Compositions, methods of making, uses, oil suspensions, and methods of nanolipid carriers

Abstract

The application belongs to the technical field of pesticide preparation, and provides a composition, a preparation method and use of a nano-lipid carrier, an oil suspension and a method.The nano-lipid carrier composition comprises an oily herbicide and an aqueous coating agent; the weight ratio of the oily herbicide to the aqueous coating agent is 1:(3-10); the oily herbicide comprises the following components in parts by weight: 1-40 parts of an oily herbicidal compound and 4-85 parts of an oily solvent; and the aqueous coating agent comprises the following components in parts by weight: 0.1-10 parts of a water-soluble coating compound and 99.9-90 parts of an aqueous solvent.The nano-lipid carrier composition can improve the stability of the oil suspension, thereby reducing the loss of the active ingredients of the pesticide, and improving the drug utilization rate and the efficacy of the pesticide.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of pesticide formulations, and more particularly relates to a composition, a preparation method and use of a nano-lipid carrier, an oil miscible flowable concentrate and a method. BACKGROUND

[0002] An oil miscible flowable concentrate (OF) is a highly efficient plant protection product that can effectively prevent and control various crop diseases and pests.

[0003] Oil miscible flowable concentrates can be divided into oil-based suspension concentrates (OD) for use in water and OFs for use in oil-based media. An oil-based suspension concentrate (OD) is a dosage form in which a type of oil that can be used as a synergistic adjuvant and does not contaminate crops is used as a dilution carrier. When used, the oil-based suspension concentrate needs to be diluted with water and then sprayed. An OF is a liquid preparation in which an effective component is stably suspended or partially dissolved in a water-insoluble liquid, and is used after being diluted and prepared with an organic solvent or oil.

[0004] Oil miscible flowable concentrates are commonly used in pesticide formulations. The physical stability of oil miscible flowable concentrates in related technologies of pesticide formulations is poor, which leads to easy loss of the effective components of pesticides, and thus low drug utilization rate and poor efficacy of pesticides. SUMMARY

[0005] The purpose of the embodiments of the application is to provide a composition, a preparation method and use of a nano-lipid carrier, an oil miscible flowable concentrate and a method, so as to improve the stability of the oil miscible flowable concentrate, reduce the easy loss of the effective components of pesticides, and improve the drug utilization rate and efficacy of pesticides.

[0006] To achieve the above purpose, the first aspect of the embodiments of the application provides a nano-lipid carrier composition, which comprises an oil-based herbicide and an aqueous coating agent, and the weight ratio of the oil-based herbicide to the aqueous coating agent is 1:(3-10). The oil-based herbicide comprises the following components in parts by weight: 1-40 parts of an oil-based herbicidal compound and 4-85 parts of an oil-based solvent. The aqueous coating agent comprises the following components in parts by weight: 0.1-10 parts of a water-soluble coating compound and 99.9-90 parts of an aqueous solvent.

[0007] Further, the oily herbicide compound includes one or more of fluroxypyr and halosafen; and / or, the oily solvent includes one or more of unsaturated glyceride and plant essential oil; and / or, the water-soluble coating compound includes one or more of polyvinyl alcohol, hydroxypropyl methyl cellulose and gelatin; and / or, the aqueous solvent includes one or more of water, ethanol, propanol or diethyl ether; and / or, the plant essential oil includes one or more of peppermint essential oil, citronella oil, cinnamon oil, rose essential oil, wintergreen essential oil, tea tree essential oil, rosemary oil, lemon oil and lavender oil.

[0008] Further, the oily solvent includes components in the following weight proportions: glycerol trioleate 1-20 parts and plant essential oil 3 parts-65 parts; the water-soluble coating agent includes components in the following weight proportions: polyvinyl alcohol 0.1-10 parts and water 99.9-90 parts.

[0009] In a second aspect, the embodiments of the present application provide a preparation method of the nano-lipid carrier, which includes:

[0010] The oily herbicide compound and the oily solvent in the nano-lipid carrier composition are mixed to prepare an oily herbicide;

[0011] The water-soluble coating compound and the aqueous solvent are mixed to prepare a water-soluble coating agent;

[0012] The oily herbicide and the water-soluble coating agent are mixed to prepare the nano-lipid carrier.

[0013] Further, the oily herbicide and the water-soluble coating agent are mixed to prepare the nano-lipid carrier; which includes:

[0014] The oily herbicide and the water-soluble coating agent are mixed, and then the mixture is emulsified by stirring, oscillation or high shear at-5℃-2℃, and then the nano-lipid carrier is prepared by ultrasonic micro-atomization, stirring and drying.

[0015] In a third aspect, the embodiments of the present application provide a use of the nano-lipid carrier for preparing a pesticide preparation.

[0016] In a fourth aspect, the embodiments of the present application provide an oil suspension agent, which includes: a first herbicide and a nano-lipid carrier.

[0017] Further, the first herbicide includes one or more of glufosinate-ammonium and haloxyfop-methyl; and / or, the oil suspension agent further includes components in the following weight proportions: a surfactant 1 part-10 parts, an auxiliary agent 1 part-5 parts and an oily carrier 1 part-80 parts.

[0018] Further, the oil suspension agent further includes components in the following weight proportions: a surfactant 1 part-10 parts, an auxiliary agent 1 part-5 parts and an oily carrier 1 part-80 parts.

[0019] Further, the surfactant includes one or more of fatty alcohol polyoxyethylene ether, triphenyl phenol polyoxyethylene ether, styryl phenol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, alkyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, lignin sulfonate and naphthalene sulfonate formaldehyde condensate; and / or, the adjuvant includes one or more of organic bentonite, attapulgite and white carbon black; and / or, the oily carrier includes one or more of methyl oleate, white mineral oil, soybean oil, cottonseed oil, corn oil and rapeseed oil.

[0020] In a fifth aspect, the embodiments of the present application provide a preparation method of the oil suspension, which comprises: mixing components for preparing the oil suspension, and obtaining the oil suspension after grinding.

[0021] The nanolipid carrier composition provided by the first aspect of the embodiments of the present application adopts the oily herbicide and the aqueous coating agent, the oily herbicide can be wrapped into oily herbicide nanoparticles with aqueous coating by the aqueous coating agent, so that the oily herbicide has good stability, the aqueous coating can make the oily herbicide nanoparticles with aqueous coating have better solubility with the aqueous solvent, and it is easier to prepare various pesticide formulations for use, thereby improving the stability of the pesticide formulation, and further reducing the loss of the active ingredients of the pesticide, improving the drug utilization rate and the drug efficacy of the pesticide.

[0022] The preparation method of the nanolipid carrier provided by the second aspect of the embodiments of the present application adopts the nanolipid carrier prepared by low-temperature mixing, emulsification and ultrasonic microization, which can load the herbicide in the core of the nanoparticle, thereby improving the physicochemical stability of the herbicide, further increasing the stability of the embedded components in the drug delivery process, and further improving the drug utilization rate; the nanoparticle can produce encapsulation and film-forming effect on the surface of the weed, so as to reduce the loss of water on the surface of the weed, thereby increasing the hydration and wetting effect on the surface of the weed, and improving the drug utilization rate.

[0023] The nanolipid carrier provided by the third aspect of the embodiments of the present application is used for preparing the pesticide formulation, the nanolipid carrier can be used for preparing the pesticide formulation, which can prolong the drug efficacy period of the pesticide formulation, make the pesticide have better affinity to the plant leaves and weed tissues, be more beneficial to the targeted transportation, and improve the absorption rate; in addition, the pesticide is slowly metabolized and degraded under the surface layer of the leaf due to the action of the nanolipid carrier, the storage stability is greatly improved, and the drug efficacy period is prolonged.

[0024] The oil suspension provided in the fourth aspect of the embodiments of the present application uses the nano-lipid carrier to prepare the oil suspension. Compared with the conventional oil suspension or the nano oil suspension prepared by high-intensity sand milling process, the particle size of the drug particles in the oil suspension of the embodiments of the present application is greatly reduced. The phosphoramidon or haloxyfop-ruin is in good synergistic effect with the nano-lipid carrier in the oil suspension. The oil suspension of the nano-lipid carrier and the phosphoramidon and other compounded compositions can not only improve the physical and chemical stability, but also increase the stability of the embedded components in the drug delivery process, thereby improving the drug utilization. The nanoparticles can produce encapsulation and film-forming effect on the surface of weeds, so as to reduce the water loss of the surface of weeds, thereby increasing the hydration and wetting effect of the surface of weeds and improving the drug utilization. Therefore, compared with the prior art, the oil suspension has better efficacy.

[0025] The preparation method of the oil suspension provided in the fifth aspect of the embodiments of the present application is simple and easy to operate. The mixing and grinding can further make the components in the oil suspension uniformly dispersed in a better particle state, so that the prepared oil suspension has better efficacy. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiments or the prior art description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0027] Figure 1 The preparation method flowchart of the nano-lipid carrier of the embodiments of the present application is shown in the figure. DETAILED DESCRIPTION

[0028] In order to make the technical problems, technical solutions and beneficial effects of the present application more clear, the present application will be further described in detail in combination with the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and not to limit the present application.

[0029] In order to improve the stability of the oil suspension, thereby reducing the easy loss of the effective components of the pesticide, improving the drug utilization rate and efficacy of the pesticide, and improving the stability of the oil suspension, thereby reducing the easy loss of the effective components of the pesticide, improving the drug utilization rate and efficacy of the pesticide.

[0030] To achieve the above object, the first aspect of the present application provides a kind of nanometer lipid carrier composition, including oily herbicide and aqueous coating agent;The weight ratio of oily herbicide and aqueous coating agent is 1:(3-10);Oily herbicide includes the following weight fraction components: 1-40 parts of oily herbicide compound and 4-85 parts of oily solvent;Aqueous coating agent includes the following weight fraction components: 0.1-10 parts of water-soluble coating compound and 99.9-90 parts of aqueous solvent.

[0031] In the embodiments of the present application, the weight ratio of oily herbicide and aqueous coating agent is 1:(3-10). For example, the weight ratio of oily herbicide and aqueous coating agent can be 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, etc. Herein, only examples are given without limitation. If the amount of aqueous coating agent is too small, the oily herbicide cannot be effectively dispersed, i.e., the oily herbicide nanoparticles cannot be fully attached to the aqueous coating, so that the stability of the oily herbicide is poor. If the amount of aqueous coating agent is too large, the aqueous coating on the outer layer of the oily herbicide is too thick, which is not conducive to the release of the oily herbicide and makes the concentration of the oily herbicide too low, affecting the herbicidal effect.

[0032] In the embodiments of the present application, the oily herbicide includes the following weight fraction components: 1-40 parts of oily herbicide compound and 4-85 parts of oily solvent. In some embodiments, the oily herbicide compound includes one or more of fluroxypyr-meptyl and metazachlor. Optionally, the oily herbicide compound can be 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts, etc. The oily solvent can include one or more of unsaturated glyceride and plant essential oil. Optionally, the oily solvent can be 4 parts, 10 parts, 15 parts, 24 parts, 34 parts, 44 parts, 54 parts, 68 parts, 72 parts, 80 parts or 85 parts, etc. Herein, only examples are given without limitation.

[0033] In the embodiments of the present application, the aqueous coating agent can include the following weight fraction components: 0.1-10 parts of water-soluble coating compound and 99.9-90 parts of aqueous solvent. In some embodiments, the water-soluble coating compound can be one or more of polyvinyl alcohol, hydroxypropyl methyl cellulose and gelatin. Optionally, the water-soluble coating compound can be 0.1 part, 0.5 part, 1 part, 2 part, 3 part, 4 part, 6 part, 8 part, 9 part or 10 part, etc. In some embodiments, the aqueous solvent can be water, ethanol, propanol or diethyl ether, etc. Optionally, the aqueous solvent is water. The aqueous solvent can be 90 parts, 91 parts, 93 parts, 95 parts, 97 parts, 99 parts, 99.5 parts or 99.9 parts, etc. Herein, only examples are given without limitation.

[0034] In the embodiments of the present application, the oily solvent can include the following components in the weight percentage: 1-20 parts of glycerol trioleate and 3-65 parts of plant essential oil; and the aqueous coating agent can include the following components in the weight percentage: 0.1-10 parts of polyvinyl alcohol and 99.9-90 parts of water.

[0035] In some embodiments, the glycerol trioleate can be 1 part, 3 parts, 5 parts, 7 parts, 9 parts, 12 parts, 13 parts, 15 parts, 17 parts, 18 parts or 20 parts, etc., and in some embodiments, the plant essential oil can be one or several of the following: peppermint essential oil, citronella oil, cinnamon oil, rose essential oil, wintergreen essential oil, tea tree essential oil, rosemary oil, lemon oil and lavender oil. Alternatively, the plant essential oil can be 3 parts, 6 parts, 9 parts, 12 parts, 15 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 62 parts or 65 parts, etc. Herein, only examples are given and no limitation is intended. The polyvinyl alcohol can be 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, 5 parts, 7 parts, 8 parts, 9 parts or 10 parts, etc., and the water can be 90 parts, 91 parts, 93 parts, 95 parts, 97 parts, 98 parts, 99 parts, 99.5 parts or 99.9 parts, etc. Herein, only examples are given and no limitation is intended.

[0036] In a second aspect, the embodiments of the present application provide a preparation method of the nano-lipid carrier, referring to Figure 1 as shown, comprising:

[0037] S101. Mixing the oily herbicidal compound and the oily solvent in the nano-lipid carrier composition to prepare an oily herbicide;

[0038] S102. Mixing the water-soluble coating compound and the aqueous solvent to prepare an aqueous coating agent;

[0039] S103. Mixing the oily herbicide and the aqueous coating agent to prepare the nano-lipid carrier.

[0040] Further, mixing the oily herbicide and the aqueous coating agent to prepare the nano-lipid carrier; comprising:

[0041] After mixing the oily herbicide and the aqueous coating agent, the mixture is emulsified by stirring, oscillation or high shear at -5℃-2℃, and then micro-sized by ultrasonic wave, stirred and dried to prepare the nano-lipid carrier. Alternatively, the mixture can be emulsified by stirring, oscillation or high shear at -5℃, -4℃, -3℃, -2℃, 1℃ or 2℃, and then micro-sized by ultrasonic wave, stirred and dried to prepare the nano-lipid carrier. Herein, only examples are given and no limitation is intended.

[0042] In a third aspect, the embodiments of the present application provide a use of the nano-lipid carrier for preparing a pesticide preparation.

[0043] The functions and effects of the technical features similar or related to the foregoing technical solutions in the technical solution are similar to those of the foregoing technical solutions, the inventive concept and beneficial effects of the technical solution are similar to those of the foregoing technical solutions, and details are not repeated.

[0044] In a fourth aspect, the embodiments of the present application provide an oil suspension agent, comprising a first herbicide and a nano-lipid carrier.

[0045] Further, the first herbicide comprises one or more of glufosinate-ammonium and haloxyfop-methyl.

[0046] Further, the oil suspension agent further comprises the following components in the following proportions by weight: 1-10 parts of a surfactant, 1-5 parts of an auxiliary agent, and 1-80 parts of an oily carrier.

[0047] In the embodiments of the present application, the surfactant can be one or more of fatty alcohol polyoxyethylene ether, triphenyl phenol polyoxyethylene ether, styryl phenol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, alkyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, lignin sulfonate, and naphthalene sulfonate formaldehyde condensate. In some embodiments, the surfactant is 1 part, 3 parts, 5 parts, 6 parts, 7 parts, 9 parts, or 10 parts, etc. Here, only examples are given without limitation. The surfactant can enhance the compatibility of the nano-liposome with each component, ensuring that the oil suspension agent has good dispersibility and stability.

[0048] The auxiliary agent can be one or more of organic bentonite, attapulgite, and white carbon black. In some embodiments, the auxiliary agent can be 1 part, 2 parts, 3 parts, 4 parts, or 5 parts, etc. Here, only examples are given without limitation. The auxiliary agent can enhance the adhesion performance of the suspension agent and slow down the loss of the nano-lipid carrier and other active ingredients.

[0049] The oily carrier can be one or more of methyl oleate, white mineral oil, soybean oil, cottonseed oil, corn oil, and rapeseed oil. In some embodiments, the oily carrier can be 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 40 parts, 50 parts, 60 parts, 64 parts, 70 parts, 75 parts, or 80 parts, etc. Here, only examples are given without limitation. The oily carrier can provide an oily protective atmosphere for each oily component in the suspension agent, slowing down the loss of each active ingredient in the oil suspension agent.

[0050] In a fifth aspect, the embodiments of the present application provide a preparation method of an oil suspension agent, comprising: mixing each component for preparing the oil suspension agent, and grinding to obtain the oil suspension agent.

[0051] The functions and effects of the technical features similar or related to the foregoing technical solutions in the technical solution are similar to those of the foregoing technical solutions, the inventive concept and beneficial effects of the technical solution are similar to those of the foregoing technical solutions, and details are not repeated.

[0052] The following will be described in combination with the content of specific embodiments.

[0053] Example 1 Preparation of nanostructured lipid carriers

[0054] Example A Preparation of nanostructured lipid carriers containing 25% of cloquintocet-mexyl

[0055]

[0056] The 257.7 grams of 97% cloquintocet-mexyl technical material, 60 grams of glyceryl oleate and 525 grams of peppermint oil were dissolved in 100 grams of chloroform, and then mixed with 2200 grams of 7.5% polyvinyl alcohol aqueous solution, and the mixture was uniformly mixed into an emulsion state by stirring or oscillation or high shear, and then micro-processed by ultrasonic wave, and then stirred for 2 hours, and finally freeze-dried to obtain nanostructured lipid carriers containing 25% of cloquintocet-mexyl.

[0057] Example B Preparation of nanostructured lipid carriers containing 40% of cloquintocet-mexyl

[0058]

[0059] The 412.3 grams of 97% cloquintocet-mexyl technical material, 60 grams of glyceryl oleate and 375 grams of tea tree oil were dissolved in 100 grams of chloroform, and then mixed with 2200 grams of 7.5% polyvinyl alcohol aqueous solution, and the mixture was uniformly mixed into an emulsion state by stirring or oscillation or high shear, and then micro-processed by ultrasonic wave, and then stirred for 2 hours, and finally freeze-dried to obtain nanostructured lipid carriers containing 40% of cloquintocet-mexyl.

[0060] Example C Preparation of nanostructured lipid carriers containing 10% of metazachlor

[0061]

[0062] The 103.1 grams of 97% metazachlor technical material, 110 grams of glyceryl oleate and 630 grams of citronella oil were dissolved in 200 grams of chloroform, and then mixed with 2000 grams of 8% polyvinyl alcohol aqueous solution, and the mixture was uniformly mixed into an emulsion state by stirring or oscillation or high shear, and then micro-processed by ultrasonic wave, and then stirred for 3.5 hours, and finally freeze-dried to obtain nanostructured lipid carriers containing 10% of metazachlor.

[0063] Example D contains nanostructured lipid carriers with a content of 20% of saflufenacil

[0064]

[0065] 206.2 grams of saflufenacil TC with a mass fraction of 97%, 110 grams of glyceryl oleate and 530 grams of wintergreen oil were dissolved in 200 grams of chloroform, and then mixed with 2000 grams of 8% polyvinyl alcohol aqueous solution, and the mixture was mixed uniformly to an emulsified state by stirring or shaking or high shear, and then micro-atomized by ultrasonic wave, and then freeze-dried after stirring for 3.5 hours to obtain nanostructured lipid carriers with a content of 20% of saflufenacil.

[0066] The active ingredients of the pesticides used in the following examples are all calculated at 100% purity. In actual operation, according to the actual purity of the TC used, the difference is adjusted with fillers or water.

[0067] Example 2

[0068] Example 2a

[0069] The preparation method of 37% glufosinate-ammonium · haloxyfop-R-methyl · fluroxypyr-meptyl nanometer oil suspension includes: uniformly mixing the mixture, sand milling for 2.5 hours to obtain the product; the mixture is composed of the following components with a weight fraction:

[0070]

[0071] Among them, the 37% glufosinate-ammonium · haloxyfop-R-methyl · fluroxypyr-meptyl nanometer oil suspension contains 10% fluroxypyr-meptyl by weight based on 100% purity.

[0072] Example 2b

[0073] The preparation method of 37% glufosinate-ammonium · haloxyfop-R-methyl · fluroxypyr-meptyl nanometer oil suspension includes: uniformly mixing the mixture, sand milling for 2.5 hours to obtain the product; the mixture is composed of the following components with a weight fraction:

[0074]

[0075] Example 2c

[0076] The preparation method of 37% glufosinate-ammonium · haloxyfop-R-methyl · fluroxypyr-meptyl nanometer oil suspension includes: uniformly mixing the mixture, sand milling for 2.5 hours to obtain the product; the mixture is composed of the following components with a weight fraction:

[0077]

[0078]

[0079] Stability test

[0080] Cold and hot storage stability test

[0081] The products of Examples 2a-2c were subjected to cold and hot storage experiments respectively to compare the stability.

[0082] The experimental samples were packaged in 6 ampoules, 2 of which were packaged samples were subjected to hot storage in a constant temperature oven at 54°C, 2 were subjected to cold storage in a refrigerator at 0°C, and 2 were placed at room temperature. The decomposition rates of the cold and hot storage samples were measured after 14 days. The experimental results are shown in Table 1.

[0083] Table 1

[0084]

[0085] Note: Cold and hot storage decomposition rate = (content of the component to be tested in the cold storage sample - content of the component to be tested in the hot storage sample) / content of the component to be tested in the cold storage sample x 100%; the cold storage sample was stored at 0°C for 14 days, and the hot storage sample was stored at 54°C for 14 days before detection.

[0086] As can be seen from Table 1, the components of the product in Example 2a are sufficiently stable after cold and hot storage experiments, and are qualified, while the products in Examples 2b and 2c are unqualified.

[0087] Example 3

[0088] Example 3a

[0089] The preparation method of 27% glufosinate-ammonium · fluroxypyr-meptyl ester nano oil suspension includes uniformly mixing the mixture, sanding for 2.5 hours to obtain the product; the mixture is composed of the following components:

[0090]

[0091] Among them, the 28% glufosinate-ammonium · fluroxypyr-meptyl ester nano oil suspension contains 7% fluroxypyr-meptyl ester by weight based on 100% purity.

[0092] Example 3b

[0093] The preparation method of 27% glufosinate-ammonium · fluroxypyr-meptyl ester nano oil suspension includes uniformly mixing the mixture, sanding for 2.5 hours to obtain the product; the mixture is composed of the following components:

[0094]

[0095] Example 3c

[0096] 27% glufosinate-ammonium · fluroxypyr-meptyl ester nano oil suspension preparation method, comprising uniformly mixing the mixture, high-strength sanding for 4.5 hours to obtain the product; the mixture consists of the following components:

[0097]

[0098] Stability test

[0099] Cold and hot storage stability test

[0100] The products of Examples 3a-3c were simultaneously subjected to cold and hot storage experiments respectively to compare the stability.

[0101] The experimental samples were packaged with 6 ampoules, 2 of which were packaged samples stored in a constant temperature oven at 54°C for hot storage, 2 were stored in a refrigerator at 0°C for cold storage, and 2 were placed at room temperature. The decomposition rates of the cold and hot storage samples were measured after 14 days. The experimental results are shown in Table 2.

[0102] Table 2

[0103]

[0104] Note: The cold and hot storage decomposition rate = (the content of the component to be tested in the cold storage sample - the content of the component to be tested in the hot storage sample) / the content of the component to be tested in the cold storage sample * 100%; the cold storage sample was stored at 0°C for 14 days, and the hot storage sample was detected after being stored at 54°C for 14 days.

[0105] As can be seen from Table 2, the components of the product in Example 3a are sufficiently stable after cold and hot storage experiments, and are qualified, while the fluroxypyr-meptyl ester in the products of Examples 3b and 3c is unqualified.

[0106] Example 4

[0107] Example 4a

[0108] 40% glufosinate-ammonium · fluroxypyr-meptyl ester nano oil suspension preparation method, comprising uniformly mixing the mixture, sanding for 2.5 hours to obtain the product, and the mixture consists of the following components:

[0109]

[0110]

[0111] Among them, the 40% glufosinate-ammonium · fluroxypyr-meptyl ester nano oil suspension contains 10% fluroxypyr-meptyl ester by weight based on 100% purity.

[0112] Example 4b

[0113] The preparation method of 40% glufosinate-ammonium · fluroxypyr-meptyl ester nano oil suspension agent comprises uniformly mixing a mixture, and sanding for 2.5 hours to obtain the product, and the mixture comprises the following components:

[0114]

[0115] Example 4c

[0116] The preparation method of 40% glufosinate-ammonium · fluroxypyr-meptyl ester nano oil suspension agent comprises uniformly mixing a mixture, and sanding for 2.5 hours to obtain the product, and the mixture comprises the following components:

[0117]

[0118] Stability test of the above examples

[0119] Cold and hot storage stability test

[0120] The products of examples 4a-4c are respectively simultaneously subjected to cold and hot storage experiments to compare the stability.

[0121] The experimental sample is packaged with 6 ampoule bottles, 2 packaged samples are taken to be stored in a constant temperature oven at 54°C for hot storage, 2 are taken to be stored in a refrigerator at 0°C for cold storage, and 2 are taken to be placed at room temperature. After 14 days, the decomposition rates of the cold storage samples and the hot storage samples are determined. The experimental results are as shown in Table 3.

[0122] Table 3

[0123]

[0124] Note: The cold and hot storage comparison decomposition rate = (the content of the detected component in the cold storage sample - the content of the detected component in the hot storage sample) / the content of the detected component in the cold storage sample * 100%; the cold storage sample is stored at 0°C for 14 days, and the hot storage sample is detected after being stored at 54°C for 14 days.

[0125] As shown in Table 3, the components of the product in example 4a are all stable enough after the cold and hot storage experiments, and are all qualified, while the fluroxypyr-meptyl ester of the products in examples 4b and 4c are both unqualified.

[0126] Example 5

[0127] Example 5a

[0128] The preparation method of 40% glufosinate-ammonium · fluroxypyr-meptyl ester nano oil suspension agent comprises uniformly mixing a mixture, and sanding for 2.5 hours to obtain the product, and the mixture comprises the following components:

[0129]

[0130] In the 50% glufosinate-ammonium · fluroxypyr-meptyl ester nano oil suspension, the fluroxypyr-meptyl ester accounts for 10% by weight based on 100% purity.

[0131] Example 5b

[0132] The preparation method of the 50% glufosinate-ammonium · fluroxypyr-meptyl ester nano oil suspension comprises uniformly mixing the above mixture and sand grinding for 2.5 hours to obtain the product. The mixture consists of the following components:

[0133]

[0134] Example 5c

[0135] The preparation method of the 50% glufosinate-ammonium · fluroxypyr-meptyl ester nano oil suspension comprises uniformly mixing the above mixture and high-intensity sand grinding for 4.5 hours to obtain the product. The mixture consists of the following components:

[0136]

[0137] Stability test of the above examples

[0138] Cold and hot storage stability test

[0139] The products of Examples 5a-5c are subjected to cold and hot storage experiments respectively to compare the stability.

[0140] The experimental samples are packaged in 6 ampoules, 2 of which are packaged for hot storage in a constant temperature oven at 54°C, 2 are packaged for cold storage in a refrigerator at 0°C, and 2 are packaged for storage at room temperature. The decomposition rates of the cold and hot storage samples are measured after 14 days. The experimental results are shown in Table 4.

[0141] Table 4

[0142]

[0143]

[0144] Note: The cold and hot storage comparison decomposition rate = (the content of the component to be tested in the cold storage sample - the content of the component to be tested in the hot storage sample) / the content of the component to be tested in the cold storage sample * 100%; the cold storage sample is stored at 0°C for 14 days, and the hot storage sample is stored at 54°C for 14 days before detection.

[0145] As shown in Table 4, the components of the product in Example 5a are all stable enough after the cold and hot storage experiments and are all qualified; however, the fluroxypyr-meptyl ester in the products of Examples 5b and 5c is unqualified.

[0146] Example 6

[0147] Example 6a

[0148] 33% glufosinate-ammonium · pyribenzoxam nano oil suspension method comprising: uniformly mixing the mixture, sanding for 2.5 hours to obtain the product, the mixture consisting of:

[0149]

[0150] In the 33% glufosinate-ammonium · pyribenzoxam nano oil suspension, the weight percentage of pyribenzoxam with a purity of 100% is 3%.

[0151] Example 6b

[0152] 33% glufosinate-ammonium · pyribenzoxam nano oil suspension method comprising: uniformly mixing the mixture, sanding for 2.5 hours to obtain the product, the mixture consisting of:

[0153]

[0154] Example 6c

[0155] 33% glufosinate-ammonium · pyribenzoxam nano oil suspension method comprising: uniformly mixing the mixture, high-intensity sanding for 4.5 hours to obtain the product, the mixture consisting of:

[0156]

[0157] Stability test of the above examples

[0158] Cold and hot storage stability test

[0159] The products of Examples 6a-6c were simultaneously subjected to cold and hot storage experiments to compare the stability.

[0160] The experimental samples were packaged with 6 ampoules, 2 of which were packaged samples were subjected to hot storage in a constant temperature oven at 54°C, 2 were subjected to cold storage in a refrigerator at 0°C, and 2 were placed at room temperature. The decomposition rates of the cold and hot storage samples were measured after 14 days. The experimental results are shown in Table 5.

[0161] Table 5

[0162]

[0163] Note: The cold and hot storage decomposition rate = (the content of the component to be tested in the cold storage sample - the content of the component to be tested in the hot storage sample) / the content of the component to be tested in the cold storage sample * 100%; the cold storage sample was stored at 0°C for 14 days, and the hot storage sample was detected after being stored at 54°C for 14 days.

[0164] From Table 5, it can be seen that each component of the product in Example 6a is stable enough after the cold and hot storage test, and is qualified; while the bensulfuron-methyl in the products of Example 6b and Example 6c is not qualified.

[0165] Example 7

[0166] Example 7a

[0167] The preparation method of 27% glufosinate-ammonium·bensulfuron-methyl nano oil suspension includes: uniformly mixing a mixture, and sand grinding for 2.5 hours to obtain the product, and the mixture is composed of the following components:

[0168]

[0169] The 27% glufosinate-ammonium·bensulfuron-methyl nano oil suspension contains 2% bensulfuron-methyl by weight based on a purity of 100%.

[0170] Example 7b

[0171] The preparation method of 27% glufosinate-ammonium·bensulfuron-methyl nano oil suspension includes: uniformly mixing a mixture, and sand grinding for 2.5 hours to obtain the product, and the mixture is composed of the following components:

[0172]

[0173] Example 7c

[0174] The preparation method of 27% glufosinate-ammonium·bensulfuron-methyl nano oil suspension includes: uniformly mixing a mixture, and sand grinding for 2.5 hours to obtain the product, and the mixture is composed of the following components:

[0175]

[0176]

[0177] Stability test of the above examples

[0178] Cold and hot storage stability test

[0179] The products of Examples 7a-7c are subjected to cold and hot storage test at the same time to compare the stability.

[0180] The experimental sample is packaged with 6 ampoule bottles, 2 packaged samples are taken for hot storage in a constant temperature oven at 54°C, 2 are taken for cold storage in a refrigerator at 0°C, and 2 are placed at room temperature. The decomposition rate of the cold storage sample and the hot storage sample is measured after 14 days. The experimental results are as follows in Table 6.

[0181] Table 6

[0182]

[0183] Note: Cold-heat storage contrast decomposition rate = (content of the component to be detected in the cold storage sample - content of the component to be detected in the heat storage sample) / content of the component to be detected in the cold storage sample * 100%; the cold storage sample is stored at 0°C for 14 days, and the heat storage sample is stored at 54°C for 14 days before detection.

[0184] As can be seen from Table 6, the components of the product in Example 7a are all stable enough after the cold-heat storage experiment, and are all qualified; while the products in Example 7b and Example 7c are both unqualified.

[0185] Example 8

[0186] Example 8a

[0187] The preparation method of 43% glufosinate-ammonium · bensulfuron-methyl nano oil suspension agent comprises: uniformly mixing a mixture, and sand grinding for 2.5 hours to obtain the product, and the mixture is composed of the following components:

[0188]

[0189]

[0190] In the 43% glufosinate-ammonium · bensulfuron-methyl nano oil suspension agent, the weight percentage of bensulfuron-methyl is 3% according to the purity of 100%.

[0191] Example 8b

[0192] Example 8a

[0193] The preparation method of 43% glufosinate-ammonium · bensulfuron-methyl nano oil suspension agent comprises: uniformly mixing a mixture, and sand grinding for 2.5 hours to obtain the product, and the mixture is composed of the following components:

[0194]

[0195] Example 8c

[0196] The preparation method of 43% glufosinate-ammonium · bensulfuron-methyl nano oil suspension agent comprises: uniformly mixing a mixture, and sand grinding for 2.5 hours to obtain the product, and the mixture is composed of the following components:

[0197]

[0198] Stability test of the above examples

[0199] Cold-heat storage stability test

[0200] Cold-heat storage experiments are carried out on Examples 8a-8c respectively to compare the stability.

[0201] The experimental sample was packaged with 6 ampoules, 2 of which were packaged and stored in a 54°C constant temperature oven, 2 of which were stored in a 0°C refrigerator, and 2 of which were placed at room temperature. The decomposition rates of the cold storage samples and the heat storage samples were determined after 14 days. The experimental results are as follows in Table 7.

[0202] Table 7

[0203]

[0204] Note: The cold and hot storage comparison decomposition rate = (the content of the component to be detected in the cold storage sample - the component to be detected in the heat storage sample) / the content of the component to be detected in the cold storage sample * 100%; The cold storage sample was stored at 0°C for 14 days, and the heat storage sample was detected after being stored at 54°C for 14 days.

[0205] As can be seen from Table 7, the components of the product in Example 8a are all stable and qualified after the cold and hot storage experiment; and the products in Example 8b and Example 8c are not qualified.

[0206] II. Field efficacy test

[0207] 1. The products of Examples 6a-6c were used for efficacy test

[0208] 1.1 Test site

[0209] Hubei Jingzhou Nuopuxin Test Base.

[0210] 1.2 Test crop

[0211] Non-cultivated land.

[0212] 1.3 Test target

[0213] The main weeds are Setaria viridis (L.) Beauv., Leersia hexandra Swartz, and Polygonum L.

[0214] 1.4 Meteorological data

[0215] Sprayed once on June 6, 2020. The weather was sunny on the day of spraying, the wind force was level 2, and the average temperature was 28.5°C.

[0216] 1.5 Test design and arrangement

[0217] 1.5.1 Dosage and number of pesticides

[0218] See Table 8.

[0219] Table 8

[0220]

[0221] 1.5.2 Cell arrangement

[0222] Table 9

[0223] 4-1 3-2 4-3 4-4 2-1 4-2 2-3 3-4 1-1 2-2 3-3 1-4 3-1 1-2 1-3 2-4

[0224] 1.5.3 Cell size and repetition

[0225] Cell size: 30 square meters, rectangular shape (10 m x 3 m);

[0226] Repetition: 4 repetitions.

[0227] 1.5.4 Method of application

[0228] 1.5.4.1 Application period and method

[0229] During the vigorous growth period of weeds, foliage spraying treatment.

[0230] 1.5.4.2 Application equipment

[0231] The spraying equipment is MATABI SUPER GREEN-16 backpack manual sprayer.

[0232] The test was conducted on June 6, 2020, and was sprayed once.

[0233] 1.5.4.4 Water usage

[0234] Each treatment in the test was diluted with 750 liters of water per hectare for spraying.

[0235] 1.5.4.5 Walking speed during application

[0236] The sprayer is a fan-shaped nozzle with a pressure of 1.5 bar, and uniform spraying is carried out at a pace of about 50 cm per step during application.

[0237] 1.5.4.6 Investigation method, time and frequency

[0238] 1.5.4.6.1 Investigation method of weed efficacy

[0239] A total of 2 investigations were conducted. Investigation time: 1) 15 days after treatment, investigate the number of weed plants; 2) 30 days after treatment, investigate the number of weed plants and fresh weight. Absolute value (number measurement) investigation method was used, 4-point sampling method along the diagonal was used, 4 quadrats were taken in each cell, each quadrat was 0.25 m2, and the symptoms, species and number of weeds were recorded respectively.

[0240] 1.5.4.6.2 Calculation method

[0241] According to GB / T 17980.51—2000 Pesticide Field Test Guidelines (I) Herbicide Control of Non-crop Land Weeds.

[0242] Preventive effect calculation method:

[0243]

[0244] Duncan's new multiple range method in DPS statistical analysis software was used for significant difference analysis. The same lowercase letters in the analysis results indicated that there was no significant difference at the 5% level.

[0245] 1.6 Herbicidal effect

[0246] Table 10 Average plant control effect (%) of non-crop land weeds - 15 days after application

[0247]

[0248]

[0249] Table 11 Average plant control effect (%) of non-crop land weeds - 30 days after application

[0250]

[0251] Table 12 Average fresh weight control effect (%) of non-crop land weeds - 30 days after application

[0252]

[0253] Table 13 Summary of non-crop land weed control results of Examples 6a-6c

[0254]

[0255] Note: The same lowercase letters after the numbers indicate no significant difference at the 0.05 level.

[0256] From the above Tables 8-13, it can be seen that the product of Example 6a has better total plant control effect and total fresh weight control effect than Examples 6b and 6c. The total plant control effect after 30 days of application can still reach 93.75%, and the total fresh weight control effect after 30 days of application can still reach 96.62%. Therefore, the product of Example 6a still has a sustained and stable efficacy after 30 days of application, and thus the product of Example 6a has good physicochemical stability and good drug utilization rate.

[0257] 2. Use the products of Examples 2a-2c for efficacy test

[0258] 1.1 Test site

[0259] Jingzhou Nopco Test Base.

[0260] 1.2 Test crop

[0261] Non-crop land.

[0262] 1.3 Test target situation

[0263] Cynodon dactylon (L.) Pers., Setaria viridis (L.) Beauv., Artemisia mongolica (Fisch. ex Bess.) Nakai.

[0264] 1.4 Meteorological information

[0265] The test was sprayed once on June 6, 2020. The weather was sunny on the spraying day, the wind force level was grade 2, and the average temperature was 28.5°C.

[0266] 2. Test design and arrangement

[0267] 2.1 Dosage and number of test agents

[0268] Table 14 Test design of test agents

[0269]

[0270] 2.2 Plot arrangement

[0271] 2.2.1 Plot arrangement

[0272] Table 15 Randomized block arrangement of plots

[0273] 1-1 3-2 1-3 4-4 4-1 1-2 4-3 2-4 3-1 2-2 3-3 1-4 2-1 4-2 2-3 3-4

[0274] 2.2.2 Plot area and repetition

[0275] Plot area: 30 square meters, in the shape of a rectangle (10 m x 3 m);

[0276] Number of repetitions: 4 repetitions.

[0277] 2.3 Method of application

[0278] 2.3.1 Time and method of use

[0279] During the vigorous growth period of weeds, stem and leaf spray treatment.

[0280] 2.3.2 Application equipment

[0281] The spray equipment was MATABI SUPER GREEN-16 backpack manual sprayer.

[0282] 2.3.3 Time and number of applications

[0283] The test was conducted on June 6, 2020, with one application of the pesticide.

[0284] 2.3.4 Water consumption

[0285] Each treatment agent was sprayed with water at a rate of 750 liters per hectare.

[0286] 2.3.5 Walking speed during spraying

[0287] The sprayer is a fan-shaped nozzle with a pressure of 1.5 bar. When applying the pesticide, the spray is carried out at a uniform speed with a step length of about 50 cm / step.

[0288] 2.4 Survey methods, time and frequency

[0289] 2.4.1 Methods for investigating the efficacy of herbal remedies

[0290] Two surveys were conducted: 1) Weed counts 15 days after treatment; 2) Weed counts and fresh weights 30 days after treatment. Using the absolute value (counting) survey method and a four-point diagonal sampling method, four plots (0.25 m2 each) were collected from each plot to record weed poisoning symptoms, species, and abundance.

[0291] 2.4.2 Calculation method

[0292] The test was carried out in accordance with GB / T 17980.51-2000 Guidelines for field efficacy tests of pesticides (I) Control of weeds in non-arable land using herbicides.

[0293] Calculation method of control effect:

[0294]

[0295] The Duncan new multiple range method in DPS statistical analysis software was used to perform significance analysis of differences. The same lowercase letters in the analysis results indicate that the differences were not significant at the 5% level.

[0296] 3. Test results:

[0297] Table 16 Average control effect of weeds in non-cultivated land (%) - 15 days after application

[0298]

[0299] Table 17 Average control effect of weeds in non-cultivated land (%) - 30 days after application

[0300]

[0301] Table 18 Average fresh weight control effect of weeds in non-cultivated land (%) - 30 days after application

[0302]

[0303] Table 19 Summary of the results of the efficacy of preventing non-cultivated land weeds

[0304]

[0305]

[0306] Note: the same lower case letters after the numbers mean no significant difference at the 0.05 level.

[0307] From Tables 14-19, it can be seen that the product of Example 2a has better total plant control effect and total fresh weight control effect than Examples 2b and 2c, and still has a stable and sustained efficacy 30 days after administration, the total plant control effect 30 days after administration can still reach 95.37%, and the total fresh weight control effect 30 days after administration can still reach 98.37%. Thus, the product of Example 2a has good physicochemical stability and good drug utilization rate.

[0308] In summary, the nano-lipid carrier composition of the embodiments of the present application can wrap the oily herbicide into an oily herbicide nanoparticle with a water-based coating by using a water-based coating agent, and can load the herbicide in the nanoparticle core, which can not only improve the physicochemical stability of the oil suspension prepared by the combination of the herbicide and glufosinate ammonium, but also increase the stability of the embedded components in the drug delivery process, thereby improving the drug utilization rate.

[0309] Compared with related technologies, the nano-lipid carrier and the pesticide preparation such as oil suspension prepared based on the nano-lipid carrier composition have better affinity to plant leaves and weed tissues, which is more conducive to targeted transportation, thereby improving the absorption rate of weed tissues. In addition, due to the action of the nano-lipid carrier, the biochemical degradation and metabolism of the pesticide product under the leaf surface layer are slowed down, the storage stability is greatly improved, and the efficacy period is prolonged, so that the product based on the nano-lipid carrier has good efficacy and drug utilization rate.

[0310] The above are only preferred embodiments of the present application and are not used to limit the present application. Any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. Oil suspension, characterized in that, include: A first herbicide and a nanolipid carrier obtained by using a nanolipid carrier composition; the nanolipid carrier composition comprises an oily herbicide and an aqueous coating agent; the weight ratio of the oily herbicide to the aqueous coating agent is 1:(3-10); the oily herbicide comprises the following components in parts by weight: 1-40 parts of an oily herbicide compound and 4-85 parts of an oily solvent; the aqueous coating agent comprises the following components in parts by weight: 0.1-10 parts of a water-soluble coating compound and 99.9-90 parts of an aqueous solvent; The first herbicide includes one or more of glufosinate-ammonium and flupyralid; the oily herbicide compound includes one or more of flupyralid and saflufenacil.

2. The oil suspension according to claim 1, wherein The oily solvent includes one or more of unsaturated glycerides and plant essential oils; and / or the water-soluble coating compound includes one or more of polyvinyl alcohol, hydroxypropyl methylcellulose and gelatin; and / or the aqueous solvent includes one or more of water, ethanol, propanol or ether; and / or the plant essential oil includes one or more of peppermint essential oil, citronella oil, cinnamon oil, rose essential oil, wintergreen essential oil, tea tree essential oil, rosemary oil, lemon oil and lavender oil.

3. The oil suspension according to claim 1, characterized in that The oily solvent comprises the following components in parts by weight: 1-20 parts of triolein and 3-65 parts of plant essential oil; the aqueous coating agent comprises the following components in parts by weight: 0.1-10 parts of polyvinyl alcohol and 99.9-90 parts of water.

4. The oil suspension according to claim 1, characterized in that The preparation method of the nano lipid carrier comprises: mixing the oily herbicide compound and the oily solvent in the nano-lipid carrier composition to prepare an oily herbicide; mixing a water-soluble coating compound and an aqueous solvent to prepare an aqueous coating agent; The oily herbicide and the aqueous coating agent are mixed to prepare a nano lipid carrier.

5. The oil suspension according to claim 4, characterized in that The oily herbicide and the aqueous coating agent are mixed to prepare a nano lipid carrier; comprising: After mixing the oily herbicide and the aqueous coating agent, the mixture is emulsified by stirring, oscillating or high shearing at -5°C to 2°C, and then micronized by ultrasonication, stirred, and dried to prepare a nano-lipid carrier.

6. The oil suspension according to claim 1, characterized in that The oil suspension further comprises the following components in parts by weight: 1-10 parts of a surfactant, 1-5 parts of an adjuvant and 1-80 parts of an oily carrier.

7. The oil suspension according to claim 6, characterized in that The surfactant includes one or more of fatty alcohol polyoxyethylene ether, triphenylphenol polyoxyethylene ether, styrylphenol polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, lignin sulfonate and naphthalene sulfonate formaldehyde condensate; and / or, the auxiliary agent includes one or more of organic bentonite, attapulgite and white carbon black; and / or, the oily carrier includes one or more of methyl oleate, white mineral oil, soybean oil, cottonseed oil, corn oil and rapeseed oil.

8. A method for preparing the oil suspension according to any one of claims 1 to 7, characterized in that: include: The oil suspension is prepared by mixing the components thereof and grinding them.

9. Use of the oil suspension according to any one of claims 1 to 7 for preparing pesticide formulations.

Images