CN116138269A - 一种含有氯溴异氰尿酸和硫酸铜的可溶粉剂及其制备方法 - Google Patents
一种含有氯溴异氰尿酸和硫酸铜的可溶粉剂及其制备方法 Download PDFInfo
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- CN116138269A CN116138269A CN202310025726.XA CN202310025726A CN116138269A CN 116138269 A CN116138269 A CN 116138269A CN 202310025726 A CN202310025726 A CN 202310025726A CN 116138269 A CN116138269 A CN 116138269A
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- China
- Prior art keywords
- cyclodextrin
- copper sulfate
- acid
- stirring
- soluble powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229910000365 copper sulfate Inorganic materials 0.000 title claims abstract description 71
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 title claims abstract description 71
- OKNPHOXYVYNIDL-UHFFFAOYSA-N 1-bromo-3-chloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)NC(=O)N(Br)C1=O OKNPHOXYVYNIDL-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000000843 powder Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 25
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical class O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000012190 activator Substances 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 10
- 239000000080 wetting agent Substances 0.000 claims abstract description 10
- 230000036039 immunity Effects 0.000 claims abstract description 6
- 229920000858 Cyclodextrin Polymers 0.000 claims description 73
- 238000003756 stirring Methods 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 21
- 239000001116 FEMA 4028 Substances 0.000 claims description 17
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 17
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 17
- 229960004853 betadex Drugs 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000001384 succinic acid Substances 0.000 claims description 13
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 11
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 11
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- ZBJKOZDGZGTMJX-UHFFFAOYSA-N 2,2,4,4-tetramethylpentanedioic acid Chemical compound OC(=O)C(C)(C)CC(C)(C)C(O)=O ZBJKOZDGZGTMJX-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims description 9
- 239000008055 phosphate buffer solution Substances 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- ATGUDZODTABURZ-UHFFFAOYSA-N thiolan-2-ylideneazanium;chloride Chemical compound Cl.N=C1CCCS1 ATGUDZODTABURZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
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- 229910000278 bentonite Inorganic materials 0.000 claims description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- -1 alkyl naphthalene sulfonate Chemical compound 0.000 claims description 4
- POJWUDADGALRAB-UHFFFAOYSA-N allantoin Chemical compound NC(=O)NC1NC(=O)NC1=O POJWUDADGALRAB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 150000002193 fatty amides Chemical class 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229940074404 sodium succinate Drugs 0.000 claims description 4
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
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- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 3
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 3
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- POJWUDADGALRAB-PVQJCKRUSA-N Allantoin Natural products NC(=O)N[C@@H]1NC(=O)NC1=O POJWUDADGALRAB-PVQJCKRUSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
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- 150000001412 amines Chemical class 0.000 claims description 2
- 229940124277 aminobutyric acid Drugs 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- KKDONKAYVYTWGY-UHFFFAOYSA-M sodium;2-(methylamino)ethanesulfonate Chemical compound [Na+].CNCCS([O-])(=O)=O KKDONKAYVYTWGY-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 abstract description 19
- 241000208125 Nicotiana Species 0.000 abstract description 18
- 241000196324 Embryophyta Species 0.000 abstract description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 4
- NYSDRHDGXAQTPT-UHFFFAOYSA-N N1C(=O)NC(=O)NC1=O.[Cl].[Br] Chemical compound N1C(=O)NC(=O)NC1=O.[Cl].[Br] NYSDRHDGXAQTPT-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001431 copper ion Inorganic materials 0.000 abstract description 4
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 6
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- 229920005551 calcium lignosulfonate Polymers 0.000 description 3
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 3
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- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 2
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- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 2
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- FFWOKTFYGVYKIR-UHFFFAOYSA-N physcion Chemical compound C1=C(C)C=C2C(=O)C3=CC(OC)=CC(O)=C3C(=O)C2=C1O FFWOKTFYGVYKIR-UHFFFAOYSA-N 0.000 description 2
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- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- AMNAZJFEONUVTD-KEWDHRJRSA-N (2s,3s,4s,5r,6r)-6-(4-amino-2-oxopyrimidin-1-yl)-4,5-dihydroxy-3-[[(2s)-3-hydroxy-2-[[2-(methylamino)acetyl]amino]propanoyl]amino]oxane-2-carboxamide Chemical compound O1[C@H](C(N)=O)[C@@H](NC(=O)[C@H](CO)NC(=O)CNC)[C@H](O)[C@@H](O)[C@@H]1N1C(=O)N=C(N)C=C1 AMNAZJFEONUVTD-KEWDHRJRSA-N 0.000 description 1
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- BITDLWAQPKSXTF-UHFFFAOYSA-M 1-[(3-nitrophenyl)methoxymethyl]pyridin-1-ium;chloride Chemical compound [Cl-].[O-][N+](=O)C1=CC=CC(COC[N+]=2C=CC=CC=2)=C1 BITDLWAQPKSXTF-UHFFFAOYSA-M 0.000 description 1
- MWSLLEWOGABAFW-UHFFFAOYSA-N 1-bromo-1,3,5-triazinane-2,4,6-trione Chemical compound BrN1C(=O)NC(=O)NC1=O MWSLLEWOGABAFW-UHFFFAOYSA-N 0.000 description 1
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- FEACDOXQOYCHKU-UHFFFAOYSA-N Gougerotin Natural products CNCC(=O)NC1=NC(=O)N(C=C1)C2OC(C(O)C(NC(=O)C(N)CO)C2O)C(=O)N FEACDOXQOYCHKU-UHFFFAOYSA-N 0.000 description 1
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- UGNZSMZSJYOGNX-UHFFFAOYSA-N Isoviocristine Natural products O=C1C=C(C)C(=O)C2=CC3=CC(OC)=CC(O)=C3C(O)=C21 UGNZSMZSJYOGNX-UHFFFAOYSA-N 0.000 description 1
- 229920001491 Lentinan Polymers 0.000 description 1
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- WLXGUTUUWXVZNM-UHFFFAOYSA-N anthraglycoside A Natural products C1=C(C)C=C2C(=O)C3=CC(OC)=CC(O)=C3C(=O)C2=C1OC1OC(CO)C(O)C(O)C1O WLXGUTUUWXVZNM-UHFFFAOYSA-N 0.000 description 1
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- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
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- HWQXBVHZYDELQG-UHFFFAOYSA-L disodium 2,2-bis(6-methylheptyl)-3-sulfobutanedioate Chemical compound C(CCCCC(C)C)C(C(C(=O)[O-])S(=O)(=O)O)(C(=O)[O-])CCCCCC(C)C.[Na+].[Na+] HWQXBVHZYDELQG-UHFFFAOYSA-L 0.000 description 1
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- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
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- OXWFFWJKUNMMSO-UHFFFAOYSA-N n-octyl-n'-[2-(octylamino)ethyl]ethane-1,2-diamine Chemical compound CCCCCCCCNCCNCCNCCCCCCCC OXWFFWJKUNMMSO-UHFFFAOYSA-N 0.000 description 1
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- NWWZPOKUUAIXIW-FLIBITNWSA-N thiamethoxam Chemical compound [O-][N+](=O)\N=C/1N(C)COCN\1CC1=CN=C(Cl)S1 NWWZPOKUUAIXIW-FLIBITNWSA-N 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
- A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
-
- 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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- A—HUMAN NECESSITIES
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Abstract
本发明公开了一种含有氯溴异氰尿酸和硫酸铜的可溶粉剂及其制备方法,该含有氯溴异氰尿酸和硫酸铜的可溶粉剂包括如下重量百分比组分:氯溴异氰尿酸40~60%、植物免疫激活剂0.2~2%、硫酸铜1~5%、改性环糊精1~5%、分散剂2~8%、填料30~40%、余量为润湿剂。与现有技术相比,本发明制备的含有氯溴异氰尿酸和硫酸铜的可溶粉剂黏附性增强,能防止产品变紫色,降低了铜离子释放速率,提高了药物利用率,减少了对作物的安全风险;并且能显著提高烟叶的质量,促进烟叶生长,适于规模化生产。
Description
技术领域
本发明涉及农药技术领域,尤其涉及一种含有氯溴异氰尿酸和硫酸铜的农药组合物及其制备方法。
背景技术
氯溴异氰尿酸是一种低毒内吸杀菌剂,其作用机理是喷施到作物表面能慢慢地释放Cl和Br,形成次氯酸(HCIO)和次溴酸(HBrO)分子。还具一定的促进作物营养生长作用。除农业上用作多种作物病害预防外,还可用于蚕具、游泳池、鱼池、禽畜舍体外消毒。及工业循环水杀菌除藻消毒,但是单独使用持效期较短,无法达到增收保产的效果。
β-环糊精是一种生物聚合物,通常由多个β-连接的葡萄糖单元组成,具有一个由外部亲水性外壳和内部疏水性空腔组成的漏斗形结构。亲水性部分使其具有水溶性,而亲水性内部使其具有捕获疏水性分子的能力。采用β-环糊精封装合成的农药制剂可增加水溶性,从而降低了应用剂量。但是现有技术中,β-环糊精的包封效果较差,不能提升黏附性,导致农药的利用率处于较低的水平。因此开发一种疗效好,持续时间长,无安全隐患的含有氯溴异氰尿酸和硫酸铜的可溶粉剂显得至关重要。
发明专利CN107027804A公开了一种含二氧化氯的抗病毒组合物,是由二氧化氯与化合物A组成的组合物;组合物中二氧化氯可以是直接含有,也可以是物质在混合后产生二氧化氯;化合物A选自:吡虫啉、啶虫脒、吡蚜酮、噻虫嗪、大黄素甲醚、甲噻诱胺、氨基寡糖素、嘧肽霉素、盐酸吗啉胍、香菇多糖、三十烷醇、氯溴异氰尿酸、宁南霉素、硫酸铜、乙酸铜、辛菌胺醋酸盐中的一种或几种。该组合物用于植物病毒病的防治。但是该发明制备的抗病毒组合物黏附性较差,硫酸铜易变色,对作物有安全风险,而且持效期较短,增收保产的效果差。
发明内容
有鉴于现有技术中含有氯溴异氰尿酸和硫酸铜的可溶粉剂黏附性较差、易变质、对作物有安全风险、持效期较短的缺点,本发明所要解决的技术问题是提供一种具有较高黏附性、不易变质、药效长和效果明显的含有氯溴异氰尿酸和硫酸铜的可溶粉剂及其制备方法。
为了实现上述发明目的,本发明采用了如下的技术方案:
本发明的含有氯溴异氰尿酸和硫酸铜的可溶粉剂,包括如下重量百分比组分:氯溴异氰尿酸40~60%、植物免疫激活剂0.2~2%、硫酸铜1~5%、分散剂2~8%、填料30~40%、余量为润湿剂。
优选的,所述含有氯溴异氰尿酸和硫酸铜的可溶粉剂,包括如下重量百分比组分:氯溴异氰尿酸40~60%、植物免疫激活剂0.2~2%、硫酸铜1~5%、改性环糊精1~5%、分散剂2~8%、填料30~40%、余量为润湿剂。
所述分散剂为木质素磺酸盐、烷基萘磺酸盐、烷基酚聚氧乙烯醚硫酸盐、烷基酚聚氧乙烯醚磷酸盐中的至少一种。
所述润湿剂为十二烷基硫酸钠、烷基苯磺酸盐、丁二酸酯磺酸钠盐、二异辛基琥珀磺酸钠、脂肪酰胺磺酸钠盐、脂肪酰胺N-甲基牛磺酸钠盐、脂肪醇聚氧乙烯醚类、烷基酚聚氧乙烯醚类中的至少一种。
所述填料为白炭黑、膨润土、硫酸铵中的至少一种。
所述植物免疫激活剂选自四甲基戊二酸、增产胺、氨基丁酸、尿囊素中的至少一种。
一种含有氯溴异氰尿酸和硫酸铜的可溶粉剂,制备方法如下:
步骤1、将原料按照重量百分比配方进行称取,将改性环糊精加入水中,搅拌10~30min,搅拌速度为100~300rpm,然后加入硫酸铜,在40~60℃下连续搅拌2~4h,搅拌速度为50~200rpm,然后在30~40℃进行超声处理1~3h,其中超声频率为25~50kHz、超声功率为200~400W,50~300目筛网过滤取滤饼,在50~80℃干燥1~10h,得到硫酸铜包合物;
步骤2、将氯溴异氰尿酸、植物免疫激活剂、分散剂、润湿剂、填料混合搅拌1~5h,搅拌速度为100~500rpm,得到混合料,将混合料进行研磨处理,研磨后过200~400目,得到粉料,向粉料中加入步骤1制备的硫酸铜包合物,进行搅拌混合,得到含有氯溴异氰尿酸和硫酸铜的可溶粉剂。
优选的,所述改性环糊精与水的质量比为1:6~15。
所述改性环糊精的制备方法如下,以重量份计:
S1、将3~8份接枝环糊精和20~30份五硫化二磷加入120~180份正丁砜中,在25~40℃搅拌20~40min,搅拌速度为100~300rpm,加入5~15份三乙胺,然后加热到120~140℃,搅拌10~15h,搅拌速度为50~200rpm,温度降至60~90℃,加入150~250份水,过滤收集沉淀物、洗涤,干燥至恒重,得到硫化环糊精;
S2、将5~15份丁二酸、15~22份步骤S1制备的硫化环糊精加入200~400份乙二醇中,然后搅拌5~20min,搅拌速度为100~200rpm,在100~120℃氮气气氛下回流20~30h,冷却至室温后,以8000~12000rpm离心10~20min,然后分别用水和乙二醇依次反复洗涤1~3次,在60~90℃真空下干燥10~20h,得到后处理环糊精;
S3、先将5~15份微晶纤维素、10~20份丁二酸、15~22份步骤S2制备的后处理环糊精加入150~250份水中,超声处理20~40min后过滤,其中超声频率为25~50kHz、超声功率为200~400W,在90~110℃烘箱中加热0.5~2h后,用水洗涤1~3次,然后50~80℃真空干燥10~30h,得到改性环糊精。
所述接枝环糊精的制备方法如下,以重量份计:
Z1、将3~7份β-环糊精和20~30份2-亚氨基硫杂环戊烷盐酸盐加入到70~120份pH值为6~8的磷酸盐缓冲液中,然后加入0.5~2份乙二胺四乙酸二钠,搅拌20~30h,搅拌速度为100~300rpm,通过截留分子量为1200~2000的透析膜透析1~4d,得到预处理环糊精;
Z2、将1~5份七水硫酸亚铁和2~5份三氯化铁加入到100~300份5~15wt%盐酸中,超声处理5~20min,其中超声频率为20~50kHz、超声功率为200~400W,然后滴加150~250份1~2wt%氢氧化钠水溶液,搅拌10~30min,搅拌速度为100~400rpm,收集沉淀,用水洗涤1~5次,直至洗涤液变为中性,得到添加剂;
Z3、将0.1~0.5份步骤Z2制备的添加剂加入到8~12份步骤Z1制备的预处理环糊精中,超声处理3~8min,超声频率为20~50kHz、超声功率为200~400W,然后搅拌10~20h,搅拌速度为100~300rpm,8000~12000rpm离心分离3~8min,收集沉淀,用水洗涤1~3次,35~50℃真空干燥5~20h,得到接枝环糊精。
氯溴异氰尿酸具有杀死细菌能力,与硫酸铜混配能进一步增强细菌杀灭能力,但是硫酸铜在贮存过程中吸潮后,容易导致产品变紫色,而且在潮湿天气,硫酸铜会快速释放铜离子,对作物有安全风险。在本发明试验前中阶段,土壤中的活性细菌急剧减少,可能是硫酸铜包合物持续释放硫酸铜,与氯溴异氰尿酸作用将细菌杀灭,土壤中的细菌减少;后阶段,除细菌逐渐恢复至正常水平,可能是氯溴异氰尿酸在土壤中被消解,失去抑制细菌或杀菌作用,进而细菌数量恢复到正常水平。可能原因在于本发明通过将β-环糊精和2-亚氨基硫杂环戊烷盐酸盐加入到磷酸盐缓冲液进行反应,在与含铁化合物进行复合,得到接枝环糊精,将接枝环糊精和五硫化二磷加入正丁砜中,再加入三乙胺,搅拌反应,得到硫化环糊精,再与丁二酸在乙二醇中反应得到后处理环糊精,与微晶纤维素复合得到改性环糊精,通过将硫酸铜采用改性环糊精进行包覆,再与氯溴异氰尿酸、四甲基戊二酸、木质素磺酸钙、二异辛基琥珀磺酸钠、膨润土进行混合,配置成含有氯溴异氰尿酸和硫酸铜的可溶粉剂。
β-环糊精和2-亚氨基硫杂环戊烷盐酸盐加入到磷酸盐缓冲液进行反应,形成硫醇基团,硫醇基团进一步通过形成强Fe-S键与β-环糊精表面结合。有利于硫酸铜通过氢键和静电相互作用与改性环糊精形成包合物,增强相互作用,抵抗分离和释放。其中,接枝环糊精在三乙胺的存在下与五硫化二磷反应,得到硫化环糊精,提高了接枝环糊精的溶解度。由于硫化作用,丁二酸与β-环糊精之间通过二硫键能形成很强的黏附,并降低了后处理环糊精的粒径,从而提升改性环糊精的在农药施药过程中粘附性能,提高利用率。微晶纤维素在酸性条件下水解,由于粒径的降低,暴露了更多的-OH基团,水解后的微晶纤维素能更充分的进行络合提升改性环糊精的包体络合功能。
氯溴异氰尿酸和硫酸铜复合属于强氧化性杀菌剂,杀菌速度快,但持效期较短,通过将植物免疫激活剂组合使用,在增强原有药效的基础上,使作物激发生长潜能,达到长时间保叶保果,增产效果优异。通过本发明烟叶质量的提高,这说明氯溴异氰尿酸的使用对烟草生长的无明显抑制作用,较为安全,并且与四甲基戊二酸进行复配后能显著提高烟叶的质量,促进烟叶生长。
与现有技术相比,本发明的有益效果:
1)本发明通过将β-环糊精和2-亚氨基硫杂环戊烷盐酸盐加入到磷酸盐缓冲液进行反应,在与含铁化合物进行复合,得到接枝环糊精,将接枝环糊精和五硫化二磷加入正丁砜中,再加入三乙胺,搅拌反应,得到硫化环糊精,再与丁二酸在乙二醇中反应得到后处理环糊精,与微晶纤维素复合得到改性环糊精,对硫酸铜具有较好的包覆效果,黏附性增强,并能防止产品变紫色,降低铜离子释放速率,药物利用率提高,减少对作物的安全风险;
2)本发明采用科学的配比通过将硫酸铜采用改性环糊精进行包覆,再与氯溴异氰尿酸、植物免疫激活剂、分散剂、润湿剂、填料进行混合,配置成含有氯溴异氰尿酸和硫酸铜的可溶粉剂,能显著提高烟叶的质量,促进烟叶生长,适于规模化生产。
具体实施方式
下面,通过具体实施例对本发明的技术方案进行详细说明,但是应该明确提出这些实施例用于举例说明,但是不解释为限制本发明的范围。
实施例1
一种含有氯溴异氰尿酸和硫酸铜的可溶粉剂,制备方法如下:
步骤1、将30g改性环糊精加入200g水中搅拌20min,搅拌速度为200rpm,然后加入20g硫酸铜,在50℃下连续搅拌3h,搅拌速度为100rpm,然后在35℃进行超声处理2h,其中超声频率为45kHz、超声功率为300W,100目筛网过滤取滤饼,在70℃干燥6h,得到硫酸铜包合物;
步骤2、将500g氯溴异氰尿酸、10g四甲基戊二酸、50g木质素磺酸钙、40g二异辛基琥珀磺酸钠、350g膨润土混合搅拌3h,搅拌速度为300rpm,得到混合料,将混合料进行研磨处理,研磨后过300目,得到粉料,向粉料中加入步骤1制备的硫酸铜包合物,进行搅拌混合,得到含有氯溴异氰尿酸和硫酸铜的可溶粉剂。
所述改性环糊精的制备方法如下:
S1、将5g接枝环糊精和24g五硫化二磷加入150g正丁砜中,在30℃搅拌30min,搅拌速度为200rpm,加入10g三乙胺,然后加热到130℃,搅拌12h,搅拌速度为100rpm,温度降至80℃,加入200g水,过滤收集沉淀物、洗涤,干燥至恒重,得到硫化环糊精;
S2、将10g丁二酸、20g步骤S1制备的硫化环糊精加入300g乙二醇中,置于带氮气入口的三颈圆底瓶中,然后搅拌10min,搅拌速度为150rpm,在110℃氮气气氛下回流24h,冷却至室温后,以10000rpm离心15min,然后分别用水和乙二醇依次反复洗涤3次,在80℃真空下干燥12h,得到后处理环糊精;
S3、先将10g微晶纤维素、15g丁二酸、20g步骤S2制备的后处理环糊精加入200g水中,超声处理30min后过滤,其中超声频率为45kHz、超声功率为300W,在105℃烘箱中加热1h后,用水洗涤3次,然后70℃真空干燥24h,得到改性环糊精。
所述接枝环糊精的制备方法如下:
Z1、将5gβ-环糊精和25g 2-亚氨基硫杂环戊烷盐酸盐加入到100gpH值为8的磷酸盐缓冲液中,然后加入1g乙二胺四乙酸二钠,搅拌24h,搅拌速度为200rpm,通过截留分子量为1200的透析膜透析2d,得到预处理环糊精;
Z2、将3g七水硫酸亚铁和3.2g三氯化铁加入到200g 10wt%盐酸中,超声处理10min,其中超声频率为25kHz、超声功率为300W,然后滴加200g 1.25wt%氢氧化钠水溶液,搅拌20min,搅拌速度为300rpm,收集沉淀,用水洗涤3次,直至洗涤液变为中性,得到添加剂;
Z3、将0.3g步骤Z2制备的添加剂加入到10g步骤Z1制备的预处理环糊精中,超声处理5min,超声频率为25kHz、超声功率为300W,然后搅拌14h,搅拌速度为200rpm,10000rpm离心分离5min,收集沉淀,用水洗涤3次,40℃真空干燥10h,得到接枝环糊精。
实施例2
一种含有氯溴异氰尿酸和硫酸铜的可溶粉剂的制备方法与实施例1基本相同,唯一区别仅仅在于:所述改性环糊精的制备方法不同。
所述改性环糊精采用如下方法制备而成:
S1、将5gβ-环糊精和24g五硫化二磷加入150g正丁砜中,在30℃搅拌30min,搅拌速度为200rpm,加入10g三乙胺,然后加热到130℃,搅拌12h,搅拌速度为100rpm,温度降至80℃,加入200g水,过滤收集沉淀物、洗涤,干燥至恒重,得到硫化环糊精;
S2、将10g丁二酸、20g步骤S1制备的硫化环糊精加入300g乙二醇中,置于带氮气入口的三颈圆底瓶中,然后搅拌10min,搅拌速度为150rpm,在110℃氮气气氛下回流24h,冷却至室温后,以10000rpm离心15min,然后分别用水和乙二醇依次反复洗涤3次,在80℃真空下干燥12h,得到后处理环糊精;
S3、先将10g微晶纤维素、15g丁二酸、20g步骤S2制备的后处理环糊精加入200g水中,超声处理30min后过滤,其中超声频率为45kHz、超声功率为300W,在105℃烘箱中加热1h后,用水洗涤3次,然后70℃真空干燥24h,得到改性环糊精。
实施例3
一种含有氯溴异氰尿酸和硫酸铜的可溶粉剂的制备方法与实施例1基本相同,唯一区别仅仅在于:含有氯溴异氰尿酸和硫酸铜的可溶粉剂的制备方法中将改性环糊精替换为接枝环糊精。
所述接枝环糊精的制备方法与实施例1相同。
实施例4
一种含有氯溴异氰尿酸和硫酸铜的可溶粉剂的制备方法与实施例1基本相同,唯一区别仅仅在于:含有氯溴异氰尿酸和硫酸铜的可溶粉剂的制备方法中不添加四甲基戊二酸。
所述改性环糊精的制备方法与实施例1相同。
所述接枝环糊精的制备方法与实施例1相同。
对比例1
一种含有氯溴异氰尿酸和硫酸铜的可溶粉剂的制备方法与实施例1基本相同,唯一区别仅仅在于:含有氯溴异氰尿酸和硫酸铜的可溶粉剂的制备方法中将改性环糊精替换为β-环糊精。
对比例2
一种含有氯溴异氰尿酸和硫酸铜的可溶粉剂的制备方法与实施例1基本相同,唯一区别仅仅在于:含有氯溴异氰尿酸和硫酸铜的可溶粉剂的制备方法中不添加改性环糊精。
对比例3
一种含有氯溴异氰尿酸和硫酸铜的可溶粉剂的制备方法与实施例1基本相同,唯一区别仅仅在于:含有氯溴异氰尿酸和硫酸铜的可溶粉剂的制备方法中不添加改性环糊精和不添加四甲基戊二酸。
测试例1
细菌数量测试
称取若干种植烟土壤土样,每份200g,加入无菌水调节湿度未60%。7d后,将本发明制备的含有氯溴异氰尿酸和硫酸铜的可溶粉剂加水配置成5mg/kg的水溶液,用微量喷雾器将配置好的水溶液均匀喷洒在土样中,采用清水作为对照组。施药时施药量保持土壤水含量达到60%为止,处理后1、7、28d后取土壤样品分析土壤的细菌数量,培养过程中均为室温、避光培养。每个试样测试三次,测试结果见表1。
表1:细菌数量测试结果
测试例2
烟叶质量测试
在云南金沙江选取烟草种植地,每组划分为1hm2,将本发明制备的含有氯溴异氰尿酸和硫酸铜的可溶粉剂加水配置成2g/L水溶液,喷洒量为400L/hm2,在烟草团颗期进行喷药处理,隔一天喷洒一次,共喷洒三次。喷药后25d、55d时分别对试验烟株进行数据记录(株高、茎围、上、中、下叶平均面积)等数据的分析从而进行产量对比。烟叶面积等于单片叶长乘以叶宽再乘以一个基数r,r=0.6345。
测试结果如表2所示。
表2:烟叶质量测试结果
从表1、表2的测试结果看出,实施例1的持久杀菌性能、烟草生长情况来看是最好的,氯溴异氰尿酸具有杀死细菌能力,与硫酸铜混配能进一步增强细菌杀灭能力,但是硫酸铜在贮存过程中吸潮后,容易导致产品变紫色,而且在潮湿天气,硫酸铜会快速释放铜离子,对作物有安全风险。在本发明试验前中阶段,土壤中的活性细菌急剧减少,可能是硫酸铜包合物持续释放硫酸铜,与氯溴异氰尿酸作用将细菌杀灭,土壤中的细菌减少;后阶段,除细菌逐渐恢复至正常水平,可能是氯溴异氰尿酸在土壤中被消解,失去抑制细菌或杀菌作用,进而细菌数量恢复到正常水平。可能原因在于本发明通过将β-环糊精和2-亚氨基硫杂环戊烷盐酸盐加入到磷酸盐缓冲液进行反应,在与含铁化合物进行复合,得到接枝环糊精,将接枝环糊精和五硫化二磷加入正丁砜中,再加入三乙胺,搅拌反应,得到硫化环糊精,再与丁二酸在乙二醇中反应得到后处理环糊精,与微晶纤维素复合得到改性环糊精,通过将硫酸铜采用改性环糊精进行包覆,再与氯溴异氰尿酸、四甲基戊二酸、木质素磺酸钙、二异辛基琥珀磺酸钠、膨润土进行混合,配置成含有氯溴异氰尿酸和硫酸铜的可溶粉剂。
β-环糊精和2-亚氨基硫杂环戊烷盐酸盐加入到磷酸盐缓冲液进行反应,形成硫醇基团,硫醇基团进一步通过形成强Fe-S键与β-环糊精表面结合。有利于硫酸铜通过氢键和静电相互作用与改性环糊精形成包合物,增强相互作用,抵抗分离和释放。其中,接枝环糊精在三乙胺的存在下与五硫化二磷反应,得到硫化环糊精,提高了接枝环糊精的溶解度。由于硫化作用,丁二酸与β-环糊精之间通过二硫键能形成很强的黏附,并降低了后处理环糊精的粒径,从而提升改性环糊精的在农药施药过程中粘附性能,提高利用率。微晶纤维素在酸性条件下水解,由于粒径的降低,暴露了更多的-OH基团,水解后的微晶纤维素能更充分的进行络合提升改性环糊精的包体络合功能。
氯溴异氰尿酸和硫酸铜复合属于强氧化性杀菌剂,杀菌速度快,但持效期较短,通过将植物免疫激活剂组合使用,在增强原有药效的基础上,使作物激发生长潜能,达到长时间保叶保果,增产效果优异。通过本发明烟叶质量的提高,这说明氯溴异氰尿酸的使用对烟草生长的无明显抑制作用,较为安全,并且与四甲基戊二酸进行复配后能显著提高烟叶的质量,促进烟叶生长。
Claims (10)
1.一种含有氯溴异氰尿酸和硫酸铜的可溶粉剂,其特征在于,包括如下组分:氯溴异氰尿酸、植物免疫激活剂、硫酸铜、分散剂、润湿剂、填料。
2.如权利要求1所述含有氯溴异氰尿酸和硫酸铜的可溶粉剂,其特征在于,包括如下重量百分比组分:氯溴异氰尿酸40~60%、植物免疫激活剂0.2~2%、硫酸铜1~5%、改性环糊精1~5%、分散剂2~8%、填料30~40%、余量为润湿剂。
3.一种制备如权利要求2所述含有氯溴异氰尿酸和硫酸铜的可溶粉剂的方法,其特征在于:
步骤1、将原料按照重量百分比配方进行称取,将改性环糊精加入水中搅拌均匀,然后加入硫酸铜,在加热搅拌反应,然后超声处理,最后过滤、干燥,得到硫酸铜包合物;
步骤2、将氯溴异氰尿酸、植物免疫激活剂、分散剂、润湿剂、填料混合搅拌,得到混合料,将混合料进行研磨处理,研磨后过筛,得到粉料,向粉料中加入步骤1制备的硫酸铜包合物,进行搅拌混合,得到含有氯溴异氰尿酸和硫酸铜的可溶粉剂。
4.如权利要求3所述的方法,其特征在于:所述分散剂为木质素磺酸盐、烷基萘磺酸盐、烷基酚聚氧乙烯醚硫酸盐、烷基酚聚氧乙烯醚磷酸盐中的至少一种。
5.如权利要求3所述的方法,其特征在于:所述润湿剂为十二烷基硫酸钠、烷基苯磺酸盐、丁二酸酯磺酸钠盐、二异辛基琥珀磺酸钠、脂肪酰胺磺酸钠盐、脂肪酰胺N-甲基牛磺酸钠盐、脂肪醇聚氧乙烯醚类、烷基酚聚氧乙烯醚类中的至少一种。
6.如权利要求3所述的方法,其特征在于:所述填料为白炭黑、膨润土、硫酸铵中的至少一种。
7.如权利要求3所述的方法,其特征在于:所述植物免疫激活剂选自四甲基戊二酸、增产胺、氨基丁酸、尿囊素中的至少一种。
8.如权利要求3所述的方法,其特征在于:所述改性环糊精与水的质量比为1:6~15。
9.如权利要求3所述的方法,其特征在于,所述改性环糊精的制备方法如下:
S1、将接枝环糊精和五硫化二磷加入正丁砜中,在25~40℃搅拌反应,加入三乙胺,然后加热到120~140℃,搅拌10~15h,温度降至60~90℃,加入水,过滤收集沉淀物、洗涤,干燥至恒重,得到硫化环糊精;
S2、将丁二酸、步骤S1制备的硫化环糊精加入乙二醇中,然后搅拌反应,在100~120℃氮气气氛下回流20~30h,冷却至室温后离心分离取沉淀,洗涤、干燥,得到后处理环糊精;
S3、将微晶纤维素、丁二酸、步骤S2制备的后处理环糊精加入水中,超声处理后过滤,在90~110℃烘箱中加热0.5~2h后,洗涤、干燥,得到改性环糊精。
10.如权利要求9所述的方法,其特征在于,所述接枝环糊精的制备方法如下:
Z1、将β-环糊精和2-亚氨基硫杂环戊烷盐酸盐加入到磷酸盐缓冲液中,然后加入乙二胺四乙酸二钠,搅拌20~30h,通过透析膜进行透析,得到预处理环糊精;
Z2、将七水硫酸亚铁和三氯化铁加入到盐酸中超声处理,然后滴加氢氧化钠水溶液搅拌反应,收集沉淀,用水洗涤,直至洗涤液变为中性,得到添加剂;
Z3、将步骤Z2制备的添加剂加入到步骤Z1制备的预处理环糊精中,超声处理,然后搅拌,最后离心分离,收集沉淀、洗涤、干燥,得到接枝环糊精。
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