CN116458509A - 一种稳定的杀虫组合物 - Google Patents
一种稳定的杀虫组合物 Download PDFInfo
- Publication number
- CN116458509A CN116458509A CN202210030441.0A CN202210030441A CN116458509A CN 116458509 A CN116458509 A CN 116458509A CN 202210030441 A CN202210030441 A CN 202210030441A CN 116458509 A CN116458509 A CN 116458509A
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- Prior art keywords
- insecticidal
- weight
- composition
- oxazinone
- insecticidal composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 230000000749 insecticidal effect Effects 0.000 title claims abstract description 44
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- 239000003120 macrolide antibiotic agent Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- UHXUZOCRWCRNSJ-QPJJXVBHSA-N methomyl Chemical compound CNC(=O)O\N=C(/C)SC UHXUZOCRWCRNSJ-QPJJXVBHSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- DWFZBUWUXWZWKD-UHFFFAOYSA-N pyridaben Chemical compound C1=CC(C(C)(C)C)=CC=C1CSC1=C(Cl)C(=O)N(C(C)(C)C)N=C1 DWFZBUWUXWZWKD-UHFFFAOYSA-N 0.000 description 1
- AEHJMNVBLRLZKK-UHFFFAOYSA-N pyridalyl Chemical group N1=CC(C(F)(F)F)=CC=C1OCCCOC1=C(Cl)C=C(OCC=C(Cl)Cl)C=C1Cl AEHJMNVBLRLZKK-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- ZLIBICFPKPWGIZ-UHFFFAOYSA-N pyrimethanil Chemical compound CC1=CC(C)=NC(NC=2C=CC=CC=2)=N1 ZLIBICFPKPWGIZ-UHFFFAOYSA-N 0.000 description 1
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- 159000000000 sodium salts Chemical class 0.000 description 1
- DEWVPZYHFVYXMZ-QCILGFJPSA-M sodium;(3ar,4as,8ar,8bs)-2,2,7,7-tetramethyl-4a,5,8a,8b-tetrahydro-[1,3]dioxolo[3,4]furo[1,3-d][1,3]dioxine-3a-carboxylate Chemical compound [Na+].O([C@H]12)C(C)(C)OC[C@@H]1O[C@]1(C([O-])=O)[C@H]2OC(C)(C)O1 DEWVPZYHFVYXMZ-QCILGFJPSA-M 0.000 description 1
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- QYPNKSZPJQQLRK-UHFFFAOYSA-N tebufenozide Chemical compound C1=CC(CC)=CC=C1C(=O)NN(C(C)(C)C)C(=O)C1=CC(C)=CC(C)=C1 QYPNKSZPJQQLRK-UHFFFAOYSA-N 0.000 description 1
- ZZYSLNWGKKDOML-UHFFFAOYSA-N tebufenpyrad Chemical compound CCC1=NN(C)C(C(=O)NCC=2C=CC(=CC=2)C(C)(C)C)=C1Cl ZZYSLNWGKKDOML-UHFFFAOYSA-N 0.000 description 1
- 229960005199 tetramethrin Drugs 0.000 description 1
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- 150000003558 thiocarbamic acid derivatives Chemical class 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WPALTCMYPARVNV-UHFFFAOYSA-N tolfenpyrad Chemical compound CCC1=NN(C)C(C(=O)NCC=2C=CC(OC=3C=CC(C)=CC=3)=CC=2)=C1Cl WPALTCMYPARVNV-UHFFFAOYSA-N 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- DQFPEYARZIQXRM-LTGZKZEYSA-N tralkoxydim Chemical compound C1C(=O)C(C(/CC)=N/OCC)=C(O)CC1C1=C(C)C=C(C)C=C1C DQFPEYARZIQXRM-LTGZKZEYSA-N 0.000 description 1
- DDVNRFNDOPPVQJ-HQJQHLMTSA-N transfluthrin Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@H]1C(=O)OCC1=C(F)C(F)=CC(F)=C1F DDVNRFNDOPPVQJ-HQJQHLMTSA-N 0.000 description 1
- GFNANZIMVAIWHM-OBYCQNJPSA-N triamcinolone Chemical compound O=C1C=C[C@]2(C)[C@@]3(F)[C@@H](O)C[C@](C)([C@@]([C@H](O)C4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 GFNANZIMVAIWHM-OBYCQNJPSA-N 0.000 description 1
- 229960005294 triamcinolone Drugs 0.000 description 1
- XOPFESVZMSQIKC-UHFFFAOYSA-N triasulfuron Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)OCCCl)=N1 XOPFESVZMSQIKC-UHFFFAOYSA-N 0.000 description 1
- NKNFWVNSBIXGLL-UHFFFAOYSA-N triazamate Chemical compound CCOC(=O)CSC1=NC(C(C)(C)C)=NN1C(=O)N(C)C NKNFWVNSBIXGLL-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- FFSJPOPLSWBGQY-UHFFFAOYSA-N triazol-4-one Chemical compound O=C1C=NN=N1 FFSJPOPLSWBGQY-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- AMFGTOFWMRQMEM-UHFFFAOYSA-N triazophos Chemical compound N1=C(OP(=S)(OCC)OCC)N=CN1C1=CC=CC=C1 AMFGTOFWMRQMEM-UHFFFAOYSA-N 0.000 description 1
- KRTNITDCKAVIFI-UHFFFAOYSA-N tridecyl benzenesulfonate Chemical class CCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 KRTNITDCKAVIFI-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
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
-
- 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
- A01N25/22—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 stabilising the active ingredients
-
- 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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Abstract
本发明涉及一种稳定的杀虫组合物,其至少含有一种嗪酮类杀虫活性物或其药学上可接受的盐及其水合物,以及至少一种功能稳定剂。该杀虫组合物具有优良的加工性能和制剂稳定性,在较长的贮存条件下可保持较高的悬浮率和分散性。
Description
技术领域
本发明涉及农业化学领域,尤其涉及一种稳定的含嗪酮类杀虫活性物或其药学上可接受的盐及其水合物的杀虫组合物,该组合物具有优良的加工性能和制剂稳定性,在较长的贮存条件下可保持较高的悬浮率和分散性。
背景技术
嗪酮类杀虫剂分为二嗪酮类杀虫剂和三嗪酮类杀虫剂。该类杀虫剂具有高效、低毒、高选择性及作用机制独特等特点而在农药研究领域受到广泛的关注。嗪酮类杀虫剂存在嗪酮环结构,非常容易与水形成水合物。
CN1219779C报道了拒嗪酮(吡蚜酮)的二水合物,这种水合物的生成会在有水的条件下自发的产生。因此加工无水拒嗪酮类杀虫剂制剂产品在湿法砂磨过程或加水捏合造粒过程或长期贮存与空气中水分结合的过程种种情况都会产生拒嗪酮的二水合物。换言之使用无水的嗪酮类杀虫剂加工制剂产品时,特别是水悬浮剂、水分散颗粒剂,干悬浮剂等,会有部分或全部的嗪酮类杀虫剂转化成嗪酮类杀虫剂的水合物;而加工不与水直接接触的油悬浮剂、可湿性粉剂等制剂产品也会因为长期贮存过程中或多或少的与环境中的水分结合形成嗪酮类杀虫剂的水合物。这类嗪酮类杀虫剂的水合物在热力学上是稳定的,然而在形成了水合物的情况下,会对制剂加工产生不利的影响,例如湿法砂磨过程中会影响砂磨效率,易发生砂磨发热、变稠、膏化等现象;加水捏合造粒过程会发热、卡机、造粒困难等现象;制成的成品贮存悬浮率低、分散差等质量问题。这些都是制备嗪酮类杀虫剂制剂产品面临的困难。
发明内容
本发明的目的是要提供一种克服了这些缺点的含嗪酮类杀虫剂的杀虫组合物。
该发明的目的是针对现有技术的缺陷,提供一种稳定的杀虫组合物,含有:
A:基于组合物总重量计,1-80重量%的嗪酮类杀虫活性物或其药学上可接受的盐及其水合物;和
B:基于组合物总重量计,0.1-20重量%苯磺酸盐或苯酚磺酸盐的缩聚物。
出人意料的发现,苯磺酸盐或苯酚磺酸盐的缩聚物的存在有效地解决了含有嗪酮类杀虫剂的杀虫组合物在加工制备过程中,例如湿法砂磨、捏合造粒等,遇到的加工问题,以及提升了最终产品的悬浮率和分散稳定性。
所述杀虫组合物中,嗪酮类杀虫活性物或其药学上可接受的盐及其水合物的含量例如可以是1重量%、5重量%、8重量%、10重量%、12重量%、15重量%、20重量%、25重量%、30重量%、35重量%、40重量%、45重量%、50重量%、55重量%、60重量%、65重量%、70重量%、75重量%或80重量%。
优选地,在本发明的杀虫组合物中,基于组合物总重量计,尤其是2-75重量%,特别是5-70重量%,更特别是8-65重量%,以及更特别是10-60重量%,甚至达到15-50重量%的嗪酮类杀虫剂。
所述的嗪酮类杀虫剂选自吡蚜酮pymetrozine(式1)、氟虫吡喹pyrifluquinazon(式2)、R-768(式3)以及式4至式78结构的化合物。
所述杀虫组合物中,苯磺酸盐或苯酚磺酸盐的缩聚物的含量例如可以是0.1重量%、0.5重量%、0.8重量%、1重量%、2重量%、5重量%、8重量%、10重量%、12重量%、15重量%、18重量%或20重量%。
优选地,在本发明的杀虫组合物中,基于组合物总重量计,尤其是0.2-18重量%,特别是0.5-15重量%,更特别是0.8-12重量%,以及更特别的是1-10重量%,甚至达到2-8重量%的苯磺酸盐或苯酚磺酸盐的缩聚物。
本文所述的“缩聚物”是指通过缩聚反应得到的高分子化合物,因此本发明所述的苯磺酸盐或苯酚磺酸盐的缩聚物一般是摩尔分子量为1,000-50,000的高分子化合物,尤其是摩尔分子量为1,500-40,000,特别是摩尔分子量为1,800-30,000,更特别是摩尔分子量为2,000-20,000,甚至摩尔分子量为3,000-15,000的高分子化合物。在具体的技术方案中,苯磺酸盐或苯酚磺酸盐缩聚物中苯环上还可以带有一个或多个烷基基团(例如甲基、乙基、丙基,C4-C20烷基)的高分子化合物。
特别的,本发明的杀虫组合物中嗪酮类杀虫活性物与苯磺酸盐或苯酚磺酸盐缩聚物的重量比为60:1-1:1,例如可以是60:1、55:1、50:1、45:1、40:1、35:1、30:1、25:1、20:1、15:1、10:1、5:1、1.8:1、1.1:1或1:1,尤其是50:1-1.1:1,特别是40:1-1.5:1,更特别是30:1-1.8:1,更特别是20:1-2:1,甚至15:1-5:1。
本发明的杀虫组合物可以选择制备成液体剂型和固体剂型。液体剂型包括:可分散油悬浮剂(OD),水悬浮剂(SC)、悬乳剂(SE)、悬浮种衣剂(FS)、微胶囊悬浮剂(FS);固体剂型包括:可湿性粉剂(WP)、可溶性粉剂(SP)、水分散颗粒剂(WDG)、可溶性粒剂(SG)、干悬浮剂(DF)、颗粒剂(Granule)。特别优选可分散油悬浮剂(OD),水悬浮剂(SC)、可湿性粉剂(WP)、水分散颗粒剂(WDG)和干悬浮剂(DF)。
本发明的杀虫组合物制备成最终制剂形态可根据各剂型的一般加工方法进行加工,具体剂型加工可参照刘光文主编的《现代农药剂型加工技术丛书》。
因此,本发明的组合物可根据最终形态选择合适的助剂类型加以辅助,合适的助剂包括溶剂、液体载体、表面活性剂,分散剂,乳化剂,润湿剂,辅助剂,保护性胶体,固体载体,增稠剂,增粘剂,杀菌剂,抗冻剂,消泡剂,着色剂,和粘合剂等。
合适的溶剂和液体载体为有机溶剂如植物或动物来源的油;醇,例如乙醇、丙醇、丁醇、环己醇;二醇;酮;酯;水;和其混合物。
合适的表面活性剂是表面活性化合物,如阴离子、阳离子、非离子和两性表面活性剂,嵌段聚合物,聚电解质,以及它们的混合物。该类表面活性剂可以用作乳化剂、分散剂、加溶剂、润湿剂、渗透剂、保护性胶体或辅助剂。
合适的阴离子表面活性剂是磺酸、硫酸、磷酸、羧酸的碱金属、碱土金属或铵盐以及它们的混合物。磺酸盐的实例是烷基芳基磺酸盐、二苯基磺酸盐、α-烯烃磺酸盐、木素磺酸盐、脂肪酸和油的磺酸盐、乙氧基化烷基酚的磺酸盐、烷氧基化芳基酚的磺酸盐、缩合萘的磺酸盐、十二烷基-和十三烷基苯的磺酸盐、萘和烷基萘的磺酸盐、磺基琥珀酸盐或磺基琥珀酰胺酸盐。硫酸盐的实例是脂肪酸和油的硫酸盐、乙氧基化烷基酚的硫酸盐、醇的硫酸盐、乙氧基化醇的硫酸盐或脂肪酸酯的硫酸盐。磷酸盐的实例是磷酸酯。羧酸盐的实例是烷基羧酸盐以及羧化醇或烷基酚乙氧基化物。优选的阴离子表面活性剂是硫酸盐和磺酸盐。
合适的非离子表面活性剂是烷氧基化物,N-取代的脂肪酸酰胺,胺氧化物,酯类,糖基表面活性剂,聚合物表面活性剂及其混合物。烷氧基化物的实例是诸如已经被1-50当量烷氧基化的醇、烷基酚、胺、酰胺、芳基酚、脂肪酸或脂肪酸酯的化合物。可以将氧化乙烯和/或氧化丙烯用于烷氧基化,优选氧化乙烯。N-取代的脂肪酸酰胺的实例是脂肪酸葡糖酰胺或脂肪酸链烷醇酰胺。酯类的实例是脂肪酸酯,甘油酯或甘油单酯。糖基表面活性剂的实例是脱水山梨醇、乙氧基化脱水山梨醇、蔗糖和葡萄糖酯或烷基聚葡糖苷。聚合物表面活性剂的实例是乙烯基吡咯烷酮、乙烯醇或乙酸乙烯酯的均聚物或共聚物。优选的非离子表面活性剂是烷氧基化物。非离子表面活性剂如烷氧基化物还可以用作辅助剂。
合适的阳离子表面活性剂是季型表面活性剂,例如具有1或2个疏水性基团的季铵化合物,或长链伯胺的盐。
合适的两性表面活性剂是烷基甜菜碱和咪唑啉类。
合适的嵌段聚合物是包含聚氧乙烯和聚氧丙烯的嵌段的A-B或A-B-A类型嵌段聚合物,或包含链烷醇、聚氧乙烯和聚氧丙烯的A-B-C类型嵌段聚合物。
合适的聚电解质是聚酸或聚碱,其中优选聚酸。聚碱的实例是聚乙烯基胺或聚乙烯胺。聚酸的实例是丙烯酸共聚物或AMPS(2-丙烯酰胺基-2-甲基丙磺酸)共聚物。优选聚电解质为以聚合形式包含含有至少一种选自N-乙烯基内酰胺、N-C1-C6烷基丙烯酰胺和N,N-二C1-C6烷基丙烯酰胺的单体的酰胺的共聚物;聚(C2-6亚烷基二醇)(甲基)丙烯酸酯和/或单C1-22烷基封端的聚(C2-6亚烷基二醇)(甲基)丙烯酸酯;C1-C8烷基(甲基)丙烯酸酯;和(甲基)丙烯酸。更优选聚电解质为以聚合形式包含含有至少一种选自N-乙烯基内酰胺的单体的酰胺的共聚物;单C1-22烷基封端的聚(C2-6亚烷基二醇)(甲基)丙烯酸酯;C1-C8烷基(甲基)丙烯酸酯;和(甲基)丙烯酸。在另一优选形式中,聚电解质为以聚合形式包含25-85wt%含有至少一种选自N-乙烯基内酰胺的单体的酰胺的共聚物;1-40wt%单C1-22烷基封端的聚(C2-6亚烷基二醇)(甲基)丙烯酸酯;5-50wt%C1-C8烷基(甲基)丙烯酸酯;和至多15wt%(甲基)丙烯酸,其中各单体的总和等于100%。在另一优选形式中,聚电解质为以聚合形式包含30-85wt%含有至少一种选自N-乙烯基内酰胺的单体的酰胺的共聚物;5-20wt%单C1-22烷基封端的聚(C2-6亚烷基二醇)(甲基)丙烯酸酯;8-35wt%C1-C8烷基(甲基)丙烯酸酯;和0.5-10wt%(甲基)丙烯酸,其中各单体的总和等于100%。在另一优选形式中,聚电解质为如下共聚物,其以聚合形式含有至少一种含有磺酸基团的烯属不饱和单体、至少一种选自C1-C4烷基(甲基)丙烯酸酯的单体和至少一种选自C6-C22烷基(甲基)丙烯酸酯的单体。在另一优选形式中,聚电解质为如下共聚物,其以聚合形式含有5-50重量%至少一种含有磺酸基团的烯属不饱和单体、20-70重量%至少一种选自C1-C4烷基(甲基)丙烯酸酯的单体和5-30重量%至少一种选自C6-C22烷基(甲基)丙烯酸酯的单体,基于单体总重量。浓缩物可包含0.5-40重量%,优选2-30重量%,尤其是5-25重量%聚电解质(例如聚酸如丙烯酸共聚物或AMPS共聚物)。
合适的辅助剂是本身具有可忽略的农药活性或者本身甚至没有农药活性且改善农药对目标物的生物学性能的化合物。实例是表面活性剂,矿物油或植物油以及其他助剂。
合适的固体载体是铵盐及粉碎的天然矿物,例如高岭土、粘土、滑石粉、白垩、石英、凹凸棒石、蒙脱石或硅酸盐,以及粉碎的合成矿物,例如高分散二氧化硅、氧化铝及硅酸盐。
合适的增稠剂是黄原胶、多糖、瓜尔胶、聚乙烯吡咯烷酮、聚乙烯醇和白炭黑。
合适的增粘剂是羧甲基纤维素,及粉末、颗粒或胶乳形式的天然及合成聚合物,例如阿拉伯树胶、聚乙烯醇及聚乙酸乙烯酯或天然磷脂,例如脑磷脂及卵磷脂,及合成磷脂。
合适的杀菌剂是拌棉醇和异噻唑啉酮衍生物如烷基异噻唑啉酮和苯并异噻唑啉酮。
合适的抗冻剂是乙二醇、丙二醇、尿素和甘油。
合适的消泡剂是聚硅氧烷、长链醇和脂肪酸盐。
合适的着色剂是无机颜料,如氧化铁、氧化钛和普鲁士蓝;以及有机颜料/染料;茜素染料、偶氮染料和金属酞菁染料;以及微量元素,例如铁盐、锰盐、硼盐、铜盐、钴盐、钼盐和锌盐。
合适的粘合剂是聚乙烯醇、可溶性淀粉、糊精、黄原胶、聚甲基吡咯烷酮、羧甲基(乙基)纤维素类。
本发明的杀虫组合物还可以包含其它具有除草、杀虫或杀菌性能的活性物,例如杀菌剂、杀虫剂、杀线虫剂、除草剂、安全剂、生物农药和/或生长调节剂的活性物质。优选的是杀菌剂、杀虫剂、除草剂和生长调节剂。尤其优选的是杀虫剂。
适合的杀菌剂例如甲氧基丙烯酸酯类:腈嘧菌酯(azoxystrobin)、甲香菌酯(couoxystrobin)、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)、唑胺菌酯(pyrametostrobin)、唑菌酯(pyraoxystrobin)、肟菌酯(trifloxystrobin);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)、氯氟醚菌唑(mefentrifluconazole)、ipfentrifluconazole;羧酰胺类:麦锈灵(benodanil)、benzovindiflupyr、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)、吡噻菌胺(penthiopyrad);苯基酰胺类或酰基氨基酸类:苯霜灵(benalaxyl)、精苯霜灵(benalaxyl-M)、甲霜灵(metalaxyl)、精甲霜灵(metalaxyl-M)(mefenoxam)、甲呋酰胺(ofurace)、霜灵(oxadixyl);苯并咪唑类:苯菌灵(benomyl)、多菌灵(carbendazim)、麦穗宁(fuberidazole)、涕必灵(thiabendazole)、甲基托布津(thiophanate-methyl);苯胺基嘧啶类:环丙嘧啶(cyprodinil)、嘧菌胺(mepanipyrim)、二甲嘧菌胺(pyrimethanil);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)等。
适合的除草剂例如乙酰胺类: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(napropamide)、萘丙胺(naproanilide)、烯草胺(pethoxamid)、丙草胺(pretilachlor)、扑草胺(propachlor)、噻醚草胺(thenylchlor);氨基酸衍生物: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)、喹禾灵(quizalofop-P-tefuryl);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(oyfluorfen);三嗪类:莠灭净(ametryn)、莠去津(atrazine)、草净津(cyanazine)、戊草津(dimethametryn)、乙嗪草酮(ethiozin)、六嗪同(hexazinone)、苯嗪草(metamitron)、赛克津(metribuzin)、扑草净(prometryn)、西玛津(simazine)、特丁津(terbuthylazine)、去草净(terbutryn)、苯氧丙胺津(triaziflam);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)、甲基碘磺隆(iodosulfuron)、甲磺胺磺隆(mesosulfuron)、嗪吡嘧磺隆(metazosulfuron)、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);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:胺唑草酮(amicarbazone)、三唑胺(aminotriazole)、莎稗磷(anilofos)、beflubutamid、草除灵(benazolin)、吡草酮(benzofenap)、噻草平(bentazone)、苯并双环酮(benzobicyclon)、氟吡草酮(bicyclopyrone)、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)、cyprosulfamide、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)、fenoxasulfone、四唑酰草胺(fentrazamide)、氟烯草酸(flumiclorac-pentyl)、氟嗪酮(flumioxazin)、胺草唑(flupoxam)、氟咯草酮(flurochloridone)、呋草酮(flurtamone)、茚草酮(indanofan)、异恶草胺(isoxaben)、异氟草(isoxaflutole)、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(oxadiazon)、氯嗪草(oxaziclomefone)、戊唑草(pentoxazone)、唑啉草酯(pinoxaden)、双唑草腈(pyraclonil)、吡草醚(pyraflufen-ethyl)、pyrasulfotole、苄草唑(pyrazoxyfen)、吡唑特(pyrazolynate)、灭藻醌(quinoclamine)、苯嘧磺草胺(saflufenacil)、磺草酮(sulcotrione)、磺胺草唑(sulfentrazone)、特草定(terbacil)、特糠酯酮(tefuryltrione)、环磺酮(tembotrione)、苯唑草酮(topramezone)等。
合适的杀虫剂例如有机磷类: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)、异噁唑磷(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)、噁虫威(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(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);昆虫生长调节剂:a)几丁质合成抑制剂: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)、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(methoxyfenozide)、双苯酰肼(tebufenozide)、艾扎丁(azadirachtin);c)保幼激素类似物:蚊蝇醚(pyriproxyfen)、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(spirotetramat);烟碱受体激动剂/拮抗剂化合物:噻虫胺(clothianidin)、呋虫胺(dinotefuran)、flupyradifurone、吡虫啉(imidacloprid)、噻虫嗪(thiamethoxam)、硝胺烯啶(nitenpyram)、吡虫清(acetamiprid)、噻虫啉(thiacloprid)、烯啶虫胺(nitenpyram);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)、多杀菌素(spinosad)、乙基多杀菌素(spinetoram);其他:氯虫酰胺(chloranthraniliprole)、氰虫酰胺(cyantraniliprole)、氟虫酰胺(flubendiamide)、喹螨醚(fenazaquin)、哒螨酮(pyridaben)、吡螨胺(tebufenpyrad)、唑虫酰胺(tolfenpyrad)、嘧虫胺(flufenerim)、联苯肼酯(bifenazate)、杀螟丹(cartap)、氟啶虫酰胺(flonicamid)、啶虫丙醚(pyridalyl)等。
合适的生长调节剂:脱落酸(abscisic acid)、先甲草胺(amidochlor)、嘧啶醇(ancymidol)、苄胺基嘌呤(6-benzylaminopurine)、油菜素内酯(brassinolide)、地乐胺(butralin)、矮壮素(chlormequat chloride)、氯化胆碱(choline chloride)、环丙酸酰胺(cyclanilide)、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)、抑芽敏(flumetralin)、呋嘧醇(flurprimidol)、达草氟(fluthiacet)、调吡脲(forchlorfenuron)、抗倒胺(inabenfide)、吲哚乙酸(heteroauxin)、抑芽丹(maleic hydrazide)、氟草磺(mefluidide)、助壮素阳离子(mepiquat)、萘乙酸、N-6-苄基腺嘌呤、多效唑(paclobutrazol)、调环酸(prohexadione)、茉莉酸丙酯(prohydrojasmone)、赛二唑素(thidiazuron)、抑芽唑(triapenthenol)、脱叶磷(tributyl phosphorotrithioate)、2,3,5-三碘苯甲酸、抗倒酯(trinexapac-ethyl)和烯效唑(uniconazole)。
本发明特别优选与嗪酮类杀虫活性物不产生拮抗的烟碱受体激动剂/拮抗剂杀虫剂,例如噻虫胺(clothianidin)、呋虫胺(dinotefuran)、flupyradifurone、吡虫啉(imidacloprid)、噻虫嗪(thiamethoxam)、硝胺烯啶(nitenpyram)、吡虫清(acetamiprid)、噻虫啉(thiacloprid)、烯啶虫胺(nitenpyram);特别优选烯啶虫胺(nitenpyram)。
与现有技术相比,本发明至少具有以下有益效果:
本发明的主要的优点是解决了含嗪酮类杀虫活性物组合物的制剂在制备过程中,例如湿法砂磨效率低,砂磨发热、变稠甚至膏化的问题;加水捏合造粒发热、卡机、造粒困难的问题;以及最终的成品悬浮率和分散性低等质量问题。按本发明组合物制备的嗪酮类杀虫剂产品很好的满足了产品加工要求和农药制剂性能指标行业标准。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
实验1:吡蚜酮30%SC
表1:组合物(所有数据以重量%计)
实施例1的制备方法为:将吡蚜酮、丙二醇、硅油消泡剂、苯磺酸钠盐缩聚物、甲基丙烯酸共聚物和水混合,搅拌均匀,然后通过砂磨机进行研磨,得到平均粒径2μm以下的母液,在母液中按比例加入黄原胶和异噻唑啉酮杀菌剂,搅拌直至均匀,得到30%吡蚜酮悬浮剂。
对比例1-4和实施例2按实施例1的制备方法制备,保持加工参数基本一致。
将上述实施例1-2和对比例1-4的样品进行热贮实验(54℃14天),检测各样品热贮前后的悬浮率和分散性,结果如下表2所示。
表2:
由表2数据可知,本发明的杀虫组合物制备吡蚜酮30%SC悬浮剂时,易砂磨,效率高,不会有膏化现象和趋势,显著优于对比例1-4的加工效果;同时制备出的悬浮剂样品热贮前后都具有非常高的悬浮率和分散性,而对比例1-4的悬浮剂样品贮前悬浮率和分散性普遍较低,热贮后有明显下降的趋势,这是悬浮剂产品不期望的。
实验2:吡蚜酮50%WDG
表3:组合物(所有数据以重量%计)
实施例3的制备方法为:将吡蚜酮、苯酚磺酸钠盐缩聚物、聚羧酸钠盐分散剂、聚甲基吡咯烷酮、煅烧高岭土混合均匀,然后通过气流粉碎机进行气流粉碎,得到平均粒径3μm以下的母粉,母粉加入12%的水进行捏合造粒,整粒,干燥得到50%吡蚜酮可分散颗粒剂。
对比例5-8和实施例4按实施例3的制备方法制备,保持加工参数基本一致。
将上述实施例3,4和对比例5-8的样品进行热贮实验(54℃14天),检测各样品热贮前后的悬浮率和分散性,结果如下表4所示。
表4
由表4数据可知,本发明的杀虫组合物制备吡蚜酮50%水分散颗粒剂时,捏合造粒流畅,发热小,容易造粒成型,效率高,显著优于对比例5-8的加工效果;同时制备出的水分散颗粒剂样品热贮前后都具有非常高的悬浮率和分散性,而对比例5-8的水分散颗粒剂样品贮前悬浮率和分散性普遍较低,热贮后有明显下降的趋势,这是水分散颗粒剂产品不期望的。
实验3:吡蚜酮60%+烯啶虫胺20%DF
表5:组合物(所有数据以重量%计)
实施例5的制备方法为:将吡蚜酮、烯啶虫胺、烷基苯磺酸钠盐缩聚物、环氧乙烷环氧丙烷嵌段共聚物、聚乙烯醇、硅油消泡剂、硅藻土混合,加足量的水,得到固含量约50%的浆料,然后通过砂磨机进行研磨,得到平均粒径2μm以下的母液,母液通过喷雾塔喷雾造粒,制得60%吡蚜酮+20%烯啶虫胺干悬浮。
对比例9-12按实施例5的制备方法制备,保持加工参数基本一致。
将上述实施例5和对比例9-12的样品进行热贮实验(54℃14天),检测各样品热贮前后的悬浮率和分散性,结果如下表6所示。
表6:
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由表6数据可知,本发明的杀虫组合物制备吡蚜酮60%+烯啶虫胺20%干悬浮剂时,易砂磨,效率高,喷雾造粒收率高,时间短,显著优于对比例9-12的加工效果;同时制备出的干悬浮剂样品热贮前后都具有非常高的悬浮率和分散性,而对比例9-12的干悬浮剂样品贮前悬浮率和分散性普遍较低,热贮后有明显下降的趋势,这是干悬浮剂产品不期望的。
实施例6
实施例6的制备方法为:将吡蚜酮、烷基苯酚磺酸盐缩聚物和硅酸镁铝混合,通过气流粉碎机进行气流粉碎,得到平均粒径3μm以下的母粉,即得70%吡蚜酮可湿性粉剂。
实施例7
实施例7制备方法:按实施例1的加工方法加工。
实施例8
实施例8制备方法:按实施例3的加工方法加工。
实施例9
实施例9制备方法:将吡蚜酮二水合物、苯磺酸盐缩聚物、三苯乙烯基苯酚乙氧基化物、蓖麻油乙氧基化物、硅油消泡剂、气相白炭黑、油酸甲酯混合,搅拌均匀,然后通过砂磨机进行研磨至平均粒径2μm以下,即得25%吡蚜酮油悬浮剂。
上述实施例6-9的样品进行热贮实验(54℃14天),检测各样品热贮前后的悬浮率和分散性,结果如下表7所示。
表7:
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Claims (10)
1.一种稳定的杀虫组合物,含有:
A:基于组合物总重量计,1-80重量%的嗪酮类杀虫活性物或其药学上可接受的盐及其水合物;和
B:基于组合物总重量计,0.1-20重量%的苯磺酸盐或苯酚磺酸盐的缩聚物。
2.根据权利要求1所述的杀虫组合物,其中,基于组合物的总重量计,含有10-60重量%的嗪酮类杀虫活性物或其药学上可接受的盐及其水合物。
3.根据权利要求1或2所述的杀虫组合物,其中,所述嗪酮类杀虫活性物选自吡蚜酮(pymetrozine)、氟虫吡喹(pyrifluquinazon)或R-768,优选吡蚜酮(pymetrozine)。
4.根据权利要求1所述的杀虫组合物,其中,基于组合物的总重量计,含有0.5-15重量%的苯磺酸盐或苯酚磺酸盐的缩聚物,优选含有1-10重量%。
5.根据权利要求1或4所述的杀虫组合物,其中,所述苯磺酸盐或苯酚磺酸盐的缩聚物具有1,000-50,000摩尔分子量,优选具有2,000-20,000摩尔分子量。
6.根据权利要求1-5中任一项所述的杀虫组合物,其中,所述嗪酮类杀虫活性物与苯磺酸盐或苯酚磺酸盐的缩聚物的重量比为60:1-1:1,优选20:1-2:1。
7.根据权利要求1所述的杀虫组合物,其组合物剂型为水悬浮剂、油悬浮剂、可湿性粉剂、水分散颗粒剂、颗粒剂。
8.根据权利要求1-7中任一项所述的杀虫组合物,其中,所述组合物还包含农业化学可接受的分散剂、润湿剂、消泡剂、增稠剂、防腐剂、pH调节剂、载体、抗冻剂、粘合剂、水。
9.根据权利要求1-8中任一项所述的杀虫组合物,其中,所述组合物还包含其他杀虫剂、杀线虫剂、杀菌剂、除草剂、安全剂、肥料,优选杀虫剂。
10.根据权利要求9所述的杀虫组合物,所述其他杀虫剂是烯啶虫胺活性物。
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