲汞,代森联(metiram),苯氧菌胺(metominostrobin),苯菌酮(metrafenone),噻菌胺(metsulfovax),代森环(milneb),吗啉类杀真菌剂,腈菌唑(myclobutanil),甲菌利(myclozolin),N-(乙基汞)-对甲苯磺苯胺,代森钠(nabam),那他霉素(natamycin),硫氰散(nitrostyrene),酞菌酯(nitrothal-isopropyl),氟苯嘧啶醇(nuarimol),OCH,辛噻酮(octhilinone),呋酰胺(ofurace),有机汞类杀真菌剂,有机磷类杀真菌剂,有机锡类杀真菌剂, 肟醚菌胺(orysastrobin),霜灵(oxadixyl),氧硫杂环己烯类杀真菌剂,唑类杀真菌剂,羟喹啉铜,咪唑(oxpoconazole),氧化萎锈灵(oxycarboxin),稻瘟酯(pefurazoate),戊菌唑(penconazole),戊菌隆(pencycuron),五氯苯酚(pentachlorophenol),吡噻菌胺(penthiopyrad),苯汞脲,乙酸苯汞,氯化苯汞,焦儿茶酚的苯汞衍生物,硝酸苯汞,水杨酸苯汞,苯磺酰胺类杀真菌剂,氯瘟磷(phosdiphen),四氯苯酞(phthalide),邻苯二甲酰亚胺类杀真菌剂,啶氧菌酯(picoxystrobin),病花灵(piperalin),代森福美锌(polycarbamate),聚二硫代氨基甲酸酯类杀真菌剂,多氧霉素(polyoxins),polyoxorim,多硫化物类杀真菌剂,叠氮化钾,多硫化钾,硫氰酸钾,烯丙苯噻唑(probenazole),咪酰胺(prochloraz),腐霉利(procymidone),霜霉威(propamocarb),丙环唑(propiconazole),丙森锌(propineb),丙氧喹啉(proquinazid),硫菌威(prothiocarb),丙硫菌唑(prothioconazole),吡喃灵(pyracarbolid),唑菌胺酯(pyraclostrobin),吡唑类杀真菌剂,吡菌磷(pyrazophos),吡啶类杀真菌剂,啶菌腈(pyridinitril),啶斑肟(pyrifenox),嘧霉胺(pyrimethanil),嘧啶类杀真菌剂,咯喹酮(pyroquilon),pyroxychlor,氯吡呋醚(pyroxyfur),吡咯类杀真菌剂,quinacetol,quinazamid,quinconazole,喹啉类杀真菌剂,醌类杀真菌剂,喹喔啉类杀真菌剂,苯氧喹啉(quinoxyfen),五氯硝基苯(quintozene),rabenzazole,防霉胺(salicylanilide),硅噻菌胺(silthiofam),硅氟唑(simeconazole),叠氮化钠,邻苯基苯酚钠,五氯酚钠,多硫化钠,螺环菌胺(spiroxamine),链霉素(streptomycin),甲氧基丙烯酸酯类杀真菌剂,磺酰苯胺类杀真菌剂,硫,sultropen,TCMTB,戊唑醇(tebuconazole),叶枯酞(tecloftalam),四氯硝基苯(tecnazene),tecoram,四氟醚唑(tetraconazole),噻菌灵(thiabendazole),thiadifluor,噻唑类杀真菌剂,噻菌腈(thicyofen),噻氟菌胺(thifluzamide),硫代氨基甲酸酯类杀真菌剂,thiochlorfenphim,硫柳汞(thiomersal),硫菌灵(thiophanate),甲基硫菌灵(thiophanate-methyl),噻吩类杀真菌剂,克杀螨(thioquinox),福美双(thiram),噻酰菌胺(tiadinil),tioxymid,tivedo,甲基立枯磷(tolclofos-methyl),托萘酯(tolnaftate),甲苯氟磺胺(tolylfluanid),乙酸甲苯汞,三唑酮(triadimefon),三唑醇(triadimenol),威菌磷(triamiphos),triarimol,叶锈特(triazbutil),三嗪类杀真菌剂,三唑杀真菌剂,咪唑嗪(triazoxide),氧化三丁锡,水杨菌胺(trichlamide),三环唑(tricyclazole),十三吗啉(tridemorph),肟菌酯(trifloxystrobin),氟菌唑(triflumizole),嗪氨灵(triforine),灭菌唑(triticonazole),未分类的杀真菌剂,十一烯酸(undecylenicacid),烯效唑(uniconazole),脲类杀真菌剂,有效霉素(validamycin),缬氨酰胺类杀真菌剂,乙烯菌核利(vinclozolin),氰菌胺(zarilamid),萘酸锌,代森锌(zineb),福美锌(ziram),苯酰菌胺(zoxamide)和它们的混合物。
除草剂:除草剂是一种用于杀死不需要的植物的杀有害物药。选择性除草剂杀死特定的目标,同时相对的对于需要的作物没有伤害。这些除草剂中的一些通过干扰杂草的生长而起作用,并且通常基于植物激素。用于清理荒地的除草剂不具有选择性并杀死与之接触的所有植物体。除草剂广泛地应用于农业和景观草坪的管理。它们也应用于总的植物控制(total vegetation control,TVC)工程来维护公路和铁路。少数除草剂用于森林、牧场系统、及留作野生动物栖息地的区域的管理。通常,杀有害物药手册,第14版,CDS Tomlin著,英国农作物保护委员会,2006(The Pesticide Manual,Fourteenthedition,ed.CDS Tomlin,BCPC 2006)记载了可用的各种化学类型的活性成分。以下选择了用于解释本发明的实例,但并不是对本发明的限制:芳氧基羧酸例如MCPA,芳氧基苯氧基丙酸酯类例如炔草酯(Clodinafop),环己二酮肟类例如稀禾定(Sethoxydim),二硝基苯胺类例如氟乐灵(Trifluralin),二苯醚类例如乙氧氟草醚(Oxyfluorfen),羟基苄腈类例如溴苯腈(Bromoxynil),磺酰脲类例如烟嘧磺隆(Nicosulfuron),三唑并嘧啶类例如五氟磺草胺(Penoxsulam),triketiones例如mesotriones,脲类例如敌草隆(Diuron)。以下说明了一些特别合适的除草剂:
●2,4-D是苯氧基组中的阔叶除草剂,其用于草坪及免耕大田作物生产。现在其主要与其它充当增效剂的除草剂混合使用,是世界上最为广泛应用的除草剂,在美国是第三常用的除草剂。其是合成茁长素(auxin)(植物激素)的一个实例。
●莠去津(Atrazine)是一种三嗪除草剂,用于玉米和高粱来控制阔叶杂草和禾本科植物。因为其成本低廉并且当其与其他除草剂混合使用时可产生协同作用,所以现在仍在使用,其是光系统I I的抑制剂。
●麦草畏(Dicamba)为苯甲酸类是一种持久性的阔叶除草剂,其在土壤中有效,用于草坪和玉米地。其是合成茁长素的另一个实例。
●草甘膦(Glyphosate)是一种内吸性非选择性的除草剂(它可杀死任何植物类型),其用于非耕灭杀(no-till burndown)及控制抗草甘膦作用的转基因作物中的杂草。其是EPSPs抑制剂的一个实例。
●甲咪唑烟酸(imazapic)为咪唑啉酮类,是一种选择性的除草剂,其用于一些一年生和多年生草及一些阔叶杂草的苗前和苗后控制。甲咪唑烟酸通过抑制蛋白质合成和细胞生长所必须的支链氨基酸(缬氨酸、亮氨酸、异亮氨酸)的产生,来杀死植物。
●异丙甲草胺(Metolachlor)为氯乙酰胺类,是一种苗前除草剂,广泛地用于控制玉米和高粱中的一年生杂草,在这些用途上其已大量代替莠去净(atrazine)。
●百草枯(Paraquat)为bypyridylium类是一种非选择性接触性除草剂,其用于免耕灭杀及大麻(marijuana)和古柯种植的空中灭杀(aerial destruction)。与广泛商业应用中的任何其它除草剂相比其对人具有更剧烈的毒性。
●氨氯吡啶酸(Picloram),二氯吡啶酸(clopyralid),和绿草定(triclopyr)为吡啶羧酸类或合成茁长素,主要用于控制不需要的木本植物和阔叶杂草。
杀虫剂:杀虫剂是一种针对所有发育形式(developmental form)的昆虫使用的杀有害物药。其包含针对昆虫卵和幼虫使用的杀卵剂和杀幼虫剂。杀虫剂用于农业、医药、工业及家用。以下提及了合适的杀虫剂:
●氯代杀虫剂,例如毒杀芬(Camphechlor),DDT,六氯环己烷,γ-六氯环己烷,甲氧滴滴涕(Methoxychlor),五氯苯酚(Pentachlorophenol),TDE,Aldrin,氯丹(Chlordane),开蓬(Chlordecone),狄氏剂(Dieldrin),硫丹(Endosulfan),异狄氏剂(Endrin),七氯(Heptachlor),Mirex和它们的混合物;
●有机磷类化合物,例如乙酰甲胺磷(Acephate),保棉磷(Azinphos-methyl),地散磷(Bensulide),氯氧磷(Chlorethoxyfos),毒死蜱(Chlorpyrifos),甲基毒死稗(Chlorpyriphos-methyl),敌匹硫磷(Diazinon),敌敌畏(Dichlorvos)(DDVP),百治磷(Dicrotophos),乐果(Dimethoate),乙拌磷(Disulfoton),灭线磷(Ethoprop),苯线磷(Fenamiphos),杀螟硫磷(Fenitrothion),倍硫磷(Fenthion),噻唑磷(Fosthiazate),马拉硫磷(Malathion),甲胺磷(Methamidophos),杀扑磷(Methidathion),甲基-对硫磷(Parathion),速灭磷(Mevinphos),二溴磷(Naled),氧乐果(Omethoate),亚砜磷(Oxydemeton-methyl),对硫磷(Parathion),甲拌磷(Phorate),伏杀硫磷(Phosalone),亚胺硫磷(Phosmet),丁基嘧啶磷(Phostebupirim),甲基嘧啶磷(Pirimiphos-methyl),丙溴磷(Profenofos),特丁磷(Terbufos),司替罗磷(Tetrachlorvinphos),脱叶磷(Tribufos),敌百虫(Trichlorfon)及其混合物;
●氨基甲酸酯(Carbamates),例如涕灭威(Aldicarb),克百威(Carbofuran),甲萘威(Carbaryl),灭多威(Methomyl),2-(1-甲基丙基)苯基氨基甲酸甲酯和它们的混合物;
●拟除虫菊酯(Pyrethroids),例如烯丙菊酯(Allethrin),联苯菊酯(Bifenthrin),溴氰菊酯(Deltamethrin),氯菊酯(Permethrin),苄呋菊酯(Resmethrin),苯醚菊酯(Sumithrin),四甲司林(Tetramethrin),四溴菊酯(Tralomethrin),四氟苯菊酯(Transfluthrin)和它们的混合物;
●源自植物毒素的化合物,例如Derris(鱼藤酮(Rotenone)),除虫菊素(Pyrethrum),Neem(印楝素(Azadirachtin)),尼古丁(Nicotine),咖啡因和它们的混合物。
●新烟碱类如吡虫啉(imidacloprid)。
●阿巴克丁类(abamectin)如甲氨基阿巴克丁(emamactin)。
●二嗪类如茚虫威(indoxacarb)。
●氨茴酸二酰胺类如氯虫苯甲酰胺(rynaxypyr)。
杀鼠剂:杀鼠剂是一类意欲杀死啮齿类动物的有害生物防治化学品。啮齿类动物的摄食行为反映了其为食腐动物,因此其难于被毒杀。它们会吃一小部分,然后等待,如果没有出现异样,它们才会继续吃。有效的杀鼠剂在致命浓度时必须是无味臭的,并且具有延迟效应。以下给出了合适的杀鼠剂的实例:
●抗凝血剂被定义为慢性(摄入致死剂量后1~2周死亡,罕有较快死亡)、单剂量(第二代)或多剂量(第一代)累积性杀鼠剂。致命剂量的抗凝血剂会引起致命的内出血,例如溴鼠灵(brodifacoum)、杀鼠醚(coumatetralyl)或华法林(warfarin)。这些有效剂量的物质为抗维生素K,阻断酶K1-2,3-环氧-还原酶(这种酶优选被4-羟基香豆素/4-羟基硫杂香豆素衍生物所阻断)和K1-醌-还原酶(这种酶优选被茚满二酮衍生物所阻断),剥夺生物体活性维生素K1的来源。这导致了维生素K循环的破坏,致使不能产生重要的凝血因子(主要是凝血因子II(凝血酶原)、VII(前转化素)、IX(Christmas因子)和X(Stuart因子))。除了这种具体的代谢破坏外,毒性剂量的4-羟基香豆素/4-羟基硫杂香豆素和茚满二酮抗凝血剂会引起微血管(毛细血管)损伤,增加毛细血管的渗透率,引起弥散性内出血(出血)。这些效应是逐步的,在数天内发展,并且不会伴随任何受伤害的感觉,例如疼痛或剧痛。在中毒的最后阶段,衰竭的啮齿类动物因为低血容量循环休克或严重的贫血而虚脱,并且平静地死亡。杀鼠抗凝血剂可以是第一代试剂(4-羟基香豆素类:华法林、杀鼠醚;茚满二酮类:鼠完(pindone)、敌鼠(diphacinone)、氯鼠酮(chlorophacinone)),这些试剂通常需要较高的浓度(通常在0.005和0.1%之间),为积聚致死剂量需在数天内连续摄取,单次摄取之后活性差或者没有活性,并且较之第二代试剂毒性低,第二代试剂是4-羟基香豆素的衍生物(鼠得克(difenacoum)、溴鼠灵(brodifacoum)、溴敌隆(bromadiolone)和氟鼠灵(flocoumafen))或4-羟基-1-benzothiin-2-酮,(4-羟基-1-硫杂香豆素(4-hydroxy-1-thiacoumarin)),有时被不正确地称为4-羟基-1-硫代香豆素(4-hydroxy-1-thiocoumarin),原因见杂环化合物),即噻鼠灵(difethialone)。第二代试剂的毒性远比第一代试剂强。其通常以较低的浓度应用于饵中(通常在0.001~0.005%数量级),在单次摄入饵后即可致死,并且对变得耐受第一代抗凝血剂的啮齿类动物品系仍然有效;因此第二代抗凝血剂有时被称为“超级华法林(superwarfarin)”。有时,抗生素可增强抗凝血杀鼠剂,最常见的为磺胺喹沙啉。这种联合(例如0.05%的华法林+0.02%的磺胺喹沙啉,或0.005%的鼠得克+0.02%的磺胺喹沙啉等)的目的在于抗生素/抑菌剂抑制代表了维生素K来源的肠/消化道共生微生物区系。因此共生细菌被杀死,或其代谢被破坏且由其产生的维生素K减少,结果从逻辑上对抗凝血剂作出贡献。也可使用非磺胺喹沙啉的抗生素试剂,例如复方新诺明(co-trimoxazole)、四环素、新霉素或甲硝唑。另外的用于灭鼠诱饵中的协同作用是将抗凝血剂与具有维生素D活性的化合物(即胆钙化醇或麦角钙化醇)一起使用(见下文)。所用的典型配方例如:0.025~0.05%的华法林+0.01%的胆钙化醇。在一些国家中甚至有固定的三组分杀鼠剂,即抗凝血剂+抗生素+维生素D,例如0.005%的鼠得克+0.02%的磺胺喹沙啉+0.01%的胆钙化醇。第二代抗凝血剂与抗生素和/或维生素D的联合被认为即使对于耐受性最强的啮齿动物品系也有效,虽然在诱饵中浓度为0.0025~0.005%的一些第二代抗凝血剂(即溴鼠灵和噻鼠灵)毒性很强,以至于不存在耐受的啮齿动物品系,甚至对任何其他衍生物耐受的啮齿动物,在应用这些毒性最为强烈的抗凝血剂时也仍然会被可靠地灭绝。
维生素K1被建议作为解毒剂,并且其已成功地作为解毒剂用于意外和故意地(对宠物投毒、企图自杀)接触了抗凝血剂有毒物的宠物或人。另外,由于这些有毒物通过抑制肝功能起作用,并且在中毒的发展期间一些凝血因子及总的循环血量缺乏,因此输血(视情况可存在凝血因子)可挽救因疏忽而接触这些有毒物的人员的生命,这比一些老式有毒物具有优势。
●金属磷化物已经作为一种杀死啮齿类动物的方法使用,并被认为是单剂量快速作用的杀鼠剂(通常单次摄取诱饵后1~3天内死亡)。将由食物和磷化物(通常是磷化锌)组成的诱饵置于啮齿类动物可以吃到的地方。啮齿动物消化系统中的酸会与磷化物反应生成有毒的磷化氢气体。这种控制有害动物的方法可能用于啮齿动物耐受某些抗凝血剂的场合,尤其是控制家鼠和田鼠;磷化锌诱饵也比大多数的第二代抗凝血剂便宜,所以在大量啮齿动物侵扰的情况下,首先通过应用大量的磷化锌减少其数量,然后持续地投予抗凝血剂诱饵彻底根除在起始快速作用有毒物下仍然存活的剩下的啮齿动物。相反地,在抗凝血剂诱饵毒杀后仍然存活的个别啮齿动物(剩下的啮齿动物)可通过预给饵给予其无毒的诱饵1或2周(这对于克服怯饵和使啮齿动物习惯于在提供特定的食物的特定的区域摄食是重要的,特别是当消灭鼠类时),随后使用与预给饵相同类型的有毒诱饵,直至诱饵停止消耗(通常在2~4天内)。如果诱饵的接受/嗜食性良好(即啮齿动物易于食用),则采用不同作用方式的交互杀鼠剂方法可实际或几乎100%地消灭区域内的啮齿动物群。
●磷化物是快速作用毒鼠剂,其可使得老鼠通常在开放区域中死亡,而不是在受侵害的建筑物中死亡。其典型的实例是磷化铝(仅为烟熏剂)、磷化钙(仅为烟熏剂)、磷化镁(仅为烟熏剂)和磷化锌(于诱饵中)。通常将磷化锌加入啮齿类动物诱饵中,加入量约为0.75~2%。由于磷化物水解会释放磷化氢,因此诱饵会具有强烈的、刺激性的大蒜味的特征。该气味会吸引(或至少不会驱散)啮齿类动物,但对其他哺乳动物具有驱散效果;但是,鸟类(特别是野生火鸡)对这种气味不敏感。它们会摄食诱饵因此产生了附带的损害。
●高钙血症:钙化醇(维生素D)、胆钙化醇(维生素D3)和麦角钙化醇(维生素D2)用作杀鼠剂,其对啮齿类动物是有毒的,由于相同的原因对哺乳类动物是有益的,即其影响生物体中钙和磷酸盐的体内稳定。微量的维生素D是必需的(数个IU每千克体重每天,仅有零点几毫克),与大多数脂溶性维生素一样,更大剂量的维生素D是有毒的,其易导致所谓的维生素过多症,即简单来说,维生素中毒。若严重中毒(即有毒物的剂量足够高),其最终会导致死亡。在啮齿动物摄食杀鼠剂诱饵时,其主要通过增加从食物中吸收钙,使骨-基质-固定钙成离子化形式(主要是碳酸氢钙阳离子,部分结合于血浆蛋白,[CaHCO3]+),从而提高钙水平,引起高钙血症,所述钙离子在血浆中溶解和循环,当摄入致死剂量后,游离钙水平升至足够高从而使得血管、肾、胃壁和肺矿化/钙化(在组织中形成钙化物、钙盐/复合物的结晶,因此损伤组织),进一步导致心脏问题(心肌对游离钙水平的变化是敏感的,游离钙水平既影响心肌收缩性又影响心房和心室间的兴奋传导)和出血(由于毛细血管损伤),并可能导致肾衰竭。其被认为是单剂量、或累积性的(取决于所用的浓度;常用的0.075%诱饵浓度可致死大多数单次摄入大部分诱饵的啮齿动物)、亚慢性的(在食用诱饵后数天至一周之内死亡)。当单独使用时,胆钙化醇和麦角钙化醇的使用浓度分别是0.075%和0.1%。钙化醇的毒性具有一个重要的特征,即它们与抗凝血毒性剂具有协同作用。这意味着在同一诱饵中的抗凝血剂和钙化醇的混合物比诱饵中抗凝血剂的毒性和钙化醇的毒性的总和更加强烈,因此诱饵中相当低的钙化醇含量即可达到大量的高血钙效果,反之亦然。若存在钙化醇,则可观察到更明显的抗凝血/出血效果。此协同作用常用于钙化醇含量低的诱饵中,因为有效浓度的钙化醇较有效浓度的大多数抗凝血剂更加昂贵。历史上首次将钙化醇应用于杀鼠诱饵中是在上世纪七十年代早期,事实上是Sorex产品D(与现在的D配方不同),其含有0.025%的华法林+0.1%的麦角钙化醇。如今的CD含有0.0025%的鼠得克+0.075%胆钙化醇组合物。许多单独含有0.075~0.1%的钙化醇(例如含有0.075%的胆钙化醇)或含有0.01~0.075%的钙化醇与抗凝血剂的组合物的其他品牌产物也在市场上销售。
杀螨剂、杀软体动物剂和杀线虫剂:杀螨剂是可杀死螨类的杀害物药剂。抗生素类杀螨剂、氨基甲酸酯类杀螨剂、甲脒类杀螨剂、螨类生长调节剂、有机氯、氯菊酯(permethrin)和有机磷杀螨剂(organophosphate miticides)均属于此类。杀软体动物剂是用于控制例如蛾类、蛞蝓(slugs)和蜗牛等软体动物的杀害物药剂。这些物质包括四聚乙醛(metaldehyde)、甲硫威(methiocarb)、硫酸铝。杀线虫剂是一类用于杀死寄生线虫(蠕虫的一门)的化学杀害物药剂。杀线虫剂从印度楝树籽饼获得;其是油提取后印度楝树籽的残余物。世界上已知印度楝树有数个名称,但是自古时起在印度首先种植。
抗微生物剂
下列实例中给出了适合本发明的农用化学品组合物的抗微生物剂。最常用的杀菌消毒剂是采用如下物质的那些:
●活性氯(即次氯酸盐、氯胺、二氯异氰尿酸盐和三氯异氰尿酸盐、湿氯、二氧化氯等),
●活性氧(过氧化物,例如过氧乙酸、过硫酸钾、过硼酸钠、过碳酸钠和尿素过氧化氢合物),
●碘(碘代聚维酮(聚维酮-碘,聚维酮碘)、Lugol′s溶液、碘酊、碘化非离子表面活性剂),
●浓缩的醇类(主要是乙醇、1-丙醇,也称为正丙醇,和2-丙醇,也称为异丙醇,及它们的混合物;另外也使用了2-苯氧基乙醇和1-苯氧基丙醇和2-苯氧基丙醇),
●苯酚类物质(例如苯酚(也称为“石炭酸”)、甲酚(称为“来苏尔”,与液体钾皂组合)、卤化的(氯代、溴代)酚(例如毒菌酚、三氯生、三氯苯酚、三溴苯酚、五氯苯酚、二溴苯酚及它们的盐)),
●阳离子表面活性剂,例如一些季铵盐阳离子(例如苯扎氯铵、十六烷基三甲基溴化铵或十六烷基三甲基氯化铵、二癸基二甲基氯化铵、西吡氯铵、苄索氯铵)及其他非季铵盐化合物,例如氯己定、葡萄糖精蛋白(glucoprotamine)、奥替尼啶二盐酸化物等,
●强氧化剂,例如臭氧和高锰酸盐溶液;
●重金属及其盐,例如胶态银、硝酸银、氯化汞、苯汞盐、硫酸铜、氧氯化铜等。重金属及其盐是毒性最为强烈并且危害环境的杀菌剂,因此其使用被强烈抑制或禁止;另外
●适当浓缩的强酸(磷酸、硝酸、硫酸、氨基磺酸、甲苯磺酸),及
●碱(氢氧化钠、氢氧化钾、氢氧化钙),在pH<1或pH>13时,尤其是在高温下(高于60℃)杀死细菌。
少数上述消毒剂可在合适的条件(主要是浓度、pH、温度及对人/动物的毒性)下,作为防腐剂使用,即可用于人体或动物体、皮肤、黏膜、伤口等的杀菌剂。其中,以下是重要的:
●一些适当稀释的氯制剂(例如Daquin′s溶液、0.5%的pH调节至7~8的次氯酸钠或次氯酸钾溶液、或0.5%~1%的苯磺酰氯胺钠溶液(氯胺B)),及一些
●碘制剂,例如碘代聚维酮的各种盖伦制剂(软膏剂、溶液、外伤膏药),其过去也被称为Lugol′s溶液,
●过氧化物,例如尿素过氧化氢合物及0.1~0.25%的过氧乙酸的pH缓冲溶液,
●加入或未加入防腐剂添加剂的醇类,其主要用于皮肤防腐,
●弱有机酸,例如山梨酸、苯甲酸、乳酸和水杨酸,
●一些酚类化合物,例如毒菌酚、三氯生和二溴苯酚,及
●阳离子活性化合物,例如0.05~0.5%的苄烷铵、0.5~4%的氯己定、0.1~2%的奥替尼啶溶液。
杀菌性抗生素杀死细菌,抑菌性抗生素仅能延缓细菌的生长和繁殖。青霉素是一种杀菌剂,如同头孢菌素。氨基糖苷类抗生素即可以通过杀菌方式(分解细胞壁前体导致细胞溶解)也可以通过抑菌方式(通过与30s核糖体亚基结合并降低翻译的准确性,从而导致错误的蛋白质合成)起作用。本发明的其他杀菌性抗生素包括,喹诺酮类、哨基呋喃类、万古霉素、单酰胺菌素类、复方新诺明和甲硝唑。
优选的活性成分为具有内吸性或部分内吸性作用方式的物质,如嘧菌酯(azoxystrobin)。
助剂组合物的优选应用
本发明进一步的实施方式涉及包含组分(a)、(b)和(c)的所述助剂组合物作为用于生产农化组合物的下列物质的具体应用:
●乳化剂,
●助剂,
●溶剂或增溶剂,或
●桶混添加剂。
所述助剂组合物可以约5至约50%w/w(浓缩液)或约0.1至约1%w/w(稀释制剂)的量添加到最终产物中。
实施例
实施例1和2,比较实施例C1和C2
通过对亚洲大豆锈病的控制,来展示本发明所述助剂混合物的效果。田间试验在巴西进行。从市场购买的两种标准杀生物剂组合物应用于大豆作物:“Opera”(BASF)包含5%w/w氟环唑和13.3%w/w唑菌胺酯,前者是一种预防和治疗性杀真菌剂,后者是保护、治疗和片层传导(translaminar)杀真菌剂。“Folicur”(Bayer CropScience)包括戊唑醇,一种具有保护、治疗和铲除性质的杀真菌剂。这两种组合物以全推荐剂量和50%全推荐剂量应用。这些实验与在上述两者中均加入本发明所述的助剂组合物且进行相似处理的植物相比较,在此本发明的助剂组合物含有(A)75%w/w大豆油+10EO,10%w/w辛基葡糖苷和15%w/w妥尔油脂肪酸,和(B)60%w/w脱水山梨醇单/双月桂酸酯+25EO,25%w/w癸基葡糖苷和15%w/w妥尔油脂肪酸,两者均以150ml/ha的浓度应用。结果见表1。
表1
亚洲大豆锈病对大豆作物产量的影响-相对于对照(=100)
实施例和对比实施例清楚地表明,加入助剂显著增加了杀真菌剂的效果。
实施例3,对比实施例C 3
关于稗草和狗尾草对烟嘧磺隆的吸收,进行单独研究以比较本发明的组合物与工业标准品、更具体的为作物油浓缩液(COC)的性能。75%水分散粒剂(Accent WDG 75)形式的烟嘧磺隆以0.031%w/v的量应用(46.7g活性成分/150l/ha)。使用前0.5小时将放射性同位素标记的烟嘧磺隆(50mCi/mmol)加入新配制的处理液中。14C烟嘧磺隆占7%质量。含单独的烟嘧磺隆(即无助剂的)的喷洒液用50%丙酮配制。结果见表2。
表2
烟嘧磺隆处理
实施例 | 加入助剂 | 助剂量(%v/v) |
对照 | 无助剂 | 0 |
3a | 加入助剂A | 0.25 |
3b | 加入助剂B | 0.24 |
C3 | 作物油浓缩物* | 1.0 |
*作物油浓缩物(COC)包含83%的油和17%乳化剂。
实施例4至6
设5个重复,稗草和狗尾草的种子播种在盆中,播种深度为5mm,在70%的相对湿度下保持达4周,且每天在约500μmol/m2光强下暴露14h。植物长至3-5叶期时进行吸收研究,在收获前全部时期充分浇水。光周期开始约6h后进行液滴处理。处理24h后对叶片取样,处理过的表面用水/丙酮洗涤以回收未被吸收的烟嘧磺隆。应用液体闪烁计数器。叶面吸收定义为未从洗涤处理过的叶片回收的放射性,并以应用剂量的百分比计算。为了统计目的,运用方差分析和最小显著差异(LSD)试验来比较这些处理。结果见表3
表3
处理24h后烟嘧磺隆制剂的吸收
实施例 | 稗草 | 狗尾草 |
4 | 81.5c | 77.0b |
5 | 97.9a | 96.0a |
6 | 95.7b | 94.6a |
具有相同后缀的种内平均数差异不显著(P=0.05)
正如表3所示,应用不管哪种助剂,处理24h后两种禾本科植物品种对烟嘧磺隆的吸收均增加。在稗草中,与COC相比,本发明的助剂在低得多的剂量下使除草剂的吸收量显著增加。对于狗尾草,与COC相比,本发明的助剂导致的吸收在数值上更大,但是从统计学的角度看,在95%置信水平下并不显著。
Claims (8)
1.农化助剂组合物,包括:
(a)60-90%w/w的具有下述通式(Ⅰ)的烷氧基化的甘油三酯
其中R1、R2和R3相互独立地代表具有5-21个碳原子的线性或分支的、饱和或不饱和的烷基和/或羟基烷基残基;n、m和p相互独立地代表0或1-50的整数,其中条件是三者之和(m+n+p)不为0;和AO代表乙二醇或丙二醇单元,
(b)5-15%w/w的烷基或烯基寡糖苷或者烷氧基化的烷基或烯基寡糖苷,
所述烷基或烯基寡糖苷(组分b1)具有下述通式(Ⅱ)
R4O-[G]p (II)
其中R4为具有4-22个碳原子的烷基和/或烯基残基,G是具有5个或6个碳原子的糖单元,和p为1-10的数值,
所述烷氧基化的烷基或烯基寡糖苷为平均1-20mol环氧乙烷和/或环氧丙烷与糖苷体上自由羟基的加合物,
和
(c)5-15%w/w的具有下述通式(Ⅲ)脂肪酸或它们的盐
R5CO-OX (III)
其中R5CO代表具有6-22个碳原子的线性或分支的、饱和或不饱和的酰基,X代表氢或者碱金属,
条件是:上述各值任选地与水一起总计为100%w/w。
2.根据权利要求4所述的组合物,其中所述的烷氧基化的甘油酯(组分a)为烷氧基化的大豆油,菜籽油,葵花籽油或亚麻籽油。
3.根据权利要求1所述的组合物,其中所述烷氧基化的多元醇酯(组分a)的HLB值在2-15的范围内。
4.农化组合物,包括根据权利要求1-3任一项的农化助剂组合物和(d)杀生物剂。
5.生产农化组合物的方法,向所述农化组合物中添加用作为乳化剂的根据权利要求1-3任一项的所述农化助剂组合物。
6.生产农化组合物的方法,向所述农化组合物中添加用作为助剂的根据权利要求1-3任一项的所述农化助剂组合物。
7.生产农化组合物的方法,向所述农化组合物中添加作为溶剂或增溶剂的根据权利要求1-3任一项的所述农化助剂组合物。
8.生产农化组合物的方法,向所述农化组合物中添加用作为桶混添加剂的根据权利要求1-3任一项的所述农化助剂组合物。
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