CN116508760A - Spinosad microcapsule powder and preparation method thereof - Google Patents
Spinosad microcapsule powder and preparation method thereof Download PDFInfo
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- CN116508760A CN116508760A CN202310154621.4A CN202310154621A CN116508760A CN 116508760 A CN116508760 A CN 116508760A CN 202310154621 A CN202310154621 A CN 202310154621A CN 116508760 A CN116508760 A CN 116508760A
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- spinosad
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- corn starch
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- microcapsule powder
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- JFLRKDZMHNBDQS-UCQUSYKYSA-N CC[C@H]1CCC[C@@H]([C@H](C(=O)C2=C[C@H]3[C@@H]4C[C@@H](C[C@H]4C(=C[C@H]3[C@@H]2CC(=O)O1)C)O[C@H]5[C@@H]([C@@H]([C@H]([C@@H](O5)C)OC)OC)OC)C)O[C@H]6CC[C@@H]([C@H](O6)C)N(C)C.CC[C@H]1CCC[C@@H]([C@H](C(=O)C2=C[C@H]3[C@@H]4C[C@@H](C[C@H]4C=C[C@H]3C2CC(=O)O1)O[C@H]5[C@@H]([C@@H]([C@H]([C@@H](O5)C)OC)OC)OC)C)O[C@H]6CC[C@@H]([C@H](O6)C)N(C)C Chemical compound CC[C@H]1CCC[C@@H]([C@H](C(=O)C2=C[C@H]3[C@@H]4C[C@@H](C[C@H]4C(=C[C@H]3[C@@H]2CC(=O)O1)C)O[C@H]5[C@@H]([C@@H]([C@H]([C@@H](O5)C)OC)OC)OC)C)O[C@H]6CC[C@@H]([C@H](O6)C)N(C)C.CC[C@H]1CCC[C@@H]([C@H](C(=O)C2=C[C@H]3[C@@H]4C[C@@H](C[C@H]4C=C[C@H]3C2CC(=O)O1)O[C@H]5[C@@H]([C@@H]([C@H]([C@@H](O5)C)OC)OC)OC)C)O[C@H]6CC[C@@H]([C@H](O6)C)N(C)C JFLRKDZMHNBDQS-UCQUSYKYSA-N 0.000 title claims abstract description 120
- 239000005930 Spinosad Substances 0.000 title claims abstract description 120
- 229940014213 spinosad Drugs 0.000 title claims abstract description 120
- 239000003094 microcapsule Substances 0.000 title claims abstract description 54
- 239000000843 powder Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 174
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 105
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229920002261 Corn starch Polymers 0.000 claims abstract description 60
- 239000008120 corn starch Substances 0.000 claims abstract description 60
- 238000003756 stirring Methods 0.000 claims abstract description 60
- 229920002472 Starch Polymers 0.000 claims abstract description 33
- 239000008107 starch Substances 0.000 claims abstract description 33
- 235000019698 starch Nutrition 0.000 claims abstract description 33
- 239000000839 emulsion Substances 0.000 claims abstract description 32
- KHRMRDJZQGQUPK-UHFFFAOYSA-N CCCCCCC=CC(CC(O)=O)(CC(O)=O)C(O)=O Chemical compound CCCCCCC=CC(CC(O)=O)(CC(O)=O)C(O)=O KHRMRDJZQGQUPK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000002148 esters Chemical class 0.000 claims abstract description 24
- 239000000725 suspension Substances 0.000 claims abstract description 16
- 238000001694 spray drying Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 230000003113 alkalizing effect Effects 0.000 claims abstract description 6
- 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 27
- 238000000265 homogenisation Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 9
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229930185156 spinosyn Natural products 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 238000006266 etherification reaction Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 abstract description 7
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 73
- 238000006303 photolysis reaction Methods 0.000 description 18
- 230000015843 photosynthesis, light reaction Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000575 pesticide Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 238000005538 encapsulation Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 240000007124 Brassica oleracea Species 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 3
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 3
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000500437 Plutella xylostella Species 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 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 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000008719 thickening Effects 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/22—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom rings with more than six members
-
- 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
- A01N25/26—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 in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
-
- 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
- A01P7/00—Arthropodicides
- A01P7/04—Insecticides
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- Toxicology (AREA)
- Insects & Arthropods (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention relates to spinosad microcapsule powder and a preparation method thereof, wherein the preparation method comprises the following steps: step 1, weighing the raw materials according to parts by weight, adding spinosad into acetone, and dissolving the spinosad into an acetone solution; step 2, adding corn starch into a methanol solution, heating to 30-40 ℃ while stirring, slowly dripping sodium hydroxide solution until the pH value of a reaction system is 8.5-9.0, then alkalizing for 40-60min, and homogenizing for 15min at 50MP under high pressure to obtain a corn starch suspension; step 3, adding corn starch suspension and carboxymethyl octenyl succinic acid starch ester into spinosad acetone solution, and uniformly stirring to prepare coarse emulsion; step 4, stirring and homogenizing the crude emulsion twice to obtain a final emulsion; step 5, spray drying the final emulsion; the invention improves the stability of spinosad, prolongs the half-life period of spinosad, and is convenient for packaging, transportation and use.
Description
Technical Field
The invention relates to the technical field of biological pesticides, in particular to spinosad microcapsule powder and a preparation method thereof.
Background
The development targets of the experts in the pesticide kingdom are changed to biological varieties, and the biological preparation teams are getting stronger. Spinosad is an excellent variety of biopharmaceuticals, and degradation products of spinosad are finally changed into carbon, hydrogen, oxygen and nitrogen, so that spinosad occupies an irreplaceable position at home and abroad. However, spinosad is easy to decompose in light, is quick to hydrolyze, and has a half-life period of 1 day in water; half-life in soil for 9-10 days; the method is not favorable for packaging, transportation and use operation of spinosad, but also favorable for the efficacy exertion of spinosad, so that the research and development of the spinosad microcapsule powder and the preparation method thereof are particularly important for improving the stability of spinosad.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides spinosad microcapsule powder and a preparation method thereof, which reduce the visible light decomposition rate and hydrolysis speed of spinosad, prolong the half-life period of spinosad and facilitate the packaging, transportation and use operations.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the technical scheme is as follows:
the preparation method of the spinosad microcapsule powder comprises the following raw materials in percentage by weight:
1-7 parts, preferably 2-6 parts, or preferably 3-5 parts or 4.5 parts of spinosad;
13-19 parts of corn starch, preferably 14-18 parts, or preferably 15-17 parts, or 16 parts of game;
75-85 parts of carboxymethyl octenyl succinic acid starch ester.
The preparation method of the spinosad microcapsule powder comprises the following steps:
step (1), mixing spinosad with acetone to obtain spinosad acetone solution;
step (2), corn starch and C 1-4 Lower alcohols or C 1-4 Mixing lower alcohol-water solution, heating to 30-40 deg.C under stirring, slowly dripping sodium hydroxideThe pH of the aqueous solution is 8.5-9.0, then alkalization treatment is carried out at 30-40 ℃, and high-pressure homogenization is carried out to prepare corn starch suspension for standby; preferably, the sodium hydroxide solution is a sodium hydroxide aqueous solution with a mass concentration of 4%.
Step (3), adding corn starch suspension and carboxymethyl octenyl succinic acid starch ester into spinosad acetone solution, and uniformly stirring to prepare coarse emulsion;
step (4), stirring and homogenizing the crude emulsion twice to obtain a final emulsion;
and (5) spray drying the final emulsion to obtain the spinosad microcapsule powder.
Furthermore, the invention provides a preparation method of spinosad microcapsule powder, which is characterized in that the mass ratio of spinosad to acetone in the step (1) is 1:3-7, preferably 1:4-6, and most preferably 1:5.
Furthermore, the invention provides a preparation method of spinosad microcapsule powder, which is characterized in that the lower alcohol in the step (2) is selected from methanol, ethanol, n-propanol, isopropanol or n-butanol, and the C is selected from the following group 1-4 C in lower alcohol-water solution of (C) 1-4 The content of lower alcohol is 80-98% (volume ratio), the corn starch and C 1-4 Lower alcohols or C 1-4 The mass ratio of the lower alcohol-water solution is 1:3-5, preferably 1:4.
Furthermore, the invention provides a preparation method of spinosad microcapsule powder, which is characterized in that the condition of high-pressure homogenization in the step (2) is 40-60Mpa homogenization treatment for 10-30 minutes, preferably 50Mpa homogenization treatment for 15 minutes.
Further, the invention provides a preparation method of spinosad microcapsule powder, which is characterized in that in the stirring and homogenizing cycle treatment process of the step (4), the stirring temperature is 50-64 ℃ (preferably 55-63 ℃), the stirring rotating speed is 150-200 rpm (preferably 160-190 rpm), and the stirring time is 20-40 minutes (preferably 30 minutes).
Furthermore, the invention provides a preparation method of spinosad microcapsule powder, which is characterized in that in the stirring and homogenizing cycle treatment process of the step (4), the high-pressure homogenizing pressure is 50-70Mpa (preferably 56 Mpa), the high-pressure homogenizing rotating speed is 1200-1800 rpm (preferably 1500 rpm), and the high-pressure homogenizing time is 15-25 minutes.
Furthermore, the invention provides a preparation method of spinosad microcapsule powder, which is characterized in that the inlet temperature of spray drying in the step (5) is 180-200 ℃, the outlet temperature is 90-100 ℃, and the feeding rate is 10-15mL/min.
Further, the invention provides a preparation method of spinosad microcapsule powder, which is characterized in that the carboxymethyl octenyl succinic acid starch ester is a commercial product or the preparation method of carboxymethyl octenyl succinic acid starch ester comprises the following steps:
step a, a corn starch methanol solution is calculated by glucose groups, a sodium hydroxide solution is calculated by sodium hydroxide, a methanol solution of octenyl succinic anhydride is calculated by octenyl succinic anhydride, and the corn starch methanol solution, a sodium hydroxide aqueous solution, monochloroacetic acid and octenyl succinic anhydride methanol solution are weighed according to the mol ratio of 1:3.5:1:1 of the glucose groups, the sodium hydroxide, the monochloroacetic acid and the octenyl succinic anhydride;
slowly dropwise adding a sodium hydroxide solution A into a corn starch methanol solution, wherein the dropwise adding amount is 1/3 of the total amount of the sodium hydroxide solution, alkalizing for 50min, adding monochloroacetic acid into a reaction system, then adding the rest sodium hydroxide solution at 55 ℃, and carrying out etherification reaction to generate carboxymethyl starch, so as to obtain carboxymethyl starch reaction solution;
step c, slowly dropwise adding an octenyl succinic anhydride methanol solution into carboxymethyl starch reaction liquid to carry out esterification reaction, then adjusting the pH value of the reaction liquid to 6.0-7.0, washing the reaction liquid by using a methanol solution with the volume concentration of 60 percent until no chloride ions exist, adding absolute methanol into the reaction liquid, carrying out suction filtration, and drying filter residues to obtain carboxymethyl octenyl succinic acid starch ester.
Further, the invention provides a preparation method of spinosad microcapsule powder, which is characterized in that the preparation method of the corn starch methanol solution comprises the following steps: adding corn starch into a methanol solution with the mass concentration of 95% according to the mass ratio of the corn starch to the methanol solution of 1:4, heating to 35 ℃, and stirring for 10min to obtain a corn starch methanol solution;
the preparation method of the methanol solution of octenyl succinic anhydride comprises the following steps: according to the mass ratio of octenyl succinic anhydride to methanol solution of 1:5, adding octenyl succinic anhydride into methanol solution with the mass concentration of 95%, and uniformly stirring to obtain methanol solution of octenyl succinic anhydride.
Furthermore, the invention provides a preparation method of spinosad microcapsule powder, which is characterized in that the sodium hydroxide solution adopts sodium hydroxide aqueous solution with the mass concentration of 4 percent.
Furthermore, the invention provides a preparation method of spinosad microcapsule powder, which is characterized in that in the step b, the drying temperature is 50 ℃.
Furthermore, the invention provides spinosad microcapsule powder prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, corn starch and carboxymethyl octenyl succinic acid starch ester are used as wall materials, and spinosad is wrapped to form a solid microcapsule, so that the visible light decomposition rate and hydrolysis speed of spinosad are reduced, the half-life period of spinosad is prolonged, and the packaging, transportation and use operations are facilitated.
The solid microcapsule formed by the invention is soluble in water, has excellent film forming, dispersing, emulsifying and thickening capabilities, can control the release of spinosad and improves the utilization rate of spinosad.
Detailed Description
The present invention will be described in further detail with reference to examples.
In the present invention,
spinosad stock (97.6% content), purchased from kada biotechnology limited, nine continents, hubei;
corn starch (73.1% glucosyl content), offered by the pharmaceutical company of the northwest Xingbai pharmaceutical industry group;
octenyl succinic anhydride, available from Hubei Xinrun chemical Co., ltd;
sodium monochloroacetate, available from Shijiuzhuang sodium chloroacetate, inc.;
reference example 1: preparation of carboxymethyl octenyl succinic acid starch ester:
the preparation method of carboxymethyl octenyl succinic acid starch ester comprises the following steps:
step a, adding corn starch (with the glucosyl content of 73.1%) into a methanol solution with the mass concentration of 95% according to the mass ratio of the corn starch to the methanol solution of 1:4, heating to 35 ℃ and stirring for 10min to obtain the corn starch methanol solution for later use;
adding octenyl succinic anhydride into a methanol solution with the mass concentration of 95% according to the mass ratio of octenyl succinic anhydride to the methanol solution of 1:5, and uniformly stirring to obtain a methanol solution of octenyl succinic anhydride for later use;
adding sodium hydroxide into deionized water to prepare sodium hydroxide solution with the mass concentration of 4% for standby;
step b, the corn starch methanol solution is calculated by glucose groups, the sodium hydroxide solution is calculated by sodium hydroxide, the methanol solution of octenyl succinic anhydride is calculated by octenyl succinic anhydride, and the corn starch methanol solution, the sodium hydroxide solution, the monochloroacetic acid and the octenyl succinic anhydride methanol solution are weighed according to the mol ratio of 1:3.5:1:1 of the glucose groups, the sodium hydroxide, the monochloroacetic acid and the octenyl succinic anhydride;
slowly dropwise adding a sodium hydroxide solution A into a corn starch methanol solution, wherein the dropwise adding amount is 1/3 of the total amount of the sodium hydroxide solution, alkalizing for 50min, adding monochloroacetic acid into a reaction system, then adding the rest sodium hydroxide solution at 55 ℃, and carrying out etherification reaction to generate carboxymethyl starch, so as to obtain carboxymethyl starch reaction solution;
step d, slowly dropwise adding an octenyl succinic anhydride methanol solution into carboxymethyl starch reaction liquid to carry out esterification reaction, then adjusting the pH value of the reaction liquid to 6.0-7.0, washing the reaction liquid by using a methanol solution with the volume concentration of 60 percent until no chloride ions exist, adding absolute methanol into the reaction liquid, carrying out suction filtration, and drying filter residues at 50 ℃ to obtain carboxymethyl octenyl succinic acid starch ester.
Example 1
The preparation method of the spinosad microcapsule powder comprises the following raw materials in parts by weight:
4.5 parts of spinosad raw medicine, calculated by spinosad;
16 parts of corn starch;
79.5 parts of carboxymethyl octenyl succinic acid starch ester;
a preparation method of spinosad microcapsule powder comprises the following steps:
step 1, weighing the raw materials according to the weight parts, adding spinosad into acetone according to the mass ratio of spinosad to acetone of 1:5, and dissolving the spinosad into a spinosad acetone solution;
step 2, adding corn starch into a methanol solution with the mass concentration of 95% according to the mass ratio of the corn starch to the methanol solution with the mass concentration of 95% of 1:4, slowly dropwise adding a sodium hydroxide solution to a reaction system until the pH value is 8.5 after stirring and heating to 35 ℃, and carrying out alkalization treatment at 35 ℃ for 50min and then homogenizing at 50MP under high pressure for 15min to prepare a corn starch suspension for later use;
step 3, adding corn starch suspension and carboxymethyl octenyl succinic acid starch ester into spinosad acetone solution, and uniformly stirring to prepare coarse emulsion;
step 4, stirring and homogenizing the crude emulsion twice to obtain a final emulsion; in the stirring and homogenizing cycle treatment process, the stirring temperature is 63 ℃, the stirring rotating speed is 180 revolutions per minute, and the stirring time is 30min; the pressure of high-pressure homogenization is 56MPa, the rotating speed of the high-pressure homogenization is 1500r/min, and the time of the high-pressure homogenization is 18min;
step 5, spray drying the final emulsion to obtain spinosad microcapsule powder; the setting parameters of the spray drying are as follows: inlet temperature is 180-200 ℃, outlet temperature is 90-100 ℃, and feeding rate is 12mL/min.
Example 2
The preparation method of the spinosad microcapsule powder comprises the following raw materials in parts by weight:
4.5 parts of spinosad raw medicine, calculated by spinosad;
20 parts of corn starch;
75.5 parts of carboxymethyl octenyl succinic acid starch ester;
a preparation method of spinosad microcapsule powder comprises the following steps:
step 1, weighing the raw materials according to the weight parts, adding spinosad into acetone according to the mass ratio of spinosad to acetone of 1:5, and dissolving the spinosad into a spinosad acetone solution;
step 2, adding corn starch into a methanol solution with the mass concentration of 95% according to the mass ratio of the corn starch to the methanol solution with the mass concentration of 95% of 1:4, slowly dropwise adding a sodium hydroxide solution to the reaction system until the pH value is 9.0 after stirring and heating to 40 ℃, and carrying out alkalization treatment at 40 ℃ for 40min, and homogenizing at 50MP under high pressure for 15min to obtain a corn starch suspension for later use;
step 3, adding corn starch suspension and carboxymethyl octenyl succinic acid starch ester into spinosad acetone solution, and uniformly stirring to prepare coarse emulsion;
step 4, stirring and homogenizing the crude emulsion twice to obtain a final emulsion; in the stirring and homogenizing cycle treatment process, the stirring temperature is 63 ℃, the stirring rotating speed is 180 revolutions per minute, and the stirring time is 30min; the pressure of high-pressure homogenization is 56MPa, the rotating speed of the high-pressure homogenization is 1500r/min, and the time of the high-pressure homogenization is 18min;
step 5, spray drying the final emulsion to obtain spinosad microcapsule powder; the setting parameters of the spray drying are as follows: inlet temperature is 180-200 ℃, outlet temperature is 90-100 ℃, and feeding rate is 12mL/min.
Example 3
The preparation method of the spinosad microcapsule powder comprises the following raw materials in parts by weight:
4.5 parts of spinosad raw medicine, calculated by spinosad;
12 parts of corn starch;
83.5 parts of carboxymethyl octenyl succinic acid starch ester;
a preparation method of spinosad microcapsule powder comprises the following steps:
step 1, weighing the raw materials according to the weight parts, adding spinosad into acetone according to the mass ratio of spinosad to acetone of 1:5, and dissolving the spinosad into a spinosad acetone solution;
step 2, adding corn starch into a methanol solution with the mass concentration of 95% according to the mass ratio of the corn starch to the methanol solution with the mass concentration of 95% of 1:4, slowly dropwise adding a sodium hydroxide solution to the reaction system until the pH value is 8.5 after stirring and heating to 30 ℃, and carrying out alkalization treatment at 30 ℃ for 60min, and homogenizing at 50MP under high pressure for 15min to obtain a corn starch suspension for later use;
step 3, adding corn starch suspension and carboxymethyl octenyl succinic acid starch ester into spinosad acetone solution, and uniformly stirring to prepare coarse emulsion;
step 4, stirring and homogenizing the crude emulsion twice to obtain a final emulsion; in the stirring and homogenizing cycle treatment process, the stirring temperature is 63 ℃, the stirring rotating speed is 180 revolutions per minute, and the stirring time is 30min; the pressure of high-pressure homogenization is 56MPa, the rotating speed of the high-pressure homogenization is 1500r/min, and the time of the high-pressure homogenization is 18min;
step 5, spray drying the final emulsion to obtain spinosad microcapsule powder; the setting parameters of the spray drying are as follows: inlet temperature is 180-200 ℃, outlet temperature is 90-100 ℃, and feeding rate is 12mL/min.
Comparative example 1
The preparation method of the spinosad microcapsule powder comprises the following raw materials in parts by weight:
4.5 parts of spinosad raw medicine, calculated by spinosad;
16 parts of corn starch;
79.5 parts of carboxymethyl octenyl succinic acid starch ester;
a preparation method of spinosad microcapsule powder comprises the following steps:
step 1, weighing the raw materials according to the weight parts, adding spinosad into acetone according to the mass ratio of spinosad to acetone of 1:5, and dissolving the spinosad into a spinosad acetone solution;
step 2, adding corn starch into a methanol solution with the mass concentration of 95% according to the mass ratio of the corn starch to the methanol solution with the mass concentration of 95% of 1:4, heating to 35 ℃ while stirring, performing heat preservation treatment for 50min at 35 ℃, homogenizing for 15min at 50MP under high pressure, and preparing a corn starch suspension for later use;
step 3, adding corn starch suspension and carboxymethyl octenyl succinic acid starch ester into spinosad acetone solution, and uniformly stirring to prepare coarse emulsion;
step 4, stirring and homogenizing the crude emulsion twice to obtain a final emulsion; in the stirring and homogenizing cycle treatment process, the stirring temperature is 63 ℃, the stirring rotating speed is 180 revolutions per minute, and the stirring time is 30min; the pressure of high-pressure homogenization is 56MPa, the rotating speed of the high-pressure homogenization is 1500r/min, and the time of the high-pressure homogenization is 18min;
step 5, spray drying the final emulsion to obtain spinosad microcapsule powder; the setting parameters of the spray drying are as follows: inlet temperature is 180-200 ℃, outlet temperature is 90-100 ℃, and feeding rate is 12mL/min.
Comparative example 2
The preparation method of the spinosad microcapsule powder comprises the following raw materials in parts by weight:
4.5 parts of spinosad raw medicine, calculated by spinosad;
16 parts of corn starch;
79.5 parts of carboxymethyl octenyl succinic acid starch ester;
a preparation method of spinosad microcapsule powder comprises the following steps:
step 1, weighing the raw materials according to the weight parts, adding spinosad into acetone according to the mass ratio of spinosad to acetone of 1:5, and dissolving the spinosad into a spinosad acetone solution;
step 2, adding corn starch into a methanol solution with the mass concentration of 95% according to the mass ratio of the corn starch to the methanol solution with the mass concentration of 95% of 1:4, slowly dropwise adding a sodium hydroxide solution to a reaction system with the pH of 8.5 at the temperature of 15-20 ℃, then alkalizing for 50min at the temperature of 15-20 ℃, and homogenizing for 15min at 50MP high pressure to prepare corn starch suspension for later use;
step 3, adding corn starch suspension and carboxymethyl octenyl succinic acid starch ester into spinosad acetone solution, and uniformly stirring to prepare coarse emulsion;
step 4, stirring and homogenizing the crude emulsion twice to obtain a final emulsion; in the stirring and homogenizing cycle treatment process, the stirring temperature is 63 ℃, the stirring rotating speed is 180 revolutions per minute, and the stirring time is 30min; the pressure of high-pressure homogenization is 56MPa, the rotating speed of the high-pressure homogenization is 1500r/min, and the time of the high-pressure homogenization is 18min;
step 5, spray drying the final emulsion to obtain spinosad microcapsule powder; the setting parameters of the spray drying are as follows: inlet temperature is 180-200 ℃, outlet temperature is 90-100 ℃, and feeding rate is 12mL/min.
Comparative example 3
A commercially available spinosyn water-dispersing agent, wherein the spinosyn water-dispersing agent comprises 4.5% spinosyn.
Effect example 1: performance index test
Detecting the encapsulation efficiency and the dissolution time of the microcapsule powder prepared in each embodiment; the results are shown in Table 1;
and (3) detecting encapsulation rate: accurately weighing spinosad microcapsule powder, adding 12 times of ethyl acetate, adding 5 times of water by volume, fully stirring to dissolve and split phases (unencapsulated spinosad in ethyl acetate phase and encapsulated spinosad in water phase), adding methanol into water phase, performing ultrasonic treatment in an ultrasonic cleaner for 10 minutes to promote spinosad to dissolve out, then sucking 300 mu L of sample liquid by using a syringe, and filtering and detecting by using a 0.22 mu m microporous membrane; and (3) calculating the drug concentration C by comparing with a spinosad solution standard curve, and calculating the encapsulation efficiency according to a formula, wherein the formula is as follows:
encapsulation efficiency% = [ (cxv)/m ] ×100%;
in the formula, V is the volume mL of a solution for measuring the water phase, c is the content mg/mL of spinosad detected by the high-efficiency liquid phase, and m is the total mass mg of spinosad microcapsule powder. The extraction measurement was repeated three times to obtain an average value and an error value.
And (3) dissolution time detection: at room temperature, 3g of spinosad microcapsule powder was added to a beaker containing 50mL of distilled water and the time required for complete dissolution was counted.
TABLE 1
| Encapsulation efficiency% | Dissolution time min | |
| Example 1 | 94.2 | 4.2 |
| Example 2 | 94.0 | 4.4 |
| Example 3 | 92.3 | 5.2 |
| Comparative example 1 | 75.4 | 3.1 |
| Comparative example 2 | 73.1 | 3.6 |
Effect example 2: stability and half-life in Water test
The formulations of each example and comparative example 1 were subjected to measurement of soil surface photodecomposition grade and photodecomposition grade in water, respectively, and the results are shown in table 2.
Determination of soil surface photolysis grade and in-water photolysis grade: according to GB/T31270.3-2014 chemical pesticide environmental safety evaluation test rule part 3.
TABLE 2
| Grade of soil surface photolysis | In-water photolysis grade | |
| Example 1 | V level (difficult photolysis) | IV level (difficult photolysis) |
| Example 2 | V level (difficult photolysis) | V level (difficult photolysis) |
| Example 3 | V level (difficult photolysis) | V level (difficult photolysis) |
| Comparative example 1 | IV level (harder photolysis) | IV level (harder photolysis) |
| Comparative example 2 | IV level (harder photolysis) | IV level (harder photolysis) |
| Comparative example 3 | IV level (harder photolysis) | IV level (harder photolysis) |
Effect example 3: field test
Selecting 1 mu of land in cabbage test fields of Hebei Xingbai pharmaceutical industry group Co., ltd, dividing the land into 2 groups for test, and applying the pesticide in the cabbage fruiting period and the low-age larva peak period of the field plutella xylostella for preventing and controlling the plutella xylostella; when the pesticide is applied, the vika electric sprayer 10L is sprayed, so that the pesticide is ensured to be uniformly applied, the front and back sides of leaves are sprayed, the number of larvae of the whole plant at each age is investigated at fixed points before the pesticide is applied, the number of residual insects is investigated on the 1 st day, the 3 rd day and the 7 th day respectively after the pesticide is applied, the rate of reduction of insect pests is calculated, the existence of phytotoxicity and the influence on natural enemies of crops are observed, and the growth vigor, leaf color change and the like of cabbages of each group of the 3d and 7d pesticide after the pesticide is observed.
Five-point sampling method is adopted when the number of larvae of all ages is investigated, 30 cabbage plants are investigated at each point, and the average value of each point is calculated and used as the number of insect population.
Grouping condition:
test group: spraying the spinosad microcapsule powder prepared in the example 1, wherein the dosage is 25 g/mu, and spraying and adding 30 kg/mu of water;
control group: the spinosad water dispersion prepared in the comparative example 1 is sprayed, the dosage is 25 g/mu, and the spray is added with 30 kg/mu of water;
TABLE 3 Table 3
The above described embodiments are only preferred examples of the invention and are not exhaustive of the possible implementations of the invention. Any obvious modifications thereof, which would be apparent to those skilled in the art without departing from the principles and spirit of the present invention, should be considered to be included within the scope of the appended claims.
Claims (10)
1. The preparation method of the spinosad microcapsule powder is characterized in that the spinosad microcapsule powder comprises the following raw materials in percentage by weight:
1-7 parts of spinosad;
13-19 parts of corn starch;
75-85 parts of carboxymethyl octenyl succinic acid starch ester;
the preparation method comprises the following steps:
step (1), mixing spinosad with acetone to obtain spinosad acetone solution;
step (2), corn starch and C 1-4 Lower alcohols or C 1-4 Mixing lower alcohol-water solution, heating to 30-40 ℃ while stirring, slowly dripping sodium hydroxide water solution until the pH value of a reaction system is 8.5-9.0, then alkalizing at 30-40 ℃, and homogenizing under high pressure to obtain corn starch suspension for later use;
step (3), adding corn starch suspension and carboxymethyl octenyl succinic acid starch ester into spinosad acetone solution, and uniformly stirring to prepare coarse emulsion;
step (4), stirring and homogenizing the crude emulsion twice to obtain a final emulsion;
and (5) spray drying the final emulsion to obtain the spinosad microcapsule powder.
2. The method for preparing spinosad microcapsule powder according to claim 1, wherein the mass ratio of spinosad to acetone in the step (1) is 1:3-7.
3. The method for preparing spinosad microcapsule powder according to claim 1, wherein C in step (2) 1-4 Lower alcohols of (C) are selected from methanol, ethanol, n-propanol, isopropanol or n-butanol 1-4 C in lower alcohol-water solution of (C) 1-4 The content of lower alcohol is 80-98% (volume ratio), the corn starch and C 1-4 Lower alcohols or C 1-4 The mass ratio of the lower alcohol-water solution is 1:3-5;
the conditions of high pressure homogenization in the step (2) are 40-60Mpa homogenization for 10-30 minutes, preferably 50Mpa homogenization for 15 minutes.
4. The method for preparing spinosad microcapsule powder according to claim 1, wherein in the stirring and homogenizing cycle treatment process of the step (4), the stirring temperature is 50-64 ℃, the stirring rotation speed is 150-200 rpm, and the stirring time is 20-40min;
in the stirring and homogenizing cycle treatment process of the step (4), the pressure of high-pressure homogenization is 50-70Mpa, the rotating speed of the high-pressure homogenization is 1200-1800r/min, and the time of the high-pressure homogenization is 15-25min.
5. The method for preparing spinosad microcapsule powder according to claim 1, wherein the spray-drying in the step (5) has an inlet temperature of 180-200 ℃, an outlet temperature of 90-100 ℃ and a feeding rate of 10-15mL/min.
6. The method for preparing spinosyn microcapsule powder according to claim 1, characterized in that the method for preparing carboxymethyl octenyl succinic acid starch ester comprises the following steps:
step a, a corn starch methanol solution is calculated by glucose groups, a sodium hydroxide solution is calculated by sodium hydroxide, a methanol solution of octenyl succinic anhydride is calculated by octenyl succinic anhydride, and the corn starch methanol solution, the sodium hydroxide solution, monochloroacetic acid and octenyl succinic anhydride methanol solution are weighed according to the mol ratio of 1:3.5:1:1 of the glucose groups, the sodium hydroxide, the monochloroacetic acid and the octenyl succinic anhydride;
slowly dropwise adding a sodium hydroxide solution A into a corn starch methanol solution, wherein the dropwise adding amount is 1/3 of the total amount of the sodium hydroxide solution, alkalizing for 50min, adding monochloroacetic acid into a reaction system, then adding the rest sodium hydroxide solution at 55 ℃, and carrying out etherification reaction to generate carboxymethyl starch, so as to obtain carboxymethyl starch reaction solution;
step c, slowly dropwise adding an octenyl succinic anhydride methanol solution into carboxymethyl starch reaction liquid to carry out esterification reaction, then adjusting the pH value of the reaction liquid to 6.0-7.0, washing the reaction liquid by using a methanol solution with the volume concentration of 60 percent until no chloride ions exist, adding absolute methanol into the reaction liquid, carrying out suction filtration, and drying filter residues to obtain carboxymethyl octenyl succinic acid starch ester.
7. The method for preparing spinosad microcapsule powder in accordance with claim 6, wherein,
the preparation method of the corn starch methanol solution comprises the following steps: adding corn starch into a methanol solution with the mass concentration of 95% according to the mass ratio of the corn starch to the methanol solution of 1:4, heating to 35 ℃, and stirring for 10min to obtain a corn starch methanol solution;
the preparation method of the methanol solution of octenyl succinic anhydride comprises the following steps: according to the mass ratio of octenyl succinic anhydride to methanol solution of 1:5, adding octenyl succinic anhydride into methanol solution with the mass concentration of 95%, and uniformly stirring to obtain methanol solution of octenyl succinic anhydride.
8. The method for preparing spinosad microcapsule powder according to claim 6, wherein the sodium hydroxide solution is a sodium hydroxide solution with a mass concentration of 4%.
9. The method for preparing spinosad microcapsule powder of claim 6, wherein in step b, the drying temperature is 50 ℃.
10. A spinosyn microcapsule powder prepared according to the method of any of claims 1-9.
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