CN103561571B - 作为农化配制剂用分散剂的n-乙烯基羧酰胺和二烯丙基二烷基铵盐的共聚物 - Google Patents
作为农化配制剂用分散剂的n-乙烯基羧酰胺和二烯丙基二烷基铵盐的共聚物 Download PDFInfo
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- CN103561571B CN103561571B CN201280025215.8A CN201280025215A CN103561571B CN 103561571 B CN103561571 B CN 103561571B CN 201280025215 A CN201280025215 A CN 201280025215A CN 103561571 B CN103561571 B CN 103561571B
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- KVWOTUDBCFBGFJ-UHFFFAOYSA-N tert-butyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC(C)(C)C KVWOTUDBCFBGFJ-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LITQZINTSYBKIU-UHFFFAOYSA-F tetracopper;hexahydroxide;sulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-]S([O-])(=O)=O LITQZINTSYBKIU-UHFFFAOYSA-F 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 1
- DNVLJEWNNDHELH-UHFFFAOYSA-N thiocyclam Chemical compound CN(C)C1CSSSC1 DNVLJEWNNDHELH-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- OBZIQQJJIKNWNO-UHFFFAOYSA-N tolclofos-methyl Chemical compound COP(=S)(OC)OC1=C(Cl)C=C(C)C=C1Cl OBZIQQJJIKNWNO-UHFFFAOYSA-N 0.000 description 1
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- PPEZWDDRWXDXOQ-UHFFFAOYSA-N tributoxy(sulfanylidene)-$l^{5}-phosphane Chemical class CCCCOP(=S)(OCCCC)OCCCC PPEZWDDRWXDXOQ-UHFFFAOYSA-N 0.000 description 1
- ONCZDRURRATYFI-TVJDWZFNSA-N trifloxystrobin Chemical compound CO\N=C(\C(=O)OC)C1=CC=CC=C1CO\N=C(/C)C1=CC=CC(C(F)(F)F)=C1 ONCZDRURRATYFI-TVJDWZFNSA-N 0.000 description 1
- HSMVPDGQOIQYSR-KGENOOAVSA-N triflumizole Chemical compound C1=CN=CN1C(/COCCC)=N/C1=CC=C(Cl)C=C1C(F)(F)F HSMVPDGQOIQYSR-KGENOOAVSA-N 0.000 description 1
- XAIPTRIXGHTTNT-UHFFFAOYSA-N triflumuron Chemical compound C1=CC(OC(F)(F)F)=CC=C1NC(=O)NC(=O)C1=CC=CC=C1Cl XAIPTRIXGHTTNT-UHFFFAOYSA-N 0.000 description 1
- AKTQJCBOGPBERP-UHFFFAOYSA-N triflusulfuron Chemical compound FC(F)(F)COC1=NC(N(C)C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2C)C(O)=O)=N1 AKTQJCBOGPBERP-UHFFFAOYSA-N 0.000 description 1
- IMEVJVISCHQJRM-UHFFFAOYSA-N triflusulfuron-methyl Chemical group COC(=O)C1=CC=CC(C)=C1S(=O)(=O)NC(=O)NC1=NC(OCC(F)(F)F)=NC(N(C)C)=N1 IMEVJVISCHQJRM-UHFFFAOYSA-N 0.000 description 1
- NRZWQKGABZFFKE-UHFFFAOYSA-N trimethylsulfonium Chemical class C[S+](C)C NRZWQKGABZFFKE-UHFFFAOYSA-N 0.000 description 1
- RVKCCVTVZORVGD-UHFFFAOYSA-N trinexapac-ethyl Chemical group O=C1CC(C(=O)OCC)CC(=O)C1=C(O)C1CC1 RVKCCVTVZORVGD-UHFFFAOYSA-N 0.000 description 1
- SBXWFLISHPUINY-UHFFFAOYSA-N triphenyltin Chemical class C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 SBXWFLISHPUINY-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- JARYYMUOCXVXNK-IMTORBKUSA-N validamycin Chemical compound N([C@H]1C[C@@H]([C@H]([C@H](O)[C@H]1O)O[C@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)CO)[C@H]1C=C(CO)[C@H](O)[C@H](O)[C@H]1O JARYYMUOCXVXNK-IMTORBKUSA-N 0.000 description 1
- DBXFMOWZRXXBRN-LWKPJOBUSA-N valifenalate Chemical compound CC(C)OC(=O)N[C@@H](C(C)C)C(=O)NC(CC(=O)OC)C1=CC=C(Cl)C=C1 DBXFMOWZRXXBRN-LWKPJOBUSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000005943 zeta-Cypermethrin Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
- AMHNZOICSMBGDH-UHFFFAOYSA-L zineb Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
Abstract
本发明涉及一种包含农化活性物质和包含掺入聚合物中的N-乙烯基羧酰胺和二烯丙基二烷基铵盐的共聚物的组合物。此外,本发明涉及一种制备该组合物的方法;该组合物在分散农化活性物质中的用途;一种防治植物病原性真菌和/或不希望的植物生长和/或不希望的昆虫或螨虫侵袭和/或调节植物生长的方法,其中使该组合物作用于相应有害物、其环境或待防止相应有害物的作物植物、土壤和/或不希望的植物和/或作物植物和/或其环境;此外,涉及包含该组合物的种子。
Description
本发明涉及一种包含农化活性物质和包含掺入聚合物中的N-乙烯基羧酰胺和二烯丙基二烷基铵盐的共聚物的组合物。此外,本发明涉及一种制备该组合物的方法;该组合物在分散农化活性物质中的用途;一种防治植物病原性真菌和/或不希望的植物生长和/或不希望的昆虫或螨虫侵袭和/或调节植物生长的方法,其中使该组合物作用于相应有害物、其环境或待防止相应有害物的植物、土壤和/或不希望的植物和/或作物植物和/或其环境;此外,涉及包含该组合物的种子。本发明包括优选特征与其他优选特征的组合。
已知宽范围的聚合物作为农业配制剂用助剂:
EP0808568公开了一种掺有农药和水溶性聚合物的多层嵌入体系。合适的为聚季铵盐-6、聚(二烯丙基二甲基氯化铵)。
US2004/0170657公开了一种水性乳液,其中水相包含作物保护剂的盐和两亲嵌段聚合物。嵌段聚合物的亲水嵌段可包含二烯丙基二烷基铵盐。
现有技术的缺点尤其在于不能实现配制剂的高储存稳定性;不能减缓或抑制经分散的农化活性物质的粒度生长;不能减缓或抑制经分散的农化活性物质的附聚;不能减缓或抑制经分散的农化活性物质的沉降;且上述缺点本身尤其在高盐浓度存在下表现出来。因此,目的为克服这些缺点。
该目的通过包含农化活性物质和包含掺入聚合物中的N-乙烯基羧酰胺和二烯丙基二烷基铵盐的共聚物的组合物实现。
该共聚物优选为无规共聚物。术语“无规”通常意指掺入所得聚合物中的至少两种不同单体是无规分布的。该无规共聚物通常为自由基聚合物,换句话说,由单体通过自由基聚合制备的聚合物。
优选的二烯丙基二烷基铵盐符合式(I):
其中R1和R2相互独立地为氢或C1-C4烷基;R3和R4相互独立地为具有1-18个碳原子的烷基、羟基烷基、羧基烷基、羧基酰氨基烷基或烷氧基烷基;和Y为阴离子。优选R1和R2相互独立地为氢或甲基,更特别是氢。优选R3和R4相互独立地为C1-C18烷基,更优选C1-C6烷基,更特别是甲基。Y优选为卤离子(如氯离子、溴离子)、硫酸根或磷酸根。
特别优选的二烯丙基二烷基铵盐为二烯丙基二甲基氯化铵(DADMAC)、二烯丙基二甲基溴化铵、二烯丙基二甲基硫酸铵、二烯丙基二甲基磷酸铵、二甲代烯丙基二甲基氯化铵、二乙代烯丙基二甲基氯化铵、二烯丙基二(β-羟基乙基)氯化铵和二烯丙基二(β-乙氧基乙基)氯化铵及其混合物。尤其优选的二烯丙基二烷基铵盐为DADMAC。
该共聚物可含有至多90重量%,优选至多60重量%,更优选至多40重量%二烯丙基二烷基铵盐。该共聚物可包含至少1重量%,优选至少5重量%,更优选至少15重量%二烯丙基二烷基铵盐。该共聚物可包含1-70重量%,优选5-50重量%,更优选10-30重量%二烯丙基二烷基铵盐。这里,以重量%计的数值在每种情况下基于共聚单体的总量。
优选的N-乙烯基羧酰胺为N-乙烯基-C1-C18烷基羧酰胺和/或N-乙烯基-N-(C1-C12烷基)-C1-C18烷基羧酰胺。特别优选的N-乙烯基羧酰胺为N-乙烯基-C1-C4烷基羧酰胺和N-乙烯基-N-(C1-C4烷基)-C1-C4烷基羧酰胺,其中更适合的为N-乙烯基-C1-C4烷基羧酰胺。
特别好的N-乙烯基羧酰胺为N-乙烯基-N-甲基甲酰胺、N-乙烯基甲酰胺、N-乙烯基-N-乙基甲酰胺、N-乙烯基-N-丙基甲酰胺、N-乙烯基-N-异丙基甲酰胺、N-乙烯基-N-异丁基甲酰胺、N-乙烯基乙酰胺、N-乙烯基-N-甲基乙酰胺、N-乙烯基丙酰胺或N-乙烯基-N-甲基丙酰胺及其混合物。最适合的N-乙烯基羧酰胺为N-乙烯基甲酰胺。
该共聚物可包含至多95重量%,优选至多90重量%N-乙烯基羧酰胺。该共聚物可包含至少5重量%,优选至少20重量%,更优选至少30重量%,尤其是至少50重量%N-乙烯基羧酰胺。该共聚物可包含20-95重量%,优选40-95重量%,更优选60-95重量%N-乙烯基羧酰胺。这里,以重量%计的数值在每种情况下基于共聚单体的总量。
在一个特别优选的形式中,该共聚物(优选呈无规形式)以共聚形式包含N-乙烯基-C1-C4烷基羧酰胺和式(I)的二烯丙基二烷基铵盐,其中R1和R2为氢。以举例方式提出式(II)的共聚物,
其中R3和R4相互独立地为C1-C18烷基,更优选C1-C6烷基,更特别是甲基;和R5为H或C1-C6烷基或C1-C6烷氧基,优选H或C1-C6烷基,更特别是H。
在一个尤其优选的形式中,该共聚物(优选呈无规形式)以共聚形式包含N-乙烯基-C1-C4烷基羧酰胺和式(I)的二烯丙基二烷基铵盐,其中R1和R2为氢。
该共聚物可总共包含至多100重量%,优选至多90重量%,更优选至多80重量%二烯丙基二烷基铵盐和N-乙烯基羧酰胺。该共聚物可总共包含至少30重量%,优选至少60重量%,更优选至少90重量%二烯丙基二烷基铵盐和N-乙烯基羧酰胺。这里,以重量%计的数值在每种情况下基于共聚单体的总量。
该共聚物可包含呈共聚形式的其他单体。可能存在的其他单体例如为乙烯基芳族单体如苯乙烯和苯乙烯衍生物,如α-甲基苯乙烯,乙烯基甲苯,邻-、间-和对甲基苯乙烯,乙基乙烯基苯,乙烯基萘,乙烯基二甲苯和相应卤化乙烯基芳族单体,带有硝基、烷氧基、卤代烷基、羧烷氧基、羧基、氨基和烷基氨基的乙烯基芳族单体,α-烯烃,例如乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、异丁烯、长链(C10-C20)烷基-α-烯烃,二烯如丁二烯和异戊二烯,乙烯基醇酯如乙酸乙烯基酯,乙烯基卤如乙烯基氯、乙烯基溴、乙烯基氟、偏二氯乙烯、偏二氟乙烯、偏二溴乙烯,乙烯基腈,乙烯基羧基化物,1-乙烯基酰胺如1-乙烯基吡咯烷酮、1-乙烯基哌啶酮,1-乙烯基己内酰胺、N-乙烯基咪唑,单烯属不饱和单体如丙烯酸、甲基丙烯酸、富马酸、马来酸和衣康酸、乙烯基磺酸的C1-C24烷基酯以及单取代和二取代和未取代的C1-C24烷基酰胺,酐如马来酸酐,不饱和醛如丙烯醛,不饱和醚如1,4-环己烷二甲醇二乙烯基醚、1,4-环己烷二甲醇单乙烯基醚、丁二醇二乙烯基醚、丁二醇单乙烯基醚、环己基乙烯基醚、二甘醇二乙烯基醚、乙二醇单乙烯基醚、乙基乙烯基醚、甲基乙烯基醚、正丁基乙烯基醚、十八烷基乙烯基醚、三甘醇乙烯基甲基醚、乙烯基异丁基醚、乙烯基2-乙基己基醚、乙烯基丙基醚、乙烯基异丙基醚、乙烯基十二烷基醚、乙烯基叔丁基醚、己二醇二乙烯基醚、己二醇单乙烯基醚、二甘醇单乙烯基醚、二乙基氨基乙基乙烯基醚、聚四氢呋喃-290二乙烯基醚、四甘醇二乙烯基醚、三烯丙基胺、乙二醇丁基乙烯基醚、乙二醇二乙烯基醚、三甘醇二乙烯基醚、三羟甲基丙烷三乙烯基醚、氨基丙基乙烯基醚。优选的其他单体为具有至少两个烯属不饱和双键的那些如三烯丙基胺。
在另一形式中,其他单体基本不含(例如含有至多5wt%,优选至多1wt%)烯属不饱和羧酸的酯,其中该羧酸酯显现出通式(A)的烷氧基化物残基:
(Ra)n-X-(CHRbCH2O)w-(CHRcCH2O)x-(CHRd(CH2)yO)z-(A),其中Ra为氢或具有3-40碳原子的脂族烃残基;Rb、Rc、Rd相互独立地为氢或C1-4烷基;w、x、z相互独立地对应于0-100的值,w、x和z的总和大于0;y对应于1-20的值;X为N或O,n为1且如果X为O,则Ra不为氢;或如果X为N,则n为2。
以共聚形式包含N-乙烯基羧酰胺和二烯丙基二烷基铵盐的共聚物及其制备为公知常识,例如由Tanaka等,J.Appl.PolymerSci.2007,104,1068-1075,WO2004/058831或EP1059316已知。
共聚物通常以常见方式借助自由基聚合合成。然而,还可使用其他聚合方法,例如受控自由基方法。聚合在单体和一种或多种引发剂存在下进行并且可以以溶剂或无溶剂在乳液或悬浮液中进行。聚合物可以以分批反应、半连续操作或连续操作进行。反应时间通常为1-12小时。反应可以在其下进行的温度范围通常为20-200℃,优选40-120℃。
可用于自由基聚合的引发剂为常规自由基形成物质。引发剂优选选自偶氮化合物、过氧化物化合物或过氧化氢化合物。可以提及的实例为过氧化乙酰基、过氧化苯甲酰基、过氧化月桂酰基、过氧异丁酸叔丁基酯、过氧化己酰基、氢过氧化枯烯、偶氮双异丁腈或2,2-偶氮二(2-甲基丁烷)腈。特别优选偶氮双异丁腈(AIBN)。
自由基聚合优选在溶液中进行。溶剂为水,醇如甲醇、乙醇、丙醇、双极性-非极性溶剂如DMF、DMSO或NMP,芳族烃,脂族烃,卤代烃或非卤代烃如己烷、氯苯、甲苯或苯。优选的溶剂为水、异丙醇、甲醇、甲苯、DMF、NMP、DMSO和己烷。
共聚物的摩尔质量Mw通常为500-250000g/mol,优选5000-250000g/mol,尤其优选20000-220000g/mol,尤其是60000-200000g/mol。聚合物的摩尔质量Mw和Mn以及多分散性由尺寸排阻色谱测定。市售PMMA标样单元可用作校对材料。
该共聚物通常可溶于水中,例如在20℃下以至少5g/l(优选至少20g/l,尤其是至少50g/l)溶于水中。三聚物优选以溶解形式存在于本发明组合物中。
本发明组合物通常包含至少0.1重量%,优选至少1重量%,尤其是至少2重量%共聚物。本发明组合物通常包含0.1-25重量%,优选0.5-15重量%,尤其是1-10重量%共聚物。
合适的农化活性物质为农药和无机肥料。
术语农药涉及至少一种选自杀真菌剂、杀虫剂、杀线虫剂、除草剂、安全剂和/或生长调节剂的活性物质。优选的农药是杀真菌剂、杀虫剂、除草剂和生长调节剂。尤其优选的农药是除草剂。还可以使用上述类别中两种或更多种农药的混合物。熟练技术人员熟知该类农药,它们例如可以在PesticideManual,第15版(2009),TheBritishCropProtectionCouncil,London中找到。例如下列农药是合适的(农药A)-K)组为杀真菌剂):
A)呼吸抑制剂
-Qo位点的配合物III抑制剂(例如嗜球果伞素类):腈嘧菌酯(azoxystrobin)、甲香菌酯(coumethoxystrobin)、丁香菌酯(coumoxystrobin)、醚菌胺(dimoxystrobin)、烯肟菌酯(enestroburin)、烯肟菌胺(fenaminstrobin)、fenoxystrobin/氟菌螨酯(flufenoxystrobin)、氟嘧菌酯(fluoxastrobin)、亚胺菌(kresoxim-methyl)、叉氨苯酰胺(metominostrobin)、肟醚菌胺(orysastrobin)、啶氧菌酯(picoxystrobin)、唑菌胺酯(pyraclostrobin)、pyrametostrobin、唑菌酯(pyraoxystrobin)、肟菌酯(trifloxystrobin)、2-[2-(2,5-二甲基苯氧基甲基)苯基]-3-甲氧基丙烯酸甲酯、2-(2-(3-(2,6-二氯苯基)-1-甲基亚烯丙基氨基氧甲基)苯基)-2-甲氧亚氨基-N-甲基乙酰胺、pyribencarb、triclopyricarb/chlorodincarb、唑酮菌(famoxadon)、咪唑菌酮(fenamidon);
-Qi位点的配合物III抑制剂:氰霜唑(cyazofamid)、amisulbrom;
-配合物II抑制剂(例如羧酰胺类):麦锈灵(benodanil)、bixafen、啶酰菌胺(boscalid)、萎锈灵(carboxin)、呋菌胺(fenfuram)、氟吡菌酰胺(fluopyram)、氟酰胺(flutolanil)、氟唑菌酰胺(fluxapyroxad)、呋吡唑灵(furametpyr)、isopyrazam、丙氧灭绣胺(mepronil)、氧化萎锈灵(oxycarboxin)、penflufen、吡噻菌胺(penthiopyrad)、sedaxane、叶枯酞(tecloftalam)、溴氟唑菌(thifluzamide)、N-(4′-三氟甲硫基联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺,N-(2-(1,3,3-三甲基丁基)苯基)-1,3-二甲基-5-氟-1H-吡唑-4-甲酰胺和N-[9-(二氯亚甲基)-1,2,3,4-四氢-1,4-亚甲基萘-5-基]-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺;
-其他呼吸抑制剂(例如配合物I,去偶剂):二氟林(diflumetorim);硝基苯基衍生物:乐杀螨(binapacryl)、敌螨通(dinobuton)、敌螨普(dinocap)、氟啶胺(fluazinam);嘧菌腙(ferimzone);有机金属化合物:三苯锡基盐,例如薯瘟锡(fentin-acetate)、三苯锡氯(fentinchloride)或毒菌锡(fentinhydroxide);ametoctradin和硅噻菌胺(silthiofam);
B)甾醇生物合成抑制剂(SBI杀真菌剂)
-C14脱甲基酶抑制剂(DMI杀真菌剂):
-三唑类:戊环唑(azaconazole)、双苯三唑醇(bitertanol)、糠菌唑(bromuconazole)、环唑醇(cyproconazole)、醚唑(difenoconazole)、烯唑醇(diniconazole)、精烯唑醇(diniconazole-M)、氧唑菌(epoxiconazole)、腈苯唑(fenbuconazole)、喹唑菌酮(fluquinconazole)、氟硅唑(flusilazole)、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)、oxpoconazole、多效唑(paclobutrazole)、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)、三唑酮(triadimefon)、唑菌醇(triadimenol)、戊叉唑菌(triticonazole)、烯效唑(uniconazole);咪唑类:烯菌灵(imazalil)、稻瘟酯(pefurazoate)、丙氯灵(prochloraz)、氟菌唑(triflumizol);嘧啶类、吡啶类和哌嗪类:异嘧菌醇(fenarimol)、氟苯嘧啶醇(nuarimol)、啶斑肟(pyrifenox)、嗪氨灵(triforine);
-δ14-还原酶抑制剂:4-十二烷基-2,6-二甲基吗啉(aldimorph)、吗菌灵(dodemorph)、吗菌灵乙酸酯(dodemorphacetate)、丁苯吗啉(fenpropimorph)、克啉菌(tridemorph)、苯锈啶(fenpropidin)、粉病灵(piperalin)、螺茂胺(spiroxamine);
-3-酮基还原酶抑制剂:环酰菌胺(fenhexamid);
C)核酸合成抑制剂
-苯基酰胺类或酰基氨基酸类杀真菌剂:苯霜灵(benalaxyl)、精苯霜灵(benalaxyl-M)、kiralaxyl、甲霜灵(metalaxyl)、精甲霜灵(metalaxyl-M)(mefenoxam)、甲呋酰胺(ofurace)、霜灵(oxadixyl);
-其他:土菌消(hymexazole)、异噻菌酮(octhilinone)、恶喹酸(oxolinicacid)、磺嘧菌灵(bupirimate);
D)细胞分裂和细胞骨架抑制剂
-微管蛋白抑制剂,如苯并咪唑类、托布津类(thiophanate):苯菌灵(benomyl)、多菌灵(carbendazim)、麦穗宁(fuberidazole)、涕必灵(thiabendazole)、甲基托布津(thiophanate-methyl);三唑并嘧啶类: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;
-其他细胞分裂抑制剂:乙霉威(diethofencarb)、噻唑菌胺(ethaboxam)、戊菌隆(pencycuron)、氟吡菌胺(fluopicolid)、苯酰菌胺(zoxamid)、苯菌酮(metrafenon)、pyriofenon;
E)氨基酸合成和蛋白质合成抑制剂
-蛋氨酸合成抑制剂(苯胺基嘧啶类):环丙嘧啶(cyprodinil)、嘧菌胺(mepanipyrim)、二甲嘧菌胺(pyrimethanil);
-蛋白质合成抑制剂:灭瘟素(blasticidin-S)、春雷素(kasugamycin)、水合春雷素(kasugamycinhydrochloridehydrate)、米多霉素(mildiomycin)、链霉素(streptomycin)、土霉素(oxytetracyclin)、多氧霉素(polyoxin)、井冈霉素(validamycinA);
F)信号转导抑制剂
-MAP/组氨酸蛋白激酶抑制剂:氟菌安(fluoroimide)、异丙定(iprodione)、杀菌利(procymidone)、烯菌酮(vinclozolin)、拌种咯(fenpiclonil)、氟菌(fludioxonil);
-G蛋白抑制剂:喹氧灵(quinoxyfen);
G)类脂和膜合成抑制剂
-磷脂生物合成抑制剂:克瘟散(edifenphos)、异稻瘟净(iprobenfos)、定菌磷(pyrazophos)、稻瘟灵(isoprothiolane);
-类脂过氧化:氯硝胺(dicloran)、五氯硝基苯(quintozene)、四氯硝基苯(tecnazene)、甲基立枯磷(tolclofos-methyl)、联苯、地茂散(chloroneb)、氯唑灵(etridiazole);
-磷脂生物合成和细胞壁附着:烯酰吗啉(dimethomorph)、氟吗啉(flumorph)、双炔酰菌胺(mandiproamid)、丁吡吗啉(pyrimorph)、苯噻菌胺(benthiavalicarb)、异丙菌胺(iprovalicarb)、valifenalate和N-(1-(1-(4-氰基苯基)乙磺酰基)丁-2-基)氨基甲酸4-氟苯基酯;
-影响细胞膜渗透性的化合物和脂肪酸:百维灵(propamocarb)、霜霉威盐酸盐(propamocarbhydrochloride);
H)“多位点”抑制剂
-无机活性物质:波尔多液(Bordeaux混合物)、醋酸铜、氢氧化铜、王铜(copperoxychloride)、碱式硫酸铜、硫;
-硫代-和二硫代氨基甲酸酯类:福美铁(ferbam)、代森锰锌(mancozeb)、代森锰(maneb)、威百亩(metam)、代森联(metiram)、甲基代森锌(propineb)、福美双(thiram)、代森锌(zineb)、福美锌(ziram);
-有机氯化合物(例如邻苯二甲酰亚胺类、硫酰胺类、氯代腈类):敌菌灵(anilazine)、百菌清(chlorothalonil)、敌菌丹(captafol)、克菌丹(captan)、灭菌丹(folpet)、抑菌灵(dichlofluanid)、双氯酚(dichlorophen)、磺菌胺(flusulfamide)、六氯苯(hexachlorobenzene)、五氯酚(pentachlorphenol)及其盐、四氯苯酞(phthalid)、对甲抑菌灵(tolylfluanid)、N-(4-氯-2-硝基苯基)-N-乙基-4-甲基苯磺酰胺;
-胍类及其他:胍、多果定(dodine)、多果定游离碱、双胍盐(guazatin)、双胍辛胺(guazatinacetate)、双胍辛醋酸盐(iminoctadin)、双胍辛胺三乙酸盐(iminoctadintriacetate)、双八胍盐(iminoctadintris(albesilate))、二噻农(dithianon);
I)细胞壁生物合成抑制剂
-葡聚糖合成抑制剂:井冈霉素(validamycin)、多氧霉素(polyoxinB);黑素合成抑制剂:咯喹酮(pyroquilon)、三环唑(tricyclazole)、氯环丙酰胺(carpropamid)、双氯氰菌胺(dicyclomet)、氰菌胺(fenoxanil);
J)抵抗力诱发剂(resistenceinductor)
-噻二唑素(acibenzolar-S-methyl)、噻菌灵(probenazol)、异噻菌胺(isotianil)、噻酰菌胺(tiadinil)、调环酸钙(prohexadione-calcium);膦酸酯类:藻菌磷(fosetyl)、乙磷铝(fosetyl-aluminum)、亚磷酸及其盐;
K)未知作用模式
-拌棉醇(bronopol)、灭螨蜢(quinomethionate)、环氟菌胺(cyflufenamid)、清菌脲(cymoxanil)、棉隆(dazomet)、咪菌威(debacarb)、哒菌清(diclomezin)、野燕枯(difenzoquat)、野燕枯甲基硫酸酯(difenzoquat-methylsulfate)、二苯胺、胺苯吡菌酮(fenpyrazamine)、氟联苯菌(flumetover)、磺菌胺(flusulfamid)、flutianil、磺菌威(methasulfocarb)、氯定(nitrapyrin)、异丙消(nitrothal-isopropyl)、喹啉铜(oxin-copper)、丙氧喹啉(proquinazid)、tebufloquin、叶枯酞(tecloftalam)、唑菌嗪(triazoxide)、2-丁氧基-6-碘-3-丙基苯并吡喃-4-酮、N-(环丙基甲氧亚氨基-(6-二氟甲氧基-2,3-二氟苯基)甲基)-2-苯基乙酰胺、N′-(4-(4-氯-3-三氟甲基苯氧基)-2,5-二甲基苯基)-N-乙基-N-甲基甲脒、N′-(4-(4-氟-3-三氟甲基苯氧基)-2,5-二甲基苯基)-N-乙基-N-甲基甲脒、N′-(2-甲基-5-三氟甲基-4-(3-三甲基硅烷基丙氧基)苯基)-N-乙基-N-甲基甲脒、N′-(5-二氟甲基-2-甲基-4-(3-三甲基硅烷基丙氧基)苯基)-N-乙基-N-甲基甲脒、2-{1-[2-(5-甲基-3-三氟甲基吡唑-1-基)乙酰基]哌啶-4-基}噻唑-4-甲酸N-甲基-(1,2,3,4-四氢萘-1-基)酯、N-甲基-(R)-1,2,3,4-四氢萘-1-基2-{1-[2-(5-甲基-3-三氟甲基吡唑-1-基)乙酰基]哌啶-4-基}噻唑-4-甲酰胺、1-[4-[4-[5-(2,6-二氟苯基)-4,5-二氢-3-异唑基]-2-噻唑基]-1-哌啶基]-2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酮、甲氧基乙酸6-叔丁基-8-氟-2,3-二甲基喹啉-4-基酯、N-甲基-2-{1-[(5-甲基-3-三氟甲基-1H-吡唑-1-基)乙酰基]哌啶-4-基}-N-[(1R)-1,2,3,4-四氢萘-1-基]-4-噻唑甲酰胺、3-[5-(4-甲基苯基)-2,3-二甲基异唑烷-3-基]吡啶、3-[5-(4-氯苯基)-2,3-二甲基异唑烷-3-基]吡啶(啶菌恶唑(pyrisoxazol))、N-(6-甲氧基吡啶-3-基)环丙烷甲酰胺、5-氯-1-(4,6-二甲氧基嘧啶-2-基)-2-甲基-1H-苯并咪唑、2-(4-氯苯基)-N-[4-(3,4-二甲氧基苯基)异唑-5-基]-2-丙-2炔基氧基乙酰胺;
M)生长调节剂
-脱落酸(abscisicacid)、先甲草胺(amidochlor)、嘧啶醇(ancymidole)、6-苄基氨基嘌呤、油菜素内酯(brassinolide)、地乐胺(butralin)、矮壮素阳离子(chlormequat)(氯化矮壮素(chlormequatchloride))、胆碱盐酸盐(cholinechloride)、环丙酸酰胺(cyclanilid)、丁酰肼(daminozide)、敌草克(dikegulac)、噻节因(dimethipin)、2,6-二甲基吡啶(2,6-dimethylpuridine)、乙烯利(ethephon)、氟节胺(flumetralin)、调嘧醇(flurprimidol)、达草氟(fluthiacet)、调吡脲(forchlorfenuron)、赤霉酸(gibberellicacid)、抗倒胺(inabenfid)、吲哚-3-乙酸、抑芽丹(maleichydrazide)、氟草磺(mefluidid)、助壮素(mepiquat)(氯化助壮素(mepiquatchloride))、环戊唑菌(metconazole)、萘乙酸、N-6-苄基腺嘌呤、多效唑、调环酸(prohexadione)(调环酸钙)、茉莉酸诱导体(prohydrojasmon)、赛二唑素(thidiazuron)、抑芽唑(triapenthenol)、三硫代磷酸三丁酯、2,3,5-三碘苯甲酸、抗倒酯(trinexapac-ethyl)和烯效唑;
N)除草剂
-乙酰胺类:乙草胺(acetochlor)、甲草胺(alachlor)、丁草胺(butachlor)、克草胺(dimethachlor)、噻吩草胺(dimethenamid)、氟噻草胺(flufenacet)、苯噻草胺(mefenacet)、异丙甲草胺(metolachlor)、吡草胺(metazachlor)、草萘胺(napropamid)、萘丙胺(naproanilid)、烯草胺(pethoxamid)、丙草胺(pretilachlor)、扑草胺(propachlor)、噻醚草胺(thenylchlor);
-氨基酸类似物:双丙氨酰膦(bilanafos)、草甘膦(glyphosate)、草铵膦(glufosinate)、草硫膦(sulfosate);
-芳氧基苯氧基丙酸酯类:炔草酯(clodinafop)、氰氟草酯(cyhalofop-butyl)、唑禾草灵(fenoxaprop)、吡氟禾草灵(fluazifop)、吡氟氯禾灵(haloxyfop)、恶唑酰草胺(metamifop)、喔草酯(propaquizafop)、喹禾灵(quizalofop)、精喹禾灵(四氢糠基酯)(quizalofop-p-tefuryl);
-联吡啶类:敌草快阳离子(diquat)、对草快阳离子(paraquat);
-氨基甲酸酯类和硫代氨基甲酸酯类:黄草灵(asulam)、苏达灭(butylate)、长杀草(carbetamide)、异苯敌草(desmedipham)、哌草丹(dimepiperat)、扑草灭(eptam)(EPTC)、禾草畏(esprocarb)、草达灭(molinate)、坪草丹(orbencarb)、苯敌草(phenmedipham)、苄草丹(prosulfocarb)、稗草畏(pyributicarb)、杀草丹(thiobencarb)、野麦畏(triallate);
-环己二酮类:丁氧环酮(butroxydim)、烯草酮(clethodim)、噻草酮(cycloxydim)、环苯草酮(profoxydim)、稀禾定(sethoxydim)、醌肟草(tepraloxydim)、肟草酮(tralkoxydim);
-二硝基苯胺类:氟草胺(benfluralin)、丁氟消草(ethalfluralin)、黄草消(oryzalin)、胺硝草(pendimethalin)、氨基丙氟灵(prodiamine)、氟乐灵(trifluralin);
-二苯基醚类:氟锁草醚(acifluorfen)、苯草醚(aclonifen)、治草醚(bifenox)、氯甲草(diclofop)、氯氟草醚(ethoxyfen)、氟黄胺草醚(fomesafen)、乳氟禾草灵(lactofen)、乙氧氟草醚(oxyfluorfen);
-羟基苄腈类:溴苯腈(bromoxynil)、敌草腈(dichlobenil)、碘苯腈(ioxynil);
-咪唑啉酮类: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);
-苯氧基乙酸类:稗草胺(clomeprop)、2,4-二氯苯氧基乙酸(2,4-滴(2,4-D))、2,4-滴丁酸(2,4-DB)、2,4-滴丙酸(dichlorprop)、2甲4氯(MCPA)、2甲4氯乙硫酯(MCPA-thioethyl)、2甲4氯丁酸(MCPB)、2甲4氯丙酸(mecoprop);
-吡嗪类:杀草敏(chloridazon)、氟哒嗪草酯(flufenpyr-ethyl)、达草氟、达草灭(norflurazon)、达草止(pyridate);
-吡啶类:氨草啶(aminopyralid)、二氯皮考啉酸(clopyralid)、吡氟草胺(diflufenican)、氟硫草定(dithiopyr)、氟草同(fluridone)、氟草烟(fluroxypyr)、毒莠定(picloram)、氟吡酰草胺(picolinafen)、噻氟啶草(thiazopyr);
-磺酰脲类:磺氨黄隆(amidosulfuron)、四唑黄隆(azimsulfuron)、苄嘧黄隆(bensulfuron)、氯嘧黄隆(chlorimuron-ethyl)、绿黄隆(chlorsulfuron)、醚黄隆(cinosulfuron)、环丙黄隆(cyclosulfamuron)、乙氧嘧黄隆(ethoxysulfuron)、啶嘧黄隆(flazasulfuron)、氟吡磺隆(flucetosulfuron)、氟啶黄隆(flupyrsulfuron)、酰胺磺隆(foramsulfuron)、吡氯黄隆(halosulfuron)、啶咪黄隆(imazosulfuron)、碘磺隆(iodosulfuron)、甲磺胺磺隆(mesosulfuron)、甲黄隆(metsulfuron-methyl)、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)、1-((2-氯-6-丙基咪唑并[1,2-b]哒嗪-3-基)磺酰基)-3-(4,6-二甲氧基嘧啶-2-基)脲;
-三嗪类:莠灭净(ametryne)、莠去津(atrazine)、草净津(cyanazine)、戊草津(dimethametryne)、乙嗪草酮(ethiozine)、六嗪同(hexazinone)、苯嗪草(metamitron)、赛克津(metribuzine)、扑草净(prometryne)、西玛津(simazine)、特丁津(terbuthylazine)、去草净(terbutryne)、苯氧丙胺津(triaziflam);
-脲类:绿麦隆(chlorotoluron)、香草隆(daimuron)、敌草隆(diuron)、伏草隆(fluometuron)、异丙隆(isoproturon)、利谷隆(linuron)、噻唑隆(methabenzthiazuron)、丁唑隆(tebuthiuron);
-其他乙酰乳酸合成酶抑制剂:双草醚钠盐(bispyribac-sodium)、氯酯磺草胺(cloransulam-methyl)、唑嘧磺胺(diclosulam)、双氟磺草胺(florasulam)、氟酮磺隆(flucarbazone)、氟唑啶草(flumetsulam)、唑草磺胺(metosulam)、嘧苯胺磺隆(orthosulfamuron)、五氟磺草胺(penoxsulam)、丙氧基卡巴腙(propoxycarbazone)、丙酯草醚(pyribambenz-propyl)、嘧苯草肟(pyribenzoxim)、环酯草醚(pyriftalide)、肟啶草(pyriminobac-methyl)、pyrimisulfan、嘧硫苯甲酸(pyrithiobac)、pyroxasulfon、甲氧磺草胺(pyroxsulam);
-其他:胺唑草酮(amicarbazone)、三唑胺(aminotriazole)、莎稗磷(anilofos)、beflubutamid、草除灵(benazolin)、bencarbazone、benfluresate、吡草酮(benzofenap)、噻草平(bentazone)、苯并双环酮(benzobicyclon)、除草定(bromacil)、溴丁酰草胺(bromobutide)、氟丙嘧草酯(butafenacil)、草胺磷(butamifos)、胺草唑(cafenstrole)、氟酮唑草(carfentrazone)、吲哚酮草酯(cinidon-ethyl)、敌草索(chlorthal)、环庚草醚(cinmethylin)、异恶草酮(clomazone)、苄草隆(cumyluron)、cyprosulfamid、麦草畏(dicamba)、苯敌快(difenzoquat)、二氟吡隆(diflufenzopyr)、稗内脐蠕孢菌(Drechsleramonoceras)、敌草腈(endothal)、乙呋草黄(ethofumesate)、乙苯酰草(etobenzanid)、四唑酰草胺(fentrazamide)、氟烯草酸(flumiclorac-pentyl)、氟嗪酮(flumioxazin)、胺草唑(flupoxam)、氟咯草酮(fluorochloridon)、呋草酮(flurtamon)、茚草酮(indanofan)、异恶草胺(isoxaben)、异氟草(isoxaflutol)、环草定(lenacil)、敌稗(propanil)、拿草特(propyzamide)、二氯喹啉酸(quinclorac)、喹草酸(quinmerac)、硝草酮(mesotrione)、甲胂酸(methylarsonicacid)、抑草生(naptalam)、炔丙唑草(oxadiargyl)、恶草灵(oxadiazone)、氯嗪草(oxaziclomefon)、戊唑草(pentoxazone)、唑啉草酯(pinoxaden)、双唑草腈(pyraclonil)、吡草醚(pyraflufen-ethyl)、pyrasulfotol、苄草唑(pyrazoxyfen)、吡唑特(pyrazolynate)、灭藻醌(quinoclamin)、嘧啶肟草醚(saflufenacil)、磺草酮(sulcotrione)、磺胺草唑(sulfentrazone)、特草定(terbacil)、tefuryltrione、tembotrione、thiencarbazone、topramezone、4-羟基-3-[2-(2-甲氧基乙氧基甲基)-6-三氟甲基吡啶-3-羰基]双环[3.2.1]辛-3-烯-2-酮、(3-[2-氯-4-氟-5-(3-甲基-2,6-二氧代-4-三氟甲基-3,6-二氢-2H-嘧啶-1-基)苯氧基]吡啶-2-基氧基)乙酸乙酯、6-氨基-5-氯-2-环丙基嘧啶-4-甲酸甲酯、6-氯-3-(2-环丙基-6-甲基苯氧基)哒嗪-4-醇、4-氨基-3-氯-6-(4-氯苯基)-5-氟吡啶-2-甲酸、4-氨基-3-氯-6-(4-氯-2-氟-3-甲氧基苯基)吡啶-2-甲酸甲酯和4-氨基-3-氯-6-(4-氯-3-二甲基氨基-2-氟苯基)吡啶-2-甲酸甲酯;
O)杀虫剂:
-有机(硫代)磷酸酯:高灭磷(acephate)、唑啶磷(azamethiphos)、谷硫磷(azinphos-methyl)、毒死蜱(chlorpyrifos)、甲基毒死蜱(chlorpyrifos-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)、异唑磷(isoxathion)、马拉硫磷(malathion)、甲胺磷(methamidophos)、杀扑磷(methidathion)、甲基对硫磷(methyl-parathion)、速灭磷(mevinphos)、久效磷(monocrotophos)、砜吸磷(oxydemeton-methyl)、对氧磷(paraoxon)、一六零五(parathion)、稻丰散(phenthoate)、伏杀硫磷(phosalone)、亚胺硫磷(phosmet)、磷胺(phosphamidon)、甲拌磷(phorate)、辛硫磷(phoxim)、虫螨磷(pirimiphos-methyl)、丙溴磷(profenofos)、丙硫磷(prothiofos)、田乐磷(sulprophos)、杀虫威(tetrachlorvinphos)、特丁磷(terbufos)、三唑磷(triazophos)、敌百虫(trichlorfon);
-氨基甲酸酯类:棉铃威(alanycarb)、涕灭威(aldicarb)、虫威(bendiocarb)、丙硫克百威(benfuracarb)、甲萘威(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);
-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(etofenprox)、甲氰菊酯(fenpropathrin)、杀灭菊酯(fenvalerate)、咪炔菊酯(imiprothrin)、氯氟氰菊酯(lambda-cyhalothrin)、氯菊酯(permethrin)、炔酮菊酯(prallethrin)、除虫菊酯(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)、丙氟菊酯(profluthrin)、四氟甲醚菊酯(dimefluthrin);
-昆虫生长抑制剂:a)几丁质合成抑制剂:苯甲酰脲类:定虫隆(chlorfluazuron)、灭蝇胺(cyramazin)、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)、茂醚(diofenolan)、噻螨酮(hexythiazox)、特苯唑(etoxazole)、四螨嗪(clofentazin);b)蜕皮激素拮抗剂:特丁苯酰肼(halofenozide)、甲氧苯酰肼(methoxyfenozide)、双苯酰肼(tebufenozide)、艾扎丁(azadirachtin);c)保幼激素类似物:蚊蝇醚(pyriproxyfen)、蒙五一五(methoprene)、双氧威;d)类脂生物合成抑制剂:螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)、螺虫乙酯(spirotetramate);
-烟碱受体激动剂/拮抗剂: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)、1-(2-氯噻唑-5-基甲基)-2-硝酰亚氨基(nitrimino)-3,5-二甲基-[1,3,5]三嗪烷(triazinane);
-GABA拮抗剂:硫丹(endosulfan)、乙虫清(ethiprole)、锐劲特(fipronil)、氟吡唑虫(vaniliprole)、pyrafluprole、pyriprole、N-5-氨基-1-(2,6-二氯-4-甲基苯基)-4-亚磺酰氨酰基(sulfinamoyl)-1H-吡唑-3-硫代甲酰胺;
-大环内酯:齐墩螨素(abamectin)、甲氨基阿维菌素(emamectin)、米尔螨素(milbemectin)、lepimectin、艾克敌105(spinosad)、乙基多杀菌素(spinetoram);
-线粒体电子传输链抑制剂(METI)I杀螨剂:喹螨醚(fenazaquin)、哒螨酮(pyridaben)、吡螨胺(tebufenpyrad)、唑虫酰胺(tolfenpyrad)、嘧虫胺(flufenerim);
-METIII和III物质:灭螨醌(acequinocyl)、fluacyprim、灭蚁腙(hydramethylnone);
-去偶剂:氟唑虫清(chlorfenapyr);
-氧化磷酸化抑制剂:三环锡(cyhexatin)、杀螨硫隆(diafenthiuron)、杀螨锡(fenbutatinoxide)、克螨特(propargite);
-昆虫蜕皮抑制剂:灭蝇胺(cryomazin);
-‘混合功能氧化酶’抑制剂:增效醚(piperonylbutoxide);
-钠通道阻断剂:二唑虫(indoxacarb)、氰氟虫胺(metaflumizon);
-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(pymetrozin)、硫、硫环杀(thiocyclam)、氟虫酰胺(flubendiamide)、氯虫酰胺(chlorantraniliprole)、cyazypyr(HGW86);cyenopyrafen、吡氟硫磷(flupyrazofos)、丁氟螨酯(cyflumetofen)、amidoflumet、imicyafos、双三氟虫脲(bistrifluron)和pyrifluquinazone。
无机肥料的实例为常规肥料组分,可以使用的氮源如硫酸铵、硝酸铵、氯化铵、硫酸铵-硝酸铵(ammoniasulfa-nitrate)、脲、氨腈、双氰胺、硝酸钠、Chile硝石或硝酸钙,和缓释肥料如草酰胺、脲/甲醛缩合物、脲/乙醛缩合物或脲/乙二醛缩合物,例如Ureaform、乙炔二脲、亚异丁基二脲或亚巴豆基二脲。也可存在包含一种或多种植物营养素磷、钾、镁、钙或硫的化合物和包含少量元素硼、铁、铜、锌、锰或钼的化合物。该类化合物的实例为磷酸单铵、磷酸二铵、过磷酸钙、托马斯碱性炉渣粉、三过磷酸钙、磷酸二钙、磷酸钾、部分或完全溶解的粗磷酸盐、硝酸钾、氯化钾、硫酸钾、磷酸二钾、硫酸镁、氯化镁、硫镁矾、白云石、白垩、硬硼酸钙石、硼酸、硼砂、硫酸铁、硫酸铜、硫酸锌、硫酸锰、钼酸铵或类似物质。
优选地,农化活性物质包含水不溶性第一农药。第一农药在大多数情况下在20℃下可以不大于10g/l,优选不大于1g/l,尤其是不大于0.5g/l溶于水中。熟练技术人员可由以上农药列举中简单选择具有合适溶解性的农药。
水不溶性农药通常具有在30℃以上,优选在40℃以上,尤其是在45℃以上的沸点。
优选的水不溶性第一农药为嘧啶肟草醚、精噻吩草胺、胺硝草、氟吡酰草胺、唑菌胺酯、锐劲特、氰氟虫胺、水不溶性唑类杀真菌剂和水不溶性植物生长素酯类(如2,4-滴的烷基酯例如2,4-滴的2-乙基己基、异丁基、异辛基酯)。水不溶性唑类杀真菌剂取决于所需溶解度可选自三唑类(如戊环唑、双苯三唑醇、糠菌唑、环唑醇、醚唑、烯唑醇、精烯唑醇、氧唑菌、腈苯唑、喹唑菌酮、氟硅唑、粉唑醇、己唑醇、酰胺唑、环戊唑醇、环戊唑菌、腈菌唑、oxpoconazole、多效唑、戊菌唑、丙环唑、丙硫菌唑、硅氟唑、戊唑醇、氟醚唑、三唑酮、唑菌醇、戊叉唑菌、烯效唑;咪唑类(如氰霜唑、烯菌灵、烯菌灵硫酸盐(imazalilsulfate)、稻瘟酯、丙氯灵、氟菌唑);苯并咪唑:苯菌灵、多菌灵、麦穗宁、涕必灵;或其他唑类(如噻唑菌胺、氯唑灵、土菌消、2-(4-氯苯基)-N-[4-(3,4-二甲氧基苯基)异唑-5-基]-2-丙-2-炔基氧基乙酰胺),其中优选三唑类。
农化活性物质尤其优选包含a)水不溶性第一农药和b)水溶性第二农药或水溶性无机肥料。
水溶性第二农药在大多数情况下在20℃下可以大于10g/l可溶于水中。优选地,它可以大于50g/l,尤其是大于100g/l溶于水中。熟练技术人员可从以上农药列举中简单选择具有合适溶解性的农药。第二农药优选为除草剂和/或生长调节剂,其中尤其优选除草剂。不同第二农药的水溶性盐的混合物同样是可能的。
优选的水溶性第二农药为草甘膦、草铵膦、2,4-滴、麦草畏、对草快阳离子、敌草快阳离子、矮壮素阳离子和助壮素。优选的第二农药为草甘膦(例如呈游离酸、钠盐、倍半钠盐、钾盐、二钾盐、铵盐、二铵盐、二甲基铵盐、三甲基锍盐或异丙胺盐)、草铵膦(例如呈铵盐)、2,4-滴(例如呈铵盐、C1-C12烷基铵盐或钠盐)和麦草畏(例如呈二甘醇胺盐、二甲基铵盐、二醇胺盐、醇胺盐、钾盐、钠盐、三醇胺盐)。第二农药尤其优选包含草甘膦(例如钾盐、铵盐、异丙胺盐)。
水溶性无机肥料在大多数情况下在20℃下可以大于10g/l溶于水中。优选地,它可以大于50g/l,尤其是大于100g/l溶于水中。熟练技术人员可从以上肥料列举中简单选择具有合适溶解性的肥料。优选的无机肥料为硫酸盐、磷酸盐或硝酸盐,尤其是硫酸铵、硝酸铵和/或磷酸铵。
本发明组合物通常包含0.5-99重量%,优选5-85重量%,尤其是15-70重量%农化活性物质如农药和/或水溶性无机肥料。
本发明组合物通常包含0.5-70重量%,优选1-50重量%,尤其是1-30重量%水不溶性第一农药。
本发明组合物通常包含至少5重量%,优选至少10重量%,尤其是至少20重量%水溶性第二农药或水溶性无机肥料。本发明组合物通常包含1-80重量%,优选5-65重量%,尤其是15-45重量%水溶性第二农药或水溶性无机肥料。
水不溶性第一农药与共聚物的重量比可在任何范围内变化,例如1:10000-10000:1,优选1:1000-1000:1,尤其优选1:100-100:1。
本发明组合物优选以农化组合物形式存在。农化组合物的常见类型为例如溶液、乳液、悬浮液、粉剂、粉末、糊剂和颗粒。组合物类型的实例为悬浮液(SC、OD、FS)、可乳化浓缩物(EC)、乳液(EW、EO、ES)、糊剂、锭剂、润湿性粉末或粉剂(WP、SP、SS、WS、DP、DS)或可溶于或分散于水中(润湿性)的颗粒(GR、FG、GG、MG),以及用于处理植物繁殖材料如种子的凝胶(GF)。农化组合物以已知方式制备(例如参见Mollet,H.和Grubemann,A.:Formulationtechnology(WileyVCHVerlag,Weinheim,2001))。
此外,农化组合物还可以包含常用于植物保护产品的常规助剂,助剂的选择取决于具体使用形式或活性物质。合适助剂的实例是溶剂、固体载体、表面活性物质(如其他加溶剂、保护性胶体、润湿剂和粘合剂),有机和无机增稠剂,杀菌剂,防冻剂,消泡剂,任选着色剂和增粘剂(例如用于种子处理)。
合适的溶剂是水,有机溶剂如中至高沸点的矿物油馏分,例如煤油和柴油,此外还有煤焦油和植物或动物来源的油,脂族、环状和芳族烃类,例如石蜡、四氢化萘、烷基化萘及其衍生物、烷基化苯及其衍生物,醇类如甲醇、乙醇、丙醇、丁醇和环己醇,二醇类,酮类如环己酮、γ-丁内酯,二甲基脂肪酸酰胺,脂肪酸和脂肪酸酯,以及强极性溶剂,例如胺类如N-甲基吡咯烷酮。原则上还可以使用溶剂混合物以及上述溶剂与水的混合物。
固体载体为矿土如硅石、硅胶、硅酸盐、滑石、高岭土、石灰石、石灰、白垩、红玄武土、黄土、粘土、白云石、硅藻土、硫酸钙、硫酸镁、氧化镁,磨碎的合成材料,肥料如硫酸铵、磷酸铵、硝酸铵、脲类,以及植物来源产品如谷粉、树皮粉、木粉和坚果壳粉,纤维素粉或其他固体载体。
合适的表面活性剂(助剂、润湿剂、粘合剂、分散剂或乳化剂)是芳族磺酸如木素磺酸(例如类型,挪威Borregaard)、苯酚磺酸、萘磺酸(类型,美国AkzoNobel)和二丁基萘磺酸(类型,德国BASF)以及脂肪酸的碱金属盐、碱土金属盐、铵盐,烷基-和烷基芳基磺酸盐,烷基硫酸盐,月桂基醚硫酸盐和脂肪醇硫酸盐,以及硫酸化十六-、十七-和十八烷醇的盐,还有脂肪醇乙二醇醚的盐,磺化萘及其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,聚氧乙烯辛基酚醚,乙氧基化异辛基-、辛基-或壬基酚,烷基苯基聚乙二醇醚,三丁基苯基聚乙二醇醚,烷基芳基聚醚醇,异十三烷醇,脂肪醇/氧化乙烯缩合物,乙氧基化蓖麻油,聚氧乙烯烷基醚或聚氧丙烯烷基醚,月桂醇聚乙二醇醚乙酸酯,山梨糖醇酯,木素亚硫酸盐废液和蛋白质,变性蛋白质,多糖(如甲基纤维素),疏水改性的淀粉,聚乙烯醇(类型,瑞士Clariant),聚羧酸盐类(类型,德国BASF),聚烷氧基化物,聚乙烯胺(类型,德国BASF),聚乙烯亚胺(类型,德国BASF),聚乙烯基吡咯烷酮及其共聚物。
增稠剂(即赋予组合物以改性的流动性能,即静止状态下的高粘度和搅拌状态下的低粘度的化合物)的实例是多糖,以及有机和无机层状矿物如黄原胶(,CPKelco,USA)、23(法国Rhodia)或(R.T.Vanderbilt,USA)或(EngelhardCorp.,NJ,USA)。
可以加入杀菌剂以稳定该组合物。杀菌剂的实例是基于双氯酚和苄醇半缩甲醛的那些(ICI的或ThorChemie的RS和Rohm&Haas的MK)以及还有异噻唑啉酮衍生物如烷基异噻唑啉酮类和苯并异噻唑啉酮类(ThorChemie的MBS)。合适防冻剂的实例是乙二醇、丙二醇、脲和甘油。消泡剂的实例是聚硅氧烷乳液(例如SRE,德国Wacker或,法国Rhodia),长链醇,脂肪酸,脂肪酸盐,有机氟化合物及其混合物。着色剂的实例为微溶于水的颜料和可溶于水的染料。增粘剂的实例为聚乙烯基吡咯烷酮、聚乙酸乙烯酯、聚乙烯醇和纤维素醚(,日本Shin-Etsu)。
组合物类型的实例为:
1.在水中稀释的组合物类型
i)水溶性浓缩物(SL、LS)
将10重量份活性物质溶于90重量份水或水溶性溶剂中。作为替代方案,添加润湿剂或其它赋形剂。这得到活性物质含量为10重量%的组合物。
ii)分散性浓缩物(DC)
将20重量份活性物质溶于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。用水稀释得到分散体。活性物质含量为20重量%。
iii)可乳化浓缩物(EC)
将15重量份活性物质溶于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5重量份)。用水稀释得到乳液。该组合物的活性物质含量为15重量%。
iv)乳液(EW、EO、ES)
将25重量份活性物质溶于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5重量份)。使用乳化机装置(例如Ultra-Turrax)将该混合物置于30重量份水中并制成均匀乳液。用水稀释得到乳液。该组合物的活性物质含量为25重量%。
v)悬浮液(SC、OD、FS)
在搅拌式球磨机中粉碎20重量份活性物质并加入10重量份分散剂和润湿剂以及70重量份水或有机溶剂,以形成细活性物质悬浮液。用水稀释得到该活性物质的稳定悬浮液。该组合物中的活性物质含量为20重量%。
vi)水分散性和水溶性颗粒(WG、SG)
细研磨50重量份活性物质并加入50重量份分散剂和润湿剂,并借助工业装置(如挤出机、喷雾塔、流化床)将其制成水分散颗粒或水溶性颗粒。用水稀释得到该活性物质的稳定分散体或溶液。该组合物的活性物质含量为50重量%。
vii)水分散性和水溶性粉末(WP、SP、SS、WS)
将75重量份活性物质在转子-定子研磨机中研磨并加入25重量份分散剂、润湿剂和硅胶。用水稀释得到该活性物质的稳定分散体或溶液。该组合物的活性物质含量为75重量%。
viii)凝胶(GF)
在球磨机中研磨20重量份活性物质、10重量份分散剂、1重量份溶胀剂和70重量份水或有机溶剂,以形成细悬浮液。用水稀释得到活性物质含量为20重量%的稳定悬浮液。
2.直接施用的组合物类型
ix)粉剂(DP、DS)
细研磨5重量份的活性物质并使其与95重量份细碎的高岭土充分混合。这得到活性物质含量为5重量%的粉剂。
x)颗粒(GR、FG、GG、MG)
细研磨0.5重量份的活性物质并使其与99.5重量份载体混合。就此而言,现行方法为挤出、喷雾干燥或流化床法。这得到活性物质含量为0.5重量%的直接施用的颗粒。
xi)ULV溶液(UL)
将10重量份的活性物质溶于90重量份有机溶剂如二甲苯中。这得到活性物质含量为10重量%的直接施用的组合物。
本发明组合物优选呈水性组合物(如SC)形式,其中水不溶性农药以悬浮颗粒形式存在。水含量可为至少10重量%,优选至少30重量%。悬浮颗粒可以晶体或无定形颗粒形式存在,其在20℃下为固体。悬浮的水不溶性农药通常具有x50值为0.1-10μm,优选0.2-5μm,尤其优选0.5-2μm的粒度分布。粒度分布可以通过激光衍射包含颗粒的水性悬浮液测定。样品制备,例如稀释至测量浓度的稀释液在该测量方法中尤其取决于悬浮液样品中的细度和浓度以及所用装置(例如MalvernMastersizer)。必须开发用于所述体系的程序且该程序对本领域熟练技术人员是已知的。
在另一形式中,本发明组合物优选呈凝胶以外的任何形式。凝胶可理解为至少两种组分的尺寸稳定、易变形、富液体和富气体、细分散的胶态体系,其对于大多数部分而言包含固体胶态分散的具有长或高度支化颗粒的物质(胶凝剂;还称为增稠试剂或增稠剂)和液体(通常为水)作为分散剂。凝胶还可描述为粘弹性流体;其流体性能可位于理想液体的那些和理想固体的那些之间。该凝胶可为尺寸稳定的,其可意指它可具有至少1000mPa·s的粘度。就本发明而言,对粘度所给出的值指使用布氏粘度计(1.5rpm,Sp63)在25摄氏度温度下得到的值。本发明组合物可具有在1000mPas以下,优选在800mPas以下,尤其是在500mPas以下的粘度。
因此,另一主题为包含本发明组合物的种子。为了处理植物繁殖材料,尤其是种子,通常使用水溶性浓缩物(LS)、悬浮液(FS)、粉剂(DS)、水分散性粉末和水溶性粉末(WS、SS)、乳液(ES)、可乳化的浓缩物(EC)和凝胶(GF)。这些组合物可以未稀释或优选稀释形式施用至植物繁殖材料,尤其是种子。这里,所述组合物可稀释2-10倍使得在要用于种子包衣的组合物中存在0.01-60重量%,优选0.1-40重量%的活性物质。施用可在播种之前或期间进行。植物繁殖材料的处理,尤其是种子的处理为本领域熟练技术人员所已知的,且通过撒粉、包衣、造粒、浸渍或浸泡植物繁殖材料进行,其中处理优选通过造粒、包衣和撒粉进行或通过犁沟内处理而进行使得防止种子的提前萌发。优选将悬浮液用于种子处理。通常,该组合物包含1-800g/l活性物质、1-200g/l表面活性剂、0-200g/l防冻剂、0-400g/l粘合剂、0-200g/l颜料和溶剂,优选水。
即用型制剂中的活性物质浓度可在显著范围内变化。通常而言,它为0.0001-10重量%,优选0.001-1重量%。所述活性物质也可成功用于超低容量法(ULV)中,其中可施用具有超过95重量%活性物质的组合物,或者实际上可施用不含添加剂的活性物质。在用于植物保护时,施用率取决于所需的效果性质为0.001-2kg活性物质/ha,优选为0.005-2kg活性物质/ha,尤其优选为0.05-0.9kg活性物质/ha,尤其为0.1-0.75kg活性物质/ha。当处理植物繁殖材料如种子时,通常使用0.1-1000g/100kg植物繁殖材料或种子,优选1-1000g/100kg植物繁殖材料或种子,尤其优选1-100g/100kg植物繁殖材料或种子,尤其是5-100g/100kg植物繁殖材料或种子的量的活性物质。当用于保护材料或储存材料时,活性物质的施用率取决于施用区域的性质和所需效果。在材料保护中,每立方米经处理材料的常规施用率例如为0.001-2kg,优选0.005-1kg活性物质。
可向所述活性物质或包含所述活性物质的组合物中混入的物质包括各种类型的油或润湿剂、助剂、除草剂、杀菌剂、其它杀真菌剂和/或农药,任选还仅在使用前添加(桶混合)。这些试剂可以1:100-100:1,优选1:10-10:1的重量比混入本发明组合物中。就此而言合适的助剂尤其为有机改性的聚硅氧烷如BreakThruS;醇烷氧基化物如245、MBA1303、LF300和ON30;EO-PO嵌段聚合物如PluronicRPE2035和B;醇乙氧基化物如XP80;以及磺基琥珀酸二辛基酯钠如RA。
另一主题为一种通过使三聚物和农化活性物质接触,例如混合而制备本发明组合物的方法。上述辅助剂也可任选与该组合物接触。其他各种类型的组合物的制备方法如上所述。
另一主题为三聚物在分散农化活性物质中的用途。优选将三聚物用于悬浮。优选的农化活性物质如上所述。
此外,本发明涉及一种防治植物病原性真菌和/或不希望的植物和/或不希望的昆虫或螨虫侵袭和/或调节植物生长的方法,其中使本发明组合物作用于相应有害物、其环境或待防止相应有害物的作物植物、土壤和/或不希望的植物和/或作物植物和/或其环境。
术语作物植物还包括已经通过育种、诱变或重组方法修饰的那些植物,包括上市销售或开发方法中的生物技术农业产品。基因修饰植物是其遗传材料不以在自然条件下通过杂交、突变或自然重组(即遗传材料的重组)进行的方式修饰的植物。这里通常将一个或多个基因整合到植物的遗传材料中以改善植物的性能。这类基因修饰还包括蛋白质、寡肽或多肽的翻译后修饰,例如通过糖基化或结合聚合物,例如异戊二烯化、乙酰化或法呢基化残基或PEG残基。
本发明的优点尤其在于可使得配制剂具有高储存稳定性;减缓或抑制经分散的农化活性物质的粒度生长;减缓或抑制经分散的农化颗粒的附聚;减缓或抑制经分散的农化活性物质的沉降;且上述优点还在高盐浓度存在下得到。
下列实施例说明本发明而不施加任何限制。
实施例
表面活性剂A:阴离子表面活性剂,烷基萘磺酸的钠盐,水溶性。
表面活性剂B:非离子表面活性剂,烷基胺乙氧基化物,水溶性,表面张力(1g/l水,室温)约为40mN/m。
实施例1–共聚物A
初始加料:216g聚乙二醇,平均摩尔质量为35000g/mol
216g聚乙二醇,平均摩尔质量为1500g/mol
164g丙醇
0.96g三烯丙基胺
进料1:384gN-乙烯基甲酰胺
147.7g二烯丙基二甲基氯化铵(DADMAC;65重量%形式)
164g丙醇
进料2:2.9g过辛酸叔丁基酯
164g丙醇
进料3:420g丙醇
进料4:100g丙醇
16g甲醇钠(30重量%)
将均化初始加料加热至90℃,其中将氮气通过该体系,并且将进料1在4小时内计量加入,并且将112g进料2在5小时内计量加入。在随后聚合一小时后,加入55g进料2并且聚合再持续1.5小时。然后,使用进料3,进行稀释和冷却。最后,将进料3的量通过蒸馏除去,加入进料4,批料在回流下加热1小时,并重复蒸馏。这得到以80/20的重量比含有N-乙烯基甲酰胺和DADMAC的共聚物A。摩尔质量Mw为151000g/mol,其中PDI为7.5。固体含量为35重量%(120℃,2小时),且pH(呈10%形式)为4.5。
实施例2–配制剂
将14g唑菌胺酯、2g实施例1的共聚物A、2g表面活性剂A、3.3g表面活性剂B、13.1g草甘膦异丙基铵盐(60重量%,在水中)和21.6g水称入容器中。加入25ml玻璃珠粒(0.75-1.0mm)并通过在实验室振摆机上振摆(4h,400rpm)而制备水性唑菌胺酯悬浮液。此后,滤出玻璃珠粒。
实施例3–配制剂(对比试验)
唑菌胺酯的水性悬浮液如实施例2中制备,其中实施例1的三聚物由如下物质代替:
A)Atlox4915,或
B)共聚物B(丙烯酸/AMPS70/30)。
Atlox4913为包含33重量%三聚物(甲基丙烯酸、甲基丙烯酸甲酯和甲氧基聚乙二醇甲基丙烯酸酯的反应产物)、33重量%丙二醇、1重量%二甲苯和33重量%水)的组合物,HLB值为11-12,可由Uniquema市购。
无规共聚物B包含掺入聚合物中的如下单体:70重量%丙烯酸和30重量%丙烯酰氨基丙磺酸的钠盐(AMPS)。
实施例4–悬浮液的稳定性测试
将实施例2、3A和3B的水性悬浮液在室温下在无搅拌下储存24小时并此后参考1(相分离,不再能通过振摆分散,结块)至10(无相分离,高度粘稠,易分散)的分值肉眼评价。
表1:
如下实施例的配制剂 | 稳定性评价 |
2 | 9 |
3Aa) | 8 |
3Ba) | 2 |
a)对比试验。
Claims (24)
1.一种组合物,包含农化活性物质和包含掺入聚合物中的基于共聚单体的总量为20-95重量%N-乙烯基羧酰胺和1-70重量%二烯丙基二烷基铵盐的共聚物,其中所述N-乙烯基羧酰胺为N-乙烯基-C1-C18烷基羧酰胺和/或N-乙烯基-N-(C1-C12烷基)-C1-C18烷基羧酰胺,
其中所述组合物包含1-20重量%所述共聚物,且包含0.5-70重量%所述农化活性物质。
2.根据权利要求1的组合物,其中所述农化活性物质包含水不溶性第一农药。
3.根据权利要求1的组合物,其中所述农化活性物质包含a)水不溶性第一农药和b)水溶性第二农药或水溶性无机肥料。
4.根据权利要求1-3中任一项的组合物,其包含至少5重量%第二农药或无机肥料。
5.根据权利要求1-3中任一项的组合物,其呈水性组合物的形式,其中所述水不溶性第一农药以悬浮颗粒的形式存在。
6.根据权利要求4的组合物,其呈水性组合物的形式,其中所述水不溶性第一农药以悬浮颗粒的形式存在。
7.根据权利要求1-3中任一项的组合物,其包含1-10重量%共聚物。
8.根据权利要求6的组合物,其包含1-10重量%共聚物。
9.根据权利要求1-3中任一项的组合物,其包含15-70重量%所述农化活性物质。
10.根据权利要求8的组合物,其包含15-70重量%所述农化活性物质。
11.根据权利要求1-3中任一项的组合物,其中所述共聚物为无规共聚物。
12.根据权利要求8或10的组合物,其中所述共聚物为无规共聚物。
13.根据权利要求1-3中任一项的组合物,其中二烯丙基二烷基铵盐对应于式(I):
其中R1和R2相互独立地为氢或C1-C4烷基;R3和R4相互独立地为具有1-18个碳原子的烷基、羟基烷基、羧基烷基、羧基酰氨基烷基或烷氧基烷基;和Y-为阴离子。
14.根据权利要求12的组合物,其中二烯丙基二烷基铵盐对应于式(I):
其中R1和R2相互独立地为氢或C1-C4烷基;R3和R4相互独立地为具有1-18个碳原子的烷基、羟基烷基、羧基烷基、羧基酰氨基烷基或烷氧基烷基;和Y-为阴离子。
15.根据权利要求1-3中任一项的组合物,其中N-乙烯基羧酰胺为N-乙烯基-N-甲基甲酰胺、N-乙烯基甲酰胺、N-乙烯基-N-乙基甲酰胺、N-乙烯基-N-丙基甲酰胺、N-乙烯基-N-异丙基甲酰胺、N-乙烯基-N-异丁基甲酰胺、N-乙烯基乙酰胺、N-乙烯基-N-甲基乙酰胺、N-乙烯基丙酰胺或N-乙烯基-N-甲基丙酰胺及其混合物。
16.根据权利要求12的组合物,其中N-乙烯基羧酰胺为N-乙烯基-N-甲基甲酰胺、N-乙烯基甲酰胺、N-乙烯基-N-乙基甲酰胺、N-乙烯基-N-丙基甲酰胺、N-乙烯基-N-异丙基甲酰胺、N-乙烯基-N-异丁基甲酰胺、N-乙烯基乙酰胺、N-乙烯基-N-甲基乙酰胺、N-乙烯基丙酰胺或N-乙烯基-N-甲基丙酰胺及其混合物。
17.根据权利要求1-3中任一项的组合物,其包含基于共聚物所有单体的总质量为40-95重量%的N-乙烯基羧酰胺。
18.根据权利要求14的组合物,其包含基于共聚物所有单体的总质量为40-95重量%的N-乙烯基羧酰胺。
19.根据权利要求1-3中任一项的组合物,其包含基于共聚物所有单体的总质量为5-50重量%的二烯丙基二烷基铵盐。
20.根据权利要求16的组合物,其包含基于共聚物所有单体的总质量为5-50重量%的二烯丙基二烷基铵盐。
21.一种制备根据权利要求1-20中任一项的组合物的方法,包括使所述共聚物和所述农化活性物质接触。
22.根据权利要求1-20中任一项的共聚物在分散农化活性物质中的用途。
23.一种防治植物病原性真菌和/或不希望的植物生长和/或不希望的昆虫或螨虫侵袭和/或调节植物生长的方法,其中使根据权利要求1-20中任一项的组合物作用于相应有害物、其环境或待防止相应有害物的作物植物、土壤和/或不希望的植物和/或作物植物和/或其环境。
24.一种通过将根据权利要求1-20中任一项的组合物施用于种子而处理种子的方法。
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EP11167952 | 2011-05-27 | ||
PCT/EP2012/059778 WO2012163808A1 (en) | 2011-05-27 | 2012-05-24 | Copolymers of n-vinylcarboxamide and diallyldialkylammonium salt as dispersant for agrochemical formulations |
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AU2012311247B2 (en) | 2011-08-23 | 2016-10-13 | Vive Crop Protection Inc. | Pyrethroid formulations |
WO2013093578A1 (en) | 2011-12-22 | 2013-06-27 | Vive Crop Protection Inc. | Strobilurin formulations |
US9961900B2 (en) | 2012-06-11 | 2018-05-08 | Vive Crop Protection Inc. | Herbicide formulations |
RU2664577C2 (ru) * | 2012-09-04 | 2018-08-21 | ДАУ АГРОСАЙЕНСИЗ ЭлЭлСи | Композиции и способы улучшения совместимости растворимых в воде солей гербицидов |
WO2014122598A1 (en) | 2013-02-05 | 2014-08-14 | Vive Crop Protection Inc. | Mectin and milbemycin formulations |
US10150712B2 (en) * | 2013-07-04 | 2018-12-11 | Basf Se | Compositions with improved urease-inhibiting effect comprising (thio)phosphoric acid triamide and further compounds |
CN107787183B (zh) * | 2015-04-20 | 2021-10-08 | 三井化学Agro株式会社 | 肥料兼农用化学品制剂 |
DE102015213635A1 (de) * | 2015-07-20 | 2017-01-26 | Clariant International Ltd | Pflanzennährstoff-Suspensionen und deren Verwendung zum Düngen von Pflanzen |
US11517013B2 (en) | 2017-08-25 | 2022-12-06 | Vive Crop Protection Inc. | Multi-component, soil-applied, pesticidal compositions |
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FR2826593B1 (fr) | 2001-06-27 | 2004-04-16 | Rhodia Chimie Sa | Dispersion comprenant une emulsion dont la phase aqueuse est de force ionique elevee, preparation et utilisation |
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