CN114847281B - Application of high-adhesion plant oil-based polymer in emamectin benzoate preparation production, emamectin benzoate preparation and preparation method of emamectin benzoate preparation - Google Patents
Application of high-adhesion plant oil-based polymer in emamectin benzoate preparation production, emamectin benzoate preparation and preparation method of emamectin benzoate preparation Download PDFInfo
- Publication number
- CN114847281B CN114847281B CN202210704169.XA CN202210704169A CN114847281B CN 114847281 B CN114847281 B CN 114847281B CN 202210704169 A CN202210704169 A CN 202210704169A CN 114847281 B CN114847281 B CN 114847281B
- Authority
- CN
- China
- Prior art keywords
- emamectin benzoate
- preparation
- water
- eco
- ethanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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
- A01N25/24—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 to enhance the sticking of the active ingredients
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Dentistry (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses application of a high-adhesion plant oil-based polymer in the production of an emamectin benzoate preparation, the emamectin benzoate preparation and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of polymer materials, in particular to application of a high-adhesion plant oil-based polymer in production of emamectin benzoate, an emamectin benzoate preparation and a preparation method thereof.
Background
Emamectin benzoate has the characteristics of wide insecticidal spectrum, high efficiency, low toxicity, low residue and the like, is widely concerned by people since the past and becomes a hot point of research of people. At present the first dimension salt medicine is not resistant to washout, in the use, at the in-process of rainfall, can wash from the blade along with the washing away of rainwater, and partly medicine flows into soil, both pollutes the water resource and extravagant medicine.
Vegetable oil is also a biomass resource with abundant content on the earth, the main component of the vegetable oil is ester generated by straight-chain higher fatty acid and glycerol, and the triglyceride in the vegetable oil is chemically modified into a vegetable oil monomer with terminal group double bonds in scientific research, and the vegetable oil monomer is further epoxidized into an epoxy vegetable oil monomer to synthesize an epoxy vegetable oil polymer. For example, chinese patent application publication No. CN113214433A provides a method for preparing a plant oil-based polymer with high adhesion, which can obtain polymers with different adhesion properties by adjusting the ratio of a first epoxy tea oil monomer to a second epoxy tea oil monomer, and after loading fluorescein, the polymer can rapidly respond to ammonia water, and thus the polymer has potential application in detecting the freshness of seafood, but it does not disclose application in other aspects, and even discloses application in production of emamectin benzoate preparations.
Disclosure of Invention
The invention aims to provide a new application of a high-adhesion vegetable oil-based polymer and prepare a scouring-resistant emamectin benzoate preparation.
The invention solves the technical problems through the following technical means:
use of a plant oil-based polymer with high adhesion in the production of a emamectin benzoate formulation, said plant oil-based polymer with high adhesion having the formula:
Has the beneficial effects that: the polymer with high adhesion property obtained by polymerizing the tea oil monomer is used in the production of the emamectin benzoate preparation, the obtained emamectin benzoate medicament has increased rain wash resistance, and the release time of the emamectin benzoate medicament can be prolonged in the using process, so that the insecticidal effect is increased.
The invention also provides a preparation method of the emamectin benzoate preparation, which comprises the following steps: and uniformly mixing the plant oil-based polymer with high adhesion with emamectin benzoate powder to obtain the emamectin benzoate preparation.
Preferably, in the emamectin benzoate preparation, the mass-to-volume ratio of the emamectin benzoate to the plant oil-based polymer with high adhesion is 1-20mg:1mL.
Preferably, the emamectin benzoate-emamectin benzoate compound preparation is obtained by adding ethanol and mixing with water uniformly.
Preferably, the preparation method of the emamectin benzoate preparation comprises the following steps: uniformly mixing the emamectin benzoate powder with a mixed solution of ethanol and water, and then adding the mixture into the vegetable oil-based polymer with high adhesion to be uniformly mixed to obtain the emamectin benzoate preparation.
Preferably, the volume ratio of the total volume of ethanol and water to the volume of the vegetable oil-based polymer with high adhesion is 1:1.
preferably, the volume ratio of ethanol to water is 1:1.
the invention also provides an emamectin benzoate preparation which is prepared by the preparation method of the emamectin benzoate preparation.
The high-adhesion vegetable oil-based polymer is prepared by copolymerizing an epoxy tea oil monomer ECO-NH and an epoxy tea oil monomer ECO; the synthetic route is as follows:
PEG 4k -CTA ECO ECO-NH
wherein x is more than or equal to 0 and less than 100, y is more than or equal to 0 and less than 100, and co in the formula represents copolymerization.
The invention has the advantages that:
the polymer obtained by polymerizing the tea oil monomer has high adhesion performance, the emamectin benzoate drug obtained by directly mixing the polymer with emamectin benzoate has increased rain wash resistance, the release time of the emamectin benzoate drug can be prolonged in the using process, the insecticidal effect is increased, the preparation method of the emamectin benzoate preparation is simple, and the obtained emamectin benzoate preparation is safe and environment-friendly.
Drawings
FIG. 1 is a DLS plot of a polymer prepared in example 2 of the present invention;
FIG. 2 is a DLS plot of a polymer prepared in example 3 of the present invention;
FIG. 3 is a DLS plot of a polymer prepared in example 4 of the present invention;
FIG. 4 is a DLS plot of a polymer prepared in example 5 of the present invention;
FIG. 5 is a DLS plot of a polymer prepared in example 6 of the present invention;
FIG. 6 is a DLS plot of a polymer prepared in example 7 of the present invention;
FIG. 7 is a DLS plot of a polymer prepared in example 8 of the present invention;
FIG. 8 is a TEM image of a polymer prepared in example 2 of the present invention;
FIG. 9 is a TEM image of a polymer prepared in example 3 of the present invention;
FIG. 10 is a TEM image of a polymer prepared in example 4 of the present invention;
FIG. 11 is a TEM image of a polymer prepared in example 5 of the present invention;
FIG. 12 is a TEM image of a polymer prepared in example 6 of the present invention;
FIG. 13 is a TEM image of a polymer prepared in example 7 of the present invention;
FIG. 14 is a TEM image of a polymer prepared in example 8 of the present invention;
FIG. 15 is an SEM image of a blank tobacco lamina;
FIG. 16 is an SEM image of tobacco lamina coated with emamectin benzoate;
FIG. 17 is an SEM image of tobacco lamina coated with the emamectin benzoate formulation prepared in example 5;
FIG. 18 is data of the emamectin benzoate formulations prepared in examples 2-8 of the present invention and simulated rainwash data of emamectin benzoate coated glass slides;
FIG. 19 is a standard curve for emamectin benzoate;
FIG. 20 is a simulated light rain washing data of tobacco lamina coated with emamectin benzoate and the emamectin benzoate formulation prepared in example 11;
FIG. 21 is rainwash data in a simulation of tobacco lamina coated with emamectin benzoate and the emamectin benzoate formulation prepared in example 11;
FIG. 22 is a simulated heavy rain washing data for tobacco lamina coated with emamectin benzoate and the emamectin benzoate formulation prepared in example 11;
FIG. 23 is data of UV exposure resistance of tobacco lamina coated with emamectin benzoate and the emamectin benzoate formulation prepared in example 11 in a simulated UV experiment I;
FIG. 24 is UV exposure data for a simulated UV experiment two in which tobacco lamina were coated with emamectin benzoate and the emamectin benzoate formulation prepared in example 11;
FIG. 25 is data of UV exposure resistance of tobacco lamina coated with emamectin benzoate and the emamectin benzoate formulation prepared in example 11 in a simulated UV experiment III;
fig. 26 is a data graph of the effect of emamectin benzoate and the emamectin benzoate preparation prepared in example 11 on the control of prodenia litura under the rainwash condition.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Those skilled in the art who do not specify any particular technique or condition in the examples can follow the techniques or conditions described in the literature in this field or follow the product specification.
Example 1
The epoxy tea oil monomer ECO-NH and the epoxy tea oil monomer ECO in the invention are respectively a second epoxy tea oil monomer and a first epoxy tea oil monomer disclosed in Chinese patent application with the publication number of CN 113214433A; the preparation method comprises the following steps:
(1) The epoxy tea oil monomer ECO-NH is prepared by the following preparation route:
preparation of tea oil precursor: weighing 100g of tea oil, adding into 250mL round bottom flask, and introducing N into oil bath at 100 deg.C 2 After blowing for 1 hour, reducing the temperature to 60 ℃, adding 33.2g of ethanolamine and 1.5mL of sodium methoxide, and reacting for 4 hours; and then adding 400mL of dichloromethane solution, fully and uniformly mixing, pouring the mixed solution into a separating funnel, adding saturated NaCl solution, washing and repeating for three times, collecting dichloromethane layer solution, adding anhydrous sodium sulfate, drying, filtering to remove the anhydrous sodium sulfate, and removing dichloromethane from the obtained solution through vacuum rotary evaporation to obtain the tea oil precursor.
Preparing a tea oil monomer: weighing 80g of tea oil precursor, 145mL of dichloromethane and 37mL of triethylamine, adding into a three-neck flask, dripping 22mL of acryloyl chloride under the condition of ice-water bath, and reacting for 12h at room temperature; after the reaction is finished, pouring the solution into a separating funnel, adding a saturated NaCl solution for washing for 2 times, and then adding saturated NaHCO 3 Washing the solution for three times, collecting a lower dichloromethane layer, adding anhydrous sodium sulfate, drying, performing suction filtration to remove the anhydrous sodium sulfate, and performing vacuum rotary evaporation on the obtained mixed solution to remove dichloromethane to obtain the tea oil monomer.
Preparing an epoxy tea oil monomer ECO-NH: weighing 30g of tea oil monomer, adding 350mL of dichloromethane solution, and then adding 10.4g of sodium carbonate; adding 18g of m-chloroperoxybenzoic acid into the ice water bath, keeping the ice water bath for 30min, and reacting for 12h at normal temperature; extracting with sodium thiosulfate aqueous solution for three times, and adding saturated NaCl solution and saturated NaHCO solution respectively 3 And washing the solution for 3 times respectively, collecting a lower dichloromethane layer, then removing dichloromethane by vacuum rotary evaporation, and then removing impurities through alkaline alumina to obtain a pure epoxy tea oil monomer ECO-NH.
(2) Preparing an epoxy tea oil monomer ECO, wherein the preparation route is as follows:
preparation of tea oil precursor: pouring 100g of camellia seed oil into a round-bottom flask, introducing nitrogen at 100 ℃ for 1h for protection, then cooling to 60 ℃, adding 33.2g of 2-methylaminoethanol and 1.5mL of sodium methoxide, reacting for 4h, adding 400mL of dichloromethane to dissolve a reaction mixture, pouring the reaction solution into a separating funnel, then adding saturated saline solution, separating to obtain a dichloromethane layer, adding anhydrous magnesium sulfate into the obtained solution, drying to remove water, filtering to remove the anhydrous magnesium sulfate, and removing dichloromethane from the obtained mixed solution through vacuum rotary evaporation to obtain a tea oil precursor;
preparing a tea oil monomer: dissolving 94g of tea oil precursor and 39mL of triethylamine in 120mL of dichloromethane, dropwise adding 22.9mL of acryloyl chloride under the condition of ice-water bath, reacting for 12h at room temperature, transferring the reacted mixed solution to a separating funnel, adding saturated saline solution for washing three times, then washing once with saturated sodium bicarbonate solution, separating to obtain a dichloromethane layer, adding anhydrous magnesium sulfate for drying and removing water, then filtering to remove the anhydrous magnesium sulfate, and removing dichloromethane from the obtained mixed solution through vacuum rotary evaporation to obtain a tea oil monomer;
preparing an epoxy tea oil monomer ECO: dissolving 40g of tea oil monomer in 500mL of dichloromethane, adding 23.3g of m-chloroperoxybenzoic acid under the condition of ice-water bath, adding 12.9g of sodium carbonate, keeping the solution in ice-water bath for 30min, then reacting at room temperature for 12h, transferring the mixed solution obtained by the reaction to a separating funnel, washing with a sodium thiosulfate solution, a saturated sodium bicarbonate solution and a saturated saline solution respectively to obtain a dichloromethane layer, adding anhydrous sodium sulfate for drying, then carrying out vacuum rotary evaporation to remove dichloromethane, and removing impurities through alkaline alumina to obtain the epoxy tea oil monomer ECO.
PEG in the present invention 4k -CTA is a water-soluble RAFT chain transfer agent PEG disclosed in Chinese patent application publication No. CN113214433A 4k -CTA; the structural formula is as follows:
the preparation method comprises the following steps: according to parts by weight, 3 parts of reversible addition fragmentation Chain Transfer Agent (CTA) and 4 parts of polyethylene glycol monomethyl ether (PEG) 4K ) Dissolved in methylene chloride, 3 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbondiyl chloride are addedImine hydrochloride and 0.4 part of 4-dimethylamino pyridine are subjected to reflux reaction at 70 ℃ for 12 hours, and after sedimentation and purification in ether, the polyethylene glycol monomethyl ether-4000-reversible addition fragmentation chain transfer agent (PEG) is prepared 4k -CTA)。PEG 4k The preparation of CTA is prior art; the synthetic process for the CTA comprises the steps of: mixing 15mL of pure water and 10.7mL of butyl mercaptan, adding 8mL of 50% NaOH aqueous solution, adding 5mL of acetone solution, reacting for 30min, adding CS 2 (7.2 mL) was reacted in an ice-water bath for 30min, then 2-bromopropionic acid (9.3 mL) was added, pure water (15 mL) was added and reacted at room temperature for 24h, after the reaction, a hydrochloric acid solution was added until a yellow solid was obtained, then suction filtration was carried out, and then recrystallization was carried out with n-hexane to obtain CTA.
Example 2
1000. Mu.L of the epoxidized tea oil monomer ECO of example 1 was measured and added to an ampoule, and 105.5mg of PEG of example 1 was added 4k CTA, dissolved in 2255. Mu.L ethanol and 1722. Mu.L purified water; azodiisobutyronidazoline hydrochloride VA-044 is prepared into 5mg/mL aqueous solution, 533 mu L of the aqueous solution is added into an ampoule bottle, and the ampoule bottle is sealed. And (3) performing freeze-thaw cycle on the mixed solution for three times, and then filling nitrogen to react for 2 hours at the temperature of 70 ℃ to obtain the pure PECO polymer.
2.5mL of the prepared pure PECO polymer liquid is taken; weighing 70.9mg of emamectin benzoate powder with the mass fraction of 70.5%, and uniformly mixing with 2.5mL of mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 1:1, then adding the mixture into pure PECO polymer liquid and uniformly mixing to obtain the emamectin benzoate preparation.
Example 3
900 μ L of the epoxidized tea oil monomer ECO of example 1 and 99mg of the epoxidized tea oil monomer ECO-NH of example 1 were measured and added to an ampoule, and 105.5mg of PEG of example 1 was added 4k CTA, dissolved in 2250. Mu.L ethanol and 1717. Mu.L purified water; azodiisobutyronidazoline hydrochloride VA-044 is prepared into 5mg/mL aqueous solution, 533 mu L of the aqueous solution is added into an ampoule bottle, and the ampoule bottle is sealed. And (3) carrying out freeze thawing cycle on the mixed solution for three times, and then filling nitrogen to react for 2h at the temperature of 70 ℃ to obtain monomer ECO: ECO-NH molar ratio =9: 1.
2.5mL of the prepared polymer liquid is taken; weighing 70.9mg of emamectin benzoate powder with the mass fraction of 70.5%, and uniformly mixing with 2.5mL of mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 1:1, then adding the mixture into polymer liquid and uniformly mixing to obtain the emamectin benzoate preparation.
Example 4
700. Mu.L of the epoxidized tea oil monomer ECO of example 1 and 296.5mg of the epoxidized tea oil monomer ECO-NH of example 1 were measured and added to an ampoule bottle, and 105.5mg of the PEG of example 1 was added 4k CTA, dissolved in 2235. Mu.L ethanol and 1702. Mu.L pure water; azodiisobutyronidazoline hydrochloride VA-044 is prepared into 5mg/mL aqueous solution, 533 mu L of the aqueous solution is added into an ampoule bottle, and the ampoule bottle is sealed. And (3) performing freeze-thaw cycle on the mixed solution for three times, introducing nitrogen, and reacting for 2 hours at the temperature of 70 ℃ to obtain monomer ECO: ECO-NH molar ratio =7: 3.
Taking 2.5mL of prepared polymer liquid; weighing 70.9mg of emamectin benzoate powder with the mass fraction of 70.5%, and uniformly mixing with 2.5mL of mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 1:1, then adding the mixture into polymer liquid and uniformly mixing to obtain the emamectin benzoate preparation.
Example 5
mu.L of the epoxidized tea oil monomer ECO of example 1 and 494.5mg of the epoxidized tea oil monomer ECO-NH of example 1 were measured out and charged into an ampoule bottle, and 105.5mg of the PEG of example 1 was added 4k CTA, dissolved in 2230. Mu.L ethanol and 1695. Mu.L purified water; azodiisobutyronidazoline hydrochloride VA-044 is prepared into 5mg/mL aqueous solution, 535 mu L of the aqueous solution is added into an ampoule bottle, and the ampoule bottle is sealed. And (3) after the mixed solution is subjected to freeze thawing cycle twice, filling nitrogen to react for 2h at the temperature of 70 ℃ to obtain monomer ECO: ECO-NH molar ratio =5: 5.
Weighing 70.9mg of emamectin benzoate powder with the mass fraction of 70.5%, and uniformly mixing with 2.5mL of mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 1:1, then adding 2.5mL of polymer liquid and mixing uniformly to obtain the emamectin benzoate preparation.
Example 6
300. Mu.L of the epoxidized tea oil monomer ECO of example 1 and 692.5mg of the epoxidized tea oil monomer ECO-NH of example 1 were measured and added to an ampouleBottle, 105.5mg of PEG of example 1 was added 4k CTA, dissolved in 2210. Mu.L of ethanol and 1675. Mu.L of purified water; azodiisobutyronidazoline hydrochloride VA-044 is prepared into 5mg/mL aqueous solution, 535 mu L of the aqueous solution is added into an ampoule bottle, and the ampoule bottle is sealed. And (3) performing four freeze-thaw cycles on the mixed solution, introducing nitrogen, and reacting for 2 hours at the temperature of 70 ℃ to obtain monomer ECO: ECO-NH molar ratio =3: 7.
Weighing 70.9mg of emamectin benzoate powder with the mass fraction of 70.5%, and uniformly mixing with 2.5mL of mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 1:1, then adding 2.5mL of polymer liquid and mixing uniformly to obtain the emamectin benzoate preparation.
Example 7
100 μ L of the epoxidized tea oil monomer ECO of example 1 and 890mg of the epoxidized tea oil monomer ECO-NH of example 1 were measured and added to an ampoule, and 105.5mg of the PEG of example 1 was added 4k CTA, dissolved in 2200. Mu.L ethanol and 1665. Mu.L purified water; azodiisobutyronidazoline hydrochloride VA-044 is prepared into 5mg/mL aqueous solution, 535 mu L of the aqueous solution is added into an ampoule bottle, and the ampoule bottle is sealed. And (3) performing freeze-thaw cycle on the mixed solution for three times, introducing nitrogen, and reacting for 2 hours at the temperature of 70 ℃ to obtain monomer ECO: ECO-NH molar ratio =1: 9.
Weighing 70.9mg of emamectin benzoate powder with the mass fraction of 70.5%, and uniformly mixing with 2.5mL of mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 1:1, then adding 2.5mL of polymer liquid and mixing uniformly to obtain the emamectin benzoate preparation.
Example 8
990mg of the epoxidized tea oil monomer ECO-NH of example 1 was measured and added to an ampoule, and 105.5mg of PEG of example 1 was added 4k CTA, dissolved in 2190. Mu.L ethanol and 1655. Mu.L purified water; azodiisobutyronidazoline hydrochloride VA-044 is prepared into 5mg/mL aqueous solution, 535 mu L of the aqueous solution is added into an ampoule bottle, and the ampoule bottle is sealed. And (3) performing freeze thawing cycle twice on the mixed solution, and introducing nitrogen to react for 2h at the temperature of 70 ℃ to obtain the pure PECO-NH polymer.
Weighing 70.9mg of emamectin benzoate powder with the mass fraction of 70.5%, and uniformly mixing with 2.5mL of mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 1:1, then adding 2.5mL of pure PECO-NH polymer liquid, and uniformly mixing to obtain the emamectin benzoate preparation.
FIGS. 1-7 are DLS plots of polymers prepared in examples 2-8 of the present invention; as can be seen from FIGS. 2 to 8, the particle sizes of the prepared polymers are concentrated on the order of hundreds of nanometers, and the prepared polymers are all in the order of nanometers.
FIGS. 8-14 are TEM images of polymers prepared in examples 2-8 of the present invention, with a scale of 500nm; as can be seen from fig. 8 to 14, the prepared polymers all have spherical morphologies and sizes of several hundred nanometers, further demonstrating that the polymer particles are small and are nano-sized polymers.
Example 9
100 μ L of the epoxidized tea oil monomer ECO of example 1 and 890mg of the epoxidized tea oil monomer ECO-NH of example 1 were measured and added to an ampoule, and 105.5mg of the PEG of example 1 was added 4k CTA, dissolved in 2200. Mu.L ethanol and 1665. Mu.L purified water; azodiisobutyronidazoline hydrochloride VA-044 is prepared into 5mg/mL aqueous solution, 535 mu L of the aqueous solution is added into an ampoule bottle, and the ampoule bottle is sealed. And (3) carrying out freeze thawing cycle on the mixed solution for three times, and then filling nitrogen to react for 2h at the temperature of 70 ℃ to obtain monomer ECO: ECO-NH molar ratio =1: 9.
Weighing 3.55mg of emamectin benzoate powder with the mass fraction of 70.5%, and uniformly mixing with 2.5mL of polymer liquid to obtain the emamectin benzoate preparation.
Example 10
500. Mu.L of the epoxidized tea oil monomer ECO of example 1 and 494.5mg of the epoxidized tea oil monomer ECO-NH of example 1 were measured and added to an ampoule, and 105.5mg of PEG of example 1 was added 4k CTA, dissolved in 2230. Mu.L ethanol and 1695. Mu.L purified water; azodiisobutyronidazoline hydrochloride VA-044 is prepared into 5mg/mL aqueous solution, 535 mu L of the aqueous solution is added into an ampoule bottle, and the ampoule bottle is sealed. And (3) after the mixed solution is subjected to freeze thawing cycle twice, filling nitrogen to react for 2h at the temperature of 70 ℃ to obtain monomer ECO: ECO-NH molar ratio =5: 5.
Weighing 23.63mg of emamectin benzoate powder with the mass fraction of 70.5 percent, and uniformly mixing the emamectin benzoate powder with 2.5mL of polymer liquid to obtain the emamectin benzoate preparation.
Example 11
500. Mu.L of the epoxidized tea oil monomer ECO of example 1 and 494.5mg of the epoxidized tea oil monomer ECO-NH of example 1 were measured and added to an ampoule, and 105.5mg of PEG of example 1 was added 4k CTA, dissolved in 2230. Mu.L ethanol and 1695. Mu.L purified water; azodiisobutyronidazoline hydrochloride VA-044 is prepared into 5mg/mL aqueous solution, 535 mu L of the aqueous solution is added into an ampoule bottle, and the ampoule bottle is sealed. And (3) after the mixed solution is subjected to freeze thawing cycle twice, filling nitrogen to react for 2h at the temperature of 70 ℃ to obtain monomer ECO: ECO-NH molar ratio =5: 5.
70.9mg of emamectin benzoate powder with the mass fraction of 70.5 percent is weighed and evenly mixed with 2.5mL of polymer liquid to obtain the emamectin benzoate preparation.
Performance detection
400uL of the emamectin benzoate preparation prepared in examples 2-8 is coated on a glass plate respectively, after drying, the coated part is washed by 20mL of pure water, the washing liquid is collected, after freeze-drying, 1.5mL of methanol solution is added to each, and the result is detected by HPLC (high performance liquid chromatography), and as shown in FIG. 18, the blank (JWY) is that the pure pesticide is washed by water to the maximum amount, and the washed emamectin benzoate containing polymer is low in content, which indicates that the polymer has a certain effect on the drug to resist rain wash.
Preparing a standard curve sample, weighing 70.5% of emamectin benzoate powder by mass percent, placing the powder into a volumetric flask, and adding ethanol: water =1:1 (volume ratio) to 0.5mg/mL, 0.4mg/mL, 0.3mg/mL, 0.2mg/mL, 0.1mg/mL, 0.05mg/mL, respectively, under the condition of liquid chromatography column C18; the column temperature is 30 ℃; the sample injection amount is 5 mu L; the wavelength is 230nm; the mobile phase is methanol: 0.1wt% phosphoric acid =80:20 (volume ratio), flow rate 1.0mL/min. The results of drawing a standard curve with the peak area of emamectin benzoate as the ordinate and the concentration of the injected sample as the abscissa are shown in FIG. 19, and it can be seen from FIG. 19 that the fitting R is shown 2 =0.9999, which illustrates successful fitting of the standard curve, yielding the standard curve equation.
FIG. 15 is an SEM image of a cleaned tobacco leaf, without any substance applied; FIG. 16 is an SEM image of tobacco leaves coated with emamectin benzoate; FIG. 17 is an SEM image of tobacco lamina coated with the emamectin benzoate formulation of example 5; the form of emamectin benzoate on the leaves can be observed from a microscopic angle, a plurality of irregular crystals can be seen in figure 16, the form of the surface of the tobacco leaf in figure 17 is similar to that of the tobacco leaf in figure 15, and a film with uniformly distributed pesticide is formed after the emamectin benzoate preparation is sprayed.
Simulating rain wash on blade
(1) Emamectin benzoate, the emamectin benzoate preparation prepared in example 11 were separately treated with absolute ethanol: water =1:1 (volume ratio) is diluted to 10mg/mL, two groups of liquid medicines are coated on tobacco leaves by a liquid transfer gun, each piece of tobacco is coated with 20 mu L of liquid medicine, after the liquid medicine is dried, the emamectin benzoate coated leaves and the emamectin benzoate coated leaves are equally divided into two groups, one group is not subjected to rain wash, the other group is subjected to rain wash with 10mm rainfall, each group is repeated for three times, and after the rain is dried, 2 groups of leaves are collected.
(2) Putting tobacco leaf into a centrifuge tube, then putting into liquid nitrogen, standing for 3min, crushing with a crusher, adding 1mL acetonitrile extract, vortex vibrating for 2min, and centrifuging for 2min at 12000r/min (repeating the above steps of adding acetonitrile extract, vortex vibrating, and centrifuging for three times). Collecting the supernatant 3mL, adding 0.1g NaCl, adding 50mg N-propyl ethylenediamine PSA, 50mg C18, 150mg anhydrous MgSO 4 Vortex mixing for 1min, centrifuging for 3min at 12000r/min, collecting supernatant 1mL, passing through 0.2 μm organic membrane, and detecting in a sample bottle by using the chromatographic conditions in the preparation of the standard curve sample. The test results are shown in fig. 20, wherein the original drug is the test result of the emamectin benzoate-coated leaf blade, and the auxiliary agent is the test result of the emamectin benzoate-coated leaf blade; by comparing before and after rainfall, the effect is more obvious, and the loss of the drug containing the auxiliary agent is less.
Simulating rain wash on blade
(1) Emamectin benzoate, the emamectin benzoate formulation of example 11 were separately treated with absolute ethanol: water =1: diluting the mixed solution of 1 (volume ratio) to 10mg/mL, coating two groups of liquid medicines on tobacco leaves by using a liquid transfer gun, coating 20 mu L of tobacco leaves, uniformly dividing the emamectin benzoate-coated leaves and the emamectin benzoate-coated leaves into two groups after the liquid medicines are dried, wherein one group is not subjected to rain wash, the other group is subjected to rain wash with rainfall of 24mm, repeating the steps for three times, and collecting 2 groups of leaves after the rain is dried.
(2) Putting tobacco leaf into a centrifuge tube, then putting into liquid nitrogen, standing for 3min, crushing with a crusher, adding 1mL acetonitrile extract, vortex vibrating for 2min, and centrifuging for 2min at 12000r/min (repeating the above steps of adding acetonitrile, vortex vibrating, and centrifuging for three times). Collecting supernatant 3mL, adding 0.1g NaCl, adding 50mg N-propylethylenediamine PSA, 50mg C18, 150mg anhydrous MgSO 4 Vortex mixing for 1min, centrifuging for 3min at 12000r/min, collecting supernatant 1mL, passing through 0.2 μm organic membrane, collecting sample, placing into an injection bottle, and detecting with the chromatography condition in the preparation of the standard curve sample; the test results are shown in fig. 21, wherein the original drug is the test result of the emamectin benzoate-coated leaf blade, and the auxiliary agent is the test result of the emamectin benzoate-coated leaf blade; the loss of the drug containing the adjuvant is less, as can be seen by comparing before and after rainfall.
Simulating heavy rain scouring on blades
(1) Emamectin benzoate, the emamectin benzoate preparation prepared in example 11 were separately treated with absolute ethanol: water =1:1 (volume ratio) is diluted to 10mg/mL, two groups of liquid medicines are coated on tobacco leaves by a liquid transfer gun, each piece of tobacco is coated with 20 mu L of liquid medicine, after the liquid medicine is dried, the emamectin benzoate coated leaves and the emamectin benzoate coated leaves are equally divided into two groups, one group is not subjected to rain wash, the other group is subjected to rain wash with rainfall of 36mm, each group is repeated for three times, and after the liquid medicine is dried, 2 groups of leaves are collected.
(2) Putting tobacco leaf into a centrifuge tube, then putting into liquid nitrogen, standing for 3min, crushing with a crusher, adding 1mL acetonitrile extract, vortex vibrating for 2min, and centrifuging for 2min at 12000r/min (repeating the above steps of adding acetonitrile, vortex vibrating, and centrifuging for three times). Collecting supernatant 3mL, adding 0.1g NaCl, adding 50mg N-propylethylenediamine PSA, 50mg C18, 150mg anhydrous MgSO 4 Vortex mixing for 1min, centrifuging for 3min at 12000r/min, collecting supernatant 1mL, passing through 0.2 μm organic membrane, collecting sample, placing into an injection bottle, and detecting with the chromatography condition in the preparation of the standard curve sample; the test results are shown in FIG. 22, in which the original drug is coatedTesting results of the emamectin benzoate leaf, wherein the auxiliary agent is a testing result of the emamectin benzoate-coated leaf; by comparing before and after rainfall, the effect is clearly evident, and the loss of the drug containing the adjuvant is less.
(1) Emamectin benzoate, the emamectin benzoate preparation prepared in example 11, was separately extracted with absolute ethanol: water =1:1 (volume ratio) of the mixed solution to 10mg/mL, coating the two groups of liquid medicines on tobacco leaves by using a liquid transfer gun, coating each tobacco leaf with 20 mu L of liquid medicine, and putting the leaves into an ultraviolet crosslinking instrument after the liquid medicines are dried; irradiating with ultraviolet intensity of 254nm for 0h, 5min, 10min, 0.5h, 1h, and 3h, respectively, and collecting leaf after irradiation.
(2) Putting tobacco leaf into a centrifuge tube, then putting into liquid nitrogen, standing for 3min, crushing with a crusher, adding 1mL acetonitrile extract, vortex vibrating for 2min, and centrifuging for 2min at 12000r/min (repeating the above steps of adding acetonitrile, vortex vibrating, and centrifuging for three times). Collecting supernatant 3mL, adding 0.1g NaCl, adding 50mg N-propylethylenediamine PSA, 50mg C18, 150mg anhydrous MgSO 4 Vortex and mix evenly for 1min, centrifuge for 3min at 12000r/min, take 1mL of supernatant fluid and cross 0.2 μm organic membrane, put the sample into the sample bottle for detection. Detecting by adopting the chromatographic condition in the preparation of the standard curve sample; the detection result is shown in fig. 23, wherein the original drug is emamectin benzoate-coated leaves, and the auxiliary agent is emamectin benzoate-coated leaves; it can be seen in FIG. 23 that the difference between the two is not large under 254nm light.
Simulated ultraviolet experiment II
(1) Emamectin benzoate, the emamectin benzoate preparation prepared in example 11, was separately extracted with absolute ethanol: water =1:1 (volume ratio) of the mixed solution to 10mg/mL, coating the two groups of liquid medicines on tobacco leaves by using a liquid transfer gun, coating each tobacco leaf with 20 mu L of liquid medicine, and putting the leaves into an ultraviolet crosslinking instrument after the liquid medicines are dried; irradiating with ultraviolet intensity of 302nm for 0h, 0.5h, 1h, 3h, 5h and 8h, and collecting leaves after irradiation.
(2) Placing tobacco leaf into centrifuge tube, placing into liquid nitrogen, standing for 3min, pulverizing with crusher, adding 1mL acetonitrile extractive solution, adding 0.1g NaCl, vortex vibrating for 2min,12000r/mCentrifuging in for 2min (repeating the above steps of adding acetonitrile, vortex shaking, and centrifuging for three times). Collecting supernatant 3mL, adding 50mg N-propylethylenediamine PSA, 50mg C18, 150mg anhydrous MgSO 4 Vortex and mix evenly for 1min, centrifuge for 3min at 12000r/min, take 1mL of supernatant fluid and cross 0.2 μm organic membrane, put the sample into the sample bottle for detection. Detecting by adopting the chromatographic condition in the preparation of the standard curve sample; the detection result is shown in fig. 24, wherein the original drug represents emamectin benzoate-coated leaves, and the auxiliary agent represents emamectin benzoate-coated leaves; it can be seen in FIG. 24 that the difference between the two is not large under 302nm light.
Simulation ultraviolet experiment III
(1) Emamectin benzoate, the emamectin benzoate preparation prepared in example 11 was dissolved in absolute ethanol: water =1:1 (volume ratio) of the mixed solution to 10mg/mL, coating the two groups of liquid medicines on tobacco leaves by using a liquid transfer gun, coating each tobacco leaf with 20 mu L of liquid medicine, and putting the leaves into an ultraviolet crosslinking instrument after the liquid medicines are dried; the ultraviolet intensity is 365nm, the irradiation is carried out for 0h, 1h, 3h, 5h, 8h, 12h, 24h, 36h and 72h respectively, and leaves are collected after the irradiation is finished.
(2) Putting tobacco leaf into a centrifuge tube, then putting into liquid nitrogen, standing for 3min, crushing with a crusher, adding 1mL acetonitrile extract, vortex vibrating for 2min, and centrifuging for 2min at 12000r/min (repeating the above steps of adding acetonitrile extract, vortex vibrating, and centrifuging for three times). Collecting the supernatant 3mL, adding 0.1g NaCl, adding 50mg N-propyl ethylenediamine PSA, 50mg C18, 150mg anhydrous MgSO 4 Vortex and mix evenly for 1min, centrifuge for 3min at 12000r/min, take 1mL of supernatant fluid and cross 0.2 μm organic membrane, put the sample into the sample bottle for detection. Detecting by adopting the chromatographic condition in the preparation of the standard curve sample; the detection result is shown in fig. 25, wherein the original drug represents emamectin benzoate, and the auxiliary agent represents an emamectin benzoate preparation; in FIG. 25, it can be seen that the difference between the two is not large under 365nm light.
Test for pesticidal Effect
Emamectin benzoate and the emamectin benzoate preparation prepared in example 11 were separately treated with absolute ethanol: water =1:1 (volume ratio) to prepare an emamectin benzoate solution with the concentration of 10mg/mL and an emamectin benzoate preparation solution; then the emamectin benzoate solution and the emamectin benzoate preparation solvent are respectively mixed with absolute ethyl alcohol: water =1:1 (volume ratio) to obtain emamectin benzoate solution and emamectin benzoate preparation solution by 10000 times dilution; spraying the emamectin benzoate solution and the emamectin benzoate preparation solution on tobacco respectively, spraying the diluted solution on every 15 tobacco plants for 20s, then drying, carrying out rainfall simulation on the tobacco plants by 10mm, 24mm and 36mm, collecting tobacco leaves with different treatments after the tobacco plants are dried by rainwater, putting the tobacco leaves into culture dishes, and putting 20-head second-instar prodenia litura into each culture dish. The breeding is carried out in a climatic chamber at the temperature of 25 +/-1 ℃, each treatment is repeated for 3 times, and the living body number and the dead insect number of each treatment are observed 24 hours after rain. The death standard is that the body of the insect is touched by a writing brush, and the insect is judged to be dead if no obvious reaction exists. The results are shown in fig. 26, in which the original drug represents the test result of emamectin benzoate solution, and the auxiliary represents the test result of emamectin benzoate solution (each group of data is repeated three times, and the average value of the three times is taken); as can be seen from FIG. 26, after the rain wash, the insecticidal effect is seen, compared with the original drug, the effect of the auxiliary agent is better, the lethality rate is higher, which shows that the loss of the drug of the auxiliary agent is less in the rain wash process, so that the insecticidal effect is better.
The above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. Use of a vegetable oil-based polymer having high adhesion in the production of emamectin benzoate formulations, said vegetable oil-based polymer having high adhesion of the formula:
2. The preparation method of the emamectin benzoate preparation is characterized by comprising the following steps: uniformly mixing the plant oil-based polymer with high adhesion as claimed in claim 1 with emamectin benzoate powder to obtain the emamectin benzoate preparation.
3. The method for preparing emamectin benzoate formulations according to claim 2, wherein: in the emamectin benzoate preparation, the mass volume ratio of emamectin benzoate to the high-adhesion vegetable oil-based polymer is 1-20mg:1mL.
4. The method for preparing emamectin benzoate formulations according to claim 2 or 3, wherein: and adding ethanol and water, and uniformly mixing to obtain the emamectin benzoate preparation.
5. The method for preparing emamectin benzoate formulations according to claim 4, wherein the step of: the method comprises the following steps: uniformly mixing emamectin benzoate powder with a mixed solution of ethanol and water, and then adding the mixture into a plant oil-based polymer with high adhesion to be uniformly mixed to obtain the emamectin benzoate preparation.
6. The method for preparing emamectin benzoate formulations according to claim 5, wherein: the volume ratio of the total volume of ethanol and water to the volume of the vegetable oil-based polymer with high adhesion is 1:1.
7. the process for the preparation of emamectin benzoate formulations according to claim 5 or 6, wherein: the volume ratio of the ethanol to the water is 1:1.
8. an emamectin benzoate preparation prepared by the method for preparing the emamectin benzoate preparation as claimed in any one of claims 2 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210704169.XA CN114847281B (en) | 2022-06-21 | 2022-06-21 | Application of high-adhesion plant oil-based polymer in emamectin benzoate preparation production, emamectin benzoate preparation and preparation method of emamectin benzoate preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210704169.XA CN114847281B (en) | 2022-06-21 | 2022-06-21 | Application of high-adhesion plant oil-based polymer in emamectin benzoate preparation production, emamectin benzoate preparation and preparation method of emamectin benzoate preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114847281A CN114847281A (en) | 2022-08-05 |
| CN114847281B true CN114847281B (en) | 2022-10-11 |
Family
ID=82626689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210704169.XA Active CN114847281B (en) | 2022-06-21 | 2022-06-21 | Application of high-adhesion plant oil-based polymer in emamectin benzoate preparation production, emamectin benzoate preparation and preparation method of emamectin benzoate preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114847281B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502266A (en) * | 2009-03-27 | 2009-08-12 | 郭正 | Liquid pesticide formulation containing avermectin pesticide and organosilicon surfactant and preparation method thereof |
| CN102754643A (en) * | 2012-08-02 | 2012-10-31 | 北京格林泰姆科技有限公司 | Methylamino abamectin benzoate suspending agent and preparation method thereof |
| CN103355288A (en) * | 2013-07-19 | 2013-10-23 | 江苏省农业科学院 | Anti-photooxidation plant oil spray adjuvant used for insecticidal pesticide preparation and its use method |
| CN106689122A (en) * | 2016-12-12 | 2017-05-24 | 北京广源益农化学有限责任公司 | Spray aid for agricultural aviation plant protection spray or ultra-low-capacity spray and application |
| CN111170966A (en) * | 2020-01-07 | 2020-05-19 | 安徽农业大学 | Epoxy tea oil monomer, monomer-based polymer, pressure-sensitive adhesive and preparation method thereof |
| CN112961273A (en) * | 2021-02-09 | 2021-06-15 | 安徽农业大学 | Epoxy tea oil monomer-based reversible addition-fragmentation chain transfer emulsion polymerization method, polymer prepared by using method and application of polymer |
| CN113214433A (en) * | 2021-05-11 | 2021-08-06 | 安徽农业大学 | Preparation method of high-adhesion vegetable oil-based polymer, product, fluorescein load of high-adhesion vegetable oil-based polymer and ammonia detection application of high-adhesion vegetable oil-based polymer |
-
2022
- 2022-06-21 CN CN202210704169.XA patent/CN114847281B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502266A (en) * | 2009-03-27 | 2009-08-12 | 郭正 | Liquid pesticide formulation containing avermectin pesticide and organosilicon surfactant and preparation method thereof |
| CN102754643A (en) * | 2012-08-02 | 2012-10-31 | 北京格林泰姆科技有限公司 | Methylamino abamectin benzoate suspending agent and preparation method thereof |
| CN103355288A (en) * | 2013-07-19 | 2013-10-23 | 江苏省农业科学院 | Anti-photooxidation plant oil spray adjuvant used for insecticidal pesticide preparation and its use method |
| CN106689122A (en) * | 2016-12-12 | 2017-05-24 | 北京广源益农化学有限责任公司 | Spray aid for agricultural aviation plant protection spray or ultra-low-capacity spray and application |
| CN111170966A (en) * | 2020-01-07 | 2020-05-19 | 安徽农业大学 | Epoxy tea oil monomer, monomer-based polymer, pressure-sensitive adhesive and preparation method thereof |
| CN112961273A (en) * | 2021-02-09 | 2021-06-15 | 安徽农业大学 | Epoxy tea oil monomer-based reversible addition-fragmentation chain transfer emulsion polymerization method, polymer prepared by using method and application of polymer |
| CN113214433A (en) * | 2021-05-11 | 2021-08-06 | 安徽农业大学 | Preparation method of high-adhesion vegetable oil-based polymer, product, fluorescein load of high-adhesion vegetable oil-based polymer and ammonia detection application of high-adhesion vegetable oil-based polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114847281A (en) | 2022-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gao et al. | Physicochemical properties and fungicidal activity of inclusion complexes of fungicide chlorothalonil with β-cyclodextrin and hydroxypropyl-β-cyclodextrin | |
| Piletska et al. | Controlled release of the herbicide simazine from computationally designed molecularly imprinted polymers | |
| CN106362162B (en) | ZnO@PMAA-b-PHPMA CdS quantum dots and its preparation and the application as pharmaceutical carrier | |
| Tang et al. | Electrolyte and pH-sensitive amphiphilic alginate: synthesis, self-assembly and controlled release of acetamiprid | |
| CN102166512B (en) | Ginsenoside Rg1 molecular imprinting material and application thereof | |
| CN114847281B (en) | Application of high-adhesion plant oil-based polymer in emamectin benzoate preparation production, emamectin benzoate preparation and preparation method of emamectin benzoate preparation | |
| CN109287627A (en) | A kind of solid dispersions matrix and its application | |
| CN104855382A (en) | Application of Pedunsaponin A and Pedunsaponin C in preparation of molluscacide | |
| CN114478521A (en) | Quinolizidine alkaloid and preparation method and application thereof | |
| CN107286349B (en) | Polyethylene glycol-polycaprolactone diblock copolymer and preparation method and application thereof | |
| CN102827125B (en) | Preparation method and application of barley allelochemical algal-inhibited optical isomer saccharomyces cerevisiae | |
| CN114031733B (en) | Preparation method of dsRNA (double-stranded ribonucleic acid) polymer nano-carrier, nano-carrier prepared by preparation method and application of nano-carrier | |
| CN1895050A (en) | Kosam seeds plant-resisting virusagent and preparation thereof | |
| CN115299445A (en) | Compound solution for improving induced disease resistance of lentinan to plants, preparation method and method thereof, and method for preventing and controlling viruses in plants in field | |
| CN112772669B (en) | Iprodione and procymidone suspending agent and preparation method thereof | |
| CN107771790A (en) | PH stimuli responsive types inorganic nano-particle/polymer combination drug carrier and its preparation method and application | |
| CN103027999A (en) | Traditional Chinese medicine winter daphne and novel application of extract of winter daphne in preparation of medicines | |
| CN109122681A (en) | A kind of salicylic acid capsule of nano sustained release agent preparation method of anti-tobacco bacteriosis | |
| CN100447129C (en) | Oximated ginger phenol and its synthesis and use | |
| CN103385248B (en) | Cotton defoliating agent as well as preparation method and application thereof | |
| CN113197200A (en) | Preparation method and application of gel drug-loading system with pesticide molecule hymexazol as gelling agent | |
| CN109061007A (en) | A kind of detection method of Pesticide Residue in Soil figured silk fabrics bacterium amine | |
| CN110771606B (en) | Adult longicorn luvifolius attractant and preparation method thereof | |
| CN102939997A (en) | Extraction method and application of flavonoids compounds in camphor trees | |
| KR100965869B1 (en) | Method for Preparation of Dihydrated Crystalline Paclitaxel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |