CN114557342B - Preparation method of fluopyram microcapsule suspending agent - Google Patents
Preparation method of fluopyram microcapsule suspending agent Download PDFInfo
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- CN114557342B CN114557342B CN202210172589.8A CN202210172589A CN114557342B CN 114557342 B CN114557342 B CN 114557342B CN 202210172589 A CN202210172589 A CN 202210172589A CN 114557342 B CN114557342 B CN 114557342B
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- Prior art keywords
- fluopyram
- agent
- curing reaction
- emulsion
- dosage
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 49
- KVDJTXBXMWJJEF-UHFFFAOYSA-N fluopyram Chemical compound ClC1=CC(C(F)(F)F)=CN=C1CCNC(=O)C1=CC=CC=C1C(F)(F)F KVDJTXBXMWJJEF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000005783 Fluopyram Substances 0.000 title claims abstract description 46
- 239000000375 suspending agent Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000000839 emulsion Substances 0.000 claims abstract description 29
- 230000001105 regulatory effect Effects 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 36
- 239000003814 drug Substances 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- 229940079593 drug Drugs 0.000 claims description 21
- 239000003995 emulsifying agent Substances 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 10
- 229920000053 polysorbate 80 Polymers 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 238000004945 emulsification Methods 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 229920001285 xanthan gum Polymers 0.000 claims description 4
- 239000000230 xanthan gum Substances 0.000 claims description 4
- 229940082509 xanthan gum Drugs 0.000 claims description 4
- 235000010493 xanthan gum Nutrition 0.000 claims description 4
- 229920004934 Dacron® Polymers 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000002562 thickening agent Substances 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- 239000002775 capsule Substances 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000012695 Interfacial polymerization Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 239000007864 aqueous solution Substances 0.000 description 19
- 239000011162 core material Substances 0.000 description 18
- 238000005538 encapsulation Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- 239000000178 monomer Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000004811 liquid chromatography Methods 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 229920001807 Urea-formaldehyde Polymers 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000008096 xylene Substances 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229940126062 Compound A Drugs 0.000 description 7
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 7
- 229920000877 Melamine resin Polymers 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 239000004640 Melamine resin Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 241001092084 Agrimonia Species 0.000 description 2
- 235000016993 Agrimonia Nutrition 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 229930040373 Paraformaldehyde Chemical group 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002866 paraformaldehyde Chemical group 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 241000221785 Erysiphales Species 0.000 description 1
- 239000005782 Fluopicolide Substances 0.000 description 1
- 239000005784 Fluoxastrobin Substances 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 239000005807 Metalaxyl Substances 0.000 description 1
- 241000233622 Phytophthora infestans Species 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 102000019259 Succinate Dehydrogenase Human genes 0.000 description 1
- 108010012901 Succinate Dehydrogenase Proteins 0.000 description 1
- 239000005857 Trifloxystrobin Substances 0.000 description 1
- 239000005942 Triflumuron Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- GBOYJIHYACSLGN-UHFFFAOYSA-N fluopicolide Chemical compound ClC1=CC(C(F)(F)F)=CN=C1CNC(=O)C1=C(Cl)C=CC=C1Cl GBOYJIHYACSLGN-UHFFFAOYSA-N 0.000 description 1
- UFEODZBUAFNAEU-NLRVBDNBSA-N fluoxastrobin Chemical compound C=1C=CC=C(OC=2C(=C(OC=3C(=CC=CC=3)Cl)N=CN=2)F)C=1C(=N/OC)\C1=NOCCO1 UFEODZBUAFNAEU-NLRVBDNBSA-N 0.000 description 1
- 244000053095 fungal pathogen Species 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000006540 mitochondrial respiration Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000009885 systemic effect Effects 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
- 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
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- A01N25/26—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 in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
-
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a preparation method of fluopyram microcapsule suspending agent, which comprises the steps of firstly preparing a polymer prepolymer as a water phase, preparing fluopyram solution as an oil phase, secondly mixing the two phases into emulsion, further regulating the acidity and alkalinity, promoting the polymer prepolymer to be separated out from the water and coated on the surface of fluopyram oil drops, continuing to perform polymerization, finally heating and solidifying, and adding an auxiliary agent after the reaction is finished to keep the microcapsule suspending agent stable. Finally, the microcapsule suspending agent of the target fluopyram is obtained. The method adopts an interfacial polymerization method to construct the capsule wall of the microcapsule, and the microcapsule suspending agent of fluopyram is obtained for the first time.
Description
Technical Field
The invention relates to the field of pesticide preparations, in particular to a preparation method of fluopyram microcapsule suspending agent.
Background
Fluopyram, english name: fluopyram, chemical name: n- {2- [ 3-chloro-5- (trifluoromethyl) -2-pyridinyl ] ethyl-a, a, a-o-trifluoromethylbenzamide }. Trade name: lufuda, CAS:658066-35-4, appearance: white powder; no obvious smell; melting point: 117.5 ℃; boiling point: 318-321 ℃; n-octanol/water partition coefficient: logp=3.3 (ph 6.5, 20 ℃); solubility: water 16 (distilled water), 15 (pH 4), 16 (pH 7), 15 (pH 9) (mg/L, 20 ℃), toluene 62.2, methylene chloride, methanol, acetone, ethyl acetate, dimethyl sulfoxide >250 (g/L, 20 ℃), the following structural formula:
fluopicolide inhibits mitochondrial respiration by inhibiting electron transfer of succinic dehydrogenase, has broad spectrum and systemic property, can prevent and treat powdery mildew and frosting disease of gray enzyme caused by fungal pathogen, and has high activity by single use and mixed use, and low dosage. The existing dosage forms comprise suspending agents. The silver-bried drug (6, 25% fluopyram plus 62.5% frosting enzyme mixture) proposed by Bayer company has good control effect on tomato late blight caused by phytophthora infestans anti-metalaxyl strain TZ 25. At present, the bayer crop science registers the original drug of fluopyram (registration number PD 20121673) and 41.7% of suspending agent (registration number PD 20121664) in China, and two kinds of compound, namely triflumuron, trifloxystrobin and fluoxastrobin suspending agents are adopted.
At present, the fluopyram preparation registered at home and abroad has no microcapsule suspending agent. The invention relates to a preparation technology and a preparation method of a fluopyram microcapsule suspension.
Disclosure of Invention
The invention aims to provide a preparation method of fluopyram microcapsule suspension, which adopts a low-cost polymer prepolymer as a wall material and solves the problems that the appearance, the particle size, the sedimentation property and the encapsulation rate of microcapsules are difficult to meet the requirements in the experimental process by changing the mass ratio of core materials to the wall material, changing the types of emulsifying agents, changing the using amount of the emulsifying agents, controlling the total time of slowly dripping acid, setting different curing temperatures and the like.
Specifically, the scheme adopted by the invention is as follows:
the preparation method of the fluopyram microcapsule suspending agent comprises the following steps:
step one: the preparation method comprises the steps of taking a monomer compound A and a monomer compound B as raw materials, adjusting the pH to 7-11 by using a base catalyst, and reacting at 25-70 ℃ for 1-5 h to obtain a polymer prepolymer; the molar ratio of the monomer compound A to the monomer compound B is 1: (0.5-2.0); emulsifying the polymer prepolymer to obtain a water phase;
step two: the fluopyram is dissolved in an organic solvent to obtain a raw medicine solution;
step three: dripping the crude drug solution obtained in the second step into the water phase in the first step, and stirring to form emulsion; the core-wall ratio is (4-1) 1.74;
step four: slowly dripping acid into the emulsion in the third step, regulating the pH to be acidic, forming microcapsules, gradually increasing the reaction temperature to carry out curing reaction, and regulating to be neutral after the curing reaction is finished; the acid is selected from hydrochloric acid, acetic acid and ammonium chloride; the acid adding time is 0.5-5 h, the pH is regulated to 1-5, the curing reaction temperature is 30-80 ℃, and the curing reaction time is 1-7 h.
Optionally, in the fourth step: the acid adding time is 2-3 h, the pH is regulated to 3-4, the curing reaction temperature is preferably 50-60 ℃, and the curing reaction time is 3h.
Optionally, the core-wall ratio is (2.5-1.5): 1.74; the molar ratio of the monomer compound A to the monomer compound B is 1: (1-1.2); the pH value is regulated to 8-9 by using a base catalyst.
Optionally, the monomer compound A is at least one selected from urea, melamine and biphenol; the monomer compound B is selected from formaldehyde and paraformaldehyde, and the polymerization degree of the paraformaldehyde is 1-10.
Optionally, the base catalyst in the step one is at least one selected from triethylamine, pyridine, sodium hydroxide, potassium hydroxide, cesium carbonate, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, sodium tert-butoxide and potassium tert-butoxide.
Optionally, the stirring speed of the emulsification of the high polymer prepolymer in the first step is 200-1000 r/min.
Optionally, the emulsifying agent for emulsifying the polymer prepolymer in the first step is selected from: k12, tween-40, EL20, EL40, EL80, agrimonia 1601#, OP-10, SMA, tween-80, agrimonia 601#, SPU9510, and polyvinyl alcohol.
Optionally, the organic solvent in step two is selected from cyclohexanone, dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloromethane, acetone, benzene, toluene, xylene, cyclohexane, N-hexane, ethyl acetate, tetrahydrofuran, acetonitrile, 1, 4-dioxane and N, N-dimethylformamide.
Optionally, the stirring speed of stirring the mixture into emulsion in the step three is 500-2000 r/min.
Optionally, adding an auxiliary agent into the curing reaction product obtained in the step four to obtain a fluopyram microcapsule suspending agent;
the auxiliary agent comprises an emulsifying agent, wherein the emulsifying agent is selected from K 12 TW-80, TW-40, EL20, EL40, EL80, agricultural emulsion 1601#, OP-10 and SMA, the dosage is 0.5% -6%;
dispersing agent: is selected from dacron D977, SCW181214, AEP-90, 925 carboxylate, EO-PO macromolecule dispersing agent and CP90 wetting dispersing agent, the dosage is 1% -6%;
defoaming agent: an organic silicone defoamer, the dosage of which is 0.1 to 0.5 percent;
and (3) a thickening agent: xanthan gum, the dosage is 0.1 to 0.3 percent;
antifreezing agent: ethylene glycol, the dosage is 0.3-0.5%.
The beneficial effects of the invention are mainly as follows:
the synthetic polymer is used as a wall material, weak base weak acid polymerization reaction is adopted to synthesize the microcapsule, and most of the medicines are wrapped in the microcapsule, so that the effects of protecting the medicines and prolonging the medicine effect can be achieved.
Detailed Description
The present invention will be described in detail with reference to the following specific embodiments, and it should not be construed that the practice of the invention is limited to the embodiments. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
In the process of preparing the fluopyram microcapsule suspending agent, the morphology, the particle size, the sedimentation property and the encapsulation rate of the microcapsule are key points. The microcapsule has irregular appearance, rough surface, nonuniform particle size, easy sedimentation, low encapsulation efficiency and the like. The wall material determines the release properties of the microcapsule product to a large extent and is a key component of the microcapsules. Too few wall materials, difficult capsule formation, low encapsulation efficiency, too many wall materials, difficult release of the medicine and influence the exertion of the medicine effect. The emulsifier is a surfactant, and the emulsifier is added into the microcapsule suspending agent to ensure that the dispersion is stable, thus being beneficial to preparing the microcapsule with uniform granularity and better surface morphology; the choice of emulsifier is important in the microcapsule preparation process, and improper selection can cause flocculation and aggregation, and is sticky and cannot be stirred. In the curing reaction process, the acid regulating speed influences the cross-linking speed of urea-formaldehyde resin. The adjustment is too fast, the urea-formaldehyde resin is quickly crosslinked, the coalescence and adhesion are caused, and the system is settled. During the curing reaction, the temperature affects the cross-linking of the urea-formaldehyde resin. The temperature is too low, the urea-formaldehyde resin is not completely crosslinked, and the temperature is too high, so that the urea-formaldehyde resin is easy to aggregate. Aiming at four factors obtained by analysis, the core-wall ratio, the emulsification condition, the acid adjusting time length and the curing temperature, countermeasures are formulated. Countermeasures include changing the mass ratio of the core material to the wall material; changing the type of the emulsifier; changing the dosage of the emulsifier; controlling the total time length of slowly adding the acid dropwise; different curing temperatures are set.
The term "core-to-wall ratio" as used herein refers to the mass ratio of the microcapsule core material to the wall material. The core material refers to a capsule core formed by adding a solvent and a cosolvent into the medicine; the wall material is urea resin capsule shell formed around the core material by the polymer reaction of urea, formaldehyde and the like.
The preparation method of the fluopyram microcapsule suspending agent provided by the invention comprises the following steps:
step one: the preparation method comprises the steps of taking a monomer compound A and a monomer compound B as raw materials, adjusting the pH to 7-11 by using a base catalyst, and reacting at 25-70 ℃ for 1-5 h to obtain a polymer prepolymer; the molar ratio of the monomer compound A to the monomer compound B is 1: (0.5-2.0); emulsifying the polymer prepolymer to obtain a water phase;
step two: the fluopyram is dissolved in an organic solvent to obtain a raw medicine solution;
step three: dripping the crude drug solution obtained in the second step into the water phase in the first step, and stirring to form emulsion; the core-wall ratio is (4-1) 1.74;
step four: slowly dripping acid into the emulsion in the third step, regulating the pH to be acidic, forming microcapsules, gradually increasing the reaction temperature to carry out curing reaction, and regulating to be neutral after the curing reaction is finished; the acid is selected from hydrochloric acid, acetic acid and ammonium chloride; the acid adding time is 0.5-5 h, the pH is regulated to 1-5, the curing reaction temperature is 30-80 ℃, and the curing reaction time is 1-7 h. Wherein the concentration of the hydrochloric acid is 3 to 12mol/L, preferably 6 to 8mol/L.
Preferably, in the fourth step: the acid adding time is 2-3 h, the pH is regulated to 3-4, the curing reaction temperature is preferably 50-60 ℃, and the curing reaction time is 3h.
More preferably, the core-wall ratio is (2.5-1.5): 1.74; the molar ratio of the monomer compound A to the monomer compound B is 1: (1-1.2); and regulating the pH value to 8-9 by using a base catalyst.
The stirring speed of the emulsification of the high polymer prepolymer in the first step is 200-1000 r/min, such as 200r/min, 300r/min, 400r/min, 600r/min, 800r/min or 1000r/min; preferably 300r/min.
The emulsifying agent for emulsifying the polymer prepolymer in the first step is selected from the following components: k12, tween-40, EL20, EL40, EL80, pesticide emulsion 1601#, OP-10, SMA, tween-80, pesticide emulsion 601#, SPU9510 and polyvinyl alcohol. Tween-80 is preferred.
The organic solvent is selected from cyclohexanone, dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloromethane, acetone, benzene, toluene, xylene, cyclohexane, cyclohexanone, N-hexane, ethyl acetate, tetrahydrofuran, acetonitrile, 1, 4-dioxane and N, N-dimethylformamide.
The stirring speed of stirring the emulsion in the third step is 500-2000 r/min, such as 500r/min, 600r/min, 800r/min, 1000r/min, 1500r/min or 2000r/min;
the organic solvent in the third step is preferably toluene or cyclohexanone;
the method also comprises the step of adding an auxiliary agent into the curing reaction product obtained in the step four to obtain the fluopyram microcapsule suspending agent;
the auxiliary agent comprises an emulsifying agent in percentage by mass, wherein the emulsifying agent is selected from K 12 TW-80, TW-40, EL20, EL40, EL80, agricultural emulsion 1601#, OP-10 and SMA, the dosage is 0.5% -6%;
dispersing agent: is selected from dacron D977, SCW181214, AEP-90, 925 carboxylate, EO-PO macromolecule dispersing agent and CP90 wetting dispersing agent, the dosage is 1% -6%;
defoaming agent: an organic silicone defoamer, the dosage of which is 0.1 to 0.5 percent;
and (3) a thickening agent: xanthan gum, the dosage is 0.1 to 0.3 percent;
antifreezing agent: ethylene glycol, 0.3-0.5%.
The present invention will be further described with reference to the following examples, which should not be construed as limiting the scope of the invention, in order to better understand the essential characteristics of the present invention.
Example 1:
(1) 1g of urea and 2g of 37% formaldehyde aqueous solution are weighed into a round bottom flask (the ratio of monomer A to monomer B is 2:3), 25g of water is added, a few drops of 5% sodium hydroxide aqueous solution are dripped into the round bottom flask, the pH is regulated to 8.0, the temperature is slowly increased to 70 ℃ at the speed of 2 ℃/min, and the reaction is carried out for 1 hour under the condition of heat preservation, so that the colorless and transparent urea-formaldehyde resin prepolymer is prepared.
(2) Pouring the mixture prepared in the step 1 into water, adding 1g of Tween-80, adding 30g of water, and uniformly stirring at the speed of 300r/min to obtain a water phase.
(3) 2.0g of fluopyram (core wall ratio 3.0:1.74) was dissolved in 1g of xylene to obtain a solution of the crude drug.
(4) Slowly dripping the crude drug solution obtained in the step 3 into an aqueous phase, and stirring for 1h at a rotating speed of 1000r/min to form emulsion.
(5) The rotation speed is reduced from 1000r/min to 300r/min, 2% hydrochloric acid aqueous solution is slowly added dropwise into the emulsion, the pH is regulated to 3.5, and the total time of acid regulation is 3 hours. Then the rotating speed is reduced to 200r/min, the temperature is gradually increased to 50 ℃, the curing reaction is caused, and the mixture is adjusted to be neutral after being cured for 3 hours.
(6) And (5) adding silicone oil and ethylene glycol into the reaction system obtained in the step (5) to keep the system stable. Thus obtaining the fluopyram microcapsule suspending agent.
(7) The encapsulation was observed under an optical microscope (100-400 times): the sample droplets were observed under an optical microscope with microcapsules of 2-20 microns. And after the sample is observed to be dried by a scanning electron microscope, part of the spheres are broken and sunken.
(8) The active ingredient of fluopyram was measured to be 2.3% by liquid chromatography.
(9) Using liquid chromatography, the encapsulation efficiency was measured to be 52.5%.
(10) Determination of stability. After standing, the product has no caking and no layering phenomenon.
From the experimental results of this example, it was found that the microcapsule breakage may be related to a large core wall ratio, and the core material is large, so that the wall becomes thin and the microcapsule is liable to be broken after drying.
Example 2: (the type of emulsifier is SMA unlike example 1)
(1) 1g of urea and 2g of 37% formaldehyde aqueous solution are weighed into a round bottom flask, 25g of water is added, a few drops of 5% sodium hydroxide aqueous solution are dripped into the round bottom flask, the pH value is regulated to 8.0, the temperature is slowly increased to 70 ℃ at the speed of 2 ℃/min, and the reaction is carried out for 1h under the condition of heat preservation, so that the colorless and transparent urea-formaldehyde resin prepolymer is prepared.
(2) Pouring the mixture prepared in the step 1 into water, adding 1g of SMA, adding 30g of water, and uniformly stirring at the speed of 300r/min to obtain a water phase.
(3) 2.0g of fluopyram was dissolved in 1g of xylene to obtain a solution of the crude drug.
(4) Slowly dripping the crude drug solution obtained in the step 3 into an aqueous phase, and stirring for 1h at a rotating speed of 1000r/min to form emulsion.
(5) The rotation speed is reduced from 1000r/min to 300r/min, 2% hydrochloric acid aqueous solution is slowly added dropwise into the emulsion, the pH is adjusted to 3.5, and the total time is 3 hours. Then the rotating speed is reduced to 200r/min, the temperature is gradually increased to 50 ℃, the curing reaction is caused, and the mixture is adjusted to be neutral after being cured for 3 hours.
(6) And (5) adding silicone oil and ethylene glycol into the reaction system obtained in the step (5) to keep the system stable. Thus obtaining the fluopyram microcapsule suspending agent.
(7) The encapsulation was observed under an optical microscope (100-400 times): the sample droplets were observed under an optical microscope, microcapsules 4-22 microns. And after the sample is observed by a scanning electron microscope to be dried, the sample is in a sphere shape, and the surface is smooth.
(8) The active ingredient of fluopyram was measured to be 2.4% by liquid chromatography.
(9) Using liquid chromatography, the encapsulation efficiency was measured to be 20.3%.
(10) Determination of stability. After standing, agglomerating and layering.
The significantly reduced encapsulation efficiency (20.3% from 52.5%) for SMA as compared to experiment 1, indicated that SMA was not a suitable emulsifier for fluopyram.
Example 3: (unlike example 1, tween-80 was used in an amount of 2g, and the core material was reduced from 2g to 1 g)
(1) 1.0g of urea and 2.0g of 37% formaldehyde aqueous solution are weighed into a round bottom flask, 25g of water is added, a few drops of 5% sodium hydroxide aqueous solution are added dropwise, the pH is regulated to 8.0, the temperature is slowly increased to 70 ℃ at the speed of 2 ℃/min, and the reaction is carried out for 1 hour under the condition of heat preservation, so that the colorless and transparent urea-formaldehyde resin prepolymer is prepared.
(2) Pouring the mixture prepared in the step 1 into water, adding 2g of Tween-80, adding 30g of water, uniformly stirring at the speed of 300r/min, and adding 30g of water to obtain a water phase.
(3) 1.0g of fluopyram (core wall ratio 2.0:1.74) was dissolved in 1g of xylene to obtain a solution of the crude drug.
(4) Slowly dripping the crude drug solution obtained in the step 3 into an aqueous phase, and stirring for 1h at a rotating speed of 1000r/min to form emulsion.
(5) The rotation speed is reduced from 1000r/min to 300r/min, 2% hydrochloric acid aqueous solution is slowly added dropwise into the emulsion, the pH is adjusted to 3.5, and the total time is 3 hours. Then the rotating speed is reduced to 200r/min, the temperature is gradually increased to 50 ℃, the curing reaction is caused, and the mixture is adjusted to be neutral after being cured for 3 hours.
(6) And (5) adding silicone oil and ethylene glycol into the reaction system obtained in the step (5) to keep the system stable. Thus obtaining the fluopyram microcapsule suspending agent.
(7) The encapsulation was observed under an optical microscope (100-400 times): the sample droplets were observed under an optical microscope with microcapsules of 6-16 microns. And after the sample is observed by a scanning electron microscope to be dried, the sample is in a sphere shape, and the surface is smooth.
(8) The active ingredient of fluopyram is 2-4% measured by liquid chromatography.
(9) Using liquid chromatography, the encapsulation efficiency was measured to be 70.0%.
(10) Determination of stability. After standing, the product has no caking and no layering phenomenon.
The experimental result is the best, and compared with experiment 1, the core material quantity is reduced, the capsule wall is firmer, the emulsifier is increased, and better oil-water emulsification is facilitated.
Example 4: (unlike example 1, tween-80 was used in an amount of 2g, and the core material was reduced from 2g to 0.5 g)
(1) 1g of urea and 2g of 37% formaldehyde aqueous solution are weighed into a round bottom flask, 25g of water is added, a few drops of 5% sodium hydroxide aqueous solution are dripped into the round bottom flask, the pH value is regulated to 8.0, the temperature is slowly increased to 70 ℃ at the speed of 2 ℃/min, and the reaction is carried out for 1h under the condition of heat preservation, so that the colorless and transparent urea-formaldehyde resin prepolymer is prepared.
(2) Pouring the mixture prepared in the step 1 into water, adding 2g of Tween-80, adding 30g of water, uniformly stirring at the speed of 300r/min, and adding 30g of water to obtain a water phase.
(3) 0.5g of fluopyram (core wall ratio 1.5:1.74) was dissolved in 1g of xylene to obtain a solution of the crude drug.
(4) Slowly dripping the crude drug solution obtained in the step 3 into an aqueous phase, and stirring for 1h at a certain rotating speed of 1000r/min to form emulsion.
(5) The rotation speed is reduced from 1000r/min to 300r/min, 2% hydrochloric acid aqueous solution is slowly added dropwise into the emulsion, the pH is adjusted to 3.5, and the total time is 3 hours. Then the rotating speed is reduced to 200r/min, the temperature is gradually increased to 50 ℃, the curing reaction is caused, and the mixture is adjusted to be neutral after being cured for 3 hours.
(6) And (5) adding silicone oil and ethylene glycol into the reaction system obtained in the step (5) to keep the system stable. Thus obtaining the fluopyram microcapsule suspending agent.
(7) The encapsulation was observed under an optical microscope (100-400 times): the sample droplets were observed under an optical microscope with microcapsules of 2-20 microns. And after the sample is observed and dried by a scanning electron microscope, the sample is in a sphere shape and has a rough surface.
(8) The active ingredient of fluopyram is 0.5-0.8% measured by liquid chromatography.
(9) Using liquid chromatography, the encapsulation efficiency was measured to be 72.0%.
(10) Determination of stability. After standing, the product has no caking and layering phenomenon.
Compared with experiment 1, the experimental result shows that the core material quantity is reduced, the capsule wall is firmer, the emulsifier is increased, better emulsification of better oil water is facilitated, but the content of effective components is reduced.
Example 5: (changing wall Material type and emulsifier type)
(1) 1.1g of melamine and 2g of 37% formaldehyde aqueous solution are weighed into a round bottom flask, 25g of water is added, a few drops of 5% sodium hydroxide aqueous solution are added dropwise, the pH is regulated to 8.0, the temperature is slowly increased to 70 ℃ at the speed of 2 ℃/min, and the reaction is carried out for 1h under heat preservation, so that the colorless and transparent melamine resin prepolymer is prepared.
(2) The mixture obtained in the step 1 was poured into water, and an aqueous polyvinyl alcohol solution (a solution of 0.2g of polyvinyl alcohol dissolved in 30g of water) was added thereto, followed by stirring at a speed of 300r/min to obtain a water phase.
(3) 1.0g of fluopyram was dissolved in 1g of xylene to give a solution of the crude drug, (core wall ratio 2.0:1.84).
(4) Slowly dripping the crude drug solution obtained in the step 3 into an aqueous phase, and stirring at a rotating speed of 2000r/min to form emulsion. Gradually heating to 35 ℃.
(5) The rotation speed is reduced from 2000r/min to 300r/min, ammonium chloride solid is slowly added into the emulsion in batches, the pH is regulated to 4.5, and the total time is 3 hours. Then the rotating speed is reduced to 200r/min, the temperature is gradually increased to 50 ℃, the curing reaction is caused, and the mixture is adjusted to be neutral after being cured for 3 hours.
(6) And 5, adding organic silicone, xanthan gum and ethylene glycol into the reaction system obtained in the step 5, so that the system is kept stable. Thus obtaining the fluopyram microcapsule suspending agent.
(7) The encapsulation was observed under an optical microscope (100-400 times): the sample droplets were observed under an optical microscope with microcapsules of 2-10 microns. And after the sample is observed by a scanning electron microscope to be dried, the sample is in an ellipsoid shape and has a rough surface.
(8) The active ingredient of fluopyram is 2-4% measured by liquid chromatography.
(9) Using liquid chromatography, the encapsulation efficiency was measured to be 52.0%.
(10) Determination of stability. After standing, the product has no caking and no layering phenomenon.
From the results of this example, melamine resin formed from melamine and formaldehyde is also a good wall material, and polyvinyl alcohol can be used as an emulsifier for fluopyram.
Example 6: (shortening the acid addition time)
(1) 1.1g of melamine and 2g of 37% formaldehyde aqueous solution are weighed into a round bottom flask, 25g of water is added, a few drops of 5% sodium hydroxide aqueous solution are added dropwise, the pH is regulated to 8.0, the temperature is slowly increased to 70 ℃ at the speed of 2 ℃/min, and the reaction is carried out for 1h under heat preservation, so that the colorless and transparent melamine resin prepolymer is prepared.
(2) The mixture obtained in the step 1 was poured into water, and an aqueous polyvinyl alcohol solution (a solution of 0.2g of polyvinyl alcohol dissolved in 30g of water) was added thereto, followed by stirring at a speed of 300r/min to obtain a water phase.
(3) 1.0g of fluopyram was dissolved in 1g of xylene to give a solution of the crude drug, (core wall ratio 2.0:1.84).
(4) Slowly dripping the crude drug solution obtained in the step 3 into an aqueous phase, and stirring at a rotating speed of 2000r/min to form emulsion. Gradually heating to 35 ℃.
(5) The rotation speed is reduced from 2000r/min to 300r/min, ammonium chloride solid is slowly added into the emulsion in batches, the pH is regulated to 4.5, and the total time is 10min. And then the rotating speed is reduced to 200r/min, the temperature is gradually increased to 50 ℃, so that the curing reaction is carried out, and the system is agglomerated and settled in the curing reaction.
Compared with the experimental result in the example 5, the acid regulating time is short, the polymerization reaction speed is too high, and aggregation and sedimentation are easy to occur.
Example 7: (curing temperature was reduced to 40 ℃ C. As compared with example 3)
(1) 1.0g of urea and 2.0g of 37% formaldehyde aqueous solution are weighed into a round bottom flask, 25g of water is added, a few drops of 5% sodium hydroxide aqueous solution are added dropwise, the pH is regulated to 8.0, the temperature is slowly increased to 70 ℃ at the speed of 2 ℃/min, and the reaction is carried out for 1 hour under the condition of heat preservation, so that the colorless and transparent urea-formaldehyde resin prepolymer is prepared.
(2) Pouring the mixture prepared in the step 1 into water, adding 2g of Tween-80, adding 30g of water, uniformly stirring at the speed of 300r/min, and adding 30g of water to obtain a water phase.
(3) 1.0g of fluopyram (core wall ratio 2.0:1.74) was dissolved in 1g of xylene to obtain a solution of the crude drug.
(4) Slowly dripping the crude drug solution obtained in the step 3 into an aqueous phase, and stirring for 1h at a rotating speed of 1000r/min to form emulsion.
(5) The rotation speed is reduced from 1000r/min to 300r/min, 2% hydrochloric acid aqueous solution is slowly added dropwise into the emulsion, the pH is adjusted to 3.5, and the total time is 3 hours. Then the rotating speed is reduced to 200r/min, the temperature is gradually increased to 40 ℃, the curing reaction is caused, and the mixture is adjusted to be neutral after being cured for 3 hours.
(6) And (5) adding silicone oil and ethylene glycol into the reaction system obtained in the step (5) to keep the system stable. Thus obtaining the fluopyram microcapsule suspending agent.
(7) The encapsulation was observed under an optical microscope (100-400 times): the sample droplets were observed under an optical microscope with microcapsules of 6-16 microns. And observing the irregular solid after the sample is dried by a scanning electron microscope.
(8) The active ingredient of fluopyram is 2-4% measured by liquid chromatography.
(9) The encapsulation efficiency was measured to be 23.0% using liquid chromatography.
(10) Determination of stability. After standing, the mixture is gathered and settled, the upper layer is water, and the lower layer is a white powder layer.
The experimental results of this example show that the microcapsule suspending agent may have low aggregation and sedimentation temperature after standing, incomplete reaction and solidification, weak microcapsule wall, high viscosity, and easy aggregation and adhesion. Resulting in microcapsule breakage and reduced encapsulation efficiency.
The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.
Claims (1)
1. The preparation method of the fluopyram microcapsule suspension is characterized by comprising the following steps of:
step one: urea and formaldehyde are used as raw materials, sodium hydroxide is used for adjusting the pH value to 8, and the polymer prepolymer is prepared by reacting for 1h at 70 ℃; the mass ratio of urea to formaldehyde is 1:0.74; emulsifying the polymer prepolymer with Tween-80 to obtain a water phase;
step two: fluopyram is dissolved in dimethylbenzene to obtain a raw medicine solution;
step three: dripping the crude drug solution obtained in the second step into the water phase in the first step, and stirring to form emulsion; the core-wall ratio is 2.0:1.74;
step four: slowly dripping hydrochloric acid into the emulsion in the third step, regulating the pH to be acidic, forming microcapsules, gradually increasing the reaction temperature to carry out curing reaction, and regulating to be neutral after the curing reaction is finished; the acid adding time is 3 hours, the pH is regulated to 3.5, the curing reaction temperature is 50 ℃, and the curing reaction time is 3 hours;
the stirring speed of the emulsification of the high polymer prepolymer in the first step is 200-1000 r/min;
the stirring speed of stirring the emulsion in the third step is 500-2000 r/min;
the method also comprises the step of adding an auxiliary agent into the curing reaction product obtained in the step four to obtain the fluopyram microcapsule suspending agent;
the auxiliary agent comprises the following components in percentage by massComprises an emulsifier selected from the group consisting of K 12 TW-80, TW-40, EL20, EL40, EL80, agricultural emulsion 1601#, OP-10 and SMA, the dosage is 0.5% -6%;
dispersing agent: is selected from dacron D977, SCW181214, AEP-90, 925 carboxylate, EO-PO macromolecule dispersing agent and CP90 wetting dispersing agent, the dosage is 1% -6%;
defoaming agent: an organic silicone defoamer, the dosage of which is 0.1 to 0.5 percent;
and (3) a thickening agent: xanthan gum, the dosage is 0.1 to 0.3 percent;
antifreezing agent: ethylene glycol, the dosage is 0.3-0.5%.
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