Hexazinone preparation and preparation method thereof

Abstract

The invention discloses a hexazinone preparation and a preparation method thereof, and belongs to the technical field of pesticide chemistry. The preparation method comprises the following steps: S1, preparing BC: adding BC, mixing and grinding with copper sulfate pentahydrate, putting into a tubular furnace, calcining, and cooling to obtain Cu-BC; s2, adding a modified silane coupling agent into an ethanol water solution, then adding the Cu-BC obtained in S1, stirring for 6-8 hours at 25-35 DEG C, filtering, washing and drying to obtain modified Cu-BC; s3, hexazinone is dissolved in absolute ethyl alcohol, then the modified Cu-BC is added, ultrasonic dispersion is conducted for 6-8 h, filtering, centrifugal washing and freeze-drying are conducted, and the hexazinone preparation is obtained. According to the preparation method of the hexazinone preparation, the slow release capacity of the preparation can be improved, the hexazinone utilization rate is increased, meanwhile, the preparation can be endowed with the sterilization effect, and the hexazinone preparation has wide application prospects.

Description

Technical Field

[0001] This invention relates to the field of pesticide chemistry, and in particular to a cycloazinone formulation and its preparation method. Background Technology

[0002] Cycloazine is a triazinone herbicide with systemic selectivity and post-emergence contact action. It effectively controls weeds and shrubs by inhibiting root and leaf absorption and suppressing photosynthesis. Cycloazine is biodegradable in soil, making it environmentally friendly and a highly effective, low-toxicity forest herbicide. However, when applied to farmland, cycloazine is easily lost due to infiltration, evaporation, and degradation (including photolysis, hydrolysis, and microbial degradation), resulting in poor efficacy and a short residual effect. This means that cycloazine fails to meet crop requirements in terms of residual effect and release characteristics. Therefore, there is an urgent need to develop a cycloazine formulation with good slow-release properties to improve crop utilization of cycloazine. Summary of the Invention

[0003] This invention provides a cycloazinone formulation and its preparation method, which can solve the problem that cycloazinone in the prior art cannot meet the crop requirements in terms of duration of action and release characteristics.

[0004] The objective of this invention can be achieved through the following technical solutions: In a first aspect, the present invention provides a method for preparing a cycloazinone formulation, comprising the following steps: S1. Preparation of Cu-BC: To prepare BC, BC is mixed and ground with copper sulfate pentahydrate, then calcined in a tube furnace and cooled to obtain Cu-BC. The mass ratio of BC to copper sulfate pentahydrate is 1:(1.2 to 1.5).

[0005] S2. Preparation of modified Cu-BC: Add the modified silane coupling agent to an aqueous ethanol solution, then add the Cu-BC obtained in S1, stir at 25-35℃ for 6-8 hours, filter, wash, and dry to obtain modified Cu-BC. The ratio of modified silane coupling agent, ethanol aqueous solution, and Cu-BC is 0.1-0.2g: 30-40mL: 0.3g; the volume ratio of anhydrous ethanol to deionized water in the ethanol aqueous solution is 8:2.

[0006] S3. Preparation of cycloazinone formulation: Dissolve cycloazinone in anhydrous ethanol, then add modified Cu-BC, ultrasonically disperse for 6-8 hours, filter, centrifuge and wash, freeze dry to obtain cycloazinone formulation.

[0007] The ratio of cycloazinone, anhydrous ethanol, and modified Cu-BC is 0.05–0.1 g: 30–40 mL: 0.05–0.2 g.

[0008] Further, in step S1, the specific steps for preparing BC are as follows: the straw is washed, dried, crushed, and then dried in a tube furnace under a nitrogen atmosphere, followed by cooling, washing, filtration, and drying to obtain BC (biochar).

[0009] Furthermore, the straw includes any one or more of rice straw, wheat straw, and corn straw.

[0010] Furthermore, the temperature of the tubular furnace pyrolysis is 600–700°C, the heating rate is 10°C / min, and the pyrolysis time is 3–5 hours.

[0011] Further, in step S1, the calcination conditions are as follows: heating to 600-700°C at a heating rate of 10°C / min under a nitrogen atmosphere, and then holding at that temperature for 2-4 hours.

[0012] Further, in step S2, the method for preparing the modified silane coupling agent is as follows: S21. Mix 2,4-dihydroxybenzophenone with K2CO3, then add 3-bromopropyne, then add acetone, reflux for 16 h, after the reaction is complete, filter, evaporate to dryness, and dry to obtain alkynylated benzophenone. The ratio of 2,4-dihydroxybenzophenone, K2CO3, 3-bromopropyne, and acetone used is 10.1g:13g:3.5mL:130-150mL.

[0013] S22. 11-Azide-undecyltrimethoxysilane, alkynylated benzophenone, ascorbic acid, and copper sulfate were added to tetrahydrofuran and reacted at 20-30°C for 5-12 hours. The mixture was then washed and dried to obtain the modified silane coupling agent. The ratio of 11-azidoundecyltrimethoxysilane, alkynylated benzophenone, ascorbic acid, copper sulfate, and tetrahydrofuran is 3.2g:2.5g:0.25~0.3g:0.13~0.14g:50~80mL.

[0014] Secondly, the present invention provides a cycloazinone formulation, which is prepared by any one of the preparation methods described above.

[0015] The beneficial effects of this invention are: 1. The preparation method of the cycloazinone formulation provided by this invention can improve the sustained-release ability of the formulation, increase the utilization rate of cycloazinone, and also endow the formulation with bactericidal effect, thus possessing broad application prospects. In S1, BC is prepared to provide a substrate for subsequent copper loading. Mixing and grinding BC with copper sulfate pentahydrate can increase the contact area, allowing copper ions to be uniformly dispersed on the BC surface. Tube furnace calcination can promote the interaction between copper ions and BC, forming a stable Cu-BC composite material. Cooling avoids the destruction of the material structure at high temperatures. In S2, the ethanol-water solution provides a suitable hydrolysis and reaction environment for the modified silane coupling agent. The temperature of 25-35℃ can ensure the coupling agent reacts fully while avoiding its excessive volatilization. Stirring for 6-8 hours allows the coupling agent to be uniformly grafted onto the Cu-BC surface, enhancing its interfacial compatibility. Filtration and washing remove unreacted coupling agent, and drying removes moisture, ensuring the stability of the modified Cu-BC. In S3, anhydrous ethanol can efficiently dissolve cycloazinone, facilitating subsequent loading; ultrasonic dispersion for 6-8 hours can uniformly load cycloazinone onto the modified Cu-BC, improving loading efficiency; filtration separates the solid; centrifugation and washing remove free cycloazinone; lyophilization removes the solvent at low temperature, preventing cycloazinone from decomposing at high temperature, ultimately yielding a cycloazinone formulation with good stability and uniform loading.

[0016] 2. In step S1 of this invention, copper sulfate pentahydrate is used to modify BC. The doping of copper regulates and optimizes the pore structure of biochar, forming more abundant macropores, which can provide sufficient space for the subsequent loading of cycloazinone, allowing it to be uniformly dispersed in the modified Cu-BC. Furthermore, the modified Cu-BC contains copper ions, which have antibacterial properties. This allows cycloazinone to exert its herbicidal effect while also having antibacterial properties, thereby further improving the herbicidal performance of the herbicide.

[0017] 3. In step S2 of this invention, a modified silane coupling agent containing hydrophobic long chains, triazole rings, and UV-absorbing (benzophenone) groups is used to modify Cu-BC. The surface of Cu-BC is highly polar due to the presence of hydroxyl groups, which has compatibility differences with the weakly polar cycloazinone, easily leading to a low loading. The silanol groups generated by the hydrolysis of the modified silane coupling agent undergo a dehydration condensation reaction with the hydroxyl groups on the surface of Cu-BC, which can stably graft the coupling agent onto its surface. This not only reduces the overall polarity of the material to match the weakly polar characteristics of cycloazinone and significantly increases the loading, but also enhances the UV resistance of the formulation by introducing benzophenone groups. It can effectively block or absorb external ultraviolet rays, avoid the photodegradation failure of the herbicide active ingredient due to ultraviolet radiation, prolong its residual effect in the field, and improve the slow-release performance. Meanwhile, the hydrophobic long chain can form a hydrophobic layer on the material surface, reducing the dissolution of cycloazinone by external moisture after loading and prolonging the efficacy of the formulation; the triazole ring, as a nitrogen-containing heterocyclic structure, can form additional binding sites with cycloazinone molecules (containing triazine rings and other heterocycles) through hydrogen bonding and other interactions, further consolidating the loading state of cycloazinone on the Cu-BC surface, preventing it from falling off during storage or use, and improving the loading rate. Detailed Implementation

[0018] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below.

[0019] In a first aspect, the present invention provides a method for preparing a cycloazinone formulation, comprising the following steps: S1. Preparation of Cu-BC: To prepare BC, BC is mixed and ground with copper sulfate pentahydrate, then calcined in a tube furnace. After cooling, Cu-BC is obtained. Cu-BC is produced by mixing and grinding BC with copper sulfate pentahydrate and calcining in a tube furnace. 2+ Stable anchoring to the BC carbon framework, it retains the porous structure of BC for physical adsorption while introducing Cu. 2+ The site achieves a dual function of adsorption and synergistic antibacterial action, providing a high-quality carrier for subsequent loading of cycloazinone.

[0020] The mass ratio of BC to copper sulfate pentahydrate is 1:(1.2–1.5). This ensures the Cu... 2+ Fully doped and non-agglomerated, below 1.2 Cu 2+ Insufficient, resulting in weak synergistic antibacterial ability; above 1.5 Cu 2+ Aggregation clogs pores, reducing adsorption capacity; this ratio balances Cu. 2+ Load capacity and carrier pore utilization rate.

[0021] S2. Preparation of modified Cu-BC: The modified silane coupling agent is added to an ethanol aqueous solution, followed by the Cu-BC obtained in S1. After stirring at 25-35℃ for 6-8 hours, the mixture is filtered, washed, and dried to obtain modified Cu-BC. Modifying Cu-BC with the modified silane coupling agent can optimize the surface polarity of the support, improve the compatibility and binding stability with cycloazinone, and provide suitable conditions for the coupling agent reaction at 25-35℃ for 6-8 hours to ensure uniform and stable modification.

[0022] The ratio of modified silane coupling agent, ethanol aqueous solution, and Cu-BC is 0.1-0.2g: 30-40mL: 0.3g, which ensures that the coupling agent uniformly modifies the carrier and avoids insufficient modification or accumulation and pore blockage. The volume ratio of anhydrous ethanol to deionized water in the ethanol aqueous solution is 8:2, which can dissolve the coupling agent and promote its hydrolysis reaction.

[0023] S3. Preparation of cycloazinone formulation: cycloazinone is dissolved in anhydrous ethanol, then modified Cu-BC is added, and the mixture is ultrasonically dispersed for 6–8 hours. After filtration, centrifugation, washing, and lyophilization, the cycloazinone formulation is obtained. This method achieves uniform drug loading, preserves carrier pores, and improves formulation stability. Ultrasonic dispersion for 6–8 hours breaks up cycloazinone agglomerates, promotes its penetration into carrier pores, and ensures uniform loading.

[0024] The ratio of cycloazinone, anhydrous ethanol, and modified Cu-BC is 0.05–0.1 g: 30–40 mL: 0.05–0.2 g. This matches the adsorption capacity of the carrier and balances the drug dosage and loading efficiency.

[0025] Further, in step S1, the specific steps for preparing BC are as follows: the straw is washed, dried, crushed, and then dried again. It is then pyrolyzed in a tube furnace under a nitrogen atmosphere, followed by cooling, washing, filtration, and drying to obtain BC. Preparing BC through straw pyrolysis not only achieves the resource utilization of agricultural waste, reducing costs and being environmentally friendly, but also provides a stable and efficient carrier basis for subsequent loading modification and adsorption loading of cycloazinone, helping to improve the drug loading performance and application potential of cycloazinone formulations.

[0026] Furthermore, the straw includes any one or more of rice straw, wheat straw, and corn straw. These types of straw are widely available, low in cost, and rich in cellulose. After pyrolysis, they can form porous BC, enhancing the subsequent Cu content. 2+ Loading and adsorption capacity of cycloazinone.

[0027] Furthermore, the pyrolysis temperature in the tubular furnace is 600–700℃, the heating rate is 10℃ / min, and the pyrolysis time is 3–5 hours. The 600–700℃ temperature ensures complete pyrolysis of the straw to form a carbon skeleton while preventing pore collapse due to excessive temperature; the 10℃ / min heating rate reduces thermal stress and prevents damage to the BC structure; the 3–5 hour pyrolysis time thoroughly removes volatiles, ensuring the porosity and stability of BC, thus providing a suitable environment for Cu production. 2+ Anchoring provides sufficient sites.

[0028] Further, in step S1, the calcination conditions are as follows: the temperature is increased to 600–700°C at a rate of 10°C / min under a nitrogen atmosphere, and then held at that temperature for 2–4 hours. The nitrogen atmosphere can prevent Cu… 2+ Oxidation ensures its activity; the combination of 600–700℃ and holding at that temperature for 2–4 hours promotes Cu oxidation. 2+ Stable integration with the BC framework, avoiding Cu 2+ It is lost in subsequent steps, enhancing the synergistic antibacterial effect of the carrier.

[0029] Further, in step S2, the method for preparing the modified silane coupling agent is as follows: S21. Mix 2,4-dihydroxybenzophenone with K2CO3, then add 3-bromopropyne, then add acetone, reflux for 16 h, after the reaction is complete, filter, evaporate to dryness, and dry to obtain alkynylated benzophenone. In the above reaction steps, the phenolic hydroxyl group in 2,4-dihydroxybenzophenone undergoes a substitution reaction with the -Br in 3-bromopropyne to obtain alkynylated benzophenone. K2CO3 generates highly active phenoxy anions through alkalinity and maintains the alkalinity of the reaction environment, while acetone serves as a reaction solvent to provide suitable reaction conditions for this substitution reaction.

[0030] The ratio of 2,4-dihydroxybenzophenone, K₂CO₃, 3-bromopropyne, and acetone used is 10.1 g: 13 g: 3.5 mL: 130–150 mL. This ensures that the phenolic hydroxyl group fully undergoes a substitution reaction with -Br to generate sufficient alkynylated benzophenone.

[0031] S22. 11-Azide-undecyltrimethoxysilane, alkynylated benzophenone, ascorbic acid, and copper sulfate were added to tetrahydrofuran and reacted at 20-30°C for 5-12 hours. The mixture was then washed and dried to obtain the modified silane coupling agent. In the above reaction steps, the azide group of 11-azidoundecyltrimethoxysilane undergoes an azide-yne ​​addition reaction with the yne group in alkynylated benzophenone to form a triazole ring, thus yielding a modified silane coupling agent. Ascorbic acid and copper sulfate serve as catalysts, and tetrahydrofuran as the solvent.

[0032] The ratio of 11-azidoundecyltrimethoxysilane, alkynylated benzophenone, ascorbic acid, copper sulfate, and tetrahydrofuran is 3.2 g: 2.5 g: 0.25–0.3 g: 0.13–0.14 g: 50–80 mL. This allows the azide group and alkynyl group to react fully to form a triazole ring.

[0033] Secondly, the present invention provides a cycloazinone formulation, which is prepared by any one of the preparation methods described above.

[0034] The specific embodiments of the present invention will be described in detail below, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments.

[0035] Preparation Example

[0036] The preparation method of the modified silane coupling agent in this preparation example is as follows: S21. Mix 10.1g of 2,4-dihydroxybenzophenone with 13g of K2CO3, then add 3.5mL of 3-bromopropyne, and then add 140mL of acetone. Reflux for 16h. After the reaction is complete, filter, evaporate to dryness, and dry to obtain alkynylated benzophenone. S22. Add 3.2g of 11-azidoundecyltrimethoxysilane, 2.5g of alkynylated benzophenone, 0.27g of ascorbic acid, and 0.14g of copper sulfate to 60mL of tetrahydrofuran, react at 25℃ for 8h, wash, and dry to obtain the modified silane coupling agent.

[0037] Comparison Example

[0038] The only difference between this comparative example and the preparation example is that "alkynylated benzophenone" is replaced with "phenylacetylene". The specific steps are as follows: 3.2 g of 11-azidoundecyltrimethoxysilane, 1 g of phenylacetylene, 0.27 g of ascorbic acid, and 0.14 g of copper sulfate were added to 60 mL of tetrahydrofuran and reacted at 25 °C for 8 h. After washing and drying, the modified silane coupling agent was obtained.

[0039] Example 1

[0040] This embodiment provides a method for preparing a cycloazinone formulation, including the following steps: S1. Preparation of Cu-BC: Corn stalks were washed, dried, crushed, and then dried. They were then pyrolyzed in a tube furnace under a nitrogen atmosphere at a temperature of 600℃, a heating rate of 10℃ / min, and a pyrolysis time of 3 hours. After cooling, the stalks were washed, filtered, and dried to obtain BC. 1g of BC was mixed and ground with 1.2g of copper sulfate pentahydrate and calcined in a tube furnace. The temperature was raised to 600℃ under a nitrogen atmosphere at a heating rate of 10℃ / min and held for 2 hours. After cooling, Cu-BC was obtained. S2. Preparation of modified Cu-BC: 0.1g of the modified silane coupling agent obtained in the preparation example was added to 30mL of ethanol aqueous solution. The volume ratio of anhydrous ethanol to deionized water in the ethanol aqueous solution was 8:2. Then, 0.3g of Cu-BC obtained in S1 was added. After stirring at 25℃ for 6h, the mixture was filtered, washed, and dried to obtain modified Cu-BC. S3. Preparation of cycloazinone formulation: Dissolve 0.08g of cycloazinone in 35mL of anhydrous ethanol, then add 0.13g of modified Cu-BC, sonicate for 6h, filter, centrifuge and wash, freeze dry to obtain cycloazinone formulation.

[0041] Example 2

[0042] This embodiment provides a method for preparing a cycloazinone formulation, including the following steps: S1. Preparation of Cu-BC: Corn stalks were washed, dried, crushed, and then dried. They were then pyrolyzed in a tube furnace under a nitrogen atmosphere at a temperature of 650℃, a heating rate of 10℃ / min, and a pyrolysis time of 4 hours. After cooling, the stalks were washed, filtered, and dried to obtain BC. 1g of BC was mixed and ground with 1.35g of copper sulfate pentahydrate and calcined in a tube furnace. The temperature was raised to 650℃ under a nitrogen atmosphere at a heating rate of 10℃ / min and held for 3 hours. After cooling, Cu-BC was obtained. S2. Preparation of modified Cu-BC: 0.1g of the modified silane coupling agent obtained in the preparation example was added to 30mL of ethanol aqueous solution. The volume ratio of anhydrous ethanol to deionized water in the ethanol aqueous solution was 8:2. Then, 0.3g of Cu-BC obtained in S1 was added. After stirring at 30℃ for 7h, the mixture was filtered, washed, and dried to obtain modified Cu-BC. S3. Preparation of cycloazinone formulation: Dissolve 0.08g of cycloazinone in 35mL of anhydrous ethanol, then add 0.13g of modified Cu-BC, sonicate for 7h, filter, centrifuge and wash, freeze dry to obtain cycloazinone formulation.

[0043] Example 3

[0044] This embodiment provides a method for preparing a cycloazinone formulation, including the following steps: S1. Preparation of Cu-BC: Corn stalks were washed, dried, crushed, and then dried. They were then pyrolyzed in a tube furnace under a nitrogen atmosphere at a temperature of 700℃, a heating rate of 10℃ / min, and a pyrolysis time of 5h. After cooling, the stalks were washed, filtered, and dried to obtain BC. 1g of BC was mixed and ground with 1.5g of copper sulfate pentahydrate and calcined in a tube furnace. The temperature was raised to 700℃ under a nitrogen atmosphere at a heating rate of 10℃ / min and held for 4h. After cooling, Cu-BC was obtained. S2. Preparation of modified Cu-BC: 0.1g of the modified silane coupling agent obtained in the preparation example was added to 30mL of ethanol aqueous solution. The volume ratio of anhydrous ethanol to deionized water in the ethanol aqueous solution was 8:2. Then, 0.3g of Cu-BC obtained in S1 was added. After stirring at 35℃ for 8h, the mixture was filtered, washed, and dried to obtain modified Cu-BC. S3. Preparation of cycloazinone formulation: Dissolve 0.08g of cycloazinone in 35mL of anhydrous ethanol, then add 0.13g of modified Cu-BC, sonicate for 8h, filter, centrifuge and wash, freeze dry to obtain cycloazinone formulation.

[0045] Example 4

[0046] This embodiment provides a method for preparing a cycloazinone formulation, including the following steps: S1. Preparation of Cu-BC: Corn stalks were washed, dried, crushed, and then dried. They were then pyrolyzed in a tube furnace under a nitrogen atmosphere at a temperature of 700℃, a heating rate of 10℃ / min, and a pyrolysis time of 5h. After cooling, the stalks were washed, filtered, and dried to obtain BC. 1g of BC was mixed and ground with 1.5g of copper sulfate pentahydrate and calcined in a tube furnace. The temperature was raised to 700℃ under a nitrogen atmosphere at a heating rate of 10℃ / min and held for 4h. After cooling, Cu-BC was obtained. S2. Preparation of modified Cu-BC: 0.15g of the modified silane coupling agent obtained in the preparation example was added to 35mL of ethanol aqueous solution. The volume ratio of anhydrous ethanol to deionized water in the ethanol aqueous solution was 8:2. Then, 0.3g of Cu-BC obtained in S1 was added. After stirring at 35℃ for 8h, the mixture was filtered, washed, and dried to obtain modified Cu-BC. S3. Preparation of cycloazinone formulation: Dissolve 0.08g of cycloazinone in 35mL of anhydrous ethanol, then add 0.13g of modified Cu-BC, sonicate for 8h, filter, centrifuge and wash, freeze dry to obtain cycloazinone formulation.

[0047] Example 5

[0048] This embodiment provides a method for preparing a cycloazinone formulation, including the following steps: S1. Preparation of Cu-BC: Corn stalks were washed, dried, crushed, and then dried. They were then pyrolyzed in a tube furnace under a nitrogen atmosphere at a temperature of 700℃, a heating rate of 10℃ / min, and a pyrolysis time of 5h. After cooling, the stalks were washed, filtered, and dried to obtain BC. 1g of BC was mixed and ground with 1.5g of copper sulfate pentahydrate and calcined in a tube furnace. The temperature was raised to 700℃ under a nitrogen atmosphere at a heating rate of 10℃ / min and held for 4h. After cooling, Cu-BC was obtained. S2. Preparation of modified Cu-BC: 0.2g of the modified silane coupling agent obtained in the preparation example was added to 40mL of ethanol aqueous solution. The volume ratio of anhydrous ethanol to deionized water in the ethanol aqueous solution was 8:2. Then, 0.3g of Cu-BC obtained in S1 was added. After stirring at 35℃ for 8h, the mixture was filtered, washed, and dried to obtain modified Cu-BC. S3. Preparation of cycloazinone formulation: Dissolve 0.08g of cycloazinone in 35mL of anhydrous ethanol, then add 0.13g of modified Cu-BC, sonicate for 8h, filter, centrifuge and wash, freeze dry to obtain cycloazinone formulation.

[0049] Comparative Example 1

[0050] The only difference between this comparative example and Example 1 is that the modified silane coupling agent obtained in the preparation example was replaced with an equal amount of the modified silane coupling agent obtained in the control example.

[0051] Comparative Example 2

[0052] The only difference between this comparative example and Example 1 is that an equal amount of methyltrimethoxysilane was used to replace the modified silane coupling agent obtained in the preparation example.

[0053] Comparative Example 3

[0054] The only difference between this comparative example and Example 1 is that the modified silane coupling agent is omitted. The specific steps are as follows: S1. Preparation of Cu-BC: Corn stalks were washed, dried, crushed, and then dried. They were then pyrolyzed in a tube furnace under a nitrogen atmosphere at a temperature of 600℃, a heating rate of 10℃ / min, and a pyrolysis time of 3 hours. After cooling, the stalks were washed, filtered, and dried to obtain BC. 1g of BC was mixed and ground with 1.2g of copper sulfate pentahydrate and calcined in a tube furnace. The temperature was raised to 600℃ under a nitrogen atmosphere at a heating rate of 10℃ / min and held for 2 hours. After cooling, Cu-BC was obtained. S2. Preparation of cycloazinone formulation: Dissolve 0.08g of cycloazinone in 35mL of anhydrous ethanol, then add 0.13g of Cu-BC, sonicate for 6h, filter, centrifuge and wash, freeze dry to obtain cycloazinone formulation.

[0055] Comparative Example 4

[0056] The only difference between this comparative example and Example 1 is that the modified silane coupling agent and Cu modification are omitted. The specific steps are as follows: S1. Preparation of BC: After washing, drying, crushing and drying the corn stalks, the stalks were pyrolyzed in a tube furnace under a nitrogen atmosphere at a temperature of 600℃, a heating rate of 10℃ / min, and a pyrolysis time of 3h. After cooling, washing, filtration and drying, BC was obtained. S2. Preparation of cycloazinone formulation: Dissolve 0.08g cycloazinone in 35mL anhydrous ethanol, then add 0.13g BC, sonicate for 6h, filter, centrifuge and wash, freeze dry to obtain cycloazinone formulation.

[0057] The performance of the cycloazinone formulations prepared in Examples 1 to 5 and Comparative Examples 1 to 4 was tested using the following methods: (1) Drug loading rate test: Weigh the drug-loaded sample (cycloazinone formulation prepared in the examples and comparative examples) into a 25 mL volumetric flask, add acetonitrile, water, and acetic acid (acetonitrile:water:acetic acid = 20:4.95:0.05) mixture, and sonicate to elute the cycloazinone pesticide loaded on it. After sonication for 2 h, make up to volume with the mixture, and use a syringe to draw 1 mL of the solution after making up to volume. After passing through a 0.45 μm organic filter membrane, the content of cycloazinone in the eluent is detected by high performance liquid chromatography. The drug loading rate of the drug-loaded sample is calculated according to the formula, and the test results are shown in Table 1.

[0058]

[0059] Table 1

[0060] As shown in Table 1, the drug loading rates of the carriers prepared in the examples are all higher than those of the carriers prepared in the comparative examples. Comparing Comparative Example 2 with Example 1, it can be seen that the triazole ring, as a nitrogen-containing heterocyclic structure, can form additional binding sites with cycloazinone molecules (containing triazine rings and other heterocycles) through hydrogen bonding and other interactions, further consolidating the loading state of cycloazinone on the Cu-BC surface, preventing it from falling off during storage or use, and improving the loading rate. The results of Comparative Examples 3 and 4 with Example 1 show that the silanol groups generated by the hydrolysis of the modified silane coupling agent undergo a dehydration condensation reaction with the hydroxyl groups on the Cu-BC surface, which can stably graft the coupling agent onto its surface. This not only reduces the overall polarity of the material to adapt to the weak polarity of cycloazinone and significantly improves the loading, but also the copper doping regulates and optimizes the pore structure of the biochar, forming richer macropores, which can provide sufficient space for subsequent loading of cycloazinone.

[0061] (2) Slow-release performance test: Nine experimental plots were selected for planting barnyard grass, each with an area of ​​25m². 2 Under identical light, soil, irrigation, and planting conditions, and with 50 barnyard grass seeds per plant, the herbicides prepared in both the example and comparative studies were used for weed control after the barnyard grass reached the 3-leaf stage. The dosage was consistently maintained. The number of days from the complete death of the barnyard grass until new leaves began to grow was recorded; a longer duration indicates a better slow-release effect. The test results are shown in Table 2.

[0062] Table 2

[0063] As shown in Table 2, the sustained-release performance of the formulations prepared in the examples is superior to that of the comparative examples. The sustained-release performance of Comparative Example 1 is lower than that of Example 1, indicating that the benzophenone group enhances the UV resistance of the formulation, effectively blocking or absorbing external ultraviolet rays, preventing the active ingredient of the herbicide from photodegrading due to ultraviolet radiation, and prolonging its residual effect in the field. The sustained-release performance of Comparative Example 2 is lower than that of Example 1, indicating that the hydrophobic long chain can form a hydrophobic layer on the material surface, reducing the dissolution of cycloazinone by external moisture after loading, and prolonging the residual effect of the formulation. The sustained-release performance of Comparative Examples 3 and 4 is lower than that of Example 1, indicating that the modified silane coupling agent and copper modification can improve the sustained-release performance.

[0064] (3) Antibacterial performance test: The filter paper method was used: The cycloazinone preparations prepared in Examples 1-5 and Comparative Examples 1-4 were placed in culture dishes containing bacterial strains and cultured at 25°C in a constant temperature incubator. After 7 days, the growth was observed and the size of the inhibition zone was measured (the bacterial strain grows to form multiple colonies, and each colony has a transparent zone around it where no colonies grow, which is the inhibition zone) to compare the toxicity of the bactericide. The bacterial strain used was Staphylococcus aureus.

[0065] Methods for recording the inhibitory effect of active ingredients on bacteria: Grade 5: Inhibition zone diameter greater than 20 mm, with obvious antibacterial effect; Grade 4: Inhibition zone diameter 16–20 mm, with strong antibacterial effect; Grade 3: Inhibition zone diameter 13–16 mm, with antibacterial effect; Grade 2: Inhibition zone diameter 10–13 mm, with no obvious antibacterial effect; Grade 1: Inhibition zone diameter 7–10 mm, with weak antibacterial effect; Grade 0: 7 mm (diameter of filter paper). The test results are shown in Table 3.

[0066] Table 3

[0067] As can be seen from Table 3, the antibacterial properties of the formulation obtained in the examples are better than those in the comparative examples.

[0068] The above-disclosed embodiments are merely a few specific examples of the present invention. However, the embodiments of the present invention are not limited thereto, and any variations that can be conceived by those skilled in the art should fall within the protection scope of the present invention.

Claims

1. A method for preparing a cycloazinone formulation, characterized in that, Includes the following steps: S1. Preparation of Cu-BC: To prepare BC, BC is mixed and ground with copper sulfate pentahydrate, then calcined in a tube furnace and cooled to obtain Cu-BC. S2. Preparation of modified Cu-BC: Add the modified silane coupling agent to an aqueous ethanol solution, then add the Cu-BC obtained in S1, stir at 25-35℃ for 6-8 hours, filter, wash, and dry to obtain modified Cu-BC. S3. Preparation of cycloazinone formulation: Dissolve cycloazinone in anhydrous ethanol, then add modified Cu-BC, ultrasonically disperse for 6-8 hours, filter, centrifuge and wash, freeze dry to obtain cycloazinone formulation.

2. The method for preparing the cycloazinone formulation according to claim 1, characterized in that, In step S1, the specific steps for preparing BC are as follows: the straw is washed, dried, crushed, and then dried in a tube furnace under a nitrogen atmosphere. After that, it is cooled, washed, filtered, and dried to obtain BC.

3. The method for preparing the cycloazinone formulation according to claim 2, characterized in that, The straw includes any one or more of rice straw, wheat straw and corn straw; The pyrolysis temperature in the tubular furnace is 600–700℃, the heating rate is 10℃ / min, and the pyrolysis time is 3–5h.

4. The method for preparing the cycloazinone formulation according to claim 1, characterized in that, In step S1, the mass ratio of BC to copper sulfate pentahydrate is 1:(1.2~1.5).

5. The method for preparing the cycloazinone formulation according to claim 1, characterized in that, In step S1, the calcination conditions are as follows: the temperature is increased to 600-700°C at a heating rate of 10°C / min under a nitrogen atmosphere, and then held at that temperature for 2-4 hours.

6. The method for preparing the cycloazinone formulation according to claim 1, characterized in that, In step S2, the modified silane coupling agent is prepared by: S21. Mix 2,4-dihydroxybenzophenone with K2CO3, then add 3-bromopropyne, then add acetone, reflux for 16 h, after the reaction is complete, filter, evaporate to dryness, and dry to obtain alkynylated benzophenone. S22. 11-Azide-undecyltrimethoxysilane, alkynylated benzophenone, ascorbic acid, and copper sulfate are added to tetrahydrofuran and reacted at 20-30°C for 5-12 hours. After washing and drying, the modified silane coupling agent is obtained.

7. The method for preparing the cycloazinone formulation according to claim 6, characterized in that, In step S21, the ratio of 2,4-dihydroxybenzophenone, K2CO3, 3-bromopropyne, and acetone is 10.1g:13g:3.5mL:130-150mL. In step S22, the ratio of 11-azidoundecyltrimethoxysilane, alkynylated benzophenone, ascorbic acid, copper sulfate, and tetrahydrofuran is 3.2g:2.5g:0.25-0.3g:0.13-0.14g:50-80mL.

8. The method for preparing the cycloazinone formulation according to claim 1, characterized in that, In step S2, the ratio of modified silane coupling agent, ethanol aqueous solution, and Cu-BC is 0.1-0.2 g: 30-40 mL: 0.3 g; The volume ratio of anhydrous ethanol to deionized water in an aqueous ethanol solution is 8:

2.

9. The method for preparing the cycloazinone formulation according to claim 1, characterized in that, In step S3, the ratio of cycloazinone, anhydrous ethanol, and modified Cu-BC is 0.05–0.1 g: 30–40 mL: 0.05–0.2 g.

10. A cycloazinone formulation, characterized in that, It is prepared by the preparation method according to any one of claims 1-9.

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