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

Technical Field

[0001] The present invention relates to the technical field of plant disease prevention and control, and in particular to a cuprous hydroxide-based bactericidal liquid, which uses a cuprous hydroxide suspension as the bactericidal liquid. The present invention also relates to a preparation method and a use method of the cuprous hydroxide-based bactericidal liquid. Background Art

[0002] Copper is an essential trace element for plants. Copper ions can not only protect plants from pathogens, but also improve their resistance to diseases. At present, the sales volume of copper-based antimicrobial compounds (CBACs), including Bordeaux mixture, ranks sixth among fungicides in the world. Due to the advantages of low processing cost, low toxicity, high stability and long residual time on leaves, a variety of copper-based compounds are used to prevent and control plant diseases caused by bacteria, fungi and oomycetes, such as Cu2(OH)3Cl, Cu2O, Cu(OH)2, CuSO4Cu(OH)2, etc. However, when these copper-based compounds are used as fungicides, large doses are usually required to achieve better prevention and control effects. However, the large-scale use of copper preparations has caused soil, surface water, groundwater pollution and copper entering the food chain, posing safety risks. In view of this, it is necessary to optimize copper preparations to reduce the amount of copper to solve the problem.

[0003] There are many types of plant diseases. For major diseases, corresponding fungicides are generally considered. However, the fungicides currently used, including copper-based fungicides, usually have a limited range of prevention and control. In most cases, two or more fungicides are often used in agricultural production to prevent and control a single disease or mixed infectious diseases. The simultaneous use of multiple fungicides not only increases costs, but also brings risks to pesticide residues and the environment.

[0004] If we can find a method to effectively prevent and control multiple major diseases at the same time, and keep the annual copper usage per mu within the organic cultivation standard (400 grams), then we can not only avoid the risk of excessive copper use, but also simplify the medication plan and solve the problem of excessive fungicide use.

[0005] In addition, copper (I) and copper (II) are two common valence states of copper, and their chemical properties and applications are very different. Cuprous ions are easily oxidized to cupric ions in the presence of water, and they also disproportionate in acidic solutions to form Cu 2+ and Cu; while divalent copper ions are more stable in the presence of water. Common fungicides are divalent copper, and monovalent inorganic copper fungicides, only cuprous oxide (which is stable in a water environment) is used in production; there are no reports of cuprous hydroxide sterilization, and it is not used as a fungicide in production. Moreover, the chemical properties of cuprous hydroxide are very unstable, and it is easily oxidized to Cu at room temperature. 2+, will also decompose into Cu2O by itself, making it difficult to store for a long time. Therefore, there are no fungicides based on cuprous hydroxide on the market. Summary of the invention

[0006] In view of this, the present invention provides a cuprous hydroxide-based fungicide liquid, which can form a relatively stable, suspended cuprous hydroxide, thereby effectively preventing and controlling plant diseases.

[0007] The first aspect of the present invention discloses a cuprous hydroxide-based bactericidal liquid, which is a cuprous hydroxide suspension, and is used to prevent and treat oomycetes, fungi and / or bacterial diseases; wherein the cuprous oxide suspension is obtained by decomposing and hydrolyzing a cuprous chloride coordination compound in a solution state by continuous stirring in water. The so-called cuprous hydroxide suspension refers to the cuprous hydroxide formed in an opaque yellow or orange suspension state.

[0008] Moreover, the cuprous hydroxide suspension of the present invention can be relatively understood with the help of the precipitation state of cuprous hydroxide: cuprous hydroxide is not easily soluble in water, and it will form cuprous hydroxide precipitation in water, and the cuprous hydroxide suspension of the present invention refers to the suspension state of cuprous hydroxide before it forms precipitation in water, which can be dispersed in water within a certain period of time (which can be within 8 hours) and presents a relatively stable suspension state. The present invention uses the relatively stable suspension state of cuprous hydroxide within the aforementioned certain period of time as a bactericidal liquid to prevent and control oomycetes, fungi and / or bacterial diseases.

[0009] In the conventional research and development path of pesticides and / or pesticide adjuvants, researchers usually consider the long-term stability of the final pesticides and / or pesticide adjuvants. Based on this, considering the instability of cuprous hydroxide, those skilled in the art would not think of a sterilizing liquid that directly uses cuprous hydroxide for sterilization. In the present invention, the applicant creatively develops suspended cuprous hydroxide into a sterilizing liquid, so that the bactericidal effect of cuprous hydroxide can be fully utilized to prevent and treat a variety of diseases. Not only is the scope of disease prevention and control wider, but it also solves the risk of excessive heavy metal residues caused by the large doses of inorganic copper fungicides in the past, while avoiding the problem of using multiple fungicides simultaneously to prevent and treat one or more diseases in the prior art.

[0010] That is to say, in the present invention, a technical idea for replacing existing fungicides is provided, that is, using cuprous hydroxide suspension as a fungicide liquid, which is of great significance for plant disease prevention and control and has great application potential in agricultural production.

[0011] Moreover, it is particularly difficult to think of that, unlike the conventional practice of adding water to the pesticide to dilute the pesticide before spraying, the present invention does the opposite, that is, the cuprous chloride coordination compound in a solution state is added dropwise to the water, and is continuously stirred during and / or after the addition. In this process, the cuprous chloride coordination compound first generates a suspension of cuprous chloride in the water, and the cuprous chloride coordination compound is added to the water and the mixed solution is continuously stirred for a period of time after the addition, so that the cuprous chloride is further hydrolyzed in the water before forming a precipitate, thereby generating a suspension of cuprous hydroxide. In other words, the present invention constructs such a disease control idea: a suspension based on cuprous hydroxide is generated based on a stable cuprous chloride coordination compound, and then disease control is performed based on the suspension of cuprous hydroxide. Since the cuprous chloride coordination compound has high stability, cuprous chloride can exist in a stable state before forming a suspension of cuprous hydroxide, which ensures the certainty of eventually forming a suspension of cuprous hydroxide, thereby ensuring the certainty of the results of disease prevention and control based on cuprous hydroxide.

[0012] It is also important to emphasize that cuprous halides formed from other halogen elements in the same family as chlorine are usually used as cuprous halide fluorescent materials in the industrial field because they have the advantages of adjustable luminescence, structural diversity, and high photoluminescence quantum yield after hybridization with fluorescent materials. In the agricultural field, there is no solution for generating a suspension of cuprous hydroxide based on a cuprous halide coordination compound and using it as a sterilizing liquid, nor is there a solution for generating a suspension of cuprous hydroxide based on a specific cuprous chloride coordination compound and using it as a sterilizing liquid.

[0013] As mentioned above, in the present invention, the cuprous chloride coordination compound is in solution state, that is, the cuprous hydroxide suspension is obtained by adding the cuprous chloride coordination compound in solution state into water and stirring. Its specific generation process can be described as: the cuprous chloride coordination compound first generates a suspension based on cuprous chloride in water, and then further generates the cuprous hydroxide suspension based on the hydrolysis of cuprous chloride in water. Stirring is to improve the stability of the cuprous hydroxide suspension, avoid the excessive local concentration of cuprous chloride and generate coarse particles, and then affect the stability of the cuprous hydroxide particles in water generated by its rehydrolysis. As for the mode of stirring, it can be selected according to actual needs, and the mode of manual stirring can be adopted, and the mode of machine stirring can also be adopted, as long as the cuprous hydroxide suspension is yellow or orange.

[0014] According to the cuprous hydroxide-based disinfectant liquid 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.

[0015] Further, the general formula of the cuprous chloride coordination compound is:

[0016] X[CuCl2] or X[Cu2Cl3Y];

[0017] 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 the cuprous chloride coordination compound, the ratio of cuprous ions to chloride ions is 1:(1.5-2).

[0018] In the present invention, the cuprous chloride coordination compound can be synthesized by the coordination compound synthesis method existing in the prior art. It can also be synthesized based on the following route: cupric chloride or basic cupric chloride is mixed with a suitable solvent, and then a reducing agent is added, and the acid generated is neutralized with a base, and the generated chloride ions are simultaneously used as ligands, and the insufficient part is supplemented in the form of hydrochloride. Specifically, cupric chloride is mixed with a solvent, and then a reducing agent, such as a hydrazine reducing agent, is added dropwise to reduce the divalent copper to cuprous, and a base is added to neutralize the generated acid to promote the reaction to be complete, that is:

[0019] CuCl2+H+NaOH→Na[CuCl2]+H2O.

[0020] Or obtained by reduction of basic copper chloride, namely:

[0021] 2Cu2(OH)3Cl+NH2NH2·2HCl+4NH4Cl→4[CuCl2]+6H2O+N2↑

[0022] 2Cu2(OH)3Cl+NH2NH2·2HCl+2NH4Cl+2Y→2NH4[Cu2Cl3Y]+6H2O+N2↑ (where Y is a solvent that can form a coordination bond, such as dimethyl sulfoxide, dimethylacetamide or polyethylene glycol).

[0023] According to the cuprous hydroxide-based bactericidal liquid disclosed in the first aspect of the present invention, the copper content in the cuprous hydroxide suspension is 10 to 160 mg / L, for example, the copper content can be any value between 10 and 160 in mg / L, including the values ​​10 and 160; preferably, it is 80 to 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 these dosages, it can replace the existing fungicides used in the field to prevent and control one or more oomycetes, fungi and / or bacterial diseases. Specifically, based on an average water spraying amount of 150 kg / mu and an average use concentration of 90 mg / L, as long as the annual use frequency is within 29 times, the organic production standard of an annual copper use of 400 grams per mu can be met.

[0024] According to the cuprous hydroxide-based disinfectant liquid disclosed in the first aspect of the present invention, the disinfectant liquid further comprises a surfactant mixed in the cuprous hydroxide suspension, preferably a polyether-modified trisiloxane surfactant. By mixing the polyether-modified trisiloxane surfactant in the cuprous hydroxide suspension, the stability of the suspension can be further enhanced, while the wettability and expansibility of the suspension can be improved, and the efficacy of the disinfectant liquid of the present invention in the disinfection function can be further improved.

[0025] That is to say, the bactericidal liquid of the present invention can be used alone in the form of a suspension of cuprous hydroxide for sterilization, or it can be used together with other substances having a bactericidal effect, for example, a polyether-modified trisiloxane surfactant can be mixed into a suspension of cuprous hydroxide to form a final bactericidal liquid.

[0026] The second aspect of the present invention also discloses a method for preparing a cuprous hydroxide-based disinfectant liquid, comprising the following steps: S1, adding a cuprous chloride coordination compound in a solution state into continuously stirred water, so that the cuprous chloride coordination compound forms a cuprous hydroxide suspension in the water.

[0027] Specifically, the cuprous chloride coordination compound in a pre-prepared solution state is added to the clear water, wherein the preferred adding method is to slowly add it into the continuously stirred clear water, so as to promote the cuprous chloride generated after the decomposition of the cuprous chloride coordination compound to be hydrolyzed into cuprous hydroxide before forming a precipitate, thereby finally forming a relatively stable cuprous hydroxide suspension. Among them, the amount of water used is preferably more than 50% of the total amount of the suspension finally formed. According to the preparation method disclosed in the second aspect of the present invention, in step S1, the cuprous chloride coordination compound in a solution state is added to the water and stirred in such a way that the copper content in the cuprous hydroxide suspension finally formed is 10 to 160 mg / L (preferably 80 to 100 mg / L). At this dosage, it can replace the existing fungicide used in the field to prevent and control one or more oomycetes, fungi and / or bacterial diseases.

[0028] According to the preparation method disclosed in the second aspect of the present invention, the general formula of the cuprous chloride coordination compound is:

[0029] X[CuCl2] or X[Cu2Cl3Y];

[0030] Wherein, X is one or more ions, preferably sodium ions or ammonium ions; Y is a solvent capable of providing a coordination bond, preferably dimethyl sulfoxide, dimethylacetamide or polyethylene glycol.

[0031] According to the preparation method disclosed in the second aspect of the present invention, it also includes step S2, adding a surfactant, preferably a polyether-modified trisiloxane surfactant, to the cuprous hydroxide suspension formed in step S1 to form a surfactant-containing bactericidal liquid. 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 the wettability and expansibility of the suspension. Among them, the polyether-modified trisiloxane surfactant can be a commercial agricultural adjuvant already available on the market, such as a product such as a full citrus-removing type.

[0032] According to the preparation method disclosed in the second aspect of the present invention, the preparation is implemented before the sterilization spraying, and is used within T hours after the suspension of cuprous hydroxide is formed, wherein T≤8. That is, in the present invention, the sterilization liquid is a freshly prepared suspension, specifically prepared before use, and needs to be used within T hours after the suspension of cuprous hydroxide is formed, that is, it needs to be used within T hours (T≤8) after preparation at the latest. Specifically, the suspension is used as a sterilization liquid before precipitation is formed within T hours (T≤8), and has a very good sterilization effect.

[0033] The third aspect of the present invention discloses a method for using a fungicide liquid. Note that when applied in the field, before spraying the fungicide, the fungicide liquid is prepared according to the preparation method disclosed in the second aspect of the present invention, and sprayed onto the target plants within T hours, where T≤8.

[0034] Beneficial effects: The innovative cuprous hydroxide suspension fungicide liquid of the present invention can replace existing fungicides to effectively prevent and treat diseases caused by a variety of oomycetes, fungi and / or bacteria, and while the single copper dosage is much lower than that of existing inorganic copper fungicides, the range of disease prevention and treatment is wider. This not only solves the risk of excessive heavy metal residues caused by the large-dose use of existing inorganic copper fungicides, but also avoids the problem of using multiple fungicides at the same time to prevent and treat one or more diseases. The fungicide liquid of the present invention is of great significance for the prevention and treatment of plant diseases and has great application potential in the agricultural market.

[0035] The cuprous hydroxide-based disinfectant liquid of the present invention and its preparation method and use method are disclosed in detail below in conjunction with specific embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 The graph shows the change in the static state of the suspension sample prepared by the preparation method of the present invention in the static test. DETAILED DESCRIPTION

[0037] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the drawings in the embodiments of the present invention. It should be noted that the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0038] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application may be combined with each other.

[0039] The present invention first discloses a cuprous hydroxide-based bactericidal liquid, which is a cuprous hydroxide suspension, and is used for preventing and treating oomycetes, fungi and / or bacterial diseases; wherein the cuprous hydroxide suspension is obtained by decomposing (hydrolyzing) a cuprous chloride coordination compound in a solution state in water by continuous stirring. The so-called cuprous hydroxide suspension refers to a suspension state in which the formed cuprous hydroxide is in an opaque yellow or orange color.

[0040] Specifically, the cuprous chloride coordination compound in the solution state first decomposes in water to generate a suspension of cuprous chloride, and the cuprous chloride coordination compound is added to water and the mixed solution is continuously stirred for a period of time after the addition, so that before the cuprous chloride forms coarser particles, the cuprous chloride further generates a suspension of cuprous hydroxide based on the hydrolysis of cuprous chloride in water. That is, in a specific embodiment of the present invention, the cuprous chloride coordination compound used to be added to water to form a suspension of cuprous hydroxide is in a solution state, and the suspension of cuprous hydroxide is obtained by adding the coordination compound of cuprous chloride in a solution state to water and stirring. In a preferred embodiment, the water is specifically tap water or well water taken from a wellhead in a field.

[0041] In a 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.

[0042] In a specific embodiment, the general formula of the cuprous chloride coordination compound is:

[0043] X[CuCl2] or X[Cu2Cl3Y];

[0044] 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).

[0045] In the present invention, the coordination compound of cuprous chloride can be synthesized by the coordination compound synthesis method existing in the prior art. It can also be synthesized based on the following route: cupric chloride or basic cupric chloride is mixed with a suitable solvent, and then a reducing agent is added, and the acid generated is neutralized with a base, and the generated chloride ions are simultaneously used as ligands, and the insufficient part is supplemented in the form of hydrochloride. Specifically, cupric chloride is mixed with a solvent, and then a reducing agent, such as a hydrazine reducing agent, is added dropwise to reduce the divalent cupric original to cuprous, and a base is added to neutralize the generated acid to promote the reaction to be complete, that is:

[0046] CuCl2+H+NaOH→Na[CuCl2]+H2O.

[0047] Or obtained by reduction of basic copper chloride, namely:

[0048] 2Cu2(OH)3Cl+NH2NH2·2HCl+4NH4Cl→4[CuCl2]+6H2O+N2↑;

[0049] 2Cu2(OH)3Cl+NH2NH2·2HCl+2NH4Cl+2Y→2[Cu2Cl3Y]+6H2O+N2↑. Wherein, Y is a solvent capable of forming a coordination bond, such as dimethyl sulfoxide, dimethylacetamide or polyethylene glycol.

[0050] In a 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 the existing fungicides used in the field to prevent and control one or more oomycetes, fungi and / or bacterial diseases. Specifically, based on an average water spraying amount of 150 kg / mu and an average use concentration of 90 mg / L, as long as the annual use frequency is within 29 times, the organic production standard of an annual copper use of 400 grams per mu can be met.

[0051] In a specific embodiment, the disinfectant liquid further comprises a surfactant mixed in the cuprous hydroxide suspension, preferably a polyether-modified trisiloxane surfactant. By mixing the polyether-modified trisiloxane surfactant in the cuprous hydroxide suspension, the stability of the suspension can be further enhanced, while improving the wettability and expansibility of the suspension.

[0052] The present invention also discloses a method for preparing a cuprous hydroxide-based disinfectant liquid, comprising the following steps: S1, adding a cuprous chloride coordination compound in a solution state into continuously stirred water, and continuously stirring the water, so that the cuprous chloride coordination compound forms a cuprous hydroxide suspension in the water.

[0053] Specifically, the cuprous chloride coordination compound in a pre-prepared solution state is added to the clear water, wherein the preferred adding method is to slowly add it into the continuously stirred clear water, so that the cuprous chloride is hydrolyzed into cuprous hydroxide before forming a coarse precipitate, thereby finally forming a relatively stable cuprous hydroxide suspension. The amount of water used is preferably more than 50% of the total amount of the suspension finally formed.

[0054] In a specific embodiment of the preparation method of the present invention, in step S1, a solution of cuprous chloride coordination compound is added to water and stirred in such a manner that the copper content in the final cuprous hydroxide suspension is 10 to 160 mg / L (preferably 80 to 100 mg / L). At this dosage, the cuprous chloride coordination compound can replace the existing fungicide used in the field to prevent and control one or more oomycete, fungal and / or bacterial diseases.

[0055] In a specific embodiment of the preparation method of the present invention, the general formula of the cuprous chloride coordination compound is:

[0056] X[CuCl2] or X[Cu2Cl3Y];

[0057] Wherein, X is one or more ions, preferably sodium ions or ammonium ions; Y is a solvent capable of providing a coordination bond, preferably dimethyl sulfoxide, dimethylacetamide or polyethylene glycol.

[0058] In a 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.

[0059] In a specific embodiment of the preparation method of the present invention, the cuprous chloride coordination compound can be synthesized by the coordination compound synthesis method existing in the prior art. It can also be synthesized based on the following route: cupric chloride or basic cupric chloride is mixed with a suitable solvent, and then a reducing agent is added, and the acid generated is neutralized with a base, and the generated chloride ions are simultaneously used as ligands, and the insufficient part can be supplemented in the form of hydrochloride. Specifically, cupric chloride is mixed with a solvent, and then a reducing agent, such as a hydrazine reducing agent, is added dropwise to reduce the divalent copper to cuprous, and a base is added to neutralize the generated acid to promote the reaction to completion, that is:

[0060] CuCl2+H+NaOH→Na[CuCl2]+H2O.

[0061] Or obtained by reduction of basic copper chloride, namely:

[0062] 2Cu2(OH)3Cl+NH2NH2·2HCl+4NH4Cl→4[CuCl2]+6H2O+N2↑

[0063] 2Cu2(OH)3Cl+NH2NH2·2HCl+2NH4Cl+2Y→2[Cu2Cl3Y]+6H2O+N2↑ (where Y is a solvent that can form a coordination bond, such as dimethyl sulfoxide, dimethylacetamide or polyethylene glycol).

[0064] In a specific embodiment of the preparation method of the present invention, step S2 is also 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 bactericidal liquid 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 the wettability and expansibility of the suspension. Among them, the polyether-modified trisiloxane surfactant can be a commercial agricultural adjuvant already available on the market, such as a full citrus-removing agricultural adjuvant product currently sold on the market.

[0065] In a specific embodiment of the preparation method of the present invention, steps S1 to S2 are implemented in field operations before sterilization spraying, and are used within 8 hours after the cuprous hydroxide suspension is formed. That is, in the present invention, the sterilization liquid is a newly prepared suspension, specifically prepared before use, and needs to be used within 8 hours after the cuprous hydroxide suspension is formed, that is, it needs to be used within 8 hours after the cuprous hydroxide suspension is prepared at the latest, which enables the suspension to be used as a sterilization liquid before precipitation is formed, and has a very good sterilization effect.

[0066] In addition, the present invention also discloses a method for using a fungicide liquid. In field operations, before spraying the fungicide, the fungicide liquid is prepared according to the preparation method disclosed hereinabove, and is sprayed on target plants within 8 hours.

[0067] In the present invention, the cuprous hydroxide-based disinfectant liquid is prepared based on a cuprous chloride coordination compound in a solution state (or referred to as a cuprous chloride coordination compound solution), and the preparation of the cuprous chloride coordination compound in a solution state can be achieved through the following Examples 1 to 3.

[0068] Embodiment 1:

[0069] Weigh 110g of anhydrous cupric chloride and 270g of polyethylene glycol 200, add 34g of 52% hydrazine hydrochloride dropwise, and after sufficient reaction, add saturated sodium hydroxide solution (50%) dropwise until the reaction liquid changes from brown to light yellow, a total of 82g. Keep the reaction liquid at 65℃ to allow it to react fully. After the reaction is completed, there is a very small amount of precipitation at the bottom of the bottle. Remove the precipitation, and the light orange liquid is the cuprous chloride coordination compound solution, containing 10% copper.

[0070] Embodiment 2:

[0071] Weigh 66.1 g of Cu2(OH)3Cl, 18.4 g of NH4Cl, and 157.2 g of dimethyl sulfoxide in a plastic bottle with a lid, mix well, and then add hydrazine hydrochloride (N2H4·2HCl) in batches to discharge the generated gas, a total of 17.7 g. When the gas generation is less, heat to 65°C to complete the reaction, and obtain 254.9 g of orange-yellow transparent liquid, which is cuprous chloride coordination compound solution with a copper content of 15.3%.

[0072] 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 plastic bottle with a lid, expel air as much as possible, add hydrazine hydrochloride in batches, expel the generated gas, a total of 14.4 g, and when the gas generation is less, heat to 65°C to complete the reaction. The supernatant is a light yellowish greenish translucent liquid, thus obtaining a cuprous chloride coordination compound solution with a copper content of 15.1%.

[0073] After the corresponding cuprous chloride coordination compound solutions are prepared based on the above-mentioned embodiments 1 to 3, the cuprous hydroxide-based disinfectant liquid can be manufactured according to the preparation method disclosed in the present invention. According to the cuprous hydroxide-based disinfectant liquid disclosed in the present invention, the prepared cuprous chloride coordination compound solution is added to the continuously stirred water, so that the cuprous chloride coordination compound forms a cuprous hydroxide suspension in the water.

[0074] Comparative Example

[0075] In order to verify that the cuprous chloride coordination compound can effectively prepare the disinfection liquid based on cuprous hydroxide of the present invention, the present invention has designed a comparative example, that is, a comparative example of preparing the disinfection liquid based on cuprous chloride. Specifically: take 0.3 grams of cuprous chloride (rather than the coordination compound of cuprous chloride), add it to 1L of clean water that is constantly stirred, generate an orange-red suspension, take the upper liquid for observation, and after 5 minutes, the top layer of liquid is nearly transparent, blue, the middle layer is turbid, and the bottom is obviously precipitated in large quantities. Based on this comparative example, it can be seen that if cuprous chloride is used to directly configure the cuprous hydroxide suspension, it is easy to cause the suspension to precipitate quickly, the stratification is too fast, and the cuprous hydroxide suspension that is relatively stable over a period of time as required in the present invention will not be obtained.

[0076] In the process of preparing a suspension based on cuprous hydroxide based on a cuprous chloride coordination compound, a stable suspension state can be obtained within at least 1 to 8 hours. The specific test process is as follows:

[0077] 0.20, 0.40, 0.80, 1.60 and 3.20 grams of the cuprous chloride coordination compound solution obtained in Example 1 were respectively taken and dropped into 1L of water that was constantly stirred, and finally the water was supplemented to 2L to obtain suspensions with copper contents of 10, 20, 40, 80 and 160 mg / L (No. 1-5); 1.60 and 3.20 grams of the solution obtained in Example 1 were respectively taken and dropped into about 1L of water that was constantly stirred, and then 200 grams of a pre-configured commercial agricultural adjuvant, 300 times of citrus type, were added respectively, and then the solution was supplemented to 2L with water and stirred evenly, and suspension samples containing 80 mg / L of copper + 3,000 times of citrus type and 160 mg / L of copper + 3,000 times of citrus type were obtained (No. 6-7), respectively.

[0078] The suspension samples 1 to 7 formed were all yellow or orange-yellow at the beginning. Figure 1 500 g of the suspension samples 1 to 7 were taken into transparent plastic bottles and left to stand for observation. The results are as follows (see Appendix Figure 1 ).

[0079] When first prepared, samples of all concentrations are suspensions with yellow or orange color.

[0080] After standing for 1 hour, a small amount of precipitation appeared in the suspensions of sample 5 (copper content 160 mg / L) and sample 7 (copper content 160 mg / L + 3,000 times of citrus type).

[0081] After standing for 2 hours, samples 5 and 7 had obvious precipitation, while all other suspension samples showed no stratification.

[0082] After standing for 4 hours, the suspension of sample 4 (copper content 80 mg / L) showed precipitation, the suspension of sample 3 (copper content 40 mg / L) showed a small amount of precipitation, and the suspension of sample 5 showed slight stratification.

[0083] After standing for 8 hours, the suspensions of citrus type (samples 1-5) were not fully filled. Except for sample 1 (copper content 10 mg / L), the suspensions of the other samples 2-5 were obviously stratified.

[0084] After standing for 18 hours, the colors of all suspensions that were not added with a full amount of citrus-removing agent faded and were basically the same. All suspensions that were treated with a full amount of 3,000 times the citrus-removing agent showed slight stratification, and the higher the copper concentration, the more obvious the stratification.

[0085] After standing for 30 hours, without adding a full amount of citrus-free suspension, the precipitation was basically complete. Sample 6 (copper content 80 mg / L + 3,000 times of a full amount of citrus-free suspension) had a little precipitation at the bottom of the suspension, and the suspension was slightly stratified. Sample 7 had obvious precipitation at the bottom of the suspension, and the suspension was more obviously stratified.

[0086] After standing for 50 hours, the suspension of sample 6 was slightly stratified, while the suspension of sample 7 was more obviously stratified. The supernatants of the other samples were basically transparent.

[0087] After standing for 97 hours, the suspension of sample 6 was obviously stratified, and the suspension of sample 7 was very obviously stratified. The supernatants of the other samples were basically transparent.

[0088] From the above static test, it can be seen that the suspension containing less than 80 mg / L of copper has a stable suspension state within 1 to 2 hours, and the suspension sample with the addition of polyether-modified trisiloxane surfactant can even be stable within 8 hours. That is, compared with the direct preparation of the suspension based on cuprous chloride, the method of preparing the cuprous hydroxide suspension based on the cuprous chloride coordination compound of the present invention can generate a suspension with a stable state within at least 1 to 2 hours, so that the relatively stable suspension can be used for sterilization.

[0089] Field trials

[0090] In order to verify the bactericidal effect of the cuprous hydroxide-based bactericidal liquid of the present invention, a field experiment was designed to test the bactericidal effect as described below.

[0091] Field trial 1

[0092] Pepper disease prevention and control experiment: The prevention and control targets are pepper (large pepper) blight, anthracnose, bacterial leaf spot, scab and gray mold in Beibei District, Chongqing.

[0093] The field experiment set up two experimental treatment groups, two positive control groups and a clean water control group (CK group), wherein the experimental treatment group 1 used the cuprous chloride coordination compound of the aforementioned Example 2 to prepare a cuprous hydroxide suspension with a copper content of 100 mg / L; and the experimental treatment group 2 used the cuprous chloride coordination compound of the aforementioned Example 2 to prepare a cuprous hydroxide suspension with a copper content of 100 mg / L, and added a 3000-fold solution of citrus-free type, that is, added a polyether-modified trisiloxane surfactant, to the cuprous hydroxide suspension.

[0094] In addition, in the three parallel treatment groups, 400 times diluted 50% carbendazim wettable powder was added to one full 3000 times diluted citrus-removing agent, 670 times diluted 50% methyl thiophanate wettable powder was added to one full 3000 times diluted citrus-removing agent, and the CK group was the clear water control group.

[0095] Each treatment group was repeated 5 times, and the dosage of insecticide was the same for all treatments. The specific application method was: spray once every 15 days from April 30 to mid-August 2024.

[0096] The results showed that without using any other fungicides, the first treatment group effectively controlled common pepper diseases, such as pepper (large pepper) blight, anthracnose, bacterial leaf spot, scab and gray mold, etc. The second treatment group not only effectively controlled common pepper diseases, but also achieved a control efficiency of 94%, which was better than the control efficiency of the first treatment group (86%).

[0097] In addition, in the parallel treatment groups using the positive control group and the clear water control group, the plants died due to serious diseases at the end of July and the harvest period ended, while the harvest period of the experimental treatment group 1 and the experimental treatment group 2 was extended to mid-September (the experiment was terminated due to the continuous high temperature and drought in Chongqing), and the experimental treatment group 2 was significantly better than the experimental treatment group 1. It can be seen that the control effect of the bactericidal liquid formed by the suspension of cuprous hydroxide in the present invention can replace the existing bactericide, and the effect is significantly better than the positive control group.

[0098] Field experiment 2

[0099] The vegetable disease prevention and control experiment targets the prevention and control of anthracnose, bacterial leaf spot, scab and blight of peppers (sweet pepper, erjingtiao, and chili pepper) in Neijiang City, Sichuan Province, brown streak disease of eggplant, and gray mold of tomatoes.

[0100] In the field test, test treatment group 1 and test treatment group 2 were set up, wherein test treatment group 1 used the cuprous chloride coordination compound of the aforementioned Example 3 to prepare a cuprous hydroxide suspension with a copper content of 100 mg / L, that is, no polyether-modified trisiloxane surfactant was added; test treatment group 2 used the cuprous chloride coordination compound of the aforementioned Example 3 to prepare a cuprous hydroxide suspension with a copper content of 100 mg / L and added a 3,000-fold solution of citrus-free to the suspension, that is, a polyether-modified trisiloxane surfactant was added.

[0101] At the same time, two positive control groups were set up, namely: 400 times diluted 50% carbendazim wettable powder plus one full 3 000 times diluted citrus-removing agent, 670 times diluted 50% methyl thiophanate wettable powder plus one full 3 000 times diluted citrus-removing agent, and a clear water control group (CK group) was also set up.

[0102] Each treatment group was replicated 5 times, and the dosage of insecticide was the same for all treatments.

[0103] The specific application method is: the test period is from May to November, spraying once every 10 to 15 days.

[0104] The two test groups effectively prevented and controlled common field diseases without using any other fungicides. All pepper varieties were harvested until the end of November, and eggplants and tomatoes were harvested until early October. In the positive control group and the clear water control group, the harvest period of sweet peppers, two gold bars and tomatoes was only maintained until early August due to diseases. This shows that the control effect of the fungicide liquid formed by the cuprous hydroxide suspension of the present invention can replace the existing fungicides, and the control effect of the test group is significantly better than that of the pesticide control group.

[0105] In addition, the disease control effect of the experimental treatment group 2 (90% to 95%) is better than that of the experimental treatment group 1 (82% to 87%), which shows that on the basis of the bactericidal liquid formed by the cuprous hydroxide suspension of the present invention, further adding a polyether-modified trisiloxane surfactant can achieve a better disease control effect.

[0106] Field Trial 3

[0107] Strawberry disease prevention and control experiment: The strawberry (Qianmei No. 1, planted at the end of July) in Dechang County, Liangshan Prefecture, Sichuan Province was targeted for prevention and control of angular leaf spot, powdery mildew and gray mold.

[0108] The test group used 20 grams of the cuprous chloride coordination compound solution prepared in the above-mentioned Example 1 (16 grams for the 3rd and 4th times), 7 grams of the commercially available product Amanchu, and 20 kilograms of water; the positive control group was 5 grams of 20% kasugamycin water dispersant + 15 grams of 40% pyrimethanil suspension + 30 grams of 10% bronopol soluble solution + 20 grams of 36% kasugamycin·quinoline copper suspension + 8 grams of Amanchu multi-effect type, 20 kilograms of water (growers mixed drugs) and a clear water control group (CK group), and each group was treated with 5 replicates.

[0109] The specific application method is: start spraying on October 20 (early fruiting period), once every 7 days, until the strawberry leaves are wet, spray 4 times in a row, and other management is the same.

[0110] The survey 6 days after the third spraying showed that the rate of new leaf infection with angular spot in the positive control group exceeded 80%, and the rate of new leaf infection with angular spot in the test treatment group was less than 20%, indicating that the bactericidal liquid based on cuprous hydroxide according to the present invention can well replace the existing bactericide in preventing and controlling strawberry angular spot, and the effect is much higher than the existing bactericide. At the same time, there is no difference in the effect of the test treatment group and the positive control group on preventing and controlling powdery mildew and gray mold, which indicates that the bactericidal liquid of cuprous hydroxide of the present invention can replace the existing commonly used bactericide combination to effectively prevent and control strawberry angular spot, powdery mildew and gray mold. Observation 7 days after the fourth spraying showed that both the test treatment group and the positive control group were able to reduce the occurrence of angular spot, and the test treatment group was more able to significantly reduce the incidence of angular spot than the positive control group, and at the same time, both were able to effectively prevent and control powdery mildew and gray mold.

[0111] Field Trial 4

[0112] Rose disease prevention and control experiment: The prevention and control targets are powdery mildew, gray mold and downy mildew of Yunnan Kunming roses (Cappuccino, Peach Snow Mountain, Manta).

[0113] The test group used the cuprous chloride coordination compound of the aforementioned Example 1 to prepare a cuprous hydroxide suspension containing 100 mg / L of copper, and added a 3,000-fold solution of Citrus-Cellulose to the suspension. The positive control was 1,000-fold solution of 50% Boscalid water dispersible granules + 1,000-fold solution of 20% Metalaxyl-Cyazofamid suspoemulsion + 1,000-fold solution of 40% Iprodione-Procymidone suspoem + 1,000-fold solution of 27% Spring Thunder-Bromthionil WP + 1,000-fold solution of 60% Propineb-Zabin-Flupyraclostrobin + 3,000-fold solution of Citrus-Cellulose (mixed by growers) and a clear water control group (CK group). Each group was treated with 5 replicates.

[0114] The specific application method is: starting from October 21, spray once every 5 to 8 days, for a total of 5 times.

[0115] Without the use of other fungicides, the test group effectively prevented and controlled common diseases of roses and can replace existing fungicides.

[0116] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the principles and methods of the present invention shall be included in the protection scope of the present invention.

[0117] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the above embodiments describe the present invention in detail, those skilled in the art should understand that modifications or equivalent substitutions of the technical solution of the present invention without departing from the purpose and scope of the technical solution of the present invention should be included in the scope of the claims of the present invention.

Claims

1. A cuprous hydroxide-based bactericidal liquid, characterized in that: The invention is a suspension of cuprous hydroxide, which is used for preventing and treating oomycetes, fungi and / or bacterial diseases; the suspension of cuprous hydroxide is obtained by decomposing a cuprous chloride coordination compound in a solution state by stirring in water.

2. The cuprous hydroxide-based disinfectant according to claim 1, characterized in that: The solution state of the cuprous chloride coordination compound can be obtained by dissolving the cuprous chloride coordination compound in a solvent; 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 one or more ions, preferably sodium ions or ammonium ions; Y is a solvent capable of providing a coordination bond, preferably dimethyl sulfoxide, dimethylacetamide or polyethylene glycol.

3. The cuprous hydroxide-based disinfectant according to claim 2, characterized in that: The cuprous hydroxide suspension contains 10 to 160 mg / L of copper, preferably 80 to 100 mg / L of copper.

4. The cuprous hydroxide-based disinfectant according to claim 3, characterized in that: The bactericidal liquid further comprises a surfactant added to the cuprous hydroxide suspension, preferably a polyether-modified trisiloxane surfactant.

5. A method for preparing a disinfectant liquid based on cuprous hydroxide, characterized in that: The following steps are involved: S1, adding a cuprous chloride coordination compound in a solution state into water and stirring the mixture to form a cuprous hydroxide suspension in the water.

6. The preparation method according to claim 5, characterized in that: In the step S1, a cuprous chloride coordination compound in a solution state is added to water and stirred in such a manner that the copper content in the finally formed cuprous hydroxide suspension is 10 to 160 mg / L.

7. The preparation method according to claim 6, characterized in that: The general formula of the cuprous chloride coordination compound is: X[CuCl2] or X[Cu2Cl3Y]; Wherein, X is one or more ions, preferably sodium ions or ammonium ions; Y is a solvent capable of providing a coordination bond, preferably dimethyl sulfoxide, dimethylacetamide or polyethylene glycol.

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

9. The preparation method according to claims 5 to 8, characterized in that: The steps S1 to S2 are implemented in field operations before sterilization spraying, and are used within T hours after the cuprous hydroxide suspension is formed, wherein T≤8.

10. A method for using a sterilizing liquid, characterized in that: In field operations, before spraying the bactericidal liquid, the bactericidal liquid is prepared according to the preparation method described in any one of claims 5 to 9, and sprayed on the target plants within T hours, wherein T≤8.

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