Coordination polymer based on pesticide ligand as well as preparation method and application of coordination polymer

Abstract

The invention provides a coordination polymer based on pesticide ligands as well as a preparation method and application thereof, and belongs to the technical field of compounds and preparation thereof. In the step process of preparing the coordination polymer based on the pesticide ligand by using the preparation method of the coordination polymer based on the pesticide ligand, a metal is used as a central metal, and pesticide molecules, carboxyl-containing organic anion ligands or N-containing ligands are used as ligands to form a double-ligand type coordination polymer. The coordination polymer has high pesticide occupancy and sensitive pH responsiveness, and release concentrations of different degrees can be achieved by adjusting the pH. The coordination polymer based on the pesticide ligand has a slow-release bactericidal effect, can prolong the action time of the pesticide, and provides a new thought for the coordination polymer material as a slow-release bactericide.

Description

Technical Field

[0001] The invention relates to the technical field of compounds and preparation thereof, in particular to a pesticide ligand-based coordination polymer, a preparation method and application thereof. Background Art

[0002] Pesticides have become an essential component of contemporary agricultural practices, providing effective and flexible protection against a wide range of pests, diseases and weeds that can hinder optimal crop growth. Their use has significantly increased crop yields. However, the application of pesticides throughout their life cycle is affected by many factors that can lead to substantial environmental losses, resulting in biotarget uptake rates of less than 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 key issues in sustainable agriculture requires advances in pesticide formulation precision, utilization efficiency and bioefficacy.

[0003] The application of coordination polymers (CPs) self-assembly strategies based on selective and directional non-covalent interactions has shown considerable promise in addressing a wide range of challenges in chemistry, materials science, and biology. The long-range crystalline order of these CPs creates a uniform pore size distribution as well as adjustable size, and the chemical tailoring of the luminal surface makes these structures potential candidates for the fabrication of nanoparticles (NPs). Specifically, the use of coordination assemblies in organic ligands, such as coordination polymers, has demonstrated effectiveness in improving the solubility, stability, release rate, and biological properties of drugs and pesticides. In summary, the use of pesticides as ligands enables coordination polymers to possess the excellent properties of both pesticides and coordination polymers, including good antibacterial ability and porosity. Pesticide complexes, as coordination polymers, can be used to synthesize slow-release pesticides due to their good biocompatibility and non-toxicity. Summary of the invention

[0004] In view of this, the present invention provides a type of pesticide ligand-based coordination polymer, a preparation method and application thereof, which has high pesticide occupancy and sensitive pH responsiveness, and can achieve different degrees of release concentration by adjusting the pH. The pesticide ligand-based coordination polymer has a slow-release bactericidal effect and can prolong the action time of the pesticide, providing a new idea for the coordination polymer material as a slow-release bactericide, thereby being more suitable for practical use.

[0005] In order to achieve the above first object, the first type of technical solution based on pesticide ligand coordination polymer provided by the present invention is as follows:

[0006] The pesticide ligand-based coordination polymer provided by the present invention has a general structural formula of:

[0007]

[0008] M: zinc, copper, cobalt, chromium, manganese, iron, magnesium, nickel, silver, calcium, molybdenum

[0009] L1: Imazalil, Tebuconazole, Azoxystrobin, Imidacloprid, Hexaconazole, Iconazole, Diniconazole, Difenoconazole, Carbendazim, 2,4-D, Fluoxepiconazole, Propiconazole, Myclobutanil, Penconazole, Triadimefon, Tricyclazole, Oximidazole, Triclosan, Thifluanid, Allylisothiazole, Flusilazole, Cyproconazole, Flutriafol, Metconazole, Tetrafluimidazole, Bifenthrin, Nibuconazole, Isoconazole, Braconazole, Imidazole, Silafluanid, Silafluanid, Silafluanid

[0010] L2: styrene tris(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-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, fumaric acid, malonic acid, citric acid, succinic acid, glutamic acid, nicotine 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, naphthoic 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-based coordination polymer ranges from 59% to 73%.

[0012] The first pesticide ligand-based coordination polymer provided by the present invention can also be further implemented by 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 imazalil, tebuconazole, myclobutanil, imidacloprid, hexaconazole, uniconazole, diniconazole, difenoconazole, carbendazim, 2,4-D, fluepiconazole, propiconazole, myclobutanil, penconazole, triadimefon, tricyclazole, oxamidazole, thiabendazole, thiophanate-methyl, allylisothiazole, flusilazole, cyproconazole, flutriafol, metconazole, tetrafluimidazole, bifenthrin, nitrobenzene, cyproconazole, oxadiazole, oxadiazole, oxadiazole, fenthionyl ...

[0015] Preferably, L1 or L2 is independently selected from trimesic acid, 2,5-furandicarboxylic acid, 1,4-furandicarboxylic acid, isophthalic acid, phthalic acid, p-aminobenzoic acid, 5-aminoisophthalic acid, biphenyldicarboxylic acid, 5-hydroxyisophthalic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, fumaric acid, malonic acid, citric acid, succinic acid, glutamic acid, citraconic 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, naphthoic 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, which is imidazole (IIIa), oxazole (IIIb), thiazole (IIIc), triazole (IIId);

[0017]

[0018] in:

[0019] M is metal zinc, copper, cobalt, chromium, manganese, iron, magnesium, silver, calcium, nickel, molybdenum; in addition, R1 is hydrogen, is a hydrogen covalent bond, a straight or branched C1-C1 with or without a substitution group; 30 Alkyl, C3-C 20 Cycloalkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C6-C 24 Aryl, C1-C 20 Carboxylates, C1-C 20 Alkoxy, C2-C 20 Alkenyloxy, C2-C 20 Alkynyloxy, C6-C 20 Aryloxy, C2-C 20 Alkoxycarbonyl, C1-C 20 Alkylthio, C6-C 20 Arylthio, C1-C 20 Alkanesulfonyl, C1-C 20 Alkyl sulfonates, C6-C 20 Aryl sulfonate, or C1-C 20 Alkylsulfinyl.

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

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

[0022] in:

[0023] M is metal zinc, copper, cobalt, chromium, manganese, iron, magnesium, silver, calcium, nickel, molybdenum; in addition, R2 is a hydrogen covalent bond, a straight or branched C1-C 30 Alkyl, C3-C 20 Cycloalkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C6-C 24 Aromatic, C4-C 24 Heterocyclic aromatic group, C1-C 20 Carboxylates, C1-C 20 Alkoxy, C2-C 20 Alkenyloxy, C2-C 20 Alkynyloxy, C6-C 20 Aryloxy, C2-C 20 Alkoxycarbonyl, C1-C 20 Alkylthio, C6-C 20 Arylthio, C1-C 20 Alkanesulfonyl, C1-C 20 Alkyl sulfonates, C6-C 20 Aryl sulfonate, or C1-C 20 Alkylsulfinyl.

[0024] In order to achieve the above first purpose, the second type of technical solution based on pesticide ligand coordination polymer provided by the present invention is as follows:

[0025] The second type of pesticide ligand coordination polymer provided by the present invention has the general structural formula:

[0026]

[0027] M: zinc, copper, cobalt, chromium, manganese, iron, magnesium, nickel, silver, calcium, molybdenum

[0028] L1: Imazalil, Tebuconazole, Azoxystrobin, Imidacloprid, Hexaconazole, Iconazole, Diniconazole, Difenoconazole, Carbendazim, 2,4-D, Fluoxepiconazole, Propiconazole, Myclobutanil, Penconazole, Triadimefon, Tricyclazole, Oximidazole, Triclosan, Thifluanid, Allylisothiazole, Flusilazole, Cyproconazole, Flutriafol, Metconazole, Tetrafluimidazole, Bifenthrin, Nibuconazole, Isoconazole, Braconazole, Imidazole, Silafluanid, Silafluanid, Silafluanid

[0029] L2: styrene tris(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-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, fumaric acid, malonic acid, citric acid, succinic acid, glutamic acid, nicotine 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, naphthoic 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-based coordination polymer ranges from 59% to 73%.

[0031] In order to achieve the above second purpose, the technical scheme of the second type of preparation method based on pesticide ligand coordination polymer provided by the present invention is as follows:

[0032] The preparation method of the pesticide ligand coordination polymer provided by the present invention comprises the following steps:

[0033] A first solvent is prepared, wherein the first solvent may 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; 100% water; the mass percentage of each component is respectively: methanol: water 50%: (40%-60%); acetonitrile: water 50%: (40%-50%); N,N-dimethylacetamide (DMA): water 10%: (80%-90%); 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 imazalil or tebuconazole, azoxystrobin, imidacloprid, hexaconazole, uniconazole, diniconazole, difenoconazole, carbendazim, 2,4-D, fluepiconazole, propiconazole, myclobutanil, penconazole, triadimefon, tricyclazole, oxamidazole, thiophanate-methyl, allylisothiazole, flusilazole, cyproconazole, flutriafol, metconazole, tetrafluimidazole, bifenthrin, nitrobenzene, cyproconazole, oxadiazole, oxadiazole, oxadiazole, succinimidazole, chloranil, chloranil, chloranil, succinimidazole, chloranil, succinimidazole, Wherein, the mass percentage of imazalil or tebuconazole, azoxystrobin, imidacloprid, hexaconazole, uniconazole, diniconazole, difenoconazole, carbendazim, 2,4-D, fluepiconazole, propiconazole, myclobutanil, penconazole, triadimefon, tricyclazole, oxamidazole, thiophanate-methyl, allylisothiazole, flusilazole, cyproconazole, flutriafol, metconazole, tetrafluimidazole, bifenthrin, fenthiocarbazole, cyproconazole, oxadiazole, chloranil, chloranil, chloranil, silymarin ...

[0035] 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 to prepare a second solvent, wherein 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] Dissolve trimesic acid or isophthalic acid, phthalic acid, p-aminobenzoic acid, 5-aminoisophthalic acid, biphenyl dicarboxylic acid, 5-hydroxyisophthalic acid, 1,4-naphthalene dicarboxylic acid, fumaric acid, malonic acid, citric acid, succinic acid, glutamic acid, citraconic 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, trimesic acid, naphthoic acid, m-methylbenzoic acid, phthalic acid, 1,2,4-benzenetricarboxylic acid, 1,2,3-benzenetricarboxylic acid, 3,4-dimethylbenzoic acid, 2,5-dimethylphenylacetic acid, and pyromellitic acid in the second solvent to obtain a second solution, wherein the In the second solution, the mass percentage of trimesic acid or isophthalic acid, phthalic acid, p-aminobenzoic acid, 5-aminoisophthalic acid, biphenyl dicarboxylic acid, 5-hydroxyisophthalic acid, 1,4-naphthalene dicarboxylic acid, fumaric acid, malonic acid, citric acid, succinic acid, glutamic acid, citraconic 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, trimesic acid, naphthoic acid, m-methylbenzoic acid, phthalic acid, 1,2,4-benzenetricarboxylic acid, 1,2,3-benzenetricarboxylic 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, and the first mixed solution is post-treated to obtain the coordination polymer based on imazalil or tebuconazole, myclobutanil, imidacloprid, hexaconazole, uniconazole, diniconazole, difenoconazole, carbendazim, 2,4-D, fluepiconazole, propiconazole, myclobutanil, penconazole, triadimefon, tricyclazole, oxamidazole, thiophanate-methyl, allylisothiazole, flusilazole, cyproconazole, flutriafol, metconazole, tetrafluimidazole, bifenthrin, nitrobenzene, imipenem, oxadiazole, silymarin, oxadiazole, silymarin, oxadiazole, silymarin, silymarin, silymarin, silymarin, silymarin, 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 polymer provided by the present invention can also be further implemented by adopting the following technical scheme.

[0039] Preferably, the first solution and the second solution are mixed to obtain a first mixed solution, and the first mixed solution is post-treated to obtain the coordination polymer based on imazalil or tebuconazole, azoxystrobin, imidacloprid, hexaconazole, uniconazole, diniconazole, difenoconazole, carbendazim, 2,4-D, fluepiconazole, propiconazole, myclobutanil, penconazole, triadimefon, tricyclazole, oxamidazole, thiophanate-methyl, allylisothiazole, flusilazole, cyproconazole, flutriafol, metconazole, tetrafluimidazole, bifenthrin, nitrobenzene, phyconazole, oxadiazole, imipenem, oxadiazole, oxadiazole, triaconazole, tricyclazole, oxamidazole, thiophanate-methyl, allylisothiazole, flusilazole, cyproconazole, flutriafol, metconazole, tetrafluimidazole, bifenthrin, nitrobenzene, phyconazole, oxadiazole, imipenem, oxadiazole, triaconazole, imipenem, silylon, and silylon ligands, and the post-treatment comprises the following steps:

[0040] The first mixed solution is dried to obtain a first intermediate product;

[0041] The first intermediate product is washed with an aqueous solution of ethanol to obtain the coordination polymer based on imazalil or tebuconazole, myclobutanil, imidacloprid, hexaconazole, uniconazole, diniconazole, difenoconazole, carbendazim, 2,4-D, fluepiconazole, propiconazole, myclobutanil, penconazole, triadimefon, tricyclazole, oxamidazole, thiophanate-methyl, allylisothiazole, flusilazole, cyproconazole, flutriafol, metconazole, tetrafluimidazole, bifenthrin, nitrobenzene, imipenem, chloranil, oxadiazole, silymarin ...

[0042] Preferably, during the step of drying the first mixed solution to obtain the first intermediate product, the first intermediate product is obtained by collecting the mixed solution by centrifugation and drying it at room temperature.

[0043] Preferably, they are formed by metal ions or atoms connected to organic ligands through coordination bonds to form a long chain structure or a two-dimensional network structure.

[0044] In order to achieve the third purpose above, the technical solution based on the application of pesticide ligand coordination polymer provided by the present invention is as follows:

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

[0046] The beneficial effects of the pesticide ligand-based coordination polymer, its preparation method and application provided by the present invention are that the double ligand coordination polymer is prepared with pesticide as ligand; wherein the pesticide as ligand has a 33%-78% occupancy rate, and the coordination polymer is a porous structure, has a large specific surface area, a high drug loading, and has a good sustained release effect. The coordination polymer prepared by the present invention has a simple synthesis method, a high yield, an easily volatile organic solvent, low equipment requirements, and little environmental pollution, and has a broad market application prospect.

[0047] When pesticides are used as ligands to form coordination polymers, their duration of action can be effectively prolonged, greatly improving drug utilization and reducing the number of times the pesticides are applied, thus achieving pesticide reduction and environmental friendliness. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Various other advantages and benefits will become apparent to those of ordinary skill in the art by reading the detailed description of the preferred embodiments below. The accompanying drawings are only for the purpose of illustrating the preferred embodiments and are not to be considered as limiting the present invention. Moreover, the same reference symbols are used throughout the accompanying drawings to represent the same components. In the accompanying drawings:

[0049] Attached Figure 1 is the structural diagram of PCP1;

[0050] Attached Figure 2 is the structural diagram of PCP2;

[0051] Attached Figure 3 This is the structural diagram of PCP3;

[0052] Attached Figure 4 a is the minimum asymmetric unit diagram of PCP1;

[0053] Attached Figure 4 b is the one-dimensional chain diagram of PCP1;

[0054] Attached Figure 5 a is the minimum asymmetric unit diagram of PCP2;

[0055] Attached Figure 5 b is the two-dimensional network diagram of PCP2;

[0056] Attached Figure 6 is the pH controlled release diagram of PCP1;

[0057] Attached Figure 7 is the pH controlled release diagram of PCP2;

[0058] Attached Figure 8 is the pH controlled release diagram of PCP3;

[0059] Attached Fig. 9 It is the antibacterial graph of imazalil;

[0060] Attached Fig.10 is the antibacterial graph of diniconazole;

[0061] Attached Fig.11 is the antibacterial graph of uniconazole;

[0062] Attached Fig.12 The antibacterial graphs of PCP1, PCP2 and PCP3. DETAILED DESCRIPTION

[0063] In view of this, the present invention provides a pesticide ligand-based coordination polymer, a preparation method and application thereof, which has high pesticide occupancy and sensitive pH responsiveness, and can achieve different degrees of release concentration by adjusting the pH. 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 the coordination polymer material as a slow-release bactericide, so that it is more suitable for practical use.

[0064] In order to further explain the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following is a detailed description of a pesticide ligand coordination polymer, its preparation method and application, its specific implementation method, structure, characteristics and effects proposed by the present invention in combination with the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "embodiment" does not necessarily refer to the same embodiment. In addition, specific features, structures, or characteristics in one or more embodiments can be combined in any suitable form.

[0065] The term "and / or" in this article is merely a description of the association relationship of associated objects, indicating that three relationships may exist, for example, A and / or B. Specifically, it is understood that: A and B may be included at the same time, A may exist alone, or B may exist alone, and any of the above three situations may be met.

[0066] Example 1

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

[0068] Imazalil was prepared into an aqueous solution of Imazalil DMA with a concentration of 8.0 mM;

[0069] Zinc sulfate hexahydrate (10.0 mM) and tris-benzoic acid (5.0 mM) were added to the aqueous solution of imazalil DMA in sequence, and the reaction was carried out at high temperature (120°C) for 96 hours. The reaction product was washed with ethanol water for 3-5 times, and then dried at room temperature to obtain a white solid, which was named PCP1. Its structure is shown in the attached figure. Figure 1 Its single crystal X-ray diffraction pattern is shown in the attached Figure 4 .

[0070] Example 2

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

[0072] Diniconazole was prepared into a Diniconazole DMA aqueous solution with a concentration of 8.0 mM;

[0073] Zinc sulfate hexahydrate (10.0 mM) and 1,4-naphthalene dicarboxylic acid were added to the DMA aqueous solution of diniconazole in sequence, and the reaction was carried out at high temperature (120°C) for 96 hours. The reaction product was washed with ethanol water for 3-5 times, and then dried at room temperature to obtain a blue solid, which was named PCP2. Its structure is shown in the attached figure. Figure 2 Its single crystal X-ray diffraction pattern is shown in the attached Figure 5 .

[0074] Example 3

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

[0076] The triadimenol was prepared into a triadimenol DMF aqueous solution with a concentration of 8.0 mM;

[0077] Copper sulfate pentahydrate (10.0 mM) and succinic acid were added to the DMF aqueous solution of imazalil in sequence, and reacted at high temperature (120°C) for 96 hours. The reaction product was washed with ethanol water for 3-5 times, and then dried at room temperature to obtain a blue solid, which was named PCP3. Its structure is shown in the attached figure. Figure 3 shown.

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

[0079] The three coordination polymers obtained in Examples 1, 2 and 3 were subjected to release experiments in response to different pH values.

[0080] Detailed description: HEPES sodium salt (20 mM) was added to ultrapure water to prepare a buffer solution, the pH was adjusted by adding sodium hydroxide and hydrochloric acid, the pH value in the solution was detected by a pH analyzer, 8 mg PCP1, 2, and 3 were weighed and added to 80 mL of three buffer solutions with different pH values ​​(pH = 5, 7, and 9), 2 mL of the solution was regularly removed, the supernatant was aspirated after centrifugation, and the pesticide release concentration was detected by high performance liquid chromatography, and each treatment was repeated 3 times.

[0081] The results show that ( Figure 6 ) shows 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 at pH 7 is slower. The release concentration reaches the highest at 60 h and continues to be released until 130 h. This indicates that PCP1 has an alkali response. For PCP2 ( Figure 7), the release concentration of imazalil at pH 5 (64 μg / mL) was higher than that at pH 7 (31 μg / mL) and 9 (23 μg / mL), while the release concentration of imazalil was slower at pH 9. The release concentration reached the highest at 60 h and continued to be released until 130 h. This indicates that PCP2 has acid response. For PCP3 ( Figure 8 ), the release concentration of imazalil at pH 9 (53 μg / mL) 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 the highest at 30 h and continued to be released until 130 h. This indicates that PCP3 has an alkali response.

[0082] Verification Test 2

[0083] The concentrations of the pesticides used in Examples 1, 2 and 3 were used for the antibacterial test on Colletotrichum gloeosporioides.

[0084] Detailed description: The growth rate method was used to conduct an antibacterial test on Colletotrichum gloeosporioide. The pesticide original drug was prepared into a suspension with sterile water, and five concentration gradients (8μg / mL, 4μg / mL, 2μg / mL, 1μg / mL, 0.5μg / mL) were diluted twice. The suspension was added to the melted PDA medium, then poured into a culture dish, and the medicine plate was made and dried. A bacterial cake with a diameter of 0.5 cm was punched out with a hole puncher and placed in the center of the medicine plate. The culture dish was sealed with a sealing film and placed in a constant temperature incubator at 28°C for 5 days. The mycelium diameter was determined by the cross method, and the data was analyzed to obtain the antibacterial efficiency and EC50 of the material. The culture medium without sample was used as a control, and each treatment was repeated 3 times.

[0085] The results are as follows Fig. 9 , 10 , 11. The results showed that after 5 days of culture, the EC50 value of Colletotrichum gloeosporioides to imazalil was 6.28μg / mL, the EC50 value of Colletotrichum gloeosporioides to triadimenol was 7.32μg / mL, and the EC50 value of Colletotrichum gloeosporioides to diniconazole was 6.97μg / mL.

[0086] Verification test 3

[0087] The release concentration of the coordination polymer obtained in Example 1 was used for the antibacterial experiment on Colletotrichum gloeosporioides.

[0088] PCP1, 2, and 3 were stirred in sterile water using a magnetic stirrer for a period of time, and the supernatant was centrifuged and the concentration of the supernatant was determined. Five concentration gradients (8 μg / mL, 4 μg / mL, 2 μg / mL, 1 μg / mL, and 0.5 μg / mL) were configured according to the measured concentrations for antibacterial experiments. The growth rate method was used, as described above, and each treatment was repeated 3 times. The results are shown in Fig.12 . The results showed that the sensitivity of Colletotrichum gloeosporioides to PCP1, PCP2 and PCP3 was significantly different, and compared with the EC50 values ​​of the original drugs imazalil, triadimenol and diniconazole, they were significantly lower, among which the EC50 value of PCP1 was 0.67μg / mL, the EC50 value of PCP2 was 0.93μg / mL, and the EC50 value of PCP3 was 1.78μg / mL. This shows that the coordination polymers prepared by combining imazalil, triadimenol and diniconazole with selective ligands have significantly better antibacterial effects than the original drugs imazalil, triadimenol and diniconazole.

[0089] Although the preferred embodiments of the present invention have been described, those skilled in the art may make other changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0090] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A pesticide ligand-based coordination polymer, characterized in that: With the general structural formula (Ⅰ), (Ⅱ): in: M is a transition metal; L1 and L2 are two identical or different ligands, which are pesticide ligands, carboxyl-containing organic anion ligands or N-containing coordination groups; L1 and L2 are two identical or different ligands, which contain a fatty chain carboxyl, an aromatic ring carboxyl, a substituted aromatic ring carboxyl, a heteroaromatic ring carboxyl, a substituted heteroaromatic ring carboxyl, a substituted fatty chain carboxyl, a substituted fatty ring carboxyl, a heterosubstituted carboxyl, a fatty chain imidazole, an aromatic ring imidazole, a substituted aromatic ring imidazole, a heteroaromatic ring imidazole, a substituted heteroaromatic ring imidazole, a substituted fatty chain imidazole, a substituted fatty ring imidazole, a heterosubstituted imidazole, a fatty chain triazole, an aromatic ring triazole, a substituted The coordination groups of the ligands include substituted aromatic ring triazoles, heteroaromatic ring triazoles, substituted heteroaromatic ring triazoles, substituted aliphatic chain triazoles, substituted aliphatic ring triazoles, heterosubstituted triazoles or other substituents; the metal coordination groups in LML include heteroatoms or carboxylic acid groups on the ring, and the metal is coordinated and connected with the ligands to produce a multi-dimensional structure, which includes a one-dimensional structure and a two-dimensional structure; the M adopts a multi-coordination mode, which includes a three-coordination mode, a four-coordination mode, a five-coordination mode, a six-coordination mode or a multi-coordination mode.

2. The coordination polymer according to claim 1, characterized in that M is zinc, copper, cobalt, chromium, manganese, iron, magnesium, nickel, silver, calcium, molybdenum.

3. The coordination polymer according to claim 1, characterized in that L1 or L2 is independently selected from imazalil, tebuconazole, azoxystrobin, imidacloprid, hexaconazole, uniconazole, diniconazole, difenoconazole, carbendazim, 2,4-D, fluepiconazole, propiconazole, myclobutanil, penconazole, triadimefon, tricyclazole, oxamidazole, thiophanate-methyl, allylisothiazole, flusilazole, cyproconazole, flutriafol, metconazole, tetrafluimidazole, bifenthrin, nitrobenzene, cyproconazole, oxadiazole, chloranil, chloranil, imipenem, and silfenazole.

4. The coordination polymer according to claim 1, characterized in that L1 or L2 is independently selected from trimesic acid, 2,5-furandicarboxylic acid, 1,4-furandicarboxylic acid, isophthalic acid, phthalic acid, p-aminobenzoic acid, 5-aminoisophthalic acid, biphenyldicarboxylic acid, 5-hydroxyisophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, fumaric acid, malonic acid, citric acid, succinic acid, glutamic acid, citraconic 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, naphthoic 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.

5. The coordination polymer according to claim 1, characterized in that One of L1 or L2 is a five-membered nitrogen-containing heterocyclic ligand, which is imidazole (IIIa), oxazole (IIIb), thiazole (IIIc), triazole (IIId); in: M is metal zinc, copper, cobalt, chromium, manganese, iron, magnesium, silver, calcium, nickel, molybdenum; in addition, R1 is a hydrogen covalent bond, a straight or branched C1-C1 with or without a substitution group. 30 Alkyl, C3-C 20 Cycloalkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C6-C 24 Aryl, C1-C 20 Carboxylates, C1-C 20 Alkoxy, C2-C 20 Alkenyloxy, C2-C 20 Alkynyloxy, C6-C 20 Aryloxy, C2-C 20 Alkoxycarbonyl, C1-C 20 Alkylthio, C6-C 20 Arylthio, C1-C 20 Alkanesulfonyl, C1-C 20 Alkyl sulfonates, C6-C 20 Aryl sulfonate, or C1-C 20 Alkylsulfinyl.

6. The coordination polymer according to claim 1, characterized in that One of L1 or L2 is a carboxylic acid-containing ligand, which is a dicarboxylic acid (IIIe); (IIIe)M-OOC-R2-COO-M in: M is metal zinc, copper, cobalt, chromium, manganese, iron, magnesium, silver, calcium, nickel, molybdenum; in addition, R2 is a hydrogen covalent bond, a straight or branched C1-C 30 Alkyl, C3-C 20 Cycloalkyl, C2-C 20 Alkenyl, C2-C 20 Alkynyl, C6-C 24 Aromatic, C4-C 24 Heterocyclic aromatic group, C1-C 20 Carboxylates, C1-C 20 Alkoxy, C2-C 20 Alkenyloxy, C2-C 20 Alkynyloxy, C6-C 20 Aryloxy, C2-C 20 Alkoxycarbonyl, C1-C 20 Alkylthio, C6-C 20 Arylthio, C1-C 20 Alkanesulfonyl, C1-C 20 Alkyl sulfonates, C6-C 20 Aryl sulfonate, or C1-C 20 Alkylsulfinyl.

7. A pesticide ligand-based coordination polymer, characterized in that: The general structural formula of the pesticide ligand coordination polymer is: M: zinc, copper, cobalt, chromium, manganese, iron, magnesium, nickel, silver, calcium, molybdenum L1: Imazalil, Tebuconazole, Azoxystrobin, Imidacloprid, Hexaconazole, Iconazole, Diniconazole, Difenoconazole, Carbendazim, 2,4-D, Fluoxepiconazole, Propiconazole, Myclobutanil, Penconazole, Triadimefon, Tricyclazole, Oximidazole, Triclosan, Thifluanid, Allylisothiazole, Flusilazole, Cyproconazole, Flutriafol, Metconazole, Tetrafluimidazole, Bifenthrin, Nibuconazole, Isoconazole, Braconazole, Imidazole, Silafluanid, Silafluanid, Silafluanid L2: styrene tris(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-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, fumaric acid, malonic acid, citric acid, succinic acid, glutamic acid, nicotine 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, naphthoic acid, m-methylbenzoic acid, 1,2,4-benzenetricarboxylic acid, 1,2,3-benzenetricarboxylic acid, 3,4-dimethylbenzoic acid, 2,5-dimethylphenylacetic acid, pyromellitic acid The mass percentage of the structure in the pesticide ligand-based coordination polymer ranges from 59% to 73%.

8. The method for preparing the pesticide ligand coordination polymer according to claim 7, characterized in that: The following steps are involved: A first solvent is prepared, wherein the first solvent may 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; 100% water; the mass percentage of each component is respectively: methanol: water 50%: (40%-60%); acetonitrile: water 50%: (40%-50%); N,N-dimethylacetamide (DMA): water 10%: (80%-90%); N,N-dimethylformamide (DMF): water 10%: (80%-90%); The pesticide is dissolved in the first solvent to obtain a first solution, wherein the pesticide is imazalil or tebuconazole, azoxystrobin, imidacloprid, hexaconazole, uniconazole, diniconazole, difenoconazole, carbendazim, 2,4-D, fluepiconazole, propiconazole, myclobutanil, penconazole, triadimefon, tricyclazole, oxamidazole, thiophanate-methyl, allylisothiazole, flusilazole, cyproconazole, flutriafol, metconazole, tetrafluimidazole, bifenthrin, nitrobenzene, cyproconazole, oxadiazole, oxadiazole, oxadiazole, succinimidazole, chloranil, chloranil, chloranil, succinimidazole, chloranil, succinimidazole, Wherein, the mass percentage of imazalil or tebuconazole, azoxystrobin, imidacloprid, hexaconazole, uniconazole, diniconazole, difenoconazole, carbendazim, 2,4-D, fluepiconazole, propiconazole, myclobutanil, penconazole, triadimefon, tricyclazole, oxamidazole, thiophanate-methyl, allylisothiazole, flusilazole, cyproconazole, flutriafol, metconazole, tetrafluimidazole, bifenthrin, fenthiocarbazole, cyproconazole, oxadiazole, chloranil, chloranil, chloranil, silymarin ... 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 to prepare a second solvent, wherein 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%; Dissolve trimesic acid or isophthalic acid, phthalic acid, p-aminobenzoic acid, 5-aminoisophthalic acid, biphenyl dicarboxylic acid, 5-hydroxyisophthalic acid, 1,4-naphthalene dicarboxylic acid, fumaric acid, malonic acid, citric acid, succinic acid, glutamic acid, citraconic 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, trimesic acid, naphthoic acid, m-methylbenzoic acid, phthalic acid, 1,2,4-benzenetricarboxylic acid, 1,2,3-benzenetricarboxylic acid, 3,4-dimethylbenzoic acid, 2,5-dimethylphenylacetic acid, and pyromellitic acid in the second solvent to obtain a second solution, wherein the In the second solution, the mass percentage of trimesic acid or isophthalic acid, phthalic acid, p-aminobenzoic acid, 5-aminoisophthalic acid, biphenyl dicarboxylic acid, 5-hydroxyisophthalic acid, 1,4-naphthalene dicarboxylic acid, fumaric acid, malonic acid, citric acid, succinic acid, glutamic acid, citraconic 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, trimesic acid, naphthoic acid, m-methylbenzoic acid, phthalic acid, 1,2,4-benzenetricarboxylic acid, 1,2,3-benzenetricarboxylic acid, 3,4-dimethylbenzoic acid, 2,5-dimethylphenylacetic acid, and pyromellitic acid is: 25%-27%; The first solution and the second solution are mixed to obtain a first mixed solution, and the first mixed solution is post-treated to obtain the coordination polymer based on imazalil or tebuconazole, myclobutanil, imidacloprid, hexaconazole, uniconazole, diniconazole, difenoconazole, carbendazim, 2,4-D, fluepiconazole, propiconazole, myclobutanil, penconazole, triadimefon, tricyclazole, oxamidazole, thiophanate-methyl, allylisothiazole, flusilazole, cyproconazole, flutriafol, metconazole, tetrafluimidazole, bifenthrin, nitrobenzene, imipenem, oxadiazole, silymarin, oxadiazole, silymarin, oxadiazole, silymarin, silymarin, silymarin, silymarin, silymarin, wherein the volume ratio of the first solution to the second solution is: 1: (1-1.5).

9. The preparation method based on pesticide ligand coordination polymer according to claim 7, characterized in that: The first solution and the second solution are mixed to obtain a first mixed solution, and the first mixed solution is post-treated to obtain the coordination polymer based on imazalil or tebuconazole, azoxystrobin, imidacloprid, hexaconazole, uniconazole, diniconazole, difenoconazole, carbendazim, 2,4-D, fluepiconazole, propiconazole, myclobutanil, penconazole, triadimefon, tricyclazole, oxamidazole, thiophanate-methyl, allylisothiazole, flusilazole, cyproconazole, flutriafol, metconazole, tetrafluimidazole, bifenthrin, nitrobenzene, phyconazole, oxadiazole, imipenem, oxadiazole, oxadiazole, oxadiazole, oxadiazole, thiophanate-methyl, oxadiazole, pyraclostrobin ... The first mixed solution is dried to obtain a first intermediate product; The first intermediate product is washed with an aqueous solution of ethanol to obtain the coordination polymer based on imazalil or tebuconazole, myclobutanil, imidacloprid, hexaconazole, uniconazole, diniconazole, difenoconazole, carbendazim, 2,4-D, fluepiconazole, propiconazole, myclobutanil, penconazole, triadimefon, tricyclazole, oxamidazole, thiophanate-methyl, allylisothiazole, flusilazole, cyproconazole, flutriafol, metconazole, tetrafluimidazole, bifenthrin, nitrobenzene, imipenem, chloranil, oxadiazole, silymarin ...

10. The preparation method based on pesticide ligand coordination polymer according to claim 7, characterized in that: The first mixed solution is dried to obtain a first intermediate product. During the drying step, the first intermediate product is obtained by collecting the mixed solution by centrifugation and drying it at room temperature.

11. The preparation method based on pesticide ligand coordination polymer according to claim 7, characterized in that: They are composed of metal ions or atoms connected to organic ligands through coordination bonds to form long chain structures or two-dimensional network structures.

12. Use of the pesticide ligand-based coordination polymer according to claim 1 or 7 for sustained-release bactericidal effect in the encapsulation and sustained-release of various pesticides.

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