A bactericidal composition preparation containing a stabilizer

Abstract

The present invention belongs to the field of pesticide formulation processing and relates to a fungicide composition formulation containing a stabilizer. This composition, when used in combination with necessary formulation components, can be prepared into a variety of formulations. After undergoing accelerated thermal storage testing (54°C, 14 days), this product demonstrated improved autodispersibility (over 95%) in high-concentration hard water (hardness 1000 ppm), as well as improved dilution stability and effective suspension rate (over 95%) at low dilution ratios (20-fold dilution) and in high-hardness hard water.

Description

Technical Field

[0001] The invention belongs to the field of pesticide formulation processing and relates to a bactericidal composition preparation containing a stabilizer. Background Art

[0002] This active ingredient belongs to the pyrimidine fungicide class, developed by Shenyang Sinochem Pesticide & Chemical Research & Development Co., Ltd., with independent intellectual property rights. This product has demonstrated effective preventive and therapeutic effects against cucumber downy mildew, cucumber powdery mildew, cucumber anthracnose, cucumber target spot, wheat powdery mildew, and rapeseed sclerotinia. The compound is patented under CN106167484 and has been granted.

[0003] It is known in the industry that most pesticide raw materials cannot be used directly and must be processed and prepared into various types of preparations before use. Therefore, according to the different methods of use and crops, corresponding preparations must be prepared and applied to improve the biological activity of pesticides, reduce the dosage, reduce costs, and reduce pollution to the environment.

[0004] However, the active ingredient is the main ingredient when formulating the preparation. The specific characteristics of the active ingredient will determine the dosage form of the final preparation. What dosage form is suitable for it and what kind of excipients it should match will be what needs to be solved at present. At present, there are no reports on the research of preparations related to the compound represented by Formula I.

[0005] In order to improve the applicability of the compound in different application scenarios, especially to adapt to the requirements of aircraft spray application, the present invention has improved the requirements of hard water hardness and dilution ratio of the corresponding preparations in the research stage. The automatic dispersibility and dilution stability of ordinary preparation products are tested by diluting 50 times under 342ppm hard water conditions, and the suspension rate is tested by diluting 250 times under 342ppm hard water conditions. The tests on the automatic dispersibility, dilution stability and suspension rate of the preparation products in the present invention are all completed by diluting 20 times under 1000ppm hard water. The detection conditions and environment involved in the present invention are much higher than those of ordinary preparation products. Compared with ordinary preparations, they are more able to adapt to the characteristics of aircraft spray tank mixing of complex types, large quantities and less water. Therefore, the composition preparation of the present invention is more of practical use significance. Summary of the Invention

[0006] The object of the present invention is to provide a bactericidal composition preparation containing a stabilizer.

[0007] To achieve the above object, the technical solution of the present invention is as follows:

[0008] A fungicide composition preparation containing a stabilizer, wherein the active ingredients of the composition preparation include a substituted pyrazole compound containing pyrimidine and at least one agriculturally acceptable adjuvant; wherein the adjuvant contains at least a stabilizer; the active ingredient accounts for 0.1-90% of the preparation mass, and the stabilizer accounts for 1-20% of the composition preparation mass, and the stabilizer is a crown ether compound.

[0009] The pyrimidine-substituted pyrazole compound is a compound represented by formula I;

[0010]

[0011] wherein R3 is selected from hydrogen, hydroxy, formyl or C1-C4 alkyl; R4 and R5 may be the same or different and are selected from hydrogen, halogen or C1-C4 alkyl; R6 and R7 may be the same or different and are selected from hydrogen, halogen or C1-C4 alkyl; R8 and R9 may be the same or different and are selected from hydrogen, cyano, halogen or C1-C4 alkyl; R11 is selected from halogen, hydroxy, amino, cyano, nitro or C1-C4 alkyl; n is an integer selected from 0 to 5, and R 14, R15, R16 or R17 may be the same or different and are respectively selected from hydrogen, halogen, hydroxyl, amino, cyano, nitro or C1-C4 alkyl; W is selected from hydrogen, halogen or C1-C4 alkyl; the salt of the compound represented by the general formula I is a salt formed by the compound of the general formula with hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid or citric acid.

[0012] The crown ether compounds are 2-(allyloxymethyl)-18-crown-6-ether, 24-crown-8-ether, 4-nitrobenzene-18-crown-6, 18-crown-5 [4-(2,4-dinitrophenylazo)phenol], N,N'-dibenzyl-4,13-diaza-18-crown-6-ether, 4-tert-butylcyclohexane-15-crown-5, 4'-aminobenzo-18-crown-6, benzoaza-15-crown-5, bis(1,4-phenylene)-34-crown-10-ether, 4'-acetylbenzo-18-crown-6-ether, 4',4" (5")-di-tert-butyldicyclohexyl-18-crown-6, 1-fluoro-tetrafluoroene, 1,4,7-triazacyclononane, 2-aminomethyl-15-crown-5, dicyclohexane-18-crown-6, 2-(hydroxymethyl)-15-crown-5-ether, dicyclohexane-24-crown-8, 2-hydroxymethyl-12-crown-4, poly(dibenzo-18-crown-6), 18-crown-6, 1,4,7-trimethyl-1,4,7-triazacyclononane, cyclohexane-18-crown-6, 1-aza-12-crown-4-ether, 1,5,9-triazacyclododecane, benzo-12-crown-4, 1-aza-15-crown-5-ether, 1-aza-18-crown-6-ether or several thereof are used in combination.

[0013] The formulation is selected from a suspension, a dispersible oil suspension, a dispersible oil, an emulsifiable concentrate, a microemulsion, an aqueous emulsion, a soluble concentrate, an ultra-low volume concentrate, a water-dispersible granule, a water-dispersible tablet, a dry suspension, a wettable powder, a soluble powder, a soluble granule, a soluble tablet or an emulsifiable powder.

[0014] When the composition is in the form of a suspension, the composition comprises, by weight, 0.1-90% active ingredient, 1-20% stabilizer, 0.1-40% wetting and dispersing agent, 0.1-10% thickening and rheological agent, 0.1-10% preservative, 1-15% antifreeze agent, 0.1-5% defoaming agent, and the remainder water;

[0015] When the composition is in the form of a dispersible oil suspension, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the thickening and rheological agent is 0.1-10%, and the rest is the medium.

[0016] When the composition is in the form of a dispersible oil formulation, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the solvent is 1-90%, the wetting and dispersing agent is 0.1-40%, and the rest is the medium.

[0017] When the composition is in the form of an emulsifiable concentrate, the active ingredient is 0.1-90% by weight, the stabilizer is 1-20% by weight, and the balance is the solvent;

[0018] When the composition is in the form of a microemulsion, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the solvent is 1-90%, the wetting and dispersing agent is 0.1-40%, and the remainder is water.

[0019] When the composition is in the form of an aqueous emulsion, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the solvent is 1-90%, the wetting and dispersing agent is 0.1-40%, and the remainder is water.

[0020] When the composition is in the form of a soluble liquid, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, and the balance is solvent or water.

[0021] When the composition is in the form of an ultra-low volume dosage form, the composition comprises, by weight, 0.1-90% active ingredient, 1-20% stabilizer, 1-90% solvent, and the remainder being a medium;

[0022] When the composition is in the form of water-dispersible granules, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest is a carrier or filler.

[0023] When the composition is in the form of a water-dispersible tablet, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest is a carrier or filler.

[0024] When the composition is in the form of a dry suspension, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest is a carrier or filler.

[0025] When the composition is in the form of a wettable powder, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest is a carrier.

[0026] When the composition is in the form of a soluble powder, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest is filler.

[0027] When the composition is in the form of a soluble granule, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest is filler.

[0028] When the composition is in the form of a soluble tablet, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest is filler.

[0029] When the composition is in the form of an emulsifiable powder, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the solvent is 1-90%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest is a carrier.

[0030] The wetting and dispersing agents in the above-mentioned preparations are selected from alkyl sulfates, lignin sulfonates, naphthalene sulfonates, polycarboxylates and the like.

[0031] The solvent is selected from xylene, solvent oil S-100, solvent oil S-150, solvent oil S-200, cyclohexanone, dimethyl sulfoxide, dimethylformamide, 1-methyl-2-pyrrolidone, octyl pyrrolidone, capramide, caprylamide, isophorone, methyl carbonate, methyl oleate, rosin oil, C2-C18 fatty acid methyl ester, methanol, isopropanol, n-butanol, polyethylene glycol, methylated vegetable oil, epoxidized soybean oil, rapeseed oil, cottonseed oil, turpentine, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, sec-butyl acetate, liquid paraffin, etc.

[0032] The thickening rheological agent is selected from sodium alginate, xanthan gum, modified xanthan gum, magnesium aluminum silicate, organic bentonite and white carbon black.

[0033] The antifreeze agent is selected from ethylene glycol, propylene glycol, glycerol, urea and complex phosphates.

[0034] The preservative is selected from sodium benzoate, kason, biological preservatives and the like.

[0035] The defoaming agent is selected from polysiloxanes, polyethers, polyether-modified silicones and higher alcohols.

[0036] The medium is selected from methyl oleate, rosin oil, C2-C18 fatty acid methyl ester, methylated vegetable oil, epoxidized soybean oil, rapeseed oil, cottonseed oil, turpentine, liquid paraffin, etc.

[0037] The carrier is selected from diatomaceous earth, kaolin, attapulgite, light calcium carbonate and the like.

[0038] The filler is selected from potassium chloride, potassium sulfate, ammonium sulfate, sodium sulfate and the like.

[0039] The water is distilled water.

[0040] The preparation product can be applied by manual spraying and aircraft spraying during use.

[0041] The advantages of the present invention are:

[0042] The bactericidal composition preparation of the present invention uses a combination of a stabilizer and an active ingredient in combination with the formula components. After undergoing a heat storage accelerated test (54°C, 14 days), the resulting preparation product can improve the automatic dispersibility of the sample in high-concentration hard water (hardness 1000ppm) (automatic dispersibility is higher than 95%), and improve the dilution stability and effective suspension rate (effective suspension rate is higher than 95%) under low dilution ratio (20-fold dilution) and high-hardness hard water conditions. DETAILED DESCRIPTION

[0043] The present invention will be further described below with reference to specific examples, but the invention is not limited to these specific embodiments. The present invention encompasses all possible alternatives, modifications, and equivalents within the scope of the claims. The original drugs and other materials in the examples are commercially available.

[0044] The active ingredient in each of the following examples is the compound described in Formula I, and the structural formula is as follows:

[0045]

[0046] Specific compounds:

[0047] R3 is selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R15, R16 or R17 are each selected from hydrogen, and W is selected from hydrogen, that is, compound A.

[0048] R3 is selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-trifluoromethyl, n=1, R14, R15, R16 or R17 are each selected from hydrogen, and W is selected from hydrogen, which is compound B;

[0049] R3 is selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R16, and R17 are each selected from hydrogen, R15=Br, and W is selected from hydrogen, which is compound C;

[0050] R3 is selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R15, and R17 are each selected from hydrogen, R16=NO2, and W is selected from hydrogen, which is compound D;

[0051] R3 is selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R15, R16 or R17 are each selected from hydrogen, and W is selected from chloro, i.e., compound E;

[0052] R3 is selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R16, and R17 are each selected from hydrogen, R15=chloro, and W is selected from hydrogen, which is compound F;

[0053] R3 is selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-chloro, n=1, R15, R16, and R17 are each selected from hydrogen, R14=chloro, and W is selected from hydrogen, i.e., compound G;

[0054] R3 is selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R16, and R17 are each selected from hydrogen, R15=methoxy, and W is selected from hydrogen, which is compound H;

[0055] R3 is selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R16, and R17 are each selected from hydrogen, R15=NO2, and W is selected from hydrogen, which is compound I;

[0056] R3 is selected from hydrogen, R4 and R5 are selected from hydrogen, R6 and R7 are selected from hydrogen, R8 and R9 are selected from hydrogen, R11 is selected from 4-chloro, n=1, R14 and R16 are selected from hydrogen, R15 and R17 are selected from chloro, and W is selected from hydrogen, that is, compound J.

[0057] The above specific compounds are reacted with concentrated hydrochloric acid in ethyl acetate under stirring at room temperature to form the hydrochloride, sulfate, phosphate, formate, acetate, trifluoroacetate, oxalate, methanesulfonate, p-toluenesulfonate, benzoate, phthalate, maleate, fumarate, sorbate, malate or citrate of the corresponding compound.

[0058] Experimental Methods: Samples were prepared according to the formulation ratios and process for each Example and Control Example, following conventional preparation procedures. Thermal storage stability testing was conducted according to the "Liquid Preparations," "Powder Preparations," and "Other Preparations" sections of GB / T 19136-2003. The samples were placed in a thermostat at (54±2)°C for 14 days. After 14 days of thermal storage, the active ingredient's self-dispersibility, the effective suspension rate of the test sample at 20-fold dilution and in 1000 ppm hard water, and its dilution stability were determined. All percentages in the formulations of the Examples are expressed by weight.

[0059] Automated Dispersion Test Method:

[0060] Equilibrate the test sample, high-hardness water (1000 ppm), graduated cylinder, and test sample to the desired temperature before testing. Determine the density of the test sample and calculate the mass (c) equivalent to 12.5 ml of sample. Pour 237.5 ml of high-hardness water into the graduated cylinder at the desired temperature. Place the cylinder on a balance and add the measured amount of preparation 1 cm above the top of the cylinder. Complete the addition within 15 seconds.

[0061] Immediately after adding the test sample, stopper the cylinder, invert it once, and allow it to rest in a place free of vibration and heat for 5 minutes ± 10 seconds. Carefully remove the stopper and aspirate the upper 225 ml of suspension within 10-15 seconds, ensuring that the tip of the tube is always 1 cm below the page to minimize disturbance of the suspension. Liquid chromatography is used to determine the mass (Q) of the active ingredient in the remaining 25 ± 1 ml of suspension in the cylinder, from which the autodispersibility of the test sample can be calculated.

[0062]

[0063] Test method for dilution stability and effective suspension rate under low dilution ratio (20 times dilution) and high hardness hard water conditions:

[0064] Dilution stability: Add 5 ml of the sample into a 100 ml graduated cylinder filled with 95 ml of high hardness water. With the middle of the cylinder as the axis, turn it upside down 30 times. Place it in a constant temperature water bath at 30°C for 24.0 hours and record the volume of floating oil / cream and sediment / precipitate.

[0065] Effective Suspension Rate: Increase the sample mass to 25 g (accurate to 0.0001 g), increase the hardness of the water to 1000 ppm, and proceed with the remaining steps according to GB / T 14825. Transfer the remaining 1 / 10 of the suspension and precipitate to a 50 mL volumetric flask. Wash the remaining 25 mL of the residue into the 50 mL volumetric flask with 20 mL of acetonitrile in three portions. Oscillate under ultrasonication for 5 minutes, return to room temperature, calibrate to volume, shake well, filter, and measure the mass to calculate the effective suspension rate.

[0066] Suspension Concentrate:

[0067] Process steps: The technical drug, stabilizer, additives and water are prepared in proportion, stirred and moistened thoroughly, and then coarsely ground and slurried using a high-shear dispersant. The slurry is then injected into a sand mill and sand-milled to a suitable particle size. The obtained sample is hot-stored for 14 days before testing.

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075] Dispersible oil suspension

[0076] Process steps: Prepare the technical, stabilizer, additive and medium in proportion, stir thoroughly and evenly, then use high shear dispersant to coarsely grind and slurry, then inject the slurry into the sand mill and grind to the appropriate particle size, and test after hot storage for 14 days.

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083] Dispersible oil:

[0084] Process steps: Prepare the technical drug, solvent, and medium in the correct proportions and stir until completely dissolved. Add the stabilizer and additives and continue stirring until completely transparent. Discard the product for later use. Store the sample in hot storage for 14 days before testing.

[0085]

[0086]

[0087]

[0088] Emulsion:

[0089] Process steps: Combine the technical drug, cosolvent, and solvent in the correct proportions and stir until completely dissolved. Add the stabilizer and cosolvent and continue stirring to dissolve until completely transparent. Discard the sample and store it in a hot container for 14 days. Test after expiration.

[0090]

[0091]

[0092]

[0093] Microemulsion:

[0094] Process steps: Mix the technical drug and solvent in the correct proportions and stir until completely dissolved. Add stabilizer and additives and continue stirring until completely transparent. Finally, inject distilled water in the correct proportions and stir until completely transparent before discharging. Store the sample in hot water for 14 days and test after expiration.

[0095]

[0096]

[0097]

[0098] Water emulsion:

[0099] Process steps: Mix the technical drug and solvent in the correct proportions and stir until completely transparent. Add stabilizers and additives and continue stirring until completely transparent. Finally, add distilled water in the correct proportions and use a high-shear emulsifier to shear until a uniform milky white product is discharged for later use. Samples are hot stored for 14 days and tested after expiration.

[0100]

[0101]

[0102]

[0103] Soluble solution:

[0104] Process steps: Mix the technical drug and solvent in the correct proportions and stir until completely dissolved. Add stabilizer and additives and continue stirring until completely transparent. Finally, top up with distilled water and continue stirring until completely transparent before discharging. Samples are stored hot for 14 days and tested after the expiration date.

[0105]

[0106]

[0107]

[0108] Ultra-low volume agent:

[0109] Process steps: Combine the technical drug and solvent in the correct proportions and stir until completely dissolved. Add the stabilizer and additives and continue stirring until completely transparent. Discard the sample and store it for later use. Store the sample in a hot storage tank for 14 days and then test it after the expiration date.

[0110]

[0111]

[0112]

[0113]

[0114] Water dispersible granules:

[0115] Thoroughly mix the technical, additive, stabilizer, and medium in the correct proportions. Grind the mixture using a jet mill / ultrafine grinder. Add water and knead the powder. Then, use a horizontal disc / twin-screw granulator for extrusion and granulation. Dry the resulting material for later use. Store the sample in hot water for 14 days and test it after expiration.

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122] Water-dispersible tablets:

[0123] The technical, auxiliary, stabilizer and medium are fully mixed in proportion, and then crushed by air flow / ultrafine grinding mill. The powder material is tableted by tablet press. The obtained material sample is hot stored for 14 days and tested after the expiration.

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130] Dry suspension:

[0131] After thoroughly mixing the technical, additive, and water, the mixture is dispersed and slurried using a high-shear disperser. The mixture is then sand-milled to a slurry of suitable viscosity and particle size. The slurry is then spray-dried to form solid particles. The resulting material is then hot-stored for 14 days and tested upon expiration.

[0132]

[0133]

[0134]

[0135]

[0136]

[0137] Wettable powder:

[0138] Prepare the technical, stabilizer, additive, and medium in the correct proportions. Mix thoroughly in a mixer, then crush using an airflow or ultrafine grinder. Store the resulting material in hot storage for 14 days and test after expiration.

[0139]

[0140]

[0141]

[0142]

[0143] Soluble powder:

[0144] Prepare the technical, stabilizer, additive, and medium in the correct proportions. Mix thoroughly in a mixer, then crush using an airflow or ultrafine grinder. Store the resulting material in hot storage for 14 days and test after expiration.

[0145]

[0146]

[0147]

[0148]

[0149] Soluble granules:

[0150] The technical, stabilizer, adjuvant, and medium are prepared in the correct proportions and thoroughly mixed in a mixer. The materials are then pulverized using an airflow or ultrafine grinder. The powder is then extruded into granules using a horizontal disc or screw extruder. After drying, the resulting material is heat-stored for 14 days and tested upon expiration.

[0151]

[0152]

[0153]

[0154]

[0155]

[0156] Emulsifiable powders:

[0157] The technical, stabilizer and part of the auxiliary agents are dissolved in a solvent and adsorbed by white carbon black. The obtained powder material is mixed with the remaining auxiliary agents and fillers. The mixed material is subjected to air flow or ultrafine grinding, and the indicators of the obtained material are tested after hot storage for 14 days.

[0158]

[0159]

[0160]

[0161] In summary, due to the structural properties of crown ether compounds, they can fully coat and anchor active ingredient particles or molecules to form more stable groups, thereby acting as stabilizers. Therefore, the stabilizer-containing composition formulation of the present invention exhibited significantly improved self-dispersibility, dilution stability, and suspension rate compared to a control formulation without stabilizer when tested in 1000 ppm hard water and diluted 20-fold.

Claims

1. A bactericidal composition preparation containing a stabilizer, characterized in that: The composition preparation is a suspension dosage form, By weight percentage, the following ingredients are: 10% compound A, 20% 2-(allyloxymethyl)-18-crown-6-ether, 2% white carbon black, 1% magnesium aluminum silicate, 0.2% xanthan gum, 0.2% kasonon, 5% alkyl vinyl aryl phenyl ether, 5% fatty alcohol polyoxyethylene ether, 3% high molecular weight benzenesulfonic acid sodium salt, 1% polysiloxane defoamer, 15% ethylene glycol, and distilled water to 100%; By weight percentage, the following ingredients are: 15% compound A, 15% 2,4-crown 8-ether, 3% white carbon black, 0.5% magnesium aluminum silicate, 0.15% xanthan gum, 0.15% kasonon, 5% lauryl alcohol polyoxyethylene ether carboxylate, 5% fatty alcohol polyoxyethylene ether, 3% methylnaphthalenesulfonic acid formaldehyde condensate, 10% propylene glycol, 5% higher alcohol defoamer, and distilled water to 100%; By weight percentage, the following ingredients: 20% compound B, 15% 4-nitrobenzene-18-crown-6, 3% white carbon black, 0.3% magnesium aluminum silicate, 0.15% modified xanthan gum, 0.15% sodium benzoate, 5% alkylphenol polyoxyethylene ether carboxylate, 5% alkyl vinyl aryl vinyl ether, 3% sodium salt of naphthalenesulfonic acid formaldehyde condensate, 3% glycerol, 1% polyether defoamer, and distilled water to 100%; By weight percentage, the following ingredients: 25% compound A, 10% 4-tert-butylcyclohexane-15-crown-5, 3% white carbon black, 2% organic bentonite, 0.1% modified xanthan gum, 0.1% biological preservative, 5% alkylphenol polyoxyethylene ether carboxylate, 5% nonionic methacrylate cosmetic copolymer, 3% benzylnaphthalenesulfonic acid formaldehyde condensate, 5% urea, 0.1% polyether modified silicone defoamer, and distilled water to 100%; By weight percentage, the following ingredients are: 30% compound C, 10% 4'-aminobenzo-18-crown ether-6, 3% white carbon black, 0.3% magnesium aluminum silicate, 0.1% xanthan gum, 0.1% biological preservative, 5% ethylene oxide propylene oxide block copolymer, 5% aryl polyoxyalkyl ether, 3% benzylnaphthalenesulfonic acid formaldehyde condensate, 1% composite phosphate, 0.5% polyether defoamer, and distilled water to 100%; By weight percentage, the following ingredients are: compound H 40%, benzoaza-15-crown-5 5%, white carbon black 2%, sodium alginate 0.2%, xanthan gum 0.1%, kason 0.1%, ethylene oxide propylene oxide block copolymer 5%, polyalkyl oxide 5%, sodium methylene bisnaphthalene sulfonate 3%, ethylene glycol 5%, polyether defoamer 1%, and distilled water to 100%; By weight percentage, the following ingredients are: compound D 50%, bis(1,4-phenylene)-3,4-crown-10-ether 5%, white carbon black 1%, sodium alginate 0.1%, xanthan gum 0.1%, kason 0.1%, fatty alcohol polyoxyethylene ether 3%, polyalkyl oxide 3%, sodium methylene bisnaphthalene sulfonate 2%, composite phosphate 1%, polyether modified silicon defoamer 1%, and distilled water to 100%; Compounds A, B, C, D, and H have the following structures: Formula I Compound A is selected from hydrogen, R4 and R5 are selected from hydrogen, R6 and R7 are selected from hydrogen, R8 and R9 are selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R15, R16 or R17 are selected from hydrogen, and W is selected from hydrogen; Compound B is selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-trifluoromethyl, n=1, R14, R15, R16 or R17 are each selected from hydrogen, and W is selected from hydrogen; Compound C is selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R16, and R17 are each selected from hydrogen, R15=Br, and W is selected from hydrogen; Compound D is selected from hydrogen, R4 and R5 are selected from hydrogen, R6 and R7 are selected from hydrogen, R8 and R9 are selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R15, R17 are selected from hydrogen, R16=NO2, and W is selected from hydrogen; Compound H is R3 selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R16, and R17 are each selected from hydrogen, R15=methoxy, and W is selected from hydrogen.

2. A bactericidal composition preparation containing a stabilizer, characterized in that: The composition preparation is a dispersible oil suspension formulation, By weight percentage, the compound G is 10%, 1,4,7-triazacyclononane is 20%, white carbon black is 4%, organic bentonite is 3%, aryl polyoxyalkyl ether is 15%, aryl ether phosphate is 15%, and methylated vegetable oil is made up to 100%; By weight percentage, the compound E is 20%, 4'-acetylbenzo-18-crown-6-ether is 15%, white carbon black is 4%, organic bentonite is 3%, nonylphenol polyoxyethylene ether carboxylate is 10%, fatty alcohol polyoxyethylene ether carboxylate is 10%, and methylated vegetable oil is made up to 100%; By weight percentage, compound F 30%, 1-fluorotetrafluoroene 10%, white carbon black 3%, organic bentonite 2%, fatty alcohol polyoxyethylene ether carboxylate 10%, aryl ether phosphate 10%, and methyl oleate to 100%; By weight percentage, compound F 40%, N,N'-dibenzyl-4,13-diaza-18-crown-6-ether 5%, white carbon black 3%, organic bentonite 1%, fatty alcohol polyoxyethylene ether carboxylate 8%, alkyl vinyl aryl vinyl ether 7%, and methyl oleate to 100%; By weight percentage, compound E 50%, 18-crown-5[4-(2,4-dinitrophenylazo)phenol] 3%, white carbon black 2%, organic bentonite 0.5%, sorbitan fatty acid ester 8%, polyoxyethylene sorbitan fatty acid ester 7%, and methyl oleate to 100%; Compound E is a compound of formula I according to claim 1, wherein R3 is selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R15, R16 or R17 are each selected from hydrogen, and W is selected from chloro; Compound F is a compound of formula I according to claim 1, wherein R3 is selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R16, and R17 are each selected from hydrogen, R15=chloro, and W is selected from hydrogen; Compound G is a compound of formula I according to claim 1, wherein R3 is selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-chloro, n=1, R15, R16, and R17 are each selected from hydrogen, R14=chloro, and W is selected from hydrogen.

3. A bactericidal composition preparation containing a stabilizer, characterized in that: The composition preparation is a dispersible oil formulation, By weight percentage, compound G 10%, ethylene glycol monobutyl ether 20%, 4'-acetylbenzo-18-crown-6-ether 20%, sorbitan fatty acid ester 8%, polyoxyethylene sorbitan fatty acid ester 7%, and methyl oleate are supplemented to 100%; By weight percentage, the following ingredients are compound D 20%, propylene glycol monomethyl ether 25%, 4', 4'' (5'')-di-tert-butyl dicyclohexyl-18-crown-6 15%, sorbitan fatty acid ester 8%, styryl polyoxyethylene ether 7%, and methyl oleate to make up to 100%; By weight percentage, the following ingredients are: 30% compound H, 30% sec-butyl acetate, 10% 4', 4'' (5'')-di-tert-butyldicyclohexyl-18-crown-6, 5% sorbitan fatty acid ester, 5% styryl polyoxyethylene ether, and liquid paraffin to 100%; Compound D is the compound D according to claim 1; Compound H is the compound H according to claim 1; Compound G is the compound G according to claim 2.

4. A bactericidal composition preparation containing a stabilizer, characterized in that: The composition preparation is in the form of an emulsifiable concentrate. By weight percentage, the compound C is 10%, sec-butyl acetate is 20%, 2-aminomethyl-15-crown-5 is 20%, polyoxyethylene-polyoxypropylene copolymer is 8%, fatty alcohol polyoxyethylene ether is 7%, and xylene is made up to 100%; By weight percentage, Compound I 20%, propylene glycol monomethyl ether 25%, dicyclohexanedio-18-crown ether 15%, polyoxyethylene-polyoxypropylene block copolymer 8%, alkylphenol polyoxyethylene ether 7%, and solvent oil S-100 to 100%; By weight percentage, 30% of compound B, 30% of sec-butyl acetate, 15% of 2-(hydroxymethyl)-15-crown 5-ether, 8% of styryl polyoxyethylene ether, 7% of alkylphenol polyoxyethylene ether, and solvent oil S-150 are added to 100%; Compound B is the compound B according to claim 1; Compound C is the compound C according to claim 1; Compound I is a compound of formula I according to claim 1, wherein R3 is selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R16, and R17 are each selected from hydrogen, R15=NO2, and W is selected from hydrogen.

5. A bactericidal composition preparation containing a stabilizer, characterized in that: The composition preparation is a microemulsion formulation, By weight percentage, compound J 10%, cyclohexanone 20%, dicyclohexanedio-2,4-crown ether 10%, styrene polyoxyethylene ether 25%, calcium dodecylbenzenesulfonate 5%, and distilled water to 100%; By weight percentage, compound A 20%, solvent oil S-200 30%, 2-hydroxymethyl-12-crown-4 10%, styrene polyoxyethylene ether 25%, calcium dodecylbenzenesulfonate 5%, and distilled water to 100%; By weight percentage, compound J 30%, n-butanol 30%, poly (dibenzo-18-crown-6) 3%, fatty alcohol polyoxyethylene ether 15%, calcium dodecylbenzenesulfonate 5%, and distilled water to 100%; Compound A is the compound A according to claim 1; Compound J is a compound of formula I according to claim 1, wherein R3 is selected from hydrogen, R4 and R5 are each selected from hydrogen, R6 and R7 are each selected from hydrogen, R8 and R9 are each selected from hydrogen, R11 is selected from 4-chloro, n=1, R14 and R16 are selected from hydrogen, R15 and R17 are selected from chloro, and W is selected from hydrogen.

6. A bactericidal composition preparation containing a stabilizer, characterized in that: The composition preparation is in the form of an aqueous emulsion, By weight percentage, compound A 10%, solvent oil S-200 20%, 18-crown ether-6 15%, alkyl vinyl aryl vinyl ether 25%, calcium dodecylbenzenesulfonate 5%, and distilled water to 100%; By weight percentage, the compound B is 20%, methyl carbonate is 20%, 1,4,7-trimethyl-1,4,7-triazacyclononane is 10%, polyoxyethylene lauryl ether carboxylate is 25%, calcium dodecylbenzenesulfonate is 5%, and distilled water is used to make up to 100%; By weight percentage, compound C 30%, cyclohexanone 30%, cyclohexane-18-crown-6 3%, aryl ether phosphate 15%, calcium dodecylbenzenesulfonate 5%, and distilled water to 100%; Compound A is the compound A according to claim 1; Compound B is the compound B according to claim 1; Compound C is the compound C according to claim 1.

7. A bactericidal composition preparation containing a stabilizer, characterized in that: The composition preparation is a soluble solution dosage form, By weight percentage, the compound D is 10%, dimethylformamide is 15%, 1-aza-12-crown-4-ether is 15%, alkyl vinyl aryl vinyl ether is 10%, lauryl alcohol polyoxyethylene ether carboxylate is 5%, and distilled water is made up to 100%; By weight percentage, the compound E is 20%, 1-methyl-2-pyrrolidone is 25%, 1,5,9-triazacyclododecane is 10%, dodecanol polyoxyethylene ether carboxylate is 10%, alkylphenol polyoxyethylene ether is 5%, and distilled water is made up to 100%; By weight percentage, compound F 30%, decylamide 30%, benzo-12-crown-4 3%, aryl ether phosphate 15%, calcium dodecylbenzenesulfonate 5%, and distilled water to 100%; Compound D is the compound D according to claim 1; Compound E is the compound E according to claim 2; Compound F is the compound F according to claim 2.

8. A bactericidal composition preparation containing a stabilizer, characterized in that: The composition preparation is an ultra-low volume preparation, By weight percentage, compound J 0.5%, sec-butyl acetate 1%, 2-aminomethyl-15-crown-5 1%, polyoxyethylene-polyoxypropylene copolymer 4%, fatty alcohol polyoxyethylene ether 6%, and rosin oil to 100%; By weight percentage, compound I 1%, propylene glycol monomethyl ether 2%, 1-aza-15-crown-5-ether 3%, polyalkyl oxide 5%, alkylphenol polyoxyethylene ether 5%, and fatty acid methyl ester are supplemented to 100%; By weight percentage, the compound H is 3%, sec-butyl acetate is 10%, 1-aza-15-crown-5-ether is 10%, styryl polyoxyethylene ether is 6%, alkylphenol polyoxyethylene ether is 4%, and rapeseed oil is made up to 100%; By weight percentage, compound G 5%, octyl pyrrolidone 10%, 1-aza-18-crown-6-ether 10%, styrene polyoxyethylene ether 6%, calcium dodecylbenzenesulfonate 4%, and cottonseed oil to 100%; Compound G is the compound G according to claim 2; Compound H is the compound H according to claim 1; Compound 1 is the compound 1 according to claim 4; Compound J is the compound J according to claim 5.

9. A bactericidal composition preparation containing a stabilizer, characterized in that: The composition preparation is in the form of water dispersible granules, By weight percentage, compound F 40%, 2,4-crown 8-ether 20%, sodium lauryl sulfate 5%, sodium lignin sulfonate 10%, naphthalenesulfonic acid formaldehyde condensate sodium salt 10%, and ammonium sulfate to 100%; By weight percentage, compound F 50%, 4-nitrobenzene-18-crown-6 15%, sodium dodecylbenzenesulfonate 5%, calcium ligninsulfonate 15%, sodium methylenebisnaphthalenesulfonate 5%, and potassium chloride to 100%; By weight percentage, the compound A is 60%, bis(1,4-phenylene)-3,4-crown-10-ether is 10%, sodium lauryl sulfate is 5%, polyoxyethylene lauryl ether carboxylate is 5%, methylnaphthalenesulfonic acid formaldehyde condensate is 10%, and sodium sulfate is made up to 100%; By weight percentage, compound B 70%, benzoaza-15-crown-5 5%, sodium lauryl sulfate 5%, nonylphenol polyoxyethylene ether carboxylate 5%, benzylnaphthalenesulfonic acid formaldehyde condensate 5%, and sodium sulfate to 100%; By weight percentage, the compound C is 80%, 1-fluorotetrafluoroene is 1%, sodium lauryl sulfate is 3%, polyalkyl oxide is 5%, benzylnaphthalenesulfonic acid formaldehyde condensate is 5%, and sodium sulfate is made up to 100%; By weight percentage, compound E 90%, benzo-12-crown-4 1%, sodium lauryl sulfate 1%, and benzylnaphthalenesulfonic acid formaldehyde condensate are supplemented to 100%; Compound A is the compound A according to claim 1; Compound B is the compound B according to claim 1; Compound C is the compound C according to claim 1; Compound E is the compound E according to claim 2; Compound F is the compound F according to claim 2.

10. A bactericidal composition preparation containing a stabilizer, characterized in that: The composition preparation is in the form of a water-dispersible tablet, By weight percentage, compound G 40%, 4'-aminobenzo-18-crown ether-6 10%, white carbon black 10%, talc 5%, sodium lauryl sulfate 3%, naphthalenesulfonic acid formaldehyde condensate sodium salt 10%, and ammonium sulfate to 100%; By weight percentage, compound J 50%; 4'-acetylbenzo-18-crown-6-ether 10%, white carbon black 10%, talc 5%, sodium lauryl sulfate 3%, sodium lignin sulfonate 10%, potassium chloride to 100%; By weight percentage, compound H 60%, 1,4,7-triazacyclononane 5%, white carbon black 10%, talc 5%, sodium dodecylbenzenesulfonate 3%, calcium ligninsulfonate 10%, and sodium sulfate to 100%; By weight percentage, the compound E is 70%, 1,4,7-triazacyclononane is 5%, white carbon black is 5%, talc is 3%, sodium dodecylbenzenesulfonate is 1%, and methylnaphthalenesulfonic acid formaldehyde condensate is made up to 100%; By weight percentage, the following components are compound I 80%, 2-aminomethyl-15-crown-5 1%, white carbon black 3%, talc 3%, sodium dodecylbenzenesulfonate 1%, and methylnaphthalenesulfonic acid formaldehyde condensate to 100%; By weight percentage, compound A 90%, dicyclohexanedio-18-crown ether 1%, white carbon black 1%, talc 1%, sodium dodecylbenzenesulfonate 1%, and methylnaphthalenesulfonic acid formaldehyde condensate are supplemented to 100%; Compound A is the compound A according to claim 1; Compound E is the compound E according to claim 2; Compound G is the compound G according to claim 2; Compound H is the compound H according to claim 1; Compound 1 is the compound 1 according to claim 4; Compound J is the compound J according to claim 5.

11. A bactericidal composition preparation containing a stabilizer, characterized in that: The composition preparation is a dry suspension dosage form, By weight percentage, compound C 50%, dicyclohexanedio-2,4-crown ether-8 10%, sodium lauryl sulfate 3%, sodium methylene bisnaphthalene sulfonate 10%, sodium lignin sulfonate 10%, and kaolin to 100%; By weight percentage, compound F 60%, 2-hydroxymethyl-12-crown-4 5%, sodium lauryl sulfate 2%, benzylnaphthalenesulfonic acid formaldehyde condensate 10%, sodium lignin sulfonate 10%, and diatomaceous earth to 100%; By weight percentage, compound H 70%, 2-hydroxymethyl-12-crown-4 5%, sodium lauryl sulfate 3%, benzylnaphthalenesulfonic acid formaldehyde condensate 5%, and sodium lignin sulfonate to 100%; By weight percentage, compound D 80%, 2-(allyloxymethyl)-18-crown-6-ether 3%, sodium lauryl sulfate 3%, benzylnaphthalenesulfonic acid formaldehyde condensate 5%, and sodium lignin sulfonate to 100%; By weight percentage, compound J 90%, 2-(allyloxymethyl)-18-crown-6-ether 1%, sodium lauryl sulfate 1%, and sodium lignin sulfonate are added to 100%; Compound C is the compound C according to claim 1; Compound D is the compound D according to claim 1; Compound F is the compound F according to claim 2; Compound H is the compound H according to claim 1; Compound J is the compound J according to claim 5.

12. A bactericidal composition preparation containing a stabilizer, characterized in that: The composition preparation is a wettable powder formulation, By weight percentage, compound B 20%, 18-crown-5[4-(2,4-dinitrophenylazo)phenol] 10%, white carbon black 10%, sodium lauryl sulfate 2%, benzylnaphthalenesulfonic acid formaldehyde condensate 10%, calcium lignin sulfonate 10%, and diatomaceous earth to 100%; By weight percentage, compound E 40%, 18-crown-5[4-(2,4-dinitrobenzeneazo)phenol] 10%, white carbon black 10%, sodium lauryl sulfate 2%, benzylnaphthalenesulfonic acid formaldehyde condensate 10%, sodium lignin sulfonate 10%, and light calcium carbonate supplemented to 100%; By weight percentage, compound G 60%, 18-crown-5[4-(2,4-dinitrophenylazo)phenol] 5%, white carbon black 5%, sodium lauryl sulfate 2%, naphthalenesulfonic acid formaldehyde condensate sodium salt 10%, sodium lignin sulfonate 10%, and attapulgite to 100%; By weight percentage, compound I 80%, 18-crown-5[4-(2,4-dinitrophenylazo)phenol] 5%, white carbon black 5%, sodium lauryl sulfate 1%, and naphthalenesulfonic acid formaldehyde condensate sodium salt are supplemented to 100%; Compound B is the compound B according to claim 1; Compound E is the compound E according to claim 2; Compound G is the compound G according to claim 2; Compound 1 is the compound 1 according to claim 4.

13. A bactericidal composition preparation containing a stabilizer, characterized in that: The composition preparation is in the form of a soluble powder, By weight percentage, the hydrochloride of compound A is 20%, N,N'-dibenzyl-4,13-diaza-18-crown-6-ether is 20%, sodium lauryl sulfate is 2%, benzylnaphthalenesulfonic acid formaldehyde condensate is 10%, sodium lignin sulfonate is 10%, and potassium sulfate is added to 100%; By weight percentage, the following ingredients are: Compound B hydrochloride 40%, 4-tert-butylcyclohexane-15-crown-5 20%, sodium lauryl sulfate 2%, methylnaphthalenesulfonic acid formaldehyde condensate sodium salt 10%, sodium ligninsulfonate 10%, and potassium sulfate to 100%; By weight percentage, the following ingredients are: Compound C hydrochloride 60%, 4', 4'' (5'')-di-tert-butyldicyclohexyl-18-crown-6 10%, sodium lauryl sulfate 1%, methylnaphthalenesulfonic acid formaldehyde condensate sodium salt 5%, sodium ligninsulfonate 10%, and potassium sulfate to 100%; By weight percentage, the following components are compound G hydrochloride 80%, poly(dibenzo-18-crown-6) 1%, sodium lauryl sulfate 1%, sodium salt of methylnaphthalenesulfonic acid formaldehyde condensate 5%, sodium ligninsulfonate 5%, and potassium sulfate to 100%; Compound A is the compound A according to claim 1; Compound B is the compound B according to claim 1; Compound C is the compound C according to claim 1; Compound G is the compound G according to claim 2.

14. A bactericidal composition preparation containing a stabilizer, characterized in that: The composition preparation is in the form of soluble granules, By weight percentage, compound E sulfate 20%, 18-crown ether-6 20%, sodium lauryl sulfate 1%, sodium methylene bisnaphthalene sulfonate 10%, sodium lignin sulfonate 10%, and ammonium sulfate to 100%; By weight percentage, compound D sulfate 40%, 1,4,7-trimethyl-1,4,7-triazacyclononane 10%, sodium lauryl sulfate 1%, methylnaphthalenesulfonic acid formaldehyde condensate 10%, sodium ligninsulfonate 10%, and potassium sulfate to 100%; By weight percentage, compound E sulfate 60%, cyclohexane-18-crown-6 3%, sodium lauryl sulfate 1%, benzylnaphthalenesulfonic acid formaldehyde condensate 10%, sodium lignin sulfonate 10%, potassium chloride to 100%; By weight percentage, the composition comprises 80% compound F sulfate, 1% 1-aza-12-crown-4-ether, 1% sodium lauryl sulfate, 5% benzylnaphthalenesulfonic acid formaldehyde condensate, and sodium ligninsulfonate to 100%; Compound D is the compound D according to claim 1; Compound E is the compound E according to claim 2; Compound F is the compound F according to claim 2.

15. A bactericidal composition preparation containing a stabilizer, characterized in that: The composition preparation is an emulsifiable powder dosage form, By weight percentage, the following ingredients are compound H 10%, 1,5,9-triazacyclododecane 10%, 1-methyl-2-pyrrolidone 8%, solvent oil S-150 5%, white carbon black 10%, sodium lauryl sulfate 1%, benzylnaphthalenesulfonic acid formaldehyde condensate 5%, sodium lignin sulfonate 10%, and kaolin to 100%; By weight percentage, the compound B is 20%, 1-aza-18-crown-6-ether is 10%, decylamide is 10%, cyclohexanone is 5%, white carbon is 15%, sodium lauryl sulfate is 1%, benzylnaphthalenesulfonic acid formaldehyde condensate is 5%, sodium ligninsulfonate is 10%, and diatomaceous earth is made up to 100%; Compound B is the compound B according to claim 1; Compound H is the compound H according to claim 1.

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