High-stability abamectin composition and preparation
Technical Field
The invention relates to the technical field of abamectin pesticides, relates to the technical field of A01N25/12IPC, and particularly relates to a high-stability abamectin composition and a preparation thereof.
Background
The abamectin is a hexadecimal macrolide compound, has strong capabilities of contact poisoning, stomach toxicity, penetration and the like, and has very good effect on the inhibition and killing of pests, mites and the like. Although the abamectin can be used for preventing and controlling pests to a certain extent, and a large amount of pest loss is recovered, the chemical agents not only pollute the environment, but also cause pest resistance and can not eradicate the pest crisis for a long time. In response to these problems, there is a need to combine chemical and physical pesticidal mechanisms to produce pharmaceutical dosage forms that include both chemical pesticidal and physical inhibition.
For example, chinese patent CN201811594784 discloses an insecticide composition for controlling nematode and mite pests, wherein an appropriate amount of abamectin and the balance of diatomaceous earth are compounded to obtain an insecticide composition, and the insecticide composition is mixed with other adjuvants to prepare a wettable powder, and excellent pest control effects are achieved by utilizing physical adsorption of diatomaceous earth and stomach toxicity contact killing of abamectin. However, the formulation of these dosage forms often produces a large amount of dust during manufacture and use. Further, since the particle diameter of the fine particles in these dosage forms such as wettable powder is large, the specific surface area of the fine particles is small, and the effect thereof is yet to be further improved. In addition, in the process of researching the pesticide preparation of abamectin and diatomite, the applicant finds that the dispersibility between the physical pesticide such as diatomite and the abamectin component is poor, and the insecticidal complementarity between the physical pesticide and the abamectin component is not obvious enough. Moreover, in the process of spraying the medicine, especially when the modern wet spraying type medicine application such as an unmanned aerial vehicle is adopted, the higher dilution multiple is found to be needed, otherwise, the blockage of a sprayer nozzle is easily caused, and the medicine spraying amount and the spraying efficiency are influenced. However, the diatom earth physical insecticide component absorbs the body fluid of pests by utilizing the loose structure of the diatom earth physical insecticide component to play a role, the sprayed diluent is required to be volatilized to take effect, and the quick-acting performance of the diatom earth physical insecticide component is further reduced by the high dilution factor.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides a high-stability abamectin composition, which comprises 0.1-10 wt% of abamectin, 1-10 wt% of a carrier, 0.2-10 wt% of an auxiliary agent and the balance of diatomite; the carrier is selected from one or more of talcum powder, modified organic bentonite, white carbon black, kaolin and montmorillonite.
The abamectin can be prepared from conventional technical products on the market, and the specific source of the abamectin is not specially limited. The diatomite is a product obtained by performing specific crushing treatment on the siliceous sedimentary rock, and the diatomite which is subjected to specific thermal drying treatment and has a fluffy internal structure and a large specific surface area is preferably used in the application, for example, the France Yirui stone Celite610 and the like can be used.
As a preferred technical solution of the present invention, the modified organic bentonite is selected from at least one of hexadecyl trimethyl ammonium salt modified bentonite, ceftazidime modified bentonite, octadecyl trimethyl ammonium salt modified bentonite and octadecyl amine modified bentonite; further, the modified organic bentonite is a mixture of ceftazidime modified bentonite and octadecyl amine modified bentonite; further, the mass of the ceftazidime modified bentonite is at least 1.5 times of that of the octadecyl amine modified bentonite.
Further, the carrier is a mixture of white carbon black and the modified organic bentonite; further, the content of the modified organic bentonite accounts for at least 20-35 wt% of the mass of the carrier. In a preferred embodiment of the present invention, the particle size of the carrier is 80 to 500nm. More preferably, the particle size of the carrier is 150 to 300nm.
The applicant has found that when the composition is prepared into wettable powder, the flowability of the medicament after grinding treatment is not high enough, and the combination property is not good when the composition is further prepared into dosage forms such as effervescent granules and the like. And the prepared wettable powder has large specific surface area and is easy to absorb moisture, and the absorbed moisture leads the diatomite with a large number of microporous structures to absorb moisture in advance, so that the surface of the diatomite becomes sticky, the agglomeration among particles is caused, and the particle size of the particles is increased even if the diatomite is diluted by water during use, thereby causing the spraying effect. In the process of completing the present invention, the applicant finds that the above problems can be significantly improved by performing corresponding optimization and improvement on the carrier used in the composition, and particularly, when a mixture of white carbon black with a specific particle size and the modified organic bentonite is used as the carrier, the flowability of the powder is significantly improved, so that the pest killing effect of the composition is further improved, and the dosage of the drug is reduced.
As a preferable technical scheme of the invention, the auxiliary agent comprises at least one of a dispersant, a wetting agent and a synergist; the synergist comprises vegetable oil.
The specific type of the dispersant in the invention is not particularly limited, and various nonionic surfactants, anionic surfactants and other components well known to those skilled in the art can be selected; further, the anionic surfactant may be a polycarboxylate type anionic surfactant or the like. The specific type of the wetting agent in the present invention is not particularly limited, and various components well known to those skilled in the art may be selected, including but not limited to fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkyl phosphate, polyoxyethylene alkylaryl ether, and the like.
The synergist disclosed by the invention is a component which is beneficial to improving the pest control efficiency of the abamectin composition, and the synergist disclosed by the invention comprises vegetable oil, and further the vegetable oil can be epoxidized soybean oil, corn oil and the like; further, the vegetable oil is epoxidized soybean oil; further, the content of the epoxidized soybean oil in the abamectin composition is 0.1-1.5 wt%.
A second aspect of the invention provides an avermectin formulation comprising a high stability avermectin composition as described above, further adjuvants; the content of the abamectin in the preparation is 0.1-8 wt%.
The other auxiliary agents in the invention can be adhesive, effervescent disintegrating agent, diluent, tackifier, adsorbent and the like, and corresponding other auxiliary agent components can be selected for use according to different actual dosage forms.
As a preferable technical scheme, the preparation formulation comprises wettable powder, water dispersible granules and effervescent granules.
The wettable powder is prepared by blending the abamectin with the components such as a carrier, an auxiliary agent and the like, then carrying out high-speed universal grinding so that the abamectin and the carrier can be uniformly mixed with each other, and then adding the diatomite component for mixing; further, the wettable powder is prepared by drying a carrier component at 95 ℃ for 1-2 hours, mixing the carrier component with abamectin, then placing the mixed mixture in a high-pressure mixing kettle, adjusting the pressure of the mixing kettle to 4.8-8.0 MPa, adding a penetrant, carrying out pressure maintaining treatment at 40-50 ℃ for 45-60 min, then releasing the pressure, recovering the penetrant, then taking out the mixture, drying at 60 ℃ for 30min, mixing the mixture with a wetting agent, a dispersing agent and other components, carrying out high-speed universal grinding until the fineness is about 400 meshes, and stirring and mixing the obtained powder with diatomite.
The applicant has found that the flowability of the powders can be better improved by the above preparation method, and in particular when a specific carrier is used, the adsorption of the carrier to abamectin and the stability of the resulting powder particles can be improved by the above treatment. In addition, in this way, the synergistic effect with the adhesive, the effervescent auxiliary agent and the like can be further improved, and the spraying effect of the preparation can be improved.
As a preferred technical scheme of the invention, when the preparation is in the form of effervescent granules, the other auxiliary agents comprise a binder and an effervescent disintegrating agent; the adhesive is a water-soluble high polymer material.
In a preferred embodiment of the present invention, the water-soluble polymer material is selected from one or more of polyoxyethylene-polyoxypropylene block copolymer, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, acrylic acid homopolymer, and sodium carboxymethyl cellulose.
Further, the water-soluble high polymer material is a mixture of polyvinyl alcohol and polyethyleneimine; further, the mass ratio of the polyvinyl alcohol to the polyethyleneimine is (3-5): 1; further, the mass ratio of the polyvinyl alcohol to the polyethyleneimine is 4.2:1.
in a preferred embodiment of the present invention, when the concentration of the water-soluble polymer material in water is 0.1 to 1.5wt%, the shear viscosity of the aqueous solution is 1.0 to 15 mPas.
Further, when the concentration of the water-soluble polymer material in water is 0.5 to 1.0wt%, the shear viscosity of the aqueous solution thereof is 1 to 6 mPas.
The term "shear viscosity" as used herein, i.e., the ratio of shear stress to shear rate at steady state, is herein measured at 120rpm at 25 ℃.
Furthermore, the alcoholysis degree of the polyvinyl alcohol is 85-90%, preferably 88%, products such as PVA-1788, PVA-2088, PVA-2288 and the like can be adopted, and the polyvinyl alcohol is preferably PVA-1788 (the polymerization degree is 1700, and the alcoholysis degree is 88%).
The applicant finds that the spraying difficulty of the dosage form can be further reduced by optimizing and compounding the water-soluble high polymer material, and the more uniform droplet size can be ensured under the lower spraying pressure, so that the dosage form can be more uniformly sprayed on a sprayed object. In addition, the applicant finds that the carrier and the water-soluble polymer material in the composition have an obvious synergistic effect, and after the carrier and the water-soluble polymer material are optimized and improved simultaneously, the spraying efficiency of the dosage form can be improved on the premise of adopting less dilution solvent, the conditions of blockage in the spraying process and the like are avoided, and the composition can be widely applied to modern drug delivery by adopting unmanned aerial vehicle spraying and the like.
In the present application, the specific selection of the effervescent disintegration agent is not particularly limited, and conventional components in the field can be selected, and include alkaline metal salts and acids, wherein the alkaline metal salts include but are not limited to sodium carbonate, sodium bicarbonate, potassium carbonate, and the like; the acid is an organic acid including, but not limited to, succinic acid, citric acid, tartaric acid, and the like.
The prepared wettable powder, the adhesive and the effervescent disintegrating agent are fully stirred, mixed uniformly and granulated to obtain the effervescent granules.
As a preferable technical scheme of the invention, under the spraying pressure of 0.10-0.55 MPa, the droplet diameter D50 of the abamectin preparation is 120-190 μm.
The technical scheme provided by the invention has the following beneficial effects:
the high-stability abamectin composition has excellent stability, has good fluidity when being prepared into a dosage form, and can easily flow from a storage bin to a packaging bag and then flow from the packaging bag to a sprayer for preparation. In addition, the abamectin is treated by adopting a specific carrier and then mixed with the diatomite to prepare a final preparation formulation, so that the flowability of the powder is obviously improved, the synergistic effect between the abamectin and the diatomite in the composition is further improved, the pest killing effect is improved, and the dosage of the pesticide is reduced. In addition, through adopting specific carrier and specific adhesive in this application, utilize the key synergism between them, improve the stability of dosage form, make it can keep fine dimensional stability at the spraying in-process, avoid the interparticle coalescence of granule, block up the atomizer shower nozzle, influence spraying effect. The dosage form can be sprayed under the spraying height of 0.6-2 m and the pressure of 0.1-1 MPa, the particle size uniformity of spraying droplets can be realized, the particle size D50 is within the range of 120-190 microns, and the particle size D90 is within the range of 205-235 microns, so that the uniform spraying can be better realized, and the dosage of a reagent is further reduced.
Detailed Description
Example 1
This example provides a high stability avermectin composition, which includes 3.6wt% avermectin, 4wt% carrier, 4.5wt% adjuvant, and the balance diatomaceous earth; the diatomite is Celite610 of France Yirui stone, the average particle size of the carrier is 200nm, the carrier is a mixed mixture of white carbon black and modified organic bentonite, the mass ratio is 3:2, the modified organic bentonite is a mixture of cefradine modified bentonite and octadecylamine modified bentonite, and the mass ratio is 1.5; the auxiliary agent comprises 2wt% of dispersing agent, 1.5wt% of wetting agent and 1wt% of synergist, the dispersing agent is HMK-D1003 of Moke chemical technology Co., ltd, beijing Han, the wetting agent is organosilicon QS-302-NP50 of Sancheng New Material Co., ltd, jiangxi, and the synergist is epoxidized soybean oil.
The embodiment also provides an abamectin foam formulation, which comprises the high-stability abamectin composition and other auxiliary agents, wherein the mass ratio of the high-stability abamectin composition to the other auxiliary agents is 1:1, the other auxiliary agents consist of 4 parts by weight of binding agents and 15 parts by weight of effervescent disintegrating agents, the binding agents are mixtures of polyvinyl alcohol (PVA-1788) and polyethyleneimine (Mw = 70000), and the mass ratio is 4.2:1 (a 0.7wt% aqueous solution thereof has a shear viscosity of 3.2 mPas); the effervescent disintegrating agent consists of 2 parts by weight of acid and 4.5 parts by weight of alkali metal salt, wherein the acid is a mixture of citric acid and tartaric acid, the volume ratio is 1:1, and the alkali metal salt is sodium bicarbonate.
The preparation method of the abamectin bubble formulation comprises the following steps: drying the carrier component for 1.5 hours at 95 ℃, mixing the carrier component with abamectin, then placing the mixed mixture in a high-pressure mixing kettle, adjusting the pressure of the mixing kettle to 5.2MPa, adding a penetrating agent (cyclopentane), carrying out pressure maintaining treatment at 45 ℃, releasing the pressure, recovering the penetrating agent, taking out the mixture, drying the mixture at 60 ℃ for 30 minutes, mixing the mixture with a wetting agent, a dispersing agent and a synergist, carrying out high-speed universal grinding until the fineness is about 400 meshes, stirring and mixing the obtained powder with diatomite to obtain powder, stirring and mixing the obtained powder with an adhesive and an effervescent disintegrant uniformly, and granulating to obtain the composite.
Example 2
This example provides a high stability avermectin composition, which includes 3.6wt% avermectin, 4wt% carrier, 4.5wt% adjuvant, and the balance diatomaceous earth; the diatomite is Celite610 of France Yirui stone, the average particle size of the carrier is 200nm, and the carrier is white carbon black; the auxiliary agent comprises 2wt% of dispersing agent, 1.5wt% of wetting agent and 1wt% of synergist, the dispersing agent is HMK-D1003 of Moke chemical technology Co., ltd, beijing Han, the wetting agent is organosilicon QS-302-NP50 of Sancheng New Material Co., ltd, jiangxi, and the synergist is epoxidized soybean oil.
The embodiment also provides an abamectin foam formulation, which comprises the high-stability abamectin composition and other auxiliary agents, wherein the mass ratio of the high-stability abamectin composition to the other auxiliary agents is 1:1, the other auxiliary agents consist of 4 parts by weight of binding agents and 15 parts by weight of effervescent disintegrating agents, the binding agents are mixtures of polyvinyl alcohol (PVA-1788) and polyethyleneimine (Mw = 70000), and the mass ratio is 4.2:1 (a 0.7wt% aqueous solution thereof has a shear viscosity of 3.2 mPas); the effervescent disintegrating agent consists of 2 parts by weight of acid and 4.5 parts by weight of alkali metal salt, wherein the acid is a mixture of citric acid and tartaric acid, the volume ratio is 1:1, and the alkali metal salt is sodium bicarbonate.
The preparation method of the abamectin foam formulation comprises the following steps: drying the carrier component for 1.5 hours at 95 ℃, mixing the carrier component with abamectin, then placing the mixed mixture in a high-pressure mixing kettle, adjusting the pressure of the mixing kettle to 5.2MPa, adding a penetrating agent (cyclopentane), maintaining the pressure at 45 ℃ for 60min, then releasing the pressure, recovering the penetrating agent, taking out the mixture, drying the mixture at 60 ℃ for 30min, mixing the mixture with a wetting agent, a dispersing agent and a synergist, carrying out high-speed universal grinding until the fineness is about 400 meshes, stirring and mixing the obtained powder with diatomite to obtain powder, stirring and mixing the obtained powder with an adhesive and an effervescent disintegrating agent uniformly, and granulating to obtain the finished product.
Example 3
This example provides a high stability avermectin composition, which includes 3.6wt% avermectin, 4wt% carrier, 4.5wt% adjuvant, and the balance diatomaceous earth; the diatomite is Celite610 of France Yirui stone, the average particle size of the carrier is 200nm, the carrier is a mixed mixture of white carbon black and modified organic bentonite, the mass ratio is 3:2, the modified organic bentonite is a mixture of cefradine modified bentonite and octadecylamine modified bentonite, and the mass ratio is 1.5; the auxiliary agent comprises 2wt% of dispersing agent, 1.5wt% of wetting agent and 1wt% of synergist, the dispersing agent is HMK-D1003 of Moke chemical technology Co., ltd, beijing Han, the wetting agent is organosilicon QS-302-NP50 of Sancheng New Material Co., ltd, jiangxi, and the synergist is epoxidized soybean oil.
The embodiment also provides an abamectin foam formulation, which comprises the high-stability abamectin composition and other auxiliary agents, wherein the mass ratio of the abamectin composition to the other auxiliary agents is 1:1, the other auxiliary agents consist of 4 parts by weight of adhesive and 15 parts by weight of effervescent disintegrating agent, and the adhesive is polyvinylpyrrolidone (PVP, the molecular weight is 369000, and the shear viscosity of 0.7wt% aqueous solution of the polyvinylpyrrolidone is 1.3mPa & s); the effervescent disintegrating agent consists of 2 parts by weight of acid and 4.5 parts by weight of alkali metal salt, wherein the acid is a mixture of citric acid and tartaric acid, the volume ratio is 1:1, and the alkali metal salt is sodium bicarbonate.
The preparation method of the abamectin bubble formulation comprises the following steps: drying the carrier component for 1.5 hours at 95 ℃, mixing the carrier component with abamectin, then placing the mixed mixture in a high-pressure mixing kettle, adjusting the pressure of the mixing kettle to 5.2MPa, adding a penetrating agent (cyclopentane), maintaining the pressure at 45 ℃ for 60min, then releasing the pressure, recovering the penetrating agent, taking out the mixture, drying the mixture at 60 ℃ for 30min, mixing the mixture with a wetting agent, a dispersing agent and a synergist, carrying out high-speed universal grinding until the fineness is about 400 meshes, stirring and mixing the obtained powder with diatomite to obtain powder, stirring and mixing the obtained powder with an adhesive and an effervescent disintegrating agent uniformly, and granulating to obtain the finished product.
Example 4
This example provides a high stability avermectin composition, which includes 3.6wt% avermectin, 4wt% carrier, 4.5wt% adjuvant, and the balance diatomaceous earth; the diatomite is Celite610 of France Yirui stone, the average particle size of the carrier is 200nm, the carrier is a mixed mixture of white carbon black and modified organic bentonite, the mass ratio is 3:2, the modified organic bentonite is a mixture of cefradine modified bentonite and octadecylamine modified bentonite, and the mass ratio is 1.5; the auxiliary agent comprises 2wt% of dispersing agent, 1.5wt% of wetting agent and 1wt% of synergist, the dispersing agent is HMK-D1003 of Moke chemical technology Co., ltd, beijing Han, the wetting agent is organosilicon QS-302-NP50 of Sancheng New Material Co., ltd, jiangxi, and the synergist is epoxidized soybean oil.
The embodiment also provides an abamectin foam formulation, which comprises the high-stability abamectin composition and other auxiliary agents in a mass ratio of 1:1, wherein the other auxiliary agents consist of 4 parts by weight of a binder and 15 parts by weight of an effervescent disintegrating agent, the binder is a mixture of polyvinyl alcohol (PVA-1788) and polyethyleneimine (Mw = 70000), and the mass ratio is 4.2:1 (a 0.7wt% aqueous solution thereof has a shear viscosity of 3.2 mPas); the effervescent disintegrating agent consists of 2 weight parts of acid and 4.5 weight parts of alkali metal salt, wherein the acid is a mixture of citric acid and tartaric acid, the volume ratio is 1:1, and the alkali metal salt is sodium bicarbonate.
The preparation method of the abamectin bubble formulation comprises the following steps: drying the carrier component for 1.5 hours at 95 ℃, mixing the carrier component with the abamectin, then mixing the mixed mixture with the wetting agent, the dispersing agent and the synergist component, carrying out high-speed universal grinding until the fineness is about 400 meshes, stirring and mixing the obtained powder with the diatomite to obtain powder, then stirring and mixing the obtained powder with the adhesive and the effervescent disintegration agent uniformly, and granulating to obtain the abamectin benzoate effervescent tablet.
Example 5
This example provides a high stability avermectin composition, which includes 3.6wt% avermectin, 4wt% carrier, 4.5wt% adjuvant, and the balance diatomaceous earth; the diatomite is Celite610 of France Yirui stone, the average grain diameter of the carrier is 200nm, the carrier is a mixed mixture of white carbon black and modified organic bentonite, the mass ratio is 3:2, the modified organic bentonite is a mixture of cefadrine modified bentonite and octadecyl amine modified bentonite, and the mass ratio is 1.5; the auxiliary agent comprises 2wt% of dispersing agent, 1.5wt% of wetting agent and 1wt% of synergist, the dispersing agent is HMK-D1003 of Moke chemical technology Co., ltd, beijing Han, the wetting agent is organosilicon QS-302-NP50 of Sanchen materials Co., ltd, jiangxi Tian, the synergist is epoxidized soybean oil.
The embodiment also provides an abamectin foam formulation, which comprises the high-stability abamectin composition and other auxiliary agents in a mass ratio of 1:1, wherein the other auxiliary agents consist of 4 parts by weight of adhesive and 15 parts by weight of effervescent disintegrating agent, and the adhesive is polyvinyl alcohol (PVA-1788); the effervescent disintegrating agent consists of 2 parts by weight of acid and 4.5 parts by weight of alkali metal salt, wherein the acid is a mixture of citric acid and tartaric acid, the volume ratio is 1:1, and the alkali metal salt is sodium bicarbonate.
The preparation method of the abamectin bubble formulation comprises the following steps: drying the carrier component for 1.5 hours at 95 ℃, mixing the carrier component with abamectin, then placing the mixed mixture in a high-pressure mixing kettle, adjusting the pressure of the mixing kettle to 5.2MPa, adding a penetrating agent (cyclopentane), maintaining the pressure at 45 ℃ for 60min, then releasing the pressure, recovering the penetrating agent, taking out the mixture, drying the mixture at 60 ℃ for 30min, mixing the mixture with a wetting agent, a dispersing agent and a synergist, carrying out high-speed universal grinding until the fineness is about 400 meshes, stirring and mixing the obtained powder with diatomite to obtain powder, stirring and mixing the obtained powder with an adhesive and an effervescent disintegrating agent uniformly, and granulating to obtain the finished product.
Performance testing
The applicant prepared the samples of the above examples as 100-fold dilutions and then sprayed them from a height of around 2m using a spray head model ST110-03 at a spray pressure of 0.4MPa and tested the particle sizes D50 and D90 of the sprayed droplets by a conical spray head droplet size analyzer, where D50 is recorded as a at 140-150 μm, B at less than 140 μm (not including 140 μm), C at 150-160 μm (not including the end points) and D at 160 μm above. Where D90 is recorded as A at 210-220 μm, B less than 210 μm, C at 220-235 μm, and D above 235 μm (inclusive).
In addition, during the preparation process of the preparation, the flowability of the powder is observed and classified into 1 to 3 grades according to whether the flowability of the powder is good, whether the powder is bonded and the like, wherein the flowability of the grade 1 is the best, and the flowability of the grade 3 is the worst. In addition, carry out the spraying two days according to above-mentioned spraying mode to observe whether the shower nozzle blocks up, if take place to block up then twist off the shower nozzle, the shower nozzle is washed to the water, washes away the jam and installs the shower nozzle once more and carry out the spraying, wherein according to what of shower nozzle jam number of times carries out spraying efficiency's good or bad, 1 level is for not appearing blockking up, 2 level is for appearing 1 or 2 times, 3 levels are for appearing 3 times and above. The results of the above tests are shown in table 1 below.
TABLE 1
|
D50/μm
|
D90/μm
|
Fluidity of the resin
|
Efficiency of spraying
|
Example 1
|
A
|
A
|
Level 1
|
Level 1
|
Example 2
|
C
|
A
|
Stage 2
|
Stage 2
|
Example 3
|
B
|
B
|
Level 1
|
Stage 2
|
Example 4
|
D
|
C
|
Grade 3
|
Grade 3
|
Example 5
|
A
|
C
|
Stage 2
|
Stage 2 |
From the above experimental results, it can be seen that the present invention has excellent stability, good fluidity when preparing dosage forms, and easy flow from the storage bin to the packaging bag and then from the packaging bag to the sprayer for preparation. Moreover, the preparation of this application is high in spraying in-process stability, is difficult to appear unstable phenomena such as shower nozzle jam.