CN115777705A - Polyurethane hybridization antioxidant biopesticide microcapsule and preparation method thereof - Google Patents
Polyurethane hybridization antioxidant biopesticide microcapsule and preparation method thereof Download PDFInfo
- Publication number
- CN115777705A CN115777705A CN202211547186.3A CN202211547186A CN115777705A CN 115777705 A CN115777705 A CN 115777705A CN 202211547186 A CN202211547186 A CN 202211547186A CN 115777705 A CN115777705 A CN 115777705A
- Authority
- CN
- China
- Prior art keywords
- antioxidant
- nanoparticles
- polyurethane
- biopesticide
- microcapsule
- 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.)
- Pending
Links
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 93
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 91
- 239000004814 polyurethane Substances 0.000 title claims abstract description 75
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 75
- 230000000853 biopesticidal effect Effects 0.000 title claims abstract description 58
- 239000003094 microcapsule Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000009396 hybridization Methods 0.000 title description 4
- 239000002105 nanoparticle Substances 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000000575 pesticide Substances 0.000 claims abstract description 25
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 24
- 239000002775 capsule Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000839 emulsion Substances 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 229920000768 polyamine Polymers 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- 230000001804 emulsifying effect Effects 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- CXEGAUYXQAKHKJ-NSBHKLITSA-N emamectin B1a Chemical compound C1=C[C@H](C)[C@@H]([C@@H](C)CC)O[C@]11O[C@H](C\C=C(C)\[C@@H](O[C@@H]2O[C@@H](C)[C@H](O[C@@H]3O[C@@H](C)[C@H](NC)[C@@H](OC)C3)[C@@H](OC)C2)[C@@H](C)\C=C\C=C/2[C@]3([C@H](C(=O)O4)C=C(C)[C@@H](O)[C@H]3OC\2)O)C[C@H]4C1 CXEGAUYXQAKHKJ-NSBHKLITSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 3
- IBSREHMXUMOFBB-JFUDTMANSA-N 5u8924t11h Chemical compound O1[C@@H](C)[C@H](O)[C@@H](OC)C[C@@H]1O[C@@H]1[C@@H](OC)C[C@H](O[C@@H]2C(=C/C[C@@H]3C[C@@H](C[C@@]4(O3)C=C[C@H](C)[C@@H](C(C)C)O4)OC(=O)[C@@H]3C=C(C)[C@@H](O)[C@H]4OC\C([C@@]34O)=C/C=C/[C@@H]2C)/C)O[C@H]1C.C1=C[C@H](C)[C@@H]([C@@H](C)CC)O[C@]11O[C@H](C\C=C(C)\[C@@H](O[C@@H]2O[C@@H](C)[C@H](O[C@@H]3O[C@@H](C)[C@H](O)[C@@H](OC)C3)[C@@H](OC)C2)[C@@H](C)\C=C\C=C/2[C@]3([C@H](C(=O)O4)C=C(C)[C@@H](O)[C@H]3OC\2)O)C[C@H]4C1 IBSREHMXUMOFBB-JFUDTMANSA-N 0.000 claims description 3
- 239000005660 Abamectin Substances 0.000 claims description 3
- 239000005878 Azadirachtin Substances 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- 229950008167 abamectin Drugs 0.000 claims description 3
- VEHPJKVTJQSSKL-UHFFFAOYSA-N azadirachtin Natural products O1C2(C)C(C3(C=COC3O3)O)CC3C21C1(C)C(O)C(OCC2(OC(C)=O)C(CC3OC(=O)C(C)=CC)OC(C)=O)C2C32COC(C(=O)OC)(O)C12 VEHPJKVTJQSSKL-UHFFFAOYSA-N 0.000 claims description 3
- FTNJWQUOZFUQQJ-IRYYUVNJSA-N azadirachtin A Natural products C([C@@H]([C@]1(C=CO[C@H]1O1)O)[C@]2(C)O3)[C@H]1[C@]23[C@]1(C)[C@H](O)[C@H](OC[C@@]2([C@@H](C[C@@H]3OC(=O)C(\C)=C/C)OC(C)=O)C(=O)OC)[C@@H]2[C@]32CO[C@@](C(=O)OC)(O)[C@@H]12 FTNJWQUOZFUQQJ-IRYYUVNJSA-N 0.000 claims description 3
- FTNJWQUOZFUQQJ-NDAWSKJSSA-N azadirachtin A Chemical compound C([C@@H]([C@]1(C=CO[C@H]1O1)O)[C@]2(C)O3)[C@H]1[C@]23[C@]1(C)[C@H](O)[C@H](OC[C@@]2([C@@H](C[C@@H]3OC(=O)C(\C)=C\C)OC(C)=O)C(=O)OC)[C@@H]2[C@]32CO[C@@](C(=O)OC)(O)[C@@H]12 FTNJWQUOZFUQQJ-NDAWSKJSSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- JUVIOZPCNVVQFO-UHFFFAOYSA-N rotenone Natural products O1C2=C3CC(C(C)=C)OC3=CC=C2C(=O)C2C1COC1=C2C=C(OC)C(OC)=C1 JUVIOZPCNVVQFO-UHFFFAOYSA-N 0.000 claims description 3
- 229940080817 rotenone Drugs 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003995 emulsifying agent Substances 0.000 abstract description 4
- 238000001782 photodegradation Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 230000004071 biological effect Effects 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- CJUUXVFWKYRHAR-UHFFFAOYSA-M 1-Naphthaleneacetic acid sodium salt Chemical compound [Na+].C1=CC=C2C(CC(=O)[O-])=CC=CC2=C1 CJUUXVFWKYRHAR-UHFFFAOYSA-M 0.000 description 1
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 description 1
- 229930192334 Auxin Natural products 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002363 auxin Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003016 pheromone Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 230000009261 transgenic effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
- Manufacturing Of Micro-Capsules (AREA)
- Polyurethanes Or Polyureas (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a polyurethane hybrid antioxidant biopesticide microcapsule and a preparation method thereof, belonging to the technical field of pesticide microcapsules. According to the invention, the interface polymerization reaction mode is adopted, so that the biological pesticide can be embedded into the polyurethane capsule wall material; the invention uses CeO 2 Nanoparticles, mn 3 O 4 The nano particles and the C60 nano particles are used as antioxidant nano particles, the antioxidant nano particles can be used as an antioxidant modifier and an emulsifier for interfacial polymerization reaction, and the antioxidant nano particles are doped into a polyurethane capsule wall material during polymerization reaction, so that the inoxidizability of the biological pesticide is enhanced, the photodegradation effect of the pesticide is reduced, and the biological activity of the pesticide is ensured. All in oneIn the invention, the biopesticide microcapsule is prepared by adopting an interfacial polymerization reaction mode, and the obtained biopesticide microcapsule has good controllable slow release property.
Description
Technical Field
The invention relates to the technical field of pesticide microcapsules, in particular to a polyurethane hybrid antioxidant biopesticide microcapsule and a preparation method thereof.
Background
Biopesticides are agents that kill or inhibit agricultural pests with living organisms (fungi, bacteria, insect viruses, transgenic organisms, natural enemies, etc.) or their metabolites (pheromones, auxins, sodium naphthylacetate, 2,4-D, etc.). The biopesticide has strong selectivity, is safe to people and livestock, has little influence on the ecological environment, has high safety and is widely used.
The microcapsule technology is a technology in which a natural or synthetic polymer material is used as a capsule wall, and an active substance (capsule core drug) is coated by a chemical method, a physical method or a physicochemical method to form a semipermeable or sealed capsule membrane. The biological pesticide is prepared into the microcapsule, so that the pesticide can be endowed with good slow release performance, and the lasting period of the pesticide can be prolonged by 2 to 3 times; after the biological pesticide is prepared into the microcapsule, the usage amount of the original pesticide can be reduced to 1/2-1/3 of the original usage amount, and the application amount of the pesticide is obviously reduced.
However, most of the active ingredients of biopesticides are living bodies or substances with poor stability, are easily oxidized and are easily affected by external environment to cause the activity of the biopesticides to lose efficacy. This may reduce the field control effect of the biopesticide microcapsules.
Disclosure of Invention
In view of the above, the invention aims to provide a polyurethane hybrid antioxidant biopesticide microcapsule and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a polyurethane hybrid antioxidant biopesticide microcapsule, which comprises the following steps:
mixing a silane coupling agent, antioxidant nanoparticles and an alcohol solvent, and carrying out silane modification to obtain silane-modified antioxidant nanoparticles; the antioxidant nano-particles are CeO 2 Nanoparticles, mn 3 O 4 One or more of nanoparticles and C60 nanoparticles;
mixing the silane-modified antioxidant nanoparticles with water to obtain a water phase;
mixing the biological pesticide, the polyurethane reaction raw material and the organic solvent to obtain an oil phase; the polyurethane reaction raw material is diisocyanate and/or polyurethane prepolymer;
adding the oil phase into the water phase, and emulsifying to obtain O/W emulsion;
mixing the O/W emulsion with polyhydric alcohol, and carrying out interfacial polymerization reaction to obtain an interfacial polymerization reaction solution;
and mixing the interfacial polymerization reaction liquid with polyamine, and carrying out curing reaction to obtain the polyurethane hybrid antioxidant biopesticide microcapsule.
Preferably, the biological pesticide is one or more of emamectin benzoate, abamectin, rotenone and azadirachtin.
Preferably, the particle size of the antioxidant nanoparticles is 1-50 nm.
Preferably, the silane coupling agent is one or more of KH550, KH560 and KHH 570;
the mass ratio of the antioxidant nanoparticles to the silane coupling agent is 1-5.
Preferably, the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate and lysine diisocyanate;
in the polyurethane prepolymer, the quantity ratio of-NCO to-OH is 1-5:2-10.
Preferably, the mass ratio of the biological pesticide to the antioxidant nanoparticles is 10-15;
the mass ratio of the polyurethane reaction raw material to the antioxidant nanoparticles is 2-15.
Preferably, the emulsifying speed is 8000-10000 rmp, and the time is 5-15 min.
Preferably, the mass ratio of the polyurethane reaction raw material to the polyol is 2-15;
the temperature of the interfacial polymerization reaction is 40-50 ℃ and the time is 1-5 h.
Preferably, the mass ratio of the polyurethane reaction raw material to the polyamine is 2-15;
the temperature of the curing reaction is 40-60 ℃, and the time is 2-5 h.
The invention provides a polyurethane hybrid antioxidant biopesticide microcapsule prepared by the preparation method, which comprises a polyurethane capsule material and biopesticide wrapped in the polyurethane capsule material;
the surface and the interior of the polyurethane capsule wall material contain antioxidant nanoparticles, and the antioxidant nanoparticles are CeO 2 Nanoparticles, mn 3 O 4 One or more of nanoparticles and C60 nanoparticles.
The invention provides a preparation method of a polyurethane hybrid antioxidant biopesticide microcapsule, which comprises the following steps: mixing a silane coupling agent, antioxidant nanoparticles and an alcohol solvent, and carrying out silane modification to obtain silane-modified antioxidant nanoparticles; the antioxidant nano-particles are CeO 2 Nanoparticles, mn 3 O 4 One or more of nanoparticles and C60 nanoparticles; mixing the silane-modified antioxidant nanoparticles with water to obtain a water phase; biological pesticideMixing the medicine, polyurethane reaction raw materials and an organic solvent to obtain an oil phase; the polyurethane reaction raw material is diisocyanate and/or polyurethane prepolymer; adding the oil phase into the water phase, and emulsifying to obtain O/W emulsion; mixing the O/W emulsion with polyhydric alcohol, and carrying out interfacial polymerization reaction to obtain an interfacial polymerization reaction solution; and mixing the interfacial polymerization reaction liquid with polyamine, and carrying out curing reaction to obtain the polyurethane hybrid antioxidant biopesticide microcapsule. The invention uses CeO 2 Nanoparticles, mn 3 O 4 Nanoparticles and C60 nanoparticles as antioxidant nanoparticles, ceO 2 Ce in the nano particles has two different oxidation states, namely Ce (III) and Ce (IV), because of the nano CeO 2 The Ce (III) and Ce (IV) on the surface can be mutually converted, so that the nano CeO 2 Has high oxidation resistance, can remove various active oxygen and nitrogen species, and protect cells from being irradiated by ultraviolet rays and X rays; mn 3 O 4 Surface Co-existence of Mn 2+ And Mn 3+ To, O 2 – 、H 2 O 2 Free radicals such as OH and the like have good elimination effect and show excellent antioxidant activity; fullerene is a third allotrope of carbon element, having a spherical or ellipsoidal structure, C60 is composed of 60 carbon atoms and has a spherical hollow structure, and the C60 molecule contains 20 six-membered rings and 12 five-membered rings, and has a total of 30 carbon-carbon double bonds. C60 is a very strong antioxidant substance and has very good scavenging capacity for free radicals. According to the invention, the interface polymerization reaction mode is adopted, so that the biological pesticide can be embedded into the polyurethane capsule wall material; in the invention, the antioxidant nanoparticles can be used as an antioxidant modifier and an emulsifier for interfacial polymerization reaction, and the antioxidant nanoparticles are doped into the polyurethane capsule material during polymerization reaction, so that the antioxidant property of the biological pesticide is enhanced, the photodegradation effect of the pesticide is reduced, and the biological activity of the pesticide is ensured. Meanwhile, the invention adopts an interfacial polymerization reaction mode to prepare the biopesticide microcapsule, and the obtained biopesticide microcapsule has good controllable slow release property.
Drawings
FIG. 1 is an SEM image of polyurethane hybrid anti-oxidation biopesticide microcapsule obtained in example 1;
FIG. 2 shows the photodegradability of the polyurethane hybrid antioxidant biopesticide microcapsule obtained in example 1;
FIG. 3 shows the photodegradability of the polyurethane hybrid antioxidant biopesticide microcapsule obtained in example 2;
FIG. 4 shows the photodegradability of the polyurethane hybrid antioxidant biopesticide microcapsule obtained in example 3;
FIG. 5 shows the slow release performance of the polyurethane hybrid antioxidant biopesticide microcapsule obtained in example 1;
FIG. 6 shows the slow release performance of the polyurethane hybrid antioxidant biopesticide microcapsule obtained in example 2;
FIG. 7 shows the slow release performance of the polyurethane hybrid anti-oxidation biopesticide microcapsule obtained in example 3.
Detailed Description
The invention provides a preparation method of polyurethane hybrid antioxidant biopesticide microcapsule, which comprises the following steps:
mixing a silane coupling agent, antioxidant nanoparticles and an alcohol solvent, and carrying out silane modification to obtain silane-modified antioxidant nanoparticles; the antioxidant nano-particles are CeO 2 Nanoparticles, mn 3 O 4 One or more of nanoparticles and C60 nanoparticles;
mixing the silane-modified antioxidant nanoparticles with water to obtain a water phase;
mixing the biological pesticide, the polyurethane reaction raw material and the organic solvent to obtain an oil phase; the polyurethane reaction raw material is diisocyanate and/or polyurethane prepolymer;
adding the oil phase into the water phase, and emulsifying to obtain O/W emulsion;
mixing the O/W emulsion with polyhydric alcohol, and carrying out interfacial polymerization reaction to obtain an interfacial polymerization reaction solution;
and mixing the interfacial polymerization reaction liquid with polyamine, and carrying out curing reaction to obtain the polyurethane hybrid antioxidant biopesticide microcapsule.
The invention couples silanesAnd mixing the agent, the antioxidant nanoparticles and an alcohol solvent, and carrying out silane modification to obtain silane-modified antioxidant nanoparticles. In the invention, the antioxidant nanoparticles are CeO 2 Nanoparticles, mn 3 O 4 One or more of nanoparticles and C60 nanoparticles; the particle size of the antioxidant nanoparticles is preferably 1 to 50nm, more preferably 5 to 30nm, and more preferably 10 to 20nm.
In the invention, the silane coupling agent is preferably one or more of KH550, KH560 and KHH 570; the mass ratio of the antioxidant nanoparticles to the silane coupling agent is preferably 1.
In the present invention, the alcohol solvent is preferably absolute ethanol.
In the present invention, the silane modification is preferably performed under ultrasonic conditions; the frequency of the ultrasonic wave is preferably 80-110 kHz, more preferably 90-100 kHz; the time is preferably 30 to 50min, more preferably 40min.
In the present invention, after the silane modification, the obtained silane modification liquid is preferably subjected to solid-liquid separation, and the obtained solid is dried and ground to obtain the silane-modified antioxidant nanoparticles.
In the present invention, the solid-liquid separation is preferably performed by filtration; in the present invention, the drying temperature is preferably 60 ℃ and the drying time is preferably 24 hours.
The silane-modified antioxidant nanoparticles are mixed with water to obtain a water phase. In the present invention, the mixing is preferably ultrasonic mixing; in the present invention, the frequency of the ultrasound is preferably 80 to 110kHz, more preferably 90 to 100kHz; the time is preferably 15 to 30min, more preferably 20 to 25min.
In the present invention, the concentration of the silane-modified antioxidant nanoparticles in the aqueous phase is preferably 1 to 10wt%, more preferably 3 to 8wt%.
According to the invention, the biological pesticide, the polyurethane reaction raw material and the organic solvent are mixed to obtain the oil phase. In the invention, the biological pesticide is preferably one or more of emamectin benzoate, abamectin, rotenone and azadirachtin.
In the present invention, the polyurethane reaction raw material is preferably diisocyanate and/or polyurethane prepolymer. In the invention, the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate and lysine diisocyanate. In the polyurethane prepolymer, the quantity ratio of-NCO to-OH is 1-5:2-10.
In the invention, the organic solvent is preferably one or more of N-butyl acetate, isobutyl acetate, sec-butyl acetate, N-dimethyl caprylamide and N, N-dimethyl capriamide.
In the invention, the mass ratio of the biological pesticide to the antioxidant nanoparticles is preferably 10-15, more preferably 12; the mass ratio of the polyurethane reaction raw material to the antioxidant nanoparticles is preferably 2-15.
The invention does not require any particular mixing means, such as stirring, known to the person skilled in the art.
The oil phase is added into the water phase for emulsification, so as to obtain the O/W emulsion. In the present invention, the emulsification is preferably shear emulsification. In the present invention, the emulsification rate is preferably 8000 to 10000rmp, and the time is preferably 5 to 15min, more preferably 8 to 10min.
The O/W emulsion is mixed with polyhydric alcohol to carry out interfacial polymerization reaction, so as to obtain an interfacial polymerization reaction solution. In the present invention, the polyhydric alcohol is preferably one or more of ethylene glycol, hexylene glycol, glycerol and pentaerythritol. In the present invention, the mass ratio of the polyurethane reaction raw material to the polyol is preferably 2 to 15, more preferably 5 to 10.
In the present invention, the temperature of the interfacial polymerization reaction is preferably 40 to 50 ℃, more preferably 45 ℃; the time is preferably 1 to 5 hours, more preferably 2 to 4 hours. In the present invention, the interfacial polymerization reaction is preferably carried out under stirring at a rate of preferably 300 to 600rpm, more preferably 400 to 500rpm.
The interfacial polymerization reaction liquid and polyamine are mixed for curing reaction to obtain the polyurethane hybridization antioxidant biopesticide microcapsule. In the invention, the polyamine is preferably one or more of triethylene tetramine, ethylene triamine and tetraethylene pentamine. In the present invention, the polyamine is preferably added in the form of an aqueous solution.
In the present invention, the mass ratio of the polyurethane reaction raw material to the polyamine is preferably 2 to 15, more preferably 5 to 10; the curing reaction is preferably carried out at a temperature of 40 to 60 ℃, more preferably 50 ℃ for a time of preferably 2 to 5 hours, more preferably 3 to 4 hours.
After the curing reaction, the present invention preferably performs a post-treatment on the obtained curing reaction liquid, and the post-treatment preferably includes the following steps:
and carrying out solid-liquid separation on the solidified reaction liquid, washing and drying the obtained solid to obtain the polyurethane hybrid antioxidant biopesticide microcapsule.
In the present invention, the solid-liquid separation is preferably performed by centrifugation. The present invention does not require any particular manner of washing and drying, and washing and drying means well known to those skilled in the art may be used.
The invention provides a polyurethane hybrid antioxidant biopesticide microcapsule prepared by the preparation method, which comprises a polyurethane capsule wall material and biopesticide wrapped in the polyurethane capsule wall material;
the surface and the interior of the polyurethane capsule wall material contain antioxidant nanoparticles, and the antioxidant nanoparticles are CeO 2 Nanoparticles, mn 3 O 4 One or more of nanoparticles and C60 nanoparticles.
In the invention, the particle size of the polyurethane hybrid antioxidant biopesticide microcapsule is preferably 400-600 nm, and more preferably 500nm.
The polyurethane hybrid antioxidant biopesticide microcapsule and the preparation method thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) 1g of dried CeO 2 Adding anhydrous ethanol into nanoparticles (with particle diameter of 5-50 nm), stirring, adding 0.1g KH550 into the system, performing ultrasonic treatment, filtering the mixture, and drying at 60 deg.C for 24 hr to obtain white powder, i.e. KH550 modified CeO 2 Grinding and sieving the nano particles at room temperature for later use;
(2) 0.5gKH550 modified CeO was weighed 2 The composite nano particles are used as an emulsifier, and are uniformly dispersed in water after ultrasonic treatment to form a water phase;
(3) Dissolving 6g of biopesticide emamectin benzoate in a butyl acetate solvent, adding 3.8g of isocyanate MDI into the solution after uniformly dissolving, and stirring and uniformly mixing to form an oil phase;
(4) Slowly dripping the oil phase into the water phase, and shearing and emulsifying at 10000r/min under a high-speed shearing emulsifying machine to obtain O/W emulsion;
(5) Transferring the emulsion into a three-neck flask, adding 0.45g of 1, 4-Butanediol (BDO), heating to 60 ℃, after 500r/min interfacial polymerization reaction for 1h, dissolving 0.35g of triethylene tetramine (TETA) in 10g of deionized water for dilution, slowly dropwise adding into the three-neck flask by using a dropping funnel, finishing dropping within 30min, and continuously stirring for reaction for 2h;
(6) And after the reaction is finished, cooling to room temperature, centrifuging, washing and drying to obtain the polyurethane hybrid antioxidant biopesticide microcapsule.
The SEM image of the polyurethane hybrid antioxidant biopesticide microcapsule obtained in example 1 is shown in figure 1. As can be seen from figure 1, the pesticide microcapsule prepared by the invention has a more regular shape, is wholly spherical and has uniform particle size distribution.
Example 2
The difference from example 1 is that CeO 2 Replacement of nanoparticles with Mn 3 O 4 The particle size of the nano particles is 20-100 nm.
Example 3
The difference from example 1 is that CeO 2 Replacement of nanoparticles by C60 nmParticles having a particle diameter of 20 to 100nm.
Performance testing
(I) photodegradation Performance test
The preparation method of the common polyurethane biopesticide microcapsule is characterized in that antioxidant nanoparticles are not added, and the used emulsifier is PVA.
Preparing the polyurethane hybrid antioxidant biopesticide microcapsule methanol dispersion liquid, emamectin benzoate technical methanol solution and common polyurethane biopesticide microcapsule methanol dispersion liquid with the same concentration, respectively placing the solutions under an ultraviolet lamp (36W, 254nm), irradiating, sampling at intervals, and calculating the concentration by using a high performance liquid chromatography.
The graph of the relationship between the residual content of raw materials and the time of the polyurethane hybrid antioxidant biopesticide microcapsule obtained in example 1 is shown in fig. 2; the graph of the relationship between the residual content of the raw materials and the time of the polyurethane hybrid antioxidant biopesticide microcapsule obtained in example 2 is shown in fig. 3; the graph of the relationship between the residual content of the raw materials and the time of the polyurethane hybrid antioxidant biopesticide microcapsule obtained in example 3 is shown in fig. 4. As can be seen from figures 2 to 4, the polyurethane hybrid antioxidant biopesticide microcapsule provided by the invention has good photodegradation resistance.
(II) Slow Release test
The methanol solution is used as a slow release medium, and a dialysis bag (molecular weight cut-off of 2000) is adopted to measure the slow release performance of the microcapsule. Weighing a proper amount of emamectin benzoate microcapsule sample, placing the weighed sample into a dialysis bag, sealing the bag opening, placing the sealed bag opening into a beaker filled with 200mL of slow-release medium, and stirring and oscillating at the rotating speed of 200 r/min. Taking 1-5 mL of slow release medium at intervals, measuring the content of emamectin benzoate in the sample at 245nm by using an ultraviolet spectrophotometer, repeatedly measuring for 3 times, taking an average value, immediately supplementing the slow release medium, and finally drawing an accumulative release curve of the slow release medium.
The graph of the cumulative release rate of the polyurethane hybrid antioxidant biopesticide microcapsule obtained in example 1 and the time is shown in fig. 5; the graph of the cumulative release rate of the polyurethane hybrid antioxidant biopesticide microcapsule obtained in example 2 and the time is shown in fig. 6; the cumulative release rate of the polyurethane hybrid antioxidant biopesticide microcapsule obtained in example 3 is shown in fig. 7 as a time-dependent graph.
As can be seen from figures 5 to 7, the polyurethane hybrid antioxidant biopesticide microcapsule provided by the invention has good slow release performance.
(III) Oxidation resistance test
Taking test tubes with plugs, and adding 1mLFeSO in sequence 4 Solution, 1mL of salicylic acid solution, 2mL of polyurethane hybridization antioxidant biopesticide microcapsule suspending agent, 10mL of deionized water, and finally adding H 2 O 2 Starting reaction is carried out, the absorbance of each concentration is measured under 237nm, a blank control group is formed by replacing a sample with distilled water, and the hydroxyl radical clearance rate is calculated by the following calculation method: [ blank control group absorbance- (absorbance after adding sample-sample background absorbance)]Blank absorbance × 100%, the results are shown in table 1.
TABLE 1 clearance of hydroxyl radical of polyurethane hybrid antioxidant biopesticide microcapsule obtained in examples 1 to 3
As can be seen from Table 1, the polyurethane hybrid antioxidant biopesticide microcapsule provided by the invention has good antioxidant performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a polyurethane hybrid antioxidant biopesticide microcapsule comprises the following steps:
mixing a silane coupling agent, antioxidant nanoparticles and an alcohol solvent, and performing silane modification to obtain the antioxidant nanoparticlesSilane modified antioxidant nanoparticles; the antioxidant nano-particles are CeO 2 Nanoparticles, mn 3 O 4 One or more of nanoparticles and C60 nanoparticles;
mixing the silane-modified antioxidant nanoparticles with water to obtain a water phase;
mixing the biological pesticide, the polyurethane reaction raw material and the organic solvent to obtain an oil phase; the polyurethane reaction raw material is diisocyanate and/or polyurethane prepolymer;
adding the oil phase into the water phase, and emulsifying to obtain O/W emulsion;
mixing the O/W emulsion with polyhydric alcohol, and carrying out interfacial polymerization reaction to obtain an interfacial polymerization reaction solution;
and mixing the interfacial polymerization reaction liquid with polyamine, and carrying out curing reaction to obtain the polyurethane hybrid antioxidant biopesticide microcapsule.
2. The preparation method according to claim 1, wherein the biopesticide is one or more of emamectin benzoate, abamectin, rotenone and azadirachtin.
3. The method of claim 1 or 2, wherein the antioxidant nanoparticles have a particle size of 1 to 50nm.
4. The preparation method according to claim 1, wherein the silane coupling agent is one or more of KH550, KH560 and KHH 570;
the mass ratio of the antioxidant nanoparticles to the silane coupling agent is 1-5.
5. The preparation method of claim 1, wherein the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate, and lysine diisocyanate;
in the polyurethane prepolymer, the quantity ratio of-NCO to-OH is 1-5:2-10.
6. The preparation method according to claim 1 or 2, wherein the mass ratio of the biopesticide to the antioxidant nanoparticles is 10 to 15;
the mass ratio of the polyurethane reaction raw material to the antioxidant nanoparticles is (2-15).
7. The method of claim 1, wherein the emulsifying is performed at a rate of 8000 to 10000rmp for 5 to 15min.
8. The preparation method according to claim 1, wherein the mass ratio of the polyurethane reaction raw material to the polyol is 2 to 15;
the temperature of the interfacial polymerization reaction is 40-50 ℃ and the time is 1-5 h.
9. The production method according to claim 1 or 8, wherein the mass ratio of the polyurethane reaction raw material to the polyamine is 2 to 15;
the temperature of the curing reaction is 40-60 ℃, and the time is 2-5 h.
10. The polyurethane hybrid antioxidant biopesticide microcapsule prepared by the preparation method of any one of claims 1 to 9 comprises a polyurethane capsule material and biopesticide wrapped in the polyurethane capsule material;
the surface and the interior of the polyurethane capsule wall material contain antioxidant nanoparticles, and the antioxidant nanoparticles are CeO 2 Nanoparticles, mn 3 O 4 One or more of nanoparticles and C60 nanoparticles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211547186.3A CN115777705A (en) | 2022-12-05 | 2022-12-05 | Polyurethane hybridization antioxidant biopesticide microcapsule and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211547186.3A CN115777705A (en) | 2022-12-05 | 2022-12-05 | Polyurethane hybridization antioxidant biopesticide microcapsule and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115777705A true CN115777705A (en) | 2023-03-14 |
Family
ID=85445522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211547186.3A Pending CN115777705A (en) | 2022-12-05 | 2022-12-05 | Polyurethane hybridization antioxidant biopesticide microcapsule and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115777705A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114287421A (en) * | 2021-12-31 | 2022-04-08 | 上海师范大学 | Anti-ultraviolet biopesticide composite microcapsule and preparation method thereof |
| CN114532335A (en) * | 2022-03-04 | 2022-05-27 | 上海师范大学 | Ionic liquid type pesticide microcapsule and preparation method thereof |
| CN115226721A (en) * | 2022-08-24 | 2022-10-25 | 中国农业科学院农业环境与可持续发展研究所 | Pyraclostrobin nano microcapsule and preparation method thereof |
-
2022
- 2022-12-05 CN CN202211547186.3A patent/CN115777705A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114287421A (en) * | 2021-12-31 | 2022-04-08 | 上海师范大学 | Anti-ultraviolet biopesticide composite microcapsule and preparation method thereof |
| CN114532335A (en) * | 2022-03-04 | 2022-05-27 | 上海师范大学 | Ionic liquid type pesticide microcapsule and preparation method thereof |
| CN115226721A (en) * | 2022-08-24 | 2022-10-25 | 中国农业科学院农业环境与可持续发展研究所 | Pyraclostrobin nano microcapsule and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 傅桂华, 钟滨, 陈建宇, 王海英, 章大诩, 王广远: "界面聚合法制备农药微胶囊剂的研究", 农药, no. 02, pages 66 - 73 * |
| 樊玉松;康占海;赤国彤;: "阿维菌素微胶囊剂的制备", 河北农业大学学报, no. 02, pages 97 - 101 * |
| 袁青梅, 杨红卫, 张发广, 王兴, 郑保忠: "生物农药微胶囊制备研究", 云南大学学报(自然科学版), no. 01, pages 57 - 59 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3318323B1 (en) | Micro- or nanocapsules having photocatalytic properties for controlled release of diffusing agents and respective methods of obtainment | |
| Ciriminna et al. | The sol–gel route to advanced silica-based materials and recent applications | |
| CN105494430B (en) | One kind carries silver-colored low-molecular weight chitoglycan complex microsphere antiseptic and preparation method thereof | |
| Ao et al. | Preparation and characterization of 1-naphthylacetic acid–silica conjugated nanospheres for enhancement of controlled-release performance | |
| EP3659590B1 (en) | Composition, particulate materials and methods for making particulate materials | |
| EP0098947B1 (en) | Polymeric mono-, di-, tri- and tetrasulfide compounds, process for preparing them and their use | |
| CN114287421B (en) | Ultraviolet-resistant biological pesticide composite microcapsule and preparation method thereof | |
| Prado et al. | Nanosized silica modified with carboxylic acid as support for controlled release of herbicides | |
| Li et al. | Functionalization of halloysite nanotubes by enlargement and hydrophobicity for sustained release of analgesic | |
| CN111406740B (en) | Nano pesticide preparation based on boron nitride nanosheet grafted hydrophilic polymer and preparation method thereof | |
| Yang et al. | A simple and green preparation process for PRO@ PIL-PHS-PEC microcapsules by using phosphonium ionic liquid as a multifunctional additive | |
| CN114009444A (en) | Preparation and application of novel multifunctional Janus type mesoporous silica nano pesticide fertilizer | |
| CN111939091B (en) | Antibacterial mesoporous silica compound and preparation method and application thereof | |
| CN111407722A (en) | Silver nanoparticle composite hydrogel, and preparation method and application thereof | |
| CN113413462A (en) | Nano material for simulating natural killer cells to efficiently treat intracellular bacteria and preparation method and application thereof | |
| EP2175979A1 (en) | Improved microcapsules and the production thereof | |
| CN114097777A (en) | Double-layer drug-loaded sustained-release microcapsule and preparation method and application thereof | |
| CN113508810A (en) | Eugenol natural antibacterial microcapsule and preparation method thereof | |
| CN104907022B (en) | Composite type aromatic microcapsule and silver-loaded aromatic microcapsule preparation method | |
| CN115777705A (en) | Polyurethane hybridization antioxidant biopesticide microcapsule and preparation method thereof | |
| EP4056262A1 (en) | Biodegradable microcapsule and method for manufacturing same | |
| CN1299577C (en) | Microporous silicon dioxide-cladding tourmaline and titanium dioxide particle composition, its preparation and application | |
| CN116530508A (en) | Pesticide microcapsule suspending agent composed of bifenthrin and chlorantraniliprole | |
| KR20210054428A (en) | A method of preparing a biodegrading microcapsule | |
| KR100684575B1 (en) | Synthetic methods for oleophillic nanoporous silica composites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |