A multi-pesticide seed suspension agent and a preparation method thereof

Abstract

The application discloses the technical field of seed suspending agent and a kind of multiple pesticide seed suspending agent and preparation method thereof, the seed suspending agent includes the following weight parts of components: modified plant polysaccharide 3-10 parts, zinc salt 10-20 parts, imidacloprid raw drug 1-2 parts, fenpropimorph raw drug 0.5-1.5 parts, propiconazole raw drug 0.8-1.2 parts, dispersing agent 5-8 parts, film forming agent 2-6 parts, crosslinking agent 0.3-0.8 parts, preservative 0.1-0.5 parts, warning agent 1-5 parts, deionized water 75-100 parts.The application proposes to treat plant polysaccharide with 4-imidazole formic acid and zinc salt solution, which improves the stability of loaded pesticide molecules and further realizes the technical effect of improving the safety of seed environment.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of seed suspending agent, and particularly relates to a seed suspending agent of multiple pesticides and a preparation method thereof. BACKGROUND

[0002] The seed suspending agent is one of seed pretreatment methods, is composed of pesticide active ingredients and film forming agents, can form a pesticide film on the seed surface, can effectively play the protection of the pesticide on the seed surrounding environment, the pesticide active ingredients include fungicides, insecticides or plant growth regulators, meets the purpose of preventing seedling diseases and insect pests, and is particularly suitable for the pretreatment of large-particle seeds such as corn, cotton and soybean; after the seed suspending agent treatment, seeding is carried out, in the seedling process, the pesticide in the seed pesticide film is affected by rainfall or irrigation, and is prone to leaching and loss, at the same time, the soil with a complex structure can fix the pesticide active substances through adsorption, so that the pesticide active ingredients in the pesticide film are difficult to play a role, the application of the slow-release technology in the seed treatment agent can improve the content of the effective components in the soil, can avoid the leaching and loss of the pesticide, and improve the biological effectiveness of the effective components; in the slow-release technology, the high molecular material is usually used as a slow-release carrier to isolate the effective components from the external environment, improve the stability of the easily-decomposed effective components, reduce the volatility of the volatile raw pesticide, and prolong the use period of the pesticide.

[0003] At present, the existing technology mainly has the following problems: the seed suspending agent forms a pesticide film on the seed surface, due to the traditional Chinese medicine preparation, the effective components carried by the seed per unit area are much higher than those by spraying or other methods, the seed is sensitive to the pesticide during seed germination, and is prone to pesticide damage, and cannot germinate or has a poor germination rate or a poor growth condition. SUMMARY

[0004] In view of the above problems, in order to overcome the defects of the prior art, the application provides a seed suspending agent of multiple pesticides and a preparation method thereof, in order to solve the problems of poor slow-release of the pesticide in the seed pesticide film and low safety of the seed surrounding environment, the application provides a method for treating plant polysaccharides by using 4-imidazole carboxylic acid and zinc salt solution, improves the stability of the loaded pesticide molecules, and further realizes the technical effect of improving the safety of the seed environment.

[0005] In order to achieve the above object, the technical scheme adopted by the present application is as follows: the present application provides a plurality of pesticide seed suspending agent, the seed suspending agent comprises the following components by weight: modified plant polysaccharide 3-10 parts, zinc salt 10-20 parts, imidacloprid raw drug 1-2 parts, azoxystrobin raw drug 0.5-1.5 parts, propiconazole raw drug 0.8-1.2 parts, dispersing agent 5-8 parts, film forming agent 2-6 parts, crosslinking agent 0.3-0.8 parts, preservative 0.1-0.5 parts, warning agent 1-5 parts, deionized water 75-100 parts.

[0006] Preferably, the plant polysaccharide comprises at least one of papaya polysaccharide, astragalus polysaccharide, seaweed polysaccharide, bletilla striata polysaccharide and medlar polysaccharide.

[0007] Preferably, the modified plant polysaccharide is a plant polysaccharide modified by 4-imidazole carboxylic acid.

[0008] Preferably, the preparation method of the modified plant polysaccharide specifically comprises the following steps:

[0009] ①Dissolve the plant polysaccharide in NaOH solution, stir at room temperature until completely dissolved, adjust the pH to 7.0, and stand at 4.0℃ overnight to obtain a hydrated plant polysaccharide solution;

[0010] ②Add 4-imidazole carboxylic acid to the hydrated plant polysaccharide solution prepared in step ①, perform magnetic stirring under nitrogen atmosphere, dropwise add H2O2 solution, react for 10-14h, add 95% ethanol solution to precipitate, stand at 4℃ overnight, centrifuge at 8000-10000rpm for 5-10min, remove the supernatant, redissolve the precipitate with deionized water, dialyze in distilled water for 2d, the molecular cut-off is 6-8kDa, and freeze-dry to obtain the modified plant polysaccharide.

[0011] Preferably, in step ①, the mass fraction of the plant polysaccharide in the NaOH solution is 1-5%; and the concentration of the NaOH solution is 1mol / L.

[0012] Preferably, in step ②, the addition amount of the 4-imidazole carboxylic acid is 8-12mg / mL.

[0013] Preferably, in step ②, the concentration of the H2O2 solution is 4-6mol / L; and the volume ratio of the dropwise added H2O2 solution to the hydrated plant polysaccharide solution is 1-2:25.

[0014] Preferably, the zinc salt is at least one of zinc nitrate, zinc chloride and zinc sulfate.

[0015] Preferably, the film forming agent is at least one of polyvinyl alcohol and polyethylene glycol.

[0016] Preferably, the cross-linking agent is at least one of glutaric acid, citric acid, succinic acid, malonic acid, glutaraldehyde, and oxalic acid.

[0017] Preferably, the preservative is at least one of carboxin, sodium benzoate, and brodaline.

[0018] Preferably, the warning agent is at least one of gentian violet dye, yellow iron oxide, and basic roseine.

[0019] Preferably, the dispersing agent is at least one of sodium dodecyl benzene sulfonate, sodium lignosulfonate, desugared condensed sodium lignosulfonate, and succinic acid ester sodium sulfonate.

[0020] The present application also provides a preparation method of the pesticide seed suspension agent, which specifically comprises the following steps:

[0021] S1, after the modified plant polysaccharide is completely dissolved in the deionized water, it is added dropwise into a zinc salt solution, stirred at a speed of 50-70 rpm for 8-12 hours, centrifuged at a speed of 8000-10000 rpm for 5 minutes, the supernatant is removed, and the deionized water is added for redissolution, ultrasonic treatment is performed, centrifuged at a speed of 5000 rpm for 5 minutes, the supernatant is removed, and then frozen drying is performed to obtain Zn-plant polysaccharide;

[0022] S2, the imidacloprid, the azoxystrobin, and the propiconazole are added into an ethanol solution, the volume fraction of ethanol in the ethanol solution is 20%-30%, a dispersing agent is added, the pesticides are fully dissolved, the Zn-plant polysaccharide prepared in step S1 is added, oscillation is performed at a speed of 200-250 rpm for 2-3 hours under room temperature, centrifuged at a speed of 8000 rpm for 5 minutes, the precipitate is collected, and then dried to obtain a mixed solution of active ingredients;

[0023] S3, the film-forming agent, the preservative, and the warning agent are added into the deionized water and stirred uniformly, and then a cross-linking agent is added and mixed uniformly to obtain a mixed solution of additives;

[0024] S4, the mixed solution of active ingredients prepared in step S2 and the mixed solution of additives prepared in step S3 are mixed uniformly to obtain a seed suspension.

[0025] Preferably, in step S1, the mass fraction of the plant polysaccharide in the deionized water is 1-3%.

[0026] Preferably, in step S1, the mass fraction of Zn 2+ in the zinc salt solution is 5%-10%.

[0027] Preferably, in step S1, the power of ultrasonic treatment is 300-450 W, and the treatment time is 5-10 minutes.

[0028] Preferably, in step S2, the concentration of the three pesticide raw materials in the ethanol solution is 10-15 g / L.

[0029] The beneficial effects obtained by the present application are as follows:

[0030] The present application provides a kind of multiple pesticide seed suspending agent and preparation method thereof, by the modification treatment of 4-imidazole formic acid to plant polysaccharide, and by Zn 2+ Cationic bond bridge formation, thereby improving the adsorption of pesticide molecules, improving the safety of seed germination, emergence and other physiological behaviors of seed suspending agent and the slow-release performance of pesticide;Plant polysaccharide can provide a large amount of ·OH free radicals at room temperature under H2O2, and free radicals can attack hydrogen atoms in the hydroxyl group of plant polysaccharide, so that the hydrogen atoms in the hydroxyl group of plant polysaccharide are lost, forming a large number of macromolecular free radicals, and 4-imidazole formic acid can form a graft product with the macromolecular free radicals of plant polysaccharide;The graft product is soaked in zinc salt solution, and the free macromolecular free radicals of polysaccharide and N atoms on imidazole groups can form complexes with Zn 2+ , forming a polysaccharide carrier skeleton with complex internal structure, and providing effective load of pesticide atoms through various active groups;After seed treatment with seed suspending agent, a polysaccharide carrier with loaded pesticide molecules can be formed on the surface of the seed, which can effectively maintain the shape of the carrier in a dry environment, and the pesticide molecules can be stably loaded on the structure;When it rains or irrigates, the amount of water in the soil increases, and the plant polysaccharide dissolves in water, and due to the action of ionic bonds and covalent bonds between imidazole groups and Zn 2+ , the dissolution rate of plant polysaccharide in rainwater or irrigation water is reduced, the decomposition rate of the carrier structure is slow, the slow-release performance of the pesticide is improved, and the rapid disintegration of plant polysaccharide to release a large amount of pesticide molecules is avoided, so that the concentration of pesticide in the environment around the seed is sharply increased, and phytotoxicity is generated, thereby improving the safety of seed germination and growth and other physiological activities. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 It is a schematic diagram of the preparation process of modified papaya polysaccharide in Example 1.

[0032] Figure 2 It is the cumulative release curve of pesticide in the seed suspending agent described in the examples and comparative examples of the present application.

[0033] Figure 3 It is a result graph of emergence rate, plant height and root length in the pot experiment of corn seeds treated with seed suspending agent described in the examples and comparative examples.

[0034] Figure 4 It is a result graph of aboveground and underground fresh weight in the pot experiment of corn seeds treated with seed suspending agent described in the examples and comparative examples.

[0035] Figure 5 SEM micrograph of seed coating formed after treating corn seeds with the seed suspension of Example 1.

[0036] The accompanying drawings are included to provide a further understanding of the application, and are incorporated in and constitute a part of this specification, illustrate embodiments of the application, and together with the description serve to explain the principles of the application, but are not intended to limit the application. DETAILED DESCRIPTION

[0037] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0038] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art. In addition, any method and material similar or equivalent to those described herein can be used in the present application. The preferred methods and materials described herein are only for demonstration, but cannot limit the content of the present application.

[0039] Unless otherwise specified, the experimental methods in the following examples are all conventional methods. Unless otherwise specified, the test materials and test strains used in the following examples are all purchased from commercial channels.

[0040] Plant polysaccharide

[0041] 4-imidazole carboxylic acid (CasNo: 1072-84-0) was purchased from Beijing Inokai Technology Co., Ltd., brand: GC105136;

[0042] Zinc nitrate hexahydrate (CasNo: 10196-18-6) was purchased from Beijing Wakai Biological Technology Co., Ltd., brand: 211660050;

[0043] Zinc chloride (CasNo: 7646-85-7) was purchased from Beijing Wakai Biological Technology Co., Ltd., brand: 196840025;

[0044] Zinc sulfate heptahydrate (CasNo: 7446-20-0) was purchased from Beijing Wakai Biological Technology Co., Ltd., brand: 205980010;

[0045] Imidacloprid technical (CasNo: 138261-41-3) was purchased from Hubei Maoerwo Biological Medicine Co., Ltd., imidacloprid content ≥95%;

[0046] Kresoxim-methyl technical (CasNo: 131860-33-8) was purchased from Hubei Maoerbo Biological Medicine Co., Ltd., and the content of kresoxim-methyl was ≥98%;

[0047] Propiconazole technical (CasNo: 178928-70-6) was purchased from Hubei Maoerbo Biological Medicine Co., Ltd., and the content of propiconazole was ≥97%;

[0048] Polyvinyl alcohol (CasNo: 9002-89-5) was purchased from Sigma-Aldrich (Shanghai) Trading Co., Ltd., and the brand was 10849;

[0049] Polyethylene glycol (CasNo: 25322-68-3) was purchased from Sigma-Aldrich (Shanghai) Trading Co., Ltd., and the brand was 03394;

[0050] Glutaraldehyde (CasNo: 111-30-8) was purchased from Shanghai McLean Biochemical Technology Co., Ltd., and the brand was G810413;

[0051] Glutaric acid (CasNo: 110-94-1) was purchased from Shanghai McLean Biochemical Technology Co., Ltd., and the brand was G810360;

[0052] Citric acid (CasNo: 77-92-9) was purchased from Shanghai McLean Biochemical Technology Co., Ltd., and the brand was C805021;

[0053] Succinic acid (CasNo: 110-15-6) was purchased from Shanghai McLean Biochemical Technology Co., Ltd., and the brand was S817845;

[0054] Sodium dodecylbenzenesulfonate (CasNo: 25155-30-0) was purchased from Shanghai Aldrich Biochemical Technology Co., Ltd., and the brand was S117593;

[0055] Sodium lignosulfonate (CasNo: 8061-51-6) was purchased from Shanghai Aldrich Biochemical Technology Co., Ltd., and the brand was S140863;

[0056] Sodium succinate sulfonate (CasNo: 577-11-7) was purchased from Shanghai Aldrich Biochemical Technology Co., Ltd., and the brand was A106730;

[0057] Sodium benzoate (CasNo: 532-32-1) was purchased from Shanghai Aldrich Biochemical Technology Co., Ltd., and the brand was S424558;

[0058] Bromogeramine (CasNo: 52-51-7) was purchased from Shanghai Aldrich Biochemical Technology Co., Ltd., and the brand was B424507;

[0059] Casson (CasNo: 80474-14-2) was purchased from Shanghai Aladdin Bio-Chem Technology Co., Ltd., brand: F409005;

[0060] Gentian violet dye (CasNo: 548-62-9) was purchased from Shanghai Aladdin Bio-Chem Technology Co., Ltd., brand: C110703;

[0061] Iron oxide yellow (CasNo: 51274-00-1) was purchased from Shanghai Aladdin Bio-Chem Technology Co., Ltd., brand: P193670;

[0062] Basic roseine (CasNo: 81-88-9) was purchased from Shanghai Aladdin Bio-Chem Technology Co., Ltd., brand: R104960.

[0063] Example 1

[0064] The present embodiment provides a kind of pesticide seed suspending agent of multiple, the seed suspending agent includes the following weight parts of component: modified papaya seed polysaccharide 3 parts, zinc nitrate 10 parts, imidacloprid raw drug 1 part, 0.5 parts of fenhexamid raw drug, propiconazole raw drug 1.2 parts, sodium dodecyl benzene sulfonate 5 parts, polyvinyl alcohol 4 parts, glutaric acid 0.5 parts, sodium benzoate 0.1 part, gentian violet dye 1 part, deionized water 75 parts.

[0065] The preparation method of the modified plant polysaccharide specifically includes the following steps:

[0066] 1, 5g papaya seed polysaccharide is dissolved in 500mL 1mol / L NaOH solution, under room temperature condition, is placed in magnetic stirrer until papaya seed polysaccharide completely dissolves, is adjusted to pH 7.0 with 1mol / L HCL, is placed at 4.0 DEG C overnight, after being fully hydrated, water-hydrated papaya seed polysaccharide solution is obtained;

[0067] 2, accurately 100mL water-hydrated papaya seed polysaccharide solution is taken in three-necked bottle, 0.8g 4-imidazole formic acid is added, under nitrogen atmosphere, is placed on magnetic stirrer and is stirred, 4mL 6mol / L H2O2 solution is added dropwise, after reaction for 12h, 400mL volume fraction 95% ethanol solution is used for precipitation, is placed at 4 DEG C overnight, after 8000rpm centrifugation for 10min, the precipitate is collected, is redissolved with deionized water, is dialyzed in distilled water with 8000kDa for 2d, after freeze-drying, modified papaya seed polysaccharide is obtained.

[0068] The present application also provides a kind of pesticide seed suspending agent of multiple preparation method, specifically includes the following steps:

[0069] S1, the modified papaya seed polysaccharide is dissolved in deionized water at a mass fraction of 1%, a zinc nitrate solution at a mass fraction of 5% is added, stirring is performed at a speed of 50 rpm for 8 hours, centrifugation is performed at a speed of 8000 rpm for 5 minutes, after the supernatant is removed, deionized water is added for redissolution, ultrasonic treatment is performed at a power of 300 W for 10 minutes, centrifugation is performed at a speed of 5000 rpm for 5 minutes, after the supernatant is removed, freeze-drying is performed, and Zn-papaya seed polysaccharide is obtained;

[0070] S2, the imidacloprid raw drug, the azoxystrobin raw drug and the prothioconazole raw drug are added into an ethanol solution, the volume fraction of ethanol in the ethanol solution is 20%, the concentration of the three pesticide raw drugs in the ethanol solution is 15 g / L, sodium dodecyl benzene sulfonate is added, after the pesticides are fully dissolved, the Zn-papaya seed polysaccharide prepared in step S1 is added, oscillation is performed at a speed of 250 rpm for 2 hours at room temperature, centrifugation is performed at a speed of 8000 rpm for 5 minutes, and then the precipitate is collected and dried to obtain an active ingredient mixture.

[0071] S3, polyvinyl alcohol, sodium benzoate and gentian violet dye are added into deionized water and stirred uniformly, and glutaric acid is added, and then mixed uniformly to obtain an auxiliary agent mixture.

[0072] S4, the active ingredient mixture prepared in step S2 and the auxiliary agent mixture prepared in step S3 are mixed uniformly to obtain a seed suspension.

[0073] The preparation process of the modified papaya seed polysaccharide in the embodiment is as shown in Figure 1 .

[0074] Embodiment 2

[0075] The embodiment provides a plurality of pesticide seed suspensions, and the seed suspensions comprise the following components in parts by weight: modified seaweed polysaccharide 10 parts, zinc chloride 15 parts, imidacloprid raw drug 1.5 parts, azoxystrobin raw drug 1 part, prothioconazole raw drug 0.8 part, sodium lignosulfonate 8 parts, polyethylene glycol 2 parts, glutaraldehyde 0.3 part, kathon 0.3 part, iron oxide yellow 4 parts, and deionized water 90 parts.

[0076] The preparation method of the modified plant polysaccharide specifically comprises the following steps:

[0077] 1, 5 g of seaweed polysaccharide is dissolved in 100 mL of 1 mol / L NaOH solution, the seaweed polysaccharide is completely dissolved in a magnetic stirrer at room temperature, 1 mol / L HCL is used to adjust the pH to 7.0, and the seaweed polysaccharide is fully hydrated after being placed at 4.0 ℃ overnight to obtain a hydrated seaweed polysaccharide solution;

[0078] ② Accurate 200 mL water-soluble seaweed polysaccharide solution is taken in a three-necked bottle, 1g 4-imidazole formic acid is added, under the atmosphere of nitrogen, stirring is carried out on a magnetic stirrer, 8mL 4mol / L H2O2 solution is added drop by drop, after 12h reaction, 800mL 95% ethanol solution is used for precipitation, after standing at 4℃ overnight, 8000rpm centrifugation is carried out for 10min, the precipitate is collected, after redissolving with deionized water, dialysis is carried out in distilled water for 2d with 8000kDa, after freeze-drying, modified seaweed polysaccharide is obtained.

[0079] The application further provides a preparation method of the seed suspension agent of multiple pesticides, and specifically comprises the following steps:

[0080] S1, the modified seaweed polysaccharide is dissolved in deionized water at a mass fraction of 3%, a zinc chloride solution at a mass fraction of 10% is added, stirring is carried out at a speed of 70rpm for 8h, 10000rpm centrifugation is carried out for 5min, after removing the supernatant, deionized water is added for redissolving, ultrasonic treatment is carried out at a power of 400W for 10min, 5000rpm centrifugation is carried out for 5min, after removing the supernatant, freeze-drying is carried out, and Zn-seaweed polysaccharide is obtained;

[0081] S2, the imidacloprid raw pesticide, the azoxystrobin raw pesticide and the prothioconazole raw pesticide are added into an ethanol solution, the volume fraction of ethanol in the ethanol solution is 30%, the concentration of the three pesticide raw materials in the ethanol solution is 10g / L, the desugared lignosulfonate sodium is added, after the pesticides are fully dissolved, the Zn-seaweed polysaccharide prepared in step S1 is added, 250rpm oscillation is carried out at room temperature for 3h, 8000rpm centrifugation is carried out for 5min, the precipitate is collected, and after drying, an active ingredient mixture is obtained.

[0082] S3, the polyethylene glycol, the kathon and the yellow iron oxide are added into deionized water and stirred uniformly, and then the glutaraldehyde is added, and after mixing uniformly, an auxiliary agent mixture is obtained.

[0083] S4, the active ingredient mixture prepared in step S2 and the auxiliary agent mixture prepared in step S3 are mixed uniformly, and a seed suspension is obtained.

[0084] Example 3

[0085] The example provides a seed suspension agent of multiple pesticides, which comprises the following components in parts by weight: modified astragalus polysaccharide 5 parts, zinc sulfate 20 parts, imidacloprid raw pesticide 2 parts, azoxystrobin raw pesticide 1 part, prothioconazole raw pesticide 1.2 parts, sodium sulfosuccinate 7 parts, polyvinyl alcohol 6 parts, citric acid 0.8 parts, brodalumide 0.5 parts, basic roseine 5 parts and deionized water 100 parts.

[0086] The preparation method of the modified plant polysaccharide specifically comprises the following steps:

[0087] ① 5g Astragalus polysaccharide is dissolved in 400mL 1mol / L NaOH solution, and placed in a magnetic stirrer at room temperature until Astragalus polysaccharide is completely dissolved, and then the pH is adjusted to 7.0 with 1mol / L HCL, and the solution is placed at 4.0℃ overnight for sufficient hydration, and then a hydrated Astragalus polysaccharide solution is obtained;

[0088] ② 100mL of the hydrated Astragalus polysaccharide solution is accurately measured in a three-necked flask, 1.2g of 4-imidazole carboxylic acid is added, and the solution is stirred in a magnetic stirrer under a nitrogen atmosphere, 4mL of 5mol / L H2O2 solution is added dropwise, and the solution is reacted for 14h, and then 400mL of 95% ethanol solution is used for precipitation, and the solution is placed at 4℃ overnight, and then centrifuged at 10000rpm for 5min, and the precipitate is collected, redissolved in deionized water, and dialyzed in distilled water for 2d with 6000kDa, and then freeze-dried to obtain modified Astragalus polysaccharide.

[0089] The application also provides a preparation method of a plurality of pesticide seed suspending agents, which specifically comprises the following steps:

[0090] S1, the modified Astragalus polysaccharide is dissolved in deionized water at a mass fraction of 2%, and then a zinc sulfate solution at a mass fraction of 10% is added, and the solution is stirred at a speed of 50rpm for 8h, and then centrifuged at 8000rpm for 5min, and then the supernatant is removed, and then the solution is redissolved in deionized water, and then ultrasonic treatment is carried out at a power of 450W for 5min, and then centrifuged at 5000rpm for 5min, and then the supernatant is removed, and then freeze-dried to obtain Zn-Astragalus polysaccharide;

[0091] S2, imidacloprid, azoxystrobin and propiconazole are added to an ethanol solution, the volume fraction of ethanol in the ethanol solution is 20%, the concentration of the three pesticide raw materials in the ethanol solution is 10g / L, sodium dodecyl benzene sulfonate is added, the pesticides are fully dissolved, and then the Zn-Astragalus polysaccharide prepared in step S1 is added, and then the solution is oscillated at a speed of 200rpm for 3h at room temperature, and then centrifuged at 8000rpm for 5min, and then the precipitate is collected and dried to obtain an active ingredient mixture.

[0092] S3, polyvinyl alcohol, brobrol and basic rose essence are added to deionized water and stirred uniformly, and then citric acid is added and mixed uniformly to obtain an auxiliary agent mixture.

[0093] S4, the active ingredient mixture prepared in step S2 and the auxiliary agent mixture prepared in step S3 are mixed uniformly to obtain a seed suspension.

[0094] Example 4

[0095] The embodiment provides a kind of multiple pesticide seed suspending agent, the seed suspending agent includes the following weight parts of components: modified seaweed polysaccharide 3 parts, zinc nitrate 10 parts, imidacloprid 1 part, kresoxim-methyl 0.5 parts, propiconazole 1.2 parts, sodium dodecyl benzene sulfonate 5 parts, polyethylene glycol 4 parts, succinic acid 0.5 parts, sodium benzoate 0.1 parts, gentian violet dye 1 part, deionized water 75 parts.

[0096] The preparation method of the modified plant polysaccharide specifically includes the following steps:

[0097] ①5g seaweed polysaccharide is dissolved in 500mL 1mol / L NaOH solution, and placed in a magnetic stirrer at room temperature until the seaweed polysaccharide is completely dissolved. The pH is adjusted to 7.0 with 1mol / L HCL, and the solution is placed at 4.0°C overnight for complete hydration. The hydrated seaweed polysaccharide solution is obtained.

[0098] ②100mL of the hydrated seaweed polysaccharide solution is accurately measured in a three-necked flask, and 0.8g of 4-imidazole formic acid is added. The flask is placed in a magnetic stirrer under a nitrogen atmosphere and stirred. 5mL of 5mol / L H2O2 solution is added dropwise, and the reaction is carried out for 12h. The solution is precipitated with 400mL of 95% ethanol solution, and placed at 4°C overnight. The precipitate is collected by centrifugation at 8000rpm for 10min. The precipitate is redissolved in deionized water, and dialyzed in distilled water with a 6000kDa membrane for 2d. The modified seaweed polysaccharide is obtained by freeze-drying.

[0099] The present application also provides a preparation method of a multiple pesticide seed suspending agent, which specifically includes the following steps:

[0100] S1, the modified seaweed polysaccharide is dissolved in deionized water at a mass fraction of 3%, and a zinc nitrate solution with a mass fraction of 5% is added. The solution is stirred at a speed of 50rpm for 8h, and then centrifuged at 10000rpm for 5min. The supernatant is removed, and the solution is redissolved in deionized water. The solution is treated with ultrasonic waves at a power of 300W for 10min, and then centrifuged at 5000rpm for 5min. The supernatant is removed, and the solution is freeze-dried to obtain Zn-seaweed polysaccharide.

[0101] S2, imidacloprid, kresoxim-methyl and propiconazole are added to an ethanol solution, and the volume fraction of ethanol in the ethanol solution is 20%. The concentration of the three pesticide raw materials in the ethanol solution is 10g / L. Sodium dodecyl benzene sulfonate is added, and the pesticides are fully dissolved. The Zn-seaweed polysaccharide prepared in step S1 is added, and the solution is oscillated at a speed of 250rpm for 2h at room temperature. The solution is centrifuged at 8000rpm for 5min, and the precipitate is collected and dried to obtain an effective ingredient mixture.

[0102] S3, polyethylene glycol, sodium benzoate and gentian violet dye are added into deionized water and stirred uniformly, then succinic acid is added, and after mixing uniformly, an additive mixture solution is obtained.

[0103] S4, the active ingredient mixture solution prepared in step S2 and the additive mixture solution prepared in S3 are mixed uniformly to obtain a seed suspension.

[0104] Example 5

[0105] The embodiment provides a plurality of pesticide seed suspensions, which comprise the following components in parts by weight: modified papaya polysaccharide 8 parts, zinc chloride 12 parts, imidacloprid 1.5 parts, azoxystrobin 1.5 parts, propiconazole 1 part, sodium dodecyl benzene sulfonate 6 parts, polyvinyl alcohol 4 parts, glutaric acid 0.5 parts, kathon 0.3 parts, gentian violet dye 3 parts, and deionized water 90 parts.

[0106] The preparation method of the modified plant polysaccharide specifically comprises the following steps:

[0107] 1. 15g papaya polysaccharide is dissolved in 500mL 1mol / L NaOH solution, and placed in a magnetic stirrer at room temperature until the papaya polysaccharide is completely dissolved, then 1mol / L HCL is used to adjust the pH to 7.0, and the solution is placed at 4.0℃ overnight after being fully hydrated to obtain a hydrated papaya polysaccharide solution;

[0108] 2. 100mL of the hydrated papaya polysaccharide solution is accurately measured in a three-necked bottle, 0.8g of 4-imidazole formic acid is added, and the solution is stirred in a magnetic stirrer under a nitrogen atmosphere, 6mL of 4mol / L H2O2 solution is added dropwise, and after 10h of reaction, 400mL of 95% ethanol solution is used for precipitation, and the solution is placed at 4℃ overnight, then centrifuged at 8000rpm for 10min, and the precipitate is collected, redissolved in deionized water, dialyzed in distilled water for 2d with 8000kDa, and freeze-dried to obtain modified papaya polysaccharide.

[0109] The embodiment also provides a preparation method of a plurality of pesticide seed suspensions, which specifically comprises the following steps:

[0110] S1, the modified papaya polysaccharide is dissolved in deionized water at a mass fraction of 2%, and a zinc chloride solution at a mass fraction of 5% is added, and after stirring at a speed of 50rpm for 8h, centrifugation is performed at 8000rpm for 5min, the supernatant is removed, deionized water is added for redissolution, ultrasonic treatment is performed at a power of 300W for 10min, centrifugation is performed at 5000rpm for 5min, the supernatant is removed, and freeze-drying is performed to obtain Zn-papaya polysaccharide;

[0111] S2, imidacloprid, azoxystrobin and propiconazole were added into ethanol solution, the volume fraction of ethanol in the ethanol solution was 20%-30%, the concentration of the three pesticide raw materials in the ethanol solution was 15g / L, sodium dodecyl benzene sulfonate was added, after the pesticides were fully dissolved, Zn-papaya seed polysaccharide prepared in step S1 was added, after oscillation at room temperature for 3h at 200rpm, centrifugation was carried out at 8000rpm for 5min, the precipitate was collected, and after drying, an effective ingredient mixture was obtained.

[0112] S3, polyvinyl alcohol, kathon and gentian violet dye were added into deionized water and stirred uniformly, then glutaric acid was added, and an additive mixture was obtained after mixing uniformly.

[0113] S4, the effective ingredient mixture prepared in step S2 and the additive mixture prepared in step S3 were mixed uniformly to obtain a seed suspension.

[0114] Comparative Example 1

[0115] The present comparative example provides a seed suspension and a preparation method thereof, which is different from Example 1 only in that no zinc salt is contained in all components, and the rest of the components and component contents are the same as those of Example 1.

[0116] Comparative Example 2

[0117] The present comparative example provides a seed suspension and a preparation method thereof, which is different from Example 1 only in that no modified plant polysaccharide is contained in all components, and the rest of the components and component contents are the same as those of Example 1.

[0118] Comparative Example 3

[0119] The present comparative example provides a seed suspension and a preparation method thereof, which is different from Example 1 only in that the plant polysaccharide is not modified by 4-imidazole carboxylic acid, but is only ordinary plant polysaccharide.

[0120] Experimental Example 1

[0121] The seed suspension agent described in the examples and comparative examples is subjected to a pesticide active ingredient release experiment. The experiment method is a dynamic dialysis method. Specifically, 10 mL of the seed suspension agent described in the examples and comparative examples is placed in a dialysis bag with a molecular cut-off of 8000. The dialysis bag is immersed in 100 mL of a release medium, which is a methanol / water solution (50:50, v / v), in a constant temperature water bath shaker at a speed of 120 rpm. Sampling is performed at 1 h, 3 h, 5 h, 10 h, 15 h, 20 h, 32 h, 48 h, 72 h, and 120 h. When sampling, 1 mL of the release medium solution outside the dialysis bag is sucked with a syringe, and the same volume of release medium is supplemented after sampling. The sample is filtered with a water phase membrane (pore size 0.22 μm), and the content of the pesticide active ingredient in the sample is determined by liquid chromatography. The cumulative release rate of the pesticide active ingredient is calculated. The pesticide active ingredient is imidacloprid.

[0122] Figure 2 The cumulative release curve of the pesticide in the seed suspension agent described in the examples and comparative examples is shown in the figure. The seed suspension agent described in examples 1-4 has a burst release stage within the initial 32 h. In the subsequent stage, the pesticide active ingredient in the seed suspension agent continues to be released, but the release rate is slowed down. After 120 h, the release equilibrium is not reached. The seed suspension agent described in comparative example 1 does not include a zinc salt. It reaches the release equilibrium at about the initial 20 h, and the cumulative release rate is about 70% at this time. In the seed suspension agent, the intermolecular hydrogen bond action is used to maintain the spatial structure of the modified plant polysaccharide. Since the solubility of the plant polysaccharide in water is good, the distance between the molecules is expanded, the intermolecular hydrogen bond force is weakened, and the slow release performance of the pesticide active ingredient is poor. The seed suspension agent described in comparative example 2 does not include a modified plant polysaccharide. The cumulative release rate reaches 90% within about the initial 20 h. The modified plant polysaccharide is the main carrier material of the pesticide active ingredient. The seed suspension agent lacking the modified plant polysaccharide does not have slow release performance. The plant polysaccharide in the seed suspension agent described in comparative example 3 is not modified by 4-imidazole formic acid. Its release performance is close to that of the examples. The cumulative release rate reaches about 60% at about 50 h. Compared with the examples, the release rate is faster. The plant polysaccharide contains a large number of ·OH groups, which can form a complex with zinc ions, thereby producing a small amount of ionic bonds to strengthen the binding strength between the plant polysaccharide molecules. However, compared with the ·OH group, it is not the best group to form a complex product with zinc ions. Therefore, the number of zinc ion complexation sites in the plant polysaccharide in comparative example 3 is less than that in the examples, and the release performance is poorer than that in the examples.

[0123] Experimental example 2

[0124] The potting test of the seed suspending agent described in the examples and the comparative examples is carried out, and the specific method is as follows: the corn seeds are treated with the seed suspending agent according to the ratio of 1:25, the treated corn seeds are evenly sowed in the plastic pots filled with soil, the number of corn seeds in each pot is 30, after sowing, a layer of soil is covered, and after uniform watering, the pots are placed in a 25℃ greenhouse, the seedling emergence and the growth of corn seedlings are observed, and the seedling emergence rate, the plant height, the root length, the aboveground fresh weight and the underground fresh weight of the corn seeds are measured.

[0125] Figure 3 The results of the seedling emergence rate, the plant height and the root length in the potting test of the corn seeds treated with the seed suspending agent described in the examples and the comparative examples are shown in the figure, after the corn seeds are treated with the seed suspending agent described in examples 1-4, the seedling emergence rate is above 80%, the seedling emergence rate treated with comparative example 1 is 63%, the seedling emergence rate treated with comparative example 2 is 21%, and the seedling emergence rate treated with comparative example 3 is 74%; the plant height of the corn seedlings treated with examples 1-4 is 18-19 cm, the plant height of the corn seedlings treated with comparative example 1 is 16.4 cm, the plant height of the corn seedlings treated with comparative example 2 is 12.3 cm, and the plant height of the corn seedlings treated with comparative example 3 is 17.8 cm; the main root length of the corn seedlings treated with examples 1-4 is 25-27 cm, the main root length of the corn seedlings treated with comparative example 1 is 20.1 cm, the main root length of the corn seedlings treated with comparative example 2 is 13.3 cm, and the main root length of the corn seedlings treated with comparative example 3 is 23.5 cm; the corn seeds need a higher water content in the soil for germination, the seed coating is formed on the corn seeds after the seeds are treated with the seed suspending agent, after watering after sowing, the modified polysaccharide in the seeds is dissolved, and the pesticide active ingredient adsorbed thereon is released; the seedling emergence is inhibited due to the high local pesticide concentration in the seed suspending agent without plant polysaccharide in comparative example 2; the plant height and the root length of the corn seedlings have similar effects, and the inhibition effect on the corn root system is more obvious.

[0126] Figure 4 The results of the aboveground fresh weight and the underground fresh weight in the potting test of the corn seeds treated with the seed suspending agent described in the examples and the comparative examples are shown in the figure, the aboveground fresh weight and the underground fresh weight of examples 1-4 are obviously higher than those of the comparative examples, and the aboveground fresh weight and the underground fresh weight of comparative example 2 are the lowest; the specific reason is the same as described above, the seed suspending agent without polysaccharide is easy to cause the burst release of the pesticide content in the seed surrounding environment, resulting in a high unit concentration of the pesticide, which inhibits the growth of corn.

[0127] Example 3

[0128] The microstructure of the seed coating formed on the surface of the corn seeds treated with the seed suspending agent prepared in example 1 is observed, the scanning electron microscope is used, and the microstructure observed after magnification of 5000 times is shown in Figure 5 .

[0129] While embodiments of the application have been shown and described, it is to be understood that the application is not limited to the details of the embodiments described, since various modifications can be made by those skilled in the art, without departing from the spirit and scope of the application, which is defined by the appended claims and their equivalents.

[0130] The above description of the application and its embodiments is not restrictive, and the embodiments shown in the drawings are only one of the embodiments of the application, and the actual application is not limited thereto. In general, if a person skilled in the art is inspired by it, without departing from the purpose of the application, without creative design, similar ways and embodiments of the technical solution should belong to the protection scope of the application.

Claims

1. A multi-pesticide seed suspension agent, characterized by: The seed suspension agent comprises the following components by weight: modified plant polysaccharide 3-10 parts, zinc salt 10-20 parts, imidacloprid raw drug 1-2 parts, azoxystrobin raw drug 0.5-1.5 parts, propiconazole raw drug 0.8-1.2 parts, dispersing agent 5-8 parts, film-forming agent 2-6 parts, crosslinking agent 0.3-0.8 parts, preservative 0.1-0.5 parts, warning agent 1-5 parts, deionized water 75-100 parts; the modified plant polysaccharide is a plant polysaccharide modified by 4-imidazole carboxylic acid; The preparation method of the modified plant polysaccharide specifically comprises the following steps: ①Dissolve the plant polysaccharide in a NaOH solution, stir at room temperature until completely dissolved, adjust the pH to 7.0, and stand overnight at 4.0°C to obtain a hydrated plant polysaccharide solution; ②Add 4-imidazole carboxylic acid to the hydrated plant polysaccharide solution prepared in step ①, perform magnetic stirring under a nitrogen atmosphere, dropwise add an H2O2 solution, react for 10-14 h, add an ethanol solution with a volume fraction of 95% to perform precipitation, stand overnight at 4°C, centrifuge at 8000-10000 rpm for 5-10 min, remove the supernatant, redissolve the precipitate with deionized water, dialyze in distilled water for 2 d, with a molecular cut-off of 6-8 kDa, and freeze-dry to obtain the modified plant polysaccharide; The plant polysaccharide is at least one of papaya polysaccharide, astragalus polysaccharide, and seaweed polysaccharide; The zinc salt is at least one of zinc nitrate, zinc chloride, and zinc sulfate; The film-forming agent is at least one of polyvinyl alcohol and polyethylene glycol; The crosslinking agent is at least one of glutaric acid, citric acid, succinic acid, and glutaraldehyde; The preparation method of the plurality of seed suspension agents of pesticides specifically comprises the following steps: S1, after the modified plant polysaccharide is completely dissolved in deionized water, it is added dropwise to a zinc salt solution, stirred at a speed of 50-70 rpm for 8-12 h, centrifuged at 8000-10000 rpm for 5 min, the supernatant is removed, deionized water is added for redissolution, ultrasonic treatment is performed, centrifuged at 5000 rpm for 5 min, the supernatant is removed, and freeze-drying is performed to obtain Zn-plant polysaccharide; S2, imidacloprid raw drug, azoxystrobin raw drug, and propiconazole raw drug are added to an ethanol solution, the volume fraction of ethanol in the ethanol solution is 20%-30%, a dispersing agent is added, the pesticides are completely dissolved, the Zn-plant polysaccharide prepared in step S1 is added, oscillated at 200-250 rpm for 2-3 h at room temperature, centrifuged at 8000 rpm for 5 min, the precipitate is collected, and dried to obtain an active ingredient mixture; S3, a film-forming agent, a preservative, and a warning agent are added to deionized water and stirred uniformly, a crosslinking agent is added, and mixed uniformly to obtain an additive mixture; S4, the active ingredient mixture prepared in step S2 and the additive mixture prepared in S3 are mixed uniformly to obtain a seed suspension.

2. The plurality of pesticide seed suspensions of claim 1, wherein: The preservative is at least one of carzone, sodium benzoate, and bromopol; the warning agent is at least one of gentian violet dye, yellow iron oxide, and basic roseine; and the dispersing agent is at least one of sodium dodecyl benzene sulfonate, sodium lignosulfonate, desugared condensed sodium lignosulfonate, and succinate sulfonate sodium.

3. The plurality of pesticide seed suspensions of claim 2, wherein: In step S1, the mass fraction of the plant polysaccharide in deionized water is 1-3%; the mass fraction of Zn 2+ in the zinc salt solution is 5%-10%; the power of ultrasonic treatment is 300-450 W, and the treatment time is 5-10 min.

4. The plurality of pesticide seed suspensions of claim 3, wherein: In step S2, the concentration of the three pesticide raw materials in the ethanol solution is 10-15 g / L.

5. The plurality of pesticide seed suspensions of claim 4, wherein: In step ①, the mass fraction of the plant polysaccharide in the NaOH solution is 1-5%, and the concentration of the NaOH solution is 1 mol / L.

6. The plurality of pesticide seed suspensions of claim 5, wherein: In step ②, the addition amount of the 4-imidazole carboxylic acid is 8-12 mg / mL, the concentration of the H2O2 solution is 4-6 mol / L, and the volume ratio of the H2O2 solution to the hydrated plant polysaccharide solution is 1-2:25.

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