CN115804373A - Nano cellulose based ultraviolet-resistant pesticide microcapsule and preparation method thereof - Google Patents
Nano cellulose based ultraviolet-resistant pesticide microcapsule and preparation method thereof Download PDFInfo
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- CN115804373A CN115804373A CN202211574514.9A CN202211574514A CN115804373A CN 115804373 A CN115804373 A CN 115804373A CN 202211574514 A CN202211574514 A CN 202211574514A CN 115804373 A CN115804373 A CN 115804373A
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- 239000000575 pesticide Substances 0.000 title claims abstract description 58
- 239000003094 microcapsule Substances 0.000 title claims abstract description 45
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000839 emulsion Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229920002678 cellulose Polymers 0.000 claims abstract description 29
- 239000001913 cellulose Substances 0.000 claims abstract description 29
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- 238000004945 emulsification Methods 0.000 claims abstract description 18
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 16
- 239000012071 phase Substances 0.000 claims description 50
- 239000002608 ionic liquid Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 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
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 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 4
- 229940080817 rotenone Drugs 0.000 claims description 4
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-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
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- 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
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 2
- 230000006750 UV protection Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 13
- 230000000853 biopesticidal effect Effects 0.000 description 11
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- 238000006303 photolysis reaction Methods 0.000 description 8
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 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 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000003405 delayed action preparation Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 2
- -1 indoleacetic acid) Natural products 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- 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 description 1
- KAVXZXUKWOTTHD-UHFFFAOYSA-N 2,4-diisocyanato-1-methylbenzene 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O.CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 KAVXZXUKWOTTHD-UHFFFAOYSA-N 0.000 description 1
- CWVRJTMFETXNAD-FWCWNIRPSA-N 3-O-Caffeoylquinic acid Natural products O[C@H]1[C@@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-FWCWNIRPSA-N 0.000 description 1
- 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 description 1
- 229930192334 Auxin Natural products 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- PZIRUHCJZBGLDY-UHFFFAOYSA-N Caffeoylquinic acid Natural products CC(CCC(=O)C(C)C1C(=O)CC2C3CC(O)C4CC(O)CCC4(C)C3CCC12C)C(=O)O PZIRUHCJZBGLDY-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
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- ZTCFKBWDKVMLMM-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1C(=O)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1C(=O)C1=CC=CC=C1 ZTCFKBWDKVMLMM-UHFFFAOYSA-N 0.000 description 1
- CWVRJTMFETXNAD-KLZCAUPSSA-N Neochlorogenin-saeure Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O CWVRJTMFETXNAD-KLZCAUPSSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
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- 230000002411 adverse Effects 0.000 description 1
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- 229920000615 alginic acid Polymers 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002363 auxin Substances 0.000 description 1
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- 238000007385 chemical modification Methods 0.000 description 1
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 description 1
- 229940074393 chlorogenic acid Drugs 0.000 description 1
- FFQSDFBBSXGVKF-KHSQJDLVSA-N chlorogenic acid Natural products O[C@@H]1C[C@](O)(C[C@@H](CC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O FFQSDFBBSXGVKF-KHSQJDLVSA-N 0.000 description 1
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
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- 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 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a nanocellulose-based ultraviolet-resistant pesticide microcapsule and a preparation method thereof, belonging to the technical field of pesticide microcapsules. In the invention, under the catalysis of organic tin, 4' -dihydroxy benzophenone and diisocyanate are subjected to prepolymerization reaction to obtain a prepolymerization product; according to the invention, a biological pesticide is added into a first oil phase, the biological pesticide is embedded into an O/W emulsion through a first emulsification effect, a second oil phase in which cellulose is dissolved is added for a crosslinking reaction, a prepolymerization product in the first oil phase contains an isocyanate group, and can be used as a crosslinking agent to crosslink with hydroxyl in nano cellulose, and 4,4' -dihydroxybenzophenone has an ultraviolet absorption effect and can endow the nano cellulose with good ultraviolet resistance.
Description
Technical Field
The invention relates to the technical field of pesticide microcapsules, in particular to a nanocellulose-based ultraviolet-resistant pesticide microcapsule and a preparation method thereof.
Background
In recent years, biopesticides have attracted attention because of their biodegradability, biocompatibility, and low toxicity. Biopesticides are generally considered to be harmless to beneficial insects and leave behind a less toxic or even non-toxic residue. In general, biopesticides include classes of auxins (e.g., indoleacetic acid), insecticides (e.g., rotenone), and herbicides (e.g., chlorogenic acid). However, the instability of many biopesticides under ultraviolet light seriously affects the efficacy and duration of the biopesticides.
The controlled release preparation can be used for prolonging the activity of the pesticide, reducing adverse side effects and reducing the application amount, and is an effective method for prolonging the lasting period of the pesticide, increasing the pesticide effect and solving the problem of pesticide pollution. The capsule wall is the key for realizing the special function of the controlled release preparation, and the capsule wall is generally divided into artificially synthesized or natural high molecular compounds, such as polyamide, polyester, animal and plant gums (such as algin, gelatin and Arabic gum) and the like.
Cellulose is one of the most abundant biomass materials in nature, has the characteristics of degradability, excellent biocompatibility and environmental friendliness compared with synthetic polymers, and can improve the lasting period of the biological microcapsule. However, cellulose lacks sufficient absorption capacity for ultraviolet rays, and as a capsule wall material, it is difficult to meet the requirement of the pesticide microcapsule on resistance to ultraviolet photolysis.
Disclosure of Invention
In view of the above, the present invention aims to provide a nanocellulose-based anti-ultraviolet pesticide microcapsule and a preparation method thereof, and the obtained nanocellulose-based biopesticide microcapsule has good anti-ultraviolet photolysis performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a nanocellulose-based ultraviolet-resistant pesticide microcapsule, which comprises the following steps:
mixing 4,4' -dihydroxy benzophenone, diisocyanate, an organotin catalyst, a first ionic liquid and an organic solvent, and carrying out prepolymerization reaction to obtain a prepolymerization product;
mixing a biological pesticide with the pre-polymerized product to obtain a first oil phase;
mixing an emulsifier with water to obtain a water phase;
mixing the nano-cellulose, the second ionic liquid and an organic solvent to obtain a second oil phase;
adding the first oil phase into the water phase, and performing first emulsification to obtain an O/W emulsion;
adding the second oil phase into the O/W emulsion for second emulsification to obtain O/W/O type multiple emulsion;
and heating the O/W/O type multiple emulsion to perform a crosslinking reaction to obtain the nano cellulose base uvioresistant pesticide microcapsule.
Preferably, the organotin catalyst is dibutyltin dilaurate;
the first ionic liquid and the second ionic liquid are independently EMIMBF 4 、[BMIm]P 6 、[VMIM]SbF 6 And [ BZMIM]NTF 2 One or more of them.
Preferably, the mass ratio of the 4,4' -dihydroxy benzophenone to the diisocyanate is 1-5;
the mass ratio of the 4,4' -dihydroxy benzophenone to the organotin catalyst is 1-5;
the mass ratio of the 4,4' -dihydroxy benzophenone to the first ionic liquid is 1-5.
Preferably, the temperature of the prepolymerization reaction is 40-80 ℃ and the time is 3-5 h.
Preferably, the biological pesticide is one or more of emamectin benzoate, abamectin, rotenone and azadirachtin;
the mass ratio of the biological pesticide to the prepolymerization product is 2-15.
Preferably, the length of the nanocellulose is 30 to 100nm.
Preferably, the mass concentration of the emulsifier in the water phase is 1-10%;
the mass concentration of the nano-cellulose in the second oil phase is 1-5%.
Preferably, the first emulsification rate is 2000-20000 rmp, and the time is 5-20 min;
the second emulsification rate is 500-10000 rmp, and the time is 5-30 min.
Preferably, the temperature of the crosslinking reaction is 60-80 ℃ and the time is 3-5 h.
The invention provides the nano cellulose base ultraviolet-resistant pesticide microcapsule prepared by the preparation method.
The invention provides a preparation method of a nanocellulose-based ultraviolet-resistant pesticide microcapsule, which comprises the following steps: mixing 4,4' -dihydroxy benzophenone, diisocyanate, an organotin catalyst, a first ionic liquid and an organic solvent, and carrying out prepolymerization reaction to obtain a prepolymerization product; mixing a biological pesticide with the pre-polymerized product to obtain a first oil phase; mixing an emulsifier with water to obtain a water phase; mixing the nano-cellulose, the second ionic liquid and an organic solvent to obtain a second oil phase; adding the first oil phase into the water phase, and performing first emulsification to obtain an O/W emulsion; adding the second oil phase into the O/W emulsion for second emulsification to obtain O/W/O type multiple emulsion; and heating the O/W/O type multiple emulsion to carry out a crosslinking reaction to obtain the nano cellulose based ultraviolet resistant pesticide microcapsule. The invention uses the nano-cellulose as the capsule wall component of the pesticide microcapsule, and because the cellulose has high polarity and strong intermolecular hydrogen bond and hydrophobic interaction in the cellulose, the cellulose is not melted or dissolved in water and common organic solvent, and the chemical modification is difficult to implement. The ionic liquid is used as the solvent of the nano-cellulose, so that the nano-cellulose can be fully dissolved, and the subsequent crosslinking modification is facilitated. The method comprises the steps of carrying out prepolymerization reaction on 4,4 '-dihydroxy benzophenone and diisocyanate under the catalysis of organic tin to obtain a prepolymerization product, wherein the prepolymerization product contains diisocyanate-4, 4' -dihydroxy benzophenone-diisocyanate prepolymer and unreacted diisocyanate; according to the invention, biological pesticide is added into a first oil phase, the biological pesticide is embedded into O/W emulsion through a first emulsification effect, a second oil phase in which cellulose is dissolved is added for a cross-linking reaction, a pre-polymerization product in the first oil phase contains isocyanate groups, and can be used as a cross-linking agent to be cross-linked with hydroxyl groups in nano-cellulose, so that the nano-cellulose forms a spatial network structure, and the nano-cellulose based ultraviolet-resistant pesticide microcapsule is obtained. According to the invention, 4 '-dihydroxy benzophenone is used for modifying the nano-cellulose through the crosslinking reaction, and the 4,4' -dihydroxy benzophenone has an ultraviolet absorption effect and can endow the nano-cellulose with good ultraviolet resistance.
Drawings
FIG. 1 is a process of a prepolymerization reaction and a crosslinking reaction when the diisocyanate is toluene diisocyanate;
FIG. 2 is a graph showing the relationship between the original drug retention rate and time of the nanocellulose-based anti-ultraviolet pesticide microcapsule obtained in example 1;
fig. 3 is a graph of the relation between the original drug retention rate and time of the nanocellulose-based ultraviolet resistant pesticide microcapsule obtained in example 2;
fig. 4 is a graph of the relationship between the original drug retention rate and time of the nanocellulose-based ultraviolet resistant pesticide microcapsule obtained in example 3.
Detailed Description
The invention provides a preparation method of a nanocellulose-based ultraviolet-resistant pesticide microcapsule, which comprises the following steps:
mixing 4,4' -dihydroxy benzophenone, diisocyanate, an organotin catalyst, a first ionic liquid and an organic solvent, and carrying out prepolymerization reaction to obtain a prepolymerization product;
mixing a biological pesticide with the pre-polymerized product to obtain a first oil phase;
mixing an emulsifier with water to obtain a water phase;
mixing the nano-cellulose, the second ionic liquid and an organic solvent to obtain a second oil phase;
adding the first oil phase into the water phase, and performing first emulsification to obtain O/W emulsion;
adding the second oil phase into the O/W emulsion for second emulsification to obtain O/W/O type multiple emulsion;
and heating the O/W/O type multiple emulsion to perform a crosslinking reaction to obtain the nano cellulose base uvioresistant pesticide microcapsule.
The preparation method comprises the steps of mixing 4,4' -dihydroxy benzophenone, diisocyanate, an organic tin catalyst, a first ionic liquid and an organic solvent, and carrying out prepolymerization reaction to obtain a prepolymerization product. In the invention, the diisocyanate is preferably one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate and lysine diisocyanate.
In the present invention, the organotin catalyst is preferably dibutyltin dilaurate.
In the present invention, the first ionic liquid is preferably EMIMBF 4 、[BMIm]P 6 、[VMIM]SbF 6 And [ BZMIM]NTF 2 One or more of them.
In the invention, the organic solvent is preferably one or more of butyl acetate, ethyl acetate, amyl acetate and sec-butyl acetate.
In the present invention, the mass ratio of the 4,4' -dihydroxybenzophenone to the diisocyanate is preferably 1 to 5, more preferably 1 to 5. In the present invention, the mass ratio of the 4,4' -dihydroxybenzophenone to the organotin catalyst is preferably 1 to 5, more preferably 1 to 5. In the present invention, the mass ratio of the 4,4' -dihydroxybenzophenone to the first ionic liquid is preferably 1 to 5. In the present invention, the mass ratio of the first ionic liquid to the organic solvent is preferably 1 to 5.
The invention does not require any particular mixing means, such as stirring, known to the person skilled in the art.
In the present invention, the temperature of the prepolymerization reaction is preferably 40 to 80 ℃, more preferably 50 to 70 ℃; the time is preferably 3 to 5 hours, more preferably 4 hours. In the present invention, the pre-polymerized product includes diisocyanate-4, 4' -dihydroxybenzophenone-diisocyanate prepolymer and unreacted diisocyanate.
According to the invention, the biological pesticide is mixed with the prepolymerization product to obtain a first 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 biopesticide is preferably added in the form of a solution, and the solvent of the biopesticide solution is preferably an ionic liquid and an organic solvent. In the present invention, the kinds of the ionic liquid and the organic solvent are the same as above, and are not described herein again.
In the present invention, the mass ratio of the biopesticide to the prepolymerization product is preferably 2 to 15, more preferably 5 to 10.
The invention mixes the emulsifier with water to obtain water phase. In the present invention, the emulsifier is preferably PVA. In the present invention, the weight average molecular weight of the PVA is preferably 16000 to 20000. In the present invention, the concentration of the emulsifier in the aqueous phase is preferably 1 to 10wt%, more preferably 5 to 8wt%.
The invention mixes the nano-cellulose, the second ionic liquid and the organic solvent to obtain the second oil phase. In the present invention, the particle size of the nanocellulose is preferably 30 to 100nm, more preferably 50 to 80nm. In the present invention, the types of the second ionic liquid and the organic solvent are the same as above, and are not described herein again. In the present invention, the mass ratio of the second ionic liquid to the organic solvent is preferably 1 to 5.
In the present invention, the mixing is preferably performed by heating and mixing, and the temperature of the heating and mixing is preferably 50 to 80 ℃, and more preferably 60 to 70 ℃.
In the present invention, the mass concentration of the nanocellulose in the second oil phase is preferably 1 to 5%, more preferably 2 to 4%.
The first oil phase is added into the water phase, and first emulsification is carried out to obtain O/W emulsion. In the present invention, the rate of the first emulsification is preferably 2000 to 20000rpm, more preferably 10000rmp, and the time is preferably 5 to 20min, more preferably 10min.
Adding the second oil phase into the O/W emulsion for second emulsification to obtain O/W/O type multiple emulsion. In the present invention, the rate of the second emulsification is preferably 500 to 10000rpm, more preferably 1000 to 5000rpm; the time is preferably 5 to 10min, more preferably 6 to 8min.
The O/W/O type multiple emulsion is heated to carry out cross-linking reaction, so that the nano cellulose based ultraviolet-resistant pesticide microcapsule is obtained. In the present invention, the temperature of the crosslinking reaction is preferably 60 to 80 ℃, more preferably 70 ℃; the time is preferably 3 to 5 hours, more preferably 4 hours. In the invention, the prepolymerization product in the first oil phase contains isocyanate groups, and can be used as a cross-linking agent to be cross-linked with hydroxyl groups in nanocellulose, so that the nanocellulose forms a spatial network structure to obtain the nanocellulose-based ultraviolet-resistant pesticide microcapsule.
In the present invention, when the diisocyanate is toluene diisocyanate, the process of the prepolymerization reaction and the crosslinking reaction is shown in FIG. 1. In the present invention, the crosslinking reaction is preferably carried out in the presence of LiCl.
The invention provides the nano cellulose base uvioresistant pesticide microcapsule prepared by the preparation method. In the invention, the drug loading rate of the nanocellulose-based anti-ultraviolet pesticide microcapsule is preferably 25-40%, and more preferably 30-35%; the particle size of the nanocellulose-based ultraviolet-resistant pesticide microcapsule is preferably 500-800 nm, and more preferably 600-700 nm.
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) Heating and stirring 6g of 4,4' -dihydroxy benzophenone, 3.5g of isophorone diisocyanate, 10g of butyl acetate, 5g of ionic liquid and 1.5g of dibutyltin dilaurate at 70 ℃ for reacting for 3 hours, and cooling to room temperature after the reaction is finished to obtain a prepolymer;
(2) Dissolving 6g of emamectin benzoate in 10g of ionic liquid, diluting with 3g of butyl acetate, adding the diluted solution into the prepolymer, and uniformly stirring to form a first oil phase;
(3) Weighing 2g of PVA, and dissolving in 100g of deionized water to prepare a water phase;
(4) Dripping the first oil phase into the water phase under the condition of 10000rmp high-speed shearing, and continuously emulsifying for 10min to obtain uniform and stable O/W emulsion;
(5) Heating and dissolving 2.5g of nano-cellulose in 10g of ionic liquid, diluting with 5g of butyl acetate, cooling to room temperature, slowly adding the solution into an O/W emulsion, stirring at the speed of 4000rpm for 8min to form O/W/O type multiple emulsion, transferring the multiple emulsion into a 250mL four-mouth flask, heating to 70 ℃, heating, stirring and carrying out crosslinking reaction for 2h to obtain the nano-cellulose based anti-ultraviolet pesticide microcapsule.
Performance test
(I) ultraviolet photolysis resistance test
Common biopesticide microcapsules were prepared in the same manner as in example 1, omitting the step (5).
Preparing the nano cellulose base uvioresistant pesticide microcapsule methanol dispersion liquid, the emamectin benzoate technical methanol solution and the common biological pesticide microcapsule methanol dispersion liquid with the same concentration, respectively placing the solutions under an ultraviolet lamp (36W, 254nm) for irradiation, sampling at intervals, and calculating the concentration by using a high performance liquid chromatography.
A graph of the relationship between the original drug retention rate and the time of the nanocellulose-based anti-ultraviolet pesticide microcapsule obtained in example 1 is shown in fig. 2; as can be seen from FIG. 2, the nanocellulose-based ultraviolet resistant pesticide microcapsule provided by the invention has good ultraviolet photolysis resistance.
Example 2
(1) Heating and stirring 6g of 4,4' -dihydroxy benzophenone, 2.6g of isophorone diisocyanate toluene diisocyanate, 10g of butyl acetate, 5g of ionic liquid and 1.5g of dibutyltin dilaurate at 70 ℃ for reacting for 3h, and cooling to room temperature after the reaction is finished to obtain a prepolymer;
(2) Dissolving 8g of emamectin benzoate in 10g of ionic liquid, diluting with 3g of butyl acetate, adding the diluted solution into the prepolymer, and uniformly stirring to form a first oil phase;
(3) Weighing 2g of PVA, and dissolving in 100g of deionized water to prepare a water phase;
(4) Dripping the first oil phase into the water phase under the condition of 10000rmp high-speed shearing, and continuously emulsifying for 10min to obtain uniform and stable O/W emulsion;
(5) Heating and dissolving 2.5g of nano-cellulose in 10g of ionic liquid, diluting with 5g of butyl acetate, cooling to room temperature, slowly adding the solution into O/W emulsion, stirring at 4000rpm for 8min to form O/W/O type multiple emulsion, transferring the multiple emulsion into a 250mL four-neck flask, heating to 70 ℃, heating, stirring and performing crosslinking reaction for 2h to obtain the nano-cellulose based ultraviolet-resistant pesticide microcapsule.
The ultraviolet photolysis resistance and the sustained release performance of the nanocellulose-based ultraviolet resistant pesticide microcapsule obtained in example 2 were tested according to the method of example 1, the graph of the relationship between the original drug retention rate and the time of the nanocellulose-based ultraviolet resistant pesticide microcapsule obtained in example 2 is shown in fig. 3, and as can be seen from fig. 3, the nanocellulose-based ultraviolet resistant pesticide microcapsule provided by the invention has good ultraviolet photolysis resistance.
Example 3
(1) Heating and stirring 6g of 4,4' -dihydroxy benzophenone, 3.5g of isophorone diisocyanate, 10g of butyl acetate, 5g of ionic liquid and 1g of dibutyltin dilaurate at 70 ℃ for reacting for 3h, and cooling to room temperature after the reaction is finished to obtain a prepolymer;
(2) Dissolving 8g of emamectin benzoate in 10g of ionic liquid, diluting with 3g of butyl acetate, adding the diluted solution into the prepolymer, and uniformly stirring to form a first oil phase;
(3) Weighing 2g of PVA, and dissolving in 100g of deionized water to prepare a water phase;
(4) Dripping the first oil phase into the water phase under the condition of 10000rmp high-speed shearing, and continuously emulsifying for 10min to obtain uniform and stable O/W emulsion;
(5) Heating and dissolving 2.5g of nano-cellulose in 10g of ionic liquid, diluting with 5g of butyl acetate, cooling to room temperature, slowly adding the solution into an O/W emulsion, stirring at the speed of 4000rpm for 8min to form O/W/O type multiple emulsion, transferring the multiple emulsion into a 250mL four-mouth flask, heating to 70 ℃, heating, stirring and carrying out crosslinking reaction for 2h to obtain the nano-cellulose based anti-ultraviolet pesticide microcapsule.
The anti-ultraviolet photolysis performance and the sustained-release performance of the nanocellulose-based anti-ultraviolet pesticide microcapsule obtained in example 3 are tested according to the mode of example 1, the raw drug retention rate and the time relation of the nanocellulose-based anti-ultraviolet pesticide microcapsule obtained in example 3 is shown in fig. 4, and as can be seen from fig. 4, the nanocellulose-based anti-ultraviolet pesticide microcapsule provided by the invention has good anti-ultraviolet photolysis 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 amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (10)
1. A preparation method of a nanocellulose-based ultraviolet-resistant pesticide microcapsule comprises the following steps:
mixing 4,4' -dihydroxy benzophenone, diisocyanate, an organic tin catalyst, a first ionic liquid and an organic solvent, and carrying out prepolymerization reaction to obtain a prepolymerization product;
mixing a biological pesticide with the pre-polymerized product to obtain a first oil phase;
mixing an emulsifier with water to obtain a water phase;
mixing the nano-cellulose, the second ionic liquid and an organic solvent to obtain a second oil phase;
adding the first oil phase into the water phase, and performing first emulsification to obtain an O/W emulsion;
adding the second oil phase into the O/W emulsion for second emulsification to obtain O/W/O type multiple emulsion;
and heating the O/W/O type multiple emulsion to perform a crosslinking reaction to obtain the nano cellulose base uvioresistant pesticide microcapsule.
2. The production method according to claim 1, wherein the organotin catalyst is dibutyltin dilaurate;
the first ionic liquid and the second ionic liquid are independently EMIMBF 4 、[BMIm]P 6 、[VMIM]SbF 6 And [ BZMIM]NTF 2 One or more of them.
3. The production method according to claim 1 or the above, wherein the mass ratio of the 4,4' -dihydroxybenzophenone to the diisocyanate is 1 to 5;
the mass ratio of the 4,4' -dihydroxy benzophenone to the organotin catalyst is 1-5;
the mass ratio of the 4,4' -dihydroxy benzophenone to the first ionic liquid is 1-5.
4. The method according to claim 1, wherein the temperature of the prepolymerization is 40 to 80 ℃ and the time is 3 to 5 hours.
5. The preparation method of claim 1, wherein the biological pesticide is one or more of emamectin benzoate, abamectin, rotenone and azadirachtin;
the mass ratio of the biological pesticide to the prepolymerization product is 2-15.
6. The method according to claim 1, wherein the length of the nanocellulose is 30 to 100nm.
7. The preparation method according to claim 1 or 6, characterized in that the mass concentration of the emulsifier in the aqueous phase is 1-10%;
the mass concentration of the nano-cellulose in the second oil phase is 1-5%;
the mass ratio of the nano-cellulose to the diisocyanate is 1-5.
8. The method of claim 1, wherein the first emulsification is carried out at a rate of 2000 to 20000rmp for a period of 5 to 20min;
the second emulsification rate is 500-10000 rmp, and the time is 5-30 min.
9. The method according to claim 1, wherein the cross-linking reaction is carried out at a temperature of 60 to 80 ℃ for 3 to 5 hours.
10. The nanocellulose-based anti-ultraviolet pesticide microcapsule prepared by the preparation method of any one of claims 1 to 9.
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