CN101616579A - 至少包含一种基于油酸或亚油酸的二烷基酰烷的杀生物剂组合物 - Google Patents
至少包含一种基于油酸或亚油酸的二烷基酰烷的杀生物剂组合物 Download PDFInfo
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- CN101616579A CN101616579A CN200880005767A CN200880005767A CN101616579A CN 101616579 A CN101616579 A CN 101616579A CN 200880005767 A CN200880005767 A CN 200880005767A CN 200880005767 A CN200880005767 A CN 200880005767A CN 101616579 A CN101616579 A CN 101616579A
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- linoleic
- oleic acid
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及杀生物剂组合物,其包含(a)至少一种基于油酸或亚油酸的二烷基酰胺,及(b)至少一种杀生物剂。所述组合物表现出增强的稳定性,即使在5~40℃之间长期存储。
Description
发明领域
本发明涉及农用化学品领域的包含某种二烷基酰胺的杀生物剂组合物,以及所述二烷基酰胺用作杀生物剂的溶剂或分散剂的用途。
发明背景
杀生物剂(biocides),特别是例如杀真菌剂(fungicides)、杀虫剂(insecticides)和除草剂(herbicides)的杀害物药剂(pesticides),是重要的农用辅助试剂,用于保护作物和提高作物产量。根据不同的及通常很具体的需求,存在着大量活性剂,它们具有不同的化学结构和性质。然而,众所周知的是在现有领域中制备表现出满意的稳定性的上述活性剂的水溶液还存在着困难,特别是在很低温度或高温下长时间贮存的活性剂溶液。事实上,上述溶液表现出强烈的分离或形成晶体的倾向,这使得为获得均匀的产品需在每次使用之前将活性剂再分散于组合物中。喷雾装置通常用于植物处理试剂的水性制剂,其中具有数个过滤器和喷嘴,这样的事实会导致出现另外的问题,这个问题与在使用基于固体活性剂化合物的水性喷雾液体的过程中,活性化合物结晶导致过滤器和喷嘴的堵塞有关。
欧洲专利申请EP 0453899B1(拜耳)公开了将源自C6-C20饱和脂肪酸的二甲基酰胺,作为唑衍生物结晶化抑制剂使用,所述唑衍生物可用作杀真菌剂。然而,该专利所述的二甲基酰胺仅能用于有限数量的活性剂。即使是用于唑或唑衍生物时,对于不必要的结晶化的抑制也仅限于在室温下,若该溶液在约5至10℃下使用,则该产品几乎无作用。
因此,本发明要解决的问题是避免现有领域的缺点,开发新的的组合物,所述组合物具有提高了的贮藏稳定性,并在5至40℃的温度范围内降低各种杀生物剂形成晶体的倾向。
发明详述
本发明涉及杀生物剂组合物,其包含:
(a)至少一种基于油酸或亚油酸的二烷基酰胺,及
(b)至少一种杀生物剂。
意外地观察到,二烷基酰胺,优选是从油酸或亚油酸获得的二甲基酰胺,特别是从菜籽、大豆、向日葵或油菜籽酸获得的二甲基酰胺,与现有领域中已知的从脂肪酸获得的二甲基酰胺相比,表现出更好的溶解能力。申请人发现即使在剧烈的条件下,不饱和二烷基酰胺可溶于或分散于多种杀生物剂中,这意味着在5至40℃的温度下贮藏至少4周不会出现相分离或沉淀。
二烷基酰胺
本发明的二烷基酰胺(组分a)可来自油酸和/或亚油酸,并且更具体地来自富含所述种类物质的工业脂肪酸。优选的二烷基酰胺具有下列通式(I),
R1CO-NR2R3(I)
其中,R1CO表示油酸或亚油酸基团,R2和R3独立地表示氢或具有1至4个碳原子的烷基基团。优选的二烷基酰胺是二甲基酰胺。最优选的种类是油酸和亚油酸二甲基酰胺的混合物,如从工业级(technical grade)菜籽、油菜籽、大豆、向日葵获得的脂肪酸,在其低温和高温下长期表现出最好的溶解或分散多种不同杀生物剂的性能,二者优选的重量比是从约10∶90至约90∶10,更优选的是从约25∶75至约75∶25,最优选的是从约40∶60至60∶40。
杀生物剂
杀生物剂(组分b)是一种可杀死不同形式的生物体的化学物质,其用于例如医药、农业、林业和蚊虫控制领域。通常,杀生物剂分成两类:
-杀害物药剂,其包括杀真菌剂、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,其包括杀菌剂(germicide)、抗生素(antibiotics)、抗菌剂(antibacterials)、抗病毒剂(antivirals)、抗真菌剂(antifungals)、抗原虫剂(antiprotozoals)和抗寄生虫剂(antiparasites)。
也可将杀生物剂加入其它物质(通常是液体)中来保护物质不受到生物的感染和侵袭。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,来保护水不受到藻类的感染和侵袭。
杀害物药剂
美国环境保护局(EPA,U.S Environmental Protection Agency)将杀害物药剂定义为“打算用于防止、毁坏、驱散或减轻任何害虫的任何物质或物质的混合物”[1]。杀害物药剂可以是化学物质或生物试剂(例如病毒或细菌),其针对害虫使用,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、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,给出了适用于农用化学品组合物的杀害物药剂:
●杀真菌剂
杀真菌剂是用于控制虫害的三种主要方法之一-在这种情况下,用化学控制真菌。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。杀真菌剂可以是接触性的或内吸性的(systemtic)。接触性杀真菌剂在喷雾于真菌表面时杀死真菌。内吸性杀菌剂在真菌死亡之前需要被真菌吸收。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((3-ethoxypropyl)mercury bromide)、2-甲氧基乙基氯化汞(2-methoxyethylmercury chloride)、邻苯基苯酚(2-phenylphenol)、8-羟基喹啉盐酸盐(8-hydroxyquinoline sulfate)、8-苯汞基氧喹啉(8-phenylmercurioxyquinoline)、噻二唑素(acibenzolar)、酰基氨基酸类杀真菌剂(acylamino acid fungicides)、八九十混酸(acypetacs)、杀螟丹(aldimorph)、脂肪族含氮类杀真菌剂(aliphatic nitrogen fungicides)、烯丙醇(allyl alcohol)、酰胺类杀真菌剂(amide fungicides)、氨丙膦酸(ampropylfos)、敌菌灵(anilazine)、酰替苯胺类杀真菌剂(nilide fungicides)、抗生素类杀真菌剂(antibiotic fungicides)、芳香族类杀真菌剂(aromaticfungicides)、多马霉素(aureofungin)、戊环唑(azaconazole)、氧化福美双(azithiram)、腈嘧菌酯(azoxystrobin),多硫化钡(barium polysulfide)、苯霜灵(benalaxyl)、精本霜灵(benalaxyl-M)、麦锈灵(benodanil)、苯菌灵(benomyl)、敌菌腙(benquinox)、丙唑草隆(bentaluron)、苯噻菌胺(benthiavalicarb)、苄菌铵(benzalkonium chloride)、苄烯酸(benzamacril)、苯甲酰胺类杀真菌剂(benzamide fungicides)、苯杂吗(benzamorf)、苯甲酰苯胺类杀真菌剂(benzanilide fungicides)、苯并咪唑类杀真菌剂(benzimidazole fungicides)、苯并咪唑前体类杀真菌剂(benzimidazoleprecursor fungicides)、苯并咪唑基氨基甲酸酯类杀真菌剂(benzimidazolylcarbamate fungicides)、苯基异羟肟酸(benzohydroxamicacid)、苯并噻唑类杀真菌剂(benzothiazole fungicides)、3-苯并[b]噻吩-2-基-5,6-二氢-1,4,2-噁噻嗪-4-氧化物(bethoxazin)、乐杀螨(binapacryl)、联苯(biphenyl)、双苯三唑醇(bitertanol)、氯赛多(bithionol)、灭瘟素(blasticidin-S)、波尔多液(Bordeaux mixture)、啶酰菌胺(boscalid)、桥连联苯类杀真菌剂(bridged diphenyl fungicides)、糠菌唑(bromuconazole)、磺嘧菌灵(bupirimate)、大土克丝(Burgundy mixture)、粉病定(buthiobate)、氨丁烷(butylamine)、石硫合剂(calcium polysulfide)、敌菌丹(captafol)、克菌丹(captan)、氨基甲酸酯类杀真菌剂(carbamate fungicides)、卡巴莫夫(carbamorph)、苯基氨基甲酸酯类杀真菌剂(carbanilate fungicides)、多菌灵(carbendazim)、萎锈灵(carboxin)、氯环丙酰胺(carpropamid)、香芹酮(carvone)、菌杀特(Cheshunt mixture)、灭螨猛(chinomethionat)、灭瘟唑(chlobenthiazone)、双胺灵(chloraniformethan)、四氯对醌(chloranil)、苯咪唑菌(chlorfenazole)、二硝萘(chlorodinitronaphthalene)、地茂散(chloroneb)、氯化苦(chloropicrin)、百菌清(chlorothalonil)、四氯喹噁啉(chlorquinox)、乙菌利(chlozolinate)、环吡司(ciclopirox)、同菌唑(climbazole)、克霉唑(clotrimazole)、康唑类杀真菌剂(conazole fungicides)、康唑类杀真菌剂(咪唑)(conazole fungicides(imidazoles))、康唑类杀真菌剂(三唑)(conazole fungicides(triazoles)),醋酸铜(copper(II)acetate)、碳酸铜(copper(II)carbonate)、碱式铜类杀真菌剂(basic,copper fungicides),、氢氧化铜(copper hydroxide)、环烷酸酮(copper naphthenate)、油酸酮(copperoleate)、王铜(copper oxychloride)、硫酸铜(copper(II)sulfate)、硫酸亚铜(copper sulfate)、碱式铬酸铜锌(basic,copper zinc chromate)、甲酚(cresol)、硫杂灵(cufraneb)、福美铜氯(cuprobam)、氧化亚铜(cuprous oxide)、氰霜唑(cyazofamid)、环糠酰胺(cyclafuramid)、环二硫代氨基甲酸盐类杀真菌剂(cyclic dithiocarbamate fungicides)、放线菌酮(cycloheximide)、环氟菌胺(cyflufenamid),清菌脲(cymoxanil)、氰菌灵(cypendazole)、环唑醇(cyproconazole)、环丙嘧啶(cyprodinil)、棉隆(dazomet)、二溴氯丙烷(DBCP)、双乙氧咪唑威(debacarb)、癸磷锡(decafentin)、保果鲜(dehydroacetic acid)、二甲酰亚胺类杀真菌剂(dicarboximide fungicides)、抑菌灵(dichlofluanid)、二氯萘醌(dichlone)、双氯酚(dichlorophen)、二氯苯基(dichlorophenyl)、二甲酰亚胺类杀真菌剂(dicarboximide fungicides)、菌核利(dichlozoline)、苄氯三唑醇(diclobutrazol)、双氯氰菌(diclocymet)、哒菌清(diclomezine)、氯硝胺(dicloran)、乙霉威(diethofencarb)、焦碳酸二乙酯(diethyl pyrocarbonate)、噁醚唑(difenoconazole)、氟嘧菌胺(diflumetorim)、甲菌定(dimethirimol)、烯酰吗啉(dimethomo[phi]h)、嘧菌胺(dimoxystrobin)、烯唑醇(diniconazole)、二硝酚类杀真菌剂(dinitrophenolfungicides)、敌螨通(dinobuton)、敌螨普(dinocap)、二硝酯(dinocton)、硝戊酯(dinopenton)、硝辛酯(dinosulfon)、硝丁酯(dinoterbon)、二苯胺(diphenylamine)、吡菌硫(dipyrithione)、双硫仑(disulfiram)、灭菌磷(ditalimfos)、二噻农(dithianon)、二硫代氨基甲酸盐类杀真菌剂(dithiocarbamate fungicides)、二硝甲酚(DNOC)、吗菌灵(dodemorph)、多敌菌(dodicin)、多果定(dodine)、DONATODINE、敌菌酮(drazoxolon)、克瘟散(edifenphos)、氧唑菌(epoxiconazole)、乙环唑(etaconazole)、代森硫(etem)、噻唑菌胺(ethaboxam)、乙菌定(ethirimol)、促长啉(ethoxyquin)、乙汞2,3-二羟基丙基硫醇盐(ethylmercury 2,3-dihydroxypropylmercaptide)、乙汞醋酸盐(ethylmercury acetate)、溴化乙汞(ethylmercurybromide)、西力生(ethylmercury chloride)、西谷生(ethylmercury phosphate)、氯唑灵(etridiazole)、噁唑酮菌(famoxadone)、咪唑菌酮(fenamidone)、地可松(fenaminosulf)、菌拿灵(fenapanil)、异嘧菌醇(fenarimol)、腈苯唑(fenbuconazole)、呋菌胺(fenfuram)、环酰菌胺(fenhexamid)、种衣酯(fenitropan)、氰菌胺(fenoxanil)、拌种咯(fenpiclonil)、苯锈啶(fenpropidin)、丁苯吗啉(fenpropimorph)、三苯锡基(fentin)、福美铁(ferbam)、嘧菌腙(ferimzone)、氟啶胺(fluazinam)、氟噁菌(fludioxonil)、氟联苯菌(flumetover)、氟吗啉(flumorph)、氟吡菌胺(fluopicolide)、氟菌胺(fluoroimide)、菌唑灵(fluotrimazole)、氟嘧菌酯(fluoxastrobin)、喹唑菌酮(fluquinconazole)、氟硅唑(flusilazole)、磺菌胺(flusulfamide)、氟酰胺(flutolanil)、粉唑醇(flutriafol)、灭菌丹(folpet)、甲醛(formaldehyde)、藻菌磷(fosetyl)、麦穗宁(fuberidazole)、呋氨丙灵(furalaxyl)、呋吡唑灵(furametpyr)、糠酰胺类杀真菌剂(furamide fungicides)、呋喃酰替苯胺类杀真菌剂(furanilide fungicides)、灭菌胺(furcarbanil)、呋菌唑(furconazole)、呋醚唑(furconazole-cis)、糠醛(furfural)、拌种胺(furmecyclox)、呋菌隆(furophanate)、果绿定(glyodin)、灰黄霉素(griseofulvin)、双胍辛醋酸盐(guazatine)、halacrinate(烯菌酯)、六氯苯(hexachlorobenzene)、六氯丁二烯(hexachlorobutadiene)、菌螨酚(hexachlorophene)、己唑醇(hexaconazole)、环己硫磷(hexylthiofos)、汞加芬(hydrargaphen)、土菌消(hymexazol)、烯菌灵(imazalil)、酰胺唑(imibenconazole)、咪唑类杀真菌剂(imidazolefungicides)、双胍辛醋酸盐(iminoctadine)、无机类杀真菌剂(inorganicfungicides)、无机汞类杀真菌剂(inorganic mercury fungicides)、甲基碘(iodomethane)、环戊唑醇(ipconazole)、异稻瘟净(iprobenfos)、异丙定(iprodione)、异森辛(iprovalicarb)、稻瘟灵(isoprothiolane)、氯苯咪菌酮(isovaledione)、春雷霉素(kasugamycin)、亚胺菌(kresoxim-methyl)、石硫合剂(lime sulphur),锰铜混剂(mancopper)、代森锰锌(mancozeb)、代森锰(maneb)、灭锈胺(mebenil)、咪卡病西(mecarbinzid)、嘧菌胺(mepanipyrim)、丙氧灭绣胺(mepronil)、升汞(mercuric chloride)、氧化汞(mercuric oxide)、甘汞(mercurous chloride)、汞类杀真菌剂(mercury fungicides),甲霜灵(metalaxyl)、精甲霜灵(metalaxyl-M)、威百亩(metam)、肼叉噁唑酮(metazoxolon)、环戊唑菌(metconazole)、磺菌威(methasulfocarb)、甲呋菌胺(methfuroxam)、溴甲烷(methyl bromide)、氰土灵(methyl isothiocyanate)、苯甲酸甲汞(methylmercury benzoate)、氰胍甲汞(methylmercurydicyandiamide)、五氯酚甲汞(methylmercury pentachlorophenoxide)、代森联(metiram)、叉氨苯酰胺(metominostrobin)、苯菌酮(metrafenone)、噻菌胺(metsulfovax)、代森环(milneb)、吗啉类杀真菌剂(morpholine fungicides)、腈菌唑(myclobutanil)、甲菌利(myclozolin)、N-(乙汞基)-对甲苯硫酰苯胺(N-(ethylmercury)-p-toluenesulphon-anilide)、代森钠(nabam),多马霉素(natamycin)、硫氰散(nitrostyrene)、异丙消(nitrothal-isopropyl)、氟苯嘧啶醇(nuarimol)、八氯酮(OCH)、异噻菌酮(octhilinone)、甲呋酰胺(ofurace)、有机汞类杀真菌剂(organomercury fungicides)、有机磷类杀真菌剂(organophosphorus fungicides)、有机锡类杀真菌剂(organotin fungicides)、肟醚菌胺(orysastrobin)、噁霜灵(oxadixyl)、氧硫杂环己二烯类杀真菌剂(oxathiin fungicides)、噁唑类杀真菌剂(oxazole fungicides)、喹啉铜(oxinecopper)、恶咪唑(oxpoconazole)、氧化莠锈灵(oxycarboxin)、稻瘟酯(pefurazoate)、戊菌唑(penconazole)、戊菌隆(pencycuron)、五氯酚(pentachlorophenol)、吡噻菌胺(penthiopyrad)、苯汞脲(phenylmercuriurea)、赛力散(phenylmercury acetate)、氯化苯汞(phenylmercury chloride)、邻苯二酚的苯汞衍生物(phenylmercury derivative of pyrocatechol)、硝酸苯汞(phenylmercury nitrate)、水杨酸苯汞(phenylmercury salicylate)、苯基磺酰胺类杀真菌剂(phenylsulfamide fungicides)、双氯苯磷(phosdiphen)、四氯苯酞(phthalide)、酞酰亚胺类杀真菌剂(phthalimide fungicides)、啶氧菌酯(picoxystrobin)、粉病灵(piperalin)、福代锌(polycarbamate)、聚二硫代氨基甲酸盐类杀真菌剂(polymeric dithiocarbamate fungicides)、多氧霉素(polyoxins)、多氧霉素(polyoxorim)、多硫化物类杀真菌剂(polysulfidefungicides)、叠氮钾(potassium azide)、多硫化钾(potassium polysulfide)、硫氰酸钾(potassium thiocyanate)、噻菌灵(probenazole)、丙氯灵(prochloraz)、杀菌利(procymidone)、百维灵(propamocarb)、丙环唑(propiconazole),甲基代森锌(propineb)、丙氧喹啉(proquinazid)、胺丙威(prothiocarb)、丙硫菌唑(prothioconazole)、比锈灵(pyracarbolid)、百克敏(pyraclostrobin)、吡唑类杀真菌剂(pyrazole fungicides)、定菌磷(pyrazophos)、吡啶类杀真菌剂(pyridine fungicides)、病定清(pyridinitril)、啶斑肟(pyrifenox)、二甲嘧菌胺(pyrimethanil)、嘧啶类杀真菌剂(pyrimidinefungicides)、咯喹酮(pyroquilon)、吡氧氯(pyroxychlor)、氯吡呋醚(pyroxyfur)、吡咯类杀真菌剂(pyrrole fungicides)、喹啉(quinacetol)、酯菌腙(quinazamid)、唑喹菌酮(quinconazole)、喹啉类杀真菌剂(quinolinefungicides)、苯醌类杀真菌剂(quinone fungicides)、喹噁啉类杀真菌剂(quinoxaline fungicides)、喹氧灵(quinoxyfen)、五氯硝基苯(quintozene)、吡咪唑菌(rabenzazole)、防霉胺(salicylanilide)、硅噻菌胺(silthiofam)、硅氟唑(simeconazole)、叠氮化钠(sodium azide)、联苯酚钠(sodiumorthophenylphenoxide)、五氯酚(sodium pentachlorophenoxide)、多硫化钠(sodium polysulfide)、螺噁茂胺(spiroxamine)、链霉素(streptomycin)、甲氧丙烯酸酯类杀真菌剂(strobilurin fungicides)、磺酰苯胺类杀真菌剂(sulfonanilide fungicides)、硫(sulfur)、戊苯砜(sultropen)、清菌噻唑(TCMTB)、戊唑醇(tebuconazole)、叶枯酞(tecloftalam)、四氯硝基苯(tecnazene)、福代硫(tecoram)、氟醚唑(tetraconazole)、涕必灵(thiabendazole)、噻二氟(thiadifluor)、噻唑类杀真菌剂(thiazole fungicides)、噻菌腈(thicyofen)、溴氟唑菌(thifluzamide)、硫代氨基甲酸酯类杀真菌剂(thiocarbamate fungicides)、苯菌胺(thiochlorfenphim)、水杨乙汞(thiomersal)、托布津(thiophanate)、甲基托布津(thiophanate-methyl)、噻吩类杀真菌剂(thiophene fungicides)、克杀螨(thioquinox)、福美双(thiram)、噻酰菌胺(tiadinil)、硫氰苯甲酰胺(tioxymid)、tivedo、甲基立枯磷(tolclofos-methyl)、托萘酯(tolnaftate)、对甲抑菌灵(tolylfluanid)、乙酸甲苯汞(tolylmercury acetate)、三唑酮(triadimefon)、唑菌醇(triadimenol)、三唑磷胺(triamiphos)、嘧菌醇(triarimol)、叶锈特(triazbutil)、敌菌灵类杀真菌剂(triazine fungicides)、三唑类杀真菌剂(triazole fungicides)、唑菌嗪(triazoxide)、丁蜗锡(tributyltin oxide)、杨菌胺(trichlamide)、三环唑(tricyclazole)、克啉菌(tridemorph)、肟菌酯(trifloxystrobin)、氟菌唑(triflumizole)、嗪氨灵(triforine)、戊叉唑菌(triticonazole)、未分类杀真菌剂(unclassified fungicides)、十一碳烯酸(undecylenic acid)、烯效唑(uniconazole)尿素类杀真菌剂(urea fungicides)、有效霉素(validamycin)、缬氨酰胺类杀真菌剂(valinamide fungicides)、烯菌酮(vinclozolin)、氯菌胺(zarilamid)、环烷酸锌(zinc naphthenate)、代森锌(zineb)、福美锌(ziram)、苯酰菌胺(zoxamide)及它们的混合物。
●除草剂
除草剂是一种杀害物药剂,其用于杀死不必要的植物。选择性的除草剂杀死特定的目标,同时相对的对于必要的作物没有伤害。这些效应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,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)工程来维护高速公路和铁路。少数除草剂用于森林、牧场、及被指定为野生动物栖息的区域的管理。以下说明了一些合适的除草剂:
○2,4-D是含有苯氧基的阔叶除草剂,其用于草坪及免耕作物生产。现在其主要与其他产生协同作用的除草剂混合使用,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。其是合成植物生长激素(植物激素)的一个实例。
○阿特拉津(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II的抑制剂。
○二氯皮考啉酸(Clopyralid)是包含吡啶基团的阔叶除草剂,主要用于草坪、牧场及控制有害蓟类植物。因其在堆肥中的持久性而臭名昭著。其是合成植物生长激素的另一个实例。
○麦草畏(Dicamba)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。其是合成植物生长激素的另一个实例。
○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),其用于免耕除草(no-till bumdown)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。
○灭草烟(Imazapyr)是一种非选择性的除草剂,用于控制多种杂草,包括陆生一年生和多年生草、及阔叶草、木本植物、和岸栖植物与挺水植物。
○甲基咪草烟(Imazapic)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萌前和萌后控制。甲基咪草烟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)的生产,来杀死植物。
○异丙甲草胺(Metoalachlor)是一种萌前除草剂,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了阿特拉津。
○百草枯(Paraquat)是一种非选择性接触性除草剂,其用于免耕除草及大麻和古柯植物的空中喷洒(aerial destruction)。在广泛商业应用的除草剂中,其与任何其他除草剂相比对人具有更剧烈的毒性。
○毒莠定(Picloram)是一种吡啶除草剂,主要用于控制在牧场和田边的不必要的树。它是合成植物生长激素的另一个实例。
○定草酯(Triclopyr)
●杀虫剂
杀虫剂是一种针对所有发育形式(developmental form)的昆虫使用的杀害物药剂。其包括针对昆虫卵和幼虫使用的杀卵剂和杀幼虫剂。杀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)、滴滴涕(DDT)、六氯环己烷(Hexachloro-cyclohexane)、γ-六氯环己烷(gamma-Hexachlorocyclohexane)、甲氧滴滴涕(Methoxychlor)、五氯酚(Pentachlorophenol)、滴滴滴(TDE)、艾氏剂(Aldrin)、氯丹(Chlordane)、狄氏剂(Dieldrin)、硫丹(Endosulfan)、异狄氏剂(Endrin)、七氯(Heptachlor)、灭蚁灵(Mirex)及它们的混合物;
○有机磷化合物,例如高灭磷(Acephate)、谷硫磷(Azinphos-methyl)、地散磷(Bensulide)、壤虫氯磷(Chlorethoxyfos)、毒死蜱(Chlorpyrifos)、甲基毒死蜱(Chlorpyriphos-methyl)、二嗪农(Diazinon)、敌敌畏(Dichlorvos(DDVP))、百治磷(Dicrotophos)、乐果(Dimethoate)、乙拌磷(Disulfoton)、灭克磷(Ethoprop)、克线磷(Fenamiphos)、杀螟松(Fenitrothion)、倍硫磷(Fenthion)、噻唑酮磷(Fosthiazate)、马拉松(Malathion)、甲胺磷(Methamidophos)、杀扑磷(Methidathion)、甲基对硫磷(Methyl-parathion)、速灭磷(Mevinphos)、二溴磷(Naled)、氧化乐果(Omethoate)、砜吸磷(Oxydemeton-methyl)、对硫磷(Parathion)、甲拌磷(Phorate)、伏杀磷(Phosalone)、亚胺硫磷(Phosmet)、嘧丙磷(Phostebupirim)、虫螨磷(Pirimiphos-methyl)、丙溴磷(Profenofos)、特丁磷(Terbufos)、杀虫畏(Tetrachlorvinphos)、脱叶磷(Tribufos)、敌百虫(Trichlorfon)及它们的混合物;
○氨基甲酸酯,例如涕灭成(Aldicarb)、虫螨威(Carbofuran)、西维因(Carbaryl)、灭多虫(methomyl)、2-(1-甲基丙基)苯基甲基氨基甲酸酯(2-(1-Methylpropyl)phenyl methylcarbamate)及它们的混合物;
○合成除虫菊酯,例如丙烯除虫菊酯(Allethrin)、氟氯菊酯(Bifenthrin)、溴氰菊酯(deltamethrin)、氯菊酯(Permethrin)、灭虫菊(Resmethrin)、苯醚菊酯(Sumithrin)、胺菊酯(Tetramethrin)、四溴菊酯(Tralomethrin)、四氟菊酯(Transfluthrin)及它们的混合物;
○源自植物毒素的化合物,例如Denis(鱼藤酮(rotenone))、除虫菊(Pyrethrum)、Neem(艾扎丁(Azadirachtin))、尼古丁(Nicotine)、咖啡因(Caffeine)及它们的混合物。
●杀鼠剂
○杀鼠剂是一类意欲杀死啮齿类动物的有害物防治化学品。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色无味的,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,很少立即死亡)、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,例如溴敌拿鼠(brodifacoum)、杀鼠迷(coumatetralyl)、杀鼠灵(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-羟基硫代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(prothrombin))、VII(前转变素(proconvertin))、IX(克里斯特马斯因子(Christmas factor))和X(司徒因子(Stuart factor)))。除了这种具体的代谢破坏外,毒性剂量的4-羟基香豆素/4-羟基硫代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:杀鼠灵、杀鼠迷;茚满二酮类:杀鼠酮(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至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(敌拿鼠(difenacoum)、溴敌拿鼠、溴敌鼠((bromadiolone)、氟鼠酮(flocoumafen)或4-羟基-1-硫代苯并吡喃-2-酮(4-hydroxyl-1-benzothiin-2-one),(4-羟基-1-硫代香豆素(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),即噻鼠酮(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系仍然有效;因此第二代抗凝血剂有时被称为“超级杀鼠灵(superwarfarin)”。有时,抗生素可增强抗凝血杀鼠剂,最常见的为磺胺喹噁啉(sulfaquinoxaline)。这种联合(例如0.05%的杀鼠灵+0.02%的磺胺喹噁啉或0.005%的敌拿鼠+0.02%的磺胺喹噁啉等)的目的在于抗生素/抑菌剂抑制代表了维生素K来源的肠/消化道共生微生物群。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。也可使用非磺胺喹噁啉的抗生素试剂,例如复方增效磺胺(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活性的化合物一起使用,即胆钙化醇或麦角钙化醇(见下文)。所用的典型配方例如:0.025~0.05%的杀鼠灵+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%的敌拿鼠+0.02%的磺胺喹噁啉+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种类也有效,虽然在诱饵中浓度为0.0025~0.005%的一些第二代抗凝血剂(即溴敌拿鼠和噻鼠酮)毒性很强,以至于不存在耐受的啮齿动物种类,甚至对任何耐受其他衍生物的啮齿动物,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除去。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偶然或意外地(宠物中毒、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,并且在毒素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)可挽救意外接触这些有毒物的人员的生命,这比其他前期有毒物具有优势。
○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天死亡)。将由食物和磷化物(通常是磷化锌)组成的一定剂量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。这种控制有害物的方法可能用于对耐受一些抗凝血剂的啮齿动物,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,然后持续地投与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1~2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(即啮齿动物直接食用),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,而不会影响建筑物。其典型的实例是磷化铝(仅用于熏蒸消毒剂)、磷化钙(仅用于熏蒸消毒剂)、磷化镁(仅用于熏蒸消毒剂)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。
○高钙血综合症。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的体内稳定。少量的维生素D是重要的(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,大剂量的维生素D是有毒的,其会直接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,部分结合血浆蛋白,[CaHCO3]+),从而提高钙水平,引起高钙血综合症,所述钙离子在血浆中溶解和循环,当摄入致死剂量后,游离的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(心肌对各种游离钙水平是敏感的,游离钙水平会影响心房和心室间心肌的收缩和兴奋的传导)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。更若存在钙化醇,则可观察到更明显的抗凝血/出血效果。此协同作用常用于诱饵中降低钙化醇含量,因为有效的钙化醇的浓度较大多数有效的抗凝血剂更加昂贵。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的产品D(与现在的D配方不同),其含有0.025%的杀鼠灵+0.1%的麦角钙化醇。如今的CD含有0.0025%的敌拿鼠+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品也在市场上销售。
●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。抗生素杀螨剂(antibioticmiticides)、氨基甲酸酯杀螨剂(carbamate miticides)、甲脒杀螨剂(formamidine miticides)、螨类生长调节剂(mite growth regulators)、有机氯(organochlorine)、氯菊酯(permethrin)和有机磷杀螨剂(organophosphatemiticides)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。这些物质包括多聚乙醛(metaldehyde)、灭虫威(methiocarb)、硫酸铝(aluminium sulfate)。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。
○杀线虫剂从栋树的油饼获得;其是油提取后油饼的残余物。世界上已知栋树有数个名称,但是自古时起由印度首先种植。
抗微生物剂
下列实例,为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:
○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(碘代聚乙烯吡咯酮(聚乙烯酮碘,聚维酮碘)、复方碘溶液、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“石碳酸”)、甲酚(称为“来苏尔”,与液体钾皂组合)、卤代(氯代、溴代)酚(例如六氯酚、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、氯化十六烷基吡啶鎓、苄索氯铵)及其他非季铵盐化合物,例如洗必泰、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
○适当的浓强酸(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,作为消毒剂使用,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:
○一些适当稀释的氯化试剂(例如氯苯三嗪胺溶液(Daquin′ssolution)、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,例如碘代聚乙烯吡咯酮的各种盖伦制剂(软膏剂、溶液、外伤膏药),其过去也被称为复方碘溶液,
○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,
○加入或未加入消毒剂添加剂的醇类,其主要用于皮肤消毒,
○有机弱酸,例如山梨酸、苯甲酸、乳酸和水杨酸,
○一些酚类化合物,例如六氯苯酚、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%的洗必泰、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,例如头孢霉素。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,氟喹诺酮类、呋喃类、万古霉素、单环-内酰胺类、磺胺类和甲硝唑。
乳化剂
在许多情况下为支持产品的稳定性,向杀生物剂组合物中加入乳化剂(组分c)是有利的。乳化剂优选的第一类别包括例如非离子表面活性剂,例如:
●2~30摩尔氧化乙烯和/或0~5摩尔氧化丙烯与直链或C8-22脂肪醇、C12-22脂肪酸和烷基部分含有8~15个碳原子的烷基酚的加成产物;
●1~30摩尔氧化乙烯与甘油的加成产物C12/18脂肪酸单酯或二酯;
●含有6~22个碳原子的饱和和不饱和脂肪酸的甘油单酯和二酯及脱水山梨糖醇的单酯和二酯及其与氧化乙烯的加成产物;
●15~60摩尔氧化乙烯与蓖麻油和/或氢化蓖麻油的加成产物;
●多元醇酯,特别是例如聚甘油酯,例如聚甘油聚蓖麻油酸酯、聚甘油聚-12-羟基硬脂酸酯或聚甘油二聚合油异硬脂酸酯(polyglyceroldimerate isostearate)。这些类型的化合物中的一些的混合物也是合适的;
●2~15摩尔氧化乙烯与蓖麻油和/或氢化蓖麻油的加成产物;
●基于直链、支链、饱和或不饱和C6/22脂肪酸、蓖麻油酸和12-羟基硬脂酸与甘油、聚甘油、季戊四醇、二季戊四醇、糖醇(例如山梨醇)、烷基糖苷(例如甲基糖苷、丁基糖苷、月桂基糖苷)和多聚葡萄糖苷(例如纤维素)的偏酯;
●单、二和三烷基磷酸酯单、二和/或三-PEG-烷基磷酸酯及其盐;
●羊毛蜡醇;
●聚硅氧烷/聚烷基聚醚共聚物和相应的衍生物;
●季戊四醇、脂肪酸、柠檬酸与脂肪醇的混合酯和/或C6-22脂肪酸、甲基葡萄糖和多元醇,优选是甘油或聚甘油的混合酯
●聚亚烷基二醇,及
●甘油碳酸酯。
氧化乙烯和/或氧化丙烯与脂肪醇、脂肪酸、烷基酚、脂肪酸的甘油单酯和二酯及山梨醇单酯和二酯的加成产物,或与蓖麻油的加成产物是已知的商业上可得产品。它们是同源的混合物,其中烷氧基化的程度与氧化乙烯和/或氧化丙烯在加成反应时与所用的底物的量的比相当。已知氧化乙烯与甘油的加成产物的C12/18脂肪酸单酯和二酯用作化妆品配制剂的脂质层增强剂。以下更详细地说明了优选的乳化剂:
●偏甘油酯
合适的偏甘油酯的典型实例是羟基硬脂酸甘油单酯、羟基硬脂酸甘油二酯、异硬脂酸甘油单酯、异硬脂酸甘油二酯、油酸甘油单酯、油酸甘油二酯、蓖麻油酸甘油单酯、蓖麻油酸甘油二酯、亚油酸甘油单酯、亚油酸甘油二酯、亚麻酸甘油单酯、亚麻酸甘油二酯、芥子酸甘油单酯、芥子酸甘油二酯、酒石酸甘油单酯、酒石酸甘油二酯、柠檬酸甘油单酯、柠檬酸甘油二酯、苹果酸甘油单酯、苹果酸甘油二酯及其工业混合物,所述工业混合物仍然会含有少量来自生产工艺的甘油三酯。上述1~30摩尔,优选5~10摩尔的氧化乙烯与偏甘油酯的加成产物也是合适的。
●脱水山梨糖醇酯
合适的脱水山梨糖醇酯是脱水山梨糖醇异硬脂酸单酯、脱水山梨糖醇倍半异硬脂酸酯、脱水山梨糖醇二异硬脂酸酯、脱水山梨糖醇三异硬脂酸酯、脱水山梨糖醇单油酸酯、脱水山梨糖醇倍半油酸酯、脱水山梨糖醇二油酸酯、脱水山梨糖醇三油酸酯、脱水山梨糖醇芥酸单酯、脱水山梨糖醇倍半芥酸酯、脱水山梨糖醇二芥酸酯、脱水山梨糖醇三芥酸酯、脱水山梨糖醇单蓖麻油酸酯、脱水山梨糖醇倍半蓖麻油酸酯、脱水山梨糖醇二蓖麻油酸酯、脱水山梨糖醇三蓖麻油酸酯、脱水山梨糖醇单羟基硬脂酸酯、脱水山梨糖醇倍半羟基硬脂酸酯、脱水山梨糖醇二羟基硬脂酸酯、脱水山梨糖醇三羟基硬脂酸酯、脱水山梨糖醇单酒石酸酯、脱水山梨糖醇倍半酒石酸酯、脱水山梨糖醇二酒石酸酯、脱水山梨糖醇三酒石酸酯、脱水山梨糖醇单柠檬酸酯、脱水山梨糖醇倍半柠檬酸酯、脱水山梨糖醇二柠檬酸酯、脱水山梨糖三柠檬酸酯、脱水山梨糖醇单马来酸酯、脱水山梨糖醇倍半马来酸酯、脱水山梨糖醇二马来酸酯、脱水山梨糖醇三马来酸酯及其工业混合物。上述1~30摩尔,优选是5~10摩尔氧化乙烯与脱水山梨糖醇酯的加成产物也是合适的。
●聚甘油酯
合适的聚甘油酯的典型实例是聚甘油基-2二聚羟基硬脂酸酯(PGPH)、聚甘油基-3二异硬脂酸酯(TGI)、聚甘油基-4异硬脂酸酯(GI 34)、聚甘油基-3油酸酯、二异硬脂酰基聚甘油基-3异硬脂酸酯(PDI)、聚甘油基-3甲基葡萄糖二硬脂酸酯(Tego450)、聚甘油基-3蜂蜡(Cera)、聚甘油基-4癸酸酯(Polyglycerol Caprate T2010/90)、聚甘油基-3十六醚(NL)、聚甘油基-3二硬脂酸酯(GS 32)及聚甘油基聚蓖麻油酸酯(WOL 1403),聚甘油二聚合油异硬脂酸酯及它们的混合物。聚油酸酯其他合适的实例是三羟甲基丙烷或季戊四醇与月桂酸、椰油酸、动物脂肪酸、棕榈酸、硬脂酸、油酸、山嵛酸等的单、二和三酯,视情况可与1~30摩尔氧化乙烯反应。
典型的阴离子乳化剂例如C12-22脂肪族脂肪酸,例如棕榈酸、硬脂酸或山嵛酸,和C12-22二羧酸,例如壬二酸或癸二酸。
其他合适的乳化剂是两性离子表面活性剂。两性离子表面活性剂是表面活性的化合物,其分子中含有至少一种季铵基团和至少一种羧酸盐基团及一个磺化基团。特别合适的两性离子表面活性剂是所谓的内铵盐,例如N-烷基-N,N-二甲基铵甘氨酸盐,例如椰油烷基二甲基铵甘氨酸盐、N-酰氨基丙基-N,N-二甲基铵甘氨酸盐,例如椰油酰氨基丙基二甲基铵甘氨酸盐,和烷基或酰基基团含有8~18个碳原子的和2-烷基-3-羧甲基-3-羟乙基咪唑啉及椰油酰氨基乙基羟乙基羧甲基甘氨酸盐。特别优选的是名称为CTFA的已知的脂肪酸酰胺衍生物——椰油酰胺丙基内铵盐。两性表面活性剂也是合适的乳化剂。两性表面活性剂是表面活性的化合物,其分子中除了C8/18烷基或酰基基团外,还含有至少一种游离的氨基和至少一种-COOH-或-SO3H-,并且可分子内成盐。合适的两性表面活性剂的实例是烷基部分含有约8~18个碳原子的N-烷基甘氨酸、N-烷基丙酸、N-烷基氨基丁酸、N-烷基亚胺基二丙酸、N-羟乙基-N-烷基氨基丙基甘氨酸、N-烷基牛磺酸、N-烷基肌氨酸、2-烷基-氨基丙酸和烷基氨基乙酸。优选的两性表面活性剂是N-椰油烷基氨基-丙酸盐(酯)、椰油酰氨基乙基氨基丙酸盐(酯)和C12/18酰基肌氨酸。
杀生物剂组合物
通常,本发明组合物包含在加水至100%重量的条件下的:
(a)约0.1%重量(by weight,即b.w.)至约99%重量,优选为约5%重量至约90%重量,最优选为约15%重量至约25%重量的源自油酸和/或亚油酸的二烷基酰胺,
(b)约1%重量至约99.1%重量,优选为约2%重量至约80%重量,最优选为约5%重量至约15%重量的杀生物剂,及
(c)0%重量至约10%重量,优选为1%重量至约5%重量的乳化剂。通常,基于总的水性组合物计算的活性物质的含量(表示组分a+b+c的和)大约是5%重量至约50%重量,优选是从约10%重量至约25%重量。
工业应用
本发明最终的实施方案涉及基于油酸和/或亚油酸的二烷基酰胺,具体是基于工业级菜籽、油菜籽、大豆或向日葵酸的二甲基酰胺用作杀生物剂的溶剂或分散剂的用途。
实施例
实施例1~6,比较实施例C1和C2
通过在水中混合杀生物剂、二甲基酰胺和乳化剂,直至得到均匀的溶液而制备一些水性浓缩物(aqueous concentrates)。随后以水稀释得到活性物质浓度为10%重量的溶液。将所得产品在5、20、40℃下存贮10至40天。通过检测观察混合物的稳定性,并通过以下标准确定混合物的稳定性:(++)=稳定;(+)=轻微的相分离/形成一些结晶;(o)=明显的相分离沉淀;(-)清楚地相分离/严重的结晶沉淀。所得结果列于表1中。数值反应了水性浓缩物的组成。
表1.杀生物组合物的稳定性
Claims (10)
1.一种杀生物剂组合物,其包含:
(a)至少一种基于油酸或亚油酸的二烷基酰胺,及
(b)至少一种杀生物剂。
2.根据权利要求1所述的组合物,其特征在于所述组合物包含通式(I)的二烷基酰胺组分(a),
R1CO-NR2R3(I)
其中,R1CO表示油酸和/或亚油酸基团,R2和R3独立地表示氢或具有1至4个碳原子的烷基基团。
3.根据权利要求1和/或2所述的组合物,其特征在于所述组合物包含基于工业级的菜籽、油菜籽、大豆或向日葵酸的二烷基酰胺组分(a)。
4.根据权利要求1-3任一项所述的组合物,其特征在于所述组合物包含基于油酸和亚油酸的二甲基酰胺组分(a),其中所述油酸和亚油酸的重量比为从10∶90至90∶10。
5.根据权利要求1-4任一项所述的组合物,其特征在于所述组合物包含选自杀害物药剂和抗微生物剂的杀生物剂(组分b)。
6.根据权利要求1-5任一项所述的组合物,其特征在于所述组合物包含选自杀真菌剂、除草剂、杀虫剂、杀鼠剂、杀螨剂、杀软体动物剂、杀线虫剂及它们的混合物的杀害物药剂。
7.根据权利要求1-6任一项所述的组合物,其特征在于所述组合物包含任选的乳化剂组分(c)。
8.根据权利要求1-7任一项所述的组合物,其特征在于所述组合物包含:
(a)0.1%重量至99%重量的源自油酸和/或亚油酸的二烷基酰胺,
(b)1%重量至99.1%重量的杀生物剂,及
(c)0%重量至10%重量的乳化剂,
如果需要加水至100%重量。
9.根据权利要求1-8任一项所述的组合物,其特征在于所述组合物中活性物质含量为5%重量至50%重量。
10.基于油酸和/或亚油酸的二烷基酰胺用作杀生物剂的溶剂或分散剂的用途。
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EP07003722A EP1961302A1 (en) | 2007-02-23 | 2007-02-23 | Biocide compositions comprising at least one dialkylamide based on oleic or linoleic acid |
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CN102067834A (zh) * | 2010-12-07 | 2011-05-25 | 北京农学院 | 亚油酸杀螨剂及其制备方法 |
CN104262419A (zh) * | 2014-09-15 | 2015-01-07 | 上海发凯化工有限公司 | 一种烷基糖苷及其脱醇工艺 |
CN105399501A (zh) * | 2015-11-24 | 2016-03-16 | 陕西省微生物研究所 | 一种用于防治果树枝干病害的注干药剂及其制备方法 |
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ES2386384T3 (es) * | 2008-04-19 | 2012-08-20 | Cognis Ip Management Gmbh | Composiciones para el desengrasado de superficies metálicas |
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AU2010338304B2 (en) | 2009-12-30 | 2014-05-08 | Akzo Nobel Chemicals International B.V. | Amides, use of amides as solvents for organic compounds, compositions and emulsions containing amides, and method for treating a plant |
GB201012585D0 (en) * | 2010-07-27 | 2010-09-08 | Syngenta Ltd | Cleaning methods |
GB2482299A (en) * | 2010-07-27 | 2012-02-01 | Syngenta Ltd | Use of a dialkylamide to reduce the phytotoxicity of an agrochemical |
US9173398B2 (en) * | 2011-07-05 | 2015-11-03 | Cognis Ip Management Gmbh | Biocide compositions |
BR112014002940B1 (pt) * | 2011-08-11 | 2019-04-09 | Bayer Intellectual Property Gmbh | Uso de carboxamidas e formulação agroquímica |
PT2827714T (pt) * | 2012-03-23 | 2019-09-30 | Dow Agrosciences Llc | Concentrados de aditivos para mistura em tanque que contenham ésteres de ácidos gordos triglicerídeos e métodos de utilização |
EP3393243B1 (en) * | 2015-12-22 | 2022-03-02 | The Procter & Gamble Company | Compositions comprising an amide |
CN113796390B (zh) * | 2020-06-15 | 2022-12-13 | 沈阳恩柽研究院有限公司 | 一种线虫提取物及其应用 |
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US3342673A (en) * | 1964-09-11 | 1967-09-19 | Mobil Oil Corp | Solvent system for formulating carbamates |
US3954977A (en) * | 1972-07-24 | 1976-05-04 | American Home Products Corporation | Insecticidal pyrethroid compositions having increased efficacy |
DE4013522A1 (de) * | 1990-04-27 | 1991-10-31 | Bayer Ag | Verwendung von alkylcarbonsaeure-dimethylamiden als kristallisationsinhibitoren |
US5213805A (en) * | 1991-07-25 | 1993-05-25 | Micro Vesicular Systems, Inc. | Lipid vesicles having n,n-dimethylamide derivatives as their primary lipid |
BR9307869A (pt) * | 1992-12-14 | 1996-07-30 | Buckman Labor Inc | Composiçao pesticida método para aumentar a eficácia de um pesticida e formulaçao pesticida concentrada |
DE4404222A1 (de) * | 1994-02-10 | 1995-08-17 | Bayer Ag | Verwendung von Dicarbonsäure-bis-dimethylamiden als Kristallisationsinhibitoren |
US5874453A (en) * | 1997-07-11 | 1999-02-23 | Buckman Laboratories International, Inc. | Synergistic antimicrobial compositions containing a dimethylamide of a carboxylic acid with mixture of 2-(thiocyanomethylthio) benzothiazone and methylenebis (thiocyanate) |
US20010019996A1 (en) * | 1998-04-24 | 2001-09-06 | Gerard G. Soula | Process and compositions promoting biological effectiveness of exogenous chemical substances in plants |
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CN102067834A (zh) * | 2010-12-07 | 2011-05-25 | 北京农学院 | 亚油酸杀螨剂及其制备方法 |
CN104262419A (zh) * | 2014-09-15 | 2015-01-07 | 上海发凯化工有限公司 | 一种烷基糖苷及其脱醇工艺 |
CN105399501A (zh) * | 2015-11-24 | 2016-03-16 | 陕西省微生物研究所 | 一种用于防治果树枝干病害的注干药剂及其制备方法 |
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