CN101534632A - 保护作物植物的方法和装置 - Google Patents
保护作物植物的方法和装置 Download PDFInfo
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- CN101534632A CN101534632A CNA2007800409223A CN200780040922A CN101534632A CN 101534632 A CN101534632 A CN 101534632A CN A2007800409223 A CNA2007800409223 A CN A2007800409223A CN 200780040922 A CN200780040922 A CN 200780040922A CN 101534632 A CN101534632 A CN 101534632A
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- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/10—Devices for affording protection against animals, birds or other pests
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
- A01M1/00—Stationary means for catching or killing insects
- A01M1/20—Poisoning, narcotising, or burning insects
- A01M1/2022—Poisoning or narcotising insects by vaporising an insecticide
- A01M1/2027—Poisoning or narcotising insects by vaporising an insecticide without heating
- A01M1/2055—Holders or dispensers for solid, gelified or impregnated insecticide, e.g. volatile blocks or impregnated pads
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
- A01M29/00—Scaring or repelling devices, e.g. bird-scaring apparatus
- A01M29/30—Scaring or repelling devices, e.g. bird-scaring apparatus preventing or obstructing access or passage, e.g. by means of barriers, spikes, cords, obstacles or sprinkled water
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
- A01M29/00—Scaring or repelling devices, e.g. bird-scaring apparatus
- A01M29/30—Scaring or repelling devices, e.g. bird-scaring apparatus preventing or obstructing access or passage, e.g. by means of barriers, spikes, cords, obstacles or sprinkled water
- A01M29/34—Scaring or repelling devices, e.g. bird-scaring apparatus preventing or obstructing access or passage, e.g. by means of barriers, spikes, cords, obstacles or sprinkled water specially adapted for insects
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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
- 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
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
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Abstract
本发明涉及一种保护作物植物以防有害生物体的方法,其包括如下步骤:将一种或多种植物用一种包含稳定结构和网眼织物的装置覆盖,其中网眼织物用农药浸渍并可通过光、空气和水。
Description
本发明涉及一种保护作物植物的方法。本发明进一步涉及一种进行本方法的装置。
有害生物体,如昆虫、螨或真菌为全世界对收获的主要威胁并且需要广泛使用植物保护剂(农药)如杀虫剂和杀真菌剂。
尽管此领域内的连续研究和开发已产生对人类具有相当低毒性和改善的环境相容性的产品,仍然存在一些施用方法导致植物上一定程度的农药残留的问题。这禁止了某些高度有效的农药的使用。用其他农药可延缓果实和蔬菜的可能消耗或加工,这可能对于相应产品的收获、储存和销售为不理想的。
因此,仍存在对可保护作物植物以防有害生物体的方法的高要求,其使得选择某种有效农药而不导致植物中的显著农药残留。
例如由WO 2005/060472已知用某种杀虫剂浸渍的蚊帐可增强网的效力并防止睡眠者以防可传播疾病如疟疾的昆虫刺伤。
然而,这种网主要用于室内,并且尽管它们应具有耐洗性,即它们应甚至在几次洗涤以后保持它们的杀虫活性,但这种网不能连续曝露于光、雨水和风下。
JP-A 08-163 950公开了一种通过将聚烯烃树脂与合成除虫菊酯杀虫剂复合而生产的树脂网,其用于防治昆虫部分以及尤其具有农业和园艺用途。然而,根据此文献的公开内容,此网的主要意欲目的为“室内”,即在温室、厩舍和住宅内使用。
WO 03/003827公开了包含具有适于防止低飞行昆虫进入露天区域的高度的基本直立结构的围墙结构。该结构用杀虫剂浸渍。由于植物不完全用此结构覆盖,由于此围墙结构,空气、水和光可易于渗透此结构是不需要的。因此,结构的耐雨水性可例如通过使它为高度防水而改善。
然而,如果整个植物通过浸渍的网状结构保护,则必须满足几个部分矛盾的要求。首先,需要空气、光和水自由到达植物以确保它的生长和良好状态,第二,必须防止有害生物体进入结构,第三,防治剂的浸渍需要一定程度地耐气候性。
现在已发现所有这些要求可通过用已用某种农药粘合剂组合浸渍的帐篷状装置保护植物而满足。
因此,在本发明一方面中,提供一种保护作物植物以防有害生物体的方法,其包括如下步骤:将一种或多种植物用包含稳定结构和网眼织物的装置覆盖,其中所述网眼织物用农药浸渍并可透过光、空气和水。
根据本发明,可以以容易且有效而对工作者无健康危害且不导致植物或由其产生的产品中的农药残留的途径而保护作物植物以防有害生物体。
在本发明的其他方面中,提供所述装置在保护作物植物以防有害生物体中的用途。
在本发明的又一方面中,提供一种保护作物植物以防有害生物体的装置,其包含稳定结构和网眼织物,其中所述网眼织物用农药浸渍且可透过光、空气和水。
这里所用术语“作物植物”意指任何种类的农作物,包括但不限于禾谷类、稻、豆类、棉花、烟草、蔬菜和水果植物。
优选高价值作物如蔬菜、水果植物和用于饮料、药物和烟草工业的植物和例如天然染料和成功用于化妆品应用、清洁和护理配制剂中的天然化合物或其他化学和/或生物技术加工来源的植物。
蔬菜植物或作物例如包括土豆,优选淀粉土豆、甘薯和餐用马铃薯;根蔬菜,优选胡萝卜、芜菁甘蓝(食用甜菜、饲用芜菁、芜菁、Brassica rapa.Var.rapa f.teltoxiensis)、鸦葱、菊芋、欧芹根、防风草、萝卜和辣根;块茎蔬菜,优选甘蓝、红甜菜、芹菜、萝卜;球根蔬菜,优选韭菜和洋葱(洋葱栽子和种子生产用洋葱);甘蓝,优选来自Capitata组的甘蓝(白球甘蓝、红球甘蓝、羽衣甘蓝、皱叶甘蓝)、花椰菜、孢子甘蓝、椰菜、Brassica oleracea.Var.sabellica,stem kale、海甘蓝和Brassica oleracea L.convar.oleraceavar.gemmifera DC.;果实蔬菜,优选西红柿(田地生西红柿、灌木丛西红柿、牛肉西红柿、温室生西红柿、鸡尾酒西红柿、加工西红柿和新鲜出售的西红柿)、甜瓜、茄子、紫茄子、辣椒(柿子椒、青椒、西班牙胡椒)、红辣椒、南瓜、西葫芦和黄瓜(田地生黄瓜、温室生黄瓜、蛇皮黄瓜、小黄瓜);蔬菜豆类,优选矮扁豆(如刀豆、beech beans、flageolet beans、棉豆;具有绿-和黄荚变种的用于煮的扁豆),豇豆(如具有绿-、蓝-和黄荚变种的刀豆、beech beans、flageolet beans、棉豆),蚕豆(field beans、蚕豆、具有白和黑斑点花的变种),豌豆(chicking vetches、嘴豆、大豌豆(marrowfatpea)、白荚豌豆、糖用豌豆、去皮豌豆、具有浅绿色和暗绿色不成熟种子的变种)和小扁豆;叶径蔬菜,优选白菜、莴苣、直立莴苣、野苣、卷心莴苣、直立莴苣、栎叶莴苣、菊苣、菊苣、红边菜、芝麻菜、苦苣、菠菜、牛皮菜(叶和径)和欧芹;其他蔬菜,优选芦笋、大黄、细香葱、朝鲜蓟、薄荷、向日葵、茴香、莳萝、独行菜、芥子、罂粟、花生、芝麻和沙拉用菊苣。
果实植物例如包括来自蔷薇(Rosacea)科的水果,如苹果、梨和温柏;核果类,如杏、樱桃、李和桃;浆果类,尤其是荆棘果,如黑莓、树莓、罗甘莓和糙莓,真果类,如蓝莓和酸果莓,其他浆果类,如鹅莓和桑树;附果类,如草莓;来自葫芦(Cucurbitacea)科的水果,如南瓜类,包括倭瓜和南瓜;甜瓜和西瓜;柑橘和其他亚热带水果,如柠檬、酸橙、葡萄柚、桔子、克莱门氏小柑橘、橘子、橙子、鳄梨、番石榴(guave)、金橘、洛根(logan)、荔枝和西番莲果;椰枣、无花果、葡萄、橄榄和石榴;和热带水果,如香蕉、椰子、榴莲、蛋黄果、芒果、莽吉柿、番木瓜、菠萝和罗望子。
用于饮料和烟草工业的植物包括茶变种、咖啡和可可变种和烟草。
其他优选的有观赏作物、坚果类、香草类和香料类。
观赏作物包括(但不限于)紫苑、杜鹃、秋海棠、黄杨木、仙人掌、贝母、马蹄莲、金盏草、荷兰石竹、菊花、锦紫苏、耧斗菜、大丽花、雏菊、黄花菜、飞燕草、石竹、复活节百合花、香薇、榕树(ficus)、毛地黄、晚樱、栀子花、老鹤草、大丁草、gladioli、木槿花、凤仙花、鸢尾花、常春藤、金盏花、旱金莲花、三色堇、芍药、矮牵牛花、竹桃、石竹花、猩猩木、迭迭香、玫瑰、印度橡胶树、鼠尾草、景天、金鱼草、马鞭草、长春花、白花紫路草和鱼尾菊。
坚果类包括扁桃、巴西坚果、胡桃、腰果、栗子、澳大利亚坚果、美洲山核桃、阿月浑子树和核桃。
香草类和香料类包括大茴香、香油、罗勒、甘菊、香菜、假荆芥、芹菜、细香葱、芫荽、小茴香、咖喱叶、蒲公英、莳萝、茴香、海索草、薄荷、芸香、鼠尾草、甜月桂、龙蒿、百里香、鹿蹄草和苦艾。
在优选实施方案中,作物植物为作物植物,更优选上述作物植物的秧苗。还优选作物植物在床或小块地中生长和/或形成苗圃的一部分。
这里所用术语“保护”或“保护”意指防治或抵抗作用。
这里所用术语“有害生物体”意指害虫,尤其是节肢动物害虫,包括昆虫和蜘蛛,和有害微生物,尤其是真菌,包括孢子、微生物和病毒。
这里所用术语“覆盖”意指织物或网在待保护的植物与有害生物体之间形成物理屏障,但不意味着植物与覆盖材料物理接触或防止有害生物体到达植物。
网眼织物由非硬质材料制得。优选选自纱、单丝、纤维如短纤维和连续散纤维织物(CBF)、织物、针织物,尤其是网材料、无纺布、箔、油布和涂料组合物的织物材料或塑料材料。网材料可通过本领域任何已知方法,例如通过编织、圆筒形针织或经编,或通过将网部分缝合以得到所需网而制备。
织物材料或塑料材料可由各种天然和合成纤维制得,还以机织或无纺形式作为织物混合物,作为针织物、纱线或纤维。天然纤维例如为棉、羊毛、丝或韧皮纤维,如黄麻、亚麻、苎麻、大麻和洋麻。合成纤维例如为聚酰胺、芳族聚酰胺、聚酯、聚丙烯腈、聚烯烃如聚丙烯、聚乙烯、聚(氯乙烯)或聚(四氟乙烯)(特氟隆)和纤维混合物,例如合成与天然纤维的混合物。优选聚酰胺、聚烯烃和聚酯。尤其优选聚对苯二甲酸乙二酯。
术语材料还包括非织物基质如带孔的箔。
另外,术语材料包括含纤维素材料,例如棉材料如服装或棉网。
优选,材料为织物材料或塑料材料,例如聚丙烯、聚乙烯、聚酯或聚酰胺。
更优选由聚酯,尤其是聚对苯二甲酸乙二酯制得的网。在其他优选实施方案中,材料为含纤维素材料。
稳定结构提供对网眼织物的支持以便它覆盖待保护植物。在一个实施方案中,它可以为简单的柱,其固定在地面且纤维由其悬浮且优选例如通过帐篷桩固定至地面以形成帐篷状结构。几个柱也可用于帐篷状结构。
在其他实施方案中,稳定结构包含一个或多个夹子状结构,织物在其上方悬浮。
在又一个实施方案中,稳定结构为网眼织物分配在其上以形成保护一种或多种植物以防有害生物体的封闭内部的框架。
也可能的是例如在果树的情况下,稳定结构由花盆或盆栽盘(pottingtray)或由待保护植物本身提供。
稳定结构可以在保护性织物内部或外部,并且可通过独立结构元件如柱、夹子等形成,或在另外的实施方案中形成笼状结构。
优选,将材料用包含农药的组合物处理,然而,本发明不限于这种实施方案,例如农药也可在纤维生产期间掺入纤维中。
这种材料在防治害虫中显示良好的结果并对作物植物提供持久保护。
在优选实施方案中,将农药掺入材料(例如掺入塑料基质中)或施用于材料表面或者二者。
在最优选实施方案中,将材料用包含如下组分的组合物处理:
a)至少一种农药(组分A),和
b)至少一种聚合粘合剂(组分B)。
农药组合物通常包含基于组合物重量0.001-95重量%,优选0.1-45重量%,更优选0.5-30重量%,最优选0.5-25重量%至少一种农药。
农药组合物优选基于组合物的固体含量包含如下组分:
a)0.1-45重量%,优选0.5-30重量%,更优选1-25重量%至少一种农药(组分A),和
b)55-99重量%,优选70-98重量%,更优选75-90重量%至少一种聚合粘合剂(组分B),
其中组分之和为100重量%农药组合物固体含量。
在其他优选实施方案中,农药组合物基于组合物的固体含量包含如下组分:
a)20-70重量%,优选25-65重量%,更优选30-65重量%至少一种农药(组分A),和
b)30-80重量%,优选35-75重量%,更优选35-70重量%至少一种聚合粘合剂(组分B),
其中组分之和为100重量%农药组合物固体含量。
这里所用的术语“农药”包括杀虫剂、驱避剂、杀真菌剂、软体动物杀灭剂和杀鼠剂。
在本上下文中,如果不另外说明,这里所用的术语“杀虫剂”包括具有杀节肢动物(具体而言为杀虫、杀蜘蛛和杀螨)活性的试剂。
在本上下文中,如果不另外说明,这里所用的术语“杀真菌剂”包括具有杀真菌、杀微生物和杀病毒活性的试剂。
优选农药为杀虫剂或驱避剂。
农药组合物尤其适于施用于如本发明所用的聚酯网。
本发明农药组合物可在织物材料或塑料材料形成所需产品以前,即当仍然为纱线或薄片形式时,或在形成所需产品以后施用于它们。
农药(组分A)
优选农药为具有快速麻痹或杀灭昆虫的效力和低哺乳动物毒性的杀虫剂/或驱避剂。适合的杀虫剂和/或驱避剂为本领域技术人员已知的。适合的杀虫剂和驱避剂例如公开于E.C.Tomlin等,The Pesticide Manual,第14版,The British Crop Protection Council,Farnham 2006,和其中所引用的文献中。
优选的杀虫剂和/或驱避剂在下面提到:
合成除虫菊酯化合物如醚菊酯(Etofenprox):2-(4-乙氧基苯基)-2-甲基丙基-3-苯氧基苄基醚,
杀灭菊酯(Fenvalerate):(RS)-α-氰基-3-苯氧基苄基(RS)-2-(4-氯苯基)-3-甲基丁酸酯,
高氰戊菊酯(Esfenvalerate):(S)-α-氰基-3-苯氧基苄基(S)-2-(4-氯苯基)-3-甲基丁酸酯,
甲氰菊酯(Fenpropathrin):(RS)-α-氰基-3-苯氧基苄基2,2,3,3-四甲基环丙烷羧酸酯,
氯氰菊酯(Cypermethrin):(RS)-α-氰基-3-苯氧基苄基(1RS)-顺,反-3-(2,2-二氯乙烯基)-2,2-二甲基环丙烷羧酸酯,
甲体氯氰菊酯(alpha-Cypermethrin):包含(S)-α-(1R)和(R)-α-(1S)非对映体的外消旋体,优选粒度为500nm-6μm,
己体氯氰菊酯(zeta-Cypermethrin),
氯菊酯(Permethrin):3-苯氧基苄基(1RS)-顺,反-3-(2,2-二氯乙烯基)-2,2-二甲基环丙烷羧酸酯,
(RS)氯氟氰菊酯(Cyhalothrin):(RS)-α-氰基-3-苯氧基苄基(Z)-(1RS)-3-(2-氯-3,3,3-三氟丙-1-烯基)-2,2-二甲基环丙烷羧酸酯,
氯氟氰菊酯(lambda-Cyhalothrine):α-氰基-3-苯氧基苄基-3-(2-氯-3,3,3-三氟丙-1-烯基)-2,2-二甲基环丙烷羧酸酯,作为(Z)-(1R,3R),R-酯与(Z)-(1S,3S),S-酯的1:1混合物,
溴氰菊酯(Deltamethrin):(S)-α-氰基-3-苯氧基苄基(1R)-顺-3-(2,2-二溴乙烯基)-2,2-二甲基环丙烷羧酸酯,
乙氰菊酯(Cycloprothrin):(RS)-α-氰基-3-苯氧基苄基(RS)-2,2-二氯-1(4-乙氧基苯基)环丙烷羧酸酯,
氟胺氰菊酯(Fluvalinate):α-氰基-3-苯氧基苄基N-(2-氯-α,α,α,α-三氟-对甲苯基)-D-缬氨酸酯,
氟氯菊酯(Bifenthrin):(2-甲基联苯-3-基甲基)0(Z)-(1RS)-顺-3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基环丙烷羧酸酯,
2-甲基-2-(4-溴二氟甲氧基苯基)丙基(3-苯氧基苄基)醚,
四溴菊酯(Tralomethrin):(S)-α-氰基-3-苯氧基苄基(1R-顺)3((1’RS)(1’,2’,2’,2’-四溴乙基))-二甲基环丙烷羧酸酯,
灭虫硅醚(Silafluofen):4-乙氧基苯基(3-(4-氟-3-苯氧基苯基)丙基)二甲基硅烷,
D-拟除虫菊酯(Fenothrin):3-苯氧基苄基(1R)-顺,反)-菊酸酯,
苯醚氰菊酯(Cyphenothrin):(RS)-α-氰基-3-苯氧基苄基(1R-顺,反)-菊酸酯,D-灭虫菊(resmethrin):5-苄基-3-呋喃基甲基(1R-顺,反)-菊酸酯,
氟丙菊酯(Acrinathrin):(S)-α-氰基-3-苯氧基苄基(1R-顺(Z))-(2,2-二甲基)-3-(氧代-3-(1,1,1,3,3,3-六氟丙基氧基)丙烯基)环丙烷羧酸酯,
氟氯氰菊酯(Cyfluthrin):(RS)-α-氰基-4-氟-3-苯氧基苄基3-(2,2-二氯乙烯基)-2,2-二甲基环丙烷羧酸酯,
七氟菊酯(Tefluthrin):2,3,5,6-四氟-4-甲基苄基(1RS-顺(Z))-3-(2-氯-3,3,3-三氟丙-1-烯基)-2,2-二甲基环丙烷羧酸酯,
四溴菊酯(Tralomethrin):2,3,5,6-四氟苄基(1R-反)-3(2,2-二氯乙烯基)-2,2-二甲基环丙烷羧酸酯,
胺菊酯(Tetramethrin):3,4,5,6-四氢苯二甲酰亚氨基甲基(1RS)-顺,反-菊酸酯,
丙烯菊酯(Allethrin):(RS)-3-烯丙基-2-甲基-4-氧代环戊-2-烯基(1RS)-顺,反-菊酸酯,
炔酮菊酯(Prallethrin):(S)-2-甲基-4-氧代-3-(2-丙炔基)环戊-2-烯基(1R)-顺,反-菊酸酯,
烯炔菊酯(Empenthrin):(RS)-1-乙炔基-2-甲基-2-戊烯基(1R)-顺,反-菊酸酯,
咪炔菊酯(Imiprothrin):2,5-二氧代-3-(丙-2-炔基)咪唑烷-1-基甲基(1R)-顺,反-2,2-二甲基-3-(2-甲基-1-丙烯基)-环丙烷羧酸酯
D-Flamethrin:5-(2-丙炔基)-糠基(1R)-顺,反-菊酸酯和5-(2-丙炔基)糠基2,2,3,3-四甲基环丙烷羧酸酯,
蚊蝇醚(Pyriproxyfen):4-苯氧基苯基(RS)-2-(2-吡啶基氧基)丙基醚,
除虫菊(Pyrethrum),
d-d,反-苯醚氰菊酯(Cyphenothrin):(RS)-α-氰基-3-苯氧基苄基(1RS,3RS;1RS,3SR)-2,2-二甲基-3-(2-甲基丙-1-烯基)环丙烷羧酸酯;
DDT,
氟氯氰菊酯(Cyfluthrin);
氨基甲酸酯化合物如:
棉铃威(Alanycarb):S-甲基-N[[N-甲基-N-[N-苄基-N(2-乙氧基-羰基乙基)氨基-硫]氨基甲酰基]硫代亚氨逐乙酸酯,
噁虫威(Bendiocarb):2,2-二甲基-1,3-苯并二噁茂-4-基-甲基氨基甲酸酯),
甲萘威(Carbaryl):1-萘基N-甲基氨基甲酸酯,
异丙威(Isoprocarb):2-(1-甲基乙基)苯基甲基氨基甲酸酯,
丁硫克百威(Carbosulfan):2,3二氢-2,2-二甲基-7-苯并呋喃基[(二丁基氨基)硫]甲基-氨基甲酸酯,
双氧威(Fenoxycarb):乙基[2-(4-苯氧基苯氧基)乙基]氨基甲酸酯,
噁二唑虫(Indoxacarb):甲基-7-氯-22,3,4°,5-四氢-2-[甲氧基羰基(-4-三氟-甲氧基苯基)],
残杀威(Propoxur):2-异丙基氧基苯酚甲基氨基甲酸酯,
抗蚜威(Pirimicarb):2-二甲基氨基-5,6-二甲基-4-嘧啶基-二甲基氨基甲酸酯,
硫双威(Thiodiocarb):二甲基N,N′(硫代双((甲基亚氨基)羰基氧基)双硫代乙酰亚胺)。
灭多虫(Methomyl):S-甲基N-((甲基氨基甲酰基)氧基)硫代乙酰胺酯,
苯虫威(Ethiofencarb):2-((乙硫基)甲基)苯基甲基氨基甲酸酯,
苯硫威(Fenothiocarb):S-(4-苯氧基丁基)-N,N-二甲基硫代氨基甲酸酯,
杀螟丹(Cartap):S,S′-(2,5二甲基氨基)三亚甲基)双(硫代氨基甲酸酯)氢氯化物,
丁苯威(Fenobucarb):2-仲丁基苯基甲基氨基甲酸酯,
二甲威(XMC):3,5-二甲基苯基-甲基氨基甲酸酯,
灭杀威(Xylylcarb):3,4-二甲基苯基甲基氨基甲酸酯;
涕灭威(aldicarb),丙硫克百威(benfuracarb),虫螨威(carbofuran),丁硫克百威(carbosulfan),灭虫威(methiocarb),丁苯威(fenobucarb),甲氨叉威(oxamyl),灭多虫(methomyl),硫双威(thiodicarb)和唑蚜威(triazamate);
有机含磷化合物如:
敌百虫(trichlorfon):磷酸,(2,2,2-三氯-1-羟基乙基)-二甲基酯,
杀螟松(fenitrothion):O,O-二甲基O-(4-硝基-间甲苯基)硫代磷酸酯,
二嗪农(diazinon):O,O-二乙基-O-(2-异丙基-6-甲基-4-嘧啶基)硫代磷酸酯,
打杀磷(Pyridaphenthion):O-(1,6二氢-6-氧代-1-苯基哒嗪-3-基)O,O-二乙基硫代磷酸酯,
乙基虫螨磷(Pirimiphos-Etyl):O,O-二乙基O-(2-(二乙基氨基)6-甲基-嘧啶基)硫代磷酸酯,
虫螨磷(Pirimiphos-methyl):O-[2-(二乙基氨基)-6-甲基-4嘧啶基]O,O-二甲基硫代磷酸酯,
氧嘧啶磷(Etrimphos):O-6-乙氧基-2-乙基-嘧啶-4-基-O,O-二甲基-硫代磷酸酯,
倍硫磷(Fenthion):O,O-二甲基-O-[-3-甲基-4-(甲硫基)苯基硫代磷酸酯,
辛硫磷(Phoxim):2-(二乙氧基硫代膦基氧基亚氨基)-2-苯基乙腈,
毒死蜱(Chlorpyrifos):O,O-二乙基-O-(3,5,6-三氯-2-吡啶基)硫代磷酸酯Chlorpyriphos-methyl:O,O-二甲基O-(3,5,6-三氯-2-吡啶基)硫代磷酸酯,
杀螟腈(Cyanophos):O,O-二甲基O-(4氰基苯基)硫代磷酸酯,
吡唑硫磷(Pyraclofos):(R,S)[4-氯苯基)-吡唑-4-基]-O-乙基-S-正丙基硫代磷酸酯,
高灭磷(Acephate):O,S-二甲基乙酰基硫代磷酰胺,
唑啶磷(Azamethiphos):S-(6-氯-2,3-二氢-氧代-1,3-噁唑并[4,5-b]吡啶-3-基甲基硫代磷酸酯,
马拉硫磷(Malathion):巯基琥珀酸二乙基酯的O,O-二甲基二硫代磷酸酯,
硫甲双磷(Temephos):(O,O′(硫代二-4-1-亚苯基)O,O,O,O-四甲基二硫代磷酸酯,
乐果(Dimethoate):((O,O-二甲基S-(正甲基氨基甲酰基乙基)二硫代磷酸酯,
安果(Formothion):S[2-甲酰基甲基氨基]-2-氧代乙基]-O,O-二甲基二硫代磷酸酯,
稻丰散(Phenthoate):O,O-二甲基S-(α-乙氧基羰基苄叉)-二硫代磷酸酯,
碘硫磷(Iodofenphos):O-(2,5-二氯-4-碘苯基)-O,O-二甲基-二硫代磷酸酯,
久效磷(monocrotophos),甲胺磷(methamidophos),甲基对硫磷(parathion-methyl),丙溴磷(profenfos)和特丁磷(terbufos);
对成虫蚊子具有灭菌效力的杀虫剂如:
1-(α-(氯-α-环丙基亚苄基氨基-氧基)-对甲苯基)-3-(2,6-二氟苯甲酰基)脲,氟脲杀(diflubenzuron):N-(((3,5-二氯-4-(1,1,2,2-四氟乙氧基)苯基氨基)羰基)2,6-二氟苯甲酰胺,
杀虫隆(triflumuron):2-氯-N-(((4-(三氟甲氧基)苯基)-氨基-)羰基)苯甲酰胺,
或三嗪如N-环丙基-1,3,5-三嗪-2,4,6-三胺;
烟碱乙酰胆碱受体拮抗剂如:吡虫清(acetamiprid)、噻虫胺(clothianidin)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)、硝胺烯啶(nitenpyram)、噻虫啉(thiacloprid)、噻虫嗪(thiamethoxam)、烟碱(nicotine)、杀虫磺(bensultap)、硫环杀(thiocyclam)、多杀菌素(spinosyns);
氯通道活化剂如:齐墩螨素(Abamectin)、甲氨基阿维菌素苯甲酸盐(emamectin benzoate)、米尔螨素(milbemectin);
保幼激素类似物如:蒙五一二(hydroprene)、蒙七七七(kinoprene)、蒙五一五(Methoprene)、双氧威(fenoxycarb)、蚊蝇醚(pyriproxyfen);
选择进料阻断剂如:冰晶石(cryolite)、拒嗪酮(pymetrozine)、氟啶虫酰胺(flonicamid);
螨生长抑制剂如:四螨嗪(clofentezine)、噻螨酮(hexythiazox)、特苯噁唑(etoxazole);
微生物杀虫剂如:苏云金芽孢杆菌(Bacillus thuringiensis)、苏云金杆菌占泽亚种(B.t.Aizawai)、苏云金杆菌库尔斯塔克亚种(B.t.kurstaki)、B.t.tenebrionis、球形芽孢杆菌(B.Sphaericus);
氧化磷酸化抑制剂、ATP形成干扰剂如:杀螨硫隆(diafenthiuron)、唑环锡(azocyclotin)、三环锡(cyhexatin)、杀螨锡(fenbutatin oxide)、克螨特(propargite)、三氯杀螨砜(tetradifon);
氧化磷酸化解偶联剂如:氟唑虫清(Chlorfenapyr)、DNOC(4,6-二硝基-邻甲酚);
几丁质生物合成抑制剂如:定虫隆(chlorfluazuron)、氟啶蜱脲(fluazuron)、氟脲杀(diflubenzuron)、氟虫脲(flufenoxuron)、氟铃脲(hexaflumuron)、双苯氟脲(novaluron)、多氟脲(noviflumuron)、伏虫隆(teflubenzuron)、杀虫隆(triflumuron)、噻嗪酮(buprofezin);
蜕皮激素拮抗剂和蜕皮干扰剂如:灭蝇胺(cyromazine)、艾扎丁(azadirachtin)、环虫酰肼(chro-mafenozide)、特丁苯酰肼(halofenozide)、甲氧苯酰肼(methoxyfenozide)、双苯酰肼(tebufenazide);
真蛸胺(octopamineergic)拮抗剂如:虫螨脒(amitraz);
耦合位II电子转移抑制剂如:灭蚁腙(hydramethylnon)、灭螨醌(acequinocyl)、嘧螨酯(fluacrypyrim);
耦合位I电子转移抑制剂如:喹螨醚(fenazaquin)、唑螨酯(fenpyroximate)、嘧胺苯醚(pyrimidifen)、哒螨酮(pyridaben)、吡螨胺(tebufenpyrad)、唑虫酰胺(tolfenpyrad)、鱼藤酮(rotenone);
电压依赖性钠通道阻断剂如:噁二唑虫(indoxacarb);
类脂合成抑制剂如:螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen);
线粒体络合物IV电子转移抑制剂如:磷化物、氰化物、膦;
二乙基溴乙酰胺抑制剂如:联苯肼酯(bifenazate);
乌头酸酶抑制剂如:fluoroacetyate;
增效剂如:增效醚(pieronyl butoxide)、DEF((BuS)2P(CO)SBu);
鱼尼汀(Ryanodine)受体调节剂:氟虫酰胺(flubendiamide);
具有未知作用模式的化合物如:苯螨特(benzoximate)、灭螨猛(chinomethionat)、开乐散(dicofol)、啶虫丙醚(pyridalyl);
混杂的非特异抑制剂如:硼砂、吐酒石。
适合的驱避剂优选选自N,N-二乙基-间-甲苯酰胺(DEET)、N,N-二乙基苯基乙酰胺(DEPA)、1-(3-环己-1-基-羰基)-2-甲基胡椒碱、(2-羟基甲基环己基)乙酸内酯、2-乙基-1,3-己二醇、避蚊酮(indalone)、甲基新癸酰胺(MNDA),不用于昆虫防治的拟除虫菊酯如{(+/-)-3-烯丙基-2-甲基-4-氧代环戊-2-(+)-烯基-(+)-反-菊酸酯(Esbiothrin),衍生于或等同于植物提取物的驱避剂如苎烯、丁子香酚、(+)-eucamalol(1)、(-)-1-epi-eucamalol或来自植物的粗植物提取物如斑皮桉(Eucalyptus maculata)、白背蔓荆(Vitexrotundifolia)、Cymbopogan martinii、Cymbopogan citratus(柠檬草)、Cymopogan nartdus(香茅)、IR3535(丁基乙酰基氨基丙酸乙酯)、icaridin(1-哌啶羧酸2-(2-羟基乙基)-1-甲基丙基酯)。
适合的软体动物杀灭剂例如为贝螺杀(niclosamide)。
适合的杀真菌剂例如为:
唑类如双苯三唑醇(bitertanol)、糠茵唑(bromoconazole)、环唑醇(cyproconazole)、噁醚唑(difenoconazole)、烯唑醇(dinitroconazole)、氧唑菌(epoxiconazole)、腈苯唑(fenbuconazole)、喹唑菌酮(fluquiconazole)、氟硅唑(flusilazole)、粉唑醇(flutriafol)、己唑醇(hexaconazole)、烯菌灵(imazalil)、环戊唑醇(ipconazole)、环戊唑菌(metconazole)、腈茵唑(myclobutanil)、戊菌唑(penconazole)、丙环唑(propiconazole)、丙氯灵(prochloraz)、丙硫菌唑(prothioconazole)、硅氟唑(simeconazole)、戊唑醇(tebuconazole)、氟醚唑(tetraconazol)、三唑酮(triadimefon)、唑菌醇(triadimenol)、氟菌唑(triflumizol)、戊叉唑菌(triticonazol);
嗜球果伞素类(strobilurins),如腈嘧茵酯(azoxystrobin)、醚菌胺(dimoxystrobin)、氟嘧茵酯(fluoxastrobin)、亚胺茵(kresoxim-methyl)、叉氨苯酰胺(metominostrobin)、肟醚茵胺(orysastrobin)、啶氧茵酯(picoxystrobin)、唑菌胺酯(pyraclostrobin)和肟茵酯(trifloxystrobin);
酰基丙氨酸类,如苯霜灵(benalaxyl)、甲霜灵(metalaxyl)、精甲霜灵(mefenoxam)、甲呋酰胺(ofurace)、噁霜灵(oxadixyl);
胺衍生物,例如4-十二烷基-2,6-二甲基吗啉(aldimorph)、多果定(dodine)、吗茵灵(dodemorph)、丁苯吗啉(fenpropimorph)、苯锈啶(fenpropidin)、双胍盐(guazatine)、双胍辛醋酸盐(iminoctadine)、螺噁茂胺(spiroxamine)、克啉茵(tridemorph);
苯胺基嘧啶类,例如二甲嘧菌胺(pyrimethanil)、嘧茵胺(mepanipyrim)、环丙嘧啶(cyprodinil);
二羧酰亚胺类,如异丙定(iprodione)、甲菌利(myclozolin)、杀菌利(procymidone)、烯茵酮(vinclozolin);
肉桂酰胺及类似物,如烯酰吗啉(dimethomorph)、氟联苯茵(flumetover)、氟吗啉(flumorph);
抗菌素,如放线茵酮(cycloheximide)、灰黄霉素(griseofulvin)、春雷素(kasugamycin)、多马霉素(natamycin)、多氧霉素(polyoxin)、链霉素(streptomycin);
二硫代氨基甲酸盐类,福美铁(ferbam)、代森钠(nabam)、代森锰(maneb)、代森锰锌(mancozeb)、威百亩(metam)、代森联(metiram)、甲基代森锌(propineb)、福代锌(polycarbamate)、福美双(thiram)、福美锌(ziram)、代森锌(zineb);
杂环化合物,如敌菌灵(anilazine)、苯菌灵(benomyl)、啶酰茵胺(boscalid)、多茵灵(carbendazim)、萎锈灵(carboxin)、氧化萎锈灵(oxycarboxin)、氰霜唑(cyazofamid)、棉隆(dazomet)、二噻农(dithianon)、噁唑酮茵(famoxadone)、咪唑菌酮(fenamidone)、异嘧茵醇(fenarimol)、麦穗宁(fuberidazole)、氟酰胺(flutolanil)、呋吡唑灵(furametpyr)、稻瘟灵(isoprothiolane)、丙氧灭绣胺(mepronil)、氟苯嘧啶醇(nuarimol)、氟吡菌胺(picobenzamid)、噻菌灵(probenazol)、丙氧喹啉(proquinazid)、啶斑肟(pyrifenox)、咯喹酮(pyroquilon)、喹氧灵(quinoxyfen)、硅噻茵胺(silthiofam)、涕必灵(thiabendazol)、溴氟唑菌(thifluzamid)、甲基托布津(thiophanate-methyl)、噻酰茵胺(tiadinil)、三环唑(tricyclazol)、嗪胺灵(triforine)M;
硝基苯基衍生物,如乐杀螨(binapacryl)、敌螨普(dinocap)、敌螨通(dinobuton)、异丙消(nitrothal-isopropyl);
苯基吡咯类,如拌种咯(fenpiclonil)、氟噁菌(fludioxonil);
无机化合物,如波尔多混合液(Bordeaux mixture)、乙酸铜、氢氧化铜、辛酸铜、氯氧化铜、硫酸铜、硫酸铜(三碱性)、硫;
次磺酸衍生物,如敌茵丹(captafol)、克菌丹(captan)、抑茵灵(dichlofluanid)、灭菌丹(folpet)、对甲抑菌灵(tolylfluanid);
其他杀真菌剂,如噻二唑素(acibenzolar-S-methyl)、苯噻茵胺(benthiavalicarb)、氯环丙酰胺(carpropamid)、百菌清(chlorothalonil)、环氟菌胺(cyflufenamid)、清茵脲(cymoxanil)、棉隆(dazomet)、哒菌清(diclomezin)、双氯氰菌胺(diclocymet)、diclofluanid、乙霉威(diethofencarb)、克瘟散(edifenphos)、噻唑茵胺(ethaboxam)、环酰茵胺(fenhexamid)、薯瘟锡(fentin-Acetat)、氰茵胺(fenoxanil)、嘧茵腙(ferimzone)、氟啶胺(fluazinam)、藻茵磷(fosetyl)、乙膦铝(fosetyl-aluminum)、磷酸、异丙菌胺(iprovalicarb)、六氯苯(hexachlorobenzene)、苯菌酮(metrafenon)、戊菌隆(pencycuron)、百维灵(propamocarb)、四氯苯酞(phthalid)、甲基立枯磷(tolclofos-methyl)、五氯硝基苯(quintozene)、苯酰茵胺(zoxamide)。
在其他优选实施方案中,农药为至少一种优选式I的N-芳基肼衍生物或其对映体或盐:
其中:
A为C-R2或N;
B为C-R3或N;
D为C-R4或N;
条件是A、B或D至少之一必须不同于N;
Z为卤素、CN、NO2、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基或C1-C6卤代烷氧基;
n为0、1或2的整数;
Q为:
其中:
R为氢;
任选由一个或多个卤素取代的C1-C10烷基;C3-C6环烷基;C1-C4烷氧基;C1-C4卤代烷氧基;(C1-C4烷基)SOx;(C1-C4卤代烷基)SOx;任选由1-3个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、(C1-C4烷基)SOx、(C1-C4卤代烷基)SOx、NO2或CN基团取代的苯基;任选由1-3个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、(C1-C4烷基)SOx、(C1-C4卤代烷基)SOx、NO2或CN基团取代的苯氧基;任选由一个或多个卤素、C1-C6烷基、C1-C6卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、(C1-C4烷基)SOx、(C1-C4卤代烷基)SOx取代的C3-C12环烷基;任选由1-3个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、NO2或CN基团取代的苯基;任选由1-3个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、NO2或CN基团取代的苯氧基;或
任选由1个或多个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、NO2或CN基团取代的苯基;或
CR17R18R19;
R17和R18各自独立地为可由1-3个卤原子取代的C1-C6烷基、C3-C6链烯基、C3-C6炔基或C3-C6环烷基;
R19为氢或C1-C6烷基;
R1和R7各自独立地为氢或C1-C4烷基;
R5和R6各自独立地为氢;
任选由1个或多个卤素、羟基、C1-C4烷氧基、(C1-C4烷基)SOx、CONR8R9、CO2R10、R11、R12取代的C1-C10烷基;
任选由1-3个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、NO2或CN基团取代的C3-C6环烷基;
任选由1个或多个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、NO2或CN基团取代的苯基;
任选由1个或多个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、NO2或CN基团取代的吡啶基;
任选由1个或多个卤素、羟基、C1-C4烷氧基、(C1-C4烷基)SOx、CONR8R9、CO2R10、R11、R12取代的C3-C10链烯基;
任选由1-3个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、NO2或CN基团取代的C3-C6环烷基;
任选由1个或多个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、NO2或CN基团取代的苯基;
任选由1个或多个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、NO2或CN基团取代的吡啶基;
任选由1个或多个卤素、羟基、C1-C4烷氧基、(C1-C4烷基)SOx、CONR8R9、CO2R10、R11、R12取代的C3-C10炔基;
任选由1-3个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、NO2或CN基团取代的C3-C6环烷基;
任选由1个或多个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、NO2或CN基团取代的苯基;
任选由1个或多个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、NO2或CN基团取代的吡啶基;
任选由1个或多个卤素、羟基、C1-C4烷氧基、(C1-C4烷基)SOx、CONR8R9、CO2R10、R11、R12取代的C3-C12环烷基;
任选由1-3个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、NO2或CN基团取代的C3-C6环烷基;
任选由1个或多个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、NO2或CN基团取代的苯基;
任选由1个或多个卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基、NO2或CN基团取代的吡啶基;
R5和R6可一起形成由如下结构表示的环:
R2、R3和R4各自独立地为氢、卤素、CN、NO2、(C1-C4烷基)SOx、(C1-C4卤代烷基)SOx、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基或C1-C6卤代烷氧基;
R8、R9和R10各自独立地为氢或C1-C4烷基;
R11为NR13R14、
R12为:
R13、R14、R15和R16各自独立地为氢或C1-C4烷基;
X为O、S或NR15;
X1为氯、溴或氟;
r为0或1的整数;
p和m各自独立地为0、1、2或3的整数,条件是p、m或r仅一个可以为0且其他条件是p+m+r必须为4、5或6;
X为0、1或2的整数。
在优选实施方案中,式I中的Q为:
更优选,至少一种N-芳基肼衍生物为式Ia的化合物或其对映体或盐:
其中:
R4为氯或三氟甲基;
Z1和Z2各自独立地为氯或溴;
R6为可由1-3个卤原子取代的C1-C6烷基、C3-C6链烯基、C3-C6炔基或C3-C6环烷基或由C1-C4烷氧基取代的C2-C4烷基;
R17和R18各自独立地为由1-3个卤原子取代的C1-C6烷基、C3-C6链烯基、C3-C6炔基或C3-C6环烷基;
R19为氢或C1-C6烷基。
在上述式I和式Ia的定义中,取代基具有如下含义:
术语“卤素”将意指氟、氯、溴和碘。
这里所用术语“烷基”指具有1-4或1-6个碳原子的支化或非支化饱和烃基,尤其是C1-C6烷基,例如甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、己基、1,1-二甲基丙基、1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基和1-乙基-2-甲基丙基。
“烷氧基”指在烷基中任何键处通过氧连接结合的具有1-4个碳原子的直链或支化烷基(甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基)。实例包括甲氧基、乙氧基、丙氧基和异丙氧基。
“环烷基”指单环3-6元饱和碳原子环,即环丙基、环丁基、环戊基和环己基。
就式I化合物的意欲目的而言,特别优选如下含义的取代基,每种情况下基于它们本身或组合:
优选其中R4为三氟甲基的式I化合物。
另外优选其中Z1和Z2都为氯的式I化合物。
此外,优选其中R6为C1-C6烷基,尤其是乙基的式I化合物。
另外优选其中R17和R18都为甲基的式I化合物。
此外,优选其中R17和R18形成未取代或由1-3个卤原子,尤其是氯和溴取代的环丙基环的式I化合物。
此外,特别优选其中R17和R18形成由2个卤原子取代的环丙基环的式I化合物。
此外,特别优选其中R17和R18形成由2个氯原子取代的环丙基环的式I化合物。
特别优选其中R17和R18形成2,2-二氯环丙基环的式I化合物。
另外优选其中R19为C1-C6烷基,尤其是甲基的式I化合物。
特别优选其中R17、R18和R19都为甲基的式I化合物。
此外,特别优选其中R17、R18和R19形成结构部分1-甲基-2,2-二氯环丙基的式I化合物。
另外优选式I化合物或其对映体或盐,其中:
R4为三氟甲基;
Z1和Z2各自独立地为氯或溴;
R6为C1-C6烷基;
R17和R18为C1-C6烷基或可一起形成由1或2个卤原子取代的C3-C6环烷基;
R19为C1-C6烷基。
特别优选N-乙基-2,2-二甲基丙酰胺-2-(2,6-二氯-α,α,α-三氟-对甲苯基)腙和N-乙基-2,2-二氯-1-甲基环丙烷甲酰胺、2-(2,6-二氯-α,α,α-三氟-对甲苯基)腙。
此外,就在本发明中的用途而言,特别优选式Ia-1的化合物(N-乙基-2,2-二甲基丙酰胺-2-(2,6-二氯-α,α,α-三氟-对甲苯基)-腙):
此外,就在本发明中的用途而言,特别优选式Ia-2的化合物(N-乙基-2,2-二氯-1-甲基环丙烷甲酰胺-2-(2,6-二氯-α,α,α-三氟-对甲苯基)-腙):
关于它们的用途,特别优选汇编于下表中的化合物Ia-A。此外,表中对于取代基所提到的基团本身,与提到它们的组合无关,为所述取代基的特别优选实施方案。
关于它们的用途,还特别优选下表化合物的盐酸、马来酸、二马来酸、富马酸、二富马酸、甲烷次磺酸、甲烷磺酸和琥珀酸加合物。
表A:
编号 | R6 | R17 | R18 | R19 | Z1 | Z2 |
A-1 | CH3 | 2,2-二氯环丙基 | H | Cl | Cl | |
A-2 | CH3 | 2,2-二溴环丙基 | H | Cl | Cl | |
A-3 | CH3 | CH3 | CH3 | CH3 | Cl | Cl |
A-4 | CH3 | CH2CH3 | CH3 | CH3 | Cl | Cl |
A-5 | CH3 | 2,2-二氯环丙基 | CH3 | Cl | Cl | |
A-6 | CH3 | 2,2-二溴环丙基 | CH3 | Cl | Cl | |
A-7 | CH3 | 2,2-二氯环丙基 | H | Br | Br | |
A-8 | CH3 | 2,2-二溴环丙基 | H | Br | Br | |
A-9 | CH3 | CH3 | CH3 | CH3 | Br | Br |
A-10 | CH3 | CH2CH3 | CH3 | CH3 | Br | Br |
A-11 | CH3 | 2,2-二氯环丙基 | CH3 | Br | Br | |
A-12 | CH3 | 2,2-二溴环丙基 | CH3 | Br | Br | |
A-13 | CH2CH3 | 2,2-二氯环丙基 | H | Cl | Cl | |
A-14 | CH2CH3 | 2,2-二溴环丙基 | H | Cl | Cl | |
A-15 | CH2CH3 | CH3 | CH3 | CH3 | Cl | Cl |
A-16 | CH2CH3 | CH2CH3 | CH3 | CH3 | Cl | Cl |
A-17 | CH2CH3 | 2,2-二氯环丙基 | CH3 | Cl | Cl | |
A-18 | CH2CH3 | 2,2-二溴环丙基 | CH3 | Cl | Cl | |
A-19 | CH2CH3 | 2,2-二氯环丙基 | H | Br | Br | |
A-20 | CH2CH3 | 2,2-二溴环丙基 | H | Br | Br | |
A-21 | CH2CH3 | CH3 | CH3 | CH3 | Br | Br |
A-22 | CH2CH3 | CH2CH3 | CH3 | CH3 | Br | Br |
A-23 | CH2CH3 | 2,2-二氯环丙基 | CH3 | Br | Br | |
A-24 | CH2CH3 | 2,2-二溴环丙基 | CH3 | Br | Br | |
A-25 | CH2CH2CH3 | 2,2-二氯环丙基 | H | Cl | Cl | |
A-26 | CH2CH2CH3 | 2,2-二溴环丙基 | H | Cl | Cl | |
A-27 | CH2CH2CH3 | CH3 | CH3 | CH3 | Cl | Cl |
A-28 | CH2CH2CH3 | CH2CH3 | CH3 | CH3 | Cl | Cl |
A-29 | CH2CH2CH3 | 2,2-二氯环丙基 | CH3 | Cl | Cl | |
A-30 | CH2CH2CH3 | 2,2-二溴环丙基 | CH3 | Cl | Cl | |
A-31 | CH2CH2CH3 | 2,2-二氯环丙基 | H | Br | Br | |
A-32 | CH2CH2CH3 | 2,2-二溴环丙基 | H | Br | Br |
A-33 | CH2CH2CH3 | CH3 | CH3 | CH3 | Br | Br |
本发明农药组合物的优选杀虫剂和/或驱避剂可以为一种或混合物。一个实施方案为具有不同分子大小和/或不同理化性能的农药的混合物。优选的农药混合物为具有相似扩散/迁移性能的杀虫剂和/或驱避剂的混合物。这组杀虫剂和/或驱避剂可包括合成除虫菊酯类如甲体氯氰菊酯(alphacypermethrin)、氟氯氰菊酯(cyfluthrin)、溴氰菊酯(deltamethrin)、醚菊酯(etofenprox)和氯菊酯(permethrin),其他拟除虫菊酯类如氟氯菊酯(bifenthrine),和非拟除虫菊酯类如丁硫克百威(carbosulphane)和氟唑虫清(chlorfenapyr)。在优选实施方案中,使用甲体氯氰菊酯(alphacypermethrin)与氟唑虫清(Chlorfenapyr)的混合物。
农药也可作为一种水基农药浓缩物或溶剂,优选有机溶剂基农药浓缩物或基于水与溶剂,优选有机溶剂的混合物的浓缩物包括在农药组合物中。水基浓缩物可以为悬浮液或如果需要的话包含适合分散剂的分散体形式或包含乳化剂、溶剂和如果合适的话助溶剂的乳液形式。纳米粒状农药配制剂可通过将农药的固体溶液溶于极性有机溶剂如聚乙烯吡咯烷酮(PVP)中而得到。水基或溶剂基浓缩物中的农药的浓度通常为0.5-60%,优选1-40%,更优选3-20%。
水基悬浮液或分散体中农药粒度通常为50nm-20μm,优选50nm-8μm,更优选50nm-4μm,最优选50nm-500nm。
聚合粘合剂(组分B)
聚合粘合剂(组分B)可以为本领域已知的任何聚合粘合剂。尤其优选用于浸渍或涂覆织物材料或塑料材料领域的聚合粘合剂。
优选的粘合剂例如为可通过至少一种选自如下的烯属不饱和单体聚合,优选自由基聚合而得到的粘合剂:丙烯酸酯,优选丙烯酸的C1-C12酯或具有交联酯官能的丙烯酸酯,甲基丙烯酸酯,优选甲基丙烯酸的C1-C12酯或具有交联酯官能的甲基丙烯酸酯,丙烯酸、甲基丙烯酸、丙烯腈、马来酸、马来酸酐、马来酸的单或二酯、苯乙烯、苯乙烯衍生物如甲基苯乙烯、丁二烯、乙酸乙烯酯、乙烯醇、乙烯、丙烯、烯丙醇、乙烯基吡咯烷酮、氯乙烯和二氯乙烯。
聚合,优选自由基聚合可例如作为本体聚合、气相聚合、溶剂聚合、乳液聚合或悬浮液聚合而进行。
通过上述单体的聚合,优选自由基聚合制备适合聚合物的条件和其他需要和适合组分为本领域技术人员已知的。
通过上述单体的聚合,优选自由基聚合得到的适合聚合粘合剂为优选选自聚丙烯酸酯、聚甲基丙烯酸酯、聚丙烯腈、聚马来酸酐、聚马来酸、聚马来酸酯和聚马来酸酰胺、聚苯乙烯、聚(甲基)苯乙烯、聚丁二烯、聚乙酸乙烯酯、聚乙烯醇的均聚物或共聚物以及通过上述单体组的至少两种不同烯属不饱和单体聚合得到的共聚物和所述均聚物和/或共聚物的配混物,例如聚(苯乙烯-丙烯酸酯)、聚(苯乙烯-丁二烯)、乙烯-丙烯酸酯共聚物、乙烯-乙酸乙烯酯共聚物,其可以部分或完全水解。
其他适合的聚合粘合剂选自聚氨酯和/或聚异氰脲酸酯,包含聚氨酯和/或聚异氰脲酸酯的配混物,优选包含聚氨酯和/或聚异氰脲酸酯和聚碳酸酯的配混物;矿物蜡、锆蜡、硅氧烷、聚硅氧烷、氟化聚丙烯酸酯和甲基丙烯酸酯、氟硅氧烷和碳氟树脂(例如公开于WO 01/37662和WO 92/16103中);三聚氰胺甲醛缩合树脂、羟甲基脲衍生物;和可固化聚酯;或包含至少一种所述聚合粘合剂的配混物或制剂。
上述聚合粘合剂为本领域已知且为市售或可通过本领域已知的制备方法制备。
其他适合的聚合粘合剂为包含增稠剂如羧基甲基纤维素和任选交联剂如三聚氰胺树脂的配制剂中的聚乙酸乙烯酯;可固化聚酯;包含反应性硅氧烷(有机聚硅氧烷)、聚乙烯醇、聚乙酸乙烯酯或丙烯酸共聚物的配制剂。交联可热或通过UV光或双固化技术进行。任选催化剂或交联剂可与聚合粘合剂一起使用。
优选的聚合粘合剂选自丙烯酸粘合剂和聚氨酯和/或聚异氰脲酸酯粘合剂。
最优选的聚会粘合剂为任选氟化的丙烯酸粘合剂。尤其优选的丙烯酸粘合剂在下面提到(组分B1)。
丙烯酸粘合剂(组分B1)
最优选为可以是均聚物或共聚物的丙烯酸粘合剂,其中优选共聚物。
丙烯酸粘合剂优选通过至少一种式II单体作为组分B1A自由基聚合,更优选自由基乳液聚合而得到:
其中:
R20、R21和R22独立地选自任选氟取代且可以为线性或支化的C1-C10烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基,优选C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基;取代或未取代的芳基,优选取代或未取代的C6-C10芳基,更优选取代或未取代的C6芳基,例如苯基或甲苯基;
R20和R21可另外为H。
优选R20为H或甲基。R21优选H;R22优选甲基、乙基、正丁基或2-乙基己基。
更优选R20为H或甲基,R21为H且R22为甲基、乙基、正丁基或2-乙基己基。
最优选式II单体(组分BA)选自丙烯酸2-乙基己基酯、丙烯酸正丁基酯、丙烯酸甲酯、甲基丙烯酸甲酯和乙基丙烯酸甲酯。最优选使用可通过至少两种不同的式II丙烯酸单体聚合得到的共聚物。
最优选丙烯酸粘合剂用作可通过如下组分乳液聚合而得到的组分B:
b1a)至少一种式II单体作为组分B1A:
其中:
R20、R21和R22独立地选自可以为线性或支化的C1-C10烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基,优选C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基;取代或未取代的芳基,优选取代或未取代的C6-C10芳基,更优选取代或未取代的C6芳基,例如苯基或甲苯基;
R20和R21可另外为H。
优选R20为H或甲基。R21优选H;R22优选甲基、乙基、正丁基或2-乙基己基。
更优选R20为H或甲基。R21为H;R22为甲基、乙基、正丁基或2-乙基己基。
B1b)至少一种式III单体作为组分B1B:
其中:
R23、R24、R25和R26独立地选自H、可以为线性或支化的C1-C10烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基和正癸基;优选R23、R24、R25和R26选自H、可以为线性或支化的C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基;取代或未取代的芳基,优选取代或未取代的C6-C10芳基,更优选取代或未取代的C6芳基,例如苯基或甲苯基;
更优选R23为H或甲基,R24、R25和R26优选相互独立地为H;
最优选R23为H或甲基且R24、R25和R26为H;
b1c)任选至少一种式IV单体作为组分B1C:
其中:
R27和R28独立地选自H、可以为线性或支化的C1-C10烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基和正癸基;优选R27和R28选自H、可以为线性或支化的C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基;取代或未取代的芳基,优选取代或未取代的C6-C10芳基,更优选取代或未取代的C6芳基,例如苯基或甲苯基;
最优选R27和R28为H;
X选自H、OH、NH2、OR29OH、缩水甘油基、羟基丙基、
下式的基团:
其中:
R30选自可以为线性或支化的C1-C10烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基;优选可以为线性或支化的C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基;取代或未取代的芳基,优选取代或未取代的C6-C10芳基,更优选取代或未取代的C6芳基,例如苯基或甲苯基;
R29选自C1-C10亚烷基,例如亚甲基、亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基、亚癸基;优选C1-C4亚烷基,例如亚甲基、亚乙基、亚丙基、亚丁基;取代或未取代的亚芳基,优选取代或未取代的C6-C10亚芳基,更优选取代或未取代的C6亚芳基,例如亚苯基;最优选X为乙酰乙酰基;
b1d)可与上述单体共聚的其他单体,其选自:
b1d1)极性单体,优选(甲基)丙烯腈和/或(甲基)丙烯酸甲酯作为组分B1D1;和/或
b1d2)非极性单体,优选苯乙烯和/或α-甲基苯乙烯作为组分B1D2。丙烯酸粘合剂优选可通过如下组分乳液聚合得到:
b1a)10-95重量%,优选30-95重量%,更优选50-90重量%组分B1A;
b1b)1-5重量%组分B1B;
b1c)0-5重量%,优选1-4重量%,更优选0.2-3重量%组分B1C;
b1d)选自如下的可与上述单体共聚的其他单体:
b1d1)0-30重量%,优选0-25重量%,更优选5-20重量%组分B1D1;和/或
b1d2)0-40重量%,优选0-30重量%,更优选5-20重量%组分B1D2;其中组分B1A、B1B和任选B1C和B1D之和为100重量%。
在其他优选实施方案中,丙烯酸粘合剂优选可通过如下组分乳液聚合得到:
b1a)10-95重量%,优选30-95重量%,更优选50-90重量%至少一种如上定义的丙烯酸粘合剂(组分B1A),其包含:
b1a1)基于丙烯酸粘合剂10-90重量%,优选15-85重量%,更优选30-85重量%丙烯酸正丁酯;
b1a2)基于丙烯酸粘合剂10-90重量%,优选12-85重量%,更优选15-65重量%至少一种不同于丙烯酸正丁酯的式II单体;
b1b)基于丙烯酸粘合剂1-5重量%至少一种式III单体(组分B1B);
b1c)基于丙烯酸粘合剂0-5重量%,优选0.1-4重量%,更优选0.2-3重量%至少一种式III单体(组分B1C);
b1d)选自如下的可与上述单体共聚的其他单体(组分B1D):
b1d1)基于丙烯酸粘合剂0-30重量%,优选0-25重量%,更优选5-20重量%至少一种极性单体,优选(甲基)丙烯腈和/或(甲基)丙烯酸甲酯(组分B1D1);和/或
b1d2)基于丙烯酸粘合剂0-40重量%,优选0-30重量%,更优选5-20重量%至少一种非极性单体,优选苯乙烯和/或α-甲基苯乙烯(组分B1D2);
其中组分B1A、B1B和任选B1C和B1D之和为100重量%。
丙烯酸粘合剂可包含本领域技术人员已知的其他添加剂,例如成膜剂和增塑剂,例如己二酸酯、邻苯二甲酸酯、丁基二乙二醇、可通过二羧酸与可以为线性或支化的醇反应而制备的二酯的混合物。适合的二羧酸和醇为本领域技术人员已知的。
当使得杀虫剂以可控速率连续释放时,包含本发明所述粘合剂的杀虫组合物为耐气候性的,以提供杀虫剂的所需生物利用率。不需要加入例如分散剂,分散剂在将组合物施用于织物上以后并一旦润湿织物降低粘合剂赋予杀虫剂的疏水性使得有限的杀虫剂释放。因此,优选本发明杀虫剂组合物除聚合粘合剂外不包含分散剂。
最优选丙烯酸粘合剂可通过如下组分乳液聚合而得到:
b1a)50-90重量%至少一种式II单体作为组分B1A:
其中:
R20为H或甲基,R21为H,R22为甲基、乙基、正丁基或2-乙基己基,作为组分B1A,最优选组分B1A为丙烯酸2-乙基己基酯、丙烯酸正丁基酯、丙烯酸甲酯、甲基丙烯酸甲酯或乙基丙烯酸甲酯;
b1b)1-5重量%至少一种式III单体作为组分B1B:
其中R23为H或甲基,R24、R25和R26各自为氢;
b1c)1-10重量%,优选1-7重量%,更优选2-5重量%至少一种式IV单体作为组分B1C:
其中R27和R28为氢,X为H、OH、NH2、OR29OH、缩水甘油基或下式的基团:
其中R30选自可以为线性或支化的C1-C10烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基;优选可以为线性或支化的C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基;取代或未取代的芳基,优选取代或未取代的C6-C10芳基,更优选取代或未取代的C6芳基,例如苯基或甲苯基;
R29选自C1-C10亚烷基,例如亚甲基、亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基、亚癸基;优选C1-C4亚烷基,例如亚甲基、亚乙基、亚丙基、亚丁基;取代或未取代的亚芳基,优选取代或未取代的C6-C10亚芳基,更优选取代或未取代的C6亚芳基,例如亚苯基;最优选X为乙酰乙酰基;
b1d)可与上述单体共聚的其他单体,其选自:
b1d1)0-30重量%,优选0-25重量%,更优选5-20重量%组分B1D1,优选(甲基)丙烯腈和/或(甲基)丙烯酸甲酯;和/或
b1d2)0-40重量%,优选0-30重量%,更优选5-20重量%组分B1D2,优选苯乙烯和/或α-甲基苯乙烯;
其中组分BA、BB和任选BC和BD之和为100重量%。
在其他最优选实施方案中,作为BA的正丁基丙烯酸酯的量为30-90重量%,其他组分B1B和任选其他式II单体(组分B1A)、B1C和B1D如前所述选择,其中组分B1A、B1B和任选B1C和B1D之和为100重量%。
本发明丙烯酸粘合剂优选可通过上述单体乳液聚合得到。适合的工艺条件为本领域技术人员已知的并例如公开于WO-A 2005/064072中。
在本发明丙烯酸粘合剂中,通常可加入至多10重量%,优选0.05-5重量%含反应性或交联基团的单-或二烯属不饱和单体。这种单体的实例特别是α,β-烯属不饱和C3-5羧酸的酰胺,特别是丙烯酰胺、甲基丙烯酰胺和马来酸二酰胺,和它们的N-羟甲基衍生物如N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺,α,β-单烯属不饱和C3-5羧酸的N-烷氧基甲基酰胺如N-甲氧基甲基丙烯酰胺和N-正丁氧基甲基丙烯酰胺,乙烯基磺酸,丙烯酸和甲基丙烯酸与链烷二醇如乙二醇、丁二醇-1,4、己二醇-1,6和3-氯丙二醇-1,2的单酯,以及α,β-烯属不饱和单-和二羧酸的烯丙基和甲基烯丙基酯如马来酸二烯丙酯、富马酸二甲基烯丙酯、丙烯酸烯丙酯和甲基丙烯酸烯丙酯、邻苯二甲酸二烯丙酯、对苯二甲酸二烯丙酯、对二乙烯基苯、亚甲基-双-丙烯酰胺和乙二醇二烯丙基醚。
得到的非交联乳液聚合物的分子量通常为40,000-250,000(通过GPC测定)。分子量通常通过使用常规量的常规链终止剂控制。常规链终止剂例如为磺基有机化合物。
本发明丙烯酸粘合剂以其水分散体形式得到并优选以水分散体形式用于本发明杀虫剂组合物。
聚氨酯粘合剂和/或聚异氰脲酸酯粘合剂(组分B2)
在其它优选实施方案中,聚合粘合剂为聚氨酯和/或聚异氰脲酸酯。所述聚氨酯和/或聚异氰脲酸酯可单独用作聚合粘合剂或与其他聚合粘合剂,尤其是上述粘合剂组合,例如与上述丙烯酸粘合剂组合。
适合的聚合粘合剂因此为:
至少一种聚氨酯作为组分B2,其可同如下组分反应而得到:
b2a)至少一种二异氰酸酯或多异氰酸酯作为组分B2A,优选脂族、脂环族、芳脂族和/或芳族异氰酸酯,更优选可任选缩二脲化(biuretisized)和/或异氰脲酸化(isocyanurized)的二异氰酸酯,最优选1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合亚甲基环己烷(IPDI)和六亚甲基二异氰酸酯-1,6(HMDI);
b2b)至少一种二醇、三醇或多元醇作为组分B2B,优选具有2-14,优选4-10个碳原子的脂族、脂环族和/或芳脂族醇,更优选1,6-己二醇或新戊二醇;
b2c)任选其他组分作为组分B2C,优选己二酸或羰基二咪唑(CDI);和
b2d)任选其他添加剂作为组分B2D。
聚氨酯优选可通过如下组分反应得到:
b2a)基于聚氨酯55-99重量%,优选70-98重量%,更优选75-90重量%至少一种二异氰酸酯或多异氰酸酯(组分B2a),优选脂族、脂环族、芳脂族和/或芳族异氰酸酯,更优选可任选缩二脲化和/或异氰脲酸化的二异氰酸酯,更优选亚烷基单元中具有4-12个碳原子的亚烷基二异氰酸酯,如1,12-十二烷二异氰酸酯、2-乙基四亚甲基二异氰酸酯-1,4、2-甲基五亚甲基二异氰酸酯-1,5、四亚甲基二异氰酸酯-1,4、赖氨酸酯二异氰酸酯(LDI)、六亚甲基二异氰酸酯-1,6(HMDI)、环己烷-1,3-和/或-1,4-二异氰酸酯、2,4-和2,6-六氢-甲苯二异氰酸酯以及相应异构混合物4,4’-2,2’-和2,4’-二环己基甲烷二异氰酸酯以及相应混合物、1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷(IPDI)、2,4-和/或2,6-甲苯二异氰酸酯、4,4’-、2,4’和/或2,2’-二苯基甲烷二异氰酸酯(单体MDI)、多苯基多亚甲基多异氰酸酯(聚合MDI)和/或包含至少2种上述异氰酸酯的混合物;可使用包含酯-、脲-、脲基甲酸酯-、碳化二亚胺-、脲二酮-和/或氨基甲酸酯基团的其它二-和/或多异氰酸酯;最优选1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合亚甲基环己烷(IPDI)和六亚甲基二异氰酸酯-1,6(HMDI);
b2b)基于聚氨酯10-90重量%,优选12-85重量%,更优选15-65重量%至少一种二醇、三醇或多元醇作为组分B2B,优选具有2-14,优选4-10个碳原子的脂族、脂环族和/或芳脂族二醇,更优选多元醇,其选自聚醚醇如聚四氢呋喃、聚酯醇、聚硫醚多元醇、含羟基的聚乙缩醛和含羟基的脂族聚碳酸酯或至少2种上述多元醇的混合物。优选聚酯醇和/或聚醚醇。多羟基化合物的羟基数通常为20-850mg KOH/g,优选25-80mg KOH/g。另外,使用分子量通常为60至<400,优选60-300g/摩尔的二醇和/或三醇。适合的二醇为具有2-14,优选4-10个碳原子的脂族、脂环族和/或芳脂族二醇,例如乙二醇、丙二醇-1,3、癸二醇-1,10、邻-、间-、对-二羟基环己烷、二乙二醇、二丙二醇以及优选丁二醇-1,4、新戊二醇、己二醇-1,6和双-(2-羟基-乙基)氢醌,三醇,如1,2,4-、1,3,5-三羟基环己烷、甘油和三羟甲基丙烷,和含基于氧化乙烯和/或1,2-氧化丙烯的低分子含羟基聚氧化烯和上述二醇和/或三醇的混合物;
b2c)基于聚氨酯0-10重量%,优选0.1-5重量%,更优选1-5重量%其他组分(组分B2C),优选己二酸或羰基二咪唑(CDI);和
b2d)基于聚氨酯0-10重量%,优选0.1-5重量%,更优选0.5-5重量%其他添加剂(组分B2D);
其中组分B2A、B2B、B2C和B2D之和为100重量%。
聚氨酯通过本领域已知方法制备。另外,本领域技术人员已知的添加剂可在本方法中用于制备聚氨酯。
组分B也可以为聚异氰脲酸酯或聚异氰脲酸酯与聚氨酯,优选上述聚氨酯的混合物。
聚异氰脲酸酯为包含下式基团的聚合物:
其中取决于用于制备异氰脲酸酯的异氰酸酯,R*为亚烷基或亚芳基残余。
聚异氰脲酸酯通常通过异氰酸酯环三聚而制备。优选的异氰酸酯与上述异氰酸酯(组分B2A)相同。用于制备聚异氰脲酸酯的制备方法和条件为本领域技术人员已知的。
农药组合物
本发明农药组合物可以为含水组合物或干组合物,即不包含水的组合物。
在优选实施方案中,农药组合物为含水组合物,优选包含基于本发明农药组合物中的组分总量55-97重量%,更优选85-95重量%水和3-45重量%,优选5-15重量%固体,其中总量为100重量%。固体优选选自至少一种如上定义作为组分A的农药和至少一种如上定义作为组分B的聚合粘合剂,和任选至少一种如下定义作为组分C的固定剂和任选如上定义取决于最终产物用途的其他组分。
将农药组合物施用于材料的处理浴优选包含基于本发明杀虫组合物中的组分总量95-99.5重量%,优选95-99重量%,更优选97-99重量%水,和0.5-5重量%,优选1-5重量%固体的含水配制剂。固体优选选自至少一种如上定义作为组分A的式I农药化合物,和至少一种如上定义作为组分B的聚合粘合剂,和任选至少一种如下定义作为组分C的固定剂和任选如上定义取决于最终产物用途的其他组分。
聚合粘合剂可有利地与固定剂C施用以改善农药在材料上的附着。优选,固定剂可包含游离异氰酸酯基团。
适合的固定剂例如为包含游离异氰酸酯基团的异氰酸酯或异氰脲酸酯。优选异氰脲酸酯基于亚烷基单元中具有4-12个碳原子的亚烷基二异氰酸酯,如1,12-十二烷二异氰酸酯、2-乙基四亚甲基二异氰酸酯-1,4、2-甲基五亚甲基二异氰酸酯-1,5、四亚甲基二异氰酸酯-1,4、赖氨酸酯二异氰酸酯(LDI)、六亚甲基二异氰酸酯-1,6(HMDI)、环己烷-1,3-和/或-1,4-二异氰酸酯、2,4-和2,6-六氢-甲苯二异氰酸酯以及相应异构混合物4,4’-2,2’-和2,4’-二环己基甲烷二异氰酸酯以及相应混合物、1-异氰酸根合-3,35-三甲基-5-异氰酸根合甲基环己烷(IPDI)、2,4-和/或2,6-甲苯二异氰酸酯、4,4’-、2,4’和/或2,2’-二苯基甲烷二异氰酸酯(单体MDI)、多苯基多亚甲基多异氰酸酯(聚合MDI)和/或包含至少2种上述异氰酸酯的混合物。更优选基于六亚甲基二异氰酸酯-1,6(HMDI)的异氰脲酸酯。
更优选异氰脲酸酯为用基于氧化乙烯和/或1,2-氧化丙烯的聚氧化烯,优选聚氧化乙烯亲水化的异氰脲酸酯。
用作固定剂的异氰脲酸酯可通过本领域已知的方法制备。优选基于用作制备异氰脲酸酯的起始原料的异氰酸酯的量5-25重量%,更优选7-20重量%,最优选10-15重量%异氰酸酯基团为游离异氰酸酯基团。
最优选用作固定剂的异氰脲酸酯溶于极性非质子溶剂如THF、DMF或碳酸亚丙酯或亚乙酯中。
所用最优选的固定剂为用聚氧化乙烯亲水化且溶于碳酸亚丙酯中(70重量%HMDI在30重量%碳酸亚丙酯中)的基于HMDI的异氰脲酸酯。游离异氰酸酯基团的量基于用作制备异氰脲酸酯的起始原料的异氰酸酯的量为11-12重量%。
如果使用固定剂的话,农药组合物优选基于组合物的固体含量包含如下组分:
a)20-70重量%,优选25-65重量%,更优选30-65重量%至少一种农药(组分A),和
b)29-72重量%,优选34-70重量%,更优选33-66重量%至少一种如上定义的聚合粘合剂(组分B);
c)1-8重量%,优选1-5重量%,更优选2-4重量%至少一种固定剂(组分C);
其中组分之和为100重量%农药组合物的固体含量。
取决于最终产物的用途,农药组合物可另外包含一种或多种选自水、防腐剂、清净剂、填料、抗冲改性剂、防雾剂、发泡剂、澄清剂、成核剂、偶联剂、传导性增强剂(抗静电剂)、稳定剂如抗氧化剂、碳和氧自由基清除剂和过氧化物分解剂等、阻燃剂、脱模剂、具有UV保护性能的试剂、荧光增白剂、涂铺剂、防粘结剂、防迁移剂、消泡剂、防污剂、增稠剂、其他杀生物剂、润湿剂、增塑剂和成膜剂、粘合剂或防粘剂、光学增白剂(荧光增白剂)、芳香剂、颜料和染料的组分。
适合的消泡剂例如为硅消泡剂。适合的保护UV敏感性杀虫剂和/或驱避剂的UV保护剂例如为对氨基苯甲酸(PABA)、octylmethoxysinameth、芪、苯乙烯基或苯并三唑衍生物、苯并噁唑衍生物、羟基取代的二苯甲酮、水杨酸盐、取代的三嗪、肉桂酸衍生物(任选由2-氰基取代)、吡唑啉衍生物、1,1’-联苯基-4,4’-双-2-(甲氧基苯基)-乙川或其他UV保护剂。适合的荧光增白剂为二氢喹啉酮衍生物、1,3-二芳基吡唑啉衍生物、芘、萘酸酰亚胺、4,4’-二苯乙烯基亚联苯、4,4’-二氨基-2,2’-芪二磺酸、香豆素衍生物和由-CH=CH-桥连接的苯并噁唑、苯并异噁唑或苯并咪唑体系或其他荧光增白剂。
用于本发明农药组合物的通常颜料为用于颜料染色或印刷方法中或用于塑料着色的颜料并且为本领域技术人员已知的。
根据它们的化学性质,颜料可以为无机或有机的。无机颜料主要用作白色颜料(例如金红石或锐钛矿形式的二氧化钛、ZnO、白垩)或黑色颜料(例如炭黑)。由于潜在的有毒危害,可使用但不优选使用有色无机颜料。对于赋予色彩,优选有机颜料或染料。有机颜料可以为单或双偶氮、萘酚、苯并咪唑酮、(硫代)靛蓝类、二噁嗪、喹吖啶酮、酞菁、异吲哚啉酮、二萘嵌苯、紫环酮、金属络合物或二酮吡咯并吡咯类颜料。颜料可以以粉末或液体形式(即作为分散体)使用。优选的颜料为颜料黄(PigmentYellow)83、颜料黄(Pigment Yellow)138、颜料橙(Pigment Orange)34、颜料红(Pigment Red)170、颜料红(Pigment Red)146、颜料紫(PigmentViolet)19、颜料紫(Pigment Violet)23、颜料蓝(Pigment Blue)15/1、颜料蓝(Pigment Blue)15/3、颜料绿(Pigment Green)7、颜料黑(Pigment Black)7。其他适合的颜料为本领域技术人员已知的。
可用于本发明的通常染料为粉末或液体形式的瓮染料、阳离子染料和分散染料。瓮染料可用作颜料或跟随瓮染(还原)和氧化程序。优选使用瓮染料形式。瓮染料可以为阴丹士林类型,例如C.I.瓮蓝(Vat Blue)4、6或14;或黄烷士林类型,例如C.I.瓮黄(Vat Yellow)1;或皮蒽酮染料类型,例如C.I.瓮橙(Vat Orange)2和9;或异苯并蒽酮(异蒽酮紫)类型,例如C.I.瓮紫(Vat Violet)1;或二苯并蒽酮(蒽酮紫)类型,例如C.I.瓮蓝(VatBlue)16、19、20和22,C.I.瓮绿(Vat Green)1、2和9和C.I.瓮黑(Vat Black)9;或蒽醌咔唑类型,例如C.I.瓮橙(Vat Orange)11和15,C.I.瓮棕(VatBrown)1、3和44,C.I.瓮绿(Vat Green)8和C.I.瓮黑(Vat Black)27;或苯并蒽酮吖啶酮类型,例如C.I.瓮绿(Vat Green)3和13和C.I.瓮黑(VatBlack)25;或蒽醌噁唑类型,例如C.I.瓮红(Vat Red)10;或二萘嵌苯四碳酸二酰亚胺类型,例如C.I.瓮红(Vat Red)23和32;或咪唑衍生物如C.I.瓮黄(Vat Yellow)46;或氨基三嗪衍生物,例如C.I.瓮蓝(Vat Blue)66。其他适合的瓮染料为本领域技术人员已知的。
通常的分散和阳离子染料为本领域技术人员已知的。
如果纤维素基质用作材料,则所述纤维素基质优选用瓮、直接、反应性或硫染料染色。
在优选实施方案中,本发明农药组合物为包含至少一种颜料和/或至少一种染料的上述农药组合物。本发明农药组合物优选包含相对于农药的固体含量总重量10-300重量%,更优选20-150重量%颜料和/或染料。
如果组合物以成套形式交付,则材料,例如织物材料或塑料材料可在使用以前浸渍(例如意指染色或其它处理)。
在其他实施方案,本发明的浸渍材料另外包含一种或多种选自防腐剂、清净剂、稳定剂、具有UV保护性能的试剂、荧光增白剂、涂铺剂、防迁移剂、消泡剂、润湿剂、防污剂、增稠剂、其他杀生物剂、增塑剂、粘合剂、颜料和染料的组分。适合的上述组分的实例为本领域技术人员已知的。
在本发明其他实施方案中,除至少一种农药和至少一种上述聚合粘合剂外,浸渍材料包含至少一种颜料和/或至少一种染料。至少一种颜料的量通常为0.05-10重量%,优选0.1-5重量%,更优选0.2-3.5重量%非生物材料的干重。至少一种染料的量通常为0.05-10重量%,优选0.1-5重量%,更优选0.2-3.5重量%所述材料的干重。材料优选包含至少一种颜料或至少一种染料。适合的颜料和染料为上述的。
材料浸渍形成网眼织物的方法
优选一种浸渍材料,例如织物材料或塑料材料的方法,包括如下步骤:
i)形成含水配制剂或熔体,其中优选含水配制剂,其包含至少一种农药和至少一种聚合粘合剂,优选如上定义的聚合粘合剂,和任选其他成分;
ii)通过如下步骤将含水配制剂施用于材料:
iia)使材料通过含水配制剂;或
iib)使材料与部分或完全浸入含水配制剂中的辊接触并将含水配制剂拉至与辊接触的材料侧,或
iic)双侧涂覆材料,或
iid)将含水配制剂喷雾至材料上,其中喷雾用用于手动或自动喷雾的任何适合装置,例如用气溶胶罐或通常用于工厂中的装置进行;或
iie)以泡沫形式施用含水配制剂;或
iif)将材料浸没含水配制剂中;或
iig)将含水配制剂刷在材料上或材料中;或
iih)将含水配制剂浇灌在材料上;或
通过压延或用刮片施涂熔体;
iii)任选除去过剩含水配制剂或过剩熔体;和
iv)干燥和/或固化材料。
在本发明上下文中,含水配制剂可以为溶液、乳液或悬浮液/分散体。
含水配制剂或熔体优选包含优选以含水配制剂形式使用的农药组合物。
在本发明上下文中,“浸渍”为一种施用农药组合物的方法。如果需要的话,此方法可包括一种使施用的农药组合物固化以得到在材料上的涂层的方法。“浸渍材料”为农药组合物施用其上的材料。如果需要的话,“浸渍材料”可通过使施用的农药组合物固化而被涂覆。
农药组合物也可通过转印法、喷墨印刷、筛印法和粉末印刷而施用于材料上。
施用农药组合物的详细资料为本领域技术人员熟知的并例如公开于WO 2005/064072中。
本发明方法用于保护作物植物。
本方法用于保护植物以防植物栽培中遇到的任何种类的害虫和病害。
这些害虫包括:
鳞翅目(Lepidoptera)昆虫,例如小地老虎(Agrotis ypsilon)、黄地老虎(Agrotis segetum)、木棉虫(Alabama argillacea)、黎豆夜蛾(Anticarsiagemmatalis)、Argyresthia conjugella、叉纹夜蛾(Autographa gamma)、树尺蠖(Bupalus piniarius)、Cacoecia murinana、Capua reticulana、Cheimatobia brumata、云杉色卷蛾(Choristoneura fumiferana)、Choristoneura occidentalis、二化螟(Cirphis unipuncta)、苹果小卷蛾(Cydia pomonella)、松毛虫(Dendrolimus pini)、Diaphania nitidalis、西南玉米杆草螟(Diatraea grandiosella)、埃及钻夜蛾(Earias insulana)、南美玉米苗斑螟(Elasmopalpus lignosellus)、Estigmene acrea、女贞细卷蛾(Eupoecilia ambiguella)、Evetria bouliana、Feltia subterranea、蜡螟(Galleria mellonella)、李小食心虫(Grapholitha funebrana)、梨小食心虫(Grapholitha molesta)、棉铃虫(Heliothis armigera)、烟芽夜蛾(Heliothisvirescens)、玉米穗虫(Heliothis zea)、菜螟(Hellula undalis)、Hiberniadefoliaria、美国白蛾(Hyphantria cunea)、苹果巢蛾(Hyponomeutamalinellus)、番茄虫蛾(Keiferia lycopersicella)、Lambdina fiscellaria、甜菜夜蛾(Laphygma exigua)、咖啡潜叶蛾(Leucoptera coffeella)、旋纹潜蛾(Leucoptera scitella)、Lithocolletis blancardella、葡萄浆果小卷蛾(Lobesia botrana)、甜菜网螟(Loxostege sticticalis)、舞毒蛾(Lymantriadispar)、模毒蛾(Lymantria monacha)、桃潜蛾(Lyonetia clerkella)、黄褐天幕毛虫(Malacosoma neustria)、甘蓝夜蛾(Mamestra brassicae)、黄杉毒蛾(Orgyia pseudotsugata)、玉米螟(Ostrinia nubilalis)、小眼夜蛾(Panolis flammea)、棉花红铃虫(Pectinophora gossypiella)、疆夜蛾(Peridroma saucia)、圆掌舟蛾(Phalera bucephala)、马铃薯麦蛾(Phthorimaea operculella)、柑桔潜叶蛾(Phyllocnistis citrella)、欧洲粉蝶(Pieris brassicae)、苜蓿绿夜蛾(Plathypena scabra)、菜蛾(Plutellaxylostella)、大豆夜蛾(Pseudoplusia includens)、Rhyacionia frustrana、Scrobipalpula absoluta、麦蛾(Sitotroga cerealella)、葡萄卷叶蛾(Sparganothis pilleriana)、草地夜蛾(Spodoptera frugiperda)、海灰翅夜蛾(Spodoptera littoralis)、斜纹夜蛾(Spodoptera Iitura)、Thaumatopoeapityocampa、绿色橡木飞蛾(Tortrix viridana)、粉纹夜蛾(Trichoplusia ni)和Zeiraphera canadensis;
甲虫(鞘翅目(Coleoptera)),例如梨窄吉丁(Agrilus sinuatus)、直条叩头虫(Agriotes lineatus)、暗色叩头虫(Agriotes obscurus)、Amphimallussolstitialis、Anisandrus dispar、墨西哥棉铃象(Anthonomus grandis)、苹花象(Anthonomus pomorum)、Aphthona euphoridae、Athoushaemorrhoidalis、甜菜隐食甲(Atomaria linearis)、纵坑切梢小蠹(Blastophagus piniperda)、Blitophaga undata、蚕豆象(Bruchusrufimanus)、豌豆象(Bruchus pisorum)、欧洲兵豆象(Bruchus lentis)、苹卷象(Byctiscus betulae)、甜菜大龟甲(Cassida nebulosa)、Cerotomatrifurcata、金花金龟(Cetonia aurata)、白菜籽龟象(Ceuthorrhynchusassimilis)、芫菁龟象(Ceuthorrhynchus napi)、甜菜胫跳甲(Chaetocnematibialis)、Conoderus vespertinus、石刁柏负泥虫(Crioceris asparagi)、Ctenicera ssp.、Diabrotica longicornis、Diabrotica semipunctata、Diabrotica 12-punctata、南美叶甲(Diabrotica speciosa)、玉米根叶甲(Diabrotica virgifera)、墨西哥豆瓢虫(Epilachna varivestis)、烟草跳甲(Epitrix hirtipennis)、棉灰蒙象变种(Eutinobothrus brasiliensis)、欧洲松树皮象(Hylobius abietis)、埃及苜蓿叶象(Hypera brunneipennis)、紫苜蓿叶象(Hypera postica)、云杉八齿小蠹(Ips typographus)、烟草负泥虫(Lema bilineata)、黑角负泥虫(Lema melanopus)、马铃薯叶甲(Leptinotarsa decemlineata)、Limonius californicus、稻水象甲(Lissorhoptrus oryzophilus)、Melanotus communis、油菜露尾甲(Meligethes aeneus)、大栗鳃金龟(Melolontha hippocastani)、五月鳃金龟(Melolontha melolontha)、水稻负泥虫(Oulema oryzae)、葡萄黑耳喙象(Ortiorrhynchus sulcatus)、草莓根象甲(Otiorrhynchus ovatus)、辣根猿叶甲(Phaedon cochleariae)、梨树叶象(Phyllobius pyri)、Phyllotretachrysocephala、食叶鳃金龟属(Phyllophaga sp.)、庭园发丽金龟(Phyllopertha horticola)、大豆淡足跳甲(Phyllotreta nemorum)、黄曲条菜跳甲(Phyllotreta striolata)、日本金龟子(Popillia japonica)、豌豆叶象(Sitona lineatus)和谷象(Sitophilus granaria);
蝇、蚊(双翅目(Diptera)),例如埃及伊蚊(Aedes aegypti)、Aedes albopictus、剌扰伊蚊(Aedes vexans)、墨西哥果蝇(Anastrepha ludens)、五斑按蚊(Anopheles maculipennis)、Anopheles crucians、白足按蚊(Anophelesalbimanus)、冈比亚按蚊(Anopheles gambiae)、Anopheles freeborni、海南岛白踝按蚊(Anopheles leucosphyrus)、云南微小按蚊(Anophelesminimus)、四斑按蚊(Anopheles quadrimaculatus)、红头丽蝇(Calliphoravicina)、地中海实蝇(Ceratitis capitata)、蛆症金蝇(Chrysomya bezziana)、Chrysomya hominivorax、Chrysomya macellaria、鹿蝇(Chrysopsdiscalis)、Chrysops silacea、Chrysops atlanticus、螺旋蝇(Cochliomyiahominivorax)、高粱瘿蚊(Contarinia sorghicola)、嗜人瘤蝇蛆(Cordylobiaanthropophaga)、狂怒库蠓(Culicoides furens)、尖音库蚊(Culex pipiens)、斑蚊(Culex nigripalpus)、致倦库蚊(Culex quinquefasciatus)、媒斑蚊(Culex tarsalis)、Culiseta inornata、Culiseta melanura、瓜蝇(Dacuscucurbitae)、油橄榄实蝇(Dacus oleae)、油菜叶瘿蚊(Dasineurabrassicae)、Delia antique、麦地种蝇(Delia coarctata)、灰地种蝇(Deliaplatura)、甘蓝地种蝇(Delia radicum)、Dermatobia hominis、小毛厕蝇(Fannia canicularis)、Geomyza Tripunctata、马蝇(Gasterophilusintestinalis)、刺舌蝇(Glossina morsitans)、须舌蝇(Glossina palpalis)、Glossina fuscipes、胶舌蝇(Glossina tachinoides)、Haematobia irritans、Haplodiplosis equestris、潜蝇属(Hippelates spp.)、花生田灰地种蝇(Hylemyia platura)、纹皮蝇(Hypoderma lineata)、Leptoconops torrens、蔬菜斑潜蝇(Liriomyza sativae)、美国潜叶蝇(Liriomyza trifolii)、Luciliacaprina、铜绿蝇(Lucilia cuprina)、丝光绿蝇(Lucilia sericata)、Lycoriapectoralis、Mansonia titillanus、麦瘿蚊(Mayetiola destructor)、家蝇(Musca domestica)、厩腐蝇(Muscina stabulans)、羊狂蝇(Oestrus ovis)、Opomyza florum、欧洲麦秆蝇(Oscinella frit)、天仙子泉蝇(Pegomyahysocyami)、葱蝇(Phorbia antiqua)、萝卜蝇(Phorbia brassicae)、麦地种蝇(Phorbia coarctata)、银足白蛉(Phlebotomus argentipes)、Psorophora columbiae、胡萝卜茎蝇(Psila rosae)、Psorophora discolor、Prosimulium mixtum、樱桃实蝇(Rhagoletis cerasi)、苹果实蝇(Rhagoletispomonella)、赤尾麻蝇(Sarcophaga haemorrhoidalis)、肉蝇属(Sarcophaga)、Simulium vittatum、厩螫蝇(Stomoxys calcitrans)、牛虻(Tabanus bovinus)、Tabanus atratus、红色原虻(Tabanus lineola)、Tabanus similis、Tipula oleracea和欧洲大蚊(Tipula paludosa),
蓟马(缨翅目(Thysanoptera)),例如兰花蓟马(Dichromothrips corbetti)、Dichromothrips ssp.、烟褐蓟马(Frankliniella fusca)、苜蓿花蓟马(Frankliniella occidentalis)、东方花蓟马(Frankliniella tritici)、桔硬蓟马(Scirtothrips citri)、稻蓟马(Thrips oryzae)、棕榈蓟马(Thrips palmi)和烟蓟马(Thrips tabaci),
白蚁(等翅目(Isoptera)),例如Calotermes flavicollis、Leucotermes flavipes、金黄异白蚁(Heterotermes aureus)、黄肢散白蚁(Reticulitermes flavipes)、美小黑散白蚁(Reticulitermes virginicus)、欧洲散白蚁(Reticulitermeslucifugus)、Termes natalensis和台湾乳白蚁(Coptotermes formosanus),
蟑螂(蜚蠊目(Blattaria)-Blattodea),例如德国小蠊(Blattella germanica)、Blattella asahinae、美洲大蠊(Periplaneta americana)、日本大蠊(Periplaneta japonica)、棕色蜚蠊(Periplaneta brunnea)、Periplanetafuligginosa、澳洲蜚蠊(Periplaneta australasiae)和东方蜚蠊(Blattaorientalis);
臭虫(半翅目(Hemiptera)包括同翅目(Homoptera)),例如拟绿蝽(Acrosternum hilare)、玉米长蝽(Blissus leucopterus)、黑斑烟盲蝽(Cyrtopeltis notatus)、棉红蝽(Dysdercus cingulatus)、Dysdercusintermedius、麦扁盾蝽(Eurygaster integriceps)、烟草蝽(Euschistusimpictiventris)、棉红铃喙缘蝽(Leptoglossus phyllopus)、美洲牧草盲蝽(Lygus lineolaris)、牧草盲蝽(Lygus pratensis)、稻绿蝽(Nezaraviridula)、甜菜拟网蝽(Piesma quadrata)、Solubea insularis、Thyantaperditor、Acyrthosiphon onobrychis、落叶松球蚜(Adelges laricis)、Aphidula nasturtii、甜菜蚜(Aphis fabae)、草莓根蚜(Aphis forbesi)、苹果蚜(Aphis pomi)、棉蚜(Aphis gossypii)、北美茶簏子蚜(Aphisgrossulariae)、希奈德蚜(Aphis schneideri)、卷叶蚜(Aphis spiraccola)、接骨木蚜(Aphis sambuci)、豌豆蚜(Acyrthosiphon pisum)、茄无网蚜(Aulacorthum solani)、银叶粉虱(Bemisia argentifolii)、飞廉短尾蚜(Brachycaudus cardui)、李短尾蚜(Brachycaudus helichrysi)、Brachycaudus persicae、桃短尾蚜(Brachycaudus prunicola)、甘蓝蚜(Brevicoryne brassicae)、Capitophorus horni、Cerosipha gossypii、草莓中瘤钉毛蚜(Chaetosiphon fragaefolii)、茶镳隐瘤蚜(Cryptomyzusribis)、高加索冷杉椎球蚜(Dreyfusia nordmannianae)、云杉椎球蚜(Dreyfusia piceae)、居根西圆尾蚜(Dysaphis radicola)、Dysaulacorthum pseudosolani、车前圆尾蚜(Dysaphis plantaginea)、梨西圆尾蚜(Dysaphis pyri)、蚕豆微叶蝉(Empoasca fabae)、桃大尾蚜(Hyalopterus pruni)、Hyperomyzus lactucae、麦长管蚜(Macrosiphumavenae)、大戟长管蚜(Macrosiphum euphorbiae)、蔷薇管蚜(Macrosiphon rosae)、巢莱修尾蚜(Megoura viciae)、Melanaphispyrarius、麦无网蚜(Metopolophium dirhodum)、Myzodes persicae、冬葱瘤额蚜(Myzus ascalonicus)、Myzus cerasi、李瘤蚜(Myzusvarians)、黑茶镳子衲长管蚜(Nasonovia ribis-nigri)、稻飞虱(Nilaparvata lugens)、囊柄瘿绵蚜(Pemphigus bursarius)、蔗飞虱(Perkinsiella saccharicida)、忽布疣蚜(Phorodon humuli)、苹木虱(Psylla mali)、梨木虱(Psylla piri)、冬葱瘤蛾蚜(Rhopalomyzusascalonicus)、玉米蚜(Rhopalosiphum maidis)、禾谷溢管蚜(Rhopalosiphum padi)、苹草缢管蚜(Rhopalosiphum insertum)、Sappaphis mala、Sappaphis mali、麦二叉蚜(Schizaphis graminum)、Schizoneura lanuginosa、麦长管蚜(Sitobion avenae)、白粉虱(Trialeurodes vaporariorum)、桔二叉蚜(Toxoptera aurantiiand)、葡萄根瘤蚜(Viteus vitifolii)、温带臭虫(Cimex lectularius)、热带臭虫(Cimexhemipterus)、Reduvius senilis、Triatoma属和Arilus critatus,蚂蚁、蜜蜂、黄蜂、锯蝇(膜翅目(Hymenoptera)),例如新疆菜叶蜂(Athalia rosae)、切叶蚁(Atta cephalotes)、Atta capiguara、切叶蚁(Atta cephalotes)、Atta laevigata、Atta robusta、Atta sexdens、Attatexana、举腹蚁属(Crematogaster)、Hoplocampa minuta、Hoplocampatestudinea、小黄家蚁(Monomorium pharaonis)、热带火蚁(Solenopsisgeminate)、红火蚁(Solenopsis invicta)、黑火蚁(Solenopsis richteri)、南方火蚁(Solenopsis xyloni)、红蚂蚁(Pogonomyrmex barbatus)、Pogonomyrmex californicus、Pheidole megacephala、天鹅绒蚂蚁(Dasymutilla occidentalis)、熊蜂属(Bombus)、大黄蜂(Vespulasquamosa)、Paravespula vulgaris、Paravespula pennsylvanica、Paravespula germanica、姬胡蜂(Dolichovespula maculata)、黄边胡蜂(Vespa crabro)、胡蜂(Polistes rubiginosa)、Campodontus floridanus和阿根廷蚁(Linepithema humile),
蟋蟀、蚱蜢、蝗虫(直翅目(Orthoptera)),例如居屋艾蟋(Achetadomestica)、蝼蛄(Gryllotalpa gryllotalpa)、飞蝗(Locusta migratoria)、双纹黑蝗(Melanoplus bivittatus)、红足黑蝗(Melanoplusfemurrubrum)、墨西哥黑蝗(Melanoplus mexicanus)、迁飞黑蝗(Melanoplus sanguinipes)、石栖黑蝗(Melanoplus spretus)、条纹红蝗(Nomadacris septemfasciata)、美洲沙漠蝗(Schistocerca americana)、沙漠蝗(Schistocerca gregaria)、摩洛哥戟纹蝗(Dociostaurusmaroccanus)、庭疾灶螽(Tachycines asynamorus)、塞纳加尔小车蝗(Oedaleus senegalensis)、Zonozerus variegatus、非洲蔗蝗(Hieroglyphus daganensis)、Kraussaria angulifera、意大利蝗(Calliptamus italicus)、澳洲草栖蝗(Chortoicetes terminifera)和褐色拟飞蝗(Locustana pardalina),
蜘蛛纲(Arachnoidea)),如蜘蛛(蜱螨目(Acarina)),例如软蜱科(Argasidae)、硬蜱科(Ixodidae)和疥螨科(Sarcoptidae),如长星形壁虱(Amblyomma americanum)、热带花蜱(Amblyomma variegatum)、Ambryomma maculatum、波斯锐缘蜱(Argas persicus)、牛壁虱(Boophilus annulatus)、Boophilus decoloratus、微小牛蜱(Boophilusmicroplus)、Dermacentor silvarum、安氏革蜱(Dermacentor andersoni)、美洲大革蜱(Dermacentor variabilis)、Hyalomma truncatum、蓖子硬蜱(Ixodes ricinus)、Ixodes rubicundus、黑脚硬蜱(Ixodes scapularis)、全环硬蜱(Ixodes holocyclus)、太平洋硬蜱(Ixodes pacificus)、Ornithodorusmoubata、Ornithodorus hermsi、Ornithodorus turicata、柏氏禽刺螨(Ornithonyssus bacoti)、Otobius megnini、鸡皮刺螨(Dermanyssusgallinae)、绵羊疥病(Psoroptes ovis)、Rhipicephalus sanguineus、Rhipicephalus appendiculatus、Rhipicephalus evertsi、人疥螨(Sarcoptesscabiei),瘿螨(Eriophyidae)属,如苹果刺锈螨(Aculus schlechtendali)、Phyllocoptrata oleivora和Eriophyes sheldoni;细螨(Tarsonemidae)属,如Phytonemus pallidus和侧多食跗线螨(Polyphagotarsonemus latus);细须螨(Tenuipalpidae)属,如紫红短须螨(Brevipalpus phoenicis);叶螨(Tetranychidae)属,如朱砂叶螨(Tetranychus cinnabarinus)、神泽叶螨(Tetranychus kanzawai)、太平洋叶螨(Tetranychus pacificus)、棉叶螨(Tetranychus telarius)和二点叶螨(Tetranychus urticae),苹果叶螨(Panonychus ulmi)、柑椐叶螨(Panonychus citri)和草地小爪螨(Oligonychus pratensis);蜘蛛目(Araneida),例如毒蜘蛛(Latrodectusmactans)和褐丝蛛(Loxosceles reclusa),
跳蚤(蚤目(Siphonaptera)),例如猫跳蚤(Ctenocephalides felis)、狗跳蚤(Ctenocephalides canis)、印鼠客蚤(Xenopsylla cheopis)、致痒蚤(Pulexirritans)、穿皮潜蚤(Tunga penetrans)和具带病蚤(Nosopsyllusfasciatus),
衣鱼、家衣鱼(缨尾目(Thysanura)),例如西洋衣鱼(Lepisma saccharina)和斑衣鱼(Thermobia domestica),
百足虫(唇足纲(Chilopoda)),例如Scutigera coleoptrata,
千足虫(倍足纲(Diplopoda)),例如Narceus属,
蠼蛸(革翅目(Dermaptera)),例如欧洲球螋(forficula auricularia),和
虱(毛虱目(Phthiraptera)),例如人头虱(Pediculus humanus capitis)、人体虱(Pediculus humanus corporis)、阴虱(Pthirus pubis)、牛血虱(Haematopinus eurysternus)、猪血虱(Haematopinus suis)、牛颚虱(Linognathus vituli)、Bovicola bovis、鸡虱(Menopon gallinae)、Menacanthus stramineus和Solenopotes capillatus,
线虫如大豆胞囊线虫(Heterodera glycines)、禾谷胞囊线虫(H.avenae)、甜菜胞囊线虫(H.schachtii)、三叶草胞囊线虫(H.trifolii)、H.gottingiana、H.cajani、H.zeae、马铃薯金线虫(Globodera rostochiensis)、G.pallida、G.tabacum.、花生根结线虫(Meloidogyne arenaria)、南方根结线虫(M.incognita)、爪哇根结线虫(M.javanica)、北方根结线虫(M.hapla)、M.chitwoodi、腐烂茎线虫(Ditylenchus destructor)、甘薯茎线虫(D.dipsaci)、D.angustus、小麦粒线虫(Anguina tritici)、A.agrostis、Afrina/Anguinawevelli、穿刺根腐线虫(Pratylenchus penetrans)、P.brachyurus、P.coffeae、P.zeae、P.goodeyi、P.thornei、P.vulnus、香蕉穿孔线虫(Radopholus similis)、Hirschmanniella oryzae、H.mucronata、H.spinicauda、Hoplolaimus columbus、H.seinhorsti、H.indicus、香蕉肾形线虫(Rotylenchus reniformis)、柑桔半穿刺线虫(Tylenchulussemipenetrans)、Helicotylenchus multicinctus、H.multicinctus、H.mucronatus、H.dihystera、H.pseudorobustus、Criconemella C.xenoplaxaxestis、C.spharocephalum。
可防治其他有害真菌。
这种真菌包括选自子囊茵纲(Ascomycetes)、半知茵纲(Deuteromycetes)、藻状茵纲(Phycomycetes)和担子茵纲(Basidiomycetes)的那些。具体实例包括水果和蔬菜上的链格孢(Alternaria)属,草莓、蔬菜、观赏植物和葡萄藤上的灰葡萄孢(Botrytis cinerea)(灰霉病),花生上的花生黑斑病菌(Cercospora arachidicola),葫芦上的二孢白粉菌(Erysiphecichoracearum)和单丝壳白粉菌(Sphaerotheca fuliginea),禾谷类中的禾白粉菌(Blumeria graminis)(白粉病),各种植物上的链孢霉(Fusarium)属和轮枝孢(Verticillium)属,禾谷类上的长蠕孢(Helminthosporium)属,香蕉和花生上的球腔菌(Mycosphaerella)属,土豆和西红柿上的致病疫霉(Phytophthora infestans),葡萄藤上的葡萄生单轴霉(Plasmopara viticola),苹果上的苹果白粉病菌(Podosphaera lcucotricha),小麦和大麦上的小麦基腐病菌(Pseudocercosporella herpotrichoides),啤酒花和黄瓜上的假霜霉(Pseudoperonospora)属,各种禾谷类上的柄锈菌(Puccinia)属,稻上的稻瘟病菌(Pyricularia oryzae),棉花、稻和草坪上的丝核菌(Rhizoctonia)属,小麦上的小麦壳针孢(Septoria tritici),葡萄藤上的葡萄钩丝壳(Uncinulanecator),禾谷类和甘蔗上的黑粉茵(Ustilago)属和苹果和梨上的黑星菌(Venturia)属(黑星病)。
本发明装置包含上述稳定结构和网眼织物。它可用来从插秧或种植至收获整个时间段中或仅在可特别易受某些害虫侵袭的这些植物生长的某阶段中覆盖一种或多种待保护植物。
织物优选网,这是由于这不干扰植物及其环境之间的空气、湿气和光交换—同时它仍提供良好保护以防害虫。
令人惊讶的是,网的使用甚至在真菌病害的情况下导致良好的保护。
本发明通过如下实施例进一步说明而不限制它。
实施例
粘合剂:
A)制备聚合物分散体
通用程序:
将250g水和3g具有30nm中值粒径的苯乙烯种子(33重量%)加热至85℃并加入5重量%的进料2。10分钟以后,开始加入包含以下所述单体的进料1和进料2。
进料2包含3.0g溶于39.9g水中的过氧二硫酸钠。
进料1的组合物列于表1中。
进料1和2在3小时内加入,并将其聚合另外0.5小时。
引发剂过氧二硫酸钠的量为0.3重量份,乳化剂包含相对于100重量份表1的单体组合物0.4重量份Dowfax 2A1(Dow)和0.6重量份LumitenIRA(BASF AG)。
简写:
MMA:甲基丙烯酸甲酯
S:苯乙烯
AN:丙烯腈
EA:丙烯酸乙酯
EHA:丙烯酸2-乙基己基酯
BA:丙烯酸正丁酯
FI:具有丙烯酸基团的可共聚二苯甲酮
GMA:缩水甘油基甲基丙烯酸酯
BMA-Acac:丁二醇单丙烯酸酯-乙酰乙酸酯(bitandiolmonoacrylateacetylacetate)
Amol:N-羟甲基丙烯酰胺
MAMol:N-羟甲基甲基丙烯酰胺
HPMA:甲基丙烯酸羟基丙酯
AS:丙烯酸
AM:丙烯酰胺
Dowfax 2A1:
Lumiten IRA:
实施例A1和A8
包含其后可用作交联剂的FI-1可聚合光引发剂的聚合物水分散体为下式的光引发剂:
其中:
R8为具有1-30个碳原子的有机基团,
R9为H或甲基,和
R10为任选取代的苯基或C1-C4烷基。
应用实施例
杀虫处理用实施例A17的水分散体在未预先洗涤的市售白色聚酯网材料(纤维纤度75旦尼尔,156目,重量28-32g/m2)上进行。含水处理浴通过将水分散体用市售的杀虫剂和/或驱避剂的乳液混合而制备,用缓冲溶液设定pH并加入固定剂(如果需要的话)。处理浴的浓度根据可能液体吸收调整(LU为60-100%之间)。处理浴通过使用实验室规模的浸轧机-拉幅机装置(Mathis AG,瑞士)施用。网材料完全浸入处理浴中,过量液体通过使它通过相反方向移动的圆筒而除去。通过选择这些圆筒之间的指定距离(和因此的指定压力),可控制液体吸收。液体吸收通过将浸渍的网片称重并减去干的、未处理的网重量而测得,作为基于网重量的%液体重量给出。干燥/固化步骤在使得控制处理温度和时间的实验室拉幅机中进行。
对于在实验室生物测定中处理昆虫,将杀虫浸渍的耐久杀虫网(LLIN,@ 200mg ai/m2)切割以适合皮氏培养皿。将网放在培养皿底部并每个皿中在网上引入10只昆虫。在曝露以后几分钟、几小时和可能几天时评估死亡率/垂死率。基于测试的处理数确定重复数。
对于田地试验,取决于作物的类型,可用几种方法。方法a)-e)为典型实例:
a)将上述耐久杀虫网松散地直接放在卷心菜的植物床上并确保不被风移除。光、空气和水可自由到达植物。网通过植物萌发和生长而升高,但不限制生长。
直至收获,记录典型害虫的侵染并与在未保护床中生长的植物和在未处理网下生长的植物的值比较。
b)将上述耐久杀虫网放在用于种植西红柿植物的杆上,以此使整个植物被网覆盖。光、空气和水可自由到达西红柿植物。
直至收获,记录典型害虫的侵染并与未保护和由未处理网保护的生长植物的值比较。
c)将上述耐久杀虫网放在木质支撑架上覆盖草莓植物生长的植物床上。光、空气和水可自由到达植物。
直至收获,记录典型害虫的侵染并与未保护和由未处理网保护的生长植物的值比较。
d)将烟草苗圃中的烟草植物放在用上述耐久杀虫网覆盖的网架下。光、空气和水可自由到达植物。
记录典型害虫的侵染并与未保护和由未处理网保护的生长植物的值比较。
e)在开花前不久将上述耐久杀虫网放在苹果树上。光、空气和水可自由到达树。
直至收获,记录典型害虫的侵染并与未保护和由未处理网保护的生长植物的值比较。
Claims (10)
1.一种保护作物植物以防有害生物体的方法,其包括如下步骤:将一种或多种植物用包含稳定结构和网眼织物的装置覆盖,其中所述网眼织物用农药浸渍并可透过光、空气和水。
2.如权利要求1的方法,其中形成所述网眼织物的材料为合成或天然织物材料、塑料材料、皮革材料、植绒织物、片、箔、包装材料或含纤维素材料。
3.如权利要求1或2的方法,其中所述材料为网。
4.如权利要求1-3中任一项的方法,其中将所述材料用包含如下组分的组合物处理:
a.至少一种农药(组分A),和
b.至少一种聚合粘合剂(组分B)。
5.如权利要求4的方法,其中所述组合物包含(基于A与B的总含量)0.001-95重量%至少一种农药和5-99.999重量%至少一种聚合粘合剂。
6.如权利要求1-5中任一项的方法,其中所述农药选自如下的杀虫剂:合成除虫菊酯化合物、氨基甲酸酯化合物、有机含磷化合物、灭菌化合物、烟碱乙酰胆碱受体拮抗剂、氯通道活化剂、保幼激素类似物、选择进料阻断剂、螨生长抑制剂、微生物杀虫剂、氧化磷酸化抑制剂、氧化磷酸化解偶联剂、几丁质生物合成抑制剂、蜕皮激素拮抗剂和蜕皮干扰剂、真蛸胺拮抗剂、耦合点II电子转移抑制剂、耦合点I电子转移抑制剂、电压依赖性钠通道阻断剂、类脂生物合成抑制剂、二乙基溴乙酰胺抑制剂、乌头酸酶抑制剂、N-芳基肼衍生物、增效剂、鱼尼汀受体调节剂、苯螨特、灭螨猛、开乐散、啶虫丙醚、硼砂和吐酒石;驱避剂、软体动物杀灭剂、杀鼠剂和杀真菌剂。
7.如权利要求4-6中任一项的方法,其中所述聚合粘合剂选自聚丙烯酸酯、聚甲基丙烯酸酯、聚丙烯腈、聚马来酸酐、聚马来酸、聚马来酸酯和聚马来酰胺、聚苯乙烯、聚(甲基)苯乙烯、聚丁二烯、聚乙酸乙烯酯、聚乙烯醇,以及通过上述单体组的至少两种不同烯属不饱和单体聚合而得到的共聚物,和所述均聚物和/或共聚物的配混物,例如聚(苯乙烯-丙烯酸酯)、聚(苯乙烯-丁二烯)、乙烯-丙烯酸酯共聚物、乙烯-乙酸乙烯酯共聚物,其可以为部分或完全水解的,聚氨酯和/或聚异氰脲酸酯,包含聚氨酯和/或聚异氰脲酸酯的配混物,优选包含聚氨酯和/或聚异氰脲酸酯和聚碳酸酯的配混物;矿物蜡、锆蜡、硅氧烷、聚硅氧烷、氟化聚丙烯酸酯和甲基丙烯酸酯、氟硅氧烷和碳氟树脂、三聚氰胺甲醛缩合树脂、羟甲基脲衍生物;和可固化聚酯和包含至少一种所述聚合粘合剂的配混物或制剂。
8.如权利要求4-7中任一项的方法,其中所述聚合粘合剂为通过至少一种式II的单体自由基聚合而得到的丙烯酸粘合剂:
其中:
R20、R21和R22独立地选自任选氟取代且可以为线性或支化的C1-C10烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基,优选C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基;取代或未取代的芳基,优选取代或未取代的C6-C10芳基,更优选取代或未取代的C6芳基,例如苯基或甲苯基;
R20和R21可另外为H。
9.如权利要求1-8任一项中所述的装置在保护作物植物以防有害生物体中的用途。
10.一种保护植物以防有害生物体的装置,其包含稳定结构和网眼织物,其中所述网眼织物用农药浸渍并且可透过光、空气和水。
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- 2007-10-24 US US12/513,173 patent/US20100064578A1/en not_active Abandoned
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MX2009004194A (es) | 2009-05-08 |
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BRPI0718152A2 (pt) | 2013-11-05 |
US20100064578A1 (en) | 2010-03-18 |
TW200836619A (en) | 2008-09-16 |
ECSP099309A (es) | 2009-06-30 |
US20140190075A1 (en) | 2014-07-10 |
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ZA200903789B (en) | 2010-08-25 |
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