CN116250529A - Suspending agent containing fluazinam and cyazofamid and preparation method thereof - Google Patents

Abstract

The invention relates to the technical field of pesticides, in particular to a suspension containing fluazinam and cyazofamid and a preparation method thereof. The suspending agent comprises an active ingredient, a dispersing agent, a wetting agent, a thickening agent, a defoaming agent, an antifreezing agent, a preservative and water; the active ingredients consist of fluazinam and cyazofamid. The invention greatly reduces the processing difficulty of the dosage form, improves the stability of the dosage form, has the advantages of good water dispersibility and high suspension rate, and effectively solves the problems of sample storage delamination, solidification, particle size growth, color change, content degradation and the like under the condition of not adding anti-decomposition factors.

Description

Suspending agent containing fluazinam and cyazofamid and preparation method thereof

Technical Field

The invention relates to the technical field of pesticides, in particular to a suspension containing fluazinam and cyazofamid and a preparation method thereof.

Background

Fluazinam (Fluazinam), chemical name: 3-chloro-N- (3-chloro-2, 6-dinitro-4-trifluoromethyl phenyl) -5-trifluoromethyl-2-pyridine amine belongs to pyridine amine derivatives and dinitroaniline bactericides and is mainly used for preventing and controlling downy mildew, gray mold, sclerotinia sclerotiorum, anthracnose on vegetables, scab, anthracnose, scab and other diseases on fruit trees; but also has more remarkable prevention effect on epidemic disease, clubroot and gray mold.

Cyazofamid (Cyazofamid), chemical name: 4-chloro-2-cyano-5-p-methylphenyl-imidazole-1-N, N-dimethyl sulfonamide belongs to sulfaimidazole bactericides and is mainly used for preventing and treating oomycete diseases such as downy mildew, epidemic disease, late blight and the like; can be used for various plants such as potato, tomato, capsicum, cucumber, melon, cabbage, lettuce, onion, grape, litchi, etc.

The bactericide variety containing single active component has the defects of different degrees in the aspect of agricultural bactericide control, such as narrow bactericidal range, poor control effect, large application dosage, easy generation of drug resistance, multiple application times, serious environmental pollution and the like. For preventing and controlling germs with resistance in agriculture, one method is to push out new active components without interactive resistance with the existing variety, however, the new active components have high development cost and long period and can never keep pace with the speed of germs for generating resistance; other methods such as crop layout adjustment, different pesticide rotation and the like are difficult to truly achieve obvious effects in the actual operation process. The compounding of different kinds of components is the most common method for preventing and treating resistant bacteria. Different active components are compounded, so that the control effect can be improved, the sterilization range can be enlarged, the dosage of the active components can be reduced, the medication cost can be saved, the environmental pollution can be reduced, and the method is an important means for comprehensively controlling field diseases.

The prior art CN103563948A discloses a compound composition of fluazinam and cyazofamid, which relates to a first active component cyazofamid and one of second active components of pyraclostrobin, fluazinam, dimethomorph, cymoxanil, benthiavalicarb-isopropyl, zoxamide or famoxadone, and mainly introduces an application of a sterilizing composition containing cyazofamid and related dosage forms thereof, proves the synergistic effect among the active components in the composition and solves the problem of component decomposition.

However, the existing fluazinam and cyazofamid compound suspending agent has poor physical stability, is easily affected by environmental changes in the storage and transportation processes, is easily subjected to the phenomena of caking, layering, particle size growth, water separation and the like, and seriously affects the efficacy exertion; the components are affected by factors such as pH and the like, so that the problems of decomposition and appearance color change are easy to occur. In the use process, the water quality is greatly influenced by different water qualities, for example, the water is intolerant to 3WHO water, and the use and popularization of the product are not facilitated.

Disclosure of Invention

In view of the above, the invention provides a suspension containing fluazinam and cyazofamid and a preparation method thereof. The technical scheme of the invention solves the problems of decomposition and appearance discoloration of effective active ingredients.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a suspending agent containing fluazinam and cyazofamid, which comprises an active ingredient, a dispersing agent, a wetting agent, a thickening agent, a defoaming agent, an antifreezing agent, a preservative and water; the active ingredients consist of fluazinam and cyazofamid.

Preferably, the mass percentages of the components are as follows:

the mass ratio of fluazinam to cyazofamid in the active ingredients is (1-6): 1.

The fluazinam and cyazofamid suspension provided by the invention overcomes the defect of rapid development of cyazofamid resistance, and the two active components have synergistic effect, thereby being beneficial to reducing the dosage and the application frequency; according to the invention, through optimizing the auxiliary agent, the stability of the product is improved, the high-low temperature range of-15 ℃ to 65 ℃ can be tolerated, the adverse effect possibly caused by environmental change in the transportation process is effectively solved, and the quality problems of products such as caking, layering, particle size growth, water separation and the like are avoided; the pH of the product is controlled within a reasonable range on the basis of solving the physical stability of the product by reasonably collocating the auxiliary agents under the condition that no anti-decomposition factor is added, so that the problems of component decomposition and appearance color change are solved; meanwhile, the invention can resist different water qualities such as C water, D water, 3WHO water and the like, meets the requirements of different countries and regions, and is favorable for wide popularization and application.

Preferably, the composition comprises the following components in percentage by mass:

preferably, the composition comprises the following components in percentage by mass:

preferably, the dispersing agent is at least one of lignin sulfonate, naphthalene sulfonate formaldehyde condensate, styrene acrylic acid copolymer sodium salt, alkylphenol polyoxyethylene sulfonate, alkylphenol polyoxyethylene phosphate, styrene maleic anhydride acrylate polymer ammonium salt, formaldehyde cresol sulfonate sodium salt or styrene maleic anhydride copolymer sodium salt.

The above-mentioned lignosulfonate is preferably sodium lignosulfonate.

The alkylphenol polyoxyethylene ether sulfonate is preferably dodecylphenol polyoxyethylene ether sulfonate sodium salt.

The alkylphenol polyoxyethylene ether phosphate is preferably octylphenol polyoxyethylene ether sodium phosphate.

Preferably, the wetting agent is at least one of tristyrylphenol polyoxyethylene ether sulfate ammonium salt, maleic rosin block polyether sulfonate ammonium salt, fatty alcohol polyoxyethylene ether phosphate, alkyl succinic acid sulfonate, alkylphenol polyoxyethylene ether sulfate, propylene oxide-ethylene oxide block polyether or castor oil polyoxyethylene ether phosphate.

The fatty alcohol polyoxyethylene ether phosphate is preferably laurinol polyoxyethylene ether phosphate.

The above-mentioned alkyl succinic acid sulfonate is preferably sodium dodecyl succinic acid sulfonate.

The alkylphenol polyoxyethylene ether sulfate is preferably octylphenol polyoxyethylene ether sodium sulfate.

Preferably, the dispersing agent is at least one of naphthalene sulfonate formaldehyde condensate, styrene acrylic acid copolymer sodium salt or styrene maleic anhydride copolymer sodium salt;

the wetting agent is at least one of tristyrylphenol polyoxyethylene ether sulfate ammonium salt, epoxypropane-epoxyethane block polyether or maleic rosin block polyether sulfonate ammonium salt.

More preferably, the dispersant is a combination of two dispersants, consisting of a first dispersant and a second dispersant; the wetting agent is a wetting agent.

Preferably, the mass ratio of the first dispersing agent to the second dispersing agent to the wetting agent is (1-5): 1-5. Further preferably, the mass ratio is (1-3): 1-3. Further preferably, the mass ratio is (1-3) 2 (2-3). In the specific embodiment provided by the invention, the mass ratio is 1:1:1.

In some embodiments of the present invention, the mass content of the first dispersant, the second dispersant and the wetting agent is 1% to 2%, 1% to 3%, and may be 1%, 2%, 1%, or 2%, 3%, or 1%, 2%, or 2%, or 2% or a range having any of the above specific values as an upper limit or a lower limit, most preferably 2%, 2%.

The first dispersing agent and the second dispersing agent are preferably any two of naphthalene sulfonate formaldehyde condensate, styrene acrylic acid copolymer sodium salt or styrene maleic anhydride copolymer sodium salt.

The wetting agent is one of tristyrylphenol polyoxyethylene ether ammonium sulfate, epoxypropane-epoxyethane block polyether or maleic rosin block polyether ammonium sulfonate.

Preferably, the thickener is at least one of common white carbon black, magnesium aluminum silicate, methyl cellulose, organic bentonite, xanthan gum or sodium polyacrylate.

Preferably, the thickener is at least one of common white carbon black, magnesium aluminum silicate, organic bentonite and xanthan gum.

The thickener is preferably two of common white carbon black, magnesium aluminum silicate, organic bentonite and xanthan gum.

The thickener is further preferably a mixture of xanthan gum and magnesium aluminum silicate. Preferably, the mass ratio of the xanthan gum to the magnesium aluminum silicate is 1: (1-6). Further preferred is a mass ratio of 1: (2-5). Further preferred is a mass ratio of 1: (3-5). More preferably, the mass ratio is 1:3.33.

in some embodiments of the present invention, the mass content of the xanthan gum and the magnesium aluminum silicate is 0.15%, 2%, or 0.15%, 0.5%, or 0.15%, 3%, or a range of values having any of the above specific values as an upper limit or a lower limit, most preferably 0.15%, 0.5% in order.

Preferably, the antifreezing agent is at least one of urea, potassium chloride, ethylene glycol, propylene glycol, glycerol, polyethylene glycol, sorbitol or sodium chloride.

Further, the antifreeze is preferably ethylene glycol.

Preferably, the mass percentage of ethylene glycol in the suspending agent is preferably 2% -20%, and specifically may be 2%, 4%, 5%, 10%, 15%, 20%, or a range value in which any of the above specific values is an upper limit or a lower limit; most preferably 5% or 10%.

Preferably, the preservative is at least one of kathon, paraformaldehyde and sodium benzoate.

Further, the preservative is preferably pinus koraiensis.

The mass percentage of the pinocembrane in the suspending agent is preferably 0.1% to 2%, specifically 0.1%, 0.2%, 0.3%, 0.5%, 1%, 2%, or a range having any of the above specific values as an upper limit or a lower limit, and most preferably 0.1%.

Preferably, the defoamer is at least one of a polyether defoamer, an organosilicon defoamer or a polyether modified polysiloxane defoamer.

Further, the antifoaming agent is preferably a silicone antifoaming agent.

The mass percentage of the silicone defoamer in the suspending agent is preferably 0.2% to 3%, specifically 0.2%, 0.3%, 0.5%, 1%, 2%, 3%, or a range having any of the above specific values as an upper limit or a lower limit, and most preferably 0.2%.

The invention also provides a preparation method of the suspending agent, which comprises the following steps: mixing water, a dispersing agent, a wetting agent and a preservative, adding a thickening agent, a defoaming agent, an antifreezing agent, cyazofamid and fluazinam under a high-speed shearing state, shearing for 10-30 minutes, and then grinding until the particle size D90 of the mixture is smaller than 7 mu m, thus obtaining the suspension containing fluazinam and cyazofamid.

Preferably, the high-speed shearing speed is 1000-10000 r/min.

In the specific embodiment provided by the invention, the thickening agent is xanthan gum and magnesium aluminum silicate, and in order to reduce the sanding difficulty, the preparation method adopted by the invention comprises the following steps: mixing water, a dispersing agent, a wetting agent, a preservative, a part of defoaming agent and a part of antifreezing agent, adding a thickening agent (magnesium aluminum silicate), cyazofamid and fluazinam under a high-speed shearing state, shearing for 10-30 minutes, grinding until the particle size D90 of the mixture is smaller than 7 mu m, adding the rest of defoaming agent, thickening agent (xanthan gum) and rest of antifreezing agent under the high-speed shearing state, and shearing for 10-30 minutes to obtain the suspension agent containing fluazinam and cyazofamid.

In the above preparation method, the grinding may be performed by any grinding method disclosed in the prior art, for example, grinding may be performed under a zirconia bead grinding medium. After grinding, the particles were measured by a laser particle size distribution analyzer until the particle diameter D90 was less than 7. Mu.m.

The invention has the following beneficial effects:

1) The pesticide composition provided by the invention overcomes the defect of rapid development of single-agent resistance of cyazofamid, and the two active components have synergistic effect, delay the generation of drug resistance, and reduce the application dosage and application frequency, thereby reducing the cost of the agent.

2) The inventor carries out a large amount of screening work on the auxiliary agent system, and finally obtains the system with the optimal matching degree among the components, particularly the screening and the combination of 3 components of dispersing agent, wetting agent and thickener, thereby greatly reducing the processing difficulty of the dosage form, improving the stability of the dosage form, having the advantages of good water-in dispersibility and high suspension rate, and effectively solving the problems of sample storage delamination, solidification, particle size growth, color change, content degradation and the like under the condition of not adding an anti-decomposition factor.

3) On the basis of 2), on the premise of ensuring physical stability, antioxidant, pH regulator and other anti-decomposition factors are not required to be added, and the reasonable pH range of the product is ensured by reasonable collocation of auxiliary agents, so that the problems of component decomposition and color change are solved.

Detailed Description

The invention discloses a suspension containing fluazinam and cyazofamid and a preparation method thereof, and the technical parameters can be properly improved by the technicians in the field with reference to the content of the suspension. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention.

The invention provides a suspending agent containing fluazinam and cyazofamid, wherein,

fluazinam: the molecular weight of the crude drug is 465.09, and the appearance is yellow crystal. Melting point 115-117 deg.C, relative density 1.757 (20 deg.C) and vapor pressure 1.47×10 ^-3 Pa (25 ℃), logp=3.56 (25 ℃). Solubility in water at 25 ℃): 0.1mg/L (pH=5.0), 1.7mg/L (pH=6.8),>1000mg/L (ph=11). Is easy to hydrolyze and change color under alkaline conditions.

Cyazofamid: the raw medicine is light yellow powdery solid. Molecular weight 342.79; the melting point is 152.7 ℃; relative density: 1.446; solubility in water: 0.107mg/L (ph=7, 20 ℃); vapor pressure: < 1.33X10 ^-5 Pa; log P value 3.2 (25 ℃); slightly soluble in (n-hexane, n-octanol, toluene, methanol, dichloroethane, acetonitrile, ethyl acetate, acetone; hydrolysis under alkaline conditions and is unstable to light.

From the two properties, the components are sensitive to pH and are easy to decompose and change color, and the problem can be solved by screening the auxiliary agent combination; because of the higher specific gravity of the raw medicine and higher content of the composition, the mixing preparation of the two active ingredients as the water suspending agent has certain difficulty, the problems of sedimentation, solidification and bottom settlement of raw medicine particles in a suspension dispersion system can be considered, and the introduction of white carbon black or magnesium aluminum silicate can be considered to improve the structural stability of the system, so that the problem of sedimentation and bottom settlement is avoided.

Chinese and english names of active ingredients and partial adjuvants:

the following percentages are by weight unless otherwise indicated.

The raw materials or auxiliary agents used in the invention can be purchased from the market.

The invention is further illustrated by the following examples:

examples 1 to 9 and comparative examples 1 to 4

The formulations of the examples and comparative examples are shown in the following table:

TABLE 1

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The preparation method comprises the following steps: adding water, a dispersing agent, a wetting agent and a preservative into a feeding kettle, fully mixing and dispersing uniformly, adding a thickening agent, a defoaming agent, an antifreezing agent, cyazofamid and fluazinam into the feeding kettle under a high-speed shearing state of 1000-10000r/min, shearing for 10-30 minutes, and grinding the materials under a zirconia bead sanding medium until the particle size D90 of the mixture is smaller than 7 mu m, thereby obtaining the suspending agent containing fluazinam and cyazofamid.

Test example 1 Performance test

The properties of the aqueous suspensions prepared in the above examples and comparative examples were examined, and the results are shown in Table 2 below. The suspension rate is detected according to a GB/T14825-2006 pesticide suspension rate measuring method, the pourability is detected according to a GB/T31737-2015 pesticide pourability measuring method, and the spontaneous dispersibility in water is detected according to a CIPAC MT160 measuring method.

Table 2 performance of aqueous suspensions formulated from fluazinam and cyazofamid

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As can be seen from Table 2, the comparative examples 1, 2, 3 and 4 were poor in quality after heat storage, wherein the samples 1 and 2 were intolerant to the high and low temperature range of-15 ℃ to 65 ℃, the samples were solidified after storage at-15 ℃ for 3 days and the problems of discoloration and content reduction were caused; the samples of comparative examples 1, 2, 3 and 4 were stored at 65℃for 3 days, and after the temperature was changed to normal temperature, the samples were subjected to crystallization, poor flowability and solidification, respectively. Examples 2 and 3 were slightly inferior in quality after heat storage, little water was evolved and the suspension rate was slightly low, examples 1, 6, 7, 8 and 9 were slightly varied in quality after heat storage and the suspension rate was slightly high; and the examples 4 and 5 have good quality before and after heat storage and good dispersion stability in different water qualities. Preferably, the adjuvants play a critical role in product quality.

The selection of the auxiliary agent is very important for the stability of the fluorspar and the cyazofamid, in particular to the use of wetting dispersing agents such as naphthalene sulfonate formaldehyde condensate and the control of pH. Through the synergistic effect of the two, the problems of stable physical quality and color change of the product are achieved, and the high-temperature storage is free from abnormal color change, decomposition, crystallization and the like.

Example 10

The mass percentages of wetting agents, dispersants and other adjuvants were adjusted on the basis of the formulation (group a) of example 5, as follows:

TABLE 3 Table 3

Test example 2 Performance test

The properties of the aqueous suspension prepared in example 10 were examined, and the results are shown in Table 4 below.

Table 4 Properties of aqueous suspension prepared by the combination of fluazinam and cyazofamid

As can be seen from table 4, the A, B, C group changed the thickener ratio, and the influence on other indexes was not obvious except the influence on the appearance of water bleeding and the like; and D, E, F groups have different degrees of reduction of the suspension rate in a qualified range after the proportion of the auxiliary agent is regulated, and other indexes are not abnormal. Preferably the proportion of auxiliary plays a critical role in the quality of the product.

Test example 3 Pepper epidemic disease field efficacy test:

the test was conducted on a vegetable base in the god market, and the control agent was 100 g/l cyazofamid suspension (commercially available) and 500 g/l fluazinam suspension (commercially available). A total of 5 treatments were set up, each: treatment 1: spraying clear water and blank control; treatment 2: example 3; treatment 3: example 5; treatment 4:100 g/l cyazofamid suspension; treatment 5:500 g/l fluorinePyrilamine suspending agent, 20m per cell ² The cells are arranged randomly.

Table 5 dosing for each experimental group

The pesticide is applied at the initial stage of the epidemic disease of the capsicum, and is applied for 1 time by using a Gongnong-16 knapsack manual sprayer, and 750kg of water is added according to the dosage of each hectare preparation to prepare the pesticide, so that the pesticide is uniformly sprayed according to the dosage of the district. The medicine is applied in good weather, the average daily temperature is 20-30 ℃, and no rain and bad weather factors occur on the day of medicine application.

The investigation, calculation and statistics method for the pepper epidemic disease field efficacy test comprises the following steps: the test was conducted 1 control investigation each before, 15 days after and 30 days after the administration, and a total of 3 surveys were conducted. 5 spots were investigated randomly per cell, 5 strains per spot. The number of plants, dead plants or plants that significantly wilt were recorded. The results are shown in Table 6.

The grading method comprises the following steps:

level 0: healthy without symptoms;

stage 1: only leaves and fruits on the ground are provided with lesions;

3 stages: brown rot spots exist on the overground stems and branches;

5 stages: brown rot spots exist on the basal part of the stem;

7 stages: brown rot spots exist on the ground stems, branches and stem bases, and part of branches are dead;

stage 9: the whole plant dies.

The drug effect calculation method comprises the following steps:

note that: CK in ₀ 、CK ₁ The disease indexes before and after the administration of the blank control area are respectively shown; PT (PT) ₀ 、PT ₁ The disease index before and after the application of the medicine in the treatment area is respectively.

Table 6 results of field efficacy test of each treatment agent for controlling pepper epidemic disease

The field efficacy test result shows that the synergistic effect is obvious after the fluazinam and the cyazofamid are compounded, the control effect on the pepper epidemic disease is obviously better than that of a single dose under the condition of lower dosage, and the example 5 obtains higher control effect by optimizing the auxiliary agent.

The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (11)

1. The suspending agent containing fluazinam and cyazofamid is characterized by comprising an active ingredient, a dispersing agent, a wetting agent, a thickening agent, a defoaming agent, an antifreezing agent, a preservative and water; the active ingredients consist of fluazinam and cyazofamid.

2. The suspending agent according to claim 1, wherein the amounts of the components in mass percent are:

in the active component, the mass ratio of the fluazinam to the cyazofamid is (1-6): 1.

3. The suspending agent according to claim 1, wherein the dispersant is at least one of lignin sulfonate, naphthalene sulfonate formaldehyde condensate, styrene acrylic acid copolymer sodium salt, alkylphenol ethoxylate sulfonate, alkylphenol ethoxylate phosphate, styrene maleic anhydride acrylate polymer ammonium salt, formaldehyde cresol sulfonate sodium salt, or styrene maleic anhydride copolymer sodium salt;

the wetting agent is at least one of tristyrylphenol polyoxyethylene ether sulfate ammonium salt, maleic rosin block polyether sulfonate ammonium salt, fatty alcohol polyoxyethylene ether phosphate, alkyl succinic acid sulfonate, alkylphenol polyoxyethylene ether sulfate, epoxypropane-epoxyethane block polyether or castor oil polyoxyethylene ether phosphate.

4. A suspension according to claim 3, wherein the lignosulfonate is sodium lignosulfonate;

the alkylphenol polyoxyethylene ether sulfonate is dodecylphenol polyoxyethylene ether sulfonate sodium salt;

the alkylphenol polyoxyethylene ether phosphate is octylphenol polyoxyethylene ether sodium phosphate;

the fatty alcohol polyoxyethylene ether phosphate is laurinol polyoxyethylene ether phosphate;

the alkyl succinic acid sulfonate is sodium dodecyl succinic acid sulfonate;

the alkylphenol polyoxyethylene ether sulfate is octylphenol polyoxyethylene ether sodium sulfate.

5. A suspension as claimed in claim 3 wherein the dispersant is at least one of naphthalene sulfonate formaldehyde condensate, styrene acrylic acid copolymer sodium salt or styrene maleic anhydride copolymer sodium salt;

the wetting agent is at least one of tristyrylphenol polyoxyethylene ether sulfate ammonium salt, epoxypropane-epoxyethane block polyether or maleic rosin block polyether sulfonate ammonium salt.

6. The suspension of claim 1, wherein the thickener is at least one of plain white carbon black, magnesium aluminum silicate, methylcellulose, organobentonite, xanthan gum, or sodium polyacrylate.

7. The suspending agent according to claim 6, wherein the thickener is at least one of plain white carbon black, magnesium aluminum silicate, organic bentonite, and xanthan gum.

8. The suspension of claim 1, wherein the anti-freeze agent is at least one of urea, potassium chloride, ethylene glycol, propylene glycol, glycerol, polyethylene glycol, sorbitol, or sodium chloride.

9. The suspension of claim 1, wherein the preservative is at least one of pinus koraiensis, paraformaldehyde, sodium benzoate.

10. The suspension of claim 1, wherein the defoamer is at least one of a polyether defoamer, a silicone defoamer, or a polyether modified silicone defoamer.

11. A process for the preparation of a suspending agent according to any one of claims 1 to 10, characterised in that it comprises the steps of: mixing water, a dispersing agent, a wetting agent and a preservative, adding a thickening agent, a defoaming agent, an antifreezing agent, cyazofamid and fluazinam under a high-speed shearing state, shearing for 10-30 minutes, and then grinding until the particle size D90 of the mixture is smaller than 7 mu m, thus obtaining the suspension containing fluazinam and cyazofamid.