Herbicide composition as well as microencapsulation preparation method and application thereof

Abstract

The invention discloses a microencapsulated herbicide composition as well as a preparation method and application thereof, and belongs to the field of pesticide processing, the microencapsulated herbicide composition comprises 23-77.5% of herbicide active ingredients and the balance of pharmaceutically acceptable auxiliaries; wherein the herbicide active component is composed of sulfentrazone, clomazone and s-metolachlor, the invention discloses the herbicide compounded by ternary combination of sulfentrazone, clomazone and s-metolachlor for the first time, and the herbicide composition has high safety to small crops such as watermelons, peas, peppers and the like, has an excellent control effect on broad leaf and cyperaceae weeds, and can be widely applied to the field of weeding. Even if the dosage is high, the growth is not inhibited, the lasting period is as long as 60 days, weeds in the whole seedling stage are thoroughly controlled, and the pesticide application frequency is reduced.

Description

Technical Field

[0001] The present invention belongs to the technical field of pesticide processing, and particularly relates to a microencapsulated herbicide composition, a preparation method thereof, and an application thereof. Background Art

[0002] China has a vast territory and rich and diverse crop cultivation. The planting area of minor crops is small, and the attention of agrochemical enterprises and scientific research institutions is low, resulting in immature pest, disease, and weed control programs, which restricts the planting level of minor crops.

[0003] Minor crops such as melons, beans, and solanaceous crops (such as zucchini, watermelon, black bean, pea, eggplant, pepper, etc.) lack herbicide registrations in China. Few available products such as metolachlor and butralin have poor control effects on broad-leaved and sedge weeds.

[0004] Although clomazone can be used for weed control in minor crops, clomazone is prone to sublimation and there is a problem of drift phytotoxicity. At home and abroad, microcapsule technology is preferably used to reduce the drift phytotoxicity of clomazone. However, microcapsule technology has disadvantages such as long reaction time, complex process, and low production capacity. Summary of the Invention

[0005] The purpose of this part is to outline some aspects of the embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this part, as well as in the abstract and title of the present application, to avoid obscuring the purpose of this part, the abstract, and the title. Such simplifications or omissions shall not be used to limit the scope of the present invention.

[0006] In view of the above and / or problems existing in the prior art, the present invention is proposed.

[0007] Therefore, the purpose of the present invention is to overcome the deficiencies in the prior art and provide a herbicide composition.

[0008] To solve the above technical problems, the present invention provides the following technical solutions: including, based on the mass percentage of the herbicide composition, containing 23% - 77.5% of herbicide active ingredients, and the balance being agriculturally acceptable adjuvants; wherein, the herbicide active ingredients are composed of sulfentrazone, clomazone, and S-metolachlor.

[0009] As a preferred embodiment of the herbicide composition of the present invention, wherein: the mass ratio of sulfentrazone, clomazone, and S-metolachlor is 2 - 3:3 - 4:18 - 24.

[0010] As a preferred embodiment of the herbicide composition of the present invention, wherein: the mass ratio of sulfentrazone, clomazone, and S-metolachlor is 2 - 3:3:18 - 24.

[0011] As a preferred embodiment of the herbicide composition of the present invention, the mass ratio of sulfentrazone, clomazone, and S-metolachlor is 2:3:18.

[0012] As a preferred embodiment of the herbicide composition of the present invention, the agrochemically acceptable adjuvants include agrochemically acceptable surfactants, agrochemically acceptable carriers, aqueous wall materials, and oily wall materials.

[0013] As a preferred embodiment of the herbicide composition of the present invention, the aqueous wall material is an oil-soluble polyamine, including one of diethyltoluenediamine, 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline), dimethylthiotoluenediamine, and 4,4-methylenebis(2-ethyl)aniline;

[0014] The oily wall material includes 1,6-hexamethylene diisocyanate derivatives, toluene diisocyanate derivatives, and isophorone diisocyanate derivatives. Among them, the 1,6-hexamethylene diisocyanate derivative is selected from one of HDI biuret and HDI trimer.

[0015] Another object of the present invention is to provide a method for microencapsulating a herbicide composition.

[0016] To solve the above technical problems, the present invention provides the following technical solutions:

[0017] Mix S-metolachlor, clomazone, and the oily wall material to obtain an oil phase;

[0018] Mix the agrochemically acceptable adjuvants with water to obtain an aqueous phase;

[0019] Use a high-shear device to quickly emulsify and disperse the oil phase in the aqueous phase to prepare an aqueous emulsion;

[0020] Add the aqueous wall material to the aqueous emulsion and carry out a polymerization reaction for 10-20 minutes to obtain a clomazone-S-metolachlor suspending agent;

[0021] Use a grinding machine to prepare a sulfentrazone suspending agent;

[0022] Mix the sulfentrazone suspending agent and the clomazone-S-metolachlor suspending agent to obtain the microencapsulated herbicide composition.

[0023] As a preferred embodiment of the method for microencapsulating the herbicide composition of the present invention, the dosage form of the herbicide composition is a microcapsule suspension-suspending agent.

[0024] Another object of the present invention is to provide the application of a herbicide prepared by the microencapsulation preparation method in controlling broadleaf, sedge, and gramineous weeds in minor crops.

[0025] As a preferred embodiment of the application of the herbicide prepared by the microencapsulation preparation method of the present invention, wherein: the minor crops include watermelon, pea, and pepper.

[0026] As a preferred embodiment of the application of the herbicide prepared by the microencapsulation preparation method of the present invention, wherein: the application dose of the herbicide composition is 690-1380 g a.i. / ha, and the duration of the drug effect is > 60 days.

[0027] Advantages of the present invention:

[0028] 1. Ternary synergistic ratio. The present invention discloses for the first time the ternary combination and compounding of sulfentrazone, clomazone and S-metolachlor, which not only has excellent control effect on gramineous weeds, but also has excellent control effect on broad-leaved and cyperaceae weeds;

[0029] 2. Wide range of applicable crops, high safety for tested watermelon, pea, pepper, etc. Even at high doses, the growth is not inhibited;

[0030] 3. The compounding of sulfentrazone can reduce the dosage of clomazone, and improve the safety of subsequent crops;

[0031] 4. Adopt a new interfacial polymerization microencapsulation process, which reduces the risk of vapor drift of clomazone while reducing energy consumption and increasing production capacity;

[0032] 5. The duration of efficacy is up to 60 days, the control of weeds throughout the seedling stage is thorough, and the number of pesticide applications is reduced. Detailed implementation manners

[0033] In order to make the above objects, features and advantages of the present invention more obvious and understandable, the following detailed description of the specific implementation manners of the present invention is made in conjunction with the embodiments of the specification.

[0034] Many specific details are set forth in the following description in order to fully understand the present invention, but the present invention can also be implemented in other ways different from those described herein. Those skilled in the art can make similar promotions without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.

[0035] Secondly, the so-called "one embodiment" or "embodiment" herein refers to a specific feature, structure or characteristic that can be included in at least one implementation manner of the present invention. The "in one embodiment" that appears in different places in this specification does not all refer to the same embodiment, nor is it a separate or alternative embodiment that excludes other embodiments.

[0036] Example 1

[0037] The raw materials used in the present invention are all commercially available in the ordinary market without special instructions.

[0038] The herbicide compositions in different dosage forms prepared in the specific embodiments of the present invention are all prepared with reference to the conventional methods in the art.

[0039] The method for measuring the weed control efficiency of the herbicide composition of the present invention is as follows:

[0040] The greenhouse pot method was used in the experiment. Seeds of Echinochloa crusgalli, Commelina communis, Amaranthus retroflexus, and Cyperus rotundus were germinated and then evenly mixed and sown in small flower pots filled with 3 / 5 culture soil. 8×8 seeds were sown in each pot, and after sowing, the soil was covered with a layer of 1-2 mm thick soil. Water was added to the tray containing the small flower pots. After the water completely soaked the culture soil, the excess water in the tray was poured out;

[0041] 24 hours after sowing, the soil was sprayed (spraying the test agent) with an ASS0-5 walking spray tower, and water was used as a blank control. Then, it was transferred to the greenhouse for continued cultivation and observation. After 20 days, the fresh weight of the above-ground parts of the weeds in each treatment was investigated. Except for not watering for 1-2 days after spraying the medicine, water was regularly added to maintain the soil humidity.

[0042] The calculation method of weed survival rate:

[0043] E Weed survival rate % = Fresh weight of weeds in the treatment group / Fresh weight of weeds in the blank control group * 100%

[0044] The herbicidal activity of the mixture was tested by the Colby method, that is, E0 = ABC / 10000;

[0045] In the formula, A is the single-agent weed survival rate of herbicide 1 (metosulam), B is the single-agent weed survival rate of herbicide 2 (clomazone), C is the single-agent weed survival rate of herbicide 3 (s-metolachlor), and E0 is the theoretical survival rate of the mixed herbicides;

[0046] E is the measured survival rate of the mixed herbicides. According to the Colby method, when E0 - E ≥ 10%, it indicates that the mixed herbicides have a synergistic effect; when E0 - E ≤ -10%, it indicates that the mixed herbicides have an antagonistic effect; when the value of E0 - E is between ±10%, it indicates that the mixed herbicides have an additive effect.

[0047] Example 1

[0048] This example provides a preparation method of a microencapsulated herbicide composition in a microcapsule suspension-suspension dosage form. Specifically:

[0049] 1) Weigh the raw materials according to the following mass percentages:

[0050]

[0051] 2) Microencapsulation processing technology:

[0052] S-metolachlor, clomazone, and HDI biuret were mixed evenly to obtain the oil phase;

[0053] An ethylene oxide - propylene oxide block copolymer, propylene glycol, sodium lignosulfonate, triphenylvinylphenol polyoxyethylene ether phosphate, xanthan gum, sodium benzoate, an antifoaming agent, and water are mixed evenly to obtain an aqueous phase;

[0054] The oil phase is rapidly emulsified and dispersed in the aqueous phase by a high - shear device to prepare an aqueous emulsion;

[0055] Diethyltoluenediamine is added to the aqueous emulsion, so that HDI biuret and diethyltoluenediamine monomers undergo an interfacial polymerization reaction. After reacting for 10 minutes, an isoxaflutole with a mass concentration of about 6.53% + S - metolachlor 960 with a mass concentration of 39.2% can be prepared;

[0056] A 50% sulfentrazone suspension concentrate is prepared by a grinder. 8 parts of the 50% sulfentrazone suspension concentrate and 92 parts of the 6.53% isoxaflutole + 39.2% S - metolachlor 960 microcapsule suspension concentrate are mixed to obtain the 4% sulfentrazone + 6% isoxaflutole + 36% S - metolachlor 960 microcapsule suspension - suspension concentrate of this example.

[0057] Comparative Example 1

[0058] The difference between this comparative example and Example 1 is that the oil - phase wall material HDI biuret in the raw material formula is adjusted to diphenylmethane diisocyanate, and the water - phase wall material diethyltoluenediamine is adjusted to ethylenediamine. As a result, in the microencapsulation process of step 2), the interfacial polymerization reaction needs to continue for more than 2 hours. Therefore, the microencapsulation process of the present invention reduces the capsule - forming time and increases the production capacity.

[0059] Application test:

[0060] Watermelon field experiment

[0061] Test site: Wuxu, Nanning, Guangxi

[0062] Transplanting time: February 15, 2024

[0063] Pesticide application time: February 14, 2024

[0064] Test pesticides: Example 1 (self - made in the laboratory), Syngenta's Golden Medal (960 g / L S - metolachlor).

[0065] Treatment area: The test is set with 4 treatments and 1 blank control. Each treatment area is 300 square meters. The common gramineous weeds in the field are: Digitaria sanguinalis, Echinochloa crusgalli, Eleusine indica, Setaria viridis. The common broad - leaved weeds in the field are: Amaranthus retroflexus, Portulaca oleracea, Solanum nigrum, Kochia scoparia, Chenopodium album, Cirsium setosum, Celosia argentea, Abutilon theophrasti, Capsella bursa - pastoris, etc.

[0066] Investigation time: February 28, 2024, March 30, 2024

[0067] The results are shown in Table 1.

[0068] Table 1

[0069]

[0070]

[0071] From the field trial results in Table 1, it can be seen that 14 days after application, for the application concentration of 690 ga.i. / ha of Example 1 of the present invention (4% sulfentrazone + 6% clomazone + 36% S-metolachlor microcapsule suspension-suspension agent) in pepper fields, the control effects on gramineous weeds and broad-leaved weeds are 98.47 - 98.66% respectively. The control effect on gramineous weeds is comparable to that of S-metolachlor, and the control effect on broad-leaved weeds is better than that of S-metolachlor. When applying at a high dose of 1380 ga.i. / ha, Example 1 is safe for watermelon. When applying at a high dose of 2760 ga.i. / ha, the watermelon leaves show slight albino but can recover. 60 days after application, for the application concentration of 690 ga.i. / ha of Example 1 (4% sulfentrazone + 6% clomazone + 36% S-metolachlor microcapsule suspension-suspension agent) in watermelon fields, the control effects on gramineous weeds and broad-leaved weeds are 96.56 - 97.38% respectively. Compared with S-metolachlor, the control effect on gramineous weeds is better than that of S-metolachlor, and S-metolachlor has almost no control effect on broad-leaved weeds in watermelon fields. When applying at a high dose of 1380 - 2760 ga.i. / ha, Example 1 is still safe for watermelon.

[0072] Field trial of peas

[0073] Test site: Ye County, Pingdingshan, Henan

[0074] Sowing time: November 15, 2024

[0075] Application time: November 17, 2024

[0076] Test agents: Example 1 (self-made in the laboratory), S-metolachlor of Syngenta (960 g / L S-metolachlor).

[0077] Treatment area: The test was set with 4 treatments and 1 blank control. The area of each treatment was 300 square meters. The commonly occurring gramineous weeds in the field were: Lolium multiflorum, Avena fatua, Poa annua, and the commonly occurring broad-leaved weeds in the field were Capsella bursa-pastoris, Descurainia sophia, Veronica didyma, Galinsoga parviflora, Galium aparine, and Lithospermum arvense, etc.

[0078] Investigation time: December 17, 2024, January 16, 2025

[0079] The results are shown in Table 2.

[0080] Table 2

[0081]

[0082] As can be seen from the field test results in Table 2, 30 days after application, for the application concentration of 690 g a.i. / ha of Example 1 of the present invention (4% sulfentrazone + 6% clomazone + 36% S-metolachlor microcapsule suspension-suspension agent) in pea fields, the control effects on gramineous weeds and broad-leaved weeds were 93.43 - 99.66% respectively. The control effect on gramineous weeds was better than that of pendimethalin, and the control effect on broad-leaved weeds was much better than that of pendimethalin. When applying at high doses of 1380 - 2760 g a.i. / ha, Example 1 was still highly safe for peas. 60 days after application, for the application concentration of 690 g a.i. / ha of Example 1 (46% sulfentrazone·clomazone·S-metolachlor microcapsule suspension-suspension agent) in pea fields, the control effects on gramineous weeds and broad-leaved weeds were 91.56 - 96.17% respectively. Compared with pendimethalin, the control effect on gramineous weeds was better than that of pendimethalin, and pendimethalin was almost ineffective against overwintering broad-leaved weeds. When applying at double dose and quadruple dose, Example 1 was still highly safe for peas.

[0083] Field test on peppers

[0084] Test site: Yanling, Xuchang, Henan

[0085] Sowing time: April 29, 2024

[0086] Application time: April 30, 2024

[0087] Treatment area: The test was set with 13 treatments and one blank control. The area of each treatment was 300 square meters. The commonly occurring gramineous weeds in the field were: Digitaria sanguinalis, Echinochloa crusgalli, Eleusine indica, Setaria viridis. The commonly occurring broad-leaved weeds in the field were: Amaranthus retroflexus, Portulaca oleracea, Solanum nigrum, Cucumis melo var. agrestis, Acalypha australis, Commelina communis, Chenopodium album, Cirsium setosum, Celosia argentea, Abutilon theophrasti, etc.

[0088] Investigation time: May 30, 2024 and June 29, 2024

[0089] The results are shown in Table 3.

[0090] Table 3

[0091]

[0092] As can be seen from the field trial results in Table 2, the field trial results show that: 30 days after application, at the application concentration of 690 ga.i. / ha of Example 1 (46% sulfentrazone · clomazone · S-metolachlor microcapsule suspension-suspension agent), the control effects on gramineous weeds and broad-leaved weeds in pepper fields were 95.17 - 97.16% respectively. The control effect on gramineous weeds was equivalent to that of pendimethalin, and the control effect on broad-leaved weeds was better than that of pendimethalin. At high application doses of 1380 - 2760 ga.i. / ha, Example 1 was still highly safe for peppers. 60 days after application, at the application concentration of 690 ga.i. / ha of Example 1 (46% sulfentrazone · clomazone · S-metolachlor microcapsule suspension-suspension agent), the control effects on gramineous weeds and broad-leaved weeds in pepper fields were 93.45 - 96.11% respectively. Compared with pendimethalin, the control effect on gramineous weeds was better than that of pendimethalin, and pendimethalin had almost no effect on broad-leaved weeds. At double-dose and quadruple-dose applications, Example 1 was still highly safe for peppers.

[0093] Example 2

[0094] This example was used to explore the survival rate tests and joint action evaluations of ternary and binary compositions of sulfentrazone, clomazone, and S-metolachlor with different combinations and ratios on the survival rates of Echinochloa crusgalli, Commelina communis, Amaranthus retroflexus, and Cyperus rotundus. The concentrations of each component, application doses, and weed survival rate results in the compositions are shown in Tables 4 - 7 in sequence.

[0095] Table 4 Survival rate test and joint action evaluation of Echinochloa crusgalli

[0096]

[0097] As can be seen from Table 4, when the ternary composition was sulfentrazone:clomazone:S-metolachlor = 4 - 6:6:36, the composition showed a synergistic effect on Echinochloa crusgalli, and other ratios showed an additive effect on Echinochloa crusgalli.

[0098] When the binary composition was sulfentrazone:clomazone = 4:6 - 8, the composition showed a synergistic effect on Echinochloa crusgalli, but its control effect was far less than that of the ternary composition. And the binary composition of sulfentrazone:S-metolachlor showed an antagonistic effect on Echinochloa crusgalli.

[0099] Table 5 Survival rate test and joint action evaluation of Commelina communis

[0100]

[0101]

[0102] As can be seen from Table 5, the results show that when the ratio of sulfentrazone: clomazone: S-metolachlor is 4:6:36, the composition shows a synergistic effect on Commelina communis, and other ratios show an additive effect on Commelina communis. When the binary composition of sulfentrazone: clomazone is 4:6 - 8, the composition shows a synergistic effect on Echinochloa crusgalli; when the binary composition of sulfentrazone: S-metolachlor is 4:36 - 48, the composition shows an additive effect on Commelina communis.

[0103] Table 6 Survival Rate Test and Evaluation of Combined Action of Amaranthus retroflexus

[0104]

[0105]

[0106] As can be seen from Table 6, when the ternary composition of sulfentrazone: clomazone: S-metolachlor is 4:6:36 - 48, the composition shows a synergistic effect on Amaranthus retroflexus, and other ratios show an additive effect on Amaranthus retroflexus. When the binary composition of sulfentrazone: clomazone is 4:6 - 8, the composition shows a synergistic effect on Amaranthus retroflexus; when the binary composition of sulfentrazone: S-metolachlor is 4:36 - 48, the composition shows an additive effect on Amaranthus retroflexus.

[0107] Table 7 Survival Rate Test and Evaluation of Combined Action of Cyperus rotundus

[0108]

[0109]

[0110] As can be seen from Table 7, when the ternary composition of sulfentrazone: clomazone: S-metolachlor is 4 - 6:6 - 8:36 - 48, the composition shows a synergistic effect on Cyperus rotundus. When the binary composition of sulfentrazone: clomazone is 4:6 - 8, the composition shows a synergistic effect on Cyperus rotundus; when the binary composition of sulfentrazone: S-metolachlor is 4:36 - 48, the composition shows an additive effect on Amaranthus retroflexus.

[0111] In summary, the present invention discloses for the first time a herbicide obtained by ternary combination and compounding of sulfentrazone, clomazone and S-metolachlor. This herbicide composition has high safety for minor crops such as watermelon, pea, pepper, etc., and has excellent control effects on broad-leaved and Cyperaceae weeds. Even at high doses, the growth is not inhibited, the effective period is up to 60 days, the weeds in the whole seedling stage are thoroughly controlled, and the number of pesticide applications is reduced.

[0112] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered by the scope of the claims of the present invention.

Claims

1. A herbicide composition, characterized in that: Comprising, Based on the mass percentage of the herbicide composition, it contains 23% - 77.5% of herbicide active ingredients, and the balance is auxiliaries acceptable in pesticide science; wherein, the herbicide active ingredients are composed of sulfentrazone, clomazone and S-metolachlor.

2. The herbicide composition according to claim 1, characterized in that: The mass ratio of sulfentrazone, clomazone and S-metolachlor is 2 - 3:3 - 4:18 - 24.

3. The herbicide composition according to claim 2, characterized in that: The mass ratio of sulfentrazone, clomazone and S-metolachlor is 2 - 3:3:18 - 24.

4. The herbicide composition according to claim 3, wherein: The mass ratio of sulfentrazone, clomazone and S-metolachlor is 2:3:

18.

5. The herbicide composition according to claim 1, characterized in that: The auxiliaries acceptable in pesticide science include surfactants acceptable in pesticide science, carriers acceptable in pesticide science, water-phase wall materials, and oil-phase wall materials.

6. The herbicide composition according to claim 5, characterized in that: The water-phase wall material is an oil-soluble polyamine, including one of diethyltoluenediamine, 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline), dimethylthiotoluenediamine, 4,4-methylene bis(2-ethyl)aniline; The oil-phase wall materials include 1,6-hexamethylene diisocyanate derivatives, toluene diisocyanate derivatives, and isophorone diisocyanate derivatives, wherein the 1,6-hexamethylene diisocyanate derivative is selected from one of HDI biuret and HDI trimer.

7. The microencapsulation preparation method of the herbicide composition according to any one of claims 1 to 6, characterized in that: Comprising, Mix S-metolachlor, clomazone and the oil-phase wall material to obtain an oil phase; Mix the auxiliaries acceptable in pesticide science with water to obtain a water phase; Use a high-shear device to rapidly emulsify and disperse the oil phase in the water phase to prepare a water emulsion; Add the water-phase wall material to the water emulsion and carry out a polymerization reaction for 10 - 20 min to obtain a clomazone-S-metolachlor suspending agent; Use a grinding machine to prepare a sulfentrazone suspending agent; Mix the sulfentrazone suspending agent and the clomazone-S-metolachlor suspending agent to obtain a microencapsulated herbicide composition.

8. The herbicide composition prepared by the microencapsulation preparation method according to claim 7, characterized in that: The dosage form of the herbicide composition is a microcapsule suspension-suspending agent.

9. Use of the herbicide composition according to claim 8 in controlling broadleaf, sedge and grass weeds in minor crops, characterized in that: The minor crops include watermelon, pea, and pepper.

10. The application according to claim 9, wherein: The application dosage of the herbicide composition is 690 - 1380 g a.i. / ha, and the duration of drug efficacy is >60 days.

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