CN115380899A - Gel type humic acid slow release pesticide and preparation method thereof - Google Patents
Gel type humic acid slow release pesticide and preparation method thereof Download PDFInfo
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- CN115380899A CN115380899A CN202211047667.8A CN202211047667A CN115380899A CN 115380899 A CN115380899 A CN 115380899A CN 202211047667 A CN202211047667 A CN 202211047667A CN 115380899 A CN115380899 A CN 115380899A
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- Prior art keywords
- cyclodextrin
- pesticide
- humic acid
- solution
- preparation
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- 239000000575 pesticide Substances 0.000 title claims abstract description 113
- 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 62
- 239000004021 humic acid Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical class 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 42
- 239000008367 deionised water Substances 0.000 claims abstract description 35
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 35
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 235000015097 nutrients Nutrition 0.000 claims abstract description 17
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940106681 chloroacetic acid Drugs 0.000 claims abstract description 16
- 238000004108 freeze drying Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical group Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 11
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical group ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000003828 vacuum filtration Methods 0.000 claims description 8
- 239000001116 FEMA 4028 Substances 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 6
- 229960004853 betadex Drugs 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 3
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-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)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 HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 3
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 3
- 239000000152 carbamate pesticide Substances 0.000 claims description 3
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-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)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 GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 3
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 244000005700 microbiome Species 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 52
- 239000000499 gel Substances 0.000 description 14
- 239000003814 drug Substances 0.000 description 9
- 238000013268 sustained release Methods 0.000 description 9
- 239000012730 sustained-release form Substances 0.000 description 9
- 230000003213 activating effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 239000007853 buffer solution Substances 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 description 5
- 229960005286 carbaryl Drugs 0.000 description 5
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- VOEYXMAFNDNNED-UHFFFAOYSA-N metolcarb Chemical compound CNC(=O)OC1=CC=CC(C)=C1 VOEYXMAFNDNNED-UHFFFAOYSA-N 0.000 description 5
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 231100000674 Phytotoxicity Toxicity 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 238000013270 controlled release Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 230000000361 pesticidal effect Effects 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229960002477 riboflavin Drugs 0.000 description 2
- 235000019192 riboflavin Nutrition 0.000 description 2
- 239000002151 riboflavin Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- URYLJCBFCXEADB-XISQNVKBSA-N 6-o-toluensulfonyl-β-cyclodextrin Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC[C@@H]1[C@H]([C@H](O)[C@H]2O)O[C@H]([C@H](O)[C@H]3O)O[C@H](CO)[C@H]3O[C@H]([C@H](O)[C@H]3O)O[C@H](CO)[C@H]3O[C@H]([C@H](O)[C@H]3O)O[C@H](CO)[C@H]3O[C@H]([C@H](O)[C@H]3O)O[C@H](CO)[C@H]3O[C@H]([C@H](O)[C@H]3O)O[C@H](CO)[C@H]3O[C@H]([C@H](O)[C@H]3O)O[C@H](CO)[C@H]3O[C@H]2O1 URYLJCBFCXEADB-XISQNVKBSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 239000003090 pesticide formulation Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 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
- A01N25/22—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
- 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
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/22—O-Aryl or S-Aryl esters thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Agronomy & Crop Science (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to the technical field of pesticide application, in particular to a gel type humic acid slow-release pesticide and a preparation method thereof; the preparation method of the slow-release pesticide comprises the following steps: dissolving an initiator and a cross-linking agent in a solvent, and stirring to obtain a solution A; adding humic acid, pesticide and nutrient solution into deionized water, and dispersing to obtain solution B; dissolving modified cyclodextrin in deionized water, adding the solution B, reacting at 60-80 ℃ for 1-2 h, cooling to obtain a prefabricated liquid, dropwise adding the solution A into the prefabricated liquid in an ice bath, reacting for 6-8 h, and freeze-drying to obtain the slow-release pesticide; wherein the modified cyclodextrin is obtained by modifying cyclodextrin with chloroacetic acid. The invention can reduce the possibility of decomposing pesticide by light, air, water and microorganism and reduce the possibility of volatilization loss of the pesticide, thereby leading the pesticide to achieve the effects of safety, durability and high efficiency.
Description
Technical Field
The invention relates to the technical field of pesticide application, in particular to a gel type humic acid slow release pesticide and a preparation method thereof.
Background
Agricultural chemicals are often sprayed to control pests and regulate plant growth. Environmental factors such as light, air, water and microorganisms can accelerate the decomposition of the pesticide, cause the volatilization loss of the pesticide and directly influence the pesticide effect, storage and transportation.
At present, the pesticide effect of the common pesticide is reduced due to the influence of environmental factors in the processes of storage, transportation and use, so that the effects of preventing and treating plant diseases and insect pests and regulating plant growth can be achieved only by repeatedly applying the pesticide during use, the use amount of the pesticide is increased, and the pesticide is low in efficiency and is wasted; and the pesticide has pungent smell and certain toxicity, and the environmental pollution can be further reduced by increasing the use amount.
The development of the pesticide formulation in the world can be summarized into two types and six characters, namely, the water-based formulation and the granulation are realized; six characters of 'safety, convenience and efficiency improvement' are achieved; therefore, it is very necessary to provide a safe and efficient pesticide.
Disclosure of Invention
The invention provides a gel type humic acid slow-release pesticide and a preparation method thereof, aiming at reducing the possibility of decomposing the pesticide by light, air, water and microorganisms and reducing the possibility of volatilization loss of a medicine, so that the pesticide achieves the effects of safety, durability and high efficiency.
In a first aspect, the invention provides a preparation method of a gel-type humic acid sustained-release pesticide, which adopts the following technical scheme:
a preparation method of gel type humic acid slow release pesticide comprises the following steps:
1) Preparation of solution a: dissolving an initiator and a cross-linking agent in a solvent, and stirring for 1h at 5-10 ℃ to obtain a solution A, wherein the mass ratio of the initiator to the cross-linking agent to the solvent is (3-5): 1: (12 to 17);
2) Preparation of solution B: adding humic acid, pesticide and nutrient solution into deionized water, and performing ultrasonic dispersion for 1-2 hours to obtain solution B; the humic acid pesticide is 1-3 parts by mass of humic acid, 2-3 parts by mass of nutrient solution and 10-15 parts by mass of deionized water;
3) Preparing a slow-release pesticide: dissolving modified cyclodextrin in deionized water, adding the solution B, reacting at 60-80 ℃ for 1-2 h, cooling to room temperature to obtain a prefabricated liquid, dropwise adding the solution A into the prefabricated liquid in an ice bath at-10-4 ℃, reacting for 6-8 h, and freeze-drying to obtain the gel-type humic acid slow-release pesticide;
based on 1 part by mass of the modified cyclodextrin, 10-15 parts by mass of deionized water, 5-8 parts by mass of solution B and 0.2-0.3 part by mass of solution A are added;
wherein the modified cyclodextrin is obtained by modifying cyclodextrin with chloroacetic acid.
Further, the modified cyclodextrin is prepared by a method comprising the following steps:
dissolving cyclodextrin in deionized water, stirring for 1-2 h at 50-60 ℃ to obtain base liquid, adding sodium hydroxide into the base liquid, then adding chloroacetic acid, reacting for 4-6 h at 50-60 ℃, cooling to room temperature, and performing vacuum filtration to obtain modified cyclodextrin;
and based on 1 part by mass of cyclodextrin, 20-25 parts by mass of deionized water, 0.1-0.2 part by mass of sodium hydroxide and 1-2 parts by mass of chloroacetic acid.
Further, the cyclodextrin is one of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, an aromatic derivative of cyclodextrin and an aliphatic derivative of cyclodextrin.
Further, the aromatic derivative of the cyclodextrin is beta-cyclodextrin-1, and the aliphatic derivative of the cyclodextrin is beta-cyclodextrin-2; wherein the chemical structure of the beta-cyclodextrin-1 is as follows:
wherein the chemical structure of the beta-cyclodextrin-2 is as follows:
further, the initiator is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
Further, the cross-linking agent is N-hydroxysuccinimide.
Further, the solvent is one of deionized water, acetone, ethanol and isopropanol.
Further, the pesticide is a carbamate pesticide.
Further, in the step of preparing the slow-release pesticide, the freeze-drying time is 24 hours.
In a second aspect, the invention provides a gel-type humic acid slow-release pesticide, which adopts the following technical scheme:
a gel type humic acid sustained release pesticide is prepared by the preparation method.
In conclusion, the invention has the following beneficial effects:
the controlled release technology is to store the original medicine in a high molecular substance, control the medicine to reach the target object to be controlled continuously and stably in a specific time according to the necessary dosage; the dosage form which is composed of the pesticide, the macromolecular compound and other auxiliary agents and can control the slow release of the pesticide is called as the slow release pesticide.
The slow-release pesticide has the advantages that: (1) the decomposition of light, air, water and microorganisms to pesticides in the environment is reduced, the possibility of volatilization and loss of the pesticides is reduced, and the release performance is changed, so that the residual effect period is prolonged, the dosage is reduced, the application interval is enlarged, and the labor and the pesticide are saved; (2) because of the controlled release measure of the slow-release pesticide, the high-toxicity pesticide is low in toxicity, the acute toxicity is reduced, the residue and the pungent smell are reduced, the pollution to the environment and the phytotoxicity to crops are reduced, and the application range of the pesticide is expanded; (3) through the slow release technology treatment, the physical properties of the pesticide are improved, the drift is reduced, the liquid pesticide is solidified, and the convenience of storage, transportation, use and treatment is improved.
The slow-release pesticide is divided into a physical type and a chemical type, and the pesticide and a high molecular compound are physically combined to form the slow-release pesticide; the pesticide and the high molecular compound are combined into the slow-release pesticide through chemical reaction, and the slow-release pesticide is called chemical type slow-release pesticide; the gel type humic acid slow release pesticide is a chemical type slow release pesticide.
The invention relates to a preparation method of gel type humic acid sustained-release pesticide, which takes cyclodextrin as a reaction main body, adopts chloroacetic acid to modify the cyclodextrin, and introduces carboxyl into the cyclodextrin to obtain modified cyclodextrin; and then, the amino in the pesticide reacts with the carboxyl in the modified cyclodextrin to generate an amido bond, and the amido bond is hydrolyzed when the pesticide is used, so that the active ingredients of the pesticide are released, the effect of slowly releasing the pesticide can be achieved, and the problems of drug waste and repeated pesticide application are avoided.
In the gel-type humic acid slow-release pesticide raw material, cyclodextrin has a conical cavity structure with a three-dimensional structure, and the cavity structure can form a host-guest inclusion compound with a small molecular compound through intermolecular interaction of non-covalent bonds, so that the pesticide can stably exist in a system, and the stability of the pesticide is further improved; the cyclodextrin has the characteristics of internal hydrophobicity and external hydrophilicity, can be used as a solubilizer of pesticides, increases the water solubility of insoluble drugs, improves the bioavailability of the drugs, improves the dissolution rate and stability of the pesticides, can reduce the toxic and side effects of the drugs, increases the stability of the drugs, and can weaken the toxicity of organic matters in soil by forming an inclusion compound with the inclusion effect of the pesticides so as to improve the soil.
In addition, in the gel-type humic acid slow-release pesticide raw material, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) is water-soluble carbodiimide, is used as a carboxyl activating reagent in amide synthesis, is also used for activating phosphate groups, crosslinking protein and nucleic acid and preparing immune conjugates, and is used together with N-hydroxysuccinimide (NHS), so that the coupling efficiency can be effectively improved.
In conclusion, the gel-type humic acid slow-release pesticide can effectively reduce the decomposition of light, air, water and microorganisms on the pesticide, reduce the volatilization loss of the pesticide, reduce the toxicity of the high-toxicity pesticide, reduce the residue and the pungent smell, and reduce the pollution of the pesticide to the environment and the phytotoxicity to crops; the gel-type humic acid slow-release pesticide is convenient to store, transport and use.
Detailed Description
The following examples are given to further illustrate the present invention in detail, and specifically are given by the following examples: the following examples, in which specific conditions are not specified, were carried out according to 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.
In the embodiment of the invention, the carbamate pesticide is one of carbaryl, metolcarb and carbofuran.
The gel type humic acid slow release pesticide preparation method of the invention comprises the following reaction processes of the materials:
in the embodiment of the invention, the beta-cyclodextrin-1 is prepared by the following method: according to the mass ratio of 4:1:1:60 putting mono- (6-p-toluenesulfonyl) -beta-cyclodextrin, anthranilic acid, sodium carbonate and N, N-dimethylformamide into a round-bottom flask, heating the flask to 85 ℃ in a water bath, reacting for 12 hours, filtering after the reaction is finished, adding the filtrate into an acetone solution to obtain a white precipitate, filtering and washing.
In the embodiment of the invention, the beta-cyclodextrin-2 is prepared by the following method: dissolving beta-cyclodextrin in a sodium hydroxide solution under continuous stirring in an ice bath, adding a certain amount of chloroacetic acid, heating to 65 ℃ after a period of time, reacting for 6 hours, cooling to room temperature after the reaction is finished, adding hydrochloric acid to adjust the pH to be =7, wherein the mass fraction of the sodium hydroxide solution is 10%, and the mass ratio of the beta-cyclodextrin to the sodium hydroxide solution to the chloroacetic acid is 15:50:1, adding enough anhydrous methanol, quickly stirring, filtering and washing.
Examples
Example 1
A preparation method of gel type humic acid slow release pesticide comprises the following steps:
1) Dissolving 1 part of beta-cyclodextrin in 20 parts of deionized water, placing the mixture in a water bath at 60 ℃ for activation for 2 hours while continuously stirring, adding 0.1 part of sodium hydroxide, slowly adding 1 part of chloroacetic acid, reacting for 4 hours in the water bath at 60 ℃, cooling to room temperature, and performing vacuum filtration to obtain modified cyclodextrin;
2) Dissolving 3 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1 part of N-hydroxysuccinimide in 12 parts of deionized water, and magnetically stirring for 0.8h at the temperature of 5 ℃ to obtain a solution A for later use;
3) Adding 1 part of humic acid, 1 part of carbaryl and 2 parts of nutrient solution into 10 parts of deionized water, and ultrasonically dispersing for 1 hour to uniformly disperse the humic acid, the carbaryl and the nutrient solution to obtain a solution B for later use;
4) Dissolving 1 part of modified cyclodextrin in 10 parts of deionized water, adding 5 parts of solution B, activating in a water bath at 60 ℃ for 1h, cooling to room temperature, placing in an ice bath at-4 ℃, dropwise adding 0.2 part of solution A, reacting for 6h, and freeze-drying for 24h to obtain the gel-type humic acid sustained-release pesticide.
Example 2
A preparation method of gel type humic acid slow release pesticide comprises the following steps:
1) Dissolving 1 part of beta-cyclodextrin in 20 parts of deionized water, placing the mixture in a water bath at 60 ℃ for activation for 2 hours while stirring continuously, adding 0.2 part of sodium hydroxide, slowly adding 2 parts of chloroacetic acid, reacting for 6 hours in the water bath at 60 ℃, cooling to room temperature, and performing vacuum filtration to obtain modified cyclodextrin;
2) Dissolving 5 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1 part of N-hydroxysuccinimide in 15 parts of ethanol, and magnetically stirring for 1.2 hours at the temperature of 5 ℃ to obtain a solution A for later use;
3) Adding 1 part of humic acid, 3 parts of metolcarb and 3 parts of nutrient solution into 15 parts of deionized water, and ultrasonically dispersing for 2 hours to uniformly disperse the humic acid, the metolcarb and the nutrient solution to obtain a solution B for later use;
4) Dissolving 1 part of modified cyclodextrin in 10 parts of deionized water, adding 8 parts of solution B, activating in a water bath at 60 ℃ for 1h, cooling to room temperature, placing in an ice bath at-4 ℃, dropwise adding 0.3 part of solution A, reacting for 6h, and freeze-drying for 24h to obtain the gel-type humic acid slow-release pesticide.
Example 3
A preparation method of gel type humic acid slow release pesticide comprises the following steps:
1) Dissolving 1 part of beta-cyclodextrin-1 in 25 parts of deionized water, placing the mixture in a water bath at 50 ℃ for activation for 1h while stirring, adding 0.1 part of sodium hydroxide, slowly adding 1 part of chloroacetic acid, reacting for 6h in the water bath at 50 ℃, cooling to room temperature, and performing vacuum filtration to obtain modified cyclodextrin;
2) Dissolving 3 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1 part of N-hydroxysuccinimide in 13 parts of acetone, and magnetically stirring for 1h at 10 ℃ to obtain a solution A for later use;
3) Adding 1 part of humic acid, 2 parts of carbofuran and 2 parts of nutrient solution into 15 parts of deionized water, and ultrasonically dispersing for 2 hours to uniformly disperse the humic acid, the carbofuran and the nutrient solution to obtain a solution B for later use;
4) Dissolving 1 part of modified beta-cyclodextrin-1 in 15 parts of deionized water, adding 5 parts of solution B, activating in a water bath at 70 ℃ for 1h, cooling to room temperature, placing in an ice bath at-8 ℃, dropwise adding 0.2 part of solution A, reacting for 8h, and freeze-drying for 24h to obtain the gel-type humic acid sustained-release pesticide.
Example 4
A preparation method of gel type humic acid slow release pesticide comprises the following steps:
1) Dissolving 1 part of beta-cyclodextrin-2 in 23 parts of deionized water, placing the mixture in a water bath at 55 ℃ for activation for 2 hours while stirring continuously, adding 0.2 part of sodium hydroxide, slowly adding 2 parts of chloroacetic acid, reacting for 6 hours in the water bath at 55 ℃, cooling to room temperature, and performing vacuum filtration to obtain modified cyclodextrin;
2) Dissolving 5 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1 part of N-hydroxysuccinimide in 16 parts of solvent, and magnetically stirring for 1h at 7 ℃ to obtain a solution A for later use;
3) Adding 1 part of humic acid, 2 parts of carbaryl and 3 parts of nutrient solution into 13 parts of deionized water, and ultrasonically dispersing for 1 hour to uniformly disperse the humic acid, the carbaryl and the nutrient solution to obtain a solution B for later use;
4) Dissolving 1 part of modified beta-cyclodextrin-1 in 10 parts of deionized water, adding 8 parts of solution B, activating in a water bath at 60 ℃ for 2 hours, cooling to room temperature, placing in an ice bath at-6 ℃, dropwise adding 0.2 part of solution A, reacting for 6 hours, and freeze-drying for 24 hours to obtain the gel-type humic acid sustained-release pesticide.
Example 5
A preparation method of gel type humic acid slow release pesticide comprises the following steps:
1) Dissolving 1 part of alpha-cyclodextrin in 24 parts of deionized water, placing the mixture in a water bath at 50 ℃ for activation for 2 hours, continuously stirring, adding 0.1 part of sodium hydroxide, slowly adding 1 part of chloroacetic acid, reacting for 4 hours in the water bath at 50 ℃, cooling to room temperature, and performing vacuum filtration to obtain modified cyclodextrin;
2) Dissolving 5 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1 part of N-hydroxysuccinimide in 17 parts of isopropanol, and magnetically stirring for 1h at 6 ℃ to obtain a solution A for later use;
3) Adding 1 part of humic acid, 1 part of metolcarb and 2 parts of nutrient solution into 10 parts of deionized water, and ultrasonically dispersing for 1 hour to uniformly disperse the humic acid, the metolcarb and the nutrient solution to obtain a solution B for later use;
4) Dissolving 1 part of modified cyclodextrin in 14 parts of deionized water, adding 6 parts of solution B, activating in a water bath at 70 ℃ for 2h, cooling to room temperature, placing in an ice bath at-4 ℃, dropwise adding 0.3 part of solution A, reacting for 7h, and freeze-drying for 24h to obtain the gel-type humic acid slow-release pesticide.
Example 6
A preparation method of gel type humic acid slow release pesticide comprises the following steps:
1) Dissolving 1 part of gamma-cyclodextrin in 25 parts of deionized water, placing the mixture in a water bath at 60 ℃ for activation for 1 hour, continuously stirring, adding 0.1 part of sodium hydroxide, slowly adding 2 parts of chloroacetic acid, reacting for 5 hours in the water bath at 60 ℃, cooling to room temperature, and performing vacuum filtration to obtain modified cyclodextrin;
2) Dissolving 4 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1 part of N-hydroxysuccinimide in 14 parts of ethanol, and magnetically stirring for 1h at 7 ℃ to obtain a solution A for later use;
3) Adding 1 part of humic acid, 3 parts of carbofuran and 2 parts of nutrient solution into 15 parts of deionized water, and ultrasonically dispersing for 2 hours to uniformly disperse the humic acid, the carbofuran and the nutrient solution to obtain solution B for later use;
4) Dissolving 1 part of modified cyclodextrin in 10 parts of deionized water, adding 7 parts of solution B, activating in a water bath at 80 ℃ for 2h, cooling to room temperature, placing in an ice bath at-10 ℃, dropwise adding 0.3 part of solution A, reacting for 6h, and freeze-drying for 24h to obtain the gel-type humic acid slow-release pesticide.
Performance detection
A method for testing the performance of a sustained-release pesticide of a gel-type humic acid sustained-release pesticide comprises the following steps: the sustained-release pesticide in each example was put into a buffer solution having pH =1.2 and pH =7.4 to obtain a stock solution, and the stock solution was stirred away from light, and 5mL of the solution was sucked at regular intervals to measure absorbance by an ultraviolet spectrophotometer. Then 5mL of buffer solution is added into the stock solution, the concentration of riboflavin in the buffer solution is calculated according to a riboflavin standard curve, and the cumulative drug release rate D (%) is calculated according to the formula (1):
in the formula: c i ，C n The concentrations of the pesticide in the solution at the moment are respectively; v i For each buffer volume removal, 5mL; v is the total volume of the buffer solution, and is 100mL; w is the pesticide content loaded in the hydrogel, mg.
Table 1 ph =1.2 slow release of pesticide
Table 2 ph =7.4 pesticide slow release situation
The data in tables 1 and 2 show that the prepared slow-release pesticide can effectively and slowly release the pesticide in the buffer solution, wherein in the buffer solution with the pH =7.4 in example 5, the slow-release amount of 40h can reach 70.2%.
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 (10)
1. The preparation method of the gel-type humic acid slow-release pesticide is characterized by comprising the following steps:
1) Preparation of solution a: dissolving an initiator and a cross-linking agent in a solvent, and stirring for 0.8-1.2h at 5-10 ℃ to obtain a solution A, wherein the mass ratio of the initiator to the cross-linking agent to the solvent is (3-5): 1: (12 to 17);
2) Preparation of solution B: adding humic acid, pesticide and nutrient solution into deionized water, and performing ultrasonic dispersion for 1-2 hours to obtain solution B; the humic acid pesticide is 1-3 parts by mass of humic acid, 2-3 parts by mass of nutrient solution and 10-15 parts by mass of deionized water;
3) Preparing a slow-release pesticide: dissolving modified cyclodextrin in deionized water, adding the solution B, reacting at 60-80 ℃ for 1-2 h, cooling to room temperature to obtain a prefabricated liquid, dropwise adding the solution A into the prefabricated liquid in an ice bath at-10-4 ℃, reacting for 6-8 h, and freeze-drying to obtain the gel-type humic acid slow-release pesticide;
based on 1 part by mass of the modified cyclodextrin, 10-15 parts by mass of deionized water, 5-8 parts by mass of solution B and 0.2-0.3 part by mass of solution A are added;
wherein the modified cyclodextrin is obtained by modifying cyclodextrin with chloroacetic acid.
2. The preparation method of the gel-type humic acid slow-release pesticide according to claim 1, which is characterized in that: the modified cyclodextrin is prepared by a method comprising the following steps:
dissolving cyclodextrin in deionized water, stirring for 1-2 h at 50-60 ℃ to obtain base liquid, adding sodium hydroxide into the base liquid, then adding chloroacetic acid, reacting for 4-6 h at 50-60 ℃, cooling to room temperature, and performing vacuum filtration to obtain modified cyclodextrin;
and based on 1 part by mass of cyclodextrin, 20-25 parts by mass of deionized water, 0.1-0.2 part by mass of sodium hydroxide and 1-2 parts by mass of chloroacetic acid.
3. The preparation method of the gel-type humic acid slow-release pesticide according to claim 1, which is characterized in that: the cyclodextrin is one of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, aromatic derivatives of cyclodextrin and aliphatic derivatives of cyclodextrin.
4. The preparation method of the gel-type humic acid slow release pesticide as claimed in claim 3, which is characterized in that: the aromatic derivative of the cyclodextrin is beta-cyclodextrin-1, and the aliphatic derivative of the cyclodextrin is beta-cyclodextrin-2; wherein the chemical structure of the beta-cyclodextrin-1 is as follows:
wherein the chemical structure of the beta-cyclodextrin-2 is as follows:
5. the preparation method of the gel-type humic acid slow-release pesticide according to claim 1, which is characterized in that: the initiator is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
6. The preparation method of the gel-type humic acid slow-release pesticide according to claim 1, which is characterized in that: the cross-linking agent is N-hydroxysuccinimide.
7. The preparation method of the gel-type humic acid slow-release pesticide according to claim 1, which is characterized in that: the solvent is one of deionized water, acetone, ethanol and isopropanol.
8. The preparation method of the gel-type humic acid slow-release pesticide according to claim 1, which is characterized in that: the pesticide is carbamate pesticide.
9. The preparation method of the gel-type humic acid slow-release pesticide according to claim 1, which is characterized in that: in the step of preparing the slow-release pesticide, the freeze-drying time is 24 hours.
10. A gel-type humic acid slow-release pesticide is characterized in that: the gel-type humic acid slow-release pesticide is prepared by the preparation method of the gel-type humic acid slow-release pesticide as claimed in any one of claims 1 to 9.
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