CN115245162A - Humic acid type magnetic slow-release pesticide and preparation method thereof - Google Patents
Humic acid type magnetic slow-release pesticide and preparation method thereof Download PDFInfo
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- CN115245162A CN115245162A CN202211051459.5A CN202211051459A CN115245162A CN 115245162 A CN115245162 A CN 115245162A CN 202211051459 A CN202211051459 A CN 202211051459A CN 115245162 A CN115245162 A CN 115245162A
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- release
- slow
- humic acid
- sustained
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- 239000000575 pesticide Substances 0.000 title claims abstract description 62
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000004021 humic acid Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000013268 sustained release Methods 0.000 claims abstract description 41
- 239000012730 sustained-release form Substances 0.000 claims abstract description 41
- 239000000696 magnetic material Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000008367 deionised water Substances 0.000 claims abstract description 30
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 24
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 17
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 16
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 14
- 230000002363 herbicidal effect Effects 0.000 claims abstract description 13
- 235000015097 nutrients Nutrition 0.000 claims abstract description 13
- 238000004108 freeze drying Methods 0.000 claims abstract description 12
- 239000004009 herbicide Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000003637 basic solution Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims description 16
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 13
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 12
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 12
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 12
- 238000003980 solgel method Methods 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910002555 FeNi Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000003337 fertilizer Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910004860 CaZn Inorganic materials 0.000 claims description 2
- 239000001116 FEMA 4028 Substances 0.000 claims description 2
- 229910005347 FeSi Inorganic materials 0.000 claims description 2
- 229910003962 NiZn Inorganic materials 0.000 claims description 2
- 239000002956 ash Substances 0.000 claims description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 2
- 229960004853 betadex Drugs 0.000 claims description 2
- 239000004088 foaming agent Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 238000009333 weeding Methods 0.000 abstract description 4
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 abstract 1
- 235000010378 sodium ascorbate Nutrition 0.000 abstract 1
- 229960005055 sodium ascorbate Drugs 0.000 abstract 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 abstract 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 46
- 241000196324 Embryophyta Species 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000017 hydrogel Substances 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 239000003405 delayed action preparation Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000003094 microcapsule Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 244000237956 Amaranthus retroflexus Species 0.000 description 2
- 235000013479 Amaranthus retroflexus Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 244000304962 green bristle grass Species 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000003020 moisturizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000375 suspending agent Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 235000002248 Setaria viridis Nutrition 0.000 description 1
- 235000010086 Setaria viridis var. viridis Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—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
- A01N25/02—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
- A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P13/00—Herbicides; Algicides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P21/00—Plant growth regulators
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
- C05F11/02—Other organic fertilisers from peat, brown coal, and similar vegetable deposits
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/18—Semi-solid fertilisers, e.g. foams or gels
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
- Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures
Abstract
The invention relates to the technical field of pesticide application, and particularly discloses a humic acid type magnetic slow-release pesticide and a preparation method thereof, wherein the preparation method of the magnetic slow-release pesticide comprises the following steps: dissolving humic acid in deionized water, adding carboxymethyl celluloseStirring sodium ascorbate and polyethyleneimine at 40-50 ℃ to obtain a basic solution; heating the basic solution to 60-70 ℃, adding ethylene glycol and a modified magnetic material, reacting for 1-3h, adding a herbicide and a nutrient solution, continuing to react for 2-3h, adding a pore-forming agent, and performing ultrasonic dispersion to obtain a slow-release gel material; wherein the modified magnetic material is obtained by modifying a magnetic material by cyclodextrin; stirring while adding FeCl 3 Dripping a sustained-release gel material into the solution to obtain sustained-release gel spheres; and washing the sustained-release gel spheres with deionized water, and freeze-drying to obtain the magnetic sustained-release pesticide. The humic acid type magnetic slow-release pesticide has the effects of being recyclable and reusable and good in weeding performance.
Description
Technical Field
The invention relates to the technical field of pesticide application, in particular to a humic acid type magnetic slow-release pesticide and a preparation method thereof.
Background
In order to meet the ever-increasing grain demand, the pesticide is used for improving the yield of grains per unit area, and the method becomes an important solution for meeting the grain demand.
With the proposal of strategies of environmental protection and pesticide application reduction and synergism, sustained-release preparations become hot spots of current research and attention. The sustained-release preparation can slowly release active ingredients, the release behavior is regulated and controlled by environmental factors (light, heat, acid, alkali and the like) and chemical conditions (oxidation reduction, enzymatic reaction and the like), and the sustained-release preparation has the advantages of reducing the application frequency of pesticides, reducing the risk to non-target organisms, improving the lasting period of the pesticides and the like. At present, pesticide microcapsule suspending agents, sustained-release granules and other different sustained-release formulations are registered and applied in the market.
Different from microcapsules and sustained-release granules, hydrogel is a polymer structure system formed by macromolecules containing hydrophilic groups through covalent bonds, hydrogen bonds, van der waals forces and the like. The composite material has a three-dimensional network structure, can absorb a large amount of water, can swell but not dissolve in water, has a porous structure inside, and can bear a high-load compound. The hydrogel has the advantages of water retention, sensitive release, simple synthesis process and the like, and has attracted a great deal of attention as a controllable release carrier in the fields of plant protection, medicine, chemical industry and the like. In the past decades, hydrogels have been widely used in the agricultural field not only to improve the water availability of plants by increasing the water retention properties of the growing medium (soil or soilless substrate), but also to achieve slow release effect and reduce pesticide residue by loading the pesticide active ingredient.
However, the cost of the existing microcapsule suspending agent, sustained-release granules or hydrogel type sustained-release pesticide is obviously improved by directly using the pesticide, and the pesticide cannot be recycled, so that waste is easily caused.
Disclosure of Invention
The invention provides a humic acid type magnetic slow-release pesticide and a preparation method thereof, aiming at realizing the effects of recycling the slow-release pesticide and achieving economy, safety and labor saving.
In a first aspect, the invention provides a preparation method of humic acid type magnetic slow-release pesticide, which adopts the following technical scheme:
a preparation method of humic acid type magnetic slow release pesticide comprises the following steps:
1) Preparing a slow-release gel material by adopting a sol-gel method: dissolving humic acid in deionized water, adding sodium carboxymethylcellulose and polyethyleneimine, and stirring at 40-50 deg.C for 20-30min to obtain basic solution; heating the basic solution to 60-70 ℃, adding ethylene glycol and a modified magnetic material, reacting for 1-3h, adding a herbicide and a nutrient solution, continuing to react for 2-3h, adding a pore-foaming agent, and performing ultrasonic dispersion for 30-45min to obtain a slow-release gel material;
the humic acid modified magnetic fertilizer comprises, by mass, 1 part of humic acid, 25-30 parts of deionized water, 5-8 parts of sodium carboxymethylcellulose, 1-2 parts of polyethyleneimine, 0.3-0.5 part of ethylene glycol, 0.5-1 part of modified magnetic material, 0.1-0.3 part of pore-forming agent, 2-4 parts of herbicide and 2-4 parts of nutrient solution;
wherein the modified magnetic material is obtained by modifying a magnetic material by cyclodextrin;
2) Preparing the slow-release gel spheres: stirring while adding FeCl 3 Dripping the sustained-release gel material into the solution to obtain sustained-release gel spheres;
3) Preparing the magnetic slow-release pesticide: and washing the sustained-release gel spheres with deionized water for 3-5 times, and freeze-drying to obtain the humic acid type magnetic sustained-release pesticide.
Further, the modified magnetic material is prepared by a method comprising the following steps:
adding a magnetic material into deionized water, performing ultrasonic dispersion at 60-70 ℃ for 2-3h, and cooling to 50-60 ℃ to obtain a mixed solution; adding cyclodextrin into the mixed solution, stirring for 2-4 times, cooling to room temperature, and separating to obtain a modified magnetic material;
the mass of the magnetic material is 1 part, the deionized water is 15-20 parts, and the cyclodextrin is 4-7 parts.
Further, the magnetic material is Fe 3 O 4 、FeNi(Mo)、FeSi、M O·Fe 2 O 3 Wherein M is O.Fe 2 O 3 M in the formula is one of NiZn, mnZn, mgZn and CaZn.
Further, the cyclodextrin is beta-cyclodextrin.
Further, the pore-forming agent is one or more of plant ash, potassium carbonate, calcium carbonate, polyethylene glycol and polyvinylpyrrolidone.
Furthermore, in the step of preparing the sustained-release gel ball, the sustained-release gel material is filled in the FeCl facing the inside of the syringe 3 The solution is added dropwise.
Further, in the step of preparing the magnetic slow-release pesticide, the freeze-drying time is 24 hours.
In a second aspect, the invention provides a humic acid type magnetic slow-release pesticide, which adopts the following technical scheme:
a humic acid type magnetic slow-release pesticide is prepared by the preparation method.
In conclusion, the invention has the following beneficial effects:
the invention provides a humic acid type magnetic slow-release pesticide and a preparation method thereof. The slow release pesticide prepared by the invention is a slow release gel ball which utilizes sodium carboxymethylcellulose and Fe 3+ The physical cross-linking effect of the gel balls forms a three-dimensional network structure, the gel balls are provided with a large number of hole structures, the pesticide and the nutrient solution are loaded in the holes for freeze drying, the freeze-dried gel balls are stable in structure and increased in hole, and can be better combined with the pesticide and the nutrient solution, when the gel balls are used, the gel balls absorb water and swell, and the medicine is slowly released from the network structure, so that the medicine is realizedSlow release; and the magnetic material is added in the raw materials, so that the slow-release pesticide has magnetism, and the effect of recycling can be achieved.
Humic acid in the raw materials is a high-efficiency organic potassium fertilizer, is also a bioactive preparation, can improve the content of quick-acting potassium in soil, reduce the loss and fixation of the potassium, increase the absorption and utilization rate of the potassium by crops, and also has the functions of improving the soil, promoting the growth of the crops, improving the stress resistance of the crops, improving the quality of the crops, protecting the agricultural ecological environment and the like; the sodium carboxymethyl cellulose is a derivative generated after cellulose undergoes carboxymethylation reaction, contains a large number of hydroxyl groups and carboxyl groups, can be crosslinked with a plurality of metal ions to form hydrogel, and the gel prepared by taking the carboxymethyl cellulose as a raw material has good hydrophilicity, high swelling rate, good biocompatibility and biodegradability and is widely applied to the field of pesticides; the polyethyleneimine has higher reaction activity, the pH value of a 5% aqueous solution of the polyethyleneimine is 8-11, the polyethyleneimine can be gelatinized in the presence of acid, and can react with hydroxyl in cellulose and perform cross-linking polymerization; the addition of the magnetic material is convenient for automatic monitoring and directional detection during use, and is convenient for recycling after use.
In conclusion, the invention provides the gel type slow-release pesticide which has magnetism, can be recycled and has good weeding performance, the slow-release pesticide is convenient to use, the waste of the pesticide can not be caused, the harm to the human body can not be caused, the frequent repeated pesticide application can be avoided, and the economic, safe and labor-saving effects can be achieved.
Detailed Description
The following examples are given to further illustrate the present invention in detail, and are intended to be given by way of illustration only: the following examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer, and the starting materials used in the following examples are available from ordinary commercial sources unless otherwise specified.
Examples of the invention Fe 3 O 4 Are all nano-scale.
Examples
Example 1
A preparation method of humic acid type magnetic slow-release pesticide comprises the following steps:
1) 1 part of nano Fe 3 O 4 Adding 15 parts of deionized water, performing ultrasonic dispersion at 60 ℃ for 2 hours, then cooling to 50 ℃, adding 4 parts of cyclodextrin, stirring for 2 hours, cooling to room temperature after the reaction is finished, and performing centrifugal separation to obtain a modified magnetic material;
2) Preparing a slow-release gel material by adopting a sol-gel method, adding 25 parts of deionized water into 1 part of humic acid, fully dissolving, adding 5 parts of sodium carboxymethylcellulose and 1 part of polyethyleneimine, stirring in a magnetic stirrer at 40 ℃ for 20min, and fully and uniformly mixing; heating to 60 ℃, adding 0.3 part of ethylene glycol and 0.5 part of modified magnetic material, reacting for 1 hour, adding 2 parts of herbicide and 2 parts of nutrient solution, reacting for 2 hours, adding 0.1 part of plant ash, and performing ultrasonic dispersion for 30 minutes to obtain a slow-release gel material;
3) Slowly dripping the sustained-release gel material into FeCl 3 Dripping while stirring in the solution to obtain slow-release gel balls;
4) And (3) washing the sustained-release gel spheres with deionized water for 3 times, and freeze-drying for 24 hours to obtain the humic acid type magnetic sustained-release pesticide.
Example 2
A preparation method of humic acid type magnetic slow-release pesticide comprises the following steps:
1) 1 part of nano Fe 3 O 4 Adding 20 parts of deionized water, performing ultrasonic dispersion at 70 ℃ for 2 hours, then cooling to 60 ℃, adding 7 parts of cyclodextrin, stirring for 4 hours, cooling to room temperature after the reaction is finished, and performing centrifugal separation to obtain a modified magnetic material;
2) Preparing a slow-release gel material by adopting a sol-gel method, adding 30 parts of deionized water into 1 part of humic acid, fully dissolving, adding 8 parts of sodium carboxymethylcellulose and 2 parts of polyethyleneimine, stirring in a magnetic stirrer at 50 ℃ for 30min, and fully and uniformly mixing; heating to 70 ℃, adding 0.5 part of ethylene glycol and 1 part of modified magnetic material, reacting for 2 hours, adding 4 parts of herbicide and 4 parts of nutrient solution, reacting for 3 hours, adding 0.3 part of plant ash, and performing ultrasonic dispersion for 45 minutes to obtain a slow-release gel material for later use;
3) Slowly dripping the sustained-release gel material into FeCl 3 Dripping while stirring to obtain slow-release gel ball；
4) And (3) washing the sustained-release gel spheres with deionized water for 5 times, and freeze-drying for 24 hours to obtain the humic acid type magnetic sustained-release pesticide.
Example 3
A preparation method of humic acid type magnetic slow-release pesticide comprises the following steps:
1) Adding 1 part of FeNi (Mo) into 17 parts of deionized water, performing ultrasonic dispersion at 60 ℃ for 2 hours, then cooling to 50 ℃, adding 5 parts of cyclodextrin, stirring for 2 hours, cooling to room temperature after the reaction is finished, and performing centrifugal separation to obtain a modified magnetic material;
2) Preparing a slow-release gel material by adopting a sol-gel method, adding 25 parts of deionized water into 1 part of humic acid, fully dissolving, adding 5 parts of sodium carboxymethylcellulose and 1 part of polyethyleneimine, stirring in a magnetic stirrer at 45 ℃ for 25min, and fully and uniformly mixing; heating to 65 ℃, adding 0.3 part of ethylene glycol and 0.7 part of modified magnetic material, reacting for 1 hour, adding 2 parts of herbicide and 2 parts of nutrient solution, reacting for 3 hours, adding 0.3 part of calcium carbonate, and performing ultrasonic dispersion for 30 minutes to obtain a slow-release gel material for later use;
3) Slowly dripping the sustained-release gel material into FeCl 3 Dripping while stirring in the solution to obtain slow-release gel balls;
4) And (3) washing the sustained-release gel spheres with deionized water for 3 times, and freeze-drying for 24 hours to obtain the humic acid type magnetic sustained-release pesticide.
Example 4
A preparation method of humic acid type magnetic slow-release pesticide comprises the following steps:
1) Adding 1 part of FeNi (Mo) into 15 parts of deionized water, performing ultrasonic dispersion at 65 ℃ for 3 hours, then cooling to 50 ℃, adding 7 parts of cyclodextrin, stirring for 3 hours, cooling to room temperature after the reaction is finished, and performing centrifugal separation to obtain a modified magnetic material;
2) Preparing a slow-release gel material by adopting a sol-gel method, adding 30 parts of deionized water into 1 part of humic acid, fully dissolving, adding 8 parts of sodium carboxymethylcellulose and 2 parts of polyethyleneimine, stirring in a magnetic stirrer at 45 ℃ for 30min, and fully and uniformly mixing; heating to 60 ℃, adding 0.5 part of ethylene glycol and 0.6 part of modified magnetic material, reacting for 1 hour, adding 3 parts of herbicide and 4 parts of nutrient solution, reacting for 3 hours, adding 0.2 part of potassium carbonate, and ultrasonically dispersing for 40min to obtain a slow-release gel material for later use;
3) Slowly dripping the sustained-release gel material into FeCl 3 Dripping while stirring in the solution to obtain sustained-release gel spheres;
4) And (3) washing the sustained-release gel spheres with deionized water for 3 times, and freeze-drying for 24 hours to obtain the humic acid type magnetic sustained-release pesticide.
Example 5
A preparation method of humic acid type magnetic slow-release pesticide comprises the following steps:
1) 1 part of NiZnO Fe 2 O 3 Adding 18 parts of deionized water, performing ultrasonic dispersion at 70 ℃ for 2 hours, then cooling to 50 ℃, adding 6 parts of cyclodextrin, stirring for 3 hours, cooling to room temperature after the reaction is finished, and performing centrifugal separation to obtain a modified magnetic material;
2) Preparing a slow-release gel material by adopting a sol-gel method, adding 28 parts of deionized water into 1 part of humic acid, fully dissolving, adding 6 parts of sodium carboxymethylcellulose and 1 part of polyethyleneimine, stirring in a magnetic stirrer at 40 ℃ for 20min, and fully and uniformly mixing; heating to 65 ℃, adding 0.4 part of ethylene glycol and 0.7 part of modified magnetic material, reacting for 1 hour, adding 4 parts of herbicide and 2 parts of nutrient solution, reacting for 3 hours, adding 0.2 part of polyethylene glycol, and performing ultrasonic dispersion for 35 minutes to obtain a slow-release gel material for later use;
3) Slowly dripping the sustained-release gel material into FeCl 3 Dripping while stirring in the solution to obtain sustained-release gel spheres;
4) And (3) washing the sustained-release gel spheres with deionized water for 3 times, and freeze-drying for 24 hours to obtain the humic acid type magnetic sustained-release pesticide.
Example 6
A preparation method of humic acid type magnetic slow-release pesticide comprises the following steps:
1) 1 part of NiZnO Fe 2 O 3 Adding 19 parts of deionized water, performing ultrasonic dispersion at 65 ℃ for 2 hours, then cooling to 50 ℃, adding 7 parts of cyclodextrin, stirring for 4 hours, cooling to room temperature after the reaction is finished, and performing centrifugal separation to obtain a modified magnetic material;
2) Preparing a slow-release gel material by adopting a sol-gel method, adding 26 parts of deionized water into 1 part of humic acid, fully dissolving, adding 7 parts of sodium carboxymethylcellulose and 1 part of polyethyleneimine, stirring in a magnetic stirrer for 30min at 40 ℃, and fully and uniformly mixing; heating to 70 ℃, adding 0.5 part of ethylene glycol and 0.5 part of modified magnetic material, reacting for 3 hours, adding 4 parts of herbicide and 2 parts of nutrient solution, reacting for 2 hours, adding 0.2 part of polyvinylpyrrolidone, and performing ultrasonic dispersion for 40 minutes to obtain a slow-release gel material for later use;
3) Slowly dripping the sustained-release gel material into FeCl 3 Dripping while stirring in the solution to obtain slow-release gel balls;
4) And (3) washing the sustained-release gel spheres with deionized water for 3 times, and freeze-drying for 24 hours to obtain the humic acid type magnetic sustained-release pesticide.
Performance detection
The application test of the humic acid type magnetic slow-release pesticide adopts a small cup method to test the biological activity of a compound, and Amaranthus retroflexus and Setaria viridis are used as test plants:
putting the same-mass examples 1-6 into a buffer solution with the pH =7.4 to obtain a test solution, soaking test plants of the amaranthus retroflexus and the green bristlegrass seeds in clear water for 24 hours, putting the soaked test plants in an incubator at 25 ℃ for accelerating germination until the seeds are exposed to the white, and selecting 10 seeds with the same size and putting the seeds in a small beaker. The sample solution is slowly added into a small beaker, the small beaker is covered with a moisturizing membrane, and holes are randomly pricked on the moisturizing membrane to ensure the air permeability. The small beaker is placed in a light incubator at 24-26 ℃ for culture. After 10d, the root length and stem length of the test plants were determined.
The experiment was provided with a control group having atrazine as a test solution.
TABLE 1 herbicidal Activity of the different examples (inhibition,%)
The data in table 1 show that the slow-release pesticide prepared by the invention has good weeding performance and improves the weeding effect of the original herbicide.
The foregoing is a more detailed description of the invention and it is not intended that the invention be limited to the specific embodiments described herein, but that various modifications, alterations, and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of a humic acid type magnetic slow-release pesticide is characterized by comprising the following steps:
1) Preparing a slow-release gel material by adopting a sol-gel method: dissolving humic acid in deionized water, adding sodium carboxymethylcellulose and polyethyleneimine, and stirring at 40-50 deg.C for 20-30min to obtain basic solution; heating the basic solution to 60-70 ℃, adding ethylene glycol and a modified magnetic material, reacting for 1-3h, adding a herbicide and a nutrient solution, continuing to react for 2-3h, adding a pore-foaming agent, and performing ultrasonic dispersion for 30-45min to obtain a slow-release gel material;
the humic acid fertilizer comprises, by mass, 1 part of humic acid, 25-30 parts of deionized water, 5-8 parts of sodium carboxymethylcellulose, 1-2 parts of polyethyleneimine, 0.3-0.5 part of ethylene glycol, 0.5-1 part of modified magnetic material, 0.1-0.3 part of pore-forming agent, 2-4 parts of herbicide and 2-4 parts of nutrient solution;
wherein the modified magnetic material is obtained by modifying a magnetic material by cyclodextrin;
2) Preparing slow-release gel spheres: stirring while adding FeCl 3 Dripping a sustained-release gel material into the solution to obtain sustained-release gel spheres;
3) Preparing the magnetic slow-release pesticide: and washing the sustained-release gel spheres with deionized water for 3-5 times, and freeze-drying to obtain the humic acid type magnetic sustained-release pesticide.
2. The preparation method of the humic acid type magnetic slow release pesticide according to claim 1, which is characterized in that: the modified magnetic material is prepared by the following method:
adding a magnetic material into deionized water, performing ultrasonic dispersion at 60-70 ℃ for 2-3h, and cooling to 50-60 ℃ to obtain a mixed solution; adding cyclodextrin into the mixed solution, stirring for 2-4 times, cooling to room temperature, and separating to obtain a modified magnetic material;
the mass of the magnetic material is 1 part, the deionized water is 15-20 parts, and the cyclodextrin is 4-7 parts.
3. The preparation method of the humic acid type magnetic slow release pesticide as claimed in claim 1, which is characterized in that: the magnetic material is Fe 3 O 4 、FeNi(Mo)、FeSi、M O·Fe 2 O 3 One or more of them, wherein MO. Fe 2 O 3 M in the formula is one of NiZn, mnZn, mgZn and CaZn.
4. The preparation method of the humic acid type magnetic slow release pesticide according to claim 1, which is characterized in that: the cyclodextrin is beta-cyclodextrin.
5. The preparation method of the humic acid type magnetic slow release pesticide according to claim 1, which is characterized in that: the pore-forming agent is one or more of plant ash, potassium carbonate, calcium carbonate, polyethylene glycol and polyvinylpyrrolidone.
6. The preparation method of the humic acid type magnetic slow release pesticide as claimed in claim 1, which is characterized in that: in the step of preparing the sustained-release gel ball, the sustained-release gel material is arranged in a syringe and faces FeCl 3 The solution was added dropwise.
7. The preparation method of the humic acid type magnetic slow release pesticide as claimed in claim 1, which is characterized in that: in the step of preparing the magnetic slow-release pesticide, the freeze drying time is 24 hours.
8. A humic acid type magnetic slow-release pesticide is characterized in that: prepared by the preparation method of any one of claims 1 to 7.
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