CN114507359A - Preparation method of modified material of lignosulfonate and application of modified material in nano pesticide - Google Patents
Preparation method of modified material of lignosulfonate and application of modified material in nano pesticide Download PDFInfo
- Publication number
- CN114507359A CN114507359A CN202210145722.0A CN202210145722A CN114507359A CN 114507359 A CN114507359 A CN 114507359A CN 202210145722 A CN202210145722 A CN 202210145722A CN 114507359 A CN114507359 A CN 114507359A
- Authority
- CN
- China
- Prior art keywords
- lignosulfonate
- nano
- modified material
- pesticide
- aliphatic
- Prior art date
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- Pending
Links
- 239000000575 pesticide Substances 0.000 title claims abstract description 91
- 229920001732 Lignosulfonate Polymers 0.000 title claims abstract description 90
- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 54
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 239000006228 supernatant Substances 0.000 claims abstract description 7
- 239000012876 carrier material Substances 0.000 claims abstract description 3
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract 2
- 239000005760 Difenoconazole Substances 0.000 claims description 39
- BQYJATMQXGBDHF-UHFFFAOYSA-N difenoconazole Chemical compound O1C(C)COC1(C=1C(=CC(OC=2C=CC(Cl)=CC=2)=CC=1)Cl)CN1N=CN=C1 BQYJATMQXGBDHF-UHFFFAOYSA-N 0.000 claims description 39
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 14
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- -1 aromatic acid chlorides Chemical class 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- 239000005822 Propiconazole Substances 0.000 claims description 5
- 239000005839 Tebuconazole Substances 0.000 claims description 5
- FLISWPFVWWWNNP-BQYQJAHWSA-N dihydro-3-(1-octenyl)-2,5-furandione Chemical compound CCCCCC\C=C\C1CC(=O)OC1=O FLISWPFVWWWNNP-BQYQJAHWSA-N 0.000 claims description 5
- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- ZXQYGBMAQZUVMI-RDDWSQKMSA-N (1S)-cis-(alphaR)-cyhalothrin Chemical compound CC1(C)[C@H](\C=C(/Cl)C(F)(F)F)[C@@H]1C(=O)O[C@@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-RDDWSQKMSA-N 0.000 claims description 2
- VMZCDNSFRSVYKQ-UHFFFAOYSA-N 2-phenylacetyl chloride Chemical compound ClC(=O)CC1=CC=CC=C1 VMZCDNSFRSVYKQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005885 Buprofezin Substances 0.000 claims description 2
- 241000238631 Hexapoda Species 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005820 Prochloraz Substances 0.000 claims description 2
- 239000005869 Pyraclostrobin Substances 0.000 claims description 2
- 241000607479 Yersinia pestis Species 0.000 claims description 2
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 2
- PRLVTUNWOQKEAI-VKAVYKQESA-N buprofezin Chemical compound O=C1N(C(C)C)\C(=N\C(C)(C)C)SCN1C1=CC=CC=C1 PRLVTUNWOQKEAI-VKAVYKQESA-N 0.000 claims description 2
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 2
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 2
- 201000010099 disease Diseases 0.000 claims description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims description 2
- 239000005910 lambda-Cyhalothrin Substances 0.000 claims description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 230000002265 prevention Effects 0.000 claims description 2
- TVLSRXXIMLFWEO-UHFFFAOYSA-N prochloraz Chemical compound C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl TVLSRXXIMLFWEO-UHFFFAOYSA-N 0.000 claims description 2
- HZRSNVGNWUDEFX-UHFFFAOYSA-N pyraclostrobin Chemical compound COC(=O)N(OC)C1=CC=CC=C1COC1=NN(C=2C=CC(Cl)=CC=2)C=C1 HZRSNVGNWUDEFX-UHFFFAOYSA-N 0.000 claims description 2
- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical compound CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002539 nanocarrier Substances 0.000 description 26
- 239000004530 micro-emulsion Substances 0.000 description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 14
- 230000002209 hydrophobic effect Effects 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000006303 photolysis reaction Methods 0.000 description 10
- 230000015843 photosynthesis, light reaction Effects 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 229920005610 lignin Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 238000001782 photodegradation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000013270 controlled release Methods 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 3
- 229920000053 polysorbate 80 Polymers 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 241000193738 Bacillus anthracis Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- JAUFWTSSYRTLLB-UHFFFAOYSA-N (2-phenylacetyl) 2-phenylacetate Chemical compound C=1C=CC=CC=1CC(=O)OC(=O)CC1=CC=CC=C1 JAUFWTSSYRTLLB-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- GUOCOOQWZHQBJI-UHFFFAOYSA-N 4-oct-7-enoxy-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OCCCCCCC=C GUOCOOQWZHQBJI-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003405 delayed action preparation Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000003090 pesticide formulation Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004557 technical material Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 230000001018 virulence Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- 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
- A01N25/22—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 ingredients stabilising the active ingredients
-
- 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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- 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
Abstract
The invention discloses a preparation method of a lignosulfonate modified material, which comprises the following steps: dissolving lignosulfonate in a solvent, adding triethylamine and aliphatic/aromatic substances, reacting for 24 +/-2 hours under the stirring condition, centrifuging to obtain a supernatant, adding isopropanol into the supernatant to obtain a precipitate, and drying the precipitate in vacuum to obtain the lignosulfonate modified material. The invention also provides the application of the modified material of the lignosulfonate, which comprises the following steps: the nano pesticide is prepared by taking the modified material of the lignosulfonate as a carrier material and loading the original pesticide.
Description
Technical Field
The invention relates to the technical field of preparation and application of agricultural nano materials, in particular to preparation and application of a lignosulfonate hydrophobic modified nano material.
Background
In the agricultural field, over 400 million tons of pesticides are used worldwide each year to protect crops. However, in recent years, abuse and high residue of agricultural chemicals have put a great burden on the environment and human health. These serious hazards are not only due to the inefficiency of the pesticide, but also due to the high use of organic solvents and surfactants in conventional formulations. Therefore, there is a need to protect crops with more efficient, green pesticides to promote the sustainable development of agriculture. Compared with the traditional pesticide, the nano pesticide has unique advantages and is considered to have wide application prospect.
The nano pesticide is a pesticide preparation with good development prospect in recent years. Compared with the traditional pesticide preparation, the nano pesticide has smaller particle size and higher specific surface area, so that the nano pesticide constructed based on the nano material has better performances such as dispersibility, permeability, persistence, photolysis resistance and the like when used in the field. In the related reports, some kinds of inorganic materials, such as mesoporous silicon, metal organic frameworks, and calcium carbonate, or organic materials, such as artificial polymers, chitosan, and cellulose, have been used to construct pesticide nanocarriers. In the field of medicine, the controlled-release nano preparation has been well applied, but due to the high material cost and the complicated technical requirements, the controlled-release preparation loaded with pesticide, namely the nano pesticide, has not been widely applied in the field of agriculture.
Lignin, the second most abundant renewable polymer in nature, is one of the major components of wood, and lignin and its numerous derivatives are available from by-products produced by the pulp and paper industries. Because lignin and derivatives thereof contain multiple functional groups such as aromatic groups, hydroxyl groups, carboxyl groups and the like, the chemical properties of the lignin and the derivatives thereof can be changed and the application fields of the lignin and the derivatives thereof can be widened by carrying out modification reactions such as graft copolymerization, acylation, sulfonation and the like on the functional groups. In recent years, lignosulfonate and modified derivatives thereof have been receiving attention in the field of nano pesticides due to advantages such as low cost, good biodegradability, and strong ultraviolet absorption capability. But due to the strong water solubility of lignosulfonates. The method limits the use of the lignosulfonate in various methods for preparing nano pesticides, such as an interfacial polymerization method, a solvent volatilization method, a solvent exchange method and the like, modifies the lignosulfonate, improves the lipid solubility of the lignosulfonate, widens the application range of the lignosulfonate and becomes a hotspot of research.
The invention patent CN110946133A discloses a nano photolysis-resistant controlled-release pesticide with lignin as a coating matrix and a preparation method thereof, the invention takes lignosulfonate as a material, a wall material for coating the pesticide is formed by crosslinking of a crosslinking agent, and a raw pesticide is taken as a core material to obtain the nano pesticide. However, the scheme directly uses lignosulfonate, no modification is carried out, the process is complicated, the used cross-linking agents, namely p-phenylenediamine and m-phenylenediamine, are listed as carcinogenic substances by the world health organization, the toxicity is high, and the environmental protection property is poor; the invention patent CN108739807B describes a nano microcapsule preparation prepared by taking a polymer formed by vegetable oleic acid-chitosan polyol and polyisocyanate as a wall material and taking a pesticide as a core material, wherein the particle size of the preparation reaches the nano level, but in some reports, the isocyanate has the problem of mutual reaction with the pesticide containing hydroxyl in a chemical formula.
The nano pesticide disclosed at present still has the defects of complex preparation process, high cost, difficult degradation in the environment, uneven particle distribution, low slow release and anti-photodegradation capabilities and the like, so that the material cost needs to be reduced, and a lignosulfonate hydrophobic modified nano material which is simple in process, environment-friendly, capable of preparing a novel nano pesticide with long lasting period and slow degradation is developed.
The invention of CN113260257A, nanometer pesticide preparation and its preparation method, discloses a nanometer pesticide preparation and its preparation method. Sodium lignosulfonate and a polystyrene-maleic anhydride copolymer are used as auxiliary agents, but the modification of a carrier is not involved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method and application of a lignosulfonate hydrophobic modified nano material.
In order to solve the technical problems, the invention provides a preparation method of a modified material of lignosulfonate (hydrophobic nano modified material of lignosulfonate):
dissolving lignosulfonate in a solvent, adding triethylamine and aliphatic/aromatic substances, reacting for 24 +/-2 hours under a stirring condition, centrifuging to obtain a supernatant, adding isopropanol into the supernatant to obtain a precipitate, and performing vacuum drying (cleaning and then performing vacuum drying) on the precipitate to obtain a lignosulfonate modified material;
the lignosulfonate is: the weight ratio of the aliphatic/aromatic substances is 1: 2-7;
aliphatic/aromatic: triethylamine is 1 (1 +/-0.05) in molar ratio;
the aliphatic/aromatic is any one of the following: aliphatic/aromatic acid anhydrides, and aliphatic/aromatic acid chlorides.
Description of the drawings: the modified material of the lignosulfonate, namely the lignosulfonate hydrophobic nano modified material is a polymer formed by lignosulfonate and aliphatic/aromatic substances and can be used as a lignosulfonate hydrophobic nano carrier.
Improvement of the preparation method of the modified material of lignosulfonate of the present invention:
the aliphatic/aromatic acid anhydride is any one of the following: benzoic anhydride (preferred), methacrylic anhydride, phthalic anhydride, maleic anhydride, phenylacetic anhydride, succinic anhydride, octenyl succinic anhydride (preferred);
the aliphatic/aromatic acid chloride is any one of the following: benzoyl chloride (preferred), methacryloyl chloride, phthaloyl chloride, phenylacetyl chloride.
Further improvement of the method for producing a modified material of lignosulfonate of the present invention:
the lignosulfonate (water-soluble lignosulfonate) is any one of the following: sodium lignosulfonate, calcium lignosulfonate, potassium lignosulfonate, and the like.
Further improvement of the method for producing a modified material of lignosulfonate of the present invention:
the solvent is N, N-dimethylformamide and dimethyl sulfoxide.
Further improvement of the method for producing a modified material of lignosulfonate of the present invention: the stirring reaction temperature is 50-70 ℃.
Description of the drawings: dissolving lignosulfonate in solvent, optionally in a form of heat-assisted dissolution (e.g. stirring in an oil bath at 90 ℃), 1g lignosulfonate typically being mixed with 10 + -3 ml solvent; and cooling to room temperature, adding triethylamine and aliphatic/aromatic substances, and stirring at 50-70 ℃ for reaction.
Further improvement of the method for producing a modified material of lignosulfonate of the present invention: the particle size of the hydrophobic nano modified material is 1-300 nm (about 100 nm).
Description of the drawings: according to the invention, the aliphatic/aromatic acid anhydride or aliphatic/aromatic acyl chloride is introduced into the lignosulfonate structure to modify the lignosulfonate structure, so that the hydrophilicity of the lignosulfonate is reduced, the hydrophobicity of the lignosulfonate is increased, the modified lignosulfonate has good hydrophilic and oleophilic properties, and the particle size of the lignosulfonate is reduced.
The invention also provides the application of the modified material of the lignosulfonate prepared by any method, which comprises the following steps:
the nano pesticide is prepared by taking the modified material of the lignosulfonate as a carrier material and loading the original pesticide.
The pesticide raw material is a pesticide with stronger lipophilicity.
The nano pesticide has high stability and good slow release effect; can be better applied to the agricultural field.
As an improvement of the use of the present invention: the pesticide raw materials are at least one (namely, one or more) of the following: difenoconazole, pyraclostrobin, tebuconazole, propiconazole, lambda-cyhalothrin, tricyclazole, buprofezin and prochloraz.
As a further improvement of the use of the present invention: the nano pesticide is applied to prevention and control of crop diseases and insect pests.
Aiming at the problems in the prior art, the invention aims to provide a method for preparing a nano pesticide preparation with slow release and photodegradation resistance by using lignosulfonate as a material and carrying out esterification reaction on a plurality of hydroxyl groups in lignosulfonate and aliphatic anhydride or aromatic anhydride or related acyl chloride thereof to generate a new nano carrier and further wrap pesticide.
The invention takes lignosulfonate as a raw material, aliphatic anhydride or aromatic anhydride or related acyl chloride thereof with different proportions is used for esterification with lignosulfonate to obtain different lipophilic lignosulfonate hydrophobic modified materials, and the pesticide nano preparation with slow release and photodegradation resistance is prepared by an emulsification method, a solvent exchange method or a solvent volatilization method.
For example: the structure of the lignosulfonate hydrophobic modified material is shown as follows:
compared with the prior art, the invention has the following advantages:
(1) the modified material (lignosulfonate hydrophobic nano modified material) of the lignosulfonate is derived from byproducts in the paper making industry, has wide sources, low cost and good biodegradability, reduces the pollution to the environment, can be synthesized by only one-step reaction without using a cross-linking agent, and has simple process.
(2) The nano pesticide preparation prepared by using the lignosulfonate hydrophobic nano modified material still has good preparation stability (figure 5) under the condition of reducing the use of toxic organic solvents and surfactants, and does not use toxic cross-linking agents.
(3) The nano pesticide preparation of the invention has the stability and the sterilization effect similar to the traditional commercial microemulsion, but has better photolysis resistance than the commercial microemulsion (figure 4).
(4) The nano pesticide preparation has an average value of about 100nm, small particle size, good dispersion degree and good affinity and adhesion to leaves (figure 2).
(5) The nano pesticide preparation has the stability and the sterilization effect similar to those of the traditional commercial microemulsion, can slowly release the coated original pesticide, has an obvious slow release effect, can effectively reduce the use times and the use amount of the field pesticide, and greatly improves the utilization rate of the existing pesticide.
(6) In the process of preparing the nano pesticide, the lignin sulfonate hydrophobic nano modified material effectively increases the hydrophobicity of the lignin sulfonate because the hydrophilicity of the existing lignin sulfonate is reduced, and greatly improves the lipophilicity of the lignin sulfonate through esterification reaction, thereby forming firmer nano pesticide particles compared with hollow micro-capsules.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is nuclear magnetic hydrogen spectrum of benzoic acid esterified lignosulfonate derivative;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a difenoconazole nano pesticide formulation;
FIG. 3 is a release profile of difenoconazole nano-pesticide;
FIG. 4 is a graph showing the photo-degradation resistance of difenoconazole nano-pesticide;
fig. 5 is a stability index (TSI) chart of difenoconazole nano pesticide.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
firstly, preparing a hydrophobic nano modified material of lignosulfonate:
example 1 preparation of sodium benzoate-esterified lignin sulfonate (weight ratio of sodium lignin sulfonate to benzoic anhydride 1: 2):
weighing 1g of sodium Lignosulfonate (LS) and adding the sodium lignosulfonate into 10ml of N, N-Dimethylformamide (DMF), and stirring in an oil bath at 90 ℃ until the sodium lignosulfonate is completely dissolved;
after cooling to room temperature, 2g of benzoic anhydride (Bma) and 1 equivalent (relative to benzoic anhydride) of Triethylamine (TEA) were added and the reaction was stirred at 60 ℃ for 24 h.
Centrifuging (8000r/min, 5min) to obtain supernatant; then, 200ml of isopropanol is poured into the mixture and then the mixture is centrifuged to obtain a precipitate, the precipitate is washed twice with the isopropanol (the dosage of the isopropanol is 200ml in each washing), and the precipitate is placed into a vacuum drying oven and dried in vacuum at 40 ℃ (dried to constant weight) to prepare the sodium benzoate-esterified lignin sulfonate (namely, the sodium benzoate-esterified lignin sulfonate nano-carrier). The particle size is about 100 nm.
Example 2, the amount of benzoic anhydride in example 1 was changed from "2 g" to "3 g", and triethylamine was still 1 equivalent (relative to benzoic anhydride); the rest is equivalent to embodiment 1. The grain diameter of the obtained sodium benzoate-esterified lignin sulfonate nano-carrier is about 100 nm.
Example 3, the amount of benzoic anhydride in example 1 was changed from "2 g" to "5 g", and triethylamine was still 1 equivalent (relative to benzoic anhydride); the rest is equivalent to embodiment 1. The grain diameter of the obtained sodium benzoate-esterified lignin sulfonate nano-carrier is about 100 nm.
Example 4, the amount of benzoic anhydride in example 1 was changed from "2 g" to "7 g", and triethylamine was still 1 equivalent (relative to benzoic anhydride); the rest is equivalent to example 1. The grain diameter of the obtained sodium benzoate-esterified lignin sulfonate nano-carrier is about 100 nm.
Example 5 "2 g of benzoic anhydride" in example 1 was changed to "3 g of phthalic anhydride", and 1 equivalent of Triethylamine (TEA) to phthalic anhydride was used, and the balance was the same as in example 1. The particle size of the obtained phthalic acid esterification sodium lignosulfonate nano-carrier is about 100 nm.
Example 6 "2 g of benzoic anhydride" in example 1 was changed to "3 g of benzoyl chloride", and 1 equivalent of Triethylamine (TEA) to the benzoyl chloride was the same as in example 1. The particle size of the obtained sodium benzoylate lignosulfonate nano-carrier is about 100 nm.
Example 7 "2 g of benzoic anhydride" in example 1 was changed to "5 g of octenyl succinic anhydride", and 1 equivalent of Triethylamine (TEA) to octenyl succinic anhydride was the same as in example 1. The grain diameter of the obtained octenyl succinate sodium lignosulfonate nano-carrier is about 100 nm.
Secondly, preparing the nano pesticide by using the hydrophobic nano modified material of the lignosulfonate:
example 8 preparation of Difenoconazole Nano pesticide Using sodium benzoate-esterified Lignosulfonate obtained in example 1
20mg of Sodium Dodecyl Sulfate (SDS) was dissolved in 10ml of water to prepare an aqueous solution containing 0.2% SDS as an aqueous phase;
dissolving 100mg of the sodium benzoate-esterified lignin sulfonate nano-carrier obtained in example 1 and 20mg of difenoconazole in 500mg of dichloromethane to serve as an oil phase;
dropping the oil phase into the water phase, placing into a high shear emulsifying machine, shearing at 10000r/min for 1min, placing into a cell disruptor, performing ultrasonic treatment at 70W power for 1min, stirring at 1000r/min for two hours, and volatilizing the dichloromethane. The needed difenoconazole nano pesticide preparation is prepared.
Example 9, the weight of the "nano-carrier prepared in example 1" used in example 8 was changed to "nano-carrier prepared in example 2", and the weight was kept unchanged, and the rest was the same as example 8.
Example 10, the weight of the "nano-carrier prepared in example 1" used in example 8 was changed to "nano-carrier prepared in example 3", and the rest was the same as example 8.
Example 11, the weight of the "nano-carrier prepared in example 1" used in example 8 was changed to "nano-carrier prepared in example 4", and the rest was the same as example 8.
Example 12 preparation of Tebuconazole Nano pesticide by using benzoic acid esterified sodium lignin sulfonate obtained in example 3
10mg of SDS was dissolved in 5ml of water to prepare an aqueous solution containing 0.2% SDS as an aqueous phase;
50mg of the sodium benzoate-esterified lignosulfonate nanocarrier prepared in example 3 (obtained by reacting sodium lignosulfonate with benzoic anhydride 1: 5) and 10mg of tebuconazole were dissolved in 250mg of dichloromethane to serve as oil phases;
dropping the oil phase into the water phase, placing into a high shear emulsifying machine, shearing at 10000r/min for 1min, placing into a cell disruptor, performing ultrasonic treatment at 70W for 1min, and stirring at 1000r/min for two hours. The tebuconazole nano pesticide preparation is prepared.
Example 13 preparation of propiconazole Nanospecies Using the sodium Benzoate Lignosulfonate obtained in example 3
10mg of SDS was dissolved in 5ml of water to prepare an aqueous solution containing 0.2% SDS as an aqueous phase;
50mg of the sodium benzoate-esterified lignosulfonate nanocarrier prepared in example 3 (obtained by reacting sodium lignosulfonate with benzoic anhydride 1: 5) and 10mg of propiconazole were dissolved in 250mg of dichloromethane to serve as oil phases;
dropping the oil phase into the water phase, placing into a high shear emulsifying machine, shearing at 10000r/min for 1min, placing into a cell disruptor, performing ultrasonic treatment at 70W for 1min, and stirring at 1000r/min for two hours. The propiconazole nano pesticide preparation is prepared.
Thirdly, nuclear magnetic hydrogen spectrum contrast picture of nano slow-release photolysis-resistant pesticide with lignosulfonate as material
Fig. 1 is a nuclear magnetic hydrogen spectrum comparison diagram of the sodium benzoate-esterified sodium lignin sulfonate nano-carrier prepared in example 3 and a sodium lignin sulfonate raw material, and compared with a nuclear magnetic spectrum of sodium lignin sulfonate, the sodium benzoate-esterified sodium lignin sulfonate nano-carrier has two new absorption peaks at a chemical shift δ of 7.2-8.2ppm, which is a benzene ring peak of benzoyl, that is, a product after esterification, that is, hydrogen on a benzene ring of the sodium benzoate-esterified sodium lignin sulfonate nano-carrier.
Fourthly, the morphological characterization of the nano pesticide prepared by taking the benzoic acid esterified lignosulfonate derivative as the raw material
Taking the difenoconazole nano pesticide preparation obtained in example 10 as a sample, microscopic morphology observation is carried out on the prepared nano pesticide particles by adopting a scanning electron microscope, and the result is shown in fig. 2. As can be seen from the figure, the nano-particle preparation particles of the invention are spherical, have smooth surfaces, have the average particle size of about 100-200nm, and belong to a nano-particle suspending agent preparation.
Fifthly, slow release experiment of nano slow release photolysis-resistant pesticide with lignosulfonate as material
Using the difenoconazole nano-pesticide prepared in example 10 and a commercially available difenoconazole microemulsion (Witamanshi Biochemical Co., Ltd.) as samples, a slow release experiment of the difenoconazole nano-pesticide preparation was carried out by weighing 2mL of the nano-pesticide microemulsion with the same difenoconazole content, placing the nano-pesticide microemulsion into a dialysis bag, and then dialyzing the nano-pesticide microemulsion in 100mL of deionized water containing 1% tween-80 under magnetic stirring at room temperature. At different intervals, 1ml of sample was taken from the 1% tween-80 solution, and the same volume of the 1% tween-80 solution was added to measure the sample concentration by high performance liquid chromatography.
Fig. 3 shows the release behavior of the difenoconazole nanopesticide and the difenoconazole microemulsion in example 10 in an aqueous solution. The micro-emulsion has a fast release speed in the initial stage, and the cumulative release rate of the micro-emulsion reaches 94.6% in 48 hours and reaches 100% in 96 hours. The release rate of the nano pesticide is in a very slow increasing trend, after 120 hours, the cumulative release rate of the nano pesticide is only 34.7 percent and is obviously lower than that of the microemulsion, and the slow release performance of the nano pesticide is proved.
The cumulative release rates after 120h of the nano-pesticides prepared by the method of different nano-carriers according to example 10 are shown in table 1 below:
TABLE 1
Thus, it can be seen that: the active ingredients of the nano photolysis-resistant controlled-release pesticide preparation taking the lignosulfonate and the derivatives thereof as the materials also have certain slow-release performance.
Sixthly, light degradation resistance experiment of nano slow-release photolysis-resistant pesticide with lignosulfonate as material
The light degradation resistance experiment of the difenoconazole nano pesticide preparation: the difenoconazole nano pesticide of example 10 and a commercial difenoconazole microemulsion (weyote biochemical engineering limited) purchased from the market are taken as samples, the nano pesticide and the microemulsion with the same concentration of the difenoconazole are respectively divided into 1mL of solution with the same amount, the solution is placed in a centrifuge tube and irradiated by ultraviolet light with the wavelength of 254nm and the wavelength of 6W. The light source is located at a distance of 10cm from the surface of the suspension. And (3) periodically selecting a test tube for high performance liquid chromatography analysis, and detecting the residual concentration of the difenoconazole.
Fig. 4 shows the light degradation resistance of the difenoconazole nano pesticide preparation and the difenoconazole microemulsion in example 10, and the difenoconazole microemulsion has a degradation rate of 89.9% after 4 hours of ultraviolet irradiation and is almost completely degraded. However, after 4 hours of ultraviolet irradiation, the degradation rate of the difenoconazole nano pesticide is 31.4%, and after 12 hours, the degradation rate is only 58.1%. The results show that the nano pesticide can improve the light stability of the difenoconazole, is beneficial to prolonging the service time of the difenoconazole and improving the utilization efficiency of the difenoconazole, thereby prolonging the pesticide effect period of the bactericide and reducing the spraying frequency.
The nano-pesticide prepared by the method of different nano-carriers according to example 10 has 12h photodegradation rate as shown in the following table 2:
TABLE 2
Seventh, bactericidal activity experiment of nano slow-release photolysis-resistant pesticide with lignosulfonate as material
The nano-scale difenoconazole preparation of example 10 is used as a testTaking difenoconazole technical material, difenoconazole microemulsion and difenoconazole nano preparation with the same concentration as a reference, testing the inhibitory activity of the three reagents on the anthrax, and calculating the EC of the three preparations according to the inhibition rate of hypha growth50Values of 0.404, 0.343 and 0.357. mu.g/mL, respectively. The result shows that the difenoconazole nanometer preparation has bacteriostatic activity, and the bacteriostatic activity of the difenoconazole nanometer preparation is not obviously different from that of the difenoconazole microemulsion sold in the market. The test results are shown in Table 3.
TABLE 3 determination of inhibitory virulence of several difenoconazole formulations on anthrax growth
Description of the drawings: other nano photolysis-resistant controlled-release pesticide preparations taking lignosulfonate and derivatives thereof as materials all have a certain sterilization effect.
Eighthly, the stability of the preparation of the nano slow-release photolysis-resistant pesticide taking lignosulfonate as the material
The nano difenoconazole preparations of examples 8, 9, 10 and 11 are used as samples, a multiple light scattering instrument is used for testing the stability of the preparations, and the influence of the reaction of sodium lignosulfonate and benzoic anhydride in different proportions on the stability of the nano pesticide is detected.
Figure 5 shows different sodium lignosulfonate concentrations at 25 ℃ over 1h for the same difenoconazole concentration: stability analyzer stability index (TSI) of benzoic anhydride reaction ratio of nano-pesticide and microemulsion. Higher TSI values indicate poorer stability of the formulation samples. It can be observed from figure 5 that the sodium lignosulfonate reacted at a lower benzoic anhydride ratio had a poorer stability, and the sample reacted at a higher benzoic anhydride ratio had a stability similar to the microemulsion. Namely, sodium lignin sulfonate: the stability of the samples was similar to that of microemulsions when benzoic anhydride was 1:5 or 1: 7.
The nano pesticide was prepared by using different nano carriers according to the method of example 10, and the nano pesticide obtained in different cases was tested according to the above method, and the results are shown in the following table 4:
TABLE 4
| Nano-carrier | TSI corresponding to 60min |
| Sodium lignosulfonate: benzoic anhydride ═ 1:5 | 0.392 |
| Sodium lignosulfonate: phthalic anhydride ═ 1:5 | 0.702 |
| Sodium lignosulfonate: methacrylic anhydride ═ 1:5 | 0.671 |
| Sodium lignosulfonate: maleic anhydride 1:5 | 0.572 |
| Sodium lignosulfonate: succinic anhydride ═ 1:5 | 0.452 |
| Sodium lignosulfonate: octenyl succinic anhydride ═ 1:5 | 0.406 |
| Difenoconazole microemulsion | 0.735 |
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (9)
1. The preparation method of the modified material of the lignosulfonate is characterized by comprising the following steps:
dissolving lignosulfonate in a solvent, adding triethylamine and aliphatic/aromatic substances, reacting for 24 +/-2 hours under a stirring condition, centrifuging to obtain a supernatant, adding isopropanol into the supernatant to obtain a precipitate, and drying the precipitate in vacuum to obtain a lignosulfonate modified material;
the lignosulfonate is: the weight ratio of the aliphatic/aromatic substances is 1: 2-7;
aliphatic/aromatic: the molar ratio of triethylamine to triethylamine is 1 (1 +/-0.05);
the aliphatic/aromatic is any one of the following: aliphatic/aromatic acid anhydrides, and aliphatic/aromatic acid chlorides.
2. The method for producing a lignosulfonate-modified material according to claim 1, wherein:
the aliphatic/aromatic acid anhydride is any one of the following: benzoic anhydride, methacrylic anhydride, phthalic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, octenyl succinic anhydride;
the aliphatic/aromatic acid chloride is any one of the following: benzoyl chloride, methacryloyl chloride, phthaloyl chloride, phenylacetyl chloride.
3. The method for producing a lignosulfonate-modified material according to claim 2, wherein:
the lignosulfonate is any one of the following: sodium lignosulfonate, calcium lignosulfonate and potassium lignosulfonate.
4. The method for producing a lignosulfonate-modified material according to claim 3, wherein:
the solvent is N, N-dimethylformamide and dimethyl sulfoxide.
5. The method for producing a lignosulfonate-modified material according to any one of claims 1 to 4, wherein: the stirring reaction temperature is 50-70 ℃.
6. The method for producing a lignosulfonate-modified material according to claim 5, wherein: the particle size of the modified material is 1-300 nm.
7. The use of the modified material of lignosulfonate prepared by the method of any one of claims 1 to 6, characterized in that:
the nano pesticide is prepared by taking the modified material of the lignosulfonate as a carrier material and loading the original pesticide.
8. Use according to claim 7, characterized in that the technical pesticide is at least one of the following: difenoconazole, pyraclostrobin, tebuconazole, propiconazole, lambda-cyhalothrin, tricyclazole, buprofezin and prochloraz.
9. Use according to claim 7 or 8, characterized in that: the nano pesticide is applied to prevention and control of crop diseases and insect pests.
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