CN114989417B - Alkyl-polyphenol 2D Janus nano-sheet, pickering emulsion and preparation method and application thereof - Google Patents
Alkyl-polyphenol 2D Janus nano-sheet, pickering emulsion and preparation method and application thereof Download PDFInfo
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- CN114989417B CN114989417B CN202110229630.6A CN202110229630A CN114989417B CN 114989417 B CN114989417 B CN 114989417B CN 202110229630 A CN202110229630 A CN 202110229630A CN 114989417 B CN114989417 B CN 114989417B
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- polyphenol
- emulsion
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- pesticide
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000001484 Pickering emulsion method Methods 0.000 title description 2
- 239000000839 emulsion Substances 0.000 claims abstract description 113
- 239000000575 pesticide Substances 0.000 claims abstract description 85
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 26
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 25
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 24
- 238000001338 self-assembly Methods 0.000 claims abstract description 11
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 53
- 239000012071 phase Substances 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 30
- 239000002064 nanoplatelet Substances 0.000 claims description 29
- 239000005660 Abamectin Substances 0.000 claims description 26
- 229940079877 pyrogallol Drugs 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 12
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 11
- 239000012047 saturated solution Substances 0.000 claims description 11
- 238000004945 emulsification Methods 0.000 claims description 10
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000007764 o/w emulsion Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000001804 emulsifying effect Effects 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 239000007762 w/o emulsion Substances 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229960001553 phloroglucinol Drugs 0.000 claims description 6
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- 239000001263 FEMA 3042 Substances 0.000 claims description 5
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 5
- 229950008167 abamectin Drugs 0.000 claims description 5
- 229940074391 gallic acid Drugs 0.000 claims description 5
- 235000004515 gallic acid Nutrition 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 235000015523 tannic acid Nutrition 0.000 claims description 5
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 5
- 229940033123 tannic acid Drugs 0.000 claims description 5
- 229920002258 tannic acid Polymers 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 3
- 239000005839 Tebuconazole Substances 0.000 claims description 3
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 3
- PFTAWBLQPZVEMU-ZFWWWQNUSA-N (+)-epicatechin Natural products C1([C@@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-ZFWWWQNUSA-N 0.000 claims description 2
- PFTAWBLQPZVEMU-UKRRQHHQSA-N (-)-epicatechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-UKRRQHHQSA-N 0.000 claims description 2
- LSHVYAFMTMFKBA-TZIWHRDSSA-N (-)-epicatechin-3-O-gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=CC=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 LSHVYAFMTMFKBA-TZIWHRDSSA-N 0.000 claims description 2
- PGOOBECODWQEAB-UHFFFAOYSA-N (E)-clothianidin Chemical compound [O-][N+](=O)\N=C(/NC)NCC1=CN=C(Cl)S1 PGOOBECODWQEAB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005888 Clothianidin Substances 0.000 claims description 2
- LSHVYAFMTMFKBA-UHFFFAOYSA-N ECG Natural products C=1C=C(O)C(O)=CC=1C1OC2=CC(O)=CC(O)=C2CC1OC(=O)C1=CC(O)=C(O)C(O)=C1 LSHVYAFMTMFKBA-UHFFFAOYSA-N 0.000 claims description 2
- 239000005906 Imidacloprid Substances 0.000 claims description 2
- 239000005941 Thiamethoxam Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 claims description 2
- LPTRNLNOHUVQMS-UHFFFAOYSA-N epicatechin Natural products Cc1cc(O)cc2OC(C(O)Cc12)c1ccc(O)c(O)c1 LPTRNLNOHUVQMS-UHFFFAOYSA-N 0.000 claims description 2
- 235000012734 epicatechin Nutrition 0.000 claims description 2
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 claims description 2
- 229940056881 imidacloprid Drugs 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- NWWZPOKUUAIXIW-FLIBITNWSA-N thiamethoxam Chemical compound [O-][N+](=O)\N=C/1N(C)COCN\1CC1=CN=C(Cl)S1 NWWZPOKUUAIXIW-FLIBITNWSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 230000000361 pesticidal effect Effects 0.000 claims 2
- 239000003995 emulsifying agent Substances 0.000 abstract description 16
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 239000004094 surface-active agent Substances 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000013270 controlled release Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 230000004043 responsiveness Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- RRZXIRBKKLTSOM-XPNPUAGNSA-N avermectin 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](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 RRZXIRBKKLTSOM-XPNPUAGNSA-N 0.000 description 21
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229960003638 dopamine Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- -1 octadecylamine-phloroglucinol compound Chemical class 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000004495 emulsifiable concentrate Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- RRQQLCXFGWWLPQ-UHFFFAOYSA-N ethanol;octadecan-1-amine Chemical compound CCO.CCCCCCCCCCCCCCCCCCN RRQQLCXFGWWLPQ-UHFFFAOYSA-N 0.000 description 2
- 238000002073 fluorescence micrograph Methods 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229940038384 octadecane Drugs 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004563 wettable powder Substances 0.000 description 2
- CJPNOLIZCWDHJK-UHFFFAOYSA-N 2-Pentadecanone Chemical compound CCCCCCCCCCCCCC(C)=O CJPNOLIZCWDHJK-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000004954 Polyphthalamide Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- VGHOWOWLIXPTOA-UHFFFAOYSA-N cyclohexane;toluene Chemical compound C1CCCCC1.CC1=CC=CC=C1 VGHOWOWLIXPTOA-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001339 phlorotannin Polymers 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006375 polyphtalamide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
-
- 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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Polymers & Plastics (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses an alkyl-polyphenol 2D Janus nano-sheet, pickering emulsion, and a preparation method and application thereof. The nano-sheet is prepared by taking alkylamine as a hydrophobic unit and polyphenol as a hydrophilic unit through a self-assembly template method. The uniform and stable Pickering emulsion containing the nano-sheets can be used as carriers of various fat-soluble pesticides, and can obviously improve the dispersibility and stability of the pesticides in aqueous solution. Compared with the traditional pesticide dispersing auxiliary (surfactant), the novel emulsifier has the advantages of small dosage, high stability, no auxiliary, easy degradation and the like; the stable Pickering emulsion has wide pH stability and pH responsiveness, and can realize slow release and controlled release of pesticides by regulating the pH of the emulsion. The preparation process of the emulsifier and pesticide Pickering emulsion has the advantages of simple process, mild condition and controllable cost, and has potential of industrial production.
Description
Technical Field
The invention belongs to the technical field of agricultural emulsions, and particularly relates to an alkyl-polyphenol 2D Janus nano-sheet, a Pickering emulsion, a preparation method and application thereof.
Background
The pesticide is used as production data for preventing and controlling diseases and insect pests, regulating and promoting the growth of crops, and plays an important role in increasing the yield and income of crops, stabilizing national economy and the like. However, the efficiency of pesticide utilization on the market today is generally low (about 30%), mainly due to the following aspects: first, most pesticides are fat-soluble compounds, which are difficult to disperse in aqueous solutions, only a small amount of pesticides can be absorbed by plants through pores on plant leaves or the systemic action of roots, and a large amount of pesticides flow into soil and the atmosphere, so that resource waste is caused, and the environment is polluted. Secondly, many pesticides have poor chemical stability and are easy to decompose in ultraviolet irradiation or acid/alkaline soil; third, existing spray application methods tend to result in too high local concentrations of pesticides, which are detrimental to plant growth and present food safety issues. Therefore, improving the dispersibility, stability and slow release/controlled release performance of pesticides in aqueous solutions is one of the key technical problems faced in the agricultural field.
Currently, in industry, additives such as an emulsifier, a dispersant, a wetting agent and the like are added to pesticides to prepare formulations such as Wettable Powder (WP), suspending agents (SC), aqueous Emulsion (EW) and the like. Although the traditional surfactant can improve the dispersibility of pesticides to a certain extent as a pesticide auxiliary agent, the traditional surfactant has a plurality of defects: such as failure of interaction between the surfactant and the pesticide, addition of various auxiliary agents, demulsification of mother liquor caused by dilution, environmental pollution caused by the surfactant, and the like. Therefore, there is a need to develop novel emulsifiers that are free of adjuvants, highly stable and easily degradable.
The appearance of the 2D Janus nano sheet is the dawn brought by the development of a novel emulsifier, and the special double-sided chemical structure of the dawn endows the material with special amphiphilicity. Based on the higher surface activity and interface stability of the material, the material can be used as a solid emulsifier for constructing a Pickering emulsion system with high dispersion and high stability. However, the preparation methods of the 2D Janus nano-sheets reported at present, such as an interface protection method, a phase separation method, a self-assembly method and the like, have various defects, such as complex operation, high cost, thicker sheets, environmental pollution and the like. Therefore, the development of the 2D Janus nano sheet which has the advantages of small dosage, high stability, no auxiliary agent and easy degradation has important significance. Cheng Wenbo et al (Angew.chem.int.ed., 2019,58,12018-12022.) reported that alkyl-polydopamine 2D Janus nanoplatelets were prepared by a simple, mild, green self-assembled templating method with dopamine as the hydrophilic unit and alkylamine as the hydrophobic unit, which material allowed toluene/water immiscible systems to form stable oil-in-water O/W Pickering emulsions.
Disclosure of Invention
The invention aims to provide a novel emulsifier alkyl-polyphenol 2D Janus nano-sheet which does not need an auxiliary agent, is high in stability and easy to degrade, a preparation method thereof and a method for preparing pesticide Pickering emulsion by using the emulsifier. The emulsifier can improve the dispersibility and stability of the pesticide in aqueous solution, and has good slow release/controlled release property.
The present invention provides an alkyl-polyphenol 2D Janus nanoplatelet comprising hydrophobic units provided by alkylamines and hydrophilic units provided by polyphenols; the alkyl-polyphenol 2D Janus nano-sheet is prepared from alkylamine and polyphenol monomers by a self-assembly template method.
According to an embodiment of the invention, the polyphenol monomer may be selected from one, two or more of tannic acid, pyrogallol, gallic acid, epicatechin and epicatechin gallate, preferably one, two or three of tannic acid, pyrogallol and gallic acid, more preferably pyrogallol.
According to an embodiment of the present invention, the alkylamine may be selected from one, two or more of alkylamines having 6 or more carbon atoms, for example, one, two or more of alkylamines having 8 to 22 carbon atoms, preferably one, two or three of eicosane, octadecane and pentadecanone, more preferably octadecane.
According to an embodiment of the invention, the morphology of the alkyl-polyphenol 2D Janus nanoplatelets is shown in fig. 2.
According to an embodiment of the present invention, the length and width of the alkyl-polyphenol 2D Janus nanoplatelets are in the order of micrometers, and the thickness of the alkyl-polyphenol 2D Janus nanoplatelets is 3.5 to 8nm (4.7 nm as shown in fig. 2).
According to an embodiment of the present invention, the alkyl-polyphenol 2D Janus nanoplatelets are octadecylamine-polyphthalol 2D Janus nanoplatelets comprising hydrophobic units provided by octadecylamine and hydrophilic units provided by polyphthalol;
the octadecylamine-poly-phloroglucinol 2D Janus nano-sheet is prepared from octadecylamine and phloroglucinol by a self-assembly template method.
The invention also provides a preparation method of the alkyl-polyphenol 2DJanus nano-sheet, which comprises the following steps: in an ethanol/water mixed solvent, alkyl amine and polyphenol monomers are subjected to a self-assembly template method to prepare the alkyl-polyphenol 2D Janus nano-sheet.
According to an embodiment of the invention, the preparation method comprises the steps of:
(1) Alkylamine self-assembly to form a bilayer template: adding alkylamine into the ethanol/water mixed solvent, and stirring to self-assemble the alkylamine into an alkylamine bilayer;
(2) Reaction of alkylamine and polyphenol: adding a polyphenol monomer into the solution in the step 1 under the stirring condition, and stirring to enable the polyphenol monomer to be adsorbed on an alkylamine bilayer and react with alkylamine to obtain an alkyl-polyphenol compound;
(3) Oxidative autopolyzation of alkyl-polyphenol compounds: stirring at a low speed, and keeping air to be introduced, so that polyphenol monomers on the alkyl-polyphenol compound are oxidized and self-polymerized, and the alkyl-polyphenol 2D Janus nano-sheet is obtained.
According to an embodiment of the invention, in step (1), the alkylamine has the choice as described above.
According to an embodiment of the present invention, in the step (1), the volume ratio of ethanol to water in the ethanol/water mixed solvent may be 1 (1-6), for example, 1:4.
According to an embodiment of the invention, in step (1), the stirring is rapid stirring. For example, the stirring speed may be 300-1200rmp, such as 600-900rmp; the stirring time may be 20-60min, for example 30-40min.
According to an embodiment of the invention, in step (2), the polyphenol monomer has the choice as described above.
According to an embodiment of the invention, in step (2), the stirring is rapid stirring. For example, the stirring speed may be 500-1200rmp, such as 600-800rmp; the stirring time may be 20-60min, for example 20-30min.
According to an embodiment of the present invention, the molar ratio of the alkylamine in step (1) and the polyphenol monomer in step (2) in the reaction system may be 1 (1-35), for example 1 (1-12), preferably 1 (1-6), and exemplified by 1:3, 1:4, 1:5.
According to an embodiment of the invention, in step (3), the low speed agitation may be at a rate of 200-600rmp, such as 250-350rmp.
According to an embodiment of the invention, the preparation method further comprises the steps of:
(4) Purification of alkyl-polyphenol 2D Janus nanoplatelets: and (3) after the reaction is finished, washing the reaction solution in the step (3) with an ethanol/water solvent for multiple times, centrifuging to remove unreacted monomers and oligomers, washing the precipitate after final centrifugation with the ethanol/water solvent by suction filtration to ensure that impurities are removed, and drying the obtained solid in a vacuum drying oven at 30-80 ℃ for 6-12 hours to obtain the alkyl-polyphenol 2D Janus nano-sheet.
According to an exemplary embodiment of the present invention, the alkyl-polyphenol 2D Janus nanosheets are octadecylamine-polyphthalol 2D Janus nanosheets, and the preparation process thereof includes the steps of:
(1) Adding octadecylamine into an ethanol/water mixed solvent, and rapidly stirring to obtain alkylamine bilayer solution;
(2) Adding pyrogallol into the alkylamine bilayer solution under the stirring condition, and continuing stirring to enable the pyrogallol to be adsorbed on the alkylamine bilayer, so that hydroxyl in the pyrogallol reacts with octadecylamine to obtain an octadecylamine-pyrogallol compound;
(3) Stirring at a low speed, and keeping air to be introduced to oxidize and self-polymerize the phloroglucinol on the octadecylamine-phloroglucinol compound to obtain the octadecylamine-poly phloroglucinol 2D Janus nano-sheet.
The invention also provides application of the alkyl-polyphenol 2D Janus nano-sheet as an emulsifier.
The invention also provides an emulsifier which contains the alkyl-polyphenol 2D Janus nano-sheet.
The invention also provides Pickering emulsion which contains the alkyl-polyphenol 2D Janus nano-sheet.
According to embodiments of the present invention, the Pickering emulsion may be a water-in-oil emulsion or an oil-in-water emulsion.
According to the embodiment of the invention, the volume ratio of the oil phase to the water phase in the Pickering emulsion is (1-99) (99-1).
According to an embodiment of the invention, the concentration of alkyl-polyphenol 2D Janus nanoplatelets in the Pickering emulsion is 2.5-10mg/mL, e.g. 2.5-6mg/mL, exemplary 3mg/mL.
According to an embodiment of the invention, when the Pickering emulsion is an oil-in-water emulsion, the oil phase is present in an amount of 1-15%, such as 3-12%, exemplary 5%, 7%, 9%, 10%, 12% of the Pickering emulsion volume.
According to an embodiment of the invention, when the Pickering emulsion is a water-in-oil emulsion, the oil phase is present in a proportion of more than 15%, preferably more than 15% and not more than 90%, such as 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70%, 80%, 90% by volume of the Pickering emulsion.
According to an embodiment of the invention, the oil phase is selected from one or more of toluene, n-hexane, carbon tetrachloride, dichloromethane, cyclohexane, n-heptane, ethyl acetate and n-butanol; preferably one or more of carbon tetrachloride, toluene and cyclohexane; toluene is more preferred.
According to an embodiment of the invention, the Pickering emulsion has pH responsiveness. Preferably, the pH response interval is ph=3 to 11, for example 3, 4, 5, 6, 7, 8, 9, 10, 11.
According to an embodiment of the invention, the Pickering emulsion has pH stability. Preferably, the pH is stable at 3 or 11.
The invention also provides a preparation method of the Pickering emulsion, which comprises the following steps: dispersing the alkyl-polyphenol 2D Janus nano-sheets into an oil phase, and mixing and emulsifying the alkyl-polyphenol 2D Janus nano-sheets with a water phase to obtain the Pickering emulsion;
or,
dispersing the alkyl-polyphenol 2D Janus nano-sheets into a water phase, and mixing and emulsifying the alkyl-polyphenol 2D Janus nano-sheets with the oil phase to obtain the Pickering emulsion.
According to an embodiment of the invention, the oil phase has the options as indicated above.
According to embodiments of the invention, the pH of the aqueous phase may be from 1 to 12, for example 3, 4, 5, 7, 9, 11. By changing the pH value, emulsions with different stabilities can be prepared, so that the release of pesticides can be controlled when the emulsions are used as pesticide carriers.
The invention also provides application of the alkyl-polyphenol 2D Janus nano-sheet and/or Pickering emulsion in pesticide emulsification.
The invention also provides a pesticide emulsion, which comprises pesticide molecules and the alkyl-polyphenol 2D Janus nano-sheet and/or Pickering emulsion.
According to an embodiment of the present invention, the pesticide molecule may be selected from one, two or more of abamectin, diafenthiuron, tebuconazole, imidacloprid, thiamethoxam, clothianidin, diazinon, preferably abamectin.
According to an embodiment of the invention, in the pesticide emulsion, the concentration of pesticide molecules encapsulated in the emulsion is 0.2-2mg/mL, for example 0.3-1mg/mL.
The invention also provides a preparation method of the pesticide emulsion, which comprises the following steps: and mixing pesticide molecules with the alkyl-polyphenol 2D Janus nano-sheet for emulsification to obtain the pesticide emulsion.
For example, pesticide molecules are dissolved in an oil phase to form a saturated solution of pesticide molecules; dispersing the alkyl-polyphenol 2D Janus nano-sheets into a water phase, mixing the saturated solution of pesticide molecules with the water phase containing the alkyl-polyphenol 2D Janus nano-sheets, and performing ultrasonic emulsification to obtain the pesticide emulsion.
Also for example, pesticide molecules are dissolved in the oil phase to form a saturated solution of pesticide molecules; dispersing the alkyl-polyphenol 2D Janus nano-sheets into an oil phase, mixing a saturated solution of pesticide molecules, the oil phase containing the alkyl-polyphenol 2D Janus nano-sheets and an aqueous phase, and performing ultrasonic emulsification to obtain the pesticide emulsion.
According to an embodiment of the invention, the oil phase has the same meaning as above.
According to embodiments of the present invention, the concentration of alkyl-polyphenol 2D Janus nanoplatelets in the pesticide emulsion may be 2.5 to 10mg/mL, for example 3 to 6mg/mL.
According to an embodiment of the invention, the pesticide emulsion is a water-in-oil emulsion or an oil-in-water emulsion. Different types of emulsions can be obtained by changing the proportion of the oil phase, and for oil-in-water emulsions, the volume ratio of the oil phase to the pesticide emulsion can be 1% -15%. For water-in-oil emulsions, the oil phase may comprise 15% to 90% by volume of the pesticide emulsion.
According to embodiments of the present invention, the pH of the aqueous phase in the pesticide emulsion may be in the range of 1 to 12, for example 3, 4, 5, 7, 9, 11.
Advantageous effects
According to the invention, different types of polyphenols are used as hydrophilic units, alkylamines are used as hydrophobic units, soft membrane plates are formed in an alcohol/water system through alkylamines, and the alkyl-polyphenol 2D Janus nano-sheet is prepared by a similar self-assembly template method. The nano-sheet can regulate and control emulsion types (oil-in-water or water-in-oil type) by simply changing the volume fraction of the oil phase, and can meet the requirements of different emulsion types in pesticide application. The nano-sheet is used as an emulsifier, and the prepared Pickering emulsion is used as a carrier of various fat-soluble pesticides, so that the dispersibility and stability of the pesticides in aqueous solution can be obviously improved. Compared with the traditional pesticide dispersing auxiliary (surfactant), the novel emulsifier has the advantages of small dosage, high stability, no auxiliary, easy degradation and the like; the stable Pickering emulsion has wide pH stability and pH responsiveness, and can realize slow release and controlled release of pesticides by regulating the pH of the emulsion. The preparation process of the emulsifier and pesticide Pickering emulsion has the advantages of simple process, mild condition and controllable cost, and has potential of industrial production.
Compared with the traditional surfactant, uniform solid particles and 3D configuration amphiphilic solid particles, the 2D nano-sheet has excellent emulsifying property due to higher specific surface area, highly anisotropic shape and chemical property and highly limited interfacial rotation. The use of alkylamine gives the nano-sheet hydrophobic property, and the natural source and the hydroxyl-rich polyphenol enable the nano-sheet to have good hydrophilicity and easy degradation, and a small amount of nano-sheet can obtain stable emulsion, raw materials with low price, and the environment-friendly simple emulsifier synthesis and emulsion preparation method enable the nano-sheet to have great application prospects in agriculture. The two types of emulsions, namely water-in-oil emulsion and oil-in-water emulsion, can be obtained by adjusting the oil-water ratio, and are suitable for different agricultural emulsion requirements. For oil-soluble pesticides, stable emulsion can be obtained by using a small amount of organic oil phase, and compared with commercial pesticide emulsifiable concentrate, the oil-soluble pesticide emulsifiable concentrate has the advantages of greatly reducing the use of organic matters and being more environment-friendly; for pesticides which are easy to decompose by visible light, such as avermectin, the polyphenol with the ultraviolet resistance can slow down the decomposition of the pesticide, prolong the service life of the pesticide, improve the utilization rate of the pesticide and reduce unnecessary waste; by adjusting the pH value of the water phase, emulsions with different pH stability can be prepared, so that the release of pesticides can be controlled by adjusting the pH.
The invention selects natural polyphenols (such as tannic acid, pyrogallol, gallic acid and the like) from sources, has similar reactivity with dopamine, but has obvious advantages compared with the dopamine in cost, and has the characteristics of degradability and ultraviolet light shielding effect, thereby endowing the emulsion with easy-degradation industrial application prospect and functionality. The novel emulsifier with different emulsifying properties can be prepared by selecting phenolic substances with different structures as hydrophilic units and alkylamines with different alkyl chains as hydrophobic units, so as to regulate and control the amphipathy of the 2D Janus nano-sheets.
Drawings
FIG. 1 is a schematic illustration of the formation of alkyl-polyphenol Janus nanoplatelets and the production of Pickering emulsions.
FIG. 2 is an AFM image and a scanning electron microscope image of an alkyl-polyphenol Janus nanosheet of example 1.
FIG. 3 is a schematic diagram of amphiphilicity of alkyl-polyphenol Janus nanoplatelets in example 1.
FIG. 4 is a zeta potential plot of alkyl-polyphenol Janus nanoplatelets of example 9.
FIG. 5 is a graph showing the behavior of stable emulsions of alkyl-polyphenol Janus nanoplatelets at various oil phase volume fractions in example 1;
wherein, figure a is an emulsion picture with toluene volume fractions of 5%, 10%, 15%, 25%, 35%, 50%, 60%, respectively;
panel B is an optical micrograph (a) - (f) and a fluorescence micrograph (a) of oil in water in emulsion at corresponding different toluene volume fractions 1 )-(d 1 ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein (a) and (a) 1 ) (b) and (b) 1 ) (c) and (c) 1 ) (d) and (d) 1 ) Respectively corresponding to the same oil-in-water emulsion;
panel C is an optical micrograph (C) - (g) and a fluorescence micrograph (C) of water-in-oil in emulsion at corresponding different toluene volume fractions 1 )-(g 1 )。
Fig. 6 is a standard graph of avermectin.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
Octadecylamine-polyphthalol Janus nanoplatelets and Pickering emulsions were prepared according to the process flow shown in FIG. 1:
firstly, octadecylamine is taken and dissolved in ethanol to prepare 2.5mg/mL of ethanol octadecylamine solution, the ethanol octadecylamine solution is added into deionized water according to the volume ratio of the ethanol to the water of 1:4, and the solution is rapidly stirred for half an hour under magnetic stirring to form the octadecylamine bilayer solution.
And secondly, weighing the pyrogallol, adding the pyrogallol into the solution in the first step to ensure that the concentration of the pyrogallol is 1mg/mL, and continuously stirring for half an hour to ensure that the pyrogallol can be adsorbed on an octadecylamine bilayer, and the hydroxyl on the pyrogallol reacts with the amino of the octadecylamine to obtain the pyrogallol grafted octadecylamine.
Thirdly, reducing the rotating speed of magnetic stirring, slowly stirring, and continuing stirring for 24 hours to enable the pyrogallol to undergo self-polymerization to form the octadecylamine-poly-pyrogallol Janus nano-sheet. And then centrifuging and drying.
Preparing Pickering emulsion:
fourthly, preparing a nano-sheet deionized water dispersion liquid with the concentration of 3mg/mL to obtain a water phase (pH=6.5), respectively weighing toluene according to the proportion of 5%, 10%, 15%, 25%, 35%, 50% and 60% of the volume fraction of the oil phase, adding the toluene into the water phase, and performing ultrasonic emulsification for 1min to form the Pickering emulsion of oil-in-water and water-in-oil.
Preparing an avermectin emulsion:
fifthly, dissolving avermectin in toluene to form an avermectin saturated solution (7 mg/mL) serving as an oil phase, preparing a certain amount of nano-sheet aqueous dispersion serving as an aqueous phase, enabling the concentration of nano-sheets in the final emulsion to be 3mg/mL, sucking the avermectin saturated solution, adding the avermectin saturated solution into the aqueous phase, enabling the volume fraction of the oil phase to be 5%, and performing ultrasonic emulsification for 1min to form the avermectin emulsion. Contains avermectin emulsion with the concentration of 0.307 mg/mL.
Sixth, a solution of 4mg/mL avermectin ethanol is prepared in a 25mL volumetric flask, and 0.2mL, 0.3mL, 0.4mL, 0.5mL and 0.6mL are respectively absorbed into the volumetric flask of 10 mL. The UV absorbance was then measured at 245nm and an avermectin standard curve was established (FIG. 6).
And seventhly, measuring the concentration of the encapsulated avermectin in the avermectin emulsion obtained in the fifth step by an ultraviolet-visible spectrophotometer, and further calculating the encapsulation efficiency of the avermectin in the avermectin emulsion. The calculation formula of fig. 6 and the encapsulation efficiency (wherein "mass of avermectin in avermectin emulsion=mass of avermectin encapsulated in avermectin emulsion") is combined, and the encapsulation efficiency of avermectin in avermectin emulsion is 87.64%.
Example 2
The difference between this embodiment and embodiment 1 is that: tannic acid is used to replace pyrogallol.
Example 3
The difference between this embodiment and embodiment 1 is that: gallic acid is used to replace pyrogallol.
Example 4
The difference between this embodiment and embodiment 1 is that: toluene was replaced with n-hexane.
Example 5
The difference between this embodiment and embodiment 1 is that: cyclohexane was used instead of toluene.
Example 6
The difference between this embodiment and embodiment 1 is that: carbon tetrachloride was used instead of toluene.
Example 7
The difference between this embodiment and embodiment 1 is that: diafenthiuron is used to replace abamectin.
Example 8
The difference between this embodiment and embodiment 1 is that: tebuconazole is used to replace abamectin.
Example 9
The difference between this embodiment and embodiment 1 is that: and (3) regulating the pH value of the water phase in the fourth step to be 3, 4, 5, 7, 9 and 11 respectively, and preparing emulsion with different pH values.
EXAMPLE 10 characterization of octadecylamine-Poly-o-phloroglucinol nanosheets and Pickering emulsions prepared in example 1
FIG. 2 demonstrates the successful synthesis of octadecylamine-polyphthalol nanoplatelets by AFM (a) and SEM (b) images, with a nanoplatelet thickness of 4.7nm.
The octadecylamine-poly-pyrogallol nano-sheet is uniformly dispersed into toluene, liquid drops are sucked and dripped on a glass sheet, and the hydrophobicity of the nano-sheet is tested. As shown in a of fig. 3, the contact angle of the glass modified with the nanoplatelets increased from 24±2° to 100±2° compared to the unmodified glass sheets, indicating that the nanoplatelets have hydrophobicity. And then emulsifying the nano-sheets from oil water to oil-in-water emulsion, and dripping the emulsion onto Polytetrafluoroethylene (PTFE) sheets to test the hydrophilicity of the nano-sheets. As shown in b of fig. 3, the contact angle of the nano-sheet modified polytetrafluoroethylene was reduced from 111±2° to 69±9° compared to the unmodified PTFE sheet, indicating that the nano-sheet has hydrophilicity. Figure 3 demonstrates that octadecylamine-polyphthalamide nanoplatelets have amphiphilic properties.
As can be seen from fig. 4, by dispersing the octadecylamine-polyphthalene amphiphilic nano-sheet into deionized water with different pH values, the zeta potential values of the nano-sheet are measured at room temperature of 25 ℃, so that the aqueous solution with different pH values is obtained, and the stronger the acidity or alkalinity of the aqueous solution, the more the zeta potential value is, the less the nano-sheet is easy to agglomerate in water, the better the emulsifying property is, and the octadecylamine-polyphthalene amphiphilic nano-sheet has pH responsiveness.
As can be seen from fig. 5, the emulsion was changed from oil-in-water to water-in-oil by oil-water emulsification with toluene of different volumes, and layering occurred from 15% toluene volume, with oil-in-water in the lower layer of the emulsion, water-in-oil in the middle layer of the emulsion, and unemulsified toluene in the upper layer. And as toluene increases, the volume of water-in-oil emulsion increases.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. A pesticide emulsion comprising pesticide molecules, alkyl-polyphenol 2d janus nanoplatelets and/or Pickering emulsions; the Pickering emulsion contains the alkyl-polyphenol 2DJanus nano-sheets; in the Pickering emulsion, the concentration of the alkyl-polyphenol 2DJanus nano-sheet is 2.5-10mg/mL; the pesticide molecule is one, two or more selected from abamectin, diafenthiuron, tebuconazole, imidacloprid, thiamethoxam, clothianidin and diazinon; in the pesticide emulsion, the concentration of pesticide molecules encapsulated in the pesticide emulsion is 0.2-2 mg/mL; the alkyl-polyphenol 2d janus nanoplatelets comprise hydrophobic units provided by alkylamines and hydrophilic units provided by polyphenols; the alkyl-polyphenol 2DJanus nano-sheet is prepared from alkylamine and polyphenol monomers by a self-assembly template method; the polyphenol monomer is selected from one, two or more of tannic acid, pyrogallol, gallic acid, epicatechin and epicatechin gallate; the alkylamine is selected from one, two or more of alkylamines with more than 6 carbon atoms.
2. A pesticide emulsion according to claim 1, wherein the alkyl-polyphenol 2d janus nanoplatelets have a length and width on the order of micrometers, the thickness of the alkyl-polyphenol 2d janus nanoplatelets being 3.5-8 nm; and/or the alkylamine is selected from one, two or more of alkylamines with 8-22 carbon atoms.
3. The pesticide emulsion of claim 1, wherein the alkyl-polyphenol 2d janus nanoplatelets are octadecylamine-polyphthalol 2d janus nanoplatelets comprising hydrophobic units provided by octadecylamine and hydrophilic units provided by polyphthalol; the octadecylamine-poly-phloroglucinol 2DJanus nano-sheet is prepared from octadecylamine and phloroglucinol by a self-assembly template method.
4. The pesticidal emulsion according to claim 1 or 2, wherein the preparation method of the alkyl-polyphenol 2d janus nanoplatelets comprises the steps of: in an ethanol/water mixed solvent, alkylamine and polyphenol monomers are prepared into the alkyl-polyphenol 2DJanus nano-sheet by a self-assembly template method.
5. A pesticide emulsion as set forth in claim 4 wherein said method of preparation comprises the steps of:
(1) Alkylamine self-assembly to form a bilayer template: adding alkylamine into the ethanol/water mixed solvent, and stirring to self-assemble the alkylamine into an alkylamine bilayer;
(2) Reaction of alkylamine and polyphenol: adding a polyphenol monomer into the solution in the step (1) under the stirring condition, and stirring to enable the polyphenol monomer to be adsorbed on an alkylamine bilayer and react with alkylamine to obtain an alkyl-polyphenol compound;
(3) Oxidative autopolyzation of alkyl-polyphenol compounds: stirring at a low speed, and keeping air to be introduced to oxidize and self-polymerize polyphenol monomers on the alkyl-polyphenol compounds, so as to obtain the alkyl-polyphenol 2DJanus nano-sheets.
6. The pesticidal emulsion of claim 5, wherein in step (1), the volume ratio of ethanol to water in the ethanol/water mixed solvent is 1 (1-6); and/or, in the step (1), the stirring rotating speed is 300-1200rmp; stirring for 20-60min; and/or, in the step (2), the stirring is rapid stirring; the rotating speed of the rapid stirring is 500-1200rmp; stirring for 20-60min; and/or the molar ratio of the alkylamine in the step (1) and the polyphenol monomer in the step (2) in the reaction system is 1 (1-35); and/or, in the step (3), the low-speed stirring speed is 200-600rmp.
7. A pesticide emulsion as set forth in claim 5 wherein said method of making further comprises the steps of: (4) purification of alkyl-polyphenol 2d janus nanoplatelets: after the reaction is finished, washing the reaction solution in the step (3) with ethanol/water solvent for multiple times, centrifuging to remove unreacted monomers and oligomers, washing the precipitate after final centrifugation with ethanol/water solvent again by suction filtration to ensure that impurities are removed, and drying the obtained solid in a vacuum drying oven at 30-80 ℃ for 6-12 hours to obtain the alkyl-polyphenol 2DJanus nano-sheet.
8. The pesticide emulsion of claim 1, wherein the Pickering emulsion is a water-in-oil emulsion or an oil-in-water emulsion; and/or, in the Pickering emulsion, the volume ratio of the oil phase to the water phase is (1-99): 99-1.
9. The pesticide emulsion of claim 8, wherein when the Pickering emulsion is an oil-in-water emulsion, the oil phase comprises 1-15% of the Pickering emulsion volume; and/or, when the Pickering emulsion is a water-in-oil emulsion, the ratio of the oil phase in the volume of the Pickering emulsion is greater than 15%; and/or the oil phase is selected from one or more of toluene, n-hexane, carbon tetrachloride, methylene dichloride, cyclohexane, n-heptane, ethyl acetate and n-butanol; and/or the pH of the aqueous phase is 1-12.
10. The pesticide emulsion of claim 1, wherein the Pickering emulsion is pH-responsive; the pH response interval is pH=3-11; and/or, the Pickering emulsion has pH stability; the pH stability value is 3 or 11.
11. The pesticide emulsion of claim 8, wherein the method for preparing the Pickering emulsion comprises the following steps: dispersing the alkyl-polyphenol 2DJanus nano-sheets into an oil phase, and mixing and emulsifying the nano-sheets with a water phase to obtain the Pickering emulsion; or dispersing the alkyl-polyphenol 2DJanus nano-sheets into a water phase, and mixing and emulsifying the nano-sheets with an oil phase to obtain the Pickering emulsion.
12. A method of preparing a pesticide emulsion as set forth in any one of claims 1 to 11 wherein the method comprises the steps of: and mixing pesticide molecules with the alkyl-polyphenol 2DJanus nano-sheet for emulsification to obtain the pesticide emulsion.
13. The method of claim 12, wherein the pesticide molecules are dissolved in the oil phase to form a saturated solution of pesticide molecules; dispersing the alkyl-polyphenol 2DJanus nano-sheets into a water phase, mixing the saturated solution of pesticide molecules with the water phase containing the alkyl-polyphenol 2DJanus nano-sheets, and performing ultrasonic emulsification to obtain the pesticide emulsion; and/or dissolving pesticide molecules in the oil phase to form a saturated solution of pesticide molecules; dispersing the alkyl-polyphenol 2DJanus nano-sheets into an oil phase, mixing a saturated solution of pesticide molecules, the oil phase containing the alkyl-polyphenol 2DJanus nano-sheets and an aqueous phase, and performing ultrasonic emulsification to obtain the pesticide emulsion.
14. The method of claim 12, wherein the concentration of alkyl-polyphenol 2d janus nanoplatelets in the pesticide emulsion is 2.5-10mg/mL; and/or, the pesticide emulsion is a water-in-oil emulsion or an oil-in-water emulsion; and/or, in the pesticide emulsion, the pH of the water phase is 1-12.
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