Efficient forest weed killer containing hexazinone and preparation method of efficient forest weed killer

Abstract

The invention discloses a hexazinone-containing efficient forest weed killer and a preparation method thereof, and belongs to the technical field of pesticides. The preparation method of the hexazinone-containing efficient forest weed killer comprises the following steps: S1, preparing a modified metal organic framework; s2, in a nitrogen atmosphere, dissolving the modified metal organic framework in deionized water, heating to 40-80 DEG C, then adding sodium lignin sulfonate to react with acrylic acid for 10-20 minutes, then adding an initiator, heating to 80-100 DEG C, reacting for 1-2 hours, cooling to room temperature, washing and drying to obtain a modified carrier; s3, dissolving hexazinone technical and the modified carrier in DMF, stirring at room temperature, centrifuging, washing and drying to obtain the herbicide. The finally obtained herbicide can realize slow release of hexazinone by virtue of a carrier, and the weeding long-term effect and the environmental safety are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of pesticides, in particular to a high-efficiency forest herbicide containing hexazinone and a preparation method thereof. BACKGROUND

[0002] Hexazinone is also known as Wilber, Linweijing, Feicaoshui, Sentai; the chemical name is 3-cyclohexyl-6-dimethylamino-1-methyl-1, 3, 5-triazine-2, 4-dione, which is a colorless, odorless crystalline solid, and belongs to the group of post-emergence contact selective triazinone herbicides. The product has strong killing power on forest weeds, shrubs, vines and other plants. It can be absorbed by the stems and leaves of plants, conducted in the plant through xylem, interfere with the photosynthesis of plants, cause metabolic disorder and lead to plant death; it can also be absorbed by the root system of plants, conducted to stems and leaves to interfere with the photosynthesis of plants, cause metabolic disorder and lead to plant death.

[0003] Forest weeds are mainly perennial plants, with long growth cycle, developed root system and strong regenerative ability. The conventional hexazinone dosage form will lose effectiveness in a short period of time due to degradation or loss after application, and frequent reapplication is required. Therefore, it is necessary to prepare a hexazinone herbicide with slow-release ability, which can effectively control weeds for a long time and greatly reduce the cost of labor and pesticide procurement, and is more economical for large-scale forest management. SUMMARY

[0004] The present application provides a high-efficiency forest herbicide containing hexazinone and a preparation method thereof, which can solve the problem that forest weeds are mainly perennial plants with long growth cycle, developed root system and strong regenerative ability in the prior art, and the conventional hexazinone dosage form will lose effectiveness in a short period of time due to degradation or loss after application, and frequent reapplication is required.

[0005] The object of the present application can be achieved by the following technical solutions: In a first aspect, the present application provides a preparation method of a high-efficiency forest herbicide containing hexazinone, comprising the following steps: S1, preparing a modified metal organic framework; S2, dissolving the modified metal organic framework in deionized water under a nitrogen atmosphere, adding sodium lignosulfonate and acrylic acid after heating to 40-80℃ for 10-20min, then adding an initiator, heating to 80-100℃, reacting for 1-2h, cooling to room temperature, washing, drying to obtain a modified carrier; S3, dissolving hexazinone technical material and the modified carrier in DMF, stirring at room temperature, centrifuging, washing, drying to obtain a herbicide.

[0006] Further, the specific step of step S1 is: stirring the iron salt, terephthalic acid, glacial acetic acid and deionized water at room temperature, adding acrylic acid, performing hydrothermal reaction, cooling to room temperature after the reaction is completed, washing, drying, and obtaining the modified metal organic framework.

[0007] Further, the amount ratio of the iron salt, terephthalic acid, glacial acetic acid, deionized water and acrylic acid is 1.6-3.2 g: 0.6-1.32 g: 2-3 mL: 30-40 mL: 0.05-0.14 mL.

[0008] Further, the iron salt is any one of ferric chloride, ferric nitrate and ferric sulfate.

[0009] Further, the temperature of the hydrothermal reaction is 180-230 DEG C, and the reaction time is 8-12 h.

[0010] Further, in step S2, the amount ratio of the modified metal organic framework, deionized water, sodium lignosulfonate, acrylic acid and initiator is 0.4 g: 30-40 mL: 0.2-0.4 g: 0.2-0.3 mL: 0.12-0.16 g.

[0011] Further, in step S2, the initiator is potassium persulfate.

[0012] Further, in step S3, the amount ratio of the cycloximidone technical material, modified carrier and DMF is 1 g: 1 g: 30-40 mL.

[0013] Further, in step S3, the stirring time at room temperature is 10-12 h.

[0014] In a second aspect, the application provides a high-efficiency forest herbicide containing cycloximidone, which is prepared by the preparation method described in any one of the above content.

[0015] The application has the following beneficial effects: The present invention discloses a method for preparing a highly efficient forest herbicide containing cycloazinone. Step S1 involves preparing a modified metal-organic framework (MOF) to provide a basic framework for subsequent functionalization. The pre-introduced active sites (carbon-carbon double bonds) enhance the binding ability with subsequent monomers. In step S2, MOFs are first dispersed in water and heated to 40–80°C. Sodium lignosulfonate and acrylic acid are then added and reacted for 10–20 minutes. The warm environment promotes the intermolecular forces that bring the three components closer together, ensuring sufficient contact between the carbon-carbon double bonds on the MOF surface, the hydroxyl groups of sodium lignosulfonate, and the double bonds of acrylic acid. Subsequently, an initiator is added and the temperature is raised to 80–80°C. At 100℃, the initiator decomposes to generate free radicals, which abstract hydrogen atoms from the hydroxyl groups of sodium lignosulfonate to form active free radicals. These free radicals then attack the double bonds of MOFs and acrylic acid, initiating chain polymerization. This allows sodium lignosulfonate and acrylic acid to be covalently grafted onto the surface of MOFs. After 1–2 hours of reaction, a stable three-dimensional copolymer coating layer is formed, ultimately yielding the modified carrier. In step S3, room temperature stirring allows cycloazinone to fully dissolve in DMF and be loaded onto the modified carrier through hydrogen bonding and other interactions. Centrifugation and washing remove free drug, and the resulting herbicide can achieve sustained release of cycloazinone with the help of the carrier group, improving the long-term effectiveness of weed control and environmental safety.

[0016] This method creatively utilizes a modified carrier, which can impart properties such as slow-release and UV resistance to herbicides, as detailed below: 1. This invention prepares a modified metal-organic framework containing carbon-carbon double bonds. The double bonds can copolymerize with acrylic acid and sodium lignosulfonate added in S2, so that the functional monomers are firmly grafted onto the surface of MOFs through covalent bonds, forming a uniform and stable coating layer, which improves the binding stability. Furthermore, the modified carrier surface contains a large number of functional groups, which can form hydrogen bonds and other interactions with the groups on the cycloazinone, thereby improving the binding stability of the cycloazinone and making it beneficial for preparing herbicides with good slow-release performance.

[0017] 2. This invention uses a modified metal-organic framework, acrylic acid, and sodium lignosulfonate as a graft copolymerization carrier. Sodium lignosulfonate has the effect of resisting ultraviolet absorption, which can reduce the photolysis of cycloazinone. In addition, sodium lignosulfonate contains sulfur, which can not only improve the UV resistance of herbicides but also serve as a nutrient element to promote crop growth. After the reaction, acrylic acid yields polyacrylic acid (PAA). Polyacrylic acid itself is a pH-responsive polymer, and its structure and permeation behavior are completely different under different pH conditions. In an acidic environment, PAA is in a non-swelling state, which is not conducive to drug exudation. However, in a neutral or alkaline environment, PAA absorbs water and swells, forming a high-permeability channel, which accelerates drug release and can improve the pH response of herbicides. Detailed Implementation

[0018] In order to make the above objectives, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application are described in detail below.

[0019] In a first aspect, the present application provides a preparation method of high-efficiency forest herbicide containing cyazofamid, comprising the following steps: S1, preparing a modified metal organic framework; providing a basic framework for subsequent functional modification, and the active sites (carbon-carbon double bonds) introduced in advance can enhance the binding capacity with subsequent monomers; S2, dissolving the modified metal organic framework in deionized water under a nitrogen atmosphere, adding sodium lignosulfonate and acrylic acid after heating to 40-80℃ for 10-20min, then adding an initiator, heating to 80-100℃, reacting for 1-2h, cooling to room temperature, washing, drying, and obtaining a modified carrier; the present application realizes the free radical copolymerization of the modified metal organic framework (MOFs), sodium lignosulfonate and acrylic acid through step-by-step control: first, dispersing the MOFs in water and heating to 40-80℃, adding sodium lignosulfonate and acrylic acid for 10-20min, using the warm environment to promote the three to approach through intermolecular forces, so that the carbon-carbon double bonds on the surface of the MOFs, the hydroxyl groups of the sodium lignosulfonate and the double bonds of the acrylic acid fully contact; then adding an initiator and heating to 80-100℃, the initiator decomposes to generate free radicals, which abstract the hydrogen atoms of the hydroxyl groups of the sodium lignosulfonate to form active free radicals, which then attack the double bonds of the MOFs and the double bonds of the acrylic acid, initiate chain polymerization, and graft the sodium lignosulfonate and the acrylic acid to the surface of the MOFs through covalent bonds, and form a stable three-dimensional copolymer coating layer after 1-2h of reaction, and finally obtain the modified carrier.

[0020] S3, dissolving cyazofamid technical material and the modified carrier in DMF, stirring at room temperature, centrifuging, washing, drying, and obtaining the herbicide. Stirring at room temperature makes cyazofamid fully dissolved in DMF and loaded on the modified carrier through hydrogen bonding and other interactions, centrifuging and washing removes free drugs, and finally the obtained herbicide can realize the slow release of cyazofamid with the help of the carrier, improving the long-acting and environmental safety of the herbicide.

[0021] Further, the specific steps of step S1 are: stirring the iron salt, terephthalic acid, glacial acetic acid and deionized water at room temperature, adding acrylic acid, carrying out hydrothermal reaction, cooling to room temperature after the reaction is completed, washing, drying, and obtaining the modified metal organic framework. Stirring the iron salt (metal source) and terephthalic acid (organic ligand) at room temperature makes them preliminarily dispersed in deionized water and form a coordination precursor. Glacial acetic acid as a regulator can control the pH of the reaction system, inhibit excessive hydrolysis of the ligand, and promote the formation of MOFs crystal nucleus. The added acrylic acid (containing carbon-carbon double bond) is partially embedded in the MOFs framework or anchored on the surface thereof through coordination with metal ions or co-ligand with terephthalic acid in the subsequent hydrothermal reaction (high temperature and high pressure environment), and the double bond activity is reserved. Finally, after cooling, washing to remove unreacted raw materials, and drying, the modified MOFs with porous structure and surface carbon-carbon double bond are obtained, which provide active sites for the graft copolymerization of S2.

[0022] Further, the amount ratio of the iron salt, terephthalic acid, glacial acetic acid, deionized water and acrylic acid is 1.6-3.2 g: 0.6-1.32 g: 2-3 mL: 30-40 mL: 0.05-0.14 mL. The amount ratio can ensure that the iron salt and terephthalic acid are fully coordinated to form a stable MOFs framework, the glacial acetic acid moderately controls the crystallization conditions, and the small amount of acrylic acid introduced reserves the carbon-carbon double bond activity and does not damage the MOFs porous structure.

[0023] Further, the iron salt is any one of ferric chloride, ferric nitrate and ferric sulfate. It can be flexibly adapted to different preparation scenes, and all can efficiently react with terephthalic acid and acrylic acid to generate a metal organic framework with stable structure, providing a reliable basis for subsequent graft modification and herbicide loading.

[0024] Further, the temperature of the hydrothermal reaction is 180-230°C, and the reaction time is 8-12 h. It can promote the full growth of MOFs crystals, ensure that the pore structure is developed and uniformly distributed, and make the acrylic acid stably anchored on the surface of the framework.

[0025] Further, in step S2, the amount ratio of the modified metal organic framework, deionized water, sodium lignosulfonate, acrylic acid and initiator is 0.4 g: 30-40 mL: 0.2-0.4 g: 0.2-0.3 mL: 0.12-0.16 g. This amount ratio can realize the proportioning of sodium lignosulfonate, acrylic acid and modified MOFs, avoid uneven grafting caused by excessive amount of a component, and ensure that the functional group density meets the loading demand

[0026] Further, in step S2, the initiator is potassium persulfate. It can efficiently decompose to generate free radicals at the reaction temperature of S2, precisely initiate the copolymerization reaction, and ensure the grafting efficiency and product stability.

[0027] Furthermore, in step S3, the ratio of cycloazinone technical grade, modified carrier, and DMF is 1g:1g:30-40mL. This ratio allows cycloazinone to completely dissolve in DMF, fully contact and efficiently bind with the modified carrier, while reducing free drug residues and improving herbicide purity.

[0028] Furthermore, in step S3, the stirring time at room temperature is 10–12 hours. This ensures that the cycloazinone technical material is fully loaded onto the modified support, while avoiding uneven loading due to too short a stirring time or energy waste due to too long a stirring time, thus balancing the loading effect and preparation efficiency.

[0029] Secondly, the present invention provides a highly efficient forest herbicide containing cycloazinone, which is prepared by any one of the preparation methods described above.

[0030] 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.

[0031] Example 1

[0032] This embodiment provides a method for preparing a highly efficient forest herbicide containing cycloazinone, comprising the following steps: S1. 1.6 g ferric nitrate, 0.6 g terephthalic acid, 2 mL glacial acetic acid and 30 mL deionized water were stirred at room temperature, and 0.05 mL acrylic acid was added to carry out a hydrothermal reaction at 180 °C for 8 h. After the reaction was completed, the mixture was cooled to room temperature, washed and dried to obtain the modified metal-organic framework. S2. Under a nitrogen atmosphere, 0.4 g of modified metal-organic framework was dissolved in 30 mL of deionized water. After heating to 40 °C, 0.2 g of sodium lignosulfonate and 0.2 mL of acrylic acid were added and reacted for 10 min. Then, 0.12 g of potassium persulfate was added, the temperature was raised to 80 °C, and the reaction was carried out for 1 h. After cooling to room temperature, the mixture was washed and dried to obtain the modified support. S3. Dissolve 1g of cycloazinone technical grade and 1g of modified carrier in 30mL of DMF, stir at room temperature for 10h, centrifuge, wash, and dry to obtain the herbicide.

[0033] Example 2

[0034] This embodiment provides a method for preparing a highly efficient forest herbicide containing cycloazinone, comprising the following steps: S1. 3.2g ferric nitrate, 1.32g terephthalic acid, 3mL glacial acetic acid and 40mL deionized water were stirred at room temperature, and 0.08mL acrylic acid was added to carry out a hydrothermal reaction at 200℃ for 10h. After the reaction was completed, the mixture was cooled to room temperature, washed and dried to obtain the modified metal-organic framework. S2, 0.4 g of the modified metal organic framework was dissolved in 35 mL of deionized water under a nitrogen atmosphere, and then 0.25 g of sodium lignosulfonate and 0.22 mL of acrylic acid were added after being heated to 50°C for 15 min, 0.13 g of potassium persulfate was then added, and the reaction was carried out at 90°C for 1.5 h, and then the reaction was cooled to room temperature, washed, and dried to obtain a modified carrier; S3, 1 g of the cyclanilide technical material and 1 g of the modified carrier were dissolved in 40 mL of DMF, and then centrifuged, washed, and dried after being stirred at room temperature for 11 h to obtain a herbicide.

[0035] Example 3

[0036] The present embodiment provides a preparation method of a high-efficiency forest herbicide containing cyclanilide, which comprises the following steps: S1, 3.2 g of ferric nitrate, 1.32 g of terephthalic acid, 3 mL of glacial acetic acid, and 40 mL of deionized water were stirred at room temperature, and then 0.1 mL of acrylic acid was added to perform a hydrothermal reaction, the reaction temperature was 200°C, the reaction time was 10 h, and then the reaction was cooled to room temperature after the reaction was completed, washed, and dried to obtain a modified metal organic framework; S2, 0.4 g of the modified metal organic framework was dissolved in 35 mL of deionized water under a nitrogen atmosphere, and then 0.25 g of sodium lignosulfonate and 0.22 mL of acrylic acid were added after being heated to 50°C for 15 min, 0.13 g of potassium persulfate was then added, and the reaction was carried out at 90°C for 1.5 h, and then the reaction was cooled to room temperature, washed, and dried to obtain a modified carrier; S3, 1 g of the cyclanilide technical material and 1 g of the modified carrier were dissolved in 40 mL of DMF, and then centrifuged, washed, and dried after being stirred at room temperature for 11 h to obtain a herbicide.

[0037] Example 4

[0038] The present embodiment provides a preparation method of a high-efficiency forest herbicide containing cyclanilide, which comprises the following steps: S1, 3.2 g of ferric nitrate, 1.32 g of terephthalic acid, 3 mL of glacial acetic acid, and 40 mL of deionized water were stirred at room temperature, and then 0.1 mL of acrylic acid was added to perform a hydrothermal reaction, the reaction temperature was 200°C, the reaction time was 10 h, and then the reaction was cooled to room temperature after the reaction was completed, washed, and dried to obtain a modified metal organic framework; S2, 0.4 g of the modified metal organic framework was dissolved in 35 mL of deionized water under a nitrogen atmosphere, and then 0.25 g of sodium lignosulfonate and 0.22 mL of acrylic acid were added after being heated to 50°C for 15 min, 0.13 g of potassium persulfate was then added, and the reaction was carried out at 90°C for 1.5 h, and then the reaction was cooled to room temperature, washed, and dried to obtain a modified carrier; S3, 1 g of the cyclanilide and 1 g of the modified carrier were dissolved in 40 mL of DMF, and stirred at room temperature for 11 h, then centrifuged, washed, and dried to obtain the herbicide.

[0039] Example 5

[0040] The present example provides a preparation method of a high-efficiency forest herbicide containing cyclanilide, comprising the following steps: S1, 3.2 g of ferric nitrate, 1.32 g of terephthalic acid, 3 mL of glacial acetic acid, and 40 mL of deionized water were stirred at room temperature, 0.14 mL of acrylic acid was added, and a hydrothermal reaction was performed, the reaction temperature was 230°C, the reaction time was 12 h, after the reaction was completed, it was cooled to room temperature, washed, and dried to obtain a modified metal organic framework; S2, 0.4 g of the modified metal organic framework was dissolved in 40 mL of deionized water under a nitrogen atmosphere, heated to 80°C, and then 0.4 g of sodium lignosulfonate and 0.3 mL of acrylic acid were added and reacted for 20 min, then 0.16 g of potassium persulfate was added, heated to 100°C, and reacted for 2 h, cooled to room temperature, washed, and dried to obtain a modified carrier; S3, 1 g of the cyclanilide and 1 g of the modified carrier were dissolved in 40 mL of DMF, and stirred at room temperature for 11 h, then centrifuged, washed, and dried to obtain the herbicide.

[0041] Comparative Example 1

[0042] The present comparative example is compared with Example 1, the only difference being that the acrylic acid in S2 is omitted, and the specific steps are as follows: S1, 1.6 g of ferric nitrate, 0.6 g of terephthalic acid, 2 mL of glacial acetic acid, and 30 mL of deionized water were stirred at room temperature, 0.05 mL of acrylic acid was added, and a hydrothermal reaction was performed, after the reaction was completed, it was cooled to room temperature, washed, and dried to obtain a modified metal organic framework; S2, 0.4 g of the modified metal organic framework was dissolved in 30 mL of deionized water under a nitrogen atmosphere, heated to 40°C, and then 0.2 g of sodium lignosulfonate was added and reacted for 10 min, then 0.12 g of potassium persulfate was added, heated to 80°C, and reacted for 1 h, cooled to room temperature, washed, and dried to obtain a modified carrier; S3, 1 g of the cyclanilide and 1 g of the modified carrier were dissolved in 40 mL of DMF, and stirred at room temperature for 11 h, then centrifuged, washed, and dried to obtain the herbicide.

[0043] Comparative Example 2

[0044] The present comparative example is compared with Example 1, the only difference being that the sodium lignosulfonate in S2 is omitted, and the specific steps are as follows: S1, 1.6 g of ferric nitrate, 0.6 g of terephthalic acid, 2 mL of glacial acetic acid and 30 mL of deionized water were stirred at room temperature, 0.05 mL of acrylic acid was added, and a hydrothermal reaction was performed, after the reaction was completed, it was cooled to room temperature, washed, and dried to obtain a modified metal organic framework; S2, 0.4 g of the modified metal organic framework was dissolved in 30 mL of deionized water under a nitrogen atmosphere, heated to 40°C, and then 0.2 mL of acrylic acid was added and reacted for 10 min, then 0.12 g of potassium persulfate was added, heated to 80°C, and reacted for 1 h, cooled to room temperature, washed, and dried to obtain a modified carrier; S3, 1 g of cycloximidate technical material and 1 g of the modified carrier were dissolved in 40 mL of DMF, stirred at room temperature for 10 h, centrifuged, washed, and dried to obtain a herbicide.

[0045] Comparative Example 3

[0046] This comparative example is compared with Example 1, the only difference is that the acrylic acid in S1 is omitted, and the specific steps are as follows: S1, 1.6 g of ferric nitrate, 0.6 g of terephthalic acid, 2 mL of glacial acetic acid and 30 mL of deionized water were stirred at room temperature, and a hydrothermal reaction was performed, the reaction temperature was 180°C, the reaction time was 8 h, after the reaction was completed, it was cooled to room temperature, washed, and dried to obtain a metal organic framework; S2, 0.4 g of the metal organic framework was dissolved in 30 mL of deionized water under a nitrogen atmosphere, heated to 40°C, and then 0.2 g of sodium lignosulfonate and 0.2 mL of acrylic acid were added and reacted for 10 min, then 0.12 g of potassium persulfate was added, heated to 80°C, and reacted for 1 h, cooled to room temperature, washed, and dried to obtain a modified carrier; S3, 1 g of cycloximidate technical material and 1 g of the modified carrier were dissolved in 40 mL of DMF, stirred at room temperature for 10 h, centrifuged, washed, and dried to obtain a herbicide.

[0047] Comparative Example 4

[0048] This comparative example is compared with Example 1, the only difference is that the sodium lignosulfonate and acrylic acid in S2 and the acrylic acid in S1 are omitted, and the specific steps are as follows: S1, 1.6 g of ferric nitrate, 0.6 g of terephthalic acid, 2 mL of glacial acetic acid and 30 mL of deionized water were stirred at room temperature, and a hydrothermal reaction was performed, the reaction temperature was 180°C, the reaction time was 8 h, after the reaction was completed, it was cooled to room temperature, washed, and dried to obtain a metal organic framework; S2, 1 g of cycloximidate technical material and 1 g of the metal organic framework were dissolved in 40 mL of DMF, stirred at room temperature for 10 h, centrifuged, washed, and dried to obtain a herbicide.

[0049] The herbicides prepared in Examples 1-5 and Comparative Examples 1-4 were subjected to performance tests, and the test items were as follows: (1) Release performance test: three different pH (4, 7, 9) release media were prepared, and the composition of the release medium was: phosphate buffer, ethanol and Tween-80, wherein the mass ratio of phosphate buffer, ethanol and Tween-80 was 70:29.5:0.5. 20 mg of the herbicide prepared in Examples 1-5 and Comparative Examples 1-4 was weighed into a dialysis bag, 2 mL of release medium was added, and after sealing, the dialysis bag was placed in a dissolution tester containing 198 mL of release medium, the temperature was controlled at 30°C, the stirring speed was 100 rpm, and the release amount of cyclozine was determined by high performance liquid chromatography, and the same volume of sample was added to ensure that the total volume of the release medium remained unchanged. The release rate of cyclozine in the herbicide was calculated as follows:

[0050] In the formula, Er is the cumulative release amount; V e is the volume of each sampling (1 mL); C i is the concentration of the release liquid at the i th sampling (mg / mL); V0 is the total volume of the release medium (250 mL); C n is the concentration of the release liquid at the n th sampling (mg / mL); n is the number of samplings; m pesticide is the loading amount of the herbicide (mg). The test results are shown in Table 1, respectively.

[0051] Table 1

[0052] As can be seen from Table 1, the release performance and pH response ability of Comparative Example 1 are lower than those of Example 1, and the release rate has little change under different pH conditions, indicating that acrylic acid is obtained as polyacrylic acid (PAA) after the reaction, and polyacrylic acid itself is a pH-responsive polymer, which has completely different structure and permeation behavior under different pH conditions. In an acidic environment, PAA is in a non-swelling state, thus being not conducive to the excretion of the drug; while in a neutral or alkaline environment, PAA swells to form high permeation channels, accelerating the release of the drug and improving the pH response ability of the herbicide.

[0053] The release performance of Comparative Example 2 is lower than that of Example 1, but the pH response ability exists, indicating that sodium lignosulfonate can improve the release performance, but does not affect the overall pH response ability, and the substance that plays a key role in pH response is polyacrylic acid.

[0054] The release performance of Comparative Example 3 is lower than that of Example 1, indicating that the carbon-carbon double bond in the modified metal-organic framework helps to prepare a compact carrier, improving the release performance of the drug.

[0055] Comparative Example 4 only used metal organic framework as carrier, and had the worst slow-release performance and pH response ability.

[0056] (2) Anti-ultraviolet photolysis performance: prepare herbicide dispersions of the same concentration from Example 1 to Example 5 and Comparative Example 1 to Comparative Example 4, and irradiate the solutions under a UV lamp (36 W, 254 nm) respectively, and take samples every certain time, and calculate the concentration by high performance liquid chromatography.

[0057]

[0058] As shown in Table 1, the anti-ultraviolet performance of the herbicides of Example 1 to Example 5 is better than that of Comparative Example.

[0059] The above disclosure is only several specific embodiments of the present application, but the embodiments of the present application are not limited thereto, and any changes that can be thought of by those skilled in the art shall fall within the protection scope of the present application.

Claims

1. A method for preparing a highly efficient forest herbicide containing cycloazinone, characterized in that, Includes the following steps: S1. Preparation of modified metal-organic frameworks; S2. Under a nitrogen atmosphere, the modified metal-organic framework is dissolved in deionized water, heated to 40-80°C, and sodium lignosulfonate is added to react with acrylic acid for 10-20 min. Then, an initiator is added, the temperature is raised to 80-100°C, and the reaction is carried out for 1-2 h. The mixture is then cooled to room temperature, washed, and dried to obtain the modified support. S3. Dissolve the cycloazinone technical and the modified carrier in DMF, stir at room temperature, centrifuge, wash, and dry to obtain the herbicide.

2. The method for preparing the highly efficient forest herbicide containing cycloazinone according to claim 1, characterized in that, The specific steps of step S1 are as follows: iron salt, terephthalic acid, glacial acetic acid and deionized water are stirred at room temperature, acrylic acid is added, and a hydrothermal reaction is carried out. After the reaction is completed, the mixture is cooled to room temperature, washed, and dried to obtain the modified metal-organic framework.

3. The method for preparing the highly efficient forest herbicide containing cycloazinone according to claim 2, characterized in that, The ratio of iron salt, terephthalic acid, glacial acetic acid, deionized water, and acrylic acid is 1.6–3.2 g : 0.6–1.32 g : 2–3 mL : 30–40 mL : 0.05–0.14 mL.

4. The method for preparing the highly efficient forest herbicide containing cycloazinone according to claim 2, characterized in that, The iron salt is any one of ferric chloride, ferric nitrate, and ferric sulfate.

5. The method for preparing the highly efficient forest herbicide containing cycloazinone according to claim 2, characterized in that, The hydrothermal reaction temperature is 180–230℃, and the reaction time is 8–12 hours.

6. The method for preparing the highly efficient forest herbicide containing cycloazinone according to claim 1, characterized in that, In step S2, the ratio of modified metal-organic framework, deionized water, sodium lignosulfonate, acrylic acid, and initiator is 0.4g: 30-40mL: 0.2-0.4g: 0.2-0.3mL: 0.12-0.16g.

7. The method for preparing the highly efficient forest herbicide containing cycloazinone according to claim 1, characterized in that, In step S2, the initiator is potassium persulfate.

8. The method for preparing the highly efficient forest herbicide containing cycloazinone according to claim 1, characterized in that, In step S3, the ratio of cycloazinone technical, modified carrier, and DMF is 1g:1g:30-40mL.

9. The method for preparing the highly efficient forest herbicide containing cycloazinone according to claim 1, characterized in that, In step S3, the stirring time at room temperature is 10–12 hours.

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

Images