Pesticide ligand-based coordination polymers, methods of making and use thereof

Abstract

The application provides a pesticide ligand-based coordination polymer, a preparation method and application thereof, and belongs to the technical field of compounds and preparation thereof. In the step process of preparing the pesticide ligand-based coordination polymer by using the preparation method, a metal is used as a central metal, a pesticide molecule, a carboxyl-containing organic anion ligand or an N-containing ligand is used as a ligand, and a double-ligand type coordination polymer is formed. The coordination polymer has a high pesticide occupancy rate and sensitive pH responsiveness, and through adjustment of pH, different degrees of release concentration can be realized. The pesticide ligand-based coordination polymer has a slow-release bactericidal effect, can prolong the action time of the pesticide, and provides a new idea for using the coordination polymer material as a slow-release bactericide.

Description

Technical Field

[0001] This invention relates to the field of compounds and their preparation technology, and in particular to pesticide ligand coordination polymers, their preparation methods and applications. Background Technology

[0002] Pesticides have become an integral part of modern agricultural practice, providing effective and flexible protection against a variety of pests, diseases, and weeds that can hinder optimal crop growth. Their use has significantly increased crop yields. However, pesticide application throughout its life cycle is influenced by numerous factors that can lead to substantial environmental losses, resulting in bioavailability rates below 1.0%. The use of highly toxic organic solvents, such as benzene and toluene, in emulsifiable concentrates further poses considerable risks to ecosystems and human well-being. Therefore, addressing the key challenges of sustainable agriculture requires advancements in the precision, utilization, and bioefficacy of pesticide formulations.

[0003] The application of self-assembly strategies for coordination polymers (CPs) based on selective and directional non-covalent interactions shows considerable promise in addressing a wide range of challenges in chemistry, materials science, and biology. The long-range crystallization sequence of these CPs creates uniform pore size distributions and tunable dimensions, and the chemical tailoring of the intracavity surfaces makes these structures potential candidates for fabricating nanoparticles (NPs). Specifically, the use of coordination assembly, such as coordination polymers, in organic ligands has demonstrated effectiveness in improving solubility, stability, release rates, and the biocompatibility of drugs and pesticides. In summary, using pesticides as ligands allows coordination polymers to possess the excellent properties of both pesticides and coordination polymers, including good antibacterial activity and porosity. Pesticide complexes, as coordination polymers, can be used in the synthesis of sustained-release pesticides due to their good biocompatibility and non-toxicity. Summary of the Invention

[0004] In view of this, the present invention provides a class of pesticide ligand coordination polymers, their preparation methods, and applications. These polymers exhibit high pesticide occupancy and sensitive pH response, allowing for different release concentrations to be achieved by adjusting the pH. These pesticide ligand coordination polymers possess sustained-release bactericidal activity, extending the pesticide's action time and providing a new approach for using coordination polymer materials as sustained-release fungicides, thus making them more suitable for practical application.

[0005] To achieve the first objective mentioned above, the present invention provides the following first type of technical solution based on pesticide ligand coordination polymers:

[0006] The pesticide ligand coordination polymer provided by this invention has the following general structural formula:

[0007]

[0008] M: Zinc, Copper, Cobalt, Chromium, Manganese, Iron, Magnesium, Nickel, Silver, Calcium, Molybdenum

[0009] L1: Imazalil, Tebuconazole, Azoxystrobin, Imidacloprid, Hexaconazole, Uniconazole, Tebuconazole, Difenoconazole, Carbendazim, 2,4-D, Fluconazole, Propiconazole, Cyproconazole, Tebuconazole, Triadimefon, Tricyclazole, Oxadiazon, Tebuconazole, Thiamethoxam, Allylisothiazide, Flusilazole, Cyproconazole, Tebuconazole, Tebuconazole, Bifenthrin, Cyproconazole, Fungicide, Imidazole, Silozolid

[0010] L2: Tribenzoic acid, 2,5-furandicarboxylic acid, 1,4-furandicarboxylic acid, isophthalic acid, phthalic acid, p-aminobenzoic acid, 5-aminoisophthalic acid, biphenyl dicarboxylic acid, 5-hydroxyisophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, fumaric acid, malonic acid, citric acid, succinic acid, glutamic acid, nitrile acid, 2,5-dimethylbenzoic acid, 2,5-dichlorobenzoic acid, 3-chlorobenzoic acid, 3,4-dihydroxyphenylacetic acid, m-hydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 4-phenylbenzoic acid, naphtholic acid, m-methylbenzoic acid, 1,2,4-benzenetricarboxylic acid, 1,2,3-benzenetricarboxylic acid, 3,4-dimethylbenzoic acid, 2,5-dimethylphenylacetic acid, pyromellitic acid

[0011] The mass percentage of the structure in the pesticide ligand coordination polymer ranges from 59% to 73%.

[0012] The first pesticide ligand coordination polymer provided by this invention can also be further implemented using the following technical solutions:

[0013] Preferably, M is zinc, copper, cobalt, chromium, manganese, iron, magnesium, nickel, silver, calcium, or molybdenum.

[0014] Preferably, L1 or L2 is independently selected from imidacloprid, tebuconazole, azoxystrobin, imidacloprid, hexaconazole, uniconazole, tebuconazole, difenoconazole, carbendazim, 2,4-D, flutriafol, propiconazole, cyproconazole, tebuconazole, triadimefon, tricyclazole, oximazole, tebuconazole, thiamethoxam, allylisothiazide, flusilazole, cyproconazole, fenbendazole, tebuconazole, bifenthrin, cyproconazole, fenbendazole, imidacloprid, and siloxyfenozide.

[0015] Preferably, L1 or L2 is independently selected from pyromellitic acid, 2,5-furandicarboxylic acid, 1,4-furandicarboxylic acid, isophthalic acid, phthalic acid, p-aminobenzoic acid, 5-aminoisophthalic acid, biphenyl dicarboxylic acid, 5-hydroxyisophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, fumaric acid, malonic acid, citric acid, succinic acid, glutamic acid, ningconic acid, 2,5-dimethylbenzoic acid, 2,5-dichlorobenzoic acid, 3-chlorobenzoic acid, 3,4-dihydroxyphenylacetic acid, m-hydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 4-phenylbenzoic acid, naphtholic acid, m-methylbenzoic acid, 1,2,4-benzenetricarboxylic acid, 1,2,3-benzenetricarboxylic acid, 3,4-dimethylbenzoic acid, 2,5-dimethylphenylacetic acid, and pyromellitic acid.

[0016] Preferably, one of L1 or L2 is a five-membered nitrogen-containing heterocyclic ligand, namely imidazole (IIIa), oxazole (IIIb), thiazole (IIIc), or triazole (IIId);

[0017]

[0018] in:

[0019] M represents the metals zinc, copper, cobalt, chromium, manganese, iron, magnesium, silver, calcium, nickel, and molybdenum; R1 represents hydrogen, which is a covalently bonded C1-C chain with or without substituent groups, either straight or branched. 30 Alkyl, C3-C 20 cycloalkyl, C2-C 20 Alkenyl, C2-C 20 alkynyl group, C6-C 24 Aryl, C1-C 20 Carboxylates, C1-C 20 Alkoxy group, C2-C 20 Alkenyl group, C2-C 20 Acryloxy group, C6-C 20 Aryloxy group, C2-C 20 Alkoxycarbonyl, C1-C 20 Alkylthio, C6-C 20 Arylthioyl, C1-C 20 Alkyl sulfonyl, C1-C 20 Alkyl sulfonates, C6-C 20 Aryl sulfonates, or C1-C 20 Alkyl sulfinyl group.

[0020] Preferably, one of L1 or L2 is a carboxylic acid ligand, which is a dicarboxylic acid (IIIe);

[0021] (IIe) M-OOC-R2-COO-M

[0022] in:

[0023] M represents the metals zinc, copper, cobalt, chromium, manganese, iron, magnesium, silver, calcium, nickel, and molybdenum; R2 is a hydrogen covalent bond, a straight-chain or branched C1-C bond with or without substituent groups. 30 Alkyl, C3-C 20 cycloalkyl, C2-C 20 Alkenyl, C2-C 20 alkynyl group, C6-C 24 Aromatic group, C4-C 24 Heterocyclic aromatic group, C1-C 20 Carboxylates, C1-C 20 Alkoxy group, C2-C 20 Alkenyl group, C2-C 20 Acryloxy group, C6-C 20 Aryloxy group, C2-C 20 Alkoxycarbonyl, C1-C 20 Alkylthio, C6-C 20 Arylthioyl, C1-C 20 Alkyl sulfonyl, C1-C 20 Alkyl sulfonates, C6-C 20 Aryl sulfonates, or C1-C 20 Alkyl sulfinyl group.

[0024] To achieve the first objective mentioned above, the second type of technical solution based on pesticide ligand coordination polymers provided by the present invention is as follows:

[0025] The second type of structural formula based on pesticide ligand coordination polymers provided by this invention is as follows:

[0026]

[0027] M: Zinc, Copper, Cobalt, Chromium, Manganese, Iron, Magnesium, Nickel, Silver, Calcium, Molybdenum

[0028] L1: Imazalil, Tebuconazole, Azoxystrobin, Imidacloprid, Hexaconazole, Uniconazole, Tebuconazole, Difenoconazole, Carbendazim, 2,4-D, Fluconazole, Propiconazole, Cyproconazole, Tebuconazole, Triadimefon, Tricyclazole, Oxadiazon, Tebuconazole, Thiamethoxam, Allylisothiazide, Flusilazole, Cyproconazole, Tebuconazole, Tebuconazole, Bifenthrin, Cyproconazole, Fungicide, Imidazole, Silozolid

[0029] L2: Tribenzoic acid, 2,5-furandicarboxylic acid, 1,4-furandicarboxylic acid, isophthalic acid, phthalic acid, p-aminobenzoic acid, 5-aminoisophthalic acid, biphenyl dicarboxylic acid, 5-hydroxyisophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, fumaric acid, malonic acid, citric acid, succinic acid, glutamic acid, nitrile acid, 2,5-dimethylbenzoic acid, 2,5-dichlorobenzoic acid, 3-chlorobenzoic acid, 3,4-dihydroxyphenylacetic acid, m-hydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 4-phenylbenzoic acid, naphtholic acid, m-methylbenzoic acid, 1,2,4-benzenetricarboxylic acid, 1,2,3-benzenetricarboxylic acid, 3,4-dimethylbenzoic acid, 2,5-dimethylphenylacetic acid, pyromellitic acid

[0030] The mass percentage of the structure in the pesticide ligand coordination polymer ranges from 59% to 73%.

[0031] To achieve the second objective mentioned above, the technical solution of the second type of preparation method based on pesticide ligand coordination polymers provided by the present invention is as follows:

[0032] The preparation method based on pesticide ligand coordination polymers provided by this invention includes the following steps:

[0033] A first solvent is prepared, wherein the solvent can be a single solvent or a multi-component solvent, wherein the single solvent is 100% methanol; 100% N,N-dimethylformamide; 100% N,N-dimethylacetamide; 100% acetonitrile; and 100% water; the mass percentages of each component are as follows: methanol:water 50%:(40%-60%); acetonitrile:water 50%:(40%-50%); N,N-dimethylacetamide (DMA):water 10%:(80%-90%); and N,N-dimethylformamide (DMF):water 10%:(80%-90%).

[0034] The pesticide is dissolved in the first solvent to obtain a first solution, wherein the pesticide is an imidacloprid or tebuconazole, azoxystrobin, imidacloprid, hexaconazole, uniconazole, tebuconazole, difenoconazole, carbendazim, 2,4-D, flutriafol, propiconazole, cyproconazole, tebuconazole, triadimefon, tricyclazole, oxadiazon, tebuconazole, thiamethoxam, allylisothiazide, flusilazole, cyproconazole, fenbendazole, tebuconazole, bifenthrin, cyproconazole, tebuconazole, tebuconazole, tebuconazole, imidacloprid, or silfluthazole. The mass percentage of imidacloprid or tebuconazole, azoxystrobin, imidacloprid, hexaconazole, uniconazole, tebuconazole, difenoconazole, carbendazim, 2,4-D, flutriafol, propiconazole, cyproconazole, tebuconazole, triadimefon, tricyclazole, oximazole, tebuconazole, thiamethoxam, allylisothiazide, flusilazole, cyproconazole, fenbendazole, tebuconazole, tetrafluoromazole, bifenthrin, cyproconazole, tebuconazole, imidacloprid, and silfluzazole in the first solution is 37%-41%.

[0035] A second solvent is prepared by dissolving zinc sulfate hexahydrate or cobalt nitrate monohydrate, magnesium chloride hexahydrate, ferric chloride hexahydrate, manganese chloride tetrahydrate, copper sulfate pentahydrate, and chromium nitrate tetrahydrate in water. The mass percentage of zinc sulfate hexahydrate or cobalt nitrate monohydrate, magnesium chloride hexahydrate, ferric chloride hexahydrate, manganese chloride tetrahydrate, copper sulfate pentahydrate, and chromium nitrate tetrahydrate in the second solution is 33%-36%.

[0036] Tris(tribenzoic acid) or isophthalic acid, phthalic acid, p-aminobenzoic acid, 5-aminoisophthalic acid, biphenyl phthalic acid, 5-hydroxyisophthalic acid, 1,4-naphthalenedicarboxylic acid, fumaric acid, malonic acid, citric acid, succinic acid, glutamic acid, nitrile acid, 2,5-dimethylbenzoic acid, 2,5-dichlorobenzoic acid, 3-chlorobenzoic acid, 3,4-dihydroxyphenylacetic acid, m-hydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 4-phenylbenzoic acid, pyromellitic acid, naphtholic acid, m-methylbenzoic acid, phthalic acid, 1,2,4-phenyltricarboxylic acid, 1,2,3-phenyltricarboxylic acid, 3,4-dimethylbenzoic acid, 2,5-dimethylphenylacetic acid, pyromellitic acid are dissolved in the second solvent to obtain the second solution, wherein... In the second solution, the mass percentage of pyromellitic acid or isophthalic acid, phthalic acid, p-aminobenzoic acid, 5-aminoisophthalic acid, biphenyl diphthalic acid, 5-hydroxyisophthalic acid, 1,4-naphthalenedicarboxylic acid, fumaric acid, malonic acid, citric acid, succinic acid, glutamic acid, ningconic acid, 2,5-dimethylbenzoic acid, 2,5-dichlorobenzoic acid, 3-chlorobenzoic acid, 3,4-dihydroxyphenylacetic acid, m-hydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 4-phenylbenzoic acid, pyromellitic acid, naphtholic acid, m-methylbenzoic acid, phthalic acid, 1,2,4-phenyltricarboxylic acid, 1,2,3-phenyltricarboxylic acid, 3,4-dimethylbenzoic acid, 2,5-dimethylphenylacetic acid, and pyromellitic acid is 25%-27%.

[0037] The first solution and the second solution are mixed to obtain a first mixed solution. The first mixed solution is then post-processed to obtain the polymer based on ligands of imidacloprid or tebuconazole, azoxystrobin, imidacloprid, hexaconazole, uniconazole, tebuconazole, difenoconazole, carbendazim, 2,4-D, flutriafol, propiconazole, cyproconazole, tebuconazole, triadimefon, tricyclazole, oximazole, tebuconazole, thiabendazole, allylisothiazide, flusilazole, cyproconazole, fenbendazole, tebuconazole, tetrafluoromazole, bifenthrin, cyproconazole, tebuconazole, imidacloprid, and siloxyfenazole, wherein the volume ratio of the first solution to the second solution is 1:(1-1.5).

[0038] The second type of preparation method based on pesticide ligand coordination polymers provided by this invention can be further implemented using the following technical solutions.

[0039] Preferably, the first solution and the second solution are mixed to obtain a first mixed solution. The first mixed solution is then post-treated to obtain the polymer based on the ligand coordination polymer of imidacloprid or tebuconazole, azoxystrobin, imidacloprid, hexaconazole, uniconazole, tebuconazole, difenoconazole, carbendazim, 2,4-D, flutriafol, propiconazole, cyproconazole, tebuconazole, triadimefon, tricyclazole, oxadiazon, tebuconazole, thiamethoxam, allylisothiazide, flusilazole, cyproconazole, fenbendazole, tebuconazole, tetrafluoromazole, bifenthrin, cyproconazole, tebuconazole, imidacloprid, or silfluzazole. The post-treatment includes the following steps:

[0040] The first mixed solution was dried to obtain the first intermediate product;

[0041] The first intermediate product is washed with an aqueous ethanol solution to obtain the coordination polymer based on ligands of imidacloprid or tebuconazole, azoxystrobin, imidacloprid, hexaconazole, uniconazole, tebuconazole, difenoconazole, carbendazim, 2,4-D, flutriafol, propiconazole, cyproconazole, tebuconazole, triadimefon, tricyclazole, oximazole, tebuconazole, thiabendazole, allylisothiazide, flusilazole, cyproconazole, fenbendazole, tebuconazole, bifenthrin, cyproconazole, fenbendazole, imidacloprid, and siloxyconazole, wherein the aqueous ethanol solution contains 40%-60% by mass of ethanol.

[0042] Preferably, in the step of drying the first mixed solution to obtain the first intermediate product, the drying process involves collecting the product by centrifugation, drying it at room temperature, and obtaining the first intermediate product.

[0043] Preferably, they are long chain structures or two-dimensional network structures formed by metal ions or atoms being linked to organic ligands through coordination bonds.

[0044] To achieve the third objective mentioned above, the technical solution provided by this invention based on the application of pesticide ligand coordination polymers is as follows:

[0045] The present invention provides the application of pesticide ligand coordination polymers in the encapsulation and sustained release of various pesticides for sustained-release bactericidal effects.

[0046] The beneficial effects of the pesticide ligand-based coordination polymer, its preparation method, and its application provided by this invention are as follows: A dual-ligand coordination polymer is prepared using pesticides as ligands; wherein the pesticide content as the ligand is 33%-78%, and the coordination polymer has a porous structure with a large specific surface area, high pesticide loading capacity, and excellent sustained-release effect. The coordination polymer prepared by this invention has a simple synthesis method, high yield, uses easily volatile organic solvents, requires low equipment standards, and causes minimal environmental pollution, thus possessing broad market application prospects.

[0047] When pesticides are used as ligands to form coordination polymers, their action time can be effectively extended, greatly improving pesticide utilization and reducing the number of applications, thus achieving pesticide reduction and environmental friendliness. Attached Figure Description

[0048] Various other advantages and benefits will become apparent to those skilled in the art upon reading the following detailed description of preferred embodiments. The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings:

[0049] Appendix Figure 1 Here is a structural diagram of PCP1;

[0050] Appendix Figure 2 This is a structural diagram of PCP2;

[0051] Appendix Figure 3 This is a structural diagram of PCP3;

[0052] Appendix Figure 4 a is the smallest asymmetric element diagram of PCP1;

[0053] Appendix Figure 4 b is a one-dimensional chain graph of PCP1;

[0054] Appendix Figure 5 a is the smallest asymmetric element diagram of PCP2;

[0055] Appendix Figure 5 b is a two-dimensional mesh of PCP2;

[0056] Appendix Figure 6 This is a pH-controlled release diagram of PCP1;

[0057] Appendix Figure 7 This is a pH-controlled release diagram of PCP2;

[0058] Appendix Figure 8 This is a pH-controlled release diagram of PCP3;

[0059] Appendix Figure 9 This is a diagram showing the antibacterial activity of imazalil;

[0060] Appendix Figure 10 This is a diagram showing the antibacterial activity of tebuconazole;

[0061] Appendix Figure 11 This is a diagram showing the antibacterial activity of tebuconazole;

[0062] Appendix Figure 12 The diagram shows the antibacterial activity of PCP1, PCP2, and PCP3. Detailed Implementation

[0063] In view of this, the present invention provides a pesticide ligand coordination polymer, its preparation method, and its application. This polymer exhibits high pesticide occupancy and sensitive pH response; by adjusting the pH, different release concentrations can be achieved. This pesticide ligand coordination polymer possesses sustained-release bactericidal activity, extending the pesticide's action time and providing a new approach for coordination polymer materials as sustained-release fungicides, thus making it more suitable for practical application.

[0064] To further illustrate the technical means and effects adopted by the present invention to achieve the intended purpose, the following, in conjunction with the accompanying drawings and preferred embodiments, provides a detailed description of the specific implementation, structure, features, and effects of a pesticide ligand coordination polymer, its preparation method, and its application according to the present invention. In the following description, different "embodiments" or "embodiments" do not necessarily refer to the same embodiment. Furthermore, specific features, structures, or characteristics in one or more embodiments can be combined in any suitable form.

[0065] In this article, the term "and / or" is merely a description of the relationship between related objects, indicating that there can be three relationships, such as A and / or B. Specifically, it can mean that A and B can be included at the same time, A can exist alone, or B can exist alone, and any of the above three situations can be met.

[0066] Example 1

[0067] This embodiment provides a hydrothermal synthesis method for preparing coordination polymers:

[0068] Iprodione was prepared into an 8.0 mM aqueous solution of imidazole DMA.

[0069] Zinc sulfate hexahydrate (10.0 mM) and mesitylene benzoic acid (5.0 mM) were added sequentially to an aqueous solution of imidacloprid DMA and reacted at high temperature (120 °C) for 96 h. The reaction product was washed 3-5 times with ethanol and water, and then dried at room temperature to obtain a white solid, which was named PCP1. Its structural diagram is attached. Figure 1 As shown, its single-crystal X-ray diffraction pattern is attached. Figure 4 .

[0070] Example 2

[0071] This embodiment provides a hydrothermal synthesis method for preparing coordination polymers:

[0072] Tebuconazole was prepared into an 8.0 mM tebuconazole DMA aqueous solution;

[0073] Zinc sulfate hexahydrate (10.0 mM) and 1,4-naphthalenedicarboxylic acid were added sequentially to an aqueous solution of tebuconazole DMA and reacted at high temperature (120 °C) for 96 h. The reaction product was washed 3-5 times with ethanol and water, and then dried at room temperature to obtain a blue solid, which was named PCP2. Its structural diagram is attached. Figure 2 As shown, its single-crystal X-ray diffraction pattern is attached. Figure 5 .

[0074] Example 3

[0075] This embodiment provides a hydrothermal synthesis method for preparing coordination polymers:

[0076] Triazole was prepared into an 8.0 mM triazole DMF aqueous solution;

[0077] Copper sulfate pentahydrate (10.0 mM) and succinic acid were added sequentially to an aqueous solution of imidacloprid DMF. The mixture was reacted at high temperature (120 °C) for 96 h. The reaction product was washed 3-5 times with ethanol and water, and then dried at room temperature to obtain a blue solid, which was named PCP3. Its structural diagram is attached. Figure 3 As shown.

[0078] In addition, to further verify and demonstrate the superiority of the technology of the present invention, the inventors also conducted the following experiments: Verification test Test 1

[0079] Release experiments of the three coordination polymers obtained in Examples 1, 2, and 3 at different pH responses.

[0080] The detailed description involves preparing a buffer solution by adding 20 mM sodium HEPES salt to ultrapure water. The pH is adjusted by adding sodium hydroxide and hydrochloric acid. The pH value of the solution is detected using a pH analyzer. 8 mg of PCP1,2,3 are weighed and added to 80 mL of three buffer solutions with different pH values ​​(pH = 5, 7, 9), respectively. 2 mL of solution is periodically transferred, centrifuged, and the supernatant is collected. The pesticide release concentration is detected by high performance liquid chromatography. Each treatment is performed in triplicate.

[0081] The results show that ( Figure 6 It can be seen that for PCP1, the release concentration of imazalil at pH 9 (50 μg / mL) is higher than that at pH 5 (38 μg / mL) and 7 (40 μg / mL), while the release concentration of imazalil is slower at pH 7. The release concentration reaches its peak at 60 h and continues to be released until 130 h. This indicates that PCP1 has an alkaline response. For PCP2 ( Figure 7At pH 5 (64 μg / mL), the release concentration of imidacloprid was higher than that at pH 7 (31 μg / mL) and 9 (23 μg / mL), while the release concentration of imidacloprid was slower at pH 9. The release concentration reached its peak at 60 h and continued to be released until 130 h. This indicates that PCP2 exhibits an acid response. For PCP3 (… Figure 8 At pH 9 (53 μg / mL), the release concentration of imazalil was higher than that at pH 5 (33 μg / mL) and 7 (42 μg / mL), while the release concentration of imazalil was slower at pH 5. The release concentration reached its peak at 30 h and continued to be released until 130 h. This indicates that PCP3 has an alkaline response.

[0082] Verification Experiment 2

[0083] Examples 1, 2, and 3: Experiments on the inhibitory effect of pesticide technical concentrations on Colletotrichum gloeosporioides.

[0084] A detailed description of the antibacterial test against *Colletotrichum gloeosporioide* was conducted using the growth rate method. The pesticide technical material was prepared into a suspension with sterile water and serially diluted twofold to five concentration gradients (8 μg / mL, 4 μg / mL, 2 μg / mL, 1 μg / mL, and 0.5 μg / mL). The suspension was added to melted PDA medium, then poured into petri dishes to form blister packs, which were then air-dried. Mycelial cakes with a diameter of 0.5 cm were punched out and placed in the center of the blister pack. The petri dishes were sealed with sealing film and incubated at 28°C for 5 days. The mycelial diameter was measured using a cross-hatching method, and the data were analyzed to determine the antibacterial efficiency and EC50 of the material. A sample-free medium was used as a control, and each treatment was performed in triplicate.

[0085] The results are as follows Figure 9 , 10 11. The results showed that after 5 days of culture, the EC50 value of *Colletotrichum gloeosporioides* against imazalil was 6.28 μg / mL, the EC50 value of *Colletotrichum gloeosporioides* against triazole was 7.32 μg / mL, and the EC50 value of *Colletotrichum gloeosporioides* against tebuconazole was 6.97 μg / mL.

[0086] Verification Experiment 3

[0087] Example 1 shows the antibacterial effect of the coordination polymer release concentration on Colloidal anthrax.

[0088] PCP1, 2, and 3 were stirred in sterile water using a magnetic stirrer for a period of time. The supernatant was collected by centrifugation, and its concentration was determined. Based on the determined concentration, five concentration gradients (8 μg / mL, 4 μg / mL, 2 μg / mL, 1 μg / mL, and 0.5 μg / mL) were prepared for antibacterial experiments using the growth rate method, as described above. Each treatment was performed in triplicate. Results are as follows... Figure 12 The results showed that *Colletotrichum gloeosporioides* exhibited significant differences in sensitivity to PCP1, PCP2, and PCP3. Compared with the original drugs imidacloprid, triadimefon, and tebuconazole, the EC50 values ​​of all three were significantly lower, with PCP1 at 0.67 μg / mL, PCP2 at 0.93 μg / mL, and PCP3 at 1.78 μg / mL. This indicates that imidacloprid, triadimefon, and tebuconazole, when combined with selective ligands to form coordination polymers, exhibit significantly better antibacterial effects than the original drugs imidacloprid, triadimefon, and tebuconazole.

[0089] Although preferred embodiments of the invention have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including both the preferred embodiments and all changes and modifications falling within the scope of the invention.

[0090] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A class of pesticide ligand coordination polymers, characterized in that, It has one or more of the following structural formulas: (Ⅰ) and (Ⅱ): in: M is zinc or copper; L1 is imazalil, tebuconazole, or triazole, and L2 is mesitylecithic acid, 1,4-naphthalenedicarboxylic acid, or succinic acid; the metal-coordinating groups in LML include heteroatoms or carboxylic acid groups on the ring, and the metal coordinates with the ligand to produce a multidimensional structure, which includes one or more of one-dimensional and two-dimensional structures; M adopts a multi-coordination mode, which includes one or more of three-coordination, four-coordination, five-coordination, and six-coordination modes. The pesticide is dissolved in a first solvent to obtain a first solution, wherein the mass percentage of imidacloprid, tebuconazole, or triazole in the first solution is 37%-41%. A second solvent is prepared by dissolving zinc sulfate hexahydrate or copper sulfate pentahydrate in water, wherein the mass percentage of zinc sulfate hexahydrate or copper sulfate pentahydrate in the second solution is 33%-36%. Tris(tribenzoic acid), 1,4-naphthalenedicarboxylic acid, or succinic acid are dissolved in the second solvent to obtain a second solution, wherein the mass percentage of tris(tribenzoic acid), 1,4-naphthalenedicarboxylic acid, or succinic acid in the second solution is 25%-27%. The first solution and the second solution are mixed and reacted at 120°C for 96 hours to obtain a first mixed solution. The first mixed solution is then post-treated to obtain the coordination polymer, wherein the volume ratio of the first solution to the second solution is 1:(1-1.5).

2. The coordination polymer according to claim 1, characterized in that, The mass percentage of the pesticide ligand-carboxylic acid ligand-metal ion structure in the coordination polymer ranges from 59% to 73%.

3. The preparation method based on pesticide ligand coordination polymer as described in claim 2, characterized in that, Includes the following steps: Prepare a first solvent, wherein the solvent in the first solvent is a single solvent or a multi-component solvent, wherein the single solvent is 100% methanol; N,N -Dimethylformamide 100%; N,N - Dimethylacetamide 100%; Acetonitrile 100%; Water 100%; The mass percentages of the multi-component solvents are: Acetonitrile: Water 50%: 50%; N,N - Dimethylacetamide (DMA): Water 10% : 90%; N,N - Dimethylformamide (DMF): Water 10% : 90%.

4. The preparation method based on pesticide ligand coordination polymer according to claim 3, characterized in that, In the step of mixing the first solution and the second solution to obtain a first mixed solution, and then performing post-processing on the first mixed solution to obtain the coordination polymer, the post-processing includes the following steps: The first mixed solution was dried to obtain the first intermediate product; The first intermediate product is washed with an aqueous solution of ethanol to obtain the coordination polymer, wherein the aqueous solution of ethanol has a mass percentage content of 40%-60%.

5. The preparation method based on pesticide ligand coordination polymer according to claim 4, characterized in that, In the step of drying the first mixed solution to obtain the first intermediate product, the drying process involves collecting the product by centrifugation, drying it at room temperature, and obtaining the first intermediate product.

6. The preparation method based on pesticide ligand coordination polymer according to claim 3, characterized in that, They are long chain-like or two-dimensional network structures formed by metal ions or atoms being linked to organic ligands through coordination bonds.

7. The application of the pesticide ligand coordination polymer as described in claim 1 for sustained-release bactericidal action in the encapsulation and sustained release of various pesticides.

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