Sterilizing liquid based on cuprous hydroxide as well as preparation method and use method of sterilizing liquid

Abstract

The invention relates to a sterilization liquid agent based on cuprous hydroxide, and also relates to a preparation method and a use method thereof, the suspension of cuprous hydroxide is used as the sterilization liquid agent, and diseases caused by various oomycetes, fungi and / or bacteria can be effectively prevented and treated; wherein the turbid liquid of cuprous hydroxide is obtained by stirring a cuprous chloride coordination compound in a solution state and decomposing the cuprous chloride coordination compound in water. According to the sterilization liquid, the single-time copper dosage is far lower than that of an existing copper ion sterilization agent, and meanwhile the prevention and treatment range of diseases is wider. Therefore, the risk of excessive heavy metal residue caused by the existing copper preparation is solved, and the problem that multiple bactericides need to be used at the same time for preventing and treating one or more diseases is also avoided. The bactericidal liquid provided by the invention has important significance for preventing and treating plant diseases, and has huge application potential in the agricultural market.

Description

[0001] This application is a divisional application of application number 202411873900.7, filed on December 18, 2024, entitled "A bactericidal liquid agent based on cuprous hydroxide and its preparation and use methods". Technical Field

[0002] This invention relates to the field of plant disease control technology, and particularly to a cuprous hydroxide-based fungicide, which is a cuprous hydroxide suspension. The invention also relates to methods for preparing and using the cuprous hydroxide-based fungicide. Background Technology

[0003] Copper is an essential micronutrient for plants. Copper ions protect plants from pathogens and enhance their resistance to diseases. Currently, copper-based antimicrobial compounds (CBACs), including Bordeaux mixture, rank sixth in global fungicide sales. Due to their advantages such as low processing cost, low toxicity, high stability, and long-lasting residue on leaves, many copper-based compounds are used to control plant diseases caused by bacteria, fungi, and oomycetes, such as Cu2(OH)3Cl, Cu2O, Cu(OH)2, CuSO4, and Cu(OH)2. However, these copper-based compounds typically require large doses to achieve good control. Furthermore, the extensive use of copper preparations has led to soil, surface water, and groundwater pollution, and poses safety risks due to copper entering the food chain. Therefore, it is necessary to optimize the selection of copper preparations to reduce the amount of copper used.

[0004] Plant diseases are numerous and varied, and corresponding fungicides are generally considered for major diseases. However, currently used fungicides, including copper-based fungicides, typically have limited coverage. In most cases, agricultural production commonly uses two or more fungicides to control single or mixed diseases. This simultaneous use of multiple fungicides not only increases costs but also introduces pesticide residues and environmental risks.

[0005] If a method can be found to effectively control multiple major diseases simultaneously, and the annual copper usage per acre can be kept within the organic cultivation standard (400 grams), then not only can the risk of excessive copper use be avoided, but the application plan can also be simplified, and the problem of excessive fungicide usage can be solved.

[0006] Furthermore, monovalent and divalent copper are two common valence states of copper, and their chemical properties and applications differ significantly. Cuprous ions are readily oxidized to divalent copper in the presence of water, and can also spontaneously disproportionate in acidic solutions to form Cu. 2+Copper ions are divalent (Cu) and copper hydroxide (Cu); however, divalent copper ions are relatively stable in the presence of water. Common bactericides are divalent copper; monovalent inorganic copper bactericides, particularly cuprous oxide (which is stable in aqueous environments), are only used in production. There are no reports of cuprous hydroxide being used for bactericidal purposes, and it is not used as a bactericide in production. Furthermore, cuprous hydroxide is chemically very unstable and readily oxidizes to Cu at room temperature. 2+ It will also decompose into Cu2O on its own, making long-term storage difficult. Therefore, there are no commercially available bactericides based on cuprous hydroxide. Summary of the Invention

[0007] In view of this, the present invention provides a cuprous hydroxide-based bactericide liquid that can form a relatively stable, suspended cuprous hydroxide, thereby effectively preventing and controlling plant diseases.

[0008] The first aspect of this invention discloses a cuprous hydroxide-based bactericidal liquid, which is a suspension of cuprous hydroxide for the prevention and control of oomycete, fungal, and / or bacterial diseases; wherein the cuprous hydroxide suspension is obtained by decomposing and hydrolyzing a cuprous chloride coordination compound in solution through continuous stirring in water. The term "cuprous hydroxide suspension" refers to a suspension in which the formed cuprous hydroxide is opaque, yellow, or orange.

[0009] Furthermore, the cuprous hydroxide suspension of the present invention can be understood relatively by referring to the precipitation state of cuprous hydroxide: cuprous hydroxide is not easily soluble in water and will form a cuprous hydroxide precipitate in water. The cuprous hydroxide suspension of the present invention refers to the suspension state of cuprous hydroxide in water before precipitation, which can be dispersed in water for a certain period of time (up to 8 hours), presenting a relatively stable suspension state. The present invention utilizes the aforementioned relatively stable suspension state of cuprous hydroxide for a certain period of time as a bactericidal liquid agent to control oomycetes, fungi, and / or bacterial diseases.

[0010] In the conventional R&D path of pesticides and / or pesticide adjuvants, researchers typically consider the long-term stability of the final pesticide and / or pesticide adjuvant. Based on this, considering the instability of cuprous hydroxide, those skilled in the art would not conceive of using cuprous hydroxide directly as a fungicide liquid. However, in this invention, the applicant has creatively developed suspended cuprous hydroxide into a fungicide liquid, thereby fully utilizing the fungicidal effect of cuprous hydroxide to control a variety of diseases. This not only broadens the scope of disease control but also solves the risk of excessive heavy metal residues caused by the need for large doses of inorganic copper fungicides, while avoiding the problem in existing technologies where multiple fungicides must be used simultaneously to control one or more diseases.

[0011] In other words, this invention provides a technical approach to replace existing fungicides, namely, using cuprous hydroxide suspension as a fungicide, which is of great significance for the prevention and control of plant diseases and has great potential for application in agricultural production.

[0012] Moreover, quite unexpectedly, unlike the conventional practice of diluting pesticides by adding water before spraying, this invention takes the opposite approach. Specifically, a cuprous chloride coordination compound in solution is added dropwise to water, with continuous stirring during and / or after the addition. During this process, the cuprous chloride coordination compound first forms a cuprous chloride suspension in the water. Through the addition of the cuprous chloride coordination compound to the water and the continuous stirring of the mixture for a period afterward, the cuprous chloride further hydrolyzes in the water before precipitation, thereby generating a cuprous hydroxide suspension. In other words, this invention constructs a disease control strategy based on the generation of a cuprous hydroxide suspension from a stable cuprous chloride coordination compound, and then using this cuprous hydroxide suspension for disease control. Because cuprous chloride coordination compounds have high stability, cuprous chloride can exist in a stable state before forming a cuprous hydroxide suspension. This ensures the certainty that a cuprous hydroxide suspension will eventually form, thus ensuring the certainty of the disease control results based on cuprous hydroxide.

[0013] It is also important to emphasize that cuprous halides formed with other halogens in the same group as chlorine are typically used as cuprous halide fluorescent materials in industrial applications due to their advantages such as tunable luminescence, structural diversity, and high photoluminescence quantum yield after hybridization. In the agricultural field, there are no existing schemes for using cuprous hydroxide suspensions, generated from cuprous halide coordination compounds, as fungicides, nor are there any schemes for using cuprous hydroxide suspensions, generated from specific cuprous chloride coordination compounds, as fungicides.

[0014] As mentioned earlier, in this invention, the cuprous chloride coordination compound is in solution form; that is, the cuprous hydroxide suspension is obtained by adding the cuprous chloride coordination compound in solution to water and stirring. The specific formation process can be described as follows: the cuprous chloride coordination compound first forms a cuprous chloride-based suspension in water, and then the cuprous chloride further hydrolyzes in water to form a cuprous hydroxide suspension. Stirring is to improve the stability of the cuprous hydroxide suspension and prevent excessively high local concentrations of cuprous chloride, which could lead to the formation of coarse particles and affect the stability of the cuprous hydroxide particles generated by further hydrolysis in water. The stirring method can be selected according to actual needs; manual stirring or machine stirring can be used, as long as the cuprous hydroxide suspension is yellow or orange.

[0015] According to the cuprous hydroxide-based bactericidal liquid agent disclosed in the first aspect of the present invention, the solution state of the cuprous chloride coordination compound can be obtained by dissolving the cuprous chloride coordination compound in a solvent; preferably, the solvent can be one or more of glycerol, ethylene glycol, dimethyl sulfoxide, dimethylacetamide or polyethylene glycol.

[0016] Furthermore, the general formula of the cuprous chloride coordination compound is:

[0017] X[CuCl2] or X[Cu2Cl3Y];

[0018] Wherein, X is one or more ions, preferably sodium ions or ammonium ions; Y is a solvent capable of providing coordination bonds, preferably dimethyl sulfoxide, dimethylacetamide, or polyethylene glycol. In cuprous chloride coordination compounds, the ratio of cuprous ions to chloride ions is 1:(1.5~2).

[0019] In this invention, the cuprous chloride coordination compound can be synthesized using existing coordination compound synthesis methods. It can also be synthesized via the following route: mixing copper chloride or basic copper chloride with a suitable solvent, adding a reducing agent, neutralizing the resulting acid with a base, and using the generated chloride ions as ligands; any deficiency is supplemented in the form of hydrochloride. Specifically, copper chloride is mixed with a solvent, then a reducing agent, such as a hydrazine-based reducing agent, is added dropwise to reduce divalent copper to cuprous chloride, and the resulting acid is neutralized with a base to promote complete reaction, i.e.:

[0020] CuCl2+H+NaOH→Na[CuCl2]+H2O.

[0021] Alternatively, it can be obtained by reduction of basic copper chloride, i.e.:

[0022] 2Cu2(OH)3Cl+NH2NH2·2HCl+4NH4Cl→4[CuCl2]+6H2O+N2↑

[0023] 2Cu2(OH)3Cl + NH2NH2·2HCl + 2NH4Cl + 2Y → 2NH4[Cu2Cl3Y] + 6H2O + N2↑ (where Y is a solvent capable of forming coordinate bonds, such as dimethyl sulfoxide, dimethylacetamide, or polyethylene glycol).

[0024] According to the cuprous hydroxide-based fungicide disclosed in the first aspect of the present invention, the cuprous hydroxide suspension contains copper at a concentration of 10-160 mg / L, for example, the copper concentration can be any value between 10 and 160 in mg / L, including the values ​​10 and 160; preferably 80-100 mg / L, that is, preferably, the copper concentration can be any value between 80 and 100 in mg / L, including the values ​​80 and 100. At these dosages, it can replace existing field fungicides for the control of one or more oomycete, fungal, and / or bacterial diseases. Specifically, based on an average spray volume of 150 kg / acre and an average application concentration of 90 mg / L, as long as the number of applications per year is within 29, the organic production standard of less than 400 grams of copper per acre per year can be met.

[0025] According to the cuprous hydroxide-based bactericidal liquid disclosed in the first aspect of the present invention, the bactericidal liquid further includes a surfactant, preferably a polyether-modified trisiloxane surfactant, mixed into the cuprous hydroxide suspension. By mixing a polyether-modified trisiloxane surfactant into the cuprous hydroxide suspension, the stability of the suspension can be further enhanced, while improving the wettability and spreadability of the suspension. In addition, the efficacy of the bactericidal liquid of the present invention in terms of bactericidal function can be further improved.

[0026] In other words, the bactericidal liquid of the present invention can be used alone in the form of a cuprous hydroxide suspension for sterilization, or it can be used in combination with other substances with bactericidal effects, for example, by mixing polyether-modified trisiloxane surfactants into the cuprous hydroxide suspension to form the final bactericidal liquid.

[0027] The second aspect of the present invention also discloses a method for preparing a bactericidal liquid agent based on cuprous hydroxide, comprising the following steps: S1, adding a cuprous chloride coordination compound in solution to water under continuous stirring, so that the cuprous chloride coordination compound forms a cuprous hydroxide suspension in the water.

[0028] Specifically, the pre-prepared cuprous chloride coordination compound in solution is added to purified water, preferably by slow addition to continuously stirred water. This promotes the hydrolysis of cuprous chloride, formed after the decomposition of the cuprous chloride coordination compound, into cuprous hydroxide before precipitation, thus ultimately forming a relatively stable cuprous hydroxide suspension. Preferably, the amount of water used is at least 50% of the total volume of the final suspension. According to the preparation method disclosed in the second aspect of the present invention, in step S1, the cuprous chloride coordination compound in solution is added to water and stirred so that the copper content in the final cuprous hydroxide suspension is 10-160 mg / L (preferably 80-100 mg / L). At this dosage, it can replace existing field fungicides for the control of one or more oomycete, fungal, and / or bacterial diseases.

[0029] According to the preparation method disclosed in the second aspect of the present invention, the general formula of the cuprous chloride coordination compound is:

[0030] X[CuCl2] or X[Cu2Cl3Y];

[0031] Wherein, X is one or more ions, preferably sodium ions or ammonium ions; Y is a solvent capable of providing coordination bonds, preferably dimethyl sulfoxide, dimethylacetamide or polyethylene glycol.

[0032] According to the preparation method disclosed in the second aspect of the present invention, the method further includes step S2, in which a surfactant, preferably a polyether-modified trisiloxane surfactant, is added to the cuprous hydroxide suspension formed in step S1 to form a surfactant-containing bactericide. That is, after step S1 is completed, a pre-diluted polyether-modified trisiloxane surfactant is added to the formed suspension, which further enhances the stability of the suspension and improves its wetting and spreading properties. The polyether-modified trisiloxane surfactant can be a commercially available agricultural adjuvant, such as a citrus-based product.

[0033] According to the preparation method disclosed in the second aspect of the present invention, the preparation is carried out before the bactericidal spray and used within T hours after the formation of the cuprous hydroxide suspension, wherein T≤8. That is, in the present invention, the bactericidal agent is a freshly prepared suspension, specifically prepared just before use, and needs to be used within T hours after the formation of the cuprous hydroxide suspension, i.e., at the latest within T hours (T≤8) after preparation. Specifically, it is used as a bactericidal agent before the suspension forms a precipitate within T hours (T≤8), and has a very good bactericidal effect.

[0034] The third aspect of this invention discloses a method for using a fungicide liquid. Note that when applying it in the field, before spraying the fungicide, the fungicide liquid is prepared according to the preparation method disclosed in the second aspect of this invention, and sprayed onto the target plants within T hours, wherein T≤8.

[0035] Beneficial Effects: This innovative cuprous hydroxide suspension fungicide can effectively control various diseases caused by oomycetes, fungi, and / or bacteria, replacing existing fungicides. Furthermore, it achieves a wider range of disease control while requiring significantly lower copper dosages per application compared to existing inorganic copper fungicides. This not only solves the risk of excessive heavy metal residues caused by the high-dose use of existing inorganic copper fungicides but also avoids the problem of needing to use multiple fungicides simultaneously to control one or more diseases. This fungicide is of great significance for plant disease control and has enormous application potential in the agricultural market.

[0036] The following detailed embodiments disclose the cuprous hydroxide-based bactericidal liquid agent of the present invention, its preparation method, and its usage method. Attached Figure Description

[0037] Figure 1 The changes in the static state of the suspension sample prepared based on the preparation method of the present invention are shown in the static test. Detailed Implementation

[0038] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. It should be noted that the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0039] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other.

[0040] This invention first discloses a cuprous hydroxide-based bactericidal liquid agent, which is a cuprous hydroxide suspension, used to control oomycete, fungal, and / or bacterial diseases; wherein the cuprous hydroxide suspension is obtained by decomposing (hydrolyzing) a cuprous chloride coordination compound in solution in water with continuous stirring. The term "cuprous hydroxide suspension" refers to a suspension in which the formed cuprous hydroxide is opaque, yellow, or orange.

[0041] Specifically, the cuprous chloride coordination compound in solution first decomposes in water to form a cuprous chloride suspension. By adding the cuprous chloride coordination compound to the water and continuously stirring the mixture for a period of time after addition, the cuprous chloride further generates a cuprous hydroxide suspension based on the hydrolysis of cuprous chloride in water before forming coarser particles. That is, in a specific embodiment of the invention, the cuprous chloride coordination compound used to form the cuprous hydroxide suspension in water is in solution, and the cuprous hydroxide suspension is obtained by adding the solution-state cuprous chloride coordination compound to water and stirring. In a preferred embodiment, the water is specifically tap water or well water taken from a field well.

[0042] In one specific embodiment, the solution state of the cuprous chloride coordination compound can be obtained by dissolving the cuprous chloride coordination compound in a solvent; wherein the preferred solvent is one or more of glycerol, ethylene glycol, dimethyl sulfoxide, dimethylacetamide or polyethylene glycol.

[0043] In one specific embodiment, the general formula of the cuprous chloride coordination compound is:

[0044] X[CuCl2] or X[Cu2Cl3Y];

[0045] Wherein, X is one or more ions, preferably sodium ions or ammonium ions; Y is a solvent capable of providing coordination bonds, preferably dimethyl sulfoxide, dimethylacetamide, or polyethylene glycol. Preferably, in the cuprous chloride coordination compound, the ratio of cuprous ions to chloride ions is 1:(1.5~2).

[0046] In this invention, the coordination compound of cuprous chloride can be synthesized using existing coordination compound synthesis methods. It can also be synthesized via the following route: mixing copper chloride or basic copper chloride with a suitable solvent, adding a reducing agent, neutralizing the resulting acid with a base, and using the generated chloride ions as ligands; any deficiency is supplemented in the form of hydrochloride. Specifically, copper chloride is mixed with a solvent, then a reducing agent, such as a hydrazine-based reducing agent, is added dropwise to reduce divalent copper to cuprous chloride, and the resulting acid is neutralized with a base to promote complete reaction, i.e.:

[0047] CuCl2+H+NaOH→Na[CuCl2]+H2O.

[0048] Alternatively, it can be obtained by reduction of basic copper chloride, i.e.:

[0049] 2Cu2(OH)3Cl+NH2NH2·2HCl+4NH4Cl→4[CuCl2]+6H2O+N2↑;

[0050] 2Cu2(OH)3Cl + NH2NH2·2HCl + 2NH4Cl + 2Y → 2[Cu2Cl3Y] + 6H2O + N2↑. Here, Y is a solvent capable of forming coordinate bonds, such as dimethyl sulfoxide, dimethylacetamide, or polyethylene glycol.

[0051] In one specific embodiment, the copper content in the cuprous hydroxide suspension is 10-160 mg / L, preferably 80-100 mg / L. That is, preferably, the copper content can be any value between 80 and 100 in mg / L, including the values ​​80 and 100. At this dosage, it can replace existing field-used fungicides for the control of one or more oomycete, fungal, and / or bacterial diseases. Specifically, based on an average spray volume of 150 kg / acre and an average application concentration of 90 mg / L, as long as the number of applications per year is within 29, the organic production standard of less than 400 grams of copper per acre per year can be met.

[0052] In one specific embodiment, the bactericidal liquid agent further includes a surfactant, preferably a polyether-modified trisiloxane surfactant, mixed into the cuprous hydroxide suspension. By mixing a polyether-modified trisiloxane surfactant into the cuprous hydroxide suspension, the stability of the suspension can be further enhanced, while improving the wettability and spreadability of the suspension.

[0053] The present invention also discloses a method for preparing a cuprous hydroxide-based bactericidal liquid, comprising the following steps: S1, adding a cuprous chloride coordination compound in solution to water under continuous stirring, and stirring continuously to form a cuprous hydroxide suspension in the water.

[0054] Specifically, the pre-prepared cuprous chloride coordination compound in solution is added to distilled water, preferably by slow addition to continuously stirred water, so that the cuprous chloride is hydrolyzed to cuprous hydroxide before a coarse precipitate forms, thus ultimately forming a relatively stable cuprous hydroxide suspension. The amount of water used is preferably more than 50% of the total volume of the final suspension.

[0055] In a specific embodiment of the preparation method of the present invention, in step S1, the cuprous chloride coordination compound in solution is added to water and stirred so that the copper content in the final cuprous hydroxide suspension is 10-160 mg / L (preferably 80-100 mg / L). At this dosage, it can replace existing field fungicides for the control of one or more oomycete, fungal, and / or bacterial diseases.

[0056] In a specific embodiment of the preparation method of the present invention, the general formula of the cuprous chloride coordination compound is:

[0057] X[CuCl2] or X[Cu2Cl3Y];

[0058] Wherein, X is one or more ions, preferably sodium ions or ammonium ions; Y is a solvent capable of providing coordination bonds, preferably dimethyl sulfoxide, dimethylacetamide or polyethylene glycol.

[0059] In one specific embodiment of the preparation method of the present invention, the solution state of the cuprous chloride coordination compound is obtained by dissolving the cuprous chloride coordination compound in a solvent. Preferably, the solvent is one or more of glycerol, ethylene glycol, dimethyl sulfoxide, dimethylacetamide, or polyethylene glycol.

[0060] In a specific embodiment of the preparation method of the present invention, the cuprous chloride coordination compound can be synthesized by existing coordination compound synthesis methods. It can also be synthesized via the following route: mixing copper chloride or basic copper chloride with a suitable solvent, adding a reducing agent, neutralizing the resulting acid with a base, and using the generated chloride ions as ligands; any deficiency can be supplemented in the form of hydrochloride. Specifically, copper chloride is mixed with a solvent, then a reducing agent, such as a hydrazine-based reducing agent, is added dropwise to reduce divalent copper to cuprous chloride, and the resulting acid is neutralized with a base to promote complete reaction, i.e.:

[0061] CuCl2+H+NaOH→Na[CuCl2]+H2O.

[0062] Alternatively, it can be obtained by reduction of basic copper chloride, i.e.:

[0063] 2Cu2(OH)3Cl+NH2NH2·2HCl+4NH4Cl→4[CuCl2]+6H2O+N2↑

[0064] 2Cu2(OH)3Cl + NH2NH2·2HCl + 2NH4Cl + 2Y → 2[Cu2Cl3Y] + 6H2O + N2↑ (where Y is a solvent capable of forming coordinate bonds, such as dimethyl sulfoxide, dimethylacetamide, or polyethylene glycol).

[0065] In a specific embodiment of the preparation method of the present invention, step S2 is further included, in which a surfactant, preferably a polyether-modified trisiloxane surfactant, is added to the cuprous hydroxide suspension formed in step S1 to form a bactericide containing a polyether-modified trisiloxane surfactant. That is, after step S1 is completed, a pre-diluted polyether-modified trisiloxane surfactant is added to the formed suspension, which can further enhance the stability of the suspension and improve its wetting and spreading properties. The polyether-modified trisiloxane surfactant can be a commercially available agricultural adjuvant, such as the currently marketed citrus-type agricultural adjuvant product.

[0066] In a specific embodiment of the preparation method of the present invention, steps S1 to S2 are carried out in field operations before fungicide spraying and are used within 8 hours after the formation of the cuprous hydroxide suspension. That is, in the present invention, the fungicide is a freshly prepared suspension, specifically prepared just before use, and must be used within 8 hours after the formation of the cuprous hydroxide suspension. In other words, it must be used no later than 8 hours after the cuprous hydroxide suspension is prepared. This allows the suspension to be used as a fungicide before precipitation, and it has a very good fungicide effect.

[0067] In addition, the present invention also discloses a method for using a fungicide liquid. In field operations, before fungicide spraying, a fungicide liquid is prepared according to the preparation method previously disclosed in the present invention, and sprayed onto the target plants within 8 hours.

[0068] In this invention, the bactericidal liquid agent based on cuprous hydroxide is prepared based on a cuprous chloride coordination compound in solution (or a cuprous chloride coordination compound solution), and the preparation of the cuprous chloride coordination compound in solution can be achieved through the following Examples 1 to 3.

[0069] Example 1:

[0070] Weigh out 110 g of anhydrous copper chloride and 270 g of polyethylene glycol 200. Add 34 g of 52% hydrazine hydrochloride dropwise. After the reaction is complete, add 50% saturated sodium hydroxide solution dropwise until the reaction solution changes from tea-colored to pale yellow. A total of 82 g of solution is used. Keep the reaction solution at 65 ℃ to ensure complete reaction. After the reaction is complete, a very small amount of precipitate will remain at the bottom of the flask. Remove the precipitate; the light orange liquid is the cuprous chloride coordination compound solution, containing 10% copper.

[0071] Example 2:

[0072] Weigh out 66.1 g of Cu2(OH)3Cl, 18.4 g of NH4Cl, and 157.2 g of dimethyl sulfoxide into a capped plastic bottle. Mix well, then add hydrazine hydrochloride (N2H4·2HCl) in batches, purging the generated gas. A total of 17.7 g of hydrazine hydrochloride was added. After the gas production was reduced, the temperature was raised to 65 °C to ensure complete reaction, yielding 254.9 g of orange-yellow transparent liquid, which is the cuprous chloride coordination compound solution with a copper content of 15.3%.

[0073] Example 3: Weigh 42.8 g of Cu2(OH)3Cl, 10.9 g of NH4Cl, and 99.8 g of dimethylacetamide, mix them in a capped plastic bottle, remove as much air as possible, add hydrazine hydrochloride in batches, and remove the generated gas. A total of 14.4 g of hydrazine hydrochloride was added. After the amount of gas generated was reduced, the temperature was raised to 65 °C to complete the reaction. The supernatant was a light yellow to greenish semi-transparent liquid, which is the cuprous chloride coordination compound solution with a copper content of 15.1%.

[0074] After preparing the corresponding cuprous chloride coordination compound solutions based on Examples 1-3 above, cuprous hydroxide-based bactericide liquids can be manufactured according to the preparation method disclosed above in this invention. According to the cuprous hydroxide-based bactericide liquids disclosed in this invention, the prepared cuprous chloride coordination compound solutions are added to continuously stirred water, so that the cuprous chloride coordination compound forms a cuprous hydroxide suspension in the water.

[0075] Comparative Examples

[0076] To verify that the cuprous hydroxide-based bactericide of this invention can be effectively prepared using cuprous chloride coordination compounds, a comparative example was designed, specifically a comparative example of preparing the bactericide based on cuprous chloride. Specifically, 0.3 g of cuprous chloride (not a cuprous chloride coordination compound) was added to 1 L of continuously stirred water, resulting in an orange-red suspension. The upper liquid was observed; after 5 minutes, the uppermost layer was nearly transparent with a bluish tint, the middle layer was turbid, and a large amount of sediment was clearly present at the bottom. This comparative example shows that if cuprous chloride is used directly to prepare the cuprous hydroxide suspension, it easily leads to rapid sedimentation and excessively rapid layering, failing to obtain the relatively stable cuprous hydroxide suspension required by this invention over a period of time.

[0077] In the preparation of cuprous hydroxide-based suspensions based on cuprous chloride coordination compounds, a stable suspension state can be obtained within at least 1 to 8 hours. The experimental procedure is as follows:

[0078] Take 0.20, 0.40, 0.80, 1.60 and 3.20 g of the cuprous chloride coordination compound solution obtained in Example 1, respectively, and add them dropwise to 1 L of water with constant stirring. Finally, add water to 2 L to obtain suspensions with copper contents of 10, 20, 40, 80 and 160 mg / L (numbered 1-5). Take 1.60 and 3.20 g of the solution obtained in Example 1, respectively, and add them dropwise to about 1 L of water with constant stirring. Then add 200 g of the pre-prepared commercial agricultural adjuvant "Manchu Citrus Type 300x Distillation". Add water to 2 L and stir evenly to obtain suspension samples with copper contents of 80 mg / L + "Manchu Citrus Type 3000x Distillation" and 160 mg / L + "Manchu Citrus Type 3000x Distillation" (numbered 6-7).

[0079] The resulting suspension samples 1-7 were initially yellow or orange-yellow, as shown in the attached... Figure 1 As shown. 500g of each of the resulting suspension samples 1-7 were placed in transparent plastic bottles and allowed to stand for observation. The results are as follows (see appendix). Figure 1 ).

[0080] When freshly prepared, all concentrations of the samples are suspensions, and the color is yellow or orange-yellow.

[0081] After standing for 1 hour, a small amount of precipitation appeared in the suspensions of Sample 5 (containing 160 mg / L of copper) and Sample 7 (containing 160 mg / L of copper + 3,000 times the amount of citrus type).

[0082] After standing for 2 hours, samples 5 and 7 showed obvious precipitation, while no stratification was observed in any of the other suspension samples.

[0083] After standing for 4 hours, a precipitate appeared in the suspension of sample 4 (containing 80 mg / L of copper), a small amount of precipitate appeared in the suspension of sample 3 (containing 40 mg / L of copper), and a slight stratification appeared in the suspension of sample 5.

[0084] After standing for 8 hours, without adding a full suspension of citrus-type suspensions (samples 1-5), except for sample 1 (containing 10 mg / L of copper), the suspensions of samples 2-5 showed obvious stratification.

[0085] After standing for 18 hours, the color of all suspensions without a full dose of citrus extract lightened and became basically uniform. All suspensions treated with a full dose of citrus extract at a 3,000-fold dilution showed slight stratification, with the stratification being more pronounced at higher copper concentrations.

[0086] After standing for 30 hours, without adding a full amount of citrus-free suspension, the precipitation was basically complete. Sample 6 (containing 80 mg / L copper + 3,000 times the amount of citrus-free suspension) had a small amount of precipitate at the bottom of the suspension and slight stratification. Sample 7 had obvious precipitate at the bottom of the suspension and more obvious stratification.

[0087] After standing for 50 hours, the suspension of sample 6 showed slight stratification, while the suspension of sample 7 showed more obvious stratification. The supernatant of the remaining samples was basically transparent.

[0088] After standing for 97 hours, the suspension of sample 6 showed clear stratification, and the suspension of sample 7 showed very clear stratification. The supernatant of the remaining samples was basically transparent.

[0089] The static tests above show that suspensions with a copper content below 80 mg / L maintain a stable suspension state within 1-2 hours, and suspensions with polyether-modified trisiloxane surfactants can even remain stable for up to 8 hours. In other words, compared to directly preparing suspensions based on cuprous chloride, the method of preparing cuprous hydroxide suspensions based on cuprous chloride coordination compounds in this invention can generate a stable suspension within at least 1-2 hours, thus enabling the use of this relatively stable suspension for sterilization.

[0090] field trials

[0091] To verify the bactericidal effect of the cuprous hydroxide-based bactericide of the present invention, a field trial was designed as described below to test the bactericidal effect.

[0092] Field Trial 1

[0093] Pepper disease control experiment: The control targets were Phytophthora blight, anthracnose, bacterial leaf spot, scab, and gray mold in peppers (large peppers) in Beibei District, Chongqing.

[0094] Honda's tests included two treatment groups, two control groups, and a water control group (CK group). Treatment group one used the cuprous chloride coordination compound from Example 2 to prepare a cuprous hydroxide suspension with a copper content of 100 mg / L. Treatment group two used the cuprous chloride coordination compound from Example 2 to prepare a cuprous hydroxide suspension with a copper content of 100 mg / L, and added a 3000-fold dilution of a citrus-type surfactant, i.e., a polyether-modified trisiloxane surfactant, to the cuprous hydroxide suspension.

[0095] In addition, the three parallel treatment groups were 50% carbendazim wettable powder at 400 times dilution plus 3000 times dilution of Yimanchu citrus type, 50% thiophanate-methyl wettable powder at 670 times dilution plus 3000 times dilution of Yimanchu citrus type, and the CK group was a water control group.

[0096] Each treatment group had 5 replicates, and the insecticide dosage was the same for all treatments. The specific application method was: spray once every 15 days from April 30th to mid-August 2024.

[0097] The results showed that, without the use of any other fungicides, treatment group 1 effectively controlled common diseases of chili peppers, such as blight, anthracnose, bacterial leaf spot, scab, and gray mold. Treatment group 2 not only effectively controlled common chili pepper diseases but also achieved a control efficacy of 94%, which was superior to the control efficacy of treatment group 1 (86%).

[0098] Furthermore, in the parallel treatment groups using the positive control group and the water control group, the plants withered and died due to severe disease by the end of July, ending the harvest period. In contrast, the harvest period for experimental treatment groups one and two was extended to mid-September (the experiment was suspended due to persistent high temperatures and drought in Chongqing), and experimental treatment group two was significantly better than experimental treatment group one. This demonstrates that the bactericidal liquid agent based on the cuprous hydroxide suspension of this invention can replace existing bactericides in its control effect, and its effect is significantly better than the positive control group.

[0099] Field Trial 2

[0100] The vegetable disease control experiment targeted anthracnose, bacterial leaf spot, scab and blight in peppers (sweet peppers, Erjingtiao peppers, and Chaotian peppers) in Neijiang City, Sichuan Province, as well as brown spot in eggplants and gray mold in tomatoes.

[0101] In the Honda test, two test treatment groups were set up. Test treatment group one used the cuprous chloride coordination compound of Example 3 to prepare a cuprous hydroxide suspension with a copper content of 100 mg / L, that is, without adding polyether-modified trisiloxane surfactants. Test treatment group two used the cuprous chloride coordination compound of Example 3 to prepare a cuprous hydroxide suspension with a copper content of 100 mg / L, and added a 3000-fold dilution of citrus-type surfactant to the suspension, that is, added polyether-modified trisiloxane surfactants.

[0102] Two positive control groups were set up: 50% carbendazim wettable powder at 400 times dilution plus 3000 times dilution of Yimanchu citrus type, and 50% thiophanate-methyl wettable powder at 670 times dilution plus 3000 times dilution of Yimanchu citrus type. A water control group (CK group) was also set up.

[0103] Each treatment group had 5 replicates, and the amount of insecticide used in all treatments was the same.

[0104] The specific application method is as follows: the trial period is from May to November, and spray once every 10 to 15 days.

[0105] Both experimental groups effectively controlled common field diseases without the use of any other fungicides. All chili pepper varieties were harvested until the end of November, and eggplant and tomato varieties until the beginning of October. In contrast, in the positive control group and the water control group, sweet peppers, Erjintiao peppers, and tomatoes were harvested only until the beginning of August due to diseases. This demonstrates that the fungicide based on the cuprous hydroxide suspension of this invention can replace existing fungicides, and the control effect of the experimental groups was significantly better than that of the pesticide control group.

[0106] Furthermore, the disease control effect of treatment group 2 (90%–95%) was better than that of treatment group 1 (82%–87%). This indicates that the addition of polyether-modified trisiloxane surfactants to the bactericidal liquid agent based on the suspension of cuprous hydroxide of this invention can achieve better disease control effect.

[0107] Field Trial 3

[0108] Strawberry disease control experiment: Angular leaf spot, powdery mildew and gray mold were controlled on strawberry (Qianmei No. 1, planted at the end of July) in Dechang County, Liangshan Prefecture, Sichuan Province.

[0109] The experimental group used 20g of the cuprous chloride coordination compound solution prepared in Example 1 above (16g for the 3rd and 4th applications), 7g of the commercially available product Yimanchu, diluted in 20kg of water; the positive control group used 5g of 20% kasugamycin water dispersible agent + 15g of 40% pyrimethanil suspension + 30g of 10% bromonitol soluble solution + 20g of 36% kasugamycin·quinoline copper suspension + 8g of Yimanchu pleiotropic agent, diluted in 20kg of water (for growers to mix and use); and a water control group (CK group). Each group was treated in 5 replicates.

[0110] The specific application method is as follows: Start spraying on October 20 (early fruiting stage), once every 7 days, spray until the strawberry leaves are wet, spray 4 times in a row, and keep other management consistent.

[0111] A survey conducted 6 days after the third spray showed that the infection rate of angular leaf spot on new leaves in the control group exceeded 80%, while the infection rate in the experimental treatment group was less than 20%. This indicates that the cuprous hydroxide-based fungicide of the present invention can effectively replace existing fungicides in the control of strawberry angular leaf spot, and its effect is far superior to that of existing fungicides. Simultaneously, there was no difference in the control efficacy against powdery mildew and gray mold between the experimental treatment group and the control group, demonstrating that the cuprous hydroxide-based fungicide of the present invention can effectively control strawberry angular leaf spot, powdery mildew, and gray mold by replacing commonly used fungicide combinations. Observations 7 days after the fourth spray showed that both the experimental treatment group and the control group experienced a reduction in angular leaf spot incidence, with the experimental treatment group showing a significantly greater reduction in angular leaf spot incidence than the control group. Both groups also effectively controlled powdery mildew and gray mold.

[0112] Field Trial 4

[0113] Rose disease control experiment: The target diseases for control were powdery mildew, gray mold and downy mildew of Yunnan Kunming roses (Cappuccino, Peach Snow Mountain and Manta).

[0114] The experimental group used the cuprous chloride coordination compound from Example 1 to prepare a cuprous hydroxide suspension with a copper content of 100 mg / L, and added a 3000-fold dilution of Yimanchu Citrus Type to the suspension. The positive control consisted of a 1000-fold dilution of 50% boscalid water-dispersible granules + a 1000-fold dilution of 20% metalaxyl-cymoxanil suspension emulsion + a 1000-fold dilution of 40% iprodione-propargyl suspension + a 1000-fold dilution of 27% kasugamycin-bromothalonil wettable powder + a 1000-fold dilution of 60% propineb-fluopyram + a 3000-fold dilution of Yimanchu Citrus Type (mixed by growers) and a water control group (CK group). Each treatment had 5 replicates.

[0115] The specific application method is as follows: starting from October 21st, spray once every 5 to 8 days, for a total of 5 sprays.

[0116] Without using other fungicides, the experimental group effectively controlled common diseases of roses and could replace existing fungicides.

[0117] The above are merely preferred embodiments of the present invention and are not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, or improvements made within the principles and methods of the present invention should be included within the scope of protection of the present invention.

[0118] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the above embodiments have described the present invention in detail, those skilled in the art should understand that any modifications or equivalent substitutions to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention should be covered within the scope of the claims of the present invention.

Claims

1. A bactericidal liquid agent based on cuprous hydroxide, characterized in that, The formulation is a cuprous hydroxide-based suspension, which is obtained by adding a cuprous chloride coordination compound in solution to water and continuously stirring during and after the addition. The solution state of the cuprous chloride coordination compound can be obtained by dissolving the cuprous chloride coordination compound in a solvent.

2. The cuprous hydroxide-based bactericidal liquid agent according to claim 1, characterized in that, The solvent can be one or more of glycerol, ethylene glycol, dimethyl sulfoxide, dimethylacetamide, or polyethylene glycol; wherein the general formula of the cuprous chloride coordination compound is: X[CuCl2] or X[Cu2Cl3Y]; Wherein, X is a sodium ion or an ammonium ion; Y is a solvent that can provide a coordinate bond, selected from dimethyl sulfoxide, dimethylacetamide or polyethylene glycol.

3. The cuprous hydroxide-based bactericidal liquid agent according to claim 2, characterized in that, The copper content in the suspension of cuprous hydroxide is 10-160 mg / L, preferably 80-100 mg / L.

4. The cuprous hydroxide-based bactericidal liquid agent according to claim 3, characterized in that, The bactericidal liquid agent also includes the addition of a polyether-modified trisiloxane surfactant to the cuprous hydroxide suspension.

5. A method for preparing a bactericidal liquid agent based on cuprous hydroxide, characterized in that, Includes the following steps: S1, the cuprous chloride coordination compound in solution is added to water and stirred to form a cuprous hydroxide-based suspension of the cuprous chloride coordination compound in water.

6. The preparation method according to claim 5, characterized in that, In step S1, the copper content in the final cuprous hydroxide suspension is 10~160 mg / L.

7. The preparation method according to claim 6, characterized in that, The general formula for cuprous chloride coordination compounds is: X[CuCl2] or X[Cu2Cl3Y]; Wherein, X is a sodium ion or an ammonium ion; Y is a solvent that can provide a coordinate bond, selected from dimethyl sulfoxide, dimethylacetamide or polyethylene glycol.

8. The preparation method according to any one of claims 5 to 7, characterized in that, It also includes step S2: adding a polyether-modified trisiloxane surfactant to the cuprous hydroxide-based suspension formed in step S1.

9. A method of using a bactericidal liquid agent, characterized in that, In field operations, before spraying the fungicide, the fungicide is prepared according to any one of claims 5 to 8 and sprayed onto the target plants within T hours, wherein T≤8.

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