CN101835372A - 种子处理组合物和方法 - Google Patents
种子处理组合物和方法 Download PDFInfo
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- CN101835372A CN101835372A CN200880102823A CN200880102823A CN101835372A CN 101835372 A CN101835372 A CN 101835372A CN 200880102823 A CN200880102823 A CN 200880102823A CN 200880102823 A CN200880102823 A CN 200880102823A CN 101835372 A CN101835372 A CN 101835372A
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Classifications
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- A—HUMAN NECESSITIES
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- 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
- A01N25/24—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 ingredients to enhance the sticking of the active ingredients
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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
- A01N25/08—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 solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Pest Control & Pesticides (AREA)
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- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
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- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pretreatment Of Seeds And Plants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及包含活性成分和超支化聚合物的种子处理组合物。将超支化聚合物用作种子包衣剂,特别用作促进活性成分与种子的粘合的粘合剂。本发明还涉及用这种组合物处理种子的方法。
Description
本发明涉及种子处理组合物和处理种子的方法。本发明还涉及超支化聚合物在种子处理组合物中的用途。
种子处理是将活性成分施用于种子,以支持各种作物萌发和/或生长的方法。典型实例包括施用农药如杀真菌剂、杀虫剂和植物生长调节剂。
作为传统的广泛喷雾农药的替换,种子处理组合物必须满足许多特殊要求,这些要求包括它们在工业装置中施用于种子的适用性,活性成分对处理的种子的粘合以及处理的种子的良好流动性。当然,处理的种子必须仍然能够萌发。
为了改善活性成分对种子的粘合,可将水溶性或水分散性成膜聚合物加入种子处理组合物中。EP-A 1 139 738描述了许多这类聚合物。
根据US 6,121,193,处理稻种子是特别具有挑战性的,这是因为在播种之前用水淋洒稻种子24-48小时。所述用水淋洒显示将粘附于种子的农业化合物活性材料浸出的缺点。为了处理该问题,US 6,121,193提出使用超支化聚乙烯亚胺以改善活性成分对稻种子的粘合。
在种子包衣中,聚合物也可对活性成分的生物利用率有影响并因此提供了缓释的作用。该作用可能是所希望的,缓释导致了活性成分延长的效率。缓释涂层也可通过降低植物发育的早期阶段的植物毒性活性成分的释放而改善种子萌发。缓释作用可通过将成膜聚合物与惰性载体如粘土结合而调节。这些作用可通过施用多层涂层而进一步微调(WO 2004/049778)。
使用聚合物将活性成分粘附于种子的缺点在于种子经常发粘。发粘的种子显示降低的流动性。这例如在播种过程中可能是有问题的。
尽管在本领域中将聚合物用于种子处理组合物是众所周知的,常用聚合物倾向于提供不完全令人满意的种子处理组合物。结合了种子的特定和一般要求的种子处理组合物仍然特别难以实现。
本发明的目的是提供种子处理组合物,其有效地用于将活性成分粘合于种子,处理的种子仍然显示良好流动性和萌发。
现在发现某些超支化聚合物可有利地用于种子处理组合物。这类组合物非常有效地将活性成分粘附于种子。处理的种子仍显示可接受的流动性和萌发性能。超支化聚合物可掺入标准种子处理组合物中或紧邻施用前与它们混合。
因此,本发明涉及包含活性成分和超支化聚合物的种子处理组合物。组合物的特定实施方案如权利要求所定义并且公开在本文中。
本发明组合物显示将活性成分良好粘合于种子并且用本发明组合物处理的种子显示良好流动性。处理的种子的萌发并不受影响。
如本文所用的“组合物”包含至少一种活性成分和至少一种助剂。
如本文所用的成分包括活性成分和助剂。
在本发明中,“活性成分”为直接表现出生物相关作用的化合物,优选为显示本文所述的农药作用的化合物。
术语“助剂”是指其本身不显示生物相关作用,但支持活性成分作用的化合物或化合物组合。当使用助剂时,它们的选择取决于活性成分以及取决于种子处理所选的程序。
因此,组合物通常包含活性成分组分(“A”)和助剂组分(“B”)。组合物的活性成分组分(“A”)包含一种或超过一种活性成分。助剂组分(“B”)包含一种或多种助剂。
如本文所用的术语“至少一种”是指1、2、3或更多种成员并包括2、3或更多种不同成员的混合物。
除非另有说明,所有以重量%表示的量是指整个组合物(或配制剂)的重量。
组合物通常包含0.005-95重量%,优选0.1-90重量%,尤其是5-50重量%活性成分组分“A”,平衡量由组分“B”形成。就此而言,活性成分以90-100%,优选95-100%的纯度(根据NMR谱)使用。
根据本发明,活性成分尤其选自植物保护活性试剂(农药)。如具有防止任何害虫侵染植物或驱除、阻止或破坏害虫或以其它方式降低由害虫造成的损害的目的或作用的试剂。植物害虫可属于不同组的生物体;较高级动物,尤其是昆虫和螨虫,包括许多种重要害虫,如线虫和蜗牛;脊椎动物,如哺乳动物和鸟类目前在工业化国家中是第二重要的。包括真菌、细菌,支原体、病毒和类病毒的微生物包括在害虫中,甚至与有用植物竞争有限的生长地或其它资源的杂草可在宽意义上归类于害虫中。农药尤其包括杀蚜虫剂、杀螨剂、干燥剂、杀菌剂、化学绝育剂、脱叶剂、拒食剂、杀真菌剂、除草剂、除草剂安全剂、昆虫引诱剂、杀虫剂、昆虫驱除剂、杀软体动物剂、杀线虫剂、交配干扰剂、植物活化剂、植物生长调节剂、杀鼠剂、哺乳动物驱除剂、协同增效剂、鸟类驱虫剂和杀病毒剂。
下列可根据本发明使用的农药意欲阐述可行的活性成分而不施加任何限制。
A.杀虫剂和杀螨剂
A.1.有机(硫代)磷酸酯类:高灭磷(acephate)、唑啶磷(azamethiphos)、谷硫磷(azinphos-methyl)、毒死蜱(chlorpyrifos)、甲基毒死蜱(chlorpyriphos-methyl)、毒虫畏(chlorfenvinphos)、二嗪农(diazinon)、敌敌畏(dichlorvos)、百治磷(dicrotophos)、乐果(dimethoate)、乙拌磷(disulfoton)、乙硫磷(ethion)、杀螟松(fenitrothion)、倍硫磷(fenthion)、异噁唑磷(isoxathion)、马拉硫磷(malathion)、甲胺磷(methamidophos)、杀扑磷(methidathion)、甲基一六零五(methyl parathion)、速灭磷(mevinphos)、久效磷(monocrotophos)、砜吸磷(oxydemetonmethyl)、对氧磷(paraoxon)、一六零五(parathion)、稻丰散(phenthoate)、伏杀磷(phosalone)、亚胺硫磷(phosmet)、磷胺(phosphamidon)、甲拌磷(phorate)、辛硫磷(phoxim)、虫螨磷(pirimiphosmethyl)、丙溴磷(profenofos)、丙硫磷(prothiofos)、乙丙硫磷(sulprofos)、杀虫畏(tetrachlorvinphos)、特丁磷(terbufos)、三唑磷(triazophos)、敌百虫(trichlorfon);
A.2.氨基甲酸酯类:棉铃威(alanycarb)、涕灭威(aldicarb)、噁虫威(bendiocarb)、丙硫克百威(benfuracarb)、甲奈威(carbaryl)、虫螨威(carbofuran)、丁硫克百威(carbosulfan)、双氧威(fenoxycarb)、呋线威(furathiocarb)、灭虫威(methiocarb)、灭多虫(methomyl)、甲氨叉威(oxamyl)、抗蚜威(pirimicarb)、残杀威(propoxur)、硫双威(thiodicarb)、唑蚜威(triazamate);
A.3.合成除虫菊酯类:丙烯除虫菊(allethrin)、氟氯菊酯(bifenthrin)、氟氯氰菊酯(cyfluthrin)、(RS)氯氟氰菊酯(cyhalothrin)、苯醚氰菊酯(cyphenothrin)、氯氰菊酯(cypermethrin)、甲体氯氰菊酯(alpha-cypermethrin)、乙体氯氰菊酯(beta-cypermethrin)、己体氯氰菊酯(zeta-cypermethrin)、溴氰菊酯(deltamethrin)、高氰戊菊酯(esfenvalerate)、醚菊酯(ethofenprox)、甲氰菊酯(fenpropathrin)、杀灭菊酯(fenvalerate)、咪炔菊酯(imiprothrin)、λ-(RS)氯氟氰菊酯(lambda-cyhalothrin)、γ-(RS)氯氟氰菊酯(gamma-cyhalothrin)、氯菊酯(permethrin)、炔酮菊酯(prallethrin)、除虫菊(pyrethrin)I和II、灭虫菊(resmethrin)、灭虫硅醚(silafluofen)、氟胺氰菊酯(tau-fluvalinate)、七氟菊酯(tefluthrin)、胺菊酯(tetramethrin)、四溴菊酯(tralomethrin)、四氟菊酯(transfluthrin)、profluthrin、四氟甲醚菊酯(dimefluthrin);
A.4.生长调节剂:a)几丁质合成抑制剂:苯甲酰脲类:定虫隆(chlorfluazuron)、氟脲杀(diflubenzuron)、氟螨脲(flucycloxuron)、氟虫脲(flufenoxuron)、氟铃脲(hexaflumuron)、氟丙氧脲(lufenuron)、双苯氟脲(novaluron)、伏虫隆(teflubenzuron)、杀虫隆(triflumuron);噻嗪酮(buprofezin)、噁茂醚(diofenolan)、噻螨酮(hexythiazox)、特苯噁唑(etoxazole)、四螨嗪(clofentazine);b)蜕皮激素拮抗剂:特丁苯酰肼(halofenozide)、甲氧苯酰肼(methoxy fenozide)、双苯酰肼(tebufenozide)、艾扎丁(azadirachtin);c)拟保幼激素:蚊蝇醚(pyriproxyfen)、蒙五一五(methoprene)、双氧威(fenoxycarb);d)类脂生物合成抑制剂:螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)、spirotetramat;
A.5.烟碱受体激动剂/拮抗剂化合物:噻虫胺(clothianidin)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)、噻虫嗪(thiamethoxam)、硝胺烯啶(nitenpyram)、吡虫清(acetamiprid)、噻虫啉(thiacloprid)、式(Γ1)的噻唑化合物:
A.6.GABA拮抗剂化合物:acetoprole、硫丹(endosulfan)、乙虫清(ethiprole)、锐劲特(fipronil)、氟吡唑虫(vaniliprole)、pyrafluprole、pyriprole、式(Γ2)的苯基吡唑化合物:
A.7.大环内酯杀虫剂:齐墩螨素(abamectin)、甲氨基阿维菌素(emamectin)、米尔螨素(milbemectin)、lepimectin、艾克敌105(spinosad)、式(Γ3)化合物(CAS No.187166-40-1):
A.8.METI I化合物:芬杀螨(fenazaquin)、哒螨酮(pyridaben)、吡螨胺(tebufenpyrad)、唑虫酰胺(tolfenpyrad)、flufenerim;
A.9.METI II和III化合物:灭醌螨(acequinocyl)、fluacyprim、灭蚁腙(hydramethylnon);
A.10.去偶化合物:氟唑虫清(chlorfenapyr);
A.11.氧化磷酸化抑制剂化合物:三环锡(cyhexatin)、杀螨硫隆(diafenthiuron)、杀螨锡(fenbutatin oxide)、克螨特(propargite);
A.12.蜕皮干扰剂化合物:cryomazine;
A.13.混合功能氧化酶抑制剂化合物:增效醚(piperonyl butoxide);
A.14.钠通道阻断剂化合物:噁二唑虫(indoxacarb)、metaflumizone;
A.15.其他:benclothiaz、联苯肼酯(bifenazate)、杀螟丹(cartap)、氟啶虫酰胺(flonicamid)、啶虫丙醚(pyridalyl)、拒嗪酮(pymetrozine)、硫、硫环杀(thiocyclam)、氟虫酰胺(flubendiamide)、cyenopyrafen、吡氟硫磷(flupyrazofos)、丁氟螨酯(cyflumetofen)、amidoflumet、式(Γ4)的氨基喹唑啉酮化合物:
N-R’-2,2-二halo-1-R”-环丙烷甲酰胺2-(2,6-二氯-α,α,α-三氟对甲苯基)腙或N-R’-2,2-二(R”’)-丙酰胺-2-(2,6-二氯-α,α,α-三氟对甲苯基)腙,其中R’为甲基或乙基,halo为氯或溴,R”为氢或甲基且R”’为甲基或乙基,式(Γ5)的邻氨基苯甲酰胺化合物:
其中A1为CH3、Cl、Br、I,X为C-H、C-Cl、C-F或N,Y′为F、Cl或Br,Y”为H、F、Cl、CF3,B1为氢、Cl、Br、I、CN,B2为Cl、Br、CF3、OCH2CF3、OCF2H且RB为氢、CH3或CH(CH3)2,以及如JP 2002284608、WO 02/89579、WO 02/90320、WO 02/90321、WO 04/06677、WO 04/20399、JP 200499597、WO 05/68423、WO 05/68432或WO 05/63694所述的丙二腈化合物,特别是丙二睛化合物CF3(CH2)2C(CN)2CH2(CF2)3CF2H、CF3(CH2)2C(CN)2CH2(CF2)5CF2H、CF3(CH2)2C(CN)2(CH2)2C(CF3)2F、CF3(CH2)2C(CN)2(CH2)2(CF2)3CF3、CF2H(CF2)3CH2C(CN)2CH2(CF2)3CF2H、CF3(CH2)2C(CN)2CH2(CF2)3CF3、CF3(CF2)2CH2C(CN)2CH2(CF2)3CF2H和CF3CF2CH2C(CN)2CH2(CF2)3CF2H。
A组的市售化合物可以在其他出版物中的The Pesticide Manual(农药手册),第13版,British Crop Protection Council(2003)中找到。
式(Γ2)的硫酰胺及其制备描述于WO 98/28279中。Lepimectin由AgroProject,PJB Publications Ltd,2004年11月已知。Benclothiaz及其制备描述于EP-A1 454621中。杀扑磷和对氧磷及其制备描述于Farm ChemicalsHandbook,第88卷,Meister Publishing Company,2001中。Acetoprole及其制备描述于WO 98/28277中。氰氟虫胺及其制备描述于EP-A1 462 456中。吡氟硫磷描述于Pesticide Science 54,1988,第237-243页和US 4822779中。Pyrafluprole及其制备描述于JP 2002193709和WO 01/00614中。Pyriprole及其制备描述于WO 98/45274和US 6335357中。Amidoflumet及其制备描述于US 6221890和JP 21010907中。Flufenerim及其制备描述于WO 03/007717和WO 03/007718中。丁氟螨酯及其制备描述于WO04/080180中。
式(Γ5)的邻氨基苯甲酰胺及其制备描述于WO 01/70671、WO02/48137、WO 03/24222、WO 03/15518、WO 04/67528、WO 04/33468和WO 05/118552中。丙二睛化合物CF3(CH2)2C(CN)2CH2(CF2)3CF2H、CF3(CH2)2C(CN)2CH2(CF2)5CF2H、CF3(CH2)2C(CN)2(CH2)2C(CF3)2F、CF3(CH2)2C(CN)2(CH2)2(CF2)3CF3、CF2H(CF2)3CH2C(CN)2CH2(CF2)3CF2H、CF3(CH2)2C(CN)2CH2(CF2)3CF3、CF3(CF2)2CH2C(CN)2CH2(CF2)3CF2H和CF3CF2CH2C(CN)2CH2(CF2)3CF2H描述于WO 05/63694中。
B.杀真菌剂:
B.1.嗜球果伞素类(Strobilurins),如腈嘧菌酯(azoxystrobin)、醚菌胺(dimoxystrobin)、烯肟菌酯(enestroburin)、氟嘧菌酯(fluoxastrobin)、亚胺菌(kresoxim-methyl)、叉氨苯酰胺(metominostrobin)、啶氧菌酯(picoxystrobin)、唑菌胺酯(pyraclostrobin)、肟菌酯(trifloxystrobin)、肟醚菌胺(orysastrobin)、(2-氯-5-[1-(3-甲基苄氧亚氨基)乙基]苄基)氨基甲酸甲酯、(2-氯-5-[1-(6-甲基吡啶-2-基甲氧基亚氨基)乙基]苄基)氨基甲酸甲酯、2-(邻-((2,5-二甲基苯氧基亚甲基)苯基)-3-甲氧基丙烯酸甲酯;
B.2.羧酰胺类,如
羧酰苯胺类:苯霜灵(benalaxyl)、麦锈灵(benodanil)、啶酰菌胺(boscalid)、萎锈灵(carboxin)、丙氧灭绣胺(mepronil)、呋菌胺(fenfuram)、环酰菌胺(fenhexamide)、氟酰胺(flutolanil)、呋吡唑灵(furametpyr)、甲霜灵(metalaxyl)、甲呋酰胺(ofurace)、噁霜灵(oxadixyl)、氧化萎锈灵(oxycarboxin)、吡噻菌胺(penthiopyrad)、溴氟唑菌(thifluzamide)、噻酰菌胺(tiadinil)、N-(4’-溴联苯-2-基)-4-二氟甲基-2-甲基噻唑-5-甲酰胺、N-(4’-三氟甲基联苯-2-基)-4-二氟甲基-2-甲基噻唑-5-甲酰胺、N-(4’-氯-3’-氟联苯-2-基)-4-二氟甲基-2-甲基噻唑-5-甲酰胺、N-(3’,4’-二氯-4-氟联苯-2-基)-3-二氟甲基-1-甲基吡唑-4-甲酰胺、N-(2-氰基苯基)-3,4-二氯异噻唑-5-甲酰胺;
羧酸吗啉化物:烯酰吗啉(dimethomorph)、氟吗啉(flumorph);
苯甲酰胺类:氟联苯菌(flumetover)、fluopicolide(氟吡菌胺(picobenzamid))、苯酰菌胺(zoxamide);
其他羧酰胺:氯环丙酰胺(carpropamid)、双氯氰菌胺(diclocymet)、双炔酰菌胺(mandipropamid)、N-(2-(4-[3-(4-氯苯基)丙-2-炔氧基]-3-甲氧基苯基)乙基)-2-甲基磺酰基氨基-3-甲基丁酰胺、N-(2-(4-[3-(4-氯苯基)丙-2-炔氧基]-3-甲氧基苯基)乙基)-2-乙烷磺酰基氨基-3-甲基丁酰胺;
B.3.唑类,如
三唑类:双苯三唑醇(bitertanol)、糠菌唑(bromuconazole)、环唑醇(cyproconazole)、噁醚唑(difenoconazole)、烯唑醇(diniconazole)、烯菌灵(enilconazole)、氧唑菌(epoxiconazole)、腈苯唑(fenbuconazole)、氟硅唑(flusilazole)、喹唑菌酮(fluquinconazole)、粉唑醇(flutriafol)、己唑醇(hexaconazole)、酰胺唑(imibenconazole)、环戊唑醇(ipconazole)、环戊唑菌(metconazole)、腈菌唑(myclobutanil)、戊菌唑(penconazole)、丙环唑(propiconazole)、丙硫菌唑(prothioconazole)、硅氟唑(simeconazole)、戊唑醇(tebuconazole)、氟醚唑(tetraconazole)、唑菌醇(triadimenol)、三唑酮(triadimefon)、戊叉唑菌(triticonazole);
咪唑类:氰霜唑(cyazofamid)、烯菌灵(imazalil)、稻瘟酯(pefurazoate)、丙氯灵(prochloraz)、氟菌唑(triflumizole);
苯并咪唑类:苯菌灵(benomyl)、多菌灵(carbendazim)、麦穗宁(fuberidazole)、涕必灵(thiabendazole);
其他:噻唑菌胺(ethaboxam)、氯唑灵(etridiazole)、土菌消(hymexazole);
B.4.含氮杂环基化合物:如吡啶类:氟啶胺(fluazinam)、啶斑肟(pyrifenox)、3-[5-(4-氯苯基)-2,3-二甲基异噁唑烷-3-基]吡啶;
嘧啶类:磺嘧菌灵(bupirimate)、环丙嘧啶(cyprodinil)、嘧菌腙(ferimzone)、异嘧菌醇(fenarimol)、嘧菌胺(mepanipyrim)、氟苯嘧啶醇(nuarimol)、二甲嘧菌胺(pyrimethanil);
哌嗪类:嗪氨灵(triforine);
吡咯类:氟噁菌(fludioxonil)、拌种咯(fenpiclonil);
吗啉类:4-十二烷基-2,6-二甲基吗啉(aldimorph)、吗菌灵(dodemorph)、丁苯吗啉(fenpropimorph)、克啉菌(tridemorph);
二羧酰亚胺类:异丙定(iprodione)、杀菌利(procymidone)、烯菌酮(vinclozolin);
其他:噻二唑素(acibenzolar-S-methyl)、敌菌灵(anilazine)、克菌丹(captan)、敌菌丹(captafol)、棉隆(dazomet)、哒菌清(diclomezine)、氰菌胺(fenoxanil)、灭菌丹(folpet)、苯锈啶(fenpropidin)、噁唑酮菌(famoxadone)、咪唑菌酮(fenamidone)、异噻菌酮(octhilinone)、噻菌灵(probenazole)、丙氧喹啉(proquinazid)、咯喹酮(pyroquilon)、喹氧灵(quinoxyfen)、三环唑(tricyclazole)、5-氯-7-(4-甲基哌啶-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶、2-丁氧基-6-碘-3-丙基苯并吡喃-4-酮、N,N-二甲基-3-(3-溴-6-氟-2-甲基吲哚-1-磺酰基)-[1,2,4]三唑-1-磺酰胺;
B.5.氨基甲酸盐和二硫代氨基甲酸盐,如
二硫代氨基甲酸盐:福美铁(ferbam)、代森锰锌(mancozeb)、代森锰(maneb)、代森联(metiram)、威百亩(metam)、甲基代森锌(propineb)、福美双(thiram)、代森锌(zineb)、福美锌(ziram);氨基甲酸盐类:乙霉威(diethofencarb)、flubenthiavalicarb、异丙菌胺(iprovalicarb)、百维灵(propamocarb)、3-(4-氯苯基)-3-(2-异丙氧羰基氨基-3-甲基丁酰氨基)丙酸甲酯、N-(1-(1-(4-氰基苯基)乙基磺酰基)丁-2-基)氨基甲酸4-氟苯基酯;
B.6.其他杀真菌剂,如
胍类:多果定(dodine)、双胍辛醋酸盐(iminoctadine)、双胍盐(guazatine);
抗菌素类:春雷素(kasugamycin)、多氧霉素(polyoxins)、链霉素(streptomycin)、井冈霉素(validamycin A);
有机金属化合物类:三苯锡基盐;
含硫的杂环基化合物:稻瘟灵(isoprothiolane)、二噻农(dithianon);
有机磷化合物:克瘟散(edifenphos)、藻菌磷(fosetyl)、乙膦铝(fosetyl-aluminum)、异稻瘟净(iprobenfos)、定菌磷(pyrazophos)、甲基立枯磷(tolclofos-methyl)、亚磷酸及其盐;
有机氯化合物:甲基托布津(thiophanate-methyl)、百菌清(chlorothalonil)、抑菌灵(dichlofluanid)、对甲抑菌灵(tolylfluanid)、磺菌胺(flusulfamide)、四氯苯酞(phthalide)、六氯苯(hexachlorobenzene)、戊菌隆(pencycuron)、五氯硝基苯(quintozene);
硝基苯基衍生物:乐杀螨(binapacryl)、敌螨普(dinocap)、敌螨通(dinobuton);
无机活性化合物:波尔多液(Bordeaux混合物)、醋酸铜、氢氧化铜、王铜(copper oxychloride)、碱式硫酸铜、硫;
其他:螺噁茂胺(spiroxamine)、环氟菌胺(cyflufenamid)、清菌脲(cymoxanil)、苯菌酮(metrafenone)。
C.除草剂
C.1类脂生物合成抑制剂,如炔禾灵(chlorazifop)、炔草酯(clodinafop)、氯丁草(clofop)、氰氟草酯(cyhalofop)、氯甲草(diclofop)、噁唑禾草灵(fenoxaprop)、高噁唑禾草灵(fenoxaprop-p)、噻唑禾草灵(fenthiaprop)、吡氟禾草灵(fluazifop)、精吡氟禾草灵(fluazifop-P)、吡氟氯禾灵(haloxyfop)、精吡氟氯禾灵(haloxyfop-P)、恶草醚(isoxapyrifop)、噁唑酰草胺(metamifop),喔草酯(propaquizafop)、喹禾灵(quizalofop)、精喹禾灵(quizalofop-P)、三氟苯氧丙酸(trifop)、枯杀达(alloxydim)、丁氧环酮(butroxydim)、烯草酮(clethodim)、环己烯草酮(cloproxydim)、噻草酮(cycloxydim)、环苯草酮(profoxydim)、稀禾定(sethoxydim)、醌肟草(tepraloxydim)、肟草酮(tralkoxydim)、苏达灭(butylate)、草灭特(cycloate)、燕麦敌(di-allate)、哌草丹(dimepiperate)、扑草灭(EPTC)、禾草畏(esprocarb)、抑草威(ethiolate)、氮草(isopolinate)、甲硫苯威(methiobencarb)、草达灭(molinate)、坪草丹(orbencarb)、克草猛(pebulate)、苄草丹(prosulfocarb)、草克死(sulfallate)、杀草丹(thiobencarb)、丁草威(tiocarbazil)、野麦畏(tri-allate)、灭草猛(vernolate)、呋草黄(benfuresate)、乙呋草黄(ethofumesate)和地散磷(bensulide);
C.2ALS抑制剂,如磺氨黄隆(amidosulfuron)、四唑黄隆(azimsulfuron)、苄嘧黄隆(bensulfuron)、氯嘧黄隆(chlorimuron)、绿黄隆(chlorsulfuron)、醚黄隆(cinosulfuron)、环丙黄隆(cyclosulfamuron)、胺苯黄隆(ethametsulfuron)、乙氧嘧黄隆(ethoxysulfuron)、啶嘧黄隆(flazasulfuron)、氟定黄隆(flupyrsulfuron)、甲酰氨磺隆(foramsulfuron)、吡氯黄隆(halosulfuron)、啶咪黄隆(imazosulfuron)、碘黄隆(iodosulfuron)、甲基二磺隆(mesosulfuron)、甲黄隆(metsulfuron)、烟嘧黄隆(nicosulfuron)、环丙氧黄隆(oxasulfuron)、氟嘧黄隆(primisulfuron)、氟丙黄隆(prosulfuron)、吡嘧黄隆(pyrazosulfuron)、玉嘧黄隆(rimsulfuron)、嘧黄隆(sulfometuron)、乙黄黄隆(sulfosulfuron)、噻黄隆(thifensulfuron)、醚苯黄隆(triasulfuron)、苯黄隆(tribenuron)、三氟啶磺隆(trifloxysulfuron)、氟胺磺隆(triflusulfuron)、三氟甲磺隆(tritosulfuron)、咪草酯(imazamethabenz)、咪草啶酸(imazamox)、甲基咪草烟(imazapic)、灭草烟(imazapyr)、灭草喹(imazaquin)、咪草烟(imazethapyr)、唑嘧磺胺盐(cloransulam)、唑嘧磺胺(diclosulam)、双氟磺草胺(florasulam)、氟唑啶草(flumetsulam)、唑草磺胺(metosulam)、五氟磺草胺(penoxsulam)、双嘧苯甲酸(bispyribac)、肟啶草(pyriminobac)、丙苯磺隆(propoxycarbazone)、氟酮磺隆(flucarbazone)、嘧苯草肟(pyribenzoxim)、环酯草醚(pyriftalid)和嘧硫苯甲酸(pyrithiobac);
C.3光合成抑制剂,如莠去通(atraton)、莠去津(atrazine)、莠灭净(ametryn)、叠氮津(aziprotryne)、草净津(cyanazine)、硫草净津(cyanatryn)、可乐津(chlorazine)、环草津(cyprazine)、敌草净(desmetryn)、戊草津(dimethametryn)、杀草净(dipropetryn)、草止津(eglinazine)、抑草津(ipazine)、麦苏百津(mesoprazine)、醚草通(methometon)、盖草津(methoprotryne)、环氰津(procyazine)、丙草止津(proglinazine)、扑灭通(prometon)、扑草净(prometryn)、扑灭津(propazine)、另丁津(sebuthylazine)、密草通(secbumeton)、西玛津(simazine)、西玛通(simeton)、西草净(simetryn)、甲氧去草净(terbumeton)、特丁津(terbuthylazine)、去草净(terbutryn)、草达津(trietazine)、特津酮(ametridione)、特草嗪酮(amibuzin)、六嗪同(hexazinone)、嗪丁草(isomethiozin)、苯嗪草(metamitron)、赛克津(metribuzin)、除草定(bromacil)、异草定(isocil)、环草定(lenacil)、特草定(terbacil)、溴杀草敏(brompyrazon)、杀草敏(chloridazon)、敌米达松(dimidazon)、异苯敌草(desmedipham)、敌克草(phenisopham)、苯敌草(phenmedipham)、乙苯敌草(phenmedipham-ethyl)、噻草隆(benzthiazuron)、丁噻隆(buthiuron)、噻二唑隆(ethidimuron)、异恶隆(isouron)、噻唑隆(methabenzthiazuron)、monoisouron、丁唑隆(tebuthiuron)、赛唑隆(thiazafluron)、疏草隆(anisuron)、播土隆(buturon)、氯溴隆(chlorbromuron)、乙氧苯隆(chloreturon)、绿麦隆(chlorotoluron)、枯草隆(chloroxuron)、枯莠隆(difenoxuron)、丁噁隆(dimefuron)、敌草隆(diuron)、非草隆(fenuron)、伏草隆(fluometuron)、氟苯隆(fluothiuron)、异丙隆(isoproturon)、利谷隆(linuron)、灭草恒(methiuron)、色满隆(metobenzuron)、秀谷隆(metobromuron)、甲氧隆(metoxuron)、绿谷隆(monolinuron)、灭草隆(monuron)、草不隆(neburon)、对伏隆(parafluron)、稀草隆(phenobenzuron)、环草隆(siduron)、氟氧隆(tetrafluron)、赛二唑素(thidiazuron)、莎草快(cyperquat)、二乙除草双(diethamquat)、苯敌快(difenzoquat)、敌草快阳离子(diquat)、伐草快(morfamquat)、对草快(paraquat)、糠草腈(bromobonil)、溴苯腈(bromoxynil)、羟敌草腈(chloroxynil)、碘草腈(iodobonil)、碘苯腈(ioxynil)、氨唑草酮(amicarbazone)、杀草全(bromofenoxim)、三氟噁嗪(flumezin)、灭草定(methazole)、噻草平(bentazone)、敌稗(propanil)、蔬草灭(pentanochlor)、达草止(pyridate)和pyridafol;
C.4原卟啉原-IX氧化酶抑制剂,如氟锁草醚(acifluorfen)、治草醚(bifenox)、氯硝醚(chlomethoxyfen)、草枯醚(chlornitrofen)、氯氟草醚(ethoxyfen)、消草醚(fluorodifen)、乙羧氟草醚(fluoroglycofen)、氯草醚(fluoronitrofen)、氟黄胺草醚(fomesafen)、氟呋草醚(furyloxyfen)、氟硝磺酰胺(halosafen)、乳氟禾草灵(lactofen)、除草醚(nitrofen)、硝氟草醚(nitrofluorfen)、氟硝草醚(oxyfluorfen)、异丙吡草酯(fluazolate)、氟唑草酯(pyraflufen)、吲哚酮草酯(cinidon-ethyl)、酰亚胺苯氧乙酸(flumiclorac)、氟噁嗪酮(flumioxazin)、炔草胺(flumipropyn)、达草氟(fluthiacet)、噻二唑胺(thidiazimin)、恶草灵(oxadiazon)、炔丙噁唑草(oxadiargyl)、唑啶炔草(azafenidin)、氟酮唑草(carfentrazone)、磺胺草唑(sulfentrazone)、戊噁唑草(pentoxazone)、双苯嘧草酮(benzfendizone)、氟丙嘧草酯(butafenacil)、双唑草腈(pyraclonil)、氟唑草胺(profluazol)、氟哒嗪草酯(flufenpyr)、flupropacil、吡氯草胺(nipyraclofen)和乙胺草醚(etnipromid);
C.5白化除草剂,如氟哒草(metflurazon)、达草灭(norflurazon)、氟苯啶草(flufenican)、吡氟草胺(diflufenican)、氟吡酰草胺(picolinafen)、氟丁酰草胺(beflubutamid)、氟草同(fluridone)、氟咯草酮(flurochloridone)、呋草酮(flurtamone)、甲基磺草酮(mesotrione)、磺草酮(sulcotrione)、异恶氯草酮(isoxachlortole)、异噁氟草(isoxaflutole)、吡草酮(benzofenap)、吡唑特(pyrazolynate)、苄草唑(pyrazoxyfen)、苯并双环酮(benzobicyclon)、杀草强(amitrole)、异恶草酮(clomazone)、苯草醚(aclonifen)、4-(3-三氟甲基苯氧基)-2-(4-三氟甲基苯基)嘧啶以及式II的3-杂环基取代的苯甲酰基衍生物(参见WO 96/26202、WO 97/41116、WO 97/41117和WO-A-97/41118):
其中变量R8-R13如下所定义:
R8、R10为氢、卤素、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6烷基亚磺酰基或C1-C6烷基磺酰基;
R9为选自如下的杂环基:如噻唑-2-基、噻唑-4-基、噻唑-5-基、异噁唑-3-基、异噁唑-4-基、异噁唑-5-基、4,5-二氢异噁唑-3-基、4,5-二氢异噁唑-4-基和4,5-二氢异噁唑-5-基,其中上述9个基团可被单取代或多取代,例如可以被卤素、C1-C4烷基、C1-C4烷氧基、C1-C4卤代烷基、C1-C4卤代烷氧基或C1-C4烷硫基单-、二-、三-或四取代;
R11为氢、卤素或C1-C6烷基;
R12为C1-C6烷基;
R13为氢或C1-C6烷基。
C.7EPSP合成酶抑制剂,如草甘膦(glyphosate);
C.8谷氨酰胺合成酶抑制剂,如草铵膦(glufosinate)和双丙氨酰磷(bilanaphos);
C.9DHP合成酶抑制剂,如黄草灵(asulam);
C.10有丝分裂抑制剂,如氟草胺(benfluralin)、地乐胺(butralin)、敌乐胺(dinitramine)、丁氟消草(ethalfluralin)、氟消草(fluchloralin)、异乐灵(isopropalin)、氟烯硝草(methalpropalin)、磺乐灵(nitralin)、黄草消(oryzalin)、胺硝草(pendimethalin)、氨基丙氟灵(prodiamine)、卡乐施(profluralin)、氟乐灵(trifluralin)、甲基胺草磷(amiprofos-methyl)、草胺磷(butamifos)、氟硫草定(dithiopyr)、噻氟啶草(thiazopyr)、拿草特(propyzamide)、丙戊草胺(tebutam)、敌草索(chlorthal)、长杀草(carbetamide)、氯草灵(chlorbufam)、氯苯胺灵(chlorpropham)和苯胺灵(propham);
C.11VLCFA抑制剂,如乙草胺(acetochlor)、甲草胺(alachlor)、丁草胺(butachlor)、丁烯草胺(butenachlor)、敌草乐(delachlor)、安塔(diethatyl)、克草胺(dimethachlor)、噻吩草胺(dimethenamid)、精噻吩草胺(dimethenamid-P)、吡草胺(metazachlor)、异丙甲草胺(metolachlor)、S-异丙甲草胺(S-metolachlor)、丙草胺(pretilachlor)、扑草胺(propachlor)、异丙草胺(propisochlor)、广草胺(prynachlor)、猛杀草(terbuchlor)、噻醚草胺(thenylchlor)、二甲苯草胺(xylachlor)、草毒死(allidochlor)、草立死(CDEA)、磺唑草(epronaz)、草乃敌(diphenamid)、草萘胺(napropamide)、萘丙胺(naproanilide)、烯草胺(pethoxamid)、氟噻草胺(flufenacet)、苯噻草胺(mefenacet)、四唑酰草胺(fentrazamide)、莎稗磷(anilofos)、哌草磷(piperophos)、胺草唑(cafenstrole)、茚草酮(indanofan)和灭草环(tridiphane);
C.12纤维素生物合成抑制剂,如敌草腈(dichlobenil)、草克乐(chlorthiamid)、异恶草胺(isoxaben)和胺草唑(flupoxam);
C.13去偶除草剂,如消草酯(dinofenate)、硝丙酚(dinoprop)、戊硝酚(dinosam)、地乐酚(dinoseb)、地乐消酚(dinoterb)、二硝甲酚(DNOC)、硝草酚(etinofen)和丁硝酚(medinoterb);
C.14植物生长素除草剂,如稗草胺(clomeprop)、2,4-滴(2,4-D)、2,4,5-涕(2,4,5-T)、2甲4氯(MCPA)、酚硫杀(MCPA-thioethyl)、2,4-滴丙酸(dichlorprop)、高2,4-滴丙酸(dichlorprop-P)、2甲4氯丙酸(mecoprop)、高2甲4氯丙酸盐(mecoprop-P)、2,4-滴丁酸(2,4-DB)、2甲4氯丁酸(MCPB)、草灭平(chloramben)、麦草畏(dicamba)、草芽平(2,3,6-TBA)、杀草畏(tricamba)、二氯喹啉酸(quinclorac)、喹草酸(quinmerac)、二氯皮考啉酸(clopyralid)、氟草烟(fluroxypyr)、毒莠定(picloram)、定草酯(triclopyr)和草除灵(benazolin);
C.15植物生长素输送抑制剂,如抑草生(naptalam)、二氟吡隆(diflufenzopyr);
C.16新燕灵(benzoylprop)、氟燕灵(flamprop)、麦草伏M(flamprop-M)、溴丁酰草胺(bromobutide)、氯甲丹(chlorflurenol)、环庚草醚(cinmethylin)、苯丙隆(methyldymuron)、乙苯酰草(etobenzanid)、膦铵素(fosamine)、威百亩(metam)、稗草畏(pyributicarb)、氯噁嗪草(oxaziclomefone)、棉隆(dazomet)、苯氧丙胺津(triaziflam)和溴甲烷(methyl bromide)。
D.安全剂
解草酮(benoxacor)、喹氧乙酸(cloquintocet)、抑害腈(cyometrinil)、抑害胺(dichlormid)、dicyclonon、dietholate、解草唑(fenchlorazole)、解草啶(fenclorim)、解草胺(flurazole)、肟草安(fluxofenim)、解草呋(furilazole)、双苯恶唑酸(isoxadifen)、吡咯二酸(mefenpyr)、mephenate、萘二甲酸酐(naphthalic anhydride)、2,2,5-三甲基-3-(二氯乙酰基)-1,3-噁唑烷(R-29148)、4-(二氯乙酰基)-1-氧杂-4-氮杂螺[4.5]癸烷(AD-67;MON 4660)和解草腈(oxabetrinil)。
优选杀虫剂选自:
吡虫清(acetamiprid)、甲体氯氰菊酯(alpha-cypermethrin)、乙体氯氰菊酯(beta-cypermethrin)、氟氯菊酯(bifenthrin)、虫螨威(carbofuran)、丁硫克百威(carbosulfan)、噻虫胺(clothianidin)、乙氰菊酯(cycloprothrin)、氟氯氰菊酯(cyfluthrin)、氯氰菊酯(cypermethrin)、溴氰菊酯(deltamethrin)、氟脲杀(diflubenzuron)、呋虫胺(dinotefuran)、醚菊酯(etofenprox)、杀螨锡(fenbutatin oxide)、甲氰菊酯(fenpropathrin)、锐劲特、氟氰戊菊酯(flucythrinate)、吡虫啉(imidacloprid)、λ-(RS)氯氟氰菊酯(Lambda-Cyhalothrin)、硝胺烯啶(nitenpyram)、信息素、艾克敌105(spinosad)、伏虫隆(teflubenzuron)、七氟菊酯(tefluthrin)、特丁磷(terbufos)、噻虫啉(thiacloprid)、噻虫嗪(thiamethoxam)、硫双灭多威(thiodicarb)、四溴菊酯(tralomethrin)、唑蚜威(triazamate)、己体氯氰菊酯(zeta-cypermethrin)、spirotetramat、flupyrazofos、NC 512、唑虫酰胺(tolfenpyrad)、氟虫酰胺(flubendiamide)、双三氟虫脲(bistrifluron)、benclothiaz、DPX-E2Y45、HGW86、pyrafluprole、pyriprole、F-7663、F-2704、amidoflumet、flufenerim、丁氟螨酯(cyflumetofen)。特别优选噻虫胺(clothianidin)、锐劲特、吡虫啉(imidacloprid)和噻虫嗪(thiamethoxam)。
优选杀真菌剂选自:
甲霜灵(metalaxyl)、噁霜灵(oxadixyl)、双胍盐(guazatine)、二甲嘧菌胺(pyrimethanil)、链霉素(streptomycin)、噁醚唑(difenoconazole)、氧唑菌(epoxiconazole)、喹唑菌酮(fluquinconazole)、粉唑醇(flutriafol)、土菌消(hymexazole)、烯菌灵(imazalil)、环戊唑菌(metconazole)、丙氯灵(prochloraz)、丙硫菌唑(prothioconazole)、戊唑醇(tebuconazole)、涕必灵(thiabendazole)、唑菌醇(triadimenol)、戊叉唑菌(triticonazole)、异丙定(iprodione)、代森锰(maneb)、代森锰锌(mancozeb)、代森联(metiram)、福美双(thiram)、苯菌灵(benomyl)、啶酰菌胺(boscalid)、多菌灵(carbendazim)、萎锈灵(carboxin)、棉隆(dazomet)、硅噻菌胺(silthiofam)、铜杀真菌剂、氟噁菌(fludioxonil)、硫、棉隆(dazomet)、腈嘧菌酯(azoxystrobin)、亚胺菌(kresoxim-methyl)、肟醚菌胺(orysastrobin)、唑菌胺酯(pyraclostrobin)、肟菌酯(trifloxystrobin)、克菌丹(captan)、烯酰吗啉(dimethomorph)。特别优选唑菌胺酯(pyraclostrobin)、戊叉唑菌(triticonazole)和喹唑菌酮(fluquinconazole)。
在本发明特定的实施方案中,组合物可包含一种或多种用于温血动物如鸟类、狗和刺猬的驱除剂,例如壬酸香草基酰胺。驱除剂的量基于组合物的总重量优选为0.1-5重量%。
在本发明上下文中,术语“超支化聚合物”非常一般地指特征在于支化结构和高官能度的聚合物。还可参考P.J.Flory,J.Am.Chem.Soc.1952,74,2718和H.Frey等人,Chem.Eur.J.2000,6,第14期,2499对超支化聚合物的通用定义,此处将其完全引入作为参考。在本发明含义内的“超支化聚合物”包括星形聚合物、树枝状聚合物、分子和结构均不均匀的超支化聚合物,不同于它们的高分子量聚合物,如梳形聚合物。“星形”聚合物为其中三个或更多个链起始于一个中心的聚合物。就此而言,中心可以是单个原子或原子基团。“树枝状聚合物”(分支聚合物(cascadepolymer),各向同性支化聚合物,等支化聚合物,星放射状聚合物)为具有高度对称结构的分子均匀大分子。树枝状聚合物在结构上源自星形聚合物,其中各链本身各自以星形方式支化。它们起始于小分子,经由连续重复依次反应,产生较高支链,在支链末端每次为官能团,该官能团又为进一步的支链的起始点。因此,在各反应步骤中单体末端数量指数增长,在最后导致球形树结构。树枝状聚合物的特征结构为进行构造它们的反应阶段数目。由于它们均匀结构,树枝状聚合物通常表现出所定义的分子量。分子和结构不均匀的超支化聚合物类似于树枝状聚合物,但是它们表现出具有变化的长度、支链,以及分子量分布的侧链。
根据本发明优选使用分子和结构不均匀的超支化聚合物。它们通常是简单的并因此比树枝状聚合物更经济地制备。然而,结构和分子均匀的树枝状聚合物和星形聚合物当然也可使用。
本发明超支化聚合物为(i)重均分子量(Mw)超过500g/mol和(ii)支化度(DB)超过5%的任何聚合物。
优选根据本发明使用的超支化聚合物的重均分子量(Mw)超过1000g/mol,优选超过1500g/mol。特别优选重均分子量为约500-200000g/mol,优选750-150000g/mol,尤其是1000-100000g/mol的聚合物。
根据本发明使用的超支化聚合物的数均分子量(Mn)通常高于400g/mol,优选高于500g/mol。特别优选数均分子量为约400-100000g/mol,优选500-80000g/mol,尤其是1000-50000g/mol的聚合物。
根据本发明使用的超支化聚合物的多分散性通常为1.2-50,优选1.4-40,特别优选1.5-30,非常特别优选2-30。
关于多分散性和数均及重均分子量Mn和Mw的数据此处涉及凝胶渗透色谱法测量的数据,其中将聚甲基丙烯酸甲酯用作标准并将四氢呋喃、二甲基甲酰胺、二甲基乙酰胺或六氟异丙醇用作洗脱液。所述方法描述于Analytiker Taschenbuch,第4卷,第433-442页,Berlin 1984。
支化度(DB)反映了每分子中树枝状链接和末端单元的平均数。优选根据本发明使用的超支化聚合物的支化度(DB)为至少10%,20%,30%或甚至35%。优选聚合物的DB为20-99%,优选30-95%,尤其是35-75%。对于“支化度”的定义此处可参考H.Frey等,Acta Polym.,1997,48,30,此处将其完全引入。
根据一个方面,超支化聚合物的玻璃化转变温度通常为-80℃或更高,-70℃或更高,或-60℃或更高。根据另一方面,超支化聚合物的玻璃化转变温度通常为至多150℃,至多100℃或至多50℃。玻璃化转变温度根据ASTM方法D3418-03使用DSC测量。
本发明超支化聚合物的酸值通常为0-500,优选0-400,更优选0-300,尤其是0-200mgKOH/g,这根据DIN 53240第2部分测定。
本发明超支化聚合物的羟值通常为0-1000,优选0-750,尤其是0-500mgKOH/g,这根据DIN 53240第2部分测定。
本发明超支化聚合物通常可溶于水或可分散于水中,即在约23℃和约1大气压下可在水中制备超支化聚合物的清澈溶液(用裸眼不可检测到凝胶颗粒)或包含至少1重量%,优选至少5重量%,尤其是至少10重量%超支化聚合物的分散体。
根据本发明的特定实施方案,超支化聚合物的10重量%水溶液在约23℃下的粘度低于1000mPas,优选低于750mPas,特别是低于500mPas,这在TA仪器CSL 500 Carri Med流变仪上用圆锥-板系统在100l/s的剪切速率下测定。
本发明超支化聚合物优选为两性聚合物。两性超支化聚合物的HLB值通常为1-20,优选3-20,尤其是4-20。
HLB值为化合物的亲水和亲油部分的量度。HLB值的测定例如描述于W.C.Griffin,Journal of the Society of Cosmetic Chemists,1949,1,311和W.C.Griffin,Journal of the Society of Cosmetic Chemists,1954,5,249中,此处将其完全引入作为参考。为此,将1g样品材料溶于4%苯和96%二噁烷的混合物中,加入水直至出现混浊。如此测定的值通常与HLB值成比例。
在具有氧化乙烯基团的超支化聚合物(聚乙二醇)的情况下,HLB值可根据C.D.Moore,M.Bell,SPC Soap,Perfum.Cosmet.1956,29.893(此处将其完全引入作为参考)中所述的方法如下测定:HLB=(氧化乙烯基团的数目)*100/(分子的亲油部分中碳原子数目)。
在本发明上下文中,超支化聚合物应理解为指,除了作为聚合物骨架部分的官能团(如超支化聚碳酸酯情况下,碳酸酯基团;超支化聚酯情况下,酯基团;超支化聚醚情况下,醚基团等)外,还包含至少4个,优选至少8个末端官能团或侧官能团(如超支化聚碳酸酯情况下,碳酸酯和/或OH基团;超支化聚酯情况下,OH和/或羧基;超支化聚醚情况下,OH基团,等)的产品。此外,超支化聚合物除了已经通过聚合反应得到官能团外可进一步包含其他官能团。
原则上对末端或侧官能团的数目没有上限限制,但具有非常高的官能团数目的产物可能具有不希望的性能,例如高粘度或不良溶解性。本发明的超支化聚合物具有通常不大于500个末端官能团或侧官能团,优选不大于100个末端官能团或侧官能团,尤其是不大于30个末端官能团或侧官能团。末端官能团或侧官能团的量优选为每分子4-100个,特别是5-30个,更特别是6-20个。
此处和下文中,术语“官能度”表示每分子或每个聚合物链的各末端官能团或侧官能团的平均数。
超支化聚合物优选选自超支化聚碳酸酯、超支化聚酯、超支化聚醚及其混合形式,如超支化聚酯碳酸酯、超支化聚醚碳酸酯、超支化聚醚酯和超支化聚醚酯碳酸酯。特别优选超支化聚合物选自超支化聚碳酸酯、超支化聚酯、超支化聚醚碳酸酯、超支化聚醚酯、超支化聚酯碳酸酯和超支化聚醚酯碳酸酯,其中特别优选超支化聚碳酸酯、超支化聚酯、超支化聚醚碳酸酯和超支化聚酯碳酸酯。此外,根据本发明可能合适的是选自超支化聚氨酯、超支化聚脲、超支化聚酰胺、超支化聚胺及其混合物形式,如超支化聚脲聚氨酯(polyureaurethane)、超支化聚酯酰胺、超支化聚酯胺,特别是超支化聚醚胺的超支化聚合物,其中强调超支化聚氨酯、超支化聚脲、超支化聚脲聚氨酯、超支化聚酯酰胺,和任选超支化聚醚胺。在另一方面,本发明超支化聚合物不为超支化聚乙烯胺、聚酰胺型酰胺(polyamidoamide)、聚乙烯亚胺或聚醚或其共聚物。
超支化聚合物尤其包括下文公开的那些和/或可通过下文公开的方法得到的那些。
所谓的ABx,优选AB2或AB3单体特别适用于合成超支化聚合物。这些单体在分子中具有两个不同的官能团A和B,其可经历相互间的分子间反应并形成键接。官能团A每分子仅包含一个且官能团B每分子可包含2个或更多个。所述ABx单体相互间的反应导致具有规则排列的支化点的非交联聚合物的形成。事实上,聚合物在链端仅具有B基团。
此外,超支化聚合物可经由Ax+By合成路线制备。此处,Ax和By为具有官能团A和B且指数x和y为每个单体的官能团数目的两种不同单体。在Ax+By合成的情况下,此处例如通过A2+B3合成表示,使双官能单体A2与三官能单体B3反应。首先形成平均具有一个官能团A和两个官能团B的A与B的1∶1加合物,然后可同样反应得到超支化聚合物。如此获得的超支化聚合物也主要具有B基团作为末端基团。
起始表示的官能团(尤其是A和B基团)可通过类似于聚合物的反应用合适的化合物转官能化。这样,可得到特别良好匹配的超支化聚合物以用于本发明。
超支化聚合物的转官能化可在制备聚合物的过程中、紧邻聚合反应之后或在单独的反应中进行。
如果在聚合物合成之前或之中加入除了A和B基团外还具有其他官能团的组分,得到具有无规分布的其他官能团,即不同于A或B基团的官能团的超支化聚合物。
用于转官能化的化合物可首先包含待新引入的所需官能团和可与用作原料的超支化聚合物的B基团反应并形成键接的第二基团。其实例为使异氰酸酯基团与羟基羧酸或氨基羧酸反应并形成酸官能团,或使OH基团与丙烯酸酐反应并形成反应性丙烯酸类双键。
可借助合适的反应物引入的合适官能团的实例尤其包括具有H原子的酸性或碱性基团及其衍生物,如-OC(O)OR、-COOH、-COOR、-CONHR、-CONH2、-OH、-SH、-NH2、-NHR、-NR2、-SO3H、-SO3R、-NHCOOR、-NHCONH2、-NHCONHR,但是并不意味着仅限于此。合适的话,官能团也可借助合适的酸或碱转化为相应的盐。此外,烷基卤化物也可用于季胺化存在的伯、仲或叔氨基。以此方式,例如可得到水溶性或水分散性超支化聚合物。
所述基团的基团R通常为直链或支化烷基或为芳基,它们也可进一步被取代。例如,它们为C1-C30烷基或为C6-C14芳基。也可使用其他官能团,如-CN或-OR。
对于使用本发明超支化聚合物,可能有利的是亲水和疏水分子结构部分具有一定的相互间比例。超支化聚合物可例如通过使用单官能疏水化合物而变为疏水的,存在的反应性基团可在聚合之前、之中或之后用其改性。因此,本发明聚合物可例如通过与单官能饱和或不饱和脂族或芳族胺、醇、羧酸、环氧化物或异氰酸酯反应而变得疏水。
此外,具有疏水基团的双官能或更高官能单体也可以聚合单元形式掺入并同时增加了分子量。为此,例如可使用除了反应性基团外还带有芳族基团或长链链烷基团、链烯基团或炔基的双官能或更高官能醇、双官能或更高官能胺、双官能或更高官能异氰酸酯、双官能或更高官能羧酸、双官能或更高官能环氧化物。
这类单体的实例为醇,如甘油单硬脂酸酯,甘油单油酸酯,己二醇,辛二醇,癸二醇,十二烷二醇,十八烷二醇或二聚脂肪醇,胺,如六亚甲基二胺,辛二胺或十二烷二胺,异氰酸酯,芳族或脂族二异氰酸酯和多异氰酸酯,例如二苯基甲烷二异氰酸酯及其更高的低聚类型,甲苯二异氰酸酯、萘二异氰酸酯、苯二亚甲基二异氰酸酯、六亚甲基二异氰酸酯、六亚甲基二异氰酸酯三聚体、异佛尔酮二异氰酸酯、双(二异氰酸根合环己基)甲烷或双(异氰酸根合甲基)环己烷,以及酸如己二酸、辛二酸、十二烷二酸、十八烷二酸和二聚脂肪酸。
此外,本发明聚合物可通过例如将包含羟基或氨基的超支化聚合物经由与氧化烯,如氧化乙烯、氧化丙烯或氧化丁烯反应转化为高官能的聚合物多元醇而变为亲水性,其中优选使用氧化乙烯。然而,作为另一选择,也可将双官能或更高官能的氧化烯-醇或氧化烯-胺也可用作聚合物的合成组分。
也可制备具有不同类型的官能团的超支化聚合物。这例如可通过与具有不同的用于转官能化的化合物的混合物反应,或通过仅使一些起始存在的官能团反应而进行。
此外,具有混合官能团的化合物可通过将ABC或AB2C类型的单体用于聚合而制备,其中C为在所选反应条件下不与A或B反应的官能团。
OH-、COOH-和/或-OC(O)OR结尾的超支化聚合物证明特别有利于用于本发明。非常特别有利的是使用具有OH和COOH基团,或OH和-OC(O)OR基团,或OH、COOH和-OC(O)OR基团的超支化聚合物。
超支化聚碳酸酯及其制备例如公开于WO 2005/026234和DE102005009166,此处将其完全引入作为参考。
超支化聚碳酸酯尤其可通过如下步骤得到:
a)使至少一种通式RO(CO)OR的有机碳酸酯(A)与至少一种具有至少3个OH基团的脂族醇(B)反应,同时消除醇ROH得到一种或多种缩合物(K),其中R在每种情况下相互独立地为具有1-20个碳原子的直链或支化的脂族、芳脂族或芳族烃基,和
b)使缩合物(K)进行分子间反应,形成超支化聚碳酸酯,
其中选择在该反应混合物中的OH基团与碳酸酯的比例,从而使缩合物(K)平均具有一个碳酸酯基团和超过一个OH基团或具有一个OH基团和超过一个碳酸酯基团。
用作原料并具有通式RO(CO)OR的有机碳酸酯(A)中的基团R在每种情况下各自相互独立地为具有1-20个碳原子的直链或支化的脂族、芳脂族或芳族烃基。两个基团R也可相互键合成环。该基团优选为脂族烃基,特别优选为具有1-5个碳原子的直链或支化烷基。
例如碳酸二烷基酯或碳酸二芳基酯可以由脂族、芳脂族或芳族醇,优选一元醇与光气反应而制备。它们还可以通过在贵金属、氧气或NOx存在下借助CO进行醇或酚的氧化羰基化而制备。有关碳酸二芳基酯或碳酸二烷基酯的制备方法还可参见“Ullmann’s Encyclopedia of IndustrialChemistry”,第6版,2000年电子版,Verlag Wiley-VCH。
合适的碳酸酯实例包括脂族或芳族碳酸酯,例如碳酸亚乙酯、碳酸1,2-或1,3-亚丙酯、碳酸二苯酯、碳酸二甲苯酯、碳酸二(二甲苯酯)、碳酸二萘酯、碳酸乙基苯基酯、碳酸二苄酯、碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二丁酯、碳酸二异丁酯、碳酸二戊酯、碳酸二己酯、碳酸二环己酯、碳酸二庚酯、碳酸二辛酯、碳酸二癸酯和碳酸二(十二烷基酯)。
优选使用脂族碳酸酯,特别是其中各基团独立地包含1-5个碳原子的那些,例如碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二丁酯或碳酸二异丁酯。
使有机碳酸酯与至少一种具有至少3个OH基团的脂族醇(B)反应。
具有至少3个OH基团的脂族醇的实例为甘油、三羟甲基甲烷、三羟甲基乙烷、三羟甲基丙烷、1,2,4-丁三醇、三(羟甲基)胺、三(羟乙基)胺、三(羟丙基)胺、季戊四醇、双(三羟甲基丙烷),或糖类如葡萄糖,基于三官能或更高官能醇和氧化乙烯、氧化丙烯或氧化丁烯的三官能或更高官能聚醚醇或聚酯醇。特别优选甘油、三羟甲基乙烷、三羟甲基丙烷、1,2,4-丁三醇、季戊四醇以及它们基于氧化乙烯或氧化丙烯的聚醚醇。
这些多官能醇还可以与二官能醇(B’)混合使用,条件是所有所用醇的平均总OH官能度大于2。合适的具有两个OH基团的化合物实例包括乙二醇,二甘醇,三甘醇,1,2-和1,3-丙二醇,二丙二醇,三丙二醇,新戊二醇,1,2-、1,3-和1,4-丁二醇,1,2-、1,3-和1,5-戊二醇,己二醇,环戊二醇,环己二醇,环己烷二甲醇和二官能聚醚醇或聚酯醇。
碳酸酯与醇或醇混合物的形成超支化聚碳酸酯的反应经由从碳酸酯分子消除单官能醇或酚而进行。
在超支化聚碳酸酯的制备中,必须调节含OH基团的化合物与碳酸酯的比例使得最简单的所得缩合物(下面称为缩合物(K))平均含有一个碳酸酯基团和超过一个OH基团或具有一个OH基团和超过一个碳酸酯基团。这里,来自碳酸酯(A)与二醇或多元醇(B)的缩合物(K)的最简单结构产生排列XYn或YXn,其中X为碳酸酯基团,Y为羟基且n通常为1-6,优选1-4,特别优选1-3的数。此时,唯一所得的反应性基团在下文通常称为“焦点基团”。
例如,若在由碳酸酯和二元醇制备最简单缩合物(K)过程中反应比为1∶1,则平均结果是通式1所示的XY型分子:
在由碳酸酯和三元醇以1∶1的反应比制备缩合物(K)的过程中,平均结果是通式2所示的XY2型分子。此时的焦点基团是碳酸酯基团。
在由碳酸酯和四元醇同样以1∶1的反应比制备缩合物(K)的过程中,平均结果是通式3所示的XY3型分子。此时的焦点基团是碳酸酯基团。
在式1-3中,R具有开头所定义的含义,并且R1优选为脂族烃基。
缩合物(K)例如还可以如通式4所示由碳酸酯和三元醇制备,其中反应摩尔比为2∶1。此时平均结果是X2Y型分子且焦点基团为OH基团。在式4中,R和R1具有与式1-3中相同的含义。
若还将二官能化合物如二碳酸酯或二醇加入各组分中,结果是例如如通式5所示延长了链。平均结果还是得到XY2型分子,其中焦点基团为碳酸酯基团。
在式5中,R2为有机基团,优选脂族基团,且R和R1如上所定义。
根据本发明,例如由式1-5所示的简单缩合物(K)优先发生分子间反应而形成超支化缩聚物,下文称为缩聚物(P)。
得到缩合物(K)和缩聚物(P)的反应通常在0-250℃,优选60-160℃的温度下在溶剂不存在下或在溶液中进行。此时通常可以使用对各原料呈惰性的所有溶剂。优选使用有机溶剂如癸烷、十二烷、苯、甲苯、氯苯、二甲苯、二甲基甲酰胺、二甲基乙酰胺或溶剂石脑油。
在优选的实施方案中,缩合反应在溶剂不存在下进行。可以通过蒸馏从反应平衡中除去在反应过程中释放的单官能醇ROH或酚,以加速该反应,合适的话在减压下蒸馏。
若进行蒸馏除去,则通常有利的是使用那些在反应期间释放沸点低于140℃的醇ROH的碳酸酯。
为了加速该反应,还可以加入催化剂或催化剂的混合物。合适的催化剂是催化酯化或酯交换反应的化合物,例如碱金属氢氧化物,碱金属碳酸盐,碱金属碳酸氢盐,优选钠、钾或铯的盐,叔胺,胍,铵化合物,鏻化合物,有机铝,有机锡,有机锌,有机钛,有机锆或有机铋化合物,以及所谓的双金属氰化物(DMC)催化剂,其例如描述于DE 10138216或DE10147712中,此处将其完全引入作为参考。
优选使用氢氧化钾,碳酸钾,碳酸氢钾,二氮杂双环辛烷(DABCO),二氮杂双环壬烯(DBN),二氮杂双环十一碳烯(DBU),咪唑类如咪唑、1-甲基咪唑或1,2-二甲基咪唑,四丁醇钛,四异丙醇钛,氧化二丁基锡,二月桂酸二丁锡,二辛酸锡,乙酰丙酮锆或其混合物。
基于醇或醇混合物的用量,催化剂的加入量通常为50-10 000重量ppm,优选100-5000重量ppm。
还可以通过加入合适的催化剂以及通过选择合适的温度来控制分子间缩聚反应。此外可借助起始组分的组成和停留时间而建立聚合物(P)的平均分子量。
在升高温度下制备的缩合物(K)或缩聚物(P)通常在室温下能较长时期地稳定。
由于缩合物(K)的性质,可由缩合反应得到具有不同结构的缩聚物(P),其具有支链但未交联。此外,理想的是缩聚物(P)具有一个碳酸酯基团作为焦点基团和超过两个OH基团或具有一个OH基团作为焦点基团和超过两个碳酸酯基团。反应性基团的数目由所用缩合物(K)的性质和缩聚度决定。
作为举例,通式2的缩合物(K)可通过三重分子间缩合而反应,形成两种由通式6和通7代表的不同缩聚物(P)。
在式6和7中,R和R1如上所定义。
为了终止分子间缩聚反应,可以采用多种方式。例如可以将温度降低到反应停止且产物(K)或缩聚物(P)储存稳定的范围。
在另一实施方案中,一旦缩合物(K)的分子间反应产生了具有所需缩聚度的缩聚物(P),就可以向产物(P)中加入具有对(P)的焦点基团呈反应性的基团的产物而终止反应。因此,在碳酸酯作为焦点基团的情况下,例如可以加入单胺、二胺或多胺。在羟基作为焦点基团的情况下,例如可以向产物(P)中加入与OH基团反应的单-、二-或多异氰酸酯、含有环氧基团的化合物或酸衍生物。
本发明的聚碳酸酯的制备通常在0.1毫巴至20巴,优选1毫巴至5巴的压力范围内在分批、半分批或连续操作的反应器或反应器级联中进行。
通过上述调节反应条件以及合适的话通过选择合适的溶剂,可以将产物在制备之后无需进一步提纯而进行进一步加工。
在另一优选实施方案中,除了通过反应得到的官能团外,聚碳酸酯还可以含有其它官能团。可以在增加分子量过程中进行官能化或随后进行,即在实际缩聚完成后进行官能化。
若在增加分子量之前或其过程中加入除羟基或碳酸酯基团外还具有其它官能团或官能单元的组分,则得到具有无规分布的不同于碳酸酯基团或羟基的官能团的聚碳酸酯聚合物。
这种效果例如可以通过在缩聚过程中加入除了羟基或碳酸酯基团以外还带有其他官能团或官能单元如巯基、伯氨基、仲氨基、叔氨基、醚基团、羧酸衍生物、磺酸衍生物、膦酸衍生物、芳基或长链烷基的化合物而实现。可借助氨基甲酸酯基团用于改性的化合物的实例为乙醇胺,丙醇胺,异丙醇胺,2-(丁基氨基)乙醇,2-(环己基氨基)乙醇,2-氨基-1-丁醇,2-(2’-氨基乙氧基)乙醇和氨的高级烷氧基化产物,4-羟基哌啶,1-羟乙基哌嗪,二乙醇胺,二丙醇胺,二异丙醇胺,三(羟甲基)氨基甲烷,三(羟乙基)氨基甲烷,乙二胺,丙二胺,六亚甲基二胺或异佛尔酮二胺。
可以用巯基进行改性的化合物例如为巯基乙醇。例如,叔氨基可通过引入N-甲基二乙醇胺、N-甲基二丙醇胺或N,N-二甲基乙醇胺而产生。例如,醚基团可以通过引入双官能或更高官能聚醚醇的缩合而产生。长链烷基可通过与长链链烷二醇反应而引入,且与烷基或芳基二异氰酸酯的反应产生具有烷基、芳基和氨基甲酸酯基团的聚碳酸酯。
随后的官能化可以通过使所得超支化聚碳酸酯与能够与聚碳酸酯的OH和/或碳酸酯基团反应的合适官能化试剂反应而得到。
例如可以通过加入包含酸基或异氰酸酯基团的分子而改性含羟基的超支化聚碳酸酯。例如,含酸基的聚碳酸酯可以通过与包含酸酐基团的化合物反应而得到。
此外,含羟基的超支化聚碳酸酯还可以通过与氧化烯如氧化乙烯、氧化丙烯或氧化丁烯反应而转化成高官能度聚碳酸酯聚醚多元醇。
通过所述方法形成的超支化聚碳酸酯易于溶于各种溶剂,如水,醇类如甲醇、乙醇或丁醇,醇/水混合物,丙酮,2-丁酮,乙酸乙酯,乙酸丁酯,乙酸甲氧基丙酯,乙酸甲氧基乙酯,四氢呋喃,二甲基甲酰胺,二甲基乙酰胺,N-甲基吡咯烷酮,碳酸亚乙酯或碳酸亚丙酯。
根据特定实施方案,本发明超支化聚碳酸酯为可通过使碳酸二烷基酯如碳酸二乙酯和聚氧乙烯三醇反应而得到的超支化聚碳酸酯。聚氧乙烯三醇优选为三羟甲基丙烷与2-25,如3或12个氧化乙烯单元的乙氧基化产物。
超支化聚酯及其制备例如公开于WO 93/17060、WO 01/46296、WO03/54204、WO 03/93343、WO 05/037893、WO 04/020503、WO 05/118677,此处将其完全引入作为参考。
超支化聚酯尤其可通过使至少一种脂族、脂环族、芳脂族或芳族二羧酸(A2)或其衍生物:
a)与至少一种至少三官能的脂族、脂环族、芳脂族或芳族醇(B3)反应而得到,或
b)与至少一种二元脂族、脂环族、芳脂族或芳族醇(B2)和至少一种具有超过2个OH基团的x-官能的脂族、脂环族、芳脂族或芳族醇(Cx)反应而得到,其中x为大于2,优选3-8,特别优选3-6,非常特别优选3或4,尤其是3的数,
或通过使至少一种其中y为大于2,优选3-8,特别优选3-6,非常特别优选3或4,尤其是3的数的具有超过2个酸基团的脂族、脂环族、芳脂族或芳族羧酸(Dy)或其衍生物,
c)与至少一种至少二官能脂族、脂环族、芳脂族或芳族醇(B2)反应而得到,或
d)与至少一种二元脂族、脂环族、芳脂族或芳族醇(B2)和至少一种具有超过2个OH基团的x-官能的脂族、脂环族、芳脂族或芳族醇(Cx)反应而得到,其中x为大于2,优选3-8,特别优选3-6,非常特别优选3或4,尤其是3的数,
e)合适的话在其他官能化结构单元E存在下进行,和
f)随后任选与一元羧酸或一元羧酸衍生物F反应,
其中选择反应混合物中的反应性基团的比例,以使OH基团与羧基或其衍生物的摩尔比为5∶1-1∶5,优选4∶1-1∶4,特别优选3∶1-1∶3,非常特别优选2∶1-1∶2。
二羧酸(A2)例如包括脂族二羧酸,如草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷-α,ω-二甲酸、十二烷-α,ω-二甲酸、顺-和反-环己烷-1,2-二甲酸、顺-和反-环己烷-1,3-二甲酸、顺-和反-环己烷-1,4-二甲酸、顺-和反-环戊烷-1,2-二甲酸以及顺-和反-环戊烷-1,3-二甲酸。此外,也可使用芳族二羧酸如邻苯二甲酸、间苯二甲酸或对苯二甲酸。也可使用不饱和二羧酸如马来酸或富马酸。
所述二羧酸也可被一个或多个选自下列的基团取代:C1-C25烷基、C3-C12环烷基、C2-C30链烯基或C5-C14芳基。可提及的取代的二羧酸的典型实例为:2-甲基丙二酸、2-乙基丙二酸、2-苯基丙二酸、2-甲基琥珀酸、2-乙基琥珀酸、C18-链烯基琥珀酸酐、2-苯基琥珀酸、衣康酸和3,3-二甲基戊二酸。
可以使用二羧酸本身也可以使用其衍生物形式。
衍生物为单体形式或聚合物形式的相关酸酐,单-或二烷基酯,优选单-或二C1-C4烷基酯,特别优选单-或二甲基酯,以及相应的单-或二乙基酯,还有单-和二乙烯基酯,以及混合酯,优选具有不同C1-C4烷基组分的混合酯,特别优选混合的甲基乙基酯,以及它们的酸酐。
此外,还可使用两种或更多种上述二羧酸的混合物。
也可以使用二羧酸和一种或多种其衍生物的混合物。同样可以使用一种或多种二羧酸的多种不同衍生物的混合物。
特别优选使用丙二酸、琥珀酸、戊二酸、己二酸,1,2-、1,3-或1,4-环己烷二甲酸(六氢苯二甲酸),邻苯二甲酸、间苯二甲酸、对苯二甲酸或其单-或二烷基酯。
可反应的三羧酸或多羧酸(Dy)例如为乌头酸、1,3,5-环己烷三甲酸、1,2,4-苯三甲酸、1,3,5-苯三甲酸、1,2,4,5-苯四甲酸(苯均四酸)和苯六甲酸以及低分子量聚丙烯酸。
可使用三羧酸或多羧酸(Dy)本身或使用其衍生物形式。
也可使用三-或多羧酸和一种或多种其衍生物的混合物,例如苯均四酸和苯均四酸酐的混合物。也可使用一种或多种三-或多羧酸的多种不同衍生物的混合物,例如1,3,5-环己烷三甲酸和苯均四酸二酐的混合物。
所用二醇(B2)的实例为乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,2-戊二醇、1,3-戊二醇、1,4-戊二醇、1,5-戊二醇、2,3-戊二醇、2,4-戊二醇、1,2-己二醇、1,3-己二醇、1,4-己二醇、1,5-己二醇、1,6-己二醇、2,5-己二醇、1,2-庚二醇、1,7-庚二醇、1,8-辛二醇、1,2-辛二醇、1,9-壬二醇、1,10-癸二醇、1,2-癸二醇、1,12-十二烷二醇、1,2-十二烷二醇、1,5-己二烯-3,4-二醇,1,2-和1,3-环戊二醇,1,2-、1,3-和1,4-环己二醇,1,1-、1,2-、1,3-和1,4-二(羟基甲基)环己烷,1,1-、1,2-、1,3-和1,4-二(羟基乙基)环己烷、新戊二醇、(2)-甲基戊烷-2,4-二醇、2,4-二甲基戊烷-2,4-二醇、2-乙基己烷-1,3-二醇、2,5-二甲基己烷-2,5-二醇、2,2,4-三甲基戊烷-1,3-二醇、频哪醇、二甘醇、三甘醇、二丙二醇、三丙二醇、聚乙二醇HO(CH2CH2O)n-H或聚丙二醇HO(CH[CH3]CH2O)n-H,其中n为整数且n≥4,聚乙二醇-丙二醇,其中氧化乙烯和氧化丙烯单元的序列可以是嵌段-嵌段或无规的,聚四亚甲基二醇,优选分子量为至多5000g/mol,聚1,3-丙二醇,优选分子量为至多5000g/mol,聚己内酯或上述化合物中两种或更多种的混合物。上述二醇中的一个或两个羟基也可以被SH基替代。优选使用的二醇为乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,8-辛二醇,1,2-、1,3-和1,4-环己二醇,1,3-和1,4-二(羟基甲基)环己烷,以及二甘醇、三甘醇、二丙二醇、三丙二醇、聚乙二醇HO(CH2CH2O)n-H或聚丙二醇HO(CH[CH3]CH2O)n-H,其中n为整数且n≥4,聚乙二醇-丙二醇,其中氧化乙烯和氧化丙烯单元的序列可以是嵌段-嵌段或无规的,或聚四亚甲基二醇,优选分子量为至多5000g/mol。
二元醇B2也可任选包含其他官能团,如羰基、羧基、烷氧羰基或磺酰基官能,如二羟甲基丙酸或二羟甲基丁酸及其C1-C4烷基酯,甘油单硬脂酸酯或甘油单油酸酯。
具有3个或更多个OH基团的醇(Cx)包括甘油、三羟甲基甲烷、三羟甲基乙烷、三羟甲基丙烷、1,2,4-丁三醇、三(羟基甲基)胺、三(羟基乙基)胺、三(羟基丙基)胺、季戊四醇、双甘油、三甘油或甘油的更高级缩合物、二(三羟甲基丙烷)、二季戊四醇、三羟基甲基异氰脲酸酯、三(羟基乙基)异氰脲酸酯(THEIC)、三(羟基丙基)异氰脲酸酯,肌醇,或糖,如葡萄糖、果糖或蔗糖,糖醇,例如山梨糖醇、甘露醇、苏糖醇(threitol)、赤藓醇、阿东醇(核醣醇)、阿糖醇、木糖醇、半乳糖醇(卫矛醇)、麦芽糖醇、异麦芽糖醇(isomalt),基于三官能或更高官能醇和氧化乙烯、氧化丙烯和/或氧化丁烯的三官能或更高官能的聚醚醇。
特别优选甘油、双甘油、三甘油、三羟甲基乙烷、三羟甲基丙烷、1,2,4-丁三醇、季戊四醇、三(羟基乙基)异氰脲酸酯及其基于氧化乙烯和/或氧化丙烯的聚醚醇。
根据特定实施方案,超支化聚合物为可通过使α,β-不饱和羧酸及其衍生物与多官能醇反应而得到的超支化聚酯。α,β-不饱和羧酸及其衍生物优选为二羧酸及其衍生物。特别优选其中双键邻近于两个羧酸基的二羧酸和衍生物。这些优选的α,β-不饱和羧酸及其衍生物包括马来酸、马来酸酐、马来酸二酰氯、富马酸、富马酸二酰氯、衣康酸和衣康酸二酰氯。特别优选马来酸酐。所述α,β-不饱和羧酸及其衍生物可单独使用或组合使用,或与其他羧酸及其衍生物,优选二-或多元羧酸及其衍生物,如己二酸一起使用,以用于制备超支化聚酯。基于马来酸酐的超支化聚酯例如公开于WO05/037893,此处将其完全引入作为参考。
根据另一特定实施方案,超支化聚合物为可通过使用AB2单体,如二羟基羧酸,如二羟甲基丙酸得到的超支化聚酯。“ABx单体”特别适用于合成超支化聚合物。这些ABx单体具有两种可相互反应形成键接的不同官能团A和B。就此而言,官能团A每分子仅存在1个且官能团B存在两个或更多个。所述ABx单体相互间反应基本产生具有规则排列的支化点的未交联聚合物。聚合物在链端几乎仅具有B基团。其他细节例如在Journal ofMolecular Science,Rev.Macromol.Chem.Phys.,C37(3),555-579(1997)中找到,此处将其完全引入作为参考。
反应可在溶剂存在或不存在下进行。合适的溶剂例如为烃,如链烷烃,芳族烃,醚和酮。反应优选在溶剂不存在下进行。反应可以在作为添加剂的脱水剂存在下进行,脱水剂在反应开始时加入。适合的脱水剂例如为分子筛,尤其是4分子筛,MgSO4和Na2SO4。也可以蒸除在反应期间形成的水或醇,以及可以例如使用水分离器,其中在水分离器中借助夹带剂除去水。
反应可以在不存在催化剂下进行。然而,优选所述程序在至少一种催化剂存在下进行。优选酸性无机催化剂、有机金属催化剂或有机催化剂,或多种酸性无机催化剂、有机金属催化剂或有机催化剂的混合物。
例如,可使用硫酸、硫酸盐和硫酸氢盐,如硫酸氢钠,磷酸,膦酸,次磷酸,硫酸铝水合物,明矾,酸性硅胶(在水中的pH为≤6,尤其是≤5),和酸性氧化铝。例如也可使用通式Al(OR2)3的铝化合物和通式Ti(OR2)4的钛酸酯作为酸性无机催化剂,其中基团R2各自可相同或不同且独立地选自丁基、异丙基或2-乙基己基。优选酸性有机金属催化剂例如选自氧化二烷基锡R3 2SnO或二烷基锡酯R3 2Sn(OR4)2,其中R3和R4可选自C1-C20烷基或C3-C12环烷基且可相同或不同。酸性有机金属催化剂的特别优选的代表为氧化二丁锡和二月桂酸二丁锡。
反应在60-250℃的温度下进行。
根据特定实施方案,本发明超支化聚酯为可通过使任选取代的琥珀酸酐和聚氧乙烯三醇反应而得到的超支化聚酯。任选取代的琥珀酸酐优选为C8-C25链烯基琥珀酸酐,如C18链烯基琥珀酸酐。聚氧化烯三醇优选为具有2-25,如3或12个氧化乙烯单元的三羟甲基丙烷的乙氧基化产物。
超支化聚酯及其制备例如公开于WO 03/062306,WO 00/56802,DE 102 11 664或DE 199 47 631中,此处将其完全引入作为参考。
超支化聚碳酸酯、聚酯和聚醚的混合形式,如超支化聚酯碳酸酯,超支化聚醚碳酸酯,聚醚酯,聚醚酯碳酸酯可以类似于超支化聚碳酸酯、聚酯和聚醚通过以合适的方式组合反应物而制备。例如,聚酯碳酸酯及其制备公开于DE 102005009166,此处将其完全引入作为参考。
超支化聚氨酯及其制备例如公开于WO 97/02304或DE 199 04 444中,此处将其完全引入作为参考。
超支化聚脲及其制备例如公开于WO 03/066702,DE 10351401.5或DE 102004006304.4,此处将其完全引入作为参考。
超支化聚脲聚氨酯及其制备例如公开于WO 97/02304或DE 199 04 444中,此处将其完全引入作为参考。
在本发明上下文中,术语“聚氨酯”不仅包括其重复单元经由氨基甲酸酯基团相互键接的那些聚合物,而且包括可通过使至少一种二和/或多异氰酸酯与至少一种具有至少一个对异氰酸酯基团呈反应性的基团的化合物反应而得到的非常一般的聚合物。这些聚合物例如包括其重复单元除了氨基甲酸酯基团外,还由脲、脲基甲酸酯、缩二脲、碳二亚胺、酰胺、脲酮亚胺(uretonimine)、缩脲二酮、异氰脲酸酯或噁唑烷酮基团连接的那些聚合物,例如参见Plastics Handbook,Saechtling,第26版,第491页及随后各页,Carl Hanser Verlag,Munich,1995,此处将其完全引入作为参考。术语“聚氨酯”尤其包括具有氨基甲酸酯和脲基团的聚合物。
氨基甲酸酯和/或脲基团(以及存在的话通过使异氰酸酯基团与相应的具有活性氢原子的反应性基团反应而得到的额外基团)的含量优选为0.5-10mol/kg,特别优选1-10mol/kg,特别是2-8mol/kg。
可根据本发明使用的超支化聚氨酯和聚脲的合成例如可如下所述进行。
在超支化聚氨酯和聚脲的合成中,优选使用同时具有异氰酸酯基团和可与异氰酸酯基团反应形成键接的基团的ABx单体。x为2-8的自然数。x优选为2或3。A为异氰酸酯基团和B为与之反应的基团,反之亦然。
与异氰酸酯基团反应的基团优选为OH、NH2、NRH、SH或COOH基团。
ABx单体可以已知的方式使用各种技术制备。
ABx单体例如可根据WO 97/02304(此处将其完全引入作为参考)中公开的方法合成,其中使用保护基团技术。例如,通过由2,4-甲苯二异氰酸酯(TDI)和三羟甲基丙烷制备AB2单体来阐述该技术。首先,将TDI的一个异氰酸酯基团以已知的方式,如通过与肟反应而封端。使剩余的游离NCO基团与三羟甲基丙烷反应,其中三个OH基团中的一个与异氰酸酯基团反应。在将保护基团离解之后,得到具有一个异氰酸酯基团和2个OH基团的分子。
在特别有利的方式中,ABx分子可根据DE-A 199 04 444中公开的方法合成,此处将其完全引入作为参考,其中不需要保护基团。在该方法中,使用二-或多异氰酸酯并使其与具有至少两个与异氰酸酯基团反应的基团的化合物反应。反应搭档(partner)中的至少一种具有相对于另一反应搭档呈变化的反应性的基团。优选反应搭档两者具有相对于另一反应搭档呈变化的反应性的基团。选择反应条件以使仅某些反应性基团可相互反应。
此外,ABx单体可如德国专利申请P 102 04 979.3所公开制备,此处将其完全引入作为参考。在这种情况下,使通过封端剂保护的异氰酸酯基团与多胺反应得到聚脲。
可行的二-或多异氰酸酯为现有技术已知的和随后举例提及的脂族、脂环族、芳脂族和芳族二-和多异氰酸酯。就此而言,可优选提及4,4′-二苯基甲烷二异氰酸酯,单体二苯基甲烷二异氰酸酯和低聚二苯基甲烷二异氰酸酯(聚合物MDI)的混合物,四亚甲基二异氰酸酯,四亚甲基二异氰酸酯三聚体,六亚甲基二异氰酸酯,六亚甲基二异氰酸酯三聚体,异佛尔酮二异氰酸酯三聚体、4,4′-亚甲基二环己烷二异氰酸酯,苯二亚甲基二异氰酸酯,四甲基苯二亚甲基二异氰酸酯,十二烷二异氰酸酯,其中烷基表示C1-C10烷基的赖氨酸烷基酯二异氰酸酯,1,4-二异氰酸根合环己烷或4-异氰酸根合甲基-1,8-八亚甲基二异氰酸酯。
具有变化反应性的NCO基团的二-或多异氰酸酯特别优选适用于合成聚氨酯和聚脲。就此而言,可提及2,4-甲苯二异氰酸酯(2,4-TDI)、2,4′-二苯基甲烷二异氰酸酯(2,4′-MDI),三异氰酸根合甲苯,异佛尔酮二异氰酸酯(IPDI),2-丁基-2-乙基五亚甲基二异氰酸酯,2,2,4-或2,4,4-三甲基-1,6-六亚甲基二异氰酸酯、2-异氰酸根合丙基环己烷异氰酸酯、3(4)-异氰酸根合甲基-1-甲基环己烷异氰酸酯、1,4-二异氰酸根合-4-甲基戊烷、2,4′-亚甲基双环己烷二异氰酸酯和4-甲基环己烷1,3-二异氰酸酯(H-TDI)。
其中异氰酸酯的NCO基团首先具有相等反应性,然而反应物首先加成到NCO基团可导致第二个NCO基团反应性降低的异氰酸酯也适用于合成聚氨酯和聚脲。其实例为其NCO基团经由离域p-电子体系连接的异氰酸酯,如1,3-和1,4-苯二异氰酸酯,1,5-萘二异氰酸酯,联苯基二异氰酸酯,联甲苯胺二异氰酸酯或2,6-甲苯二异氰酸酯。
此外,例如可使用低聚或聚异氰酸酯,其可由上述二-或多异氰酸酯或其混合物借助氨基甲酸酯、脲基甲酸酯、脲、缩二脲、缩脲二酮、酰胺、异氰脲酸酯、碳二亚胺、脲酮亚胺(uretonimine)、噁二嗪三酮或亚氨基噁二嗪二酮结构连接制备。
作为具有至少两个对异氰酸酯呈反应性的基团的化合物,优选使用二-、三-或四官能化合物,其官能团对NCO基团具有变化的反应性。
对于聚氨酯和聚脲-聚氨酯的制备,优选具有至少一个伯羟基和至少一个仲羟基的化合物,至少一个羟基和至少一个巯基的化合物,特别优选分子中具有至少一个羟基和至少一个氨基的化合物,尤其是氨基醇,氨基二醇和氨基三醇,这是因为在与异氰酸酯的反应中,氨基的反应性明显高于羟基。
上述具有至少两个与异氰酸酯反应的基团的化合物的实例为丙二醇、甘油、巯基乙醇、乙醇胺、N-甲基乙醇胺、二乙醇胺、乙醇丙醇胺、二丙醇胺、二异丙醇胺、2-氨基-1,3-丙二醇、2-氨基-2-甲基-1,3-丙二醇或三(羟基甲基)氨基甲烷。此外,也可使用上述化合物的混合物。
优选将在分子中具有至少两个氨基的异氰酸酯反应性产物用于制备聚脲。
它们例如为乙二胺、N-烷基乙二胺、丙二胺、N-烷基丙二胺、六亚甲基二胺、N-烷基六亚甲基二胺、二氨基二环己基甲烷、苯二胺、异佛尔酮二胺、胺封端的聚氧化烯多元醇(称作Jeffamine)、二(氨基乙基)胺、二(氨基丙基)胺、二(氨基己基)胺、三(氨基乙基)胺、三(氨基丙基)胺、三(氨基己基)胺、三氨基己烷、4-氨基甲基-1,8-八亚甲基二胺、N′-(3-氨基丙基)-N,N-二甲基-1,3-丙二胺、三氨基壬烷或蜜胺。此外,也可使用上述化合物的混合物。
此处,通过举例说明由二异氰酸酯和氨基二醇制备用于制备聚氨酯的ABx分子。就此而言,首先使1摩尔二异氰酸酯与1摩尔氨基二醇在低温下,优选在-10℃至30℃的温度下反应。在该温度范围中,形成氨基甲酸酯的反应事实上被完全抑制并且异氰酸酯的NCO基团仅与氨基二醇的氨基反应。形成的ABx分子(在这种情况下为AB2类型)具有游离NCO基团和两个游离OH基团并且可用于合成超支化聚氨酯。
该AB2分子可通过温热和/或加入催化剂而分子间反应得到超支化聚氨酯。该超支化聚氨酯可有利地在升高温度,优选30-80℃下合成,而不在额外反应步骤中预先分离AB2分子。在使用所述具有两个OH基团和一个NCO基团的AB2分子时,产生了超支化聚合物,其每分子具有一个游离NCO基团,以及取决于聚合度的或多或少的大量OH基团。该反应可进行至高转化率,通过该反应得到非常高分子量的结构。然而,在达到所需分子量时,也可通过加入合适的单官能化合物或通过加入用于制备AB2分子的一种起始化合物而封端。取决于用于封端的起始化合物,产生或者完全NCO封端或者完全OH封端的分子。
或者,AB2分子也可例如由1摩尔甘油和2摩尔2,4-TDI制备。在低温下,伯醇基团和4位的异氰酸酯基团优选反应并且形成具有一个OH基团和两个异氰酸酯基团的加合物,该加合物可如上所述在较高温度下转化为超支化聚氨酯。首先产生具有一个游离OH基团以及取决于聚合度的或多或少的大量NCO基团的超支化聚合物。
超支化聚氨酯和聚脲的制备原则上可在无溶剂下进行,但优选在溶液中进行。所有在反应温度下为液体并且对单体和聚合物呈惰性的化合物适合作为溶剂。
其它产物可通过额外的替代合成形式得到。此处例如可提及:
AB3分子例如可通过使二异氰酸酯与具有至少4个对异氰酸酯呈反应性的基团的化合物反应而得到。例如可提及甲苯二异氰酸酯与三(羟甲基)氨基甲烷的反应。
多官能化合物也可用于结束聚合,其中该化合物可与各A基团反应。这样,数个小的超支化分子可链接在一起产生大的超支化分子。
具有扩链的支链的超支化聚氨酯和聚脲例如可通过在聚合反应中除了ABx分子外,以1∶1的摩尔比额外使用二异氰酸酯和具有两个与异氰酸酯基团反应的基团的化合物而得到。这些额外的AA或BB化合物也可甚至具有在反应条件下可能对A或B基团不具有反应性的额外官能团。以这种方式,可将额外官能团引入超支化聚合物中。
超支化聚酰胺及其制备例如公开于US 4 507 466、US 6 541 600、US-A-2003055209、US 6 300 424、US 5 514 764、WO 92/08749和DE102004039101.7,此处将其完全引入作为参考。
适用于制备超支化聚酰胺的程序起始于多官能胺和多元羧酸,其中使用至少一种具有3个或超过3个(如4、5、6个等)官能团的多官能化合物。在形式上,在该程序中,使具有两个相同官能团的第一类单体A2(如二羧酸或二胺)与第二类单体Bn反应,该第二类单体包括至少一种具有多于相等官能团的化合物(如至少一种三羧酸(n=3)或高于三元的羧酸或至少一种三胺(n=3)或高于三元的胺)。优选第二类单体包括至少一种具有两个与单体A2互补官能团的二元单体B2。优选单体Bn的平均官能度为至少2.1(n=2.1)。对于根据该替代形式制备超支化聚酰胺而言,单体A2相对于单体Bn以摩尔过量使用。优选单体A2与单体Bn的摩尔比为1∶1-20∶1,特别优选1.1∶1-10∶1,尤其是1.2∶1-5∶1。在优选实施方案中,首先制备具有末端基团A的超支化预聚物,然后使其与至少一种单体B2和/或Bn反应。为了制备预聚物,优选以1∶1-20∶1,特别优选1.1∶1 to 10∶1,特别是1.2∶1-5∶1的摩尔比使用单体A2和单体Bn。
另外适用于制备超支化聚酰胺的程序起始于多官能氨基羧酸,其中使用至少一种具有3个或超过3个(如4、5、6个等)官能团的多官能化合物,即称为ABx单体(x大于或等于2)的化合物。然后可使它们与额外的单体AB、A2和/或B2反应。
合适的二羧酸例如为草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷-α,ω-二甲酸、十二烷-α,ω-二甲酸、顺-和反-环己烷-1,2-二甲酸、顺-和反-环己烷-1,3-二甲酸、顺-和反-环己烷-1,4-二甲酸、顺-和反-环戊烷-1,2-二甲酸、顺-和反-环戊烷-1,3-二甲酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸及其混合物。
上述二羧酸也可被取代。合适的取代的二羧酸可具有一个或多个优选选自下列的残基:如开头所定义的烷基、环烷基和芳基。合适的取代的二羧酸例如为2-甲基丙二酸、2-乙基丙二酸、2-苯基丙二酸、2-甲基琥珀酸、2-乙基琥珀酸、2-苯基琥珀酸、衣康酸、3,3-二甲基戊二酸等。
可以使用二羧酸本身或使用其衍生物形式。合适的衍生物为酸酐及其低聚物和聚合物,单-和二酯,优选单-和二烷基酯,和酰卤,优选酰氯。合适的酯为单甲基酯或二甲基酯,单乙基酯或二乙基酯,高级醇如正丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、正戊醇、正己醇等的单酯和二酯,以及单-和二乙烯基酯和混合酯,优选甲基乙基酯。
在本发明上下文中,也可以使用二羧酸和一种或多种其衍生物的混合物。在本发明上下文中,同样可以使用一种或多种二羧酸的数种不同衍生物的混合物。
特别优选使用琥珀酸、戊二酸、己二酸,邻苯二甲酸、间苯二甲酸、对苯二甲酸或其单-或二烷基酯。非常特别优选使用己二酸。
适用于制备超支化聚酰胺的多官能胺具有2个或超过2个(如3、4、5、6个等)能够形成酰胺的伯氨基或仲氨基。
合适的二胺为通常具有约2-30,优选约2-20个碳原子的直链和支化脂族和环脂族胺。合适的二胺例如为具有通式R1-NH-R2-NH-R3的那些,其中R1和R3相互独立地表示氢、烷基、环烷基或芳基且R2表示亚烷基、亚环烷基或亚芳基。这些包括乙二胺、1,2-二氨基丙烷、1,3-二氨基丙烷、1,4-二氨基丁烷、1,5-二氨基戊烷、1,6-二氨基己烷、1,7-二氨基庚烷、1,8-二氨基辛烷、1,9-二氨基壬烷、1,10-二氨基癸烷、1,11-二氨基十一烷、1,12-二氨基十二烷,N-烷基乙二胺,如N-甲基乙二胺和N-乙基乙二胺,N,N′-二烷基乙二胺,如N,N′-二甲基乙二胺、N-烷基六亚甲基二胺,如N-甲基六亚甲基二胺、哌嗪、二(4-氨基环己基)甲烷、苯二胺、异佛尔酮二胺、二(2-氨基乙基)醚、1,2-二(2-氨基乙氧基)乙烷和胺封端的聚氧化烯多元醇(″Jeffamine″或α,ω-二氨基聚醚),其可例如通过用氨将聚氧化烯胺化而制备。
合适的三胺例如为二(2-氨基乙基)胺(=二亚乙基三胺)、N,N′-二乙基二亚乙基三胺、二(3-氨基丙基)胺、二(6-氨基己基)胺、4-氨基甲基-1,8-八亚甲基二胺、N′-(3-氨基丙基)-N,N-二甲基-1,3-丙烷二胺、蜜胺等。
合适的多元胺为N,N′-二(2-氨基乙基)乙二胺(=三亚乙基四胺)、N,N′-二(2-氨基乙基)-1,3-二氨基丙烷、N,N′-二(3-氨基丙基)-1,4-二氨基丁烷(=精胺)、N,N′-二(2-氨基乙基)哌嗪、N,N′-二(3-氨基丙基)哌嗪、三(2-氨基乙基)胺、三(3-氨基丙基)胺、三(6-氨基己基)胺等。
聚合型多胺也是合适的。它们的数均分子量通常为约400-10 000,优选约500-8000。这些例如包括具有末端伯氨基或仲氨基的多胺,聚亚烷基亚胺,优选聚乙烯亚胺,通过水解聚-N-乙烯基酰胺,如聚-N-乙烯基乙酰胺得到的乙烯基酰胺,基于胺化的聚氧化烯的上述α,ω-二胺,以及包含共聚的具有合适的官能团的α,β-烯属不饱和单体,如丙烯酸氨基甲酯、丙烯酸氨基乙酯、丙烯酸(N-甲基)氨基乙酯、甲基丙烯酸(N-甲基)氨基乙酯等的共聚物。
上述超支化聚酰胺通常可直接用于本发明组合物中。在另外的实施方案中,使上述超支化聚酰胺进行额外的类似聚合物的反应,这例如描述于下文中。适合于此的例如是单羧酸,单胺,一元醇或多元醇,以及单羧酸和多羧酸,氨基羧酸,单胺和多胺,以及具有用于改性超支化聚酰胺性能的特定官能团的一元醇和多元醇。
超支化聚酰胺的制备可在常规催化剂存在下进行。这些例如包括金属氧化物和碳酸盐,强酸,对苯二甲酸盐,卤化钛,醇盐和羧酸盐等。合适的催化剂例如公开于US 2 244 192、US 2 669 556、SU 775 106和US 3 705881中。额外合适的催化剂为随后对聚酯酰胺提及的那些。
超支化聚酯酰胺及其制备例如公开于WO 99/16810、EP 1 036 106、WO 00/56804和WO 06/018126中,此处将其完全引入作为参考。
聚酯酰胺非常一般地为具有酯基和酰胺基的聚合的化合物。为制备超支化聚酯酰胺,原则上可使用选自多元羧酸、羟基羧酸、氨基羧酸、氨基醇、多胺、多元醇和上述化合物的衍生物的至少二元化合物。就此而言,首先适用如下条件,其中选择化合物,从而使所得聚合物具有酯基和酰胺基团两者。就此而言,还适用如下条件,其中选择化合物,从而使用至少一种具有3个或超过3个(如4、5、6个等)官能团的多官能化合物。
适合制备超支化聚酯酰胺的程序起始于多官能氨基醇和多元羧酸,其中使用至少一种具有3个或超过3个(如4、5、6个等)官能团的多官能化合物。
另外的适合制备超支化聚酯酰胺的程序起始于多官能胺、多官能醇和多元羧酸,其中使用至少一种具有3个或超过3个(如4、5、6个等)官能团的多官能化合物。
适用于制备超支化聚酯酰胺的多官能氨基醇具有两个或超过两个(如3、4、5、6个等)官能团,该官能团选自羟基和伯氨基和仲氨基。如上所定义,氨基醇就此而言总是具有至少一个羟基和至少一个伯氨基或仲氨基。合适的氨基醇为通常具有2-30,优选2-20个碳原子的直链和支化脂族和脂环族氨基醇。
合适的二元氨基醇例如为2-氨基乙醇(=单乙醇胺)、3-氨基-1-丙醇、2-氨基-1-丙醇、1-氨基-2-丙醇、2-氨基-3-苯基丙醇、2-氨基-2-甲基-1-丙醇、2-氨基-1-丁醇、4-氨基-1-丁醇、2-氨基异丁醇、2-氨基-3-甲基-1-丁醇、2-氨基-3,3-二甲基丁醇、1-氨基-1-戊醇、5-氨基-1-戊醇、2-氨基-1-戊醇、2-氨基-4-甲基-1-戊醇、2-氨基-3-甲基-1-戊醇、2-氨基环己醇、4-氨基环己醇、3-(氨基甲基)-3,5,5-三甲基环己醇、2-氨基-1,2-二苯基乙醇、2-氨基-1,1-二苯基乙醇、2-氨基-2-苯基乙醇、2-氨基-1-苯基乙醇、2-(4-氨基苯基)乙醇、2-(2-氨基苯基)乙醇、1-(3-氨基苯基)乙醇、2-氨基-1-己醇、6-氨基-1-己醇、6-氨基-2-甲基-2-庚醇、N-甲基异丙醇胺、N-乙基异丙醇胺、N-甲基乙醇胺、1-乙基氨基丁-2-醇、4-甲基-4-氨基戊-2-醇、2-(2-氨基乙氧基)乙醇、N-(2-羟基乙基)哌嗪、1-氨基-2-茚满醇、N-(2-羟基乙基)苯胺,氨基糖,如D-葡糖胺、D-半乳糖胺、4-氨基-4,6-二脱氧-α-D-吡喃型葡萄糖及其混合物。
合适的三元氨基醇和更多元的氨基醇例如为N-(2-羟基乙基)乙二胺、二乙醇胺、二丙醇胺、二异丙醇胺、2-氨基-1,3-丙二醇、3-氨基-1,2-丙二醇等。
适用于制备超支化聚酯酰胺的多元羧酸为上文对制备超支化聚酰胺所描述的那些。可完全参考其中提及的合适和优选的实施方案。
适用于制备超支化聚酯酰胺的多官能胺为上文对制备超支化聚酰胺所描述的那些。可完全参考其中提及的合适和优选的实施方案。
适用于制备超支化聚酯酰胺的多官能醇具有两个或超过两个(如3、4、5、6个等)羟基。就此而言,羟基也可部分或全部被巯基替换。
合适的二醇为通常具有约2-30,优选约2-20个碳原子的直链和支化脂族和脂环族醇。这些包括1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,2-戊二醇、1,3-戊二醇、1,4-戊二醇、1,5-戊二醇、2,3-戊二醇、2,4-戊二醇1,2-己二醇、1,3-己二醇、1,4-己二醇、1,5-己二醇、1,6-己二醇、2,5-己二醇、1,2-庚二醇、1,7-庚二醇、1,2-辛二醇、1,8-辛二醇、1,2-壬二醇、1,9-壬二醇、1,2-癸二醇、1,10-癸二醇、1,12-十二烷二醇、2-甲基-1,3-丙二醇、2-甲基-2-丁基-1,3-丙二醇、2,2-二甲基-1,3-丙二醇、2,2-二甲基-1,4-丁二醇、频哪醇、2-乙基-2-丁基-1,3-丙二醇、二甘醇、三甘醇、二丙二醇、三丙二醇、聚亚烷基二醇、环戊二醇、环己二醇等。
合适的三醇例如为甘油、1,2,4-丁三醇、正戊烷-1,2,5-三醇、正戊烷-1,3,5-三醇、正己烷-1,2,6-三醇、正己烷-1,2,5-三醇、三羟甲基丙烷和三羟甲基丁烷。合适的三醇还有羟基羧酸与三元醇的三酯。就此而言,优选它们为羟基羧酸,如乳酸、羟基硬脂酸和蓖麻油酸的甘油三酯。天然产生的包含羟基羧酸甘油三酯,尤其是蓖麻油的混合物也是合适的。合适的更多元的多元醇例如为糖醇及其衍生物,如赤藓醇、季戊四醇、双季戊四醇、苏糖醇、肌醇和山梨糖醇。多元醇与氧化烯如氧化乙烯和/或氧化丙烯的反应产物也是合适的。也可使用数均分子量为约400-6000g/mol,优选500-4000g/mol的较高分子量多元醇。这些例如包括基于脂族、脂环族和/或芳族二-、三-和/或更多元羧酸与二醇、三醇和/或更多元醇的聚酯醇,以及基于内酯的聚酯醇。它们进一步包括可例如通过将环醚聚合或通过使氧化烯与起始分子反应而得到的聚醚醇。它们还包括本领域技术人员已知的具有端羟基的常规聚碳酸酯,其可通过使上述二醇或双酚如双酚A与光气或碳酸二酯反应而得到。α,ω-聚酰胺二醇、聚(甲基)丙烯酸甲酯α,ω-二醇和/或聚(甲基)丙烯酸丁酯α,ω-二醇,如购至Goldschmidt的MD-1000和BD-1000也是合适的。
超支化聚酯酰胺的制备可根据本领域技术人员已知的常规方法进行。在第一实施方案中,超支化聚酯酰胺的制备以单段以一锅(one-pot)法起始于多官能氨基醇和二羧酸进行,其中使用至少一种具有3个或超过3个(如4、5、6个等)官能团的多官能氨基醇。二羧酸与氨基醇的摩尔比优选为2∶1-1.1∶1,特别优选1.5∶1-1.2∶1。在该单段工艺的合适实施方案中,如果仅使用二羧酸,即类型A2的单体和三官能氨基醇,即类型B3的单体,则有利的是在达到凝胶点之前中断反应。对于凝胶点的定义,参见Flory,Principles of Polymer Chemistry(聚合物化学原理),Cornell UniversityPress,1953,第387-398页,此处将其完全引入作为参考。凝胶点可根据Flory的理论计算以及可通过检测反应混合物的粘度而测定。可行的是,一旦观察到粘度快速升高,就中断反应。
在第二实施方案中,以两段一锅法制备超支化聚酯酰胺。就此而言,在第一段中,首先制备具有游离羧酸基团的预聚物,随后使其在第二段中与具有能够形成酯或酰胺的官能团的多官能化合物反应。在合适的实施方案中,在第一段中,将羧酸A2和氨基醇B3用于制备预聚物。二羧酸和氨基醇的摩尔比优选为2∶1-10∶1,特别优选2.5∶1-5∶1,特别是2.7∶1-4∶1。在该程序中,甚至在高反应速率下反应混合物的凝胶化可通常易于避免。对于预聚物在第二段中的进一步反应,可使用上述多官能胺、氨基醇和多胺,合适的话与额外的多元羧酸结合。对于这些化合物的合适和优选实施方案,优选参考上述内容。在第二反应段中,根据链增长优选主要或仅使用二元化合物。
如果对上述单段一锅法之后得到的超支化聚酯酰胺根据类似聚合物的反应进行随后改性,则也可得到与两段一锅法之后得到的那些相当的聚合物,因此可将上述多官能胺、醇、氨基醇和羧酸用于该类似聚合物的反应。如下文更具体描述,单段方法之后得到的超支化聚酯酰胺和两段方法之后得到的超支化聚酯酰胺与单官能化合物,如一元醇、单胺和单羧酸的类似聚合物的反应自然均是可行的。这些单官能化合物可具有用于额外改性聚合物性能的额外官能团。合适的终止剂例如为具有额外官能团的脂肪酸、脂肪酸衍生物,如酸酐和酯,脂肪醇,酸和酸衍生物,以及具有额外官能团的醇和胺。
用于制备超支化聚酯酰胺的酯化和胺化反应,以及用于制备超支化聚酰胺的胺化反应可在至少一种催化剂存在下进行。合适的催化剂例如为酸性催化剂,有机金属催化剂,酶等。
合适的酸性催化剂例如为硫酸、磷酸、膦酸、次磷酸、水合硫酸铝、明矾、酸性硅胶和酸性氧化铝。合适的催化剂还有通式Al(OR)3的有机铝化合物和通式Ti(OR)4的有机钛化合物,R残基相互独立地表示如开头所定义的烷基或环烷基。优选R残基例如选自异丙基和2-乙基己基。
优选酸性有机金属催化剂例如选自通式R2SnO的氧化二烷基锡,其中R相互独立地表示如开头所定义的烷基和环烷基。这些优选包括氧化二正丁基锡,其可以″Oxo-Tin″市购。
合适的酸性有机催化剂还有具有至少一个选自磷酸基、膦酸基、次硫酸基、磺酸基等的酸基的酸性有机化合物。例如优选对甲苯磺酸。合适的催化剂还有酸性离子交换材料,如用磺酸基改性的聚苯乙烯树脂,其以常规方式如用二乙烯基苯交联。
超支化聚胺及其制备例如公开于U.Steuerle,R.Feuerhake,″Aziridines(氮杂环丙烷)″,Ullmann’s Encyclopedia of IndustrialChemistry,Wiley-VCH和G.Scherr,U.Steuerle,R.Fikentscher,″Imines,Cyclic(亚胺,环状)″,Kirk-Othmer Encyclopedia of Chemical Technology,Wiley and Sons,2004-2007中,此处将其完全引入作为参考。
超支化聚胺及其制备例如公开于DE 10331770.8中,此处将其完全引入作为参考。
聚醚胺(也称为聚醚胺多元醇)通常通过催化醚化,如酸或碱催化在消除水下由三链烷醇胺,如三乙醇胺、三丙醇胺、三异丙醇胺,任选作为与单链烷醇胺或二链烷醇胺的混合物得到。
这些聚合物的制备例如描述于US 2,178,173、US 2,290,415、US2,407,895和DE 40 03 243,此处将其完全引入作为参考。聚合方法可统计进行,或可由单种链烷醇胺制备交替嵌段状结构,其在另一步骤中相互连接。也参见US 4,404,362,此处将其完全引入作为参考。
原料可以是三乙醇胺、三丙醇胺、三异丙醇胺或三丁醇胺,其任选与二链烷醇胺如二乙醇胺、二丙醇胺、二异丙醇胺、二丁醇胺、N,N′-二羟基烷基哌啶(烷基=C1-C8)结合,或与基于氧化乙烯和/或氧化丙烯的二官能或更高官能的聚醚醇结合。优选使用三乙醇胺和三异丙醇胺或其混合物作为原料。
在反应之后,不进行进一步改性,在上述方法中形成的超支化聚醚胺多元醇为羟基结尾的。它们可良好地溶于多种溶剂。
这类溶剂的实例包括芳族和/或(环)脂族烃及其混合物,卤代烃、酮、酯和醚。
聚醚胺多元醇的制备在溶剂不存在下或在溶液中进行。应考虑的溶剂如上所述。在优选实施方案中,反应在溶剂不存在下进行。
制备过程中的温度应高至足以使氨基醇反应。所需温度通常为100-350℃,优选150-300℃,更优选180-280℃,尤其是200-250℃。
在优选实施方案中,缩合反应在溶剂不存在下进行。在反应过程中形成的水或低分子反应产物可例如通过蒸馏除去,合适的话在减压下蒸馏除去,以增加反应速率。
可通过通入在反应条件下基本惰性的气流(汽提),如氮气或稀有气体,如氦气、氖气或氩气而促进水或低分子量反应产物的分离。可加入催化剂或催化剂混合物以增加反应速率。合适的催化剂为催化醚化和再醚化(reetherification)反应的化合物,如碱金属氢氧化物,碱金属碳酸盐,碱金属碳酸氢盐,优选碳酸氢钠、碳酸氢钾或碳酸氢铯,酸性化合物,如氯化铁或氯化锌,甲酸,草酸,或含磷的酸性化合物,如磷酸,聚磷酸,膦酸或次膦酸(phosphinic acid)。优选使用磷酸,膦酸或次膦酸,并任选用水将其稀释。
催化剂的加入量基于所用链烷醇或链烷醇混合物的量通常为0.001-10mol%,优选0.005-7mol%,更优选0.01-5mol%。
此外,也可通过加入合适的催化剂,如通过选择合适的温度那样进行分子内缩聚反应。也可通过起始组分的组成和停留时间来调节聚合物的平均分子量。
在升高温度下制备的聚合物通常在室温下经延长时间,如经至少6周是稳定的,而不显示混浊、沉淀和/或粘度升高。
终止分子内缩聚反应存在数种方式。可例如将温度降至终止反应并产生储存稳定的缩聚产物的范围。这通常在低于60℃,优选低于50℃,更优选低于40℃,尤其是室温下发生。
此外,在碱性催化剂的情况下例如可通过加入酸组分,如路易斯酸或有机或无机质子酸,以及在酸性催化剂的情况下加入碱性组分,如路易斯碱或有机或无机碱来钝化催化剂。
终止反应的另一可能性为通过用预冷却的溶剂稀释。这在反应混合物的粘度必须通过加入溶剂调节时特别优选。
聚醚胺多元醇的制备通常在0.1毫巴至20巴,优选1毫巴至5巴的压力下在使用分批、半分批或连续法的反应器或反应器级联中进行。
由于反应条件的上述设定和合适溶剂的选择,需要的话,本发明产物可在制备后不经进一步提纯而加工。
需要的话,可例如用活性炭或金属氧化物,如氧化铝,氧化硅、氧化镁、氧化锆、氧化硼或其混合物例如以0.1-50重量%,优选0.5-25重量%,更优选1-10重量%的量,在例如10-100℃,优选20-80℃,更优选30-60℃的温度下处理而对反应混合物进行脱色。
需要的话,也可将反应混合物过滤以除去沉淀。
在另一优选实施方案中,对产物汽提,即除去低分子量挥发性化合物。为此,可任选在达到所需转化度之后将催化剂钝化,并且需要的话可通过蒸馏,并任选引入气体,优选氮气或稀有气体,在减压下除去低分子量挥发性组分,如水,用作原料的氨基链烷醇或挥发性低聚或环状化合物。
在反应之后,因此不经过进一步改性,根据所述方法制备的超支化聚醚胺为羟基结尾的。它们可良好地溶于多种溶剂,如水,醇,如甲醇、乙醇、丁醇,醇/水混合物,丙酮、2-丁酮,乙酸乙酯,乙酸丁酯,乙酸甲氧基丙酯,乙酸甲氧基乙酯,四氢呋喃,二甲基甲酰胺,二甲基乙酰胺,N-甲基吡咯烷酮,碳酸亚乙酯或碳酸亚丙酯。
超支化聚酯胺及其制备例如公开于DE 10331770,此处将其完全引入作为参考。
在本发明上下文中,表述“聚酯胺”描述了非常一般的链中具有酯基和氨基的聚合化合物,其中氨基不为酰胺基团的一部分。原则上,具有一个氨基,优选该氨基不再可用于随后反应,以及至少两个可加成或缩合反应的额外官能团的至少两元化合物可用于制备超支化聚酯胺。这些例如包括N-烷基-N-(羟基烷基)氨基链烷羧酸和羧酸衍生物,N,N-二(羟基烷基)氨基链烷羧酸和羧酸衍生物,N烷基-N-(氨基烷基)氨基链烷羧酸和羧酸衍生物,N,N-二(氨基烷基)氨基链烷羧酸和羧酸衍生物等。除了这些单体外,根据本发明使用的超支化聚酯胺可包含掺入的具有2个或超过2个(如3、4、5、6个等)官能团的额外多官能化合物。这些包括上述多元羧酸,多官能胺,多官能醇和多官能氨基醇,此处将其完全引入作为参考。
超支化聚酯胺的制备优选使用AB2和/或AB3单体进行,所述单体可通过根据迈克尔加成类型的反应而得到。
在通过迈克尔加成制备AB2单体的第一实施方案中,使具有仲氨基和2个羟基的氨基醇与具有活性双键的化合物,如乙烯基类的羰基化合物反应。
合适的具有仲氨基和2个羟基的氨基醇例如为二乙醇胺、二丙醇胺、二异丙醇胺、2-氨基-1,3-丙二醇、3-氨基-1,2-丙二醇、二异丁醇胺、二环己醇胺等。
具有活性双键的合适化合物优选选自α,β-烯属不饱和单-和二羧酸与一元醇的酯。α,β-烯属不饱和单-和二羧酸优选选自丙烯酸、甲基丙烯酸、富马酸、马来酸、衣康酸、巴豆酸、马来酸酐、马来酸单丁酯及其混合物。优选将丙烯酸、甲基丙烯酸及其混合物用作酸组分。优选乙烯基类化合物为(甲基)丙烯酸甲酯、乙基丙烯酸甲酯、(甲基)丙烯酸乙酯、乙基丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸叔丁酯、乙基丙烯酸叔丁酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸1,1,3,3-四甲基丁酯、(甲基)丙烯酸乙基己酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸正十一烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸肉豆蔻基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸棕榈酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯、(甲基)丙烯酸山萮基酯、(甲基)丙烯酸二十四烷基(lignoceryl)酯、(甲基)丙烯酸鲸蜡酯、(甲基)丙烯酸正蜂花酯、(甲基)丙烯酸十六碳烯基酯、(甲基)丙烯酸油基酯、(甲基)丙烯酸亚油基(linolyl)酯、(甲基)丙烯酸亚麻基(linolenyl)酯、(甲基)丙烯酸硬脂醇酯、(甲基)丙烯酸月桂酯及其混合物。特别优选丙烯酸甲酯和丙烯酸正丁酯。
在通过迈克尔加成制备AB2单体的第二实施方案中,使具有伯氨基和羟基的氨基醇与具有活性双键的化合物反应。
具有伯氨基和羟基的合适的氨基醇为上文对制备超支化聚酯酰胺(此处对其参考)所述的二元氨基醇。具有活性双键的合适的化合物为在上述第一实施方案中对通过迈克尔加成制备AB2单体的第一实施方案中所述的那些。
在通过迈克尔加成制备AB3单体的第三实施方案中,使具有伯氨基、仲氨基和羟基的氨基醇与具有三个活性双键的化合物反应。
具有伯氨基、仲氨基和羟基的合适氨基醇为羟基乙基乙二胺。具有活性双键的合适化合物为上文对通过迈克尔加成制备AB2单体的第一实施方案中所述的那些。
根据迈克尔加成类型的反应优选在本体进行或在于反应条件下惰性的溶剂中进行。合适的溶剂例如为高沸点醇,如甘油,芳族烃,如苯、甲苯、二甲苯等。反应优选在0-100℃,特别优选5-80℃,特别是10-70℃的温度下进行。反应优选在惰性气体,如氮气、氦气或氩气存在下和/或在自由基抑制剂存在下进行。将氨基醇加成至活性双键上的一般程序对本领域熟练技术人员是已知的。在优选实施方案中,通过迈克尔加成制备单体及其随后在缩聚中反应以一锅法反应形式进行。
由上述或其他ABx单体制备超支化聚酯胺根据本领域熟练技术人员已知的常规方法进行。在合适的程序中,使用可通过迈克尔加成得到的上述AB2单体制备本发明的合适聚酯胺。它们可另外在额外的多官能单体存在下反应。合适的多官能单体为在上文对制备超支化聚酯胺(此处参考其全部内容)提及的多官能氨基醇、多官能胺、多官能醇和多元羧酸。需要的话,羟基羧酸可额外用作增链剂。它们例如包括乳酸、羟基乙酸等。
在合适的实施方案中,超支化聚酯胺的制备在A2B2单体存在下进行。所述单体优选选自2-氨基-2-乙基-1,3-丙二醇、2-氨基-2-甲基-1,3-丙二醇、1-氨基-2,3-丙二醇、2-氨基-1,3-丙二醇或2-氨基-1-苯基-1,3-丙二醇。
在另外合适的实施方案中,超支化聚酯胺的制备在“核分子”存在下进行。合适的核分子例如为三羟甲基丙烷,季戊四醇、烷氧基化多元醇,如乙氧基化三羟甲基丙烷、乙氧基化甘油、丙氧基化三羟甲基丙烷或丙氧基化甘油,多胺,如三(2-氨基乙基)胺、乙二胺或六亚甲基二胺、二乙醇胺、二异丙醇胺等。成核单体可在反应开始或反应过程中加入。
在另外合适的实施方案中,超支化聚酯胺的制备使用芳族AB2单体进行,合适的芳族AB2单体例如为啊米酚(amidol)、氨基苄醇、2-氨基-5-氯苄醇、2-氨基-9-芴醇等。
制备超支化聚酯胺的缩聚反应可在催化剂存在下进行。合适的催化剂为上文对制备超支化聚酯酰胺(此处参考其全部内容)所述的催化剂。酶如脂酶或酯酶也是合适的催化剂。合适的脂酶或酯酶可得至柱状假丝酵母(Candida cylindracea)、解脂假丝酵母(Candida lipolytica)、皱褶假丝酵母(Candida rugosa)、南极假丝酵母(Candida antarctica)、产朊假丝酵母(Candida utilis)、Chromobacterium viscosum、Geolrichum viscosum、白地霉(Geotrichum candidum)、爪哇毛霉(Mucor javanicus)、米黑毛霉(Mucor mihei)、猪胰腺、假单胞菌属(pseudomonas)、荧光假单胞菌(pseudomonas fluorescens)、洋葱假单胞菌(Pseudomonas cepacia)、少根根霉(Rhizopus arrhizus)、德氏根霉(Rhizopus delemar)、雪白根霉(Rhizopusniveus)、米根霉(Rhizopus oryzae)、黑曲霉(Aspergillus niger)、娄地青霉(Penicillium roquefortii)、沙门柏干酪青霉(Penicillium camembertii)或来自芽孢杆菌属(Bacillus)和Bacillus thermoglucosidasius的酯酶。优选酶为南极假丝酵母脂酶B,特别优选固定化的南极假丝酵母脂酶B,其可由Novozymes Biotech Inc.以名称Novozyme 435购得。
有利的是,使用酶促催化的反应可在约40-90℃,优选60-70℃的低温下进行。优选酶促反应在惰性气体,如二氧化碳、氮气、氩气或氦气存在下进行。
根据本发明的优选实施方案,超支化聚合物包含疏水结构部分。
疏水结构部分尤其包括长链脂族烃基,如长链烷基或链烯基,芳族烃基或芳脂族烃基。它们可在超支化聚合物的合成中通过使用合适的反应物掺入超支化聚合物中,或可在合成超支化骨架之后,例如以类似于聚合物的反应掺入超支化聚合物中。
例如,长链脂族羧酸如辛酸、癸酸、十二烷酸和十四烷酸(tetraundecanoic acid);脂肪酸,如硬脂酸、油酸、月桂酸、棕榈酸、亚油酸和亚麻油酸;芳族羧酸如邻苯二甲酸、间苯二甲酸、对苯二甲酸和偏苯三酸;环脂族羧酸,如环己烷二甲酸;二羧酸,如辛二酸、癸二酸、十二烷二酸、十四烷二酸和二聚脂肪酸适用于制备具有疏水结构部分的超支化聚合物。同样,脂族醇,如辛醇、癸醇、十二烷醇和十四烷醇;脂肪醇,如硬脂醇和油醇;不饱和醇如烯丙醇和巴豆醇;芳族醇如苄醇;环脂族醇如环己醇;甘油单脂肪酸酯如甘油单硬脂醇酯、甘油单油酸酯和甘油单棕榈酸酯也适用于制备具有疏水结构部分的超支化聚合物。
适用于类似于聚合物反应的疏水基团优选选自具有8-40个,优选9-35个,尤其是10-30个碳原子的饱和或不饱和烃残基。它们优选为烷基、链烯基、环烷基或芳基残基。环烷基或芳基残基可具有1、2或3个取代基,优选烷基或链烯基取代基。
例如,对于类似于聚合物的反应,可使用具有一个本文所述的疏水结构部分的一元醇。这类醇和醇混合物例如可通过氢化来自天然脂肪和油的脂肪酸,或氢化例如来自链烷烃的催化氧化的合成脂肪酸而得到。合适的醇和醇混合物还可如下得到,将烯烃加氢甲酰化同时将醛氢化,这通常产生直链和支化伯醇(羰基合成醇)的混合物。合适的醇和醇混合物还可通过将正链烷烃根据已知方法部分氧化,主要产生线性仲醇而得到。可通过有机铝合成得到的基本直链和奇数齐格勒伯醇也是合适的。
适用于类似于聚合物反应的一元醇例如为单官能醇,如辛醇、壬醇、癸醇、十一烷醇、十二烷醇、十三烷醇、十四烷醇、十五烷醇、十六烷醇、十七烷醇、十八烷醇等及其混合物。
根据优选实施方案,超支化聚合物包含疏水结构部分且可如下得到:
a)使至少一种具有至少一个聚异丁烯基的二羧酸(A2)或其衍生物,合适的话以与其他二羧酸(D2)或其衍生物的混合物与至少一种具有至少3个相同或不同的对酸基或其衍生物具有反应性的基团的脂族或芳族化合物(Cx)反应,
或
b)使至少一种具有至少一个聚异丁烯基的二羧酸(A2)或其衍生物,合适的话以与其他二羧酸(D2)或其衍生物的混合物与至少一种具有2个相同或不同的对酸基或其衍生物具有反应性的基团的脂族或芳族化合物(B2)和至少一种具有至少超过2个相同或不同的对酸基或其衍生物具有反应性的基团的脂族或芳族化合物(Cx)反应,并消除水或醇R1OH,其中为R1为具有1-20个碳原子的直链或支化的脂族、脂环族、芳脂族或芳族烃基,且x大于2,优选为3-8,
或
c)使至少一种具有2个相同或不同的对酸基或其衍生物具有反应性的基团的脂族或芳族化合物(B2)与至少一种具有聚异丁烯基的二羧酸(A2)或其衍生物,合适的话以与其他二羧酸(D2)或其衍生物的混合物,和至少一种具有超过2个酸基的脂族或芳族羧酸(Dy)或其衍生物反应,并消除水或醇R1OH,其中为R1为具有1-20个碳原子的直链或支化的脂族、脂环族、芳脂族或芳族烃基,且y大于2,优选为3-8,
其中选择反应混合物中反应搭档的比例,从而使具有对酸基呈反应性的基团的分子与具有酸基的分子的摩尔比为2∶1-1∶2,优选1.5∶1-1∶2,更优选0.9∶1-1∶1.5,最优选1∶1。
化合物(A2)为具有至少一个,优选精确地1个聚异丁烯基团和至少两个,优选精确地两个羧基或其衍生物的化合物。
优选聚异丁烯和富马酰氯、富马酸、衣康酸、衣康酰氯、马来酰氯、马来酸酐和/或马来酸和/或所述酸的酯之间的烯烃反应的反应产物。
在优选实施方案中,它们为聚异丁烯与富马酰氯、富马酸、衣康酸、衣康酰氯、马来酰氯、马来酸酐和/或马来酸和/或所述酸的酯,优选与马来酸酐或马来酰氯,更优选与马来酸酐的烯烃反应的1∶1(mol/mol)反应产物。
聚异丁烯优选为至少60mol%的端基由乙烯基异构体和/或亚乙烯基异构体形成的那些。
化合物(A2)的数均分子量Mn优选为至少100g/mol,更优选至少800g/mol。化合物(A2)的数均分子量Mn通常为至多5000g/mol,更优选至多2000g/mol。
在特别优选的实施方案中,化合物(A2)的数均分子量Mn为1000+/-500g/mol。
二羧酸(D2)精确地具有2个羧基或其衍生物。这些化合物可为脂族、脂环族、芳脂族或芳族的且优选具有至多20个碳原子,更优选至多12个碳原子。
二羧酸(D2)例如包括脂族二羧酸,如草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二甲酸、十二烷二甲酸、顺-和反-环己烷-1,2-二甲酸、顺-和反-环己烷-1,3-二甲酸、顺-和反-环己烷-1,4-二甲酸、顺-和反-环戊烷-1,2-二甲酸、顺-和反-环戊烷-1,3-二甲酸。此外,也可使用芳族二羧酸如邻苯二甲酸、间苯二甲酸或对苯二甲酸。也可使用不饱和二羧酸如马来酸或富马酸。
所述二羧酸也可被一个或多个选自下列的基团取代:。取代的二羧酸的代表性实例为:2-甲基丙二酸、2-乙基丙二酸、2-苯基丙二酸、2-甲基琥珀酸、2-乙基琥珀酸、2-苯基琥珀酸、衣康酸、3,3-二甲基戊二酸。
此外,还可使用两种或更多种上述二羧酸的混合物。
二羧酸可以以质子化或未质子化形式,优选以质子化形式本身或以衍生物形式使用。
衍生物优选理解为指:
-单体形式或聚合物形式的所述酸酐,
-单-或二烷基酯,优选单-或二甲基酯,或相应的单-或二乙基酯,或衍生于更高级醇的单-或二烷基酯,所述更高级醇例如为正丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、正戊醇、正己醇,
-还有单-和二乙烯基酯,以及
-混合酯,优选甲基乙基酯。
在本发明上下文中,也可以使用二羧酸和一种或多种其衍生物的混合物。在本发明上下文中,同样可以使用一种或多种二羧酸的两种或更多种不同衍生物的混合物。
特别优选使用丙二酸、琥珀酸、戊二酸、己二酸,1,2-、1,3-或1,4-环己烷二甲酸(六氢苯二甲酸),邻苯二甲酸、间苯二甲酸、对苯二甲酸或其单-或二烷基酯。
化合物(Dy)具有超过两个羧基或其衍生物,优选3-8,更优选3-6个羧基。这些化合物可为脂族、环脂族或芳脂族或芳族的且具有优选至多20个碳原子,更优选至多12个碳原子。
可转化的三羧酸或多羧酸(Dy)例如为乌头酸、1,3,5-环己烷三甲酸、1,2,4-苯三甲酸、1,3,5-苯三甲酸、1,2,4,5-苯四甲酸(苯均四酸)和苯六甲酸以及低分子量聚丙烯酸,例如其分子量为至多2000g/mol,优选至多1000g/mol,更优选至多500g/mol。
在反应中,可使用三羧酸或多羧酸(Dy)本身或使用其衍生物形式。
衍生物优选理解为指:
-单体或聚合物形式的相关酸酐,
-单-、二-或三烷基酯,优选单-、二或三甲基酯,或相应的单-、二-或三乙基酯,以及衍生于更高级醇的单-、二-和三酯,所述更高级醇例如为正丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、正戊醇、正己醇,以及单-、二-或三乙烯基酯,
-以及混合的甲基乙基酯。
也可使用三-或多羧酸和一种或多种其衍生物的混合物,例如苯均四酸和苯均四酸二酐的混合物。在本发明上下文中,也可使用一种或多种三-或多羧酸的多种不同衍生物的混合物,例如1,3,5-环己烷三甲酸和苯均四酸二酐的混合物。
对酸基或其衍生物呈反应性的基团优选为羟基(-OH)、伯氨基(-NH2)、仲氨基(-NHR)或硫醇基团(-SH),更优选羟基或伯氨基,最优选羟基。
仲氨基可被作为R基团的C1-C10烷基、C3-C12环烷基、芳烷基或C6-C14芳基取代。
根据本发明使用的具有对酸基呈反应性的基团的化合物(B2)例如为二官能醇,乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,2-戊二醇、1,3-戊二醇、1,4-戊二醇、1,5-戊二醇、2,3-戊二醇、2,4-戊二醇、1,2-己二醇、1,3-己二醇、1,4-己二醇、1,5-己二醇、1,6-己二醇、2,5-己二醇、1,2-庚二醇、1,7-庚二醇、1,8-辛二醇、1,2-辛二醇、1,9-壬二醇、1,10-癸二醇、1,2-癸二醇、1,12-十二烷二醇、1,2-十二烷二醇、1,5-己二烯-3,4-二醇,1,2-或1,3-环戊二醇,1,2-、1,3-或1,4-环己二醇,1,2-、1,3-或1,4-二(羟基甲基)环己烷,二(羟基乙基)环己烷、新戊二醇、2-甲基戊烷-2,4-二醇、2,4-二甲基戊烷-2,4-二醇、2-甲基-1,3-戊二醇、2-乙基己烷-1,3-二醇、2-丙基-1,3-庚二醇、2,4-二乙基辛烷-1,3-二醇、2,5-二甲基己烷-2,5-二醇、2,2,4-三甲基戊烷-1,3-二醇、频哪醇、二甘醇、三甘醇、二丙二醇、三丙二醇、聚乙二醇HO(CH2CH2O)n-H 或聚丙二醇HO(CH[CH3]CH2O)n-H,其中n为整数且n≥4,分子量至多2000的聚四氢呋喃,聚己内酯或上述化合物的两种或更多种的混合物。上述二醇中的一个或甚至两个羟基也可以被SH基替代。优选乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,8-辛二醇,1,3-和1,4-二(羟基甲基)环己烷,以及二甘醇、三甘醇、双丙二醇和三丙二醇。
所用化合物(B2)也可为具有一个羟基和一个氨基的分子,例如乙醇胺、2-氨基丙醇、3-氨基丙醇、异丙醇胺,2-、3-或4-氨基-1-丁醇,6-氨基-1-己醇、N-甲基-乙醇胺、2-(乙基氨基)乙醇、1-(乙基氨基)-2-丙醇2-(丁基氨基)乙醇、2-(环己基氨基)乙醇、2-氨基-2-甲基-1-丙醇、2-(2-氨基乙氧基)乙醇、9-氨基-3,6-二氧杂壬-1-醇或2-(苯基氨基)乙醇。
所用化合物(B2)还有二官能胺,如乙二胺、N-烷基乙二胺,丙二胺(1,2-二氨基丙烷和1,3-二氨基丙烷)、2,2-二甲基-1,3-丙二胺、N-烷基丙二胺、哌嗪、四亚甲基二胺(1,4-二氨基丁烷)、N-烷基丁二胺、N,N’-二甲基乙二胺、戊二胺、六亚甲基二胺、N-烷基六亚甲基二胺、庚二胺、辛二胺、壬二胺、癸二胺、十二烷二胺、十六烷二胺、1,3-二氨基-2,2-二乙基丙烷、1,3-二(甲基氨基)丙烷、1,5-二氨基-2-甲基戊烷、3-(丙基氨基)丙基胺、N,N’-二(3-氨基丙基)哌嗪、N,N’-二(3-氨基丙基)哌嗪、异佛尔酮二胺(IPDA)、甲苯二胺、二甲苯二胺、二氨基二苯基甲烷、环己二胺、二(氨基甲基)环己烷、二氨基二苯基砜、2-丁基-2-乙基-1,5-五亚甲基二胺、2,2,4-或2,4,4-三甲基-1,6-六亚甲基二胺、2-氨基丙基环己基胺、3(4)-氨基甲基-1-甲基环己基胺、1,4-二氨基-4-甲基戊烷、胺封端的聚氧化烯多元醇(所谓的Jeffamine,购自Huntsmann Corp.,Houston,Texas)或胺封端的聚四亚甲基二醇。
这类二胺的实例为所谓的或ED系列。D系列为氨基官能化的包含如下单元的聚丙二醇:3-4个1,2-亚丙基单元(D-230,平均分子量230),6-7个1,2-亚丙基单元(D-400,平均分子量400),平均约34个1,2-亚丙基单元(D-2000,平均分子量2000)或平均约69个1,2-亚丙基单元(XTJ-510(D-4000),平均分子量4000)。这些产品也可部分以氨基醇形式存在。ED系列为基于在两侧理想地丙氧基化的聚氧乙烯的二胺,例如包含2个氧化乙烯单元和2个氧化丙烯单元且平均分子量为220的HK-511(XTJ-511),包含9个氧化乙烯单元和3.6个氧化丙烯单元且平均分子量为600的XTJ-500(ED-600),以及包含38.7个氧化乙烯单元和6个氧化丙烯单元且平均分子量为2000的XTJ-502(ED-2003)。
化合物(B2)也可具有其它官能团,如羧基或酯基。这类化合物的实例为二羟甲基丙酸、二羟甲基丁酸和新戊二醇羟基戊酸酯。
然而,优选化合物(B2)除了羧基或其衍生物外不带有任何其它官能团。
优选化合物(B2)为醇或氨基醇,更优选醇。
化合物(Cx)平均具有超过2个,优选3-8个,更优选3-6个对酸基及其衍生物呈反应性的基团。
它们可为脂族、脂环族、芳脂族或芳族的且通常具有不超过100个,优选不超过50个,更优选不超过20个碳原子。
具有对酸基呈反应性的基团的至少三官能化合物(Cx)包括三官能或更高官能的醇,如甘油、三羟甲基甲烷、三羟甲基乙烷、三羟甲基丙烷、1,2,4-丁三醇、三羟基甲基异氰脲酸酯、三(羟基乙基)异氰脲酸酯(THEIC)、季戊四醇、双甘油、三甘油或甘油的更高级缩合物、二(三羟甲基丙烷)、二季戊四醇、肌醇,山梨糖醇,或糖,如葡萄糖、果糖或蔗糖,基于三官能或更高官能醇和氧化乙烯、氧化丙烯或氧化丁烯的三官能或更高官能的聚醚醇。特别优选甘油、双甘油、三甘油、三羟甲基乙烷、三羟甲基丙烷、1,2,4-丁三醇、季戊四醇及其基于氧化乙烯或氧化丙烯的聚醚醇。
优选化合物(B2)或化合物(Cx)为下式(Ia)-(Id)的化合物:
其中R7和R8各自独立地为氢或任选被芳基、烷基、芳氧基、烷氧基、杂原子和/或杂环取代的C1-C18烷基,
k、l、m、q各自独立地为1-15,优选1-10,更优选1-7的整数,和对于i=1-k、1-l、1-m和1-q的各Xi可各自独立地选自如下基团:-CH2-CH2-O-、-CH2-CH(CH3)-O-、-CH(CH3)-CH2-O-、-CH2-C(CH3)2-O-、-C(CH3)2-CH2-O-、-CH2-CHVin-O-、-CHVin-CH2-O-、-CH2-CHPh-O-和-CHPh-CH2-O-,优选选自如下基团:-CH2-CH2-O-、-CH2-CH(CH3)-O-和-CH(CH3)-CH2-O-,更优选-CH2-CH2-O-,
其中Ph为苯基且Vin为乙烯基。
在这些式中,任选被芳基、烷基、芳氧基、烷氧基、杂原子和/或杂环取代的C1-C18烷基例如为甲基、乙基、丙基、异丙基、正丁基、仲丁基、叔丁基、戊基、己基、庚基、辛基、2-乙基己基、2,4,4-三甲基戊基、癸基、十二烷基、十四烷基、十七烷基、十八烷基、1,1-二甲基丙基、1,1-二甲基丁基、1,1,3,3-四甲基丁基,优选甲基、乙基或正丙基,最优选甲基或乙基。
优选1至30重,特别优选3至20重乙氧基化、丙氧基化或混合乙氧基化和丙氧基化,特别是仅乙氧基化的新戊二醇、三羟甲基丙烷、三羟甲基乙烷或季戊四醇或甘油。
具有对酸基呈反应性的基团的至少三官能化合物(Cx)进一步包括三官能或更高官能的氨基醇,如三(羟基甲基)胺、三(羟基乙基)胺、三(羟基丙基)胺、二乙醇胺、二丙醇胺、二异丙醇胺、二-仲丁醇胺、三(羟基甲基)氨基甲烷、三(羟基乙基)氨基甲烷、3-氨基-1,2-丙二醇、1-氨基-1-脱氧-D-山梨糖醇和2-氨基-2-乙基-1,3-丙二醇。
具有对酸基呈反应性的基团的至少三官能化合物(Cx)进一步包括三官能或更高官能的胺,如三(2-氨基乙基)胺、三(3-氨基丙基)胺、三(氨基己基)胺、三氨基己烷、4-氨基甲基-1,8-八亚甲基二胺、三氨基壬烷、二亚乙基三胺(DETA)、二亚丙基三胺、二亚丁基三胺、二亚己基三胺、N-(2-氨基乙基)丙二胺、蜜胺、三亚乙基四胺(TETA)、四亚乙基五胺(TEPA)、异亚丙基三胺、二亚丙基三胺和N,N’-二(3-氨基丙基乙二胺),低聚二氨基二苯基甲烷、N,N′-二(3-氨基丙基)乙二胺、N,N′-二(3-氨基丙基)丁二胺、N,N,N′,N′-四(3-氨基丙基)乙二胺、N,N,N′,N′-四(3-氨基丙基)丁二胺,三官能或更高官能的胺封端的聚氧化烯多元醇(所谓的Jeffamine),三官能或更高官能的聚乙烯亚胺或三官能或更高官能的聚丙烯亚胺。
三胺的实例为T-403,基于用5-6个1,2-亚丙基单元改性的三羟甲基丙烷的三胺,T-5000,基于用约85个1,2-亚丙基单元改性的甘油的三胺,和XTJ-509(T-3000),基于用50个1,2-亚丙基单元改性的甘油的三胺。
优选化合物(Cx)为醇或氨基醇,更优选醇。
本方法在本体中或在溶剂存在下进行。合适的溶剂例如为烃如链烷烃或芳族烃。特别合适的链烷烃为正庚烷和环己烷。特别合适的芳族烃为甲苯、邻二甲苯、间二甲苯、对二甲苯、作为异构体混合物的二甲苯、乙苯、氯苯和邻二氯苯和间二氯苯。还适合作为溶剂的是醚,如二噁烷或四氢呋喃,和酮,如甲基乙基酮和甲基异丁基酮。
如上所述,未转化的聚异丁烯也可作为惰性稀释剂存在。
其他有用的芳族烃混合物为主要包含C7-C14芳族烃并且可包含沸程为110-300℃的那些,更优选甲苯、邻二甲苯、间二甲苯、对二甲苯、三甲基苯异构体、四甲基苯异构体、乙苯、枯烯、四氢萘和包含它们的混合物。它们的实例为购自ExxonMobil Chemical的牌,特别是100(CAS No.64742-95-6,主要为C9和C10芳族烃,沸程约154-178℃),150(沸程约182-207℃)和200(CAS No.64742-94-5),以及购自Shell的牌。链烷烃、环烷烃和芳族烃的混合物也可以如下牌市购:(例如30,沸程约158-198℃,或60:CAS No.64742-82-1),石油溶剂油(同样如CAS No.64742-82-1),或溶剂石脑油(轻:沸程约155-180℃,重:沸程约225-300℃)。这类烃混合物的芳族烃含量通常超过90重量%,优选超过95重量%,更优选超过98重量%,最优选超过99重量%。有利的是,可使用具有特别降低的萘含量的烃混合物。
溶剂的加入量基于所用待转化的原料的质量为至少0.1重量%,优选至少1重量%,更优选至少10重量%。也可基于所用待转化的原料的质量使用过量溶剂,例如1.01-10倍。溶剂量超过所用待转化原料质量100倍并不有利,因为在反应物浓度明显较低的情况下,反应速率显著下降,这导致不经济的长反应时间。
为进行该方法,也可在作为添加剂的脱水剂存在下进行,脱水剂在反应开始时加入。合适的实例为分子筛,特别是4分子筛,MgSO4和Na2SO4。也可在反应过程中加入其它脱水剂或用新鲜脱水剂替换脱水剂。在反应期间也可以蒸除反应过程中形成的醇或水以及例如可使用水分离器,其中在水分离器中借助共沸剂除去水。
该方法可以在不存在催化剂下进行。然而当使用催化剂时,优选使用酸性无机催化剂、有机金属催化剂或有机催化剂,或多种酸性无机催化剂、有机金属催化剂或有机催化剂的混合物。
在本发明上下文中,酸性无机催化剂例如为硫酸、硫酸盐和硫酸氢盐,如硫酸氢钠,磷酸,膦酸,次磷酸,水合硫酸铝,明矾,酸性硅胶(在水中的pH为≤6,尤其是≤5),和酸性氧化铝。例如也可使用通式Al(OR2)3的铝化合物和通式Ti(OR2)4的钛酸酯作为酸性无机催化剂,其中基团R2各自可相同或不同且独立地选自丁基、异丙基或2-乙基己基。优选酸性有机金属催化剂例如选自氧化二烷基锡R3 2SnO或二烷基锡酯R3 2Sn(OR4)2,其中R3和R4可选自C1-C20烷基或C3-C12环烷基且可相同或不同。酸性有机金属催化剂的特别优选的代表为氧化二丁锡和二月桂酸二丁锡。
优选酸性有机催化剂为例如具有磷酸基、磺酸基、硫酸基或膦酸基的酸性有机化合物。特别优选磺酸,如对甲苯磺酸。所用酸性有机催化剂也可为酸性离子交换剂,例如含有磺酸基并用约2mol%二乙烯基苯交联的聚苯乙烯树脂。
也可以使用两种或更多种上述催化剂的组合。也可以使用呈离散分子形式的固定形式的这类有机或有机金属或无机催化剂,例如固定在硅胶或沸石上。
当需要使用酸性无机催化剂、有机金属催化剂或有机催化剂时,根据本发明,催化剂用量为0.1-10重量%,优选0.2-2重量%。
本发明方法优选在惰性气氛中进行,例如在二氧化碳、氮气或稀有气体中进行,其中可尤其提到氩气。
也可优选使反应条件下惰性的气体通过反应混合物,从而将挥发性化合物汽提出反应混合物。
本发明方法在60-250℃的温度下进行。优选在80-200℃,更优选在100-180℃的温度下操作。
本发明方法的压力条件本身并不重要。其可以在显著减压下例如在10-500毫巴下操作。本发明方法也可在高于500毫巴的压力下进行。由于简单,优选在大气压下反应;然而,反应也可以在略有增加的压力下进行,例如至多1200毫巴。还可以在显著增加的压力下进行,例如在至多10巴的压力下进行。优选反应在大气压和减压下进行。
本发明方法的反应时间通常为10分钟至48小时,优选30分钟至24小时,更优选1至12小时。
在反应结束后,可容易地分离超支化聚合物,例如通过过滤除去催化剂以及合适的话除去溶剂,这里溶剂的除去通常在减压下进行。其它合适的后处理方法为添加水后的聚合物沉淀法,随后进行洗涤和干燥。
这些超支化聚合物除了聚异丁烯基团和形成聚合物骨架的酯或酰胺基团外,还具有至少3个,优选至少6个,更优选至少10个末端或侧官能团。所述官能团为酸基和/或氨基或羟基。原则上对末端或侧官能团的数目没有上限限制,但具有非常高的官能团数目的产物可能具有不希望的性能,例如高粘度。可用于本发明的超支化聚酯具有通常不大于500个末端官能团或侧官能团,优选不大于100个末端官能团或侧官能团。
在另一优选实施方案中,本发明聚合物除了通过反应获得的官能团外还可得到其他官能团。官能化可在分子量增加过程中或者随后,即在实际缩聚结束之后进行。
当在分子量增加之前或之中加入除了羟基、氨基或羧基之外还具有其他官能团或官能单元的组分时,所得聚合物除了羧基、氨基或羟基外还具有无规分布的官能团。
这种效果例如可通过在缩聚过程中加入除了羟基、伯或仲氨基或羧基外还带有其他官能团或官能单元,如巯基,叔氨基,醚基,尤其是聚氧化乙烯和/或氧化丙烯,羰基、磺酸基或磺酸基衍生物,亚磺酸基或亚磺酸基衍生物,膦酸基或膦酸基衍生物,次膦酸基或次膦酸基衍生物,硅烷基,硅氧烷基,芳基或长链烷基,或氟化或全氟化芳基或烷基的化合物而实现。
对于用巯基改性,例如可使用巯基乙醇。叔氨基例如可通过掺入N-甲基二乙醇胺、N-甲基二丙醇胺或N,N-二甲基乙醇胺而得到。醚基可例如通过经由缩合掺入二官能或更高官能的聚醚醇而产生。与长链的链烷二醇的反应可引入长链烷基;与烷基或芳基二异氰酸酯的反应产生具有烷基、芳基和氨基甲酸酯或脲基的聚合物。
为了改性,也可有利地使用带有至少一个伯氨基和/或仲氨基以及至少一个羧基、磺酸基或膦酸基的化合物。
它们的实例为氨基酸,羟基烷基-或羟基芳基磺酸,例如牛磺酸或N-甲基牛磺酸,或N-环己基氨基丙烷磺酸和N-环己基氨基乙烷磺酸。
氨基酸的实例为甘氨酸、丙氨酸、β-丙氨酸、缬氨酸、赖氨酸、亮氨酸、异亮氨酸、叔亮氨酸、苯丙氨酸、酪氨酸、色氨酸、脯氨酸、天冬氨酸、谷氨酸、天门冬酰胺(asparagine)、谷氨酰胺、丝氨酸、苏氨酸、半胱氨酸、蛋氨酸、精氨酸、组氨酸、4-氨基丁酸、胱氨酸、瓜氨酸、茶氨酸、高半胱氨酸、4-羟基脯氨酸、蒜氨酸或鸟氨酸。
随后的官能化可通过使所得超支化聚合物在额外的工艺步骤中与合适的可与聚合物的OH和/或NH和/或羧基反应的官能化试剂反应而得到。
包含羟基或氨基的超支化聚合物可例如通过加入包含异氰酸酯基团的分子而改性。例如,包含氨基甲酸酯基团或脲基团的聚合物可通过与烷基或芳基异氰酸酯反应而得到。
此外,包含羟基或氨基的超支化聚合物也可通过与氧化烯,如氧化乙烯、氧化丙烯或氧化丁烯反应而转化为高官能度聚醚多元醇。因此,这些化合物例如可以水溶性形式得到。
也可将额外的亲水残基掺入本发明超支化聚合物中。例如,可使用数均分子量为约500-10000g/mol,优选1000-5000g/mol的一元聚醚醇。一元聚醚醇可通过将一元起始分子,如甲醇、乙醇或正丁醇与用作烷氧基化剂的氧化乙烯或氧化乙烯与其他氧化烯,尤其是氧化丙烯的混合物烷氧基化而得到。
本发明组合物可含有一种超支化聚合物或含有两种或超过两种不同超支化聚合物的共混物。
根据特定实施方案,本发明种子处理组合物包含至少1重量%,优选至少2重量%,尤其是至少5重量%超支化聚合物。
根据另一特定实施方案,种子处理组合物包含至多50重量%,优选至多30重量%,尤其是至多20重量%超支化聚合物。
根据一个方面,超支化聚合物与活性成分的重量比为至少0.1∶1,优选至少0.2∶1,尤其是至少0.5∶1。
根据另一方面,超支化聚合物与活性成分的重量比为至多50∶1,优选至多10∶1,尤其是至多5∶1。
在本发明组合物中,超支化聚合物用作种子包衣剂,特别是用作粘合剂以促进活性成分与种子的粘合。活性成分与种子的粘合可通过剪切处理的种子并测定剪切前后的活性成分负载量而确定。
因此,本发明也涉及本文所定义的超支化聚合物作为种子包衣剂的用途。
本发明组合物为种子处理组合物。本发明种子处理组合物包含至少一种特别适用于种子处理的助剂,即尤其促进活性成分与种子粘合和/或穿透入种子中和/或另外改善组合物或用该组合物处理的种子的稳定性和/或可操作性的助剂。因此,本发明种子处理组合物包含至少一种种子处理助剂和任选一种或多种其他助剂。
本发明组合物包含适用于种子包衣材料的试剂,即超支化聚合物。组合物可包含其他种子处理助剂,其尤其选自适用于固体基质打底材料、促进种子吸收的穿透提高剂、着色剂、防冻剂和胶凝剂。
根据本发明,本发明组合物的种子包衣材料包含超支化聚合物作为粘合剂(或增粘剂)。因此,通常无需将其他粘合剂加入组合物中。然而,可能有利的是将超支化聚合物与一种或超过一种常规粘合剂组合。
其他粘合剂(或增粘剂)为可用于种子处理组合物的所有常规粘合剂(或增粘剂)。可用于本发明的粘合剂(或增粘剂)优选包含可以是天然或部分或全部合成的且对待包衣的种子没有植物毒性作用的粘合聚合物。优选其他粘合剂(或增粘剂)可生物降解。
其他粘合剂(或增粘剂)可选自聚酯、聚醚酯、聚酸酐、聚酯型聚氨酯、聚酯酰胺;聚乙酸乙烯酯;聚乙酸乙烯酯共聚物;聚乙烯醇和纤基乙酸钠;聚乙烯醇共聚物;聚乙烯基吡咯烷酮;多糖,包括淀粉、改性淀粉和淀粉衍生物,糊精,麦芽糊精,藻酸盐,壳聚糖和纤维素,纤维素酯,纤维素醚和纤维素醚酯,包括乙基纤维素、甲基纤维素、羟甲基纤维素、羟丙基纤维素和羧甲基纤维素;脂;油;蛋白质,包括酪蛋白、明胶和玉米蛋白;阿拉伯胶;紫胶;偏二氯乙烯和偏二氯乙烯共聚物;木素磺酸盐,尤其是木素磺酸钙;聚丙烯酸酯、聚甲基丙烯酸酯和丙烯酸类共聚物;聚乙烯基丙烯酸酯;聚氧乙烯;聚丁烯、聚异丁烯、聚苯乙烯、聚乙烯胺、聚乙烯酰胺;丙烯酰胺聚合物和共聚物;聚丙烯酸羟乙酯、甲基丙烯酰胺单体;和聚氯丁二烯。
其他粘合剂的量通常不超过10重量%。优选其基于组合物的总重量不超过5重量%,尤其是1重量%。根据一个特定实施方案,本发明组合物不含有显著量的其他粘合剂,即它们不含其他粘合剂,或其他粘合剂的量基于组合物的总重量低于0.5重量%,优选低于0.1重量%。
包衣材料还任选包含一种或多种选自填料和增塑剂的额外的种子处理助剂。
填料可为吸收剂或惰性填料,如本领域已知的那些且可包括木细粉,谷粉,树皮粉,木粉和坚果壳粉,糖类,尤其是多糖,活性炭,细颗粒无机固体,硅胶,硅酸盐,粘土,白垩,硅藻土,碳酸钙,碳酸镁,白云石,氧化镁,硫酸钙等。可使用的粘土和无机固体包括钙膨润土、高岭土、陶土、滑石、珍珠岩、云母、蛭石、硅酸盐、石英粉、蒙脱土、绿坡缕石、红玄武土、黄土、石灰石、石灰及其混合物。可使用的糖类包括糊精和麦芽糊精。谷粉包括小麦粉、燕麦粉和大麦粉。填料也可包含肥料物质如硫酸铵、磷酸铵、硝酸铵、尿类及其混合物。
选择填料以使其对种子提供合适的小气候,例如使用填料以增加活性成分的负载率和调节活性成分的控制-释放。填料可有助于种子的生产或包衣加工。填料量可变化,但如果存在的话填料组分的重量通常为总重量的约0.05-约75%,更优选约0.1-约50%,甚至更优选约0.5-15%。
优选选择粘合剂(或增粘剂)以使其可用作活性成分的基质。虽然如上所公开的粘合剂均可用作基质,优选形成一种或多种粘合剂化合物的固体连续相,其中分布活性成分的非连续相。任选填料和/或其它组分也可存在于基质中。术语“基质”应理解为包括视为基质体系、储存体系或微胶囊体系的那些。通常而言,基质体系由均匀分散在聚合物中的活性成分和填料组成,而储存体系由包含活性成分的分散相组成,活性成分物理分散在周围的限制速率的聚合物相。微胶囊化包括小颗粒或液滴包衣,以及固体基质中的分散体。
尤其是如果用于包衣的活性成分为油性类型的组合物并且存在少量或不存在惰性填料,则可能有用的是通过干燥组合物加速干燥过程。该任选步骤可伴随本领域众所周知的措施且可包括加入填料,如碳酸钙、高岭土或膨润土粘土、珍珠岩、硅藻土,或任何吸收材料,其优选与活性成分的包衣层一起加入以吸收油或过量水分。有效提供干燥包衣所需吸收剂量为种子重量的约0.5-约10%。
任选包衣材料包含增塑剂。增塑剂常用于使包衣层形成的膜更柔软,以改进粘合和伸展性,以及改进加工速率。改进的膜的柔软性对储存、处理和播种过程中的碎片、碎裂或剥落最小化具有重要性。可使用许多种增塑剂,然而,有用的增塑剂包括聚乙二醇、低聚亚烷基二醇、甘油、烷基苄基邻苯二甲酸酯,尤其是丁基苄基邻苯二甲酸酯,二醇苯甲酸酯和相关的化合物。如果存在的话,增塑剂在包衣层中的量为约0.1-约20重量%。
适用于可用于本发明的固体基质打底材料的试剂包括聚丙烯酰胺、淀粉、粘土、硅石、氧化铝、土壤、沙、聚脲、聚丙烯酸酯,或能够吸收或吸附活性成分并能够将活性成分释放入种子中或种子上的任何其它材料。其用于确保活性成分和固体基质材料相互相容。例如,应选择固体基质材料,以使其可以合理的速率,例如经数分钟、数小时或数天释放活性成分。
适合促进种子吸收的穿透提高剂包括可农用表面活性化合物。如果存在的话,穿透提高剂的量基于配制剂总重量通常不超过20重量%。优选穿透提高剂的量为2-20重量%。
本发明着色剂为常用于此的所有染料和颜料。就此而言,可以使用微溶于水的颜料和可溶于水的染料。例如作为实例可以提到如下已知的着色剂:若丹明B、C.I.颜料红112和C.I.溶剂红1、颜料蓝15:4、颜料蓝15:3、颜料蓝15:2、颜料蓝15:1、颜料蓝80、颜料黄1、颜料黄13、颜料红48:2、颜料红48:1、颜料红57:1、颜料红53:1、颜料橙43、颜料橙34、颜料橙5、颜料绿36、颜料绿7、颜料白6、颜料棕25、碱性紫10、碱性紫49、酸性红51、酸性红52、酸性红14、酸性蓝9、酸性黄23、碱性红10、碱性红108。如果存在的话,着色剂量通常不超过组合物的20重量%,优选基于组合物总重量为1-15重量%。通常优选着色剂也用作温血动物的驱除剂,如氧化铁、二氧化钛、普鲁士蓝、蒽醌染料、偶氮染料和金属酞菁染料。
可特别用于含水组合物的防冻剂原则上为所有导致水的熔点降低的那些物质。合适的防冻剂包括醇类如甲醇、乙醇、异丙醇、丁醇、乙二醇、甘油、二乙基乙二醇等。防冻剂的量基于组合物总重量通常不超过20重量%,以及如果存在的话,经常为1-15重量%。
合适的胶凝剂为可为此用于农业化学组合物中的所有物质,例如纤维素衍生物、聚丙烯酸衍生物,黄原胶,改性粘土,尤其是有机改性的层状硅酸盐和高度分散的硅酸盐。特别合适的胶凝剂为角叉菜胶。胶凝剂的量基于组合物的总重量不超过组合物的5重量%,以及如果存在的话,优选为0.5-5重量%。
可存在于种子处理组合物中的其它助剂包括溶剂、润湿剂、分散剂、乳化剂、表面活性剂、增稠剂、保护胶体、消泡剂和防腐剂。
水为优选溶剂。根据特定实施方案,本发明组合物包含至少5重量%,优选至少10重量%,尤其是至少30重量%水。另一方面,本发明组合物通常包含至多99重量%,优选至多90重量%,尤其是至多80重量%水。
合适的溶剂的其他实例为有机溶剂如芳族溶剂(如Solvesso产品、二甲苯)、石蜡(如矿物油馏分)、醇类(如甲醇、丁醇、戊醇、苄醇)、酮类(如环己酮、γ-丁内酯)、吡咯烷酮(NMP、NOP)、乙酸酯(乙二醇二乙酸酯)、二元醇、脂肪酸二甲基酰胺、脂肪酸及脂肪酸酯。原则上还可以使用溶剂混合物。然而,根据特定的实施方案,本发明组合物含有小于15重量%,优选小于6重量%的所述有机溶剂。
合适的表面活性化合物为所有适合配制农业活性成分,尤其是活性成分的那些表面活性剂,其可以是非离子、阳离子、阴离子或两性的。根据它们的作用,表面活性剂-有时称作“添加剂”-可分为润湿剂、分散剂、乳化剂或保护胶体;然而,这些特定的组可重叠并且不可严格划分。表面活性剂的量基于组合物的总重量通常不超过20重量%,以及如果存在的话,经常为1-15重量%。
合适的润湿剂为所有促进润湿且常用于配制农业活性成分的那些物质。可优选使用烷基萘磺酸盐如二异丙基-或二异丁基萘磺酸盐。
合适的分散剂和/或乳化剂为所有常用于配制农业活性成分的非离子、阴离子和阳离子分散剂或乳化剂。可优选使用以下那些:非离子或阴离子分散剂和/或乳化剂,或非离子或阴离子分散剂和/或乳化剂的混合物。
可使用的合适的非离子分散剂和/或乳化剂尤其为氧化乙烯/氧化丙烯嵌段共聚物、烷基酚聚乙二醇醚和三苯乙烯基酚聚乙二醇醚,例如聚氧乙烯辛基酚醚,乙氧基化异辛基酚、辛基酚、壬基酚,烷基酚聚乙二醇醚,三丁基苯基聚乙二醇醚,三硬脂基苯基聚乙二醇醚,烷基芳基聚醚醇,醇和脂肪醇氧化乙烯缩合物,乙氧基化蓖麻油,聚氧乙烯烷基醚,乙氧基化聚氧丙烯,月桂醇聚乙二醇醚缩醛,山梨醇酯和甲基纤维素。
可使用的合适的分散剂和/或乳化剂尤其为木素磺酸、萘磺酸、苯酚磺酸、二丁基萘磺酸的碱金属盐、碱土金属盐和铵盐,烷基芳基磺酸盐,烷基硫酸盐,烷基磺酸盐,脂肪醇硫酸盐,脂肪酸和硫酸化脂肪醇乙二醇醚,还有芳基磺酸盐/甲醛缩合物,如磺化萘和萘衍生物与甲醛的缩合物,萘或萘磺酸与苯酚和甲醛的缩合物,木素磺酸盐,木素亚硫酸盐废液,磷酸化或硫酸化甲基纤维素衍生物和聚丙烯酸的盐。
增稠剂为典型的水溶性聚合物,其在含水介质中具有合适的塑性。实例包括阿拉伯胶、刺梧桐树胶、黄蓍树胶、瓜尔胶、蝗虫豆树脂、黄原胶、角叉菜胶、藻酸盐、酪蛋白、葡聚糖、果胶、琼脂、2-羟基乙基淀粉、2-氨基乙基淀粉、2-羟基乙基纤维素、甲基纤维素、羧甲基纤维素盐、纤维素硫酸盐。优选黄原胶。增稠剂的量通常不超过20重量%,并且如果存在的话,经常基于组合物的总重量为1-15重量%。
保护胶体通常为水溶性的两性聚合物。实例包括蛋白质和变性蛋白如酪蛋白,多糖如水溶性淀粉衍生物和纤维素衍生物,尤其是疏水改性淀粉和纤维素,还有聚羧酸化物如聚丙烯酸和丙烯酸共聚物,聚乙烯醇,聚乙烯基吡咯烷酮,乙烯基吡咯烷酮共聚物,聚乙烯胺,聚乙烯亚胺和聚亚烷基醚。保护胶体的量通常不超过组合物的3重量%,如果存在的话,优选基于组合物的总重量为0.1-2重量%。
可使用的消泡剂为所有抑制泡沫形成且常用于配制农业化学活性成分的那些物质。特别合适的是聚硅氧烷消泡剂,即聚硅氧烷含水乳液(例如Wacker的SRE,或Rhodia的),长链醇类,脂肪酸及其盐,如硬脂酸镁。消泡剂的量通常不超过组合物的3重量%,如果存在的话,基于组合物的总重量优选为0.1-2重量%。
可使用的防腐剂为所有为此用于农业化学组合物的防腐剂。可提及的实例为双氯芬、异噻唑啉酮(isothiazolene)和异噻唑酮(isothiazolone)类,如1,2-苯并异噻唑-3(2H)-酮、2-甲基-2H-异噻唑-3-酮-盐酸盐、5-氯-2-(4-氯苄基)-3(2H)-异噻唑酮、5-氯-2-甲基-2H-异噻唑-3-酮、5-氯-2-甲基-2H-异噻唑-3-酮、5-氯-2-甲基-2H-异噻唑-3-酮-盐酸盐、4,5-二氯-2-环己基-4-异噻唑啉-3-酮、4,5-二氯-2-辛基-2H-异噻唑-3-酮、2-甲基-2H-异噻唑-3-酮、2-甲基-2H-异噻唑-3-酮-氯化钙配合物、2-辛基-2H-异噻唑-3-酮和苄醇半缩醛。防腐剂的量通常不超过配制剂的2重量%,以及如果存在的话,基于配制剂的总重量优选为0.01-1重量%。
熟练技术人员熟知活性成分的农业组合物(例如参见Ullmann’sEncyclopedia of Industrial Chemistry,Fungicides(杀真菌剂),第4章,第5版,CD-ROM,Wiley-VCH,1997和Mollet,H.,Grubemann,A.,Formulation technology(配制技术),Wiley VCH Verlag GmbH,Weinheim(德意志联邦共和国),2001,此处将其完全引入作为参考)。
其实例包括水溶性浓缩物(SL、LS)、分散性浓缩物(DC)、乳油(EC)、乳液(EW、EO、ES)、悬浮液(SC、OD、FS)、水分散性颗粒(WG、SG)、水分散性或水溶性粉末(WP、SP、SS、WS)、粉剂或可撒粉粉末(DP、DS)、颗粒(GR、FG、GG、MG)、ULV溶液(UL)和凝胶配制剂(GF)。对种子处理而言,这类组合物可直接施用或在加入合适的液体,尤其是水以溶解、乳化、分散、悬浮或稀释组合物之后施用。因此,施用于种子的即用制剂的类型取决于所用组合物的类型和用于处理种子的方法。
这类组合物可以以已知方式制备(例如参见综述US 3,060,084,EP-A707 445(对于液体浓缩物),Browning,“Agglomeration”(团聚),ChemicalEngineering,1967年,12月4日,147-48,Perry’s Chemical Engineer’sHandbook,第4版,McGraw-Hill,New York,1963,第8-57页及随后各页。WO 91/13546,US 4,172,714,US 4,144,050,US 3,920,442,US5,180,587,US 5,232,701,US 5,208,030,GB 2,095,558,US 3,299,566,Klingman,Weed Control as a Science(杂草防治科学),John Wiley andSons,Inc.,New York,1961,Hance等,Weed Control Handbook(杂草防治手册),第8版,Blackwell Scientific Publications,Oxford,1989和Mollet,H.,Grubemann,A.,Formulation technology(配制技术),WileyVCH Verlag GmbH,Weinheim(德国),2001,2.D.A.Knowles,Chemistryand Technology of Agrochemical Formulations(农业配制剂化合物和技术),Kluwer Academic Publishers,Dordrecht,1998(ISBN 0-7514-0443-8)),例如通过将活性成分组分与一种或多种助剂粘附而制备,此处完全引入这些文献作为参考。
如下配制剂简单阐述所述组合物,其中将合适量的超支化聚合物加入配制剂:
A水溶性浓缩物,溶液(SL、LS)
将10重量份活性成分和任选润湿剂或其他助剂溶于90重量份水或水溶性溶剂中。由此得到活性成分含量为10重量%的配制剂。用水稀释得到溶液。
B分散性浓缩物(DC)
将20重量份活性成分溶于70重量份环己酮中并加入10重量份分散剂如聚乙烯基吡咯烷酮。由此得到活性成分含量为20重量%的配制剂。用水稀释得到分散体。
C乳油(EC)
将15重量份活性成分溶于75重量份二甲苯中并加入十二烷基苯磺酸钙和蓖麻油乙氧基化物(在每种情况下为5重量份)。由此得到活性成分含量为15重量%的配制剂。用水稀释得到乳液。
D乳液(EW、EO、ES)
将25重量份活性成分溶于35重量份二甲苯中并加入十二烷基苯磺酸钙和蓖麻油乙氧基化物(在每种情况下为5重量份)。借助乳化机(如Ultraturrax)将该混合物引入30重量份水中并制成均相乳液。由此得到活性成分含量为25重量%的配制剂。用水稀释得到乳液。
E悬浮液(SC、OD、FS)
在搅拌的球磨机中,将20重量份活性成分粉碎并加入10重量份分散剂和/或湿润剂以及70重量份水或有机溶剂,得到细碎活性化合物悬浮液。由此得到活性成分含量为20重量%的配制剂。用水稀释得到稳定的活性成分悬浮液。
F水分散性颗粒(WG、SG)
将50重量份活性成分细碎研磨并加入50重量份分散剂和/或湿润剂,借助工业装置(如挤出机、喷雾塔、流化床)将其制成水分散性或水溶性颗粒。由此得到活性成分含量为50重量%的配制剂。用水稀释得到稳定的活性化合物分散体或溶液。
G水分散性粉末和水溶性粉末(WP、SP、SS、WS)
将75重量份活性成分在转子-定子磨机中研磨并加入25重量份分散剂和/或湿润剂和硅胶。由此得到活性成分含量为75重量%的配制剂。用水稀释得到稳定的活性成分分散体或溶液。
H凝胶配制剂(GF)
在搅拌的球磨机中,将20重量份活性成分粉碎并加入10重量份分散剂、1重量份胶凝剂以及70重量份水或有机溶剂,得到细碎活性化合物悬浮液。由此得到具有20重量%活性成分的配制剂。用水稀释得到稳定的活性成分悬浮液。
I粉剂和可撒粉产品(DP、DS)
将5重量份活性成分细碎研磨并与95重量份细碎高岭土充分混合。这得到活性成分含量为5重量%的可撒粉产品。
J颗粒(GR、FG、GG、MG)
将0.5重量份活性成分细碎研磨并结合99.5重量份载体,这得到活性成分含量为0.5重量%的配制剂。现行方法是挤出、喷雾干燥或流化床方法。
K ULV溶液(UL)
将10重量份活性成分溶于90重量份有机溶剂中。这得到活性成分含量为10重量%的产品。
配制剂A-K可在施用前用水稀释或直接施用。
根据本发明的特定实施方案,种子处理组合物为液体或以液体施用。优选悬浮液,特别是含水悬浮液。悬浮颗粒为熔点高于30℃的活性成分或助剂。
根据本发明特别优选如下配制剂:可流动浓缩物(特别是FS)。这些配制剂可经稀释或不经稀释而施用于种子。
根据特定的实施方案,本发明涉及FS配制剂。通常而言,FS配制剂可包含1-800g/l活性成分,1-200g/l分散剂,0-200g/l防冻剂,1-400g/l超支化聚合物,0-200g/l着色剂和至多1升溶剂,优选水。
根据另一特定实施方案,本发明种子处理组合物为种子包衣配制剂。
这类种子包衣配制剂包含活性成分、至少一种粘合剂(或增粘剂),即本文所定义的超支化聚合物和任选至少一种选自填料和增塑剂的其它助剂。
包含粘合剂、填料和/或增塑剂的种子包衣配制剂在本领域是众所周知的。种子包衣配制剂例如公开于美国专利号5,939,356、5,882,713、5,876,739、5,849,320、5,834,447、5,791,084、5,661,103、5,622,003、5,580,544、5,328,942、5,300,127、4,735,015、4,634,587、4,383,391、4,372,080、4,339,456、4,272,417和4,245,432和其它文献中。
包括在包衣配制剂中的活性成分的量取决于种子类型而变化,但包衣配制剂应含有农药有效量的活性成分。活性成分在包衣配制剂中的量通常为总重量的约0.005-约75%。活性成分的更优选的范围是约0.01-约40%;更优选约0.05-约20%。
包括在包衣配制剂中的活性成分确切量由本领域熟练技术人员容易地确定且取决于待包衣的种子的尺寸和其它特征(表面结构等)而变化。包衣配制剂的活性成分不准抑制种植萌发且应在目标害虫对种子或植物造成损害的其生命周期中有效保护种子和/或植物。包衣通常应在播种后有效约0-120天,优选约0-60天。
由活性成分形成的包衣配制剂能够通过扩散或运动经由基质以缓慢速率释放活性成分至种子或周围介质中。
本发明还涉及本文所定义的组合物在处理种子中的用途。
本发明也涉及一种用本文所述的组合物处理种子的方法,其包括向一批种子施用有效量的如本文所定义的组合物。
术语“批次”或“批”是指经受种子处理的一组种子。种子的量和重量可取决于处理而变化。
术语“负载量”是指粘附于各种子的基于种子整体量的活性成分或超支化聚合物的实际量。
如本文所用的术语“种子”是指与植物的生长阶段物理分离和/或可储存延长时间和/或可用于再长出相同种类的另一植物个体的植物任何休眠阶段。此处,术语“休眠”是指其中在合理限度内,尽管没有生长(即非种子)阶段所必需的光、水和/或营养品,植物保持发育能力的阶段。该术语尤其指真正种子,而不包括植物繁殖体如吸根、球根、鳞茎、果实、块茎、谷物、插条(cutting)和伐枝(cut shoot)。
如本文所用的术语“植物”是指整个植物或植物部分。术语“整个植物”是指植物生长,即非种子阶段的整个植物个体,其特征在于存在根、枝和叶的排列,取决于植物发育阶段还有花和/或果实,所有这些物理连接形成个体,该个体在合理条件下可无需人工措施而生存。该术语也指直接收获的整个植物。
术语“植物部分”是指根、枝、叶、花或植物生长阶段的其他部分,这些部分当离开剩余部分和与剩余部分分离时,除非有人工措施支持否则不能存活,或者不能再长出失去的部分以形成整个植物。如本文所用的果实也认为是植物部分。
如本文所用的术语“根”是指为了履行其生理功能通常位于土壤表面以下的植物部分。优选,该术语是指在种子下面并且直接从种子长出,或从其他根长出,而不是从枝或叶长出的植物部分。
如本文所用的植物的“枝和叶”应理解为指在种子萌发后的植物的枝、茎、枝条、叶以及茎和枝条的其他附属物,但不包括植物的根。优选植物的枝和叶应理解为指从种子长出并且距离其长出的种子(种子的外部区域)至少一英寸的距离的非根的植物部分,更优选理解为指在土壤表面处或以上的非根的植物部分。
如本文所用的“果实”理解为指含有种子和/或用于传播种子和/或可从植物中取出而不损害其生存能力的植物部分。
根据本发明,种子处理包括将本发明组合物施用于种子。尽管本发明方法可使用于任何生理阶段的种子,优选种子处于在处理方法中不发生显著损害的足够耐久的阶段。该种子通常为从田间收获的种子;从植物中取出的种子;和/或从果实和任何穗轴、荚、秆、外壳和围绕的果肉或其他非种子的植物材料中分离的种子。还优选种子生物学上足够稳定,以使处理不会对种子造成生物损害。在一个实施方案中,例如处理可施用于已经收获、清洁并干燥至水分含量低于约15重量%的种子。在替代实施方案中,种子可以是已经干燥,然后用水或其他材料打底,然后在用本发明组合物处理之前或之中再干燥。
根据本发明的优选实施方案,待处理的种子因此基本干燥。“基本干燥”的种子包括具有其中使种子在20-30℃和30-90%的相对湿度,如在25℃和50%相对湿度的气氛下平衡而获得的水分含量的种子,
术语种子处理包括本领域已知的所有合适的种子处理,特别是拌种技术,如种子包衣(如种子造粒)、种子撒粉和种子吸收(如种子浸泡)。此处,“种子处理”是指使种子和本发明组合物相互接触的所有方法,“拌种”是指向种子提供一定量活性成分的种子处理方法,即该方法产生包含活性成分的种子。原则上,处理可施用于从种子收获至种子播种的任何时间的种子。种子例如可使用“播种箱”或“种植箱”方法紧邻种植种子之前或种植种子的过程中处理。然而,处理也可在种植种子之前数周或数月,例如至多12个月,例如以拌种处理的形式进行处理,而没有观察到效力的显著降低。
有利的是将处理施用于未播种的种子。如本文所用的术语“未播种种子”意味着包括从种子收获到将种子播种到地面以使植物萌发和生长的任何时间中的种子。优选种子不是催芽的种子,如催芽的稻种。
当提及“处理”未播种种子时,该处理并不意味着包括其中将农药施用于土壤,而不是直接施用于种子的那些措施。
通过在种子播种之前将处理施用于种子使操作简化。以此方式例如可在中心场所处理种子,然后将种子分配用于种植。这允许种植种子的人避免处理和使用活性成分,并且仅以常用于未处理种子的常规方式处理和种植处理的种子,这减少了对人的暴露。
具体而言,种子处理根据如下程序进行,其中将种子暴露于具体所需量的包含活性成分的制剂。制剂可以是直接施用或例如用水预先稀释的本发明组合物;例如,可能有利的是以2-10倍稀释种子处理组合物,从而产生0.01-60重量%,优选0.1-40重量%的活性化合物在即用制剂中的浓度。在某些情况下,可能有利的是,在不具有粘合剂或粘合剂量不足的组合物中加入本发明的超支化聚合物。当加入超支化聚合物并任选用水稀释时,所得组合物适用于种子处理。
因此,活性成分在即用制剂中的浓度可在显著范围内变化。它们基于制剂总重量通常为0.01-80重量%,常常0.1-50重量%,优选0.5-20重量%。活性成分也可成功地以浓缩形式施用,其中可以向种子施用超过80重量%活性成分的制剂,或甚至不含添加剂的活性成分。添加剂的量具有在每种情况下基于制剂总重量通常不超过30重量%,优选20重量%,尤其为0.1-20重量%。
通常使用适合于种子处理的装置,例如用于固体或固体/液体组分的混合器,直至制剂均匀分布在种子上。因此,制剂可通过标准种子处理方法施用至种子,其包括但不限于在容器(如瓶、袋或转鼓)混合,机械施用,转鼓处理,喷雾和浸渍。合适的话,随后干燥。
本发明的特定实施方案包括种子包衣和吸收(如浸泡)。“包衣”是指赋予种子外表面部分或完整的非植物材料层的任何方法,“吸收”是指导致活性成分穿透入种子的可萌发部分和/或其天然外壳(sheath)、(内)壳(husk)、皮(hull)、壳、荚和/或珠被(integument)的任何方法。因此,本发明还涉及包括向种子提供包含活性成分的包衣的种子处理,以及包括使种子吸收活性成分的种子处理。
在容许高负载的活性成分中,包衣特别有效,所述高负载在处理典型的难以防治的害虫时需要,同时防止由于活性成分的负载增加而引起的不可接受的植物毒性。
包衣可使用常规包衣技术和机器如流化床技术、辊研磨机方法、滚动静态(rotostatic)种子处理器和转鼓涂敷机而施用于种子。其它方法如喷淋床技术也可能是有用的。种子可在包衣之前预施胶。在包衣之后,通常将种子干燥,然后转移至施胶机中施胶。
这类程序在本领域是已知的。种子包衣方法和应用它们的装置例如公开于美国专利号5,918,413、5,891,246、5,554,445、5,389,399、5,107,787、5,080,925、4,759,945和4,465,017中。
在另一特定实施方案中,固体的活性成分,例如作为固体细颗粒配制剂,如粉末或粉剂可直接与种子混合。可任选使用增粘剂以将固体,如粉末粘附至种子表面。例如,可将一定量的种子与增粘剂(其增加颗粒在种子表面上的粘附)混合并任选搅动以促进增粘剂对种子的均匀涂敷。例如,种子可与足够量的增粘剂混合,这导致增粘剂对种子的部分或完全涂敷。然后将如此预处理的种子与含有活性成分的固体配制剂混合,以实现固体配制剂在种子材料表面上的粘附。该混合物例如可通过转鼓搅动,以促进增粘剂与活性成分的接触,由此导致固体活性成分粘附在种子上。
用活性成分处理种子的另一特定方法为吸收。例如,可使种子与在溶剂如水中包含约1-约75重量%活性成分的水溶液结合一段时间。优选,溶液的浓度为约5-约50重量%,更优选约10-约25重量%。在种子与溶液结合的过程中,种子吸收(吸收)至少部分活性成分。任选地,可例如通过振摇、滚动、转鼓或其它手段搅动种子和溶液的混合物。在吸收方法之后,可将种子与溶液分离,并任选以合适的方式,如通过轻拍或风干而干燥。
在本发明的又一特定的实施方案中,活性成分可通过使用固体基质打底(priming)而引至种子上或种子内。例如,可将一定量的活性成分与固体基质材料混合,然后可放入种子,使其与固体基质材料接触一段时间,以允许将活性成分引至种子。然后可任选将种子的混合物与固体基质材料分离并储存或使用,或可优选将固体基质材料加上种子的混合物直接储存或种植/播种。
在本发明的各实施方案中,优选将本发明组合物以有效量施用于种子,即对种子和由种子长出的植物提供足以防止害虫的保护量。当然,本发明的种子处理不仅保护种子,而且保护由种子长出的植物。
与未处理种子或由未处理种子长出的植物相比,如果对种子和/或植物的进食损害百分数在害虫侵染10天后(侵染后天数(DAI))对于处理的种子和由处理的种子长出的植物显著降低,则实现了如本文所用的“保护”。为了有效保护,活性成分的用量通常为0.1-500g/100kg种子,优选0.5-200g/100kg种子,尤其是0.75-100g/100kg种子。
根据本发明,所述种子处理的一个目的是防治害虫。因此,该种子处理涉及对种子和/或由种子长出的植物提供防止害虫造成损害的保护的农药作用或农药活性。种子处理可尤其用于保护种子和秧苗防止较早季节的病害和昆虫害虫影响作物出苗和生长。
如本文所用的术语“农药作用”和“农药活性”是指对目标害虫任何直接或间接作用,分别与未处理种子或由未处理种子长出的植物相比,其导致对处理种子的进食损害的减少,以及还导致对由处理的种子长出的植物的果实、根、枝和/或叶的进食损害的减少。术语“对(第一或第二)害虫的活性”也具有相同含义。该直接或间接作用包括杀死害虫、从植物种子、果实、根、枝和/或叶中驱除害虫,以及抑制害虫,或延迟其在植物种子、果实、根、枝和/或叶上进食或产卵,以及抑制或防止害虫的繁殖。
害虫尤其包括土生(soil-borne)和土居(soil-dwelling),枝和叶面害虫。
待防治的真菌尤其包括如下:
观赏植物、蔬菜和向日葵上的白锈属(Albugo)(白锈病)(如蔬菜上的白锈菌(A.candida)和向日葵上的婆罗门参白锈(A.tragopogonis);蔬菜、油菜籽、糖用甜菜、水果、稻、大豆、土豆和小麦上的链格孢(Alternaria)属(链格孢叶斑病),油菜籽上的芸苔链格孢(A.brassicola或brassicae),糖用甜菜上的细极链格孢(A.tenuis),如土豆上的早疫链格孢(A.solani)或细交链孢(A.alternate),西红柿上的早疫链格孢(A.solani)或细交链孢(A.alternata);糖用甜菜和蔬菜上的丝囊霉(Aphanomyces)属;禾谷类和蔬菜上的壳二孢(Ascochyta)属,例如小麦上的小麦裾叶炫菌(Ascochytatritici)(炭疽病)和大麦上的大麦锈病菌(P.hordei);玉米、禾谷类、稻和草坪中的平脐蠕孢(Bipolaris)属和内脐蠕孢(Drechslera)属(有性型:旋孢腔菌(Cochliobolus)属),例如玉米上的玉米小斑病菌(D.maydis)),禾谷类上的小麦根腐平脐蠕孢(B.sorokiniana):叶斑病,稻上的稻平脐蠕孢菌(B.oryzae);禾谷类(例如小麦或大麦)中的禾白粉菌(Blumeria(以前为Erysiphe)graminis)(白粉病);水果和浆果(如草莓)、蔬菜(如莴苣、萝卜、芹菜和卷心菜)、油菜籽、花卉、葡萄藤、森林植物和小麦上的灰葡萄孢(Botrytiscinerea(有性型:灰霉病菌(Botryotinia fuckeliana):灰霉病));莴苣上的莴苣盘梗霉(Bremia lactucae)(霜霉病);阔叶树和常绿树上的长喙壳属(Ceratocystis)(同义词Ophiostoma)属(立枯病或枯萎),如榆树上的榆长喙壳(C.Ulmi)(榆枯萎病);玉米、稻、糖用甜菜、甘蔗、蔬菜、咖啡、大豆和稻上的尾孢属(Cercospora)(尾孢叶斑病),如糖用甜菜上的C.beticola,例如大豆上的大豆尾孢(Cercospora sojina)或菊池尾孢(Cercosporakikuchii);土豆和禾谷类上的枝孢属(Cladosporium)(如黄枝孢(C.Fulvum):叶霉病),如小麦上的扁豆枝孢(Cladosporium herbarum)(黑霉病);禾谷类上的麦角菌(Claviceps purpurea)(麦角病);玉米、禾谷类和稻上的旋孢腔菌(无性型:Cochliobolus)属(平脐蠕孢属的长蠕孢(Helminthosporium)属),如玉米上的C.carbonum,禾谷类上的禾旋孢腔菌(Cochliobolus sativus),无性型:B.Sorokiniana,和稻上的宫部旋孢腔菌(Cochliobolus miyabeanus,无性型:H.oryzae));棉花、玉米、无核小水果、土豆、豆类和大豆上的剌盘孢(Colletotricum)属(有性型:小丛壳属(Glomerella))(炭疽病),如棉花上的棉刺盘孢(C.gossypii)、玉米上的禾生刺盘孢(C.graminicola)、土豆上的C.coccodes:黑斑病、豆类上的豆刺盘孢(C.lindemuthianum)和大豆上的大豆上的平头刺盘孢(Colletotrichumtruncatum或C.gloeosporioides);伏革菌属(Corticium),如稻上的笹木伏革菌(Corticium sasakii)(枯纹病);大豆和观赏植物上的山扁豆生棒孢(Corynespora cassiicola)(叶斑病);Cycloconium属,如橄榄树上的油橄榄孔雀斑病菌(C.oleaginum);果树、葡萄藤和观赏植物上的柱孢(Cylindrocarpon)属(如果树蛀孔或幼葡萄藤下垂,有性型:丛赤壳(Nectria或Neonectria)属),如葡萄藤上的C.liriodendri,有性型:Neonectrialiriodendri:黑脚病(Black Foot);大豆上的白纹羽束丝菌(Dematophoranecatrix)(有性型:褐座坚壳(Rosellinia necatrix))(根/颈腐病);间座壳属(Diaporthe),如大豆上的菜豆间座壳(D.Phaseolorum)(立枯病);玉米、禾谷类、稻和草坪上的内脐蠕孢(Drechslera)属(同义词长蠕孢(Helminthosporium)属,有性型:核腔菌(Pyrenophora)属,例如大麦上的大麦网斑内脐蠕孢(D.Teres,网斑病)和小麦上的D.tritci-repentis:褐斑病);由Formitipora punctata(同义词斑孔木层孔菌(Phellinus punctatus))、F.mediterranea、Phaeoacremonium chlamydosporium(以前称为Phaeoacremonium chlamydosporum)、Phaeoacremonium Aleophilum和/或葡萄座腔菌属(Botryosphaeria obtusa)引起的葡萄藤上的埃斯卡(Esca)(顶枯病,干枯病);仁果、无核小水果和葡萄藤上的痂囊腔菌(Elsinoe)属,如仁果上的E.pyri、无核小水果上的E.veneta:炭疽病和葡萄藤上的痂囊腔菌(Elsinoe ampelina:炭疽病);稻上的Entyloma oryzae(叶黑粉病);小麦上的附球菌属(Epicoccum)(黑霉病);糖用甜菜、蔬菜、卷心菜、油菜籽上的白粉菌(Erysiphe)属(白粉病),如糖用甜菜上的E.betae,蔬菜上的豌豆白粉菌(E.Pisi),如葫芦上的二孢白粉菌(Erysiphe cichoracearum),油菜籽上的克鲁白粉菌(E.Cruciferarum);果树、葡萄藤和观赏木材上的Eutypalata(Eutypa蛀孔或顶枯病,无性型:Cytosporina lata,同义词Libertellablepharis);玉米上的突脐蠕孢(Exserohilum)属(同义词长蠕孢(Helminthosporium)属),如E.turcicum;各种植物上的镰孢霉(Fusarium)属(有性型:赤霉(Gibberella)属)(枯萎、根腐病或茎腐病),例如禾谷类(如小麦或大麦)上的禾谷镰刀菌(F.graminearum)或大刀镰孢(F.culmorum)(根腐病;疮痂病或赤霉病),西红柿上的尖镰孢(F.oxysporum),大豆上的真马特腐皮镰孢(Fusarium Solani)和玉米上的轮状镰刀霉(F.verticillioides);禾谷类,如大麦或小麦和玉米上的禾顶囊壳(Gaeumannomyces graminis)属(小麦全蚀病);禾谷类和稻上的赤霉(Gibberella)属,例如禾谷类上的玉蜀黍赤霉(G.zeae)和稻上的藤仓赤霉(Gibberella fujikuroi:稻恶苗病);葡萄藤、仁果和其它植物上的围小丛壳(Glomerella cingulata)以及棉花上的G.gossypii;稻上的革兰氏染色配合物(Grainstaining complex);葡萄藤上的葡萄球座菌(Guignardia bidwellii)(黑腐病);蔷薇植物和刺柏属上的Gymnosporangium属,如梨上的G.sabinae(锈病);玉米、禾谷类和稻上的长蠕孢(Helminthosporium)属(同义词Drechslera,有性型:旋孢腔菌(Cochliobolus)属);咖啡上的Hemileia属,如H.vastatrix(咖啡叶锈病);葡萄藤上的褐斑拟棒束孢(Isariopsisclavispora)(同义词Cladosporium vitis);大豆和棉花上的菜豆格孢(Macrophomina phaseolina)(同义词phaseoli)(根腐病和茎腐病);禾谷类(如小麦或大麦)上的Michrodochium(同义词Fusarium)nivale(紫雪霉病);大豆上的Microsphaera diffusa(白粉病);核果和其它蔷薇植物上的链核盘菌(Monilinia)属,如核果链核盘菌(M.laxa),M.fructicola和果生链核盘菌(M.fructigena)(花和嫩枝疫病,褐腐病);禾谷类、香蕉、无核小水果和花生上的球腔菌(Mycosphaerella)属,例如小麦上的禾生球腔菌(M.graminicola)(无性型:小麦壳针孢(Septoria tritici),壳针孢叶斑病)或香蕉上的M.fijiesis(香蕉叶斑病);甘蓝、油菜籽、洋葱、烟草和大豆上的霜霉(Peronospora)属(霜霉病),例如甘蓝上的芸苔霜霉(P.brassicae),洋葱上的P.destructor,烟草上的P.tabacina和大豆上的东北霜霉(Peronosporamanshurica);大豆上的豆薯层锈菌(Phakopsora pachyrhizi)和山马蟥层锈菌(Phakopsara meibomiae)(大豆锈病);葡萄藤和大豆上的瓶霉病(Phialophora)属,如葡萄藤上的P.tracheiphila和P.tetraspora,和大豆的Phialophora gregata:茎腐病;油菜籽和卷心菜以及糖用甜菜上的黑胫茎点霉(Phoma lingam)(根腐病和茎腐病)和甜菜茎点霉(P.betae)(根腐病、叶斑病和幼苗或插枝腐烂);向日葵、葡萄藤和大豆上的拟茎点霉(Phomopsis)属,如葡萄藤上的葡萄拟茎点霉(P.viticola:can和叶斑病),大豆上的茎腐病:P.phaseoli:有性型:菜豆间座壳(Diaporthe phaseolorum));玉米上的玉蜀黍节壶菌(Physoderma maydis)(褐斑病);各种植物上的疫霉属(Phytophthora)(枯萎,根、叶、果实和茎腐病),例如胡椒和葫芦上的辣椒疫霉(P.capsici),大豆上的大雄疫霉(P.megasperma,同义词P.sojae),土豆和西红柿上的致病疫霉(P.infestans:晚疫病),和阔叶树上的(P.ramorum:栎树突然死亡);卷心菜、油菜籽、萝卜和其它植物上的芸苔根肿菌(Plasmodiophora brassicae)(根肿病);Plasmopara属,如葡萄藤上的葡萄生单轴霉(Plasmopara viticola,葡萄霜霉病)和向日葵上的P.halstedii;蔷薇植物、啤酒花、梨果和无核小水果上的叉丝单囊壳(Podosphaera)属(白粉病),如苹果上的苹果白粉病菌(Podosphaera leucotricha);禾谷类如大麦和小麦以及糖用甜菜上的多粘霉(Polymyxa)属,如小麦上的多粘霉(P.graminis)和糖用甜菜上的P.betae,以及由此转变的病毒病害;禾谷类上如小麦或大麦的小麦基腐病菌(Pseudocercosporella herpotrichoides)(眼斑病,有性型:Tapesia yallundae);各种植物上的假霜霉(Pseudoperonospora)属(霜霉病),例如黄瓜上的古巴假霜霉(P.cubenis)或啤酒花上的葎草假霜霉(P.humili);葡萄藤上的Pseudopezicula tracheiphilai(红火病(red firedisease)或,rotbrenner’,无性型:瓶霉属(Phialophora));各种植物上的柄锈菌(Puccinia)属(锈病),例如禾谷类如小麦、大麦和燕麦上的小麦锈病菌(P.triticina)(褐锈病或叶锈病),条锈病菌(P.striformis)(条锈病),大麦锈病菌(P.hordei)(矮锈病)或禾柄锈菌(P.graminis)(茎锈病或黑锈病),隐匿柄锈菌(P.recondite)(褐锈病或叶锈病),以及芦笋上的芦笋锈病菌(P.asparagi);小麦上的Pyrenophora(无性型:内脐蠕孢属)tritici-repentis(褐斑病)或大麦上的Pyrenophora teres(网斑病);Pyricularia属,如稻上的稻瘟病菌(Pyricularia oryzae)(有性型:Magnaporthe grisea,稻瘟病)以及草坪和禾谷类上的稻梨孢菌(Pyricularia grisea);草坪、稻、玉米、小麦、棉花、油菜籽、向日葵、大豆、糖用甜菜、蔬菜和其他植物上的腐霉(Pythium)属(立枯病),例如终极腐霉(P.ultimum)或瓜果腐霉(P.aphanidermatum));大麦上的Ramularia collo-cygni(柱隔孢(Ramularia)叶斑病,生理叶斑病)和糖用甜菜上的R.beticola;棉花、稻、土豆、草坪、玉米、油菜籽、土豆、糖用甜菜、蔬菜和各种植物上的丝核菌(Rhizoctonia)属,例如大豆上的立枯丝核病菌(Rhizoctonia solani)(根和茎腐病),稻上的立枯丝核病菌(Rhizoctonia solani)(鞘枯病)或小麦或大麦上的禾谷丝核菌(Rhizoctoniacerealis)(Rhizoctonia spring blight);草莓、萝卜、卷心菜、葡萄藤和西红柿上的匍枝根霉(Rhizopus stolonifer)(黑霉病,软腐病);大麦、黑麦和黑小麦上的黑麦喙孢(Rhynchosporium secalis)(褐斑病);稻上的帚梗柱孢属(Sarocladium oryzae)和稻叶鞘腐败病菌(S.attenuatum)(鞘腐病);蔬菜、大田作物如油菜籽、向日葵和大豆上的核盘菌(Sclerotinia)属(根腐病或白霉病),例如向日葵上的核盘菌(S.sclerotiorum)和大豆上的Sclerotiniarolfsii或核盘菌(S.sclerotiorum);各种植物上的壳针孢(Septoria)属,如大豆上的大豆壳针孢(Septoria glycines)(褐斑病),小麦上的小麦壳针孢(Septoria tritici)(小麦壳针孢斑病)和禾谷类上的颖枯壳多孢(Stagonospora(同义词Stagonospora)nodorum)(颖枯壳多孢斑病);葡萄藤上的葡萄钩丝壳(Erysiphe(同义词Uncinula necator)(白粉病,无性型:葡萄粉孢(Oidium tuckeri));玉米和草坪上的Setospaeria属(叶枯病)(如S.turcicum,同义词大斑病长蠕孢(Helminthosporium turcicum));玉米、高粱和甘蔗上的Sphacelotheca属(黑穗病),如玉米上的丝轴黑粉菌(Sphacelotheca reilinia:丝黑穗病);葫芦上的单丝壳白粉菌(Sphaerothecafuliginea)(白粉病);土豆上的Spongospora subterranea(粉痂病)和由其转变的病毒病害;禾谷类上的壳多孢(Stagonospora)属,如小麦上的颖枯壳多孢(Stagonospora nodorum)(壳多孢斑病,有性型:小麦小球腔菌(Leptosphaeria[同义词Phaeosphaeria]nodorum));土豆上的内生集壶菌(Synchytrium endobioticum)(土豆癌肿病);外囊菌(Taphrina)属,如桃上的畸形外囊菌(T.deformans)(缩叶病)和李子上的李外囊菌(T.pruni)(李囊果病);烟草、仁果、蔬菜、大豆和棉花上的根串珠霉属(Thielaviopsis)(黑根腐病),如根串珠霉(T.basicola)(同义词Chalara elegans);禾谷类上的腥黑粉菌(Tilletia)属(普通腥黑穗病或麦类黑穗病),如小麦上的T.tritici(同义词小麦网腥黑粉菌(T.caries),小麦腥黑穗病)和小麦矮腥黑粉菌(T.controversa)(矮黑穗病);小麦或大麦上的肉孢核瑚菌(Typhulaincarnate)(灰雪霉病);黑麦上的条黑粉菌(Urocystis)属,如隐条黑粉菌(U.Occulta)(秆黑粉病);蔬菜、豆类和糖用甜菜上的单胞锈菌(Uromyces)属(锈病),如豆类上的疣顶单胞锈菌(U.appendiculatus),同义词U.Phaseoli,和糖用甜菜上的甜菜单胞锈菌(U.betae);禾谷类、玉米和甘蔗上的黑粉菌(Ustilago)属(黑穗病),例如禾谷类上的裸黑粉菌(U.nuda)和燕麦散黑粉菌(U.avaenae),玉米上的玉蜀黍黑粉菌(U.maydis:玉米黑粉病);苹果和梨上的黑星菌(Venturia)属(黑星病),例如苹果上的苹果黑星病(V.inaequalis),以及各种植物如水果和观赏植物、葡萄藤、无核小水果、蔬菜和大田作物上的轮枝孢(Verticillium)属(枯萎),例如草莓、油菜籽、土豆和西红柿上的大丽花轮枝孢(V.dahliae)。
待防治的昆虫特别包括下列:
鳞翅目昆虫(鳞翅目(Lepidoptera)),例如小地老虎(Agrotis ypsilon)、黄地老虎(Agrotis segetum)、木棉虫(Alabama argillacea)、黎豆夜蛾(Anticarsia gemmatalis)、Argyresthia conjugella、叉纹夜蛾(Autographagamma)、树尺蠖(Bupalus piniarius)、Cacoecia murinana、Capuareticulana、Cheimatobia brumata、云杉色卷蛾(Choristoneurafumiferana)、Choristoneura occidentalis、二化螟(Cirphis unipuncta)、苹果小卷蛾(Cydia pomonella)、松毛虫(Dendrolimus pini)、Diaphanianitidalis、西南玉米杆草螟(Diatraea grandiosella)、埃及钻夜蛾(Eariasinsulana)、南美玉米苗斑螟(Elasmopalpus lignosellus)、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(Lobesiabotrana)、甜菜网螟(Loxostege sticticalis)、舞毒蛾(Lymantria dispar)、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(Orgyiapseudotsugata)、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(Plutella xylostella)、大豆夜蛾(Pseudoplusiaincludens)、Rhyacionia frustrana、Scrobipalpula absoluta、麦蛾(Sitotrogacerealella)、葡萄卷叶蛾(Sparganothis pilleriana)、草地夜蛾(Spodopterafrugiperda)、海灰翅夜蛾(Spodoptera littoralis)、斜纹夜蛾(Spodopteralitura)、Thaumatopoea pityocampa、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.、长角叶甲(Diabrotica longicornis)、Diabroticasemipunctata、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(Ipsm typographus)、烟草负泥虫(Lema bilineata)、黑角负泥虫(Lema melanopus)、马铃薯叶甲(Leptinotarsadecemlineata)、Limonius californicus、稻水象甲(Lissorhoptrusoryzophilus)、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(Otiorrhynchus sulcatus)、草莓根象甲(Otiorrhynchus ovatus)、辣根猿叶甲(Phaedon cochleariae)、梨树叶象(Phyllobius pyri)、Phyllotreta chrysocephala、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)、白纹伊蚊(Aedes albopictus)、剌扰伊蚊(Aedes vexans)、墨西哥果蝇(Anastrephaludens)、五斑按蚊(Anopheles maculipennis)、Anopheles crucians、白足按蚊(Anopheles albimanus)、冈比亚按蚊(Anopheles gambiae)、Anophelesfreeborni、海南岛白踝按蚊(Anopheles leucosphyrus)、云南微小按蚊(Anopheles minimus)、四斑按蚊(Anopheles quadrimaculatus)、红头丽蝇(Calliphora vicina)、地中海实蝇(Ceratitis capitata)、蛆症金蝇(Chrysomyabezziana)、Chrysomya hominivorax、Chrysomya macellaria、鹿蝇(Chrysops discalis)、Chrysops silacea、Chrysops atlanticus、螺旋蝇(Cochliomyia hominivorax)、高粱瘿蚊(Contarinia sorghicola)、嗜人瘤蝇蛆(Cordylobia anthropophaga)、狂怒库蠓(Culicoides furens)、尖音库蚊(Culex pipiens)、斑蚊(Culex nigripalpus)、致倦库蚊(Culexquinquefasciatus)、媒斑蚊(Culex tarsalis)、Culiseta inornata、Culisetamelanura、瓜蝇(Dacus cucurbitae)、油橄榄实蝇(Dacus oleae)、油菜叶瘿蚊(Dasineura brassicae)、Delia antique、麦地种蝇(Delia coarctata)、灰地种蝇(Delia platura)、甘蓝地种蝇(Delia radicum)、Dermatobia hominis、小毛厕蝇(Fannia canicularis)、Geomyza Tripunctata、马蝇(Gasterophilus intestinalis)、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)、Lucilia caprina、铜绿蝇(Lucilia cuprina)、丝光绿蝇(Lucilia sericata)、Lycoria pectoralis、Mansonia titillanus、麦瘿蚊(Mayetiola destructor)、秋家蝇(Musca autumnalis)、家蝇(Muscadomestica)、厩腐蝇(Muscina stabulans)、羊狂蝇(Oestrus ovis)、Opomyzaflorum、欧洲麦秆蝇(Oscinella frit)、天仙子泉蝇(Pegomya hysocyami)、葱蝇(Phorbia antiqua)、萝卜蝇(Phorbia brassicae)、麦地种蝇(Phorbiacoarctata)、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(Rhagoletis pomonella)、赤尾麻蝇(Sarcophaga haemorrhoidalis)、肉蝇属(Sarcophaga)、Simuliumvittatum、厩螫蝇(Stomoxys calcitrans)、牛虻(Tabanus bovinus)、Tabanus atratus、红色原虻(Tabanus lineola)、Tabanus similis、Tipulaoleracea和欧洲大蚊(Tipula paludosa);
蓟马(缨翅目(Thysanoptera)),例如兰花蓟马(Dichromothripscorbetti)、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、Leucotermesflavipes、金黄异白蚁(Heterotermes aureus)、黄肢散白蚁(Reticulitermesflavipes)、美小黑散白蚁(Reticulitermes virginicus)、欧洲散白蚁(Reticulitermes lucifugus)、Reticulitermes santonensis、Reticulitermesgrassei、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、蚜虫、叶蝉、粉虱、介壳虫、蝉(半翅目(Hemiptera)),例如拟绿蝽(Aerosternum 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 spiraecola)、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)、桃短尾蚜(Brachycaudus persicae)、Brachycaudus prunicola、甘蓝蚜(Brevicorynebrassicae)、Capitophorus horni、Cerosipha gossypii、草莓中瘤钉毛蚜(Chaetosiphon fragaefolii)、茶镳隐瘤蚜(Cryptomyzus ribis)、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)、Hyperomyzuslactucae、麦长管蚜(Macrosiphum avenae)、大戟长管蚜(Macrosiphumeuphorbiae)、蔷薇管蚜(Macrosiphon rosae)、巢莱修尾蚜(Megouraviciae)、Melanaphis pyrarius、麦无网蚜(Metopolophium dirhodum)、Myzodes persicae、冬葱瘤额蚜(Myzus ascalonicus)、Myzus cerasi、李瘤蚜(Myzus varians)、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(Psyllamali)、梨木虱(Psylla piri)、冬葱瘤蛾蚜(Rhopalomyzus ascalonicus)、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(Cimexlectularius)、热带臭虫(Cimex hemipterus)、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、Atta laevigata、Atta robusta、Atta sexdens、Atta texana、举腹蚁属(Crematogaster)、Hoplocampa minuta、Hoplocampa testudinea、黑毛蚁(Lasius niger)、小黄家蚁(Monomorium pharaonis)、热带火蚁(Solenopsis geminate)、红火蚁(Solenopsis invicta)、黑火蚁(Solenopsis richteri)、南方火蚁(Solenopsisxyloni)、红蚂蚁(Pogonomyrmex barbatus)、Pogonomyrmex californicus、Pheidole megacephala、天鹅绒蚂蚁(Dasymutilla occidentalis)、熊蜂属(Bombus)、大黄蜂(Vespula squamosa)、Paravespula vulgaris、Paravespulapennsylvanica、Paravespula germanica、姬胡蜂(Dolichovespula maculata)、黄边胡蜂(Vespa crabro)、胡蜂(Polistes rubiginosa)、Campodontusfloridanus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(Melanoplus femurrubrum)、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(Dociostaurus maroccanus)、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(Calliptamusitalicus)、澳洲草栖蝗(Chortoicetes terminifera)和褐色拟飞蝗(Locustanapardalina),
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(Boophilusannulatus)、Boophilus decoloratus、微小牛蜱(Boophilus microplus)、Dermacentor silvarum、安氏革蜱(Dermacentor andersoni)、美洲大革蜱(Dermacentor variabilis)、Hyalomma truncatum、蓖子硬蜱(Ixodesricinus)、Ixodes rubicundus、黑脚硬蜱(Ixodes scapularis)、全环硬蜱(Ixodesholocyclus)、太平洋硬蜱(Ixodes pacificus)、Ornithodorus moubata、Ornithodorus hermsi、Ornithodorus turicata、柏氏禽刺螨(Ornithonyssusbacoti)、Otobius megnini、鸡皮刺螨(Dermanyssus gallinae)、绵羊疥病(Psoroptes ovis)、Rhipicephalus sanguineus、Rhipicephalusappendiculatus、Rhipicephalus evertsi、人疥螨(Sarcoptes scabiei),瘿螨(Eriophyidae)属,如苹果刺锈螨(Aculus schlechtendali)、Phyllocoptrataoleivora和Eriophyes sheldoni;细螨(Tarsonemidae)属,如Phytonemuspallidus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(Oligonychuspratensis);蜘蛛目(Araneida),例如毒蜘蛛(Latrodectus mactans)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(Nosopsyllus fasciatus),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),
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,
弹尾目(collembola)(跳虫),如棘跳属(Onychiurus),
本发明组合物还适用于防治线虫:植物寄生线虫如根结线虫,北方根结线虫(Meloidogyne hapla)、南方根结线虫(Meloidogyne incognita)、爪哇根结线虫(Meloidogyne javanica)和其他根结线虫属(Meloidogyne);形成胞囊的线虫,马铃薯金线虫(Globodera rostochiensis)和其他球胞囊属(Globodera);禾谷胞囊线虫(Heterodera avenae)、大豆胞囊线虫(Heterodera glycines)、甜菜胞囊线虫(Heterodera schachtii)、三叶草胞囊线虫(Heterodera trifolii)和其他胞囊线虫属(Heterodera);种子肿瘿线虫,粒线虫属(Anguina);茎叶线虫,滑刃线虫属(Aphelenchoides);刺线虫,杂草刺线虫(Belonolaimus longicaudatus)和其他针刺线虫属(Belonolaimus);松线虫,松材线虫(Bursaphelenchus xylophilus)和其他伞滑刃线虫属(Bursaphelenchus);环形线虫,环纹线虫属(Criconema)、小环线虫属(Criconemella)、轮线虫属(Criconemoides)、中环线虫属(Mesocriconema);球茎线虫,腐烂茎线虫(Ditylenchus destructor)、甘薯茎线虫(Ditylenchus dipsaci)和其他茎线虫属(Ditylenchus);锥线虫,锥线虫属(Dolichodorus);螺旋形线虫,Heliocotylenchus multicinctus和其他Helicotylenchus属;鞘线虫和鞘形(sheathoid)线虫,鞘线虫属(Hemicycliophora)和Hemicriconemoides属;Hirshmanniella属;冠线虫,Hoploaimus属;伪根结线虫,珍珠线虫属(Nacobbus);针线虫,Longidoruselongatus和其他长针线虫属(Longidorus);根腐线虫,疏忽短体线虫(Pratylenchus neglectus)、穿刺根腐线虫(Pratylenchus penetrans)、Pratylenchus curvitatus、古迪短体线虫(Pratylenchus goodeyi)和其他根腐线虫属(Pratylenchus);穿孔线虫,香蕉穿孔线虫(Radopholus similis)和其他穿孔线虫属(Radopholus);肾形线虫,Rotylenchus robustus和其他盘旋线虫属(Rotylenchus);Scutellonema属;残根线虫,Trichodorus primitivus和其他毛刺线虫属(Trichodorus)、拟毛刺属(Paratrichodorus);阻长线虫,克莱顿矮化线虫(Tylenchorhynchus claytoni)、不定矮化线虫(Tylenchorhynchus dubius)和其他矮化线虫属(Tylenchorhynchus);柑桔线虫,垫刃线虫属(Tylenchulus);剑线虫,剑线虫属(Xiphinema);以及其他植物寄生线虫属。
本发明组合物也用于防治蛛形纲(Arachnoidea),如蜘蛛(蜱螨目),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)、波斯锐缘蜱(Argas persicus)、牛壁虱(Boophilus annulatus)、Boophilusdecoloratus、微小牛蜱(Boophilus microplus)、Dermacentor silvarum、Hyalomma truncatum、蓖子硬蜱(Ixodes ricinus)、Ixodes rubicundus、Ornithodorus moubata、Otobius megnini、鸡皮刺螨(Dermanyssusgallinae)、绵羊疥病(Psoroptes ovis)、Rhipicephalus appendiculatus、Rhipicephalus evertsi、人疥螨(Sarcoptes scabiei),以及瘿螨科(Eriophyidae),如斯氏刺瘿螨(Aculus schlechtendali)、桔皱叶刺瘿螨(Phyllocoptrata oleivora)和桔芽瘿螨(Eriophyes sheldoni);跗绒螨科(Tarsonemidae),如Phytonemus pallidus和侧多食跗线螨(Polyphagotarsonemus latus);细须螨科(Tenuipalpidae),如紫红短须螨(Brevipalpus phoenicis);叶螨科(Tetranychidae),如朱砂叶螨(Tetranychuscinnabarinus)、神泽叶螨(Tetranychus kanzawai)、太平洋叶螨(Tetranychuspacificus)、棉叶螨(Tetranychus telarius)和二点叶螨(Tetranychus urticae),苹果全爪螨(Panonychus ulmi)、柑桔全爪螨(Panonychus citri)和草地小爪螨(oligonychus pratensis)。
在一个方面,如果种子为稻,则超支化聚合物不为超支化聚乙烯胺、聚酰胺型酰胺、聚乙烯亚胺或聚醚,或其共聚物。
根据本发明,特别有利的是用所要求保护的组合物处理选自玉米、小麦、大麦、燕麦、黑麦、斯佩耳特小麦(spelt)、大豆、油菜或蔬菜种子,特别强调选自玉米、小麦、大麦、大豆或油菜种子。
本发明还提供了通过本文所述方法处理的种子。还提供了可通过本文所述方法得到的种子。
此外,本发明还提供了用本文所述的种子处理组合物处理的种子,尤其是用组合物包衣的种子或含有组合物的种子。还提供了可通过使用本文所述的组合物得到的种子。
根据特定实施方案,用本发明组合物处理的种子的活性成分的负载量为0.1-500g/100kg种子,优选0.5-200g/100kg种子,尤其是0.75-100g/100kg种子。
根据另一特定实施方案,用本发明组合物处理的种子的超支化聚合物的负载量为1-1000g/100kg种子,优选2-500g/100kg种子,尤其是5-250g/100kg种子。
此处,术语“涂有和/或含有”是指活性成分在施用时绝大部分在种子表面上,然而,取决于施用方法或多或少的部分活性成分可穿透入种子中。当(再)种植所述种子时,其可吸收活性成分。
根据一个实施方案,这种包含活性成分的种子具有包衣,其中包衣包含活性成分。根据另一实施方案,这种包含活性成分的种子为其可萌发部分和/或其天然外壳、壳、荚或珠被包含活性成分的种子。活性成分也可同时存在于包衣和种子的可萌发部分和/或其天然外壳、壳、荚和/或珠被中。
优选这类种子包含有效量的活性成分。因此,以此方式包衣、浸渍或包衣并浸渍种子降低了萌发和出苗过程中的害虫损害。
用本发明组合物处理的种子也可用膜外涂层包封以保护活性成分包衣。该外涂层在本领域是已知的且可使用常规流化床和转鼓膜涂覆技术施用。
本发明种子可用于繁殖植物。可将种子储存、处理、种植/播种和耕作。
在本发明上下文中,脂族烃基尤其包括烷基、亚烷基、链烯基和环烷基。芳族烃基尤其包括芳基和亚芳基。芳脂族烃基尤其包括芳烷基。
术语“烷基”包括直链和支化烷基。合适的短链烷基例如为直链或支化的C1-C7烷基,优选C1-C6烷基,特别优选C1-C4烷基。这些尤其包括甲基、乙基、丙基、异丙基、正丁基、2-丁基、仲丁基、叔丁基、正戊基、2-戊基、2-甲基丁基、3-甲基丁基、1,2-二甲基丙基、1,1-二甲基丙基、2,2-二甲基丙基、1-乙基丙基、正己基、2-己基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,2-二甲基丁基、1,3-二甲基丁基、2,3-二甲基丁基、1,1-二甲基丁基、2,2-二甲基丁基、3,3-二甲基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基丁基、2-乙基丁基、1-乙基-2-甲基丙基、正庚基、2-庚基、3-庚基、2-乙基戊基、1-丙基丁基、辛基等。合适的长链C8-C30烃基为直链和支化烷基或链烯基。就此而言,它们优选主要为线性烷基残基,如存在于天然或合成脂肪酸和脂肪醇以及羰基合成醇中的那些,合适的话它们还可以是单-、二-或多不饱和的。这些例如包括正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基、正十七烷基、正十八烷基、正十九烷基等。
表述“亚烷基”在本发明的含义中表示具有1-7个碳原子的直链或支化链烷二基(短链),如亚甲基、1,2-亚乙基、1,3-亚丙基等,或具有8-40个碳原子的直链或支化链烷二基(长链)。
链烯基优选表示具有2-40个碳原子的直链和支化链烯基,其可以是单不饱和、二不饱和或多不饱和的。它们优选为C9-C35,尤其是C10-C30,特别是C12-C26链烯基。这些尤其包括辛烯基、壬烯基、癸烯基、十一碳烯基、十二碳烯基、十三碳烯基、十四碳烯基、十五碳烯基、十六碳烯基、十七碳烯基、十八碳烯基、十九碳烯基、亚油基(linolyl)、亚麻基(linoleyl)、9,11,13-十八碳三烯基等,尤其是油基(9-十八碳烯基)。
环烷基优选表示C3-C12环烷基,例如环丙基、环丁基、环戊基、环己基、环庚基、环辛基、环壬基、环癸基、环十一烷基和环十二烷基;优选环戊基、环己基和环庚基。通常优选C5-C8环烷基,如环戊基、环己基、环庚基或环辛基。
芳基包括通常具有6-14个碳原子的未取代和取代的芳基且优选表示苯基、甲苯基、二甲苯基、2,4,6-三甲苯基、萘基、芴基、蒽基、菲基、并四苯基,尤其是苯基、甲苯基、二甲苯基或2,4,6-三甲苯基。
芳烷基包括与通常具有1-7个碳原子的亚烷基连接的通常具有6-14个碳原子的未取代和取代的芳基。
实施例
本发明通过如下实施例说明,所述实施例不应理解为限制本发明。
参考实施例:制备超支化聚合物
参考实施例1:
碳酸二乙酯和聚氧乙烯三醇的超支化聚碳酸酯,其具有265mg KOH/g的OH值
在配有搅拌器、内部温度计和回流冷凝器的6L烧瓶中,使碳酸二乙酯(1183g,10.0摩尔)与三醇(2700g,10.0摩尔;通过用3单元氧化乙烯将三羟甲基丙烷乙氧基化而制备)在145℃、常压和氮气气氛下在碳酸钾(0.4g)存在下反应。在反应中,乙醇作为缩合副产物恒定地形成,因此在5小时内沸点降低至约100℃。在沸腾温度保持恒定之后,用蒸馏单元代替回流冷凝器,该蒸馏单元包含20cm的填充柱、向下的冷却器和接收器,并且连续蒸除反应过程中形成的乙醇。在除去约810g乙醇(总共)之后(对应于基于乙醇为约88%的转化率),将反应混合物冷却至100℃,并用85%的磷酸将pH值调节至<7,以中和碳酸钾。将混合物在140℃下搅拌1小时。然后将反应装置装配气体进入管并在180℃下将混合物用氮气汽提3小时。以这种方式,除去其他残留乙醇或低分子量化合物(总共约10g)。
随后将产物冷却并分析。OH值为265mg KOH/g。通过GPC(洗脱液=DMAC,校准=PMMA)测定的分子量为Mn=2150g/mol,Mw=7400g/mol。10重量%的产物水溶液的粘度为13mPas(在TA仪器CSL 500 Carri MedRheometer上,用圆锥-板系统在100l/s的剪切速率下测定)。
参考实施例2:
链烯基琥珀酸酐(Pentasize 8)和聚氧乙烯三醇的超支化聚酯,其具有70mg KOH/g的OH值和28mg KOH/g的酸值。
将698g(2摩尔)C18链烯基琥珀酸酐(Pentasize 8,Trigon ChemieGmbH,分子量为349g/mol)、1340g(2.0摩尔)基于聚醚醇的三羟甲基丙烷(统计上接枝有12单元氧化乙烯)和0.1g二月桂酸二丁锡称重入配有搅拌器、内部温度计、具有管式真空连接器的向下的冷却器的4L玻璃烧瓶中,并在搅拌下缓慢加热至180℃。持续施加真空并且装置的内部压力降至至多40毫巴。由于形成的气泡,混合物略微发泡。将反应混合物在180℃和40毫巴下搅拌4小时,并在180℃和20毫巴下再搅拌2小时,同时连续蒸除反应过程中形成水。
周期性地检测酸值的降低,直到酸值低于30mg KOH/g。随后,将产物冷却并分析。
OH值为70mg KOH/g,酸值为28mg KOH/g。通过GPC(洗脱液=DMAC,校准=PMMA)测定的分子量为Mn=3400g/mol,Mw=21000g/mol。10重量%的产物水溶液的粘度为216mPas(在TA仪器CSL 500Carri MedRheometer上,用圆锥-板系统在100l/s的剪切速率下测定)。
参考实施例3:
碳酸二乙酯和聚氧乙烯三醇的超支化聚碳酸酯,其具有150mg KOH/g的OH值
在配有搅拌器、内部温度计和回流冷凝器的6L烧瓶中,使碳酸二乙酯(590.7g,5.0摩尔)与聚氧乙烯三醇(3350g,5.0摩尔;通过用12单元氧化乙烯将三羟甲基丙烷乙氧基化而制备)在145℃、常压和氮气气氛下在碳酸钾(0.5g)存在下反应。在反应中,乙醇作为缩合副产物恒定地形成,因此在6小时内沸点降低至约120℃。在沸腾温度保持恒定之后,用蒸馏单元代替回流冷凝器,该蒸馏单元包含20cm的填充柱、向下的冷却器和接收器,并且连续蒸除反应过程中形成的乙醇。在除去约405g乙醇(总共)之后(对应于基于乙醇为约88%的转化率),将反应混合物冷却至100℃,并用85%的磷酸(约1.2g)将pH值调节至<7,以中和碳酸钾。将混合物在140℃下搅拌1小时。然后将反应装置装配气体进入管并在180℃下将混合物用氮气汽提3小时。以这种方式,除去其他残留乙醇或低分子量化合物(总共约10g)。
随后将产物冷却并分析。OH值为150mg KOH/g。通过GPC(洗脱液=DMAC,校准=PMMA)测定的分子量为Mn=2750g/mol,Mw=5700g/mol。10重量%的产物水溶液的粘度为2mPas(在TA仪器CSL 500 Carri MedRheometer上,用圆锥-板系统在100l/s的剪切速率下测定)。
实施例1-3:种子处理组合物
即用处理浆料通过将如下所示的所有成分混合而制备
1 | 2 | 3 | 对照 | |
REGENT 500 FS | 40g | 40g | 40g | 40g |
参考实施例1的聚合物 | 10g | |||
参考实施例2的聚合物 | 10g | |||
参考实施例3的聚合物 | 10g | |||
水 | 50g | 50g | 50g | 60g |
1 | 2 | 3 | 对照 | |
活性成分的损失 | 16 | 19 | 18 | 41 |
流动性 | 24.0 | 23 | 19.5 | 20.5 |
REGENT 500 FS为购至BASF的市售种子处理产品,其含有500g/L的杀虫剂锐劲特。
通过向购至SATEC的微型Rotostat分批处理器中的2kg未处理玉米施用10g浆料而用该浆料进行种子处理实验。以2kg玉米流动通过具有如下尺寸的振动的金属漏斗所需时间来测定处理的玉米的流动性:290mm(直径)、30mm(出口)、290mm(长度)。
通过在相同的Rotostat中以“模拟”处理将处理的种子剪切30秒并测定剪切前后的锐劲特负载量而测定处理之后24小时的与种子的粘合。活性成分的损失测定为这两个值之间的差。
Claims (25)
1.一种包含活性成分和超支化聚合物的种子处理组合物。
2.根据权利要求1的组合物,其中所述超支化聚合物的支化度(DB)为20-99%。
3.根据权利要求1或2的组合物,其中所述超支化聚合物的重均分子量超过1000g/mol。
4.根据权利要求1-3中任一项的组合物,其中所述超支化聚合物的玻璃化转变温度为-80℃至50℃。
5.根据权利要求1-4中任一项的组合物,其中所述超支化聚合物可溶于水或可分散于水中。
6.根据权利要求1-5中任一项的组合物,其中所述超支化聚合物的10重量%水溶液的粘度低于1000mPas。
7.根据权利要求1-6中任一项的组合物,其中所述超支化聚合物选自超支化聚碳酸酯、超支化聚酯、超支化聚醚、超支化聚酯碳酸酯、超支化聚醚碳酸酯、超支化聚醚酯、超支化聚醚酯碳酸酯、超支化聚氨酯、超支化聚脲、超支化聚酰胺、超支化聚胺、超支化聚脲聚氨酯、超支化聚酯酰胺、超支化聚酯胺和超支化聚醚胺。
8.根据权利要求7的组合物,其中所述超支化聚合物选自超支化聚碳酸酯、超支化聚酯、超支化聚酯碳酸酯、超支化聚醚碳酸酯、超支化聚醚酯、超支化聚醚酯碳酸酯、超支化聚氨酯、超支化聚脲、超支化聚脲聚氨酯、超支化聚酯酰胺和超支化聚酯胺。
9.根据权利要求7的组合物,其中所述超支化聚合物选自超支化聚碳酸酯、超支化聚酯、超支化聚醚碳酸酯、超支化聚醚酯、超支化聚酯碳酸酯和超支化聚醚酯碳酸酯。
10.根据权利要求1-9中任一项的组合物,其中所述超支化聚合物包含疏水结构部分。
11.根据权利要求1-10中任一项的组合物,其包含至少1重量%,优选至少2重量%,尤其是至少5重量%超支化聚合物。
12.根据权利要求1-11中任一项的组合物,其包含至多50重量%,优选至多30重量%,尤其是至多20重量%超支化聚合物。
13.根据权利要求1-12中任一项的组合物,其进一步包含固体基质材料。
14.根据权利要求1-13中任一项的组合物,其进一步包含穿透提高剂。
15.根据权利要求1-14中任一项的组合物,其进一步包含着色剂。
16.根据权利要求1-15中任一项的组合物,其进一步包含防冻剂。
17.根据权利要求1-16中任一项的组合物,其进一步包含胶凝剂。
18.根据权利要求1-17中任一项的组合物,其进一步包含水。
19.根据权利要求18的组合物,其包含至少5重量%,优选至少10重量%,尤其是至少30重量%水。
20.根据权利要求18或19的组合物,其包含至多99重量%,优选至多90重量%,尤其是至多80重量%水。
21.超支化聚合物作为种子包衣剂的用途。
22.根据权利要求21的用途,其中所述超支化聚合物如权利要求1-20中任一项所定义。
23.一种处理种子的方法,其包括向一批种子施用有效量的根据权利要求1-20中任一项的组合物。
24.根据权利要求23的方法,其中在施用有效量的组合物之前所述种子为基本干燥的。
25.根据权利要求23或24的方法,其中所述种子为玉米、小麦、大麦、燕麦、黑麦、斯佩耳特小麦、蔬菜、大豆或油菜种子。
Applications Claiming Priority (3)
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EP07114464.6 | 2007-08-16 | ||
EP07114464 | 2007-08-16 | ||
PCT/EP2008/060673 WO2009021986A1 (en) | 2007-08-16 | 2008-08-14 | Seed treatment compositions and methods |
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US (1) | US20110105333A1 (zh) |
EP (1) | EP2175709B1 (zh) |
CN (1) | CN101835372A (zh) |
AR (1) | AR068195A1 (zh) |
AU (1) | AU2008288386B2 (zh) |
BR (1) | BRPI0815153A2 (zh) |
CA (1) | CA2695553A1 (zh) |
ES (1) | ES2423755T3 (zh) |
MX (1) | MX2010001460A (zh) |
PL (1) | PL2175709T3 (zh) |
RU (1) | RU2517857C2 (zh) |
UA (1) | UA100526C2 (zh) |
WO (1) | WO2009021986A1 (zh) |
ZA (1) | ZA201001811B (zh) |
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- 2008-08-14 CA CA2695553A patent/CA2695553A1/en not_active Abandoned
- 2008-08-14 WO PCT/EP2008/060673 patent/WO2009021986A1/en active Application Filing
- 2008-08-14 AU AU2008288386A patent/AU2008288386B2/en not_active Ceased
- 2008-08-14 EP EP08803030.9A patent/EP2175709B1/en not_active Not-in-force
- 2008-08-14 CN CN200880102823A patent/CN101835372A/zh active Pending
- 2008-08-14 ES ES08803030T patent/ES2423755T3/es active Active
- 2008-08-14 RU RU2010109451/13A patent/RU2517857C2/ru not_active IP Right Cessation
- 2008-08-14 PL PL08803030T patent/PL2175709T3/pl unknown
- 2008-08-14 UA UAA201002971A patent/UA100526C2/ru unknown
- 2008-08-14 MX MX2010001460A patent/MX2010001460A/es active IP Right Grant
- 2008-08-14 BR BRPI0815153-9A patent/BRPI0815153A2/pt not_active IP Right Cessation
- 2008-08-15 AR ARP080103598A patent/AR068195A1/es unknown
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CN103875492A (zh) * | 2014-04-09 | 2014-06-25 | 象州县科学技术局 | 一种有机糯米种植方法 |
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CN116970062B (zh) * | 2022-04-29 | 2024-04-09 | 南京知和医药科技有限公司 | 一种超长效glp-1多肽衍生物及其制备方法和用途 |
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Also Published As
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US20110105333A1 (en) | 2011-05-05 |
AU2008288386A1 (en) | 2009-02-19 |
CA2695553A1 (en) | 2009-02-19 |
AR068195A1 (es) | 2009-11-11 |
WO2009021986A8 (en) | 2010-09-02 |
UA100526C2 (ru) | 2013-01-10 |
WO2009021986A1 (en) | 2009-02-19 |
MX2010001460A (es) | 2010-03-01 |
EP2175709A1 (en) | 2010-04-21 |
RU2010109451A (ru) | 2011-09-27 |
RU2517857C2 (ru) | 2014-06-10 |
PL2175709T3 (pl) | 2013-11-29 |
ES2423755T3 (es) | 2013-09-24 |
ZA201001811B (en) | 2011-05-25 |
AU2008288386B2 (en) | 2013-08-29 |
BRPI0815153A2 (pt) | 2014-09-23 |
EP2175709B1 (en) | 2013-06-19 |
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