Composition, preparation method and application of nano-lipid carrier, oil suspension and method

Abstract

The invention belongs to the technical field of pesticide preparations, the embodiment of the invention provides a composition, a preparation method and application of a nano-lipid carrier, an oil suspension and a method, and the nano-lipid carrier composition comprises an oily herbicide and a water-based coating agent; the weight ratio of the oily herbicide to the water-based coating agent is 1: (3-10); the oily herbicide comprises the following components in parts by weight: 1-40 parts of an oily weeding compound and 4-85 parts of an oily solvent, the water-based 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 a water-based solvent. The nano-lipid carrier composition provided by the embodiment of the invention can improve the stability of the oil suspension, thereby reducing the easy loss of effective components of the pesticide, and improving the utilization rate and efficacy of the pesticide.

Description

Technical Field

[0001] The present application belongs to the technical field of pesticide preparation, and more specifically, relates to a composition, a preparation method, a use, an oil suspension and a method of a nano lipid carrier. Background Art

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

[0003] Oil suspension concentrates can be divided into dispersible oil suspension concentrates (OD) dispersed in water and oil suspension concentrates (OF) dispersed in oil-based media according to different usage methods. Dispersible oil suspension concentrate (OD): refers to a dosage form that uses a type of oil that has been tested as a synergistic adjuvant and does not pollute crops as a dilution carrier. When used, it needs to be diluted with water and then sprayed. Oil suspension concentrate (OF): A liquid preparation in which the active ingredient is stably suspended in or partially dissolved in a water-immiscible liquid, and is used after dilution and preparation with an organic solvent or oil.

[0004] Oil suspensions are often used in pesticide preparations. In the related technologies of pesticide preparations, the physical stability of oil suspensions is poor, which leads to the easy loss of the active ingredients of the pesticides, and then leads to low drug utilization rate and poor drug efficacy of the pesticides. Summary of the invention

[0005] The purpose of the embodiments of the present application is to provide a composition, a preparation method, a use, an oil suspension and a method of a nano-lipid carrier to improve the stability of the oil suspension, thereby reducing the easy loss of the active ingredients of the pesticide and improving the drug utilization rate and efficacy of the pesticide.

[0006] To achieve the above-mentioned objectives, in a first aspect, an embodiment of the present application provides a nanolipid carrier composition, comprising 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.

[0007] Further, the oily herbicidal compound includes one or more of clofopyralid and saflufenacil; and / or 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.

[0008] Furthermore, 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.

[0009] In a second aspect, the present invention provides a method for preparing a nanolipid carrier, comprising:

[0010] mixing the oily herbicide compound and the oily solvent in the nanolipid carrier composition to prepare an oily herbicide;

[0011] Mixing a water-soluble coating compound and an aqueous solvent to prepare an aqueous coating agent;

[0012] The oily herbicide and the aqueous coating agent are mixed to prepare a nano lipid carrier.

[0013] Furthermore, the oily herbicide and the aqueous coating agent are mixed to prepare a nano lipid carrier; comprising:

[0014] After the oily herbicide and the aqueous coating agent are mixed, the mixed solution is emulsified by stirring, oscillating or high shearing at -5°C to 2°C, and then ultrasonically micronized, stirred and dried to obtain a nano lipid carrier.

[0015] In a third aspect, the embodiments of the present application provide a use of a nanolipid carrier for preparing a pesticide formulation.

[0016] In a fourth aspect, an embodiment of the present application provides an oil suspension, comprising: a first herbicide and a nano-lipid carrier.

[0017] Furthermore, the first herbicide includes one or more of glufosinate-ammonium and fluazifop-ethyl; and / or, the oil suspension further includes the following components in parts by weight: 1 to 10 parts of a surfactant, 1 to 5 parts of an adjuvant and 1 to 80 parts of an oily carrier.

[0018] Furthermore, the oil suspension also includes the following components in parts by weight: 1 to 10 parts of a surfactant, 1 to 5 parts of an adjuvant and 1 to 80 parts of an oily carrier.

[0019] Furthermore, 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.

[0020] In a fifth aspect, an embodiment of the present application provides a method for preparing an oil suspension, comprising: uniformly mixing the components for preparing the oil suspension and grinding the mixture.

[0021] The nano lipid carrier composition provided in the first aspect of the embodiment of the present application uses an oily herbicide and an aqueous coating agent. The oily herbicide can be wrapped by the aqueous coating agent into individual oily herbicide nanoparticles with an aqueous coat, so that the oily herbicide has better stability. The aqueous coat can make the oily herbicide nanoparticles with the aqueous coat have better compatibility with the aqueous solvent, making it easier to be formulated into various pesticide preparations for use, thereby improving the stability of the pesticide preparation, thereby reducing the easy loss of the active ingredients of the pesticide, and improving the drug utilization rate and efficacy of the pesticide.

[0022] The preparation method of the nano lipid carrier provided in the second aspect of the embodiment of the present application adopts the nano lipid carrier prepared by low temperature mixing, emulsification, ultrasonic micronization and the like to encapsulate the herbicide in the nanoparticle core, thereby improving the physical and chemical stability of the herbicide, and further increasing the stability of the embedded components in the drug delivery process, thereby improving the utilization of the drug; the nanoparticles can produce encapsulation and film-forming effects on the surface of weeds, so that the water loss on the surface of the weeds is reduced, thereby increasing the hydration and wetting effect on the surface of the weeds, and improving the utilization rate of the drug.

[0023] The third aspect of the embodiment of the present application provides the use of the nano-lipid carrier for preparing pesticide preparations. The use of the nano-lipid carrier to prepare pesticide preparations can prolong the efficacy of the pesticide preparations, so that the pesticide has better affinity for plant leaves and weed tissues, is more conducive to targeted transport, and improves the absorption rate; in addition, due to the action of the nano-lipid carrier, the biochemical degradation metabolism of the pesticide under the surface of the leaves is slowed down, the storage stability is greatly improved, and the efficacy period is extended.

[0024] The oil suspension provided in the fourth aspect of the embodiment of the present application uses nano lipid carriers to prepare the oil suspension. Compared with the traditional oil suspension or the nano oil suspension prepared by the high-intensity sand milling process, the particle size of the drug particles in the oil suspension of the embodiment of the present application is greatly reduced. The glufosinate or fluazifop-ethyl in the oil suspension has a good synergistic effect with the nano lipid carrier, which can not only improve the physicochemical stability of the composite composition oil suspension of the nano lipid carrier and glufosinate, but also increase the stability of the embedded components in the drug delivery process, thereby improving the utilization of the drug. The nanoparticles can produce encapsulation and film-forming effects on the surface of weeds, so that the water loss on the surface of the weeds is reduced, thereby increasing the hydration and wetting effect on the surface of the weeds, and improving the utilization rate of the drug. Therefore, compared with the prior art, it has better efficacy.

[0025] The fifth aspect of the present application provides a method for preparing an oil suspension, which is simple and easy to operate. Through mixing and grinding, the components in the oil suspension can be further evenly dispersed in a better particle state, so that the prepared oil suspension has better efficacy. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0027] Figure 1 Schematic diagram of the preparation process of the nano lipid carrier according to the embodiment of the present application. DETAILED DESCRIPTION

[0028] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

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

[0030] To achieve the above-mentioned objectives, in a first aspect, an embodiment of the present application provides a nanolipid carrier composition, comprising 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.

[0031] In the embodiments of the present application, the weight ratio of the oily herbicide to the aqueous coating agent is 1:(3-10). For example, the weight ratio of the oily herbicide to the aqueous coating agent can be 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, etc. This is only an example and not a limitation. If the amount of the aqueous coating agent is too small, the oily herbicide cannot be effectively dispersed, that is, the oily herbicide nanoparticles cannot be fully attached to the aqueous coat, resulting in poor stability of the oily herbicide; if the amount of the aqueous coating agent is too large, the aqueous coat of 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 weed control effect.

[0032] In an embodiment of the present application, the oily herbicide includes the following components in parts by weight: 1-40 parts of an oily herbicide compound and 4-85 parts of an oily solvent. In some embodiments, the oily herbicide compound includes one or more of clofopyralid and saflufenacil; optionally, the oily herbicide compound may be 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts, etc.; the oily solvent may include one or more of unsaturated glycerides and plant essential oils; optionally, the oily solvent may 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. This is only an example and is not limited.

[0033] In an embodiment of the present application, the aqueous coating agent may include 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. In some embodiments, the water-soluble coating compound may be one or more of polyvinyl alcohol, hydroxypropyl methylcellulose, and gelatin; alternatively, the water-soluble coating compound may be 0.1 parts, 0.5 parts, 1 parts, 2 parts, 3 parts, 4 parts, 6 parts, 8 parts, 9 parts, or 10 parts, etc. In some embodiments, the aqueous solvent may be water, ethanol, propanol, or ether, etc., and alternatively, the aqueous solvent is water; the aqueous solvent may be 90 parts, 91 parts, 93 parts, 95 parts, 97 parts, 99 parts, 99.5 parts, or 99.9 parts, etc. This is only an example and is not limited.

[0034] In an embodiment of the present application, the oily solvent may include the following components in parts by weight: 1-20 parts of triolein and 3-65 parts of plant essential oil; the aqueous coating agent may include the following components in parts by weight: 0.1-10 parts of polyvinyl alcohol and 99.9-90 parts of water.

[0035] In some embodiments, triolein 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. In some embodiments, the plant essential oil can be 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. Optionally, 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. This is only an example and is not limited. The amount of polyvinyl alcohol may be 0.1 parts, 0.5 parts, 1 parts, 2 parts, 3 parts, 5 parts, 7 parts, 8 parts, 9 parts or 10 parts, etc., and the amount of water may be 90 parts, 91 parts, 93 parts, 95 parts, 97 parts, 98 parts, 99 parts, 99.5 parts or 99.9 parts, etc. These are merely examples and are not limiting.

[0036] In a second aspect, the present invention provides a method for preparing a nano lipid carrier, referring to Figure 1 As shown, including:

[0037] S101. The oily herbicide compound and the oily solvent in the nanolipid carrier composition are mixed to prepare an oily herbicide;

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

[0039] S103. The oily herbicide and the aqueous coating agent are mixed to prepare a nano lipid carrier.

[0040] Furthermore, the oily herbicide and the aqueous coating agent are mixed to prepare a nano lipid carrier; comprising:

[0041] After the oily herbicide and the aqueous coating agent are mixed, the mixed solution is emulsified by stirring, oscillating or high shearing at -5°C to 2°C, and then ultrasonically micronized, stirred, and dried to obtain a nano lipid carrier. Alternatively, the mixed solution can be emulsified by stirring, oscillating or high shearing at -5°C, -4°C, -3°C, -2°C, 1°C or 2°C, and then ultrasonically micronized, stirred, and dried to obtain a nano lipid carrier, which is only an example and not limited here.

[0042] In a third aspect, the embodiments of the present application provide a use of a nanolipid carrier for preparing a pesticide formulation.

[0043] The functions and effects of the technical features in this technical solution that are similar or related to the aforementioned technical solution are similar to those of the aforementioned technical solution. The inventive concept and beneficial effects of this technical solution are similar to those of the aforementioned technical solution, and are not elaborated here.

[0044] In a fourth aspect, an embodiment of the present application provides an oil suspension comprising a first herbicide and a nanolipid carrier.

[0045] Further, the first herbicide includes one or more of glufosinate and haloxyfop-methyl; specifically, the first herbicide may include glufosinate and a nano lipid carrier; the first herbicide may also include glufosinate, haloxyfop-methyl and a nano lipid carrier. This is not limited here.

[0046] Furthermore, the oil suspension also includes the following components in parts by weight: 1 to 10 parts of a surfactant, 1 to 5 parts of an adjuvant and 1 to 80 parts of an oily carrier.

[0047] In the embodiment of the present application, the surfactant can be 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; in some embodiments, the surfactant is 1 part, 3 parts, 5 parts, 6 parts, 7 parts, 9 parts or 10 parts, etc. This is only an example and not limited here. The surfactant can enhance the compatibility of nanoliposomes with each component, ensuring that the oil suspension 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. This is only an example and not limited. The auxiliary agent can enhance the adhesion performance of the suspending agent and slow down the loss of nano lipid carriers and other effective 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. This is only an example and not limited. The oily carrier can provide an oily protective atmosphere for each oily component in the suspension, slowing down the loss of each effective component in the oil suspension.

[0050] In a fifth aspect, an embodiment of the present application provides a method for preparing an oil suspension, comprising: uniformly mixing the components for preparing the oil suspension and grinding the mixture.

[0051] The functions and effects of the technical features in this technical solution that are similar or related to the aforementioned technical solution are similar to those of the aforementioned technical solution. The inventive concept and beneficial effects of this technical solution are similar to those of the aforementioned technical solution, and are not elaborated here.

[0052] The following is a description of the contents in conjunction with specific embodiments.

[0053] Example 1 Preparation of Nanostructured Lipid Carrier

[0054] Example A Preparation of Nanostructured Lipid Carrier Containing 25% of Fluopyrrolidone

[0055]

[0056] 257.7 grams of fluroxypyr 2-ethylhexyl ester original drug with a mass fraction of 97%, 60 grams of olein and 525 grams of peppermint essential oil are dissolved in 100 grams of chloroform, and then mixed with 2200 grams of 7.5% polyvinyl alcohol aqueous solution, and the mixture is mixed evenly to form an emulsified state through stirring, oscillation or high shearing, and then micronized by ultrasound, stirred for 2 hours, and finally freeze-dried to obtain a nanostructured lipid carrier containing fluroxypyr 2-ethylhexyl ester with a content of 25%.

[0057] Example B Preparation of Nanostructured Lipid Carrier Containing 40% of Fluopyrrolidone

[0058]

[0059] 412.3 g of 97% clofopyralid original drug, 60 g of olein and 375 g of tea tree essential oil are dissolved in 100 g of chloroform, and then mixed with 2200 g of 7.5% polyvinyl alcohol aqueous solution, and the mixture is mixed evenly into an emulsified state by stirring, oscillating or high shearing, and then micronized by ultrasound, stirred for 2 hours, and finally freeze-dried to obtain a nanostructured lipid carrier containing 40% clofopyralid.

[0060] Example C Preparation of Nanostructured Lipid Carrier Containing 10% Safensulfuron

[0061]

[0062] 103.1 g of 97% saflufenacil technical drug, 110 g of olein and 630 g of citronella oil are dissolved together in 200 g of chloroform, and then mixed with 2000 g of 8% polyvinyl alcohol aqueous solution, and the mixture is mixed evenly to an emulsified state by stirring, oscillating or high shearing, and then micronized by ultrasonic wave, stirred for 3.5 hours and then freeze-dried to obtain a nanostructured lipid carrier containing 10% saflufenacil.

[0063] Example D Nanostructured lipid carrier containing 20% ​​saflufenacil

[0064]

[0065] 206.2 g of 97% saflufenacil technical drug, 110 g of olein and 530 g of wintergreen essential oil are dissolved together in 200 g of chloroform, and then mixed with 2000 g of 8% polyvinyl alcohol aqueous solution, and the mixture is mixed evenly to an emulsified state by stirring, oscillating or high shearing, and then micronized by ultrasonication, stirred for 3.5 hours, and then freeze-dried to obtain a nanostructured lipid carrier containing 20% ​​saflufenacil.

[0066] Unless otherwise noted, the active ingredients of pesticides used in the following examples are all calculated based on 100% purity. In actual operation, the actual purity of the original pesticide used is converted, and the difference is adjusted with fillers or water.

[0067] Example 2

[0068] Example 2a

[0069] The preparation method of 37% glufosinate-ammonium·high-efficiency fluazifop-ethyl·isothiazol-1-ethyl nano oil suspension comprises: uniformly mixing the mixture and sand-milling for 2.5 hours to obtain the product; the mixture is composed of the following components by weight:

[0070]

[0071] The 37% glufosinate-ammonium·halpyralid·isooctyl clofopyralid nano oil suspension contains 10% by weight of isooctyl clofopyralid based on 100% purity.

[0072] Example 2b

[0073] The preparation method of 37% glufosinate-ammonium·high-efficiency fluazifop-ethyl·isothiazol-1-yl clofopyralid nano oil suspension comprises the steps of uniformly mixing the mixture and sand-milling for 2.5 hours to obtain the product; the mixture is composed of the following components by weight:

[0074]

[0075] Example 2c

[0076] The preparation method of 37% glufosinate-ammonium·high-efficiency fluazifop-ethyl·isothiazol-1-yl clofopyralid nano oil suspension comprises the steps of uniformly mixing the mixture and high-intensity sand milling for 4.5 hours to obtain the product; the mixture is composed of the following components by weight:

[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 tests simultaneously to compare their stability.

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

[0083] Table 1

[0084]

[0085] Note: Decomposition rate of cold and hot storage comparison = (content of the component to be detected in the cold storage sample - content of the component to be detected in the hot storage sample) / content of the component to be detected in the cold storage sample × 100%; the cold storage samples were stored at 0℃ for 14 days, and the hot storage samples were stored at 54℃ for 14 days before testing.

[0086] As shown in Table 1, the components of the product in Example 2a are sufficiently stable after the cold and hot storage tests and are all qualified, while the clofopyralid 2-ethylhexyl ester of the products in Example 2b and Example 2c are both unqualified.

[0087] Example 3

[0088] Example 3a

[0089] The preparation method of 27% glufosinate-isooctyl clofopyralid nano oil suspension comprises the steps of uniformly mixing the mixture and sand-milling for 2.5 hours to obtain the product; the mixture comprises the following components:

[0090]

[0091] The 28% glufosinate-ammonium-clofopyralid 2-ethylhexyl nano oil suspension contains 7% by weight of clofopyralid 2-ethylhexyl based on 100% purity.

[0092] Example 3b

[0093] The preparation method of 27% glufosinate-isooctyl clofopyralid nano oil suspension comprises the steps of uniformly mixing the mixture and sand-milling for 2.5 hours to obtain the product; the mixture comprises the following components:

[0094]

[0095] Example 3c

[0096] The preparation method of 27% glufosinate-isooctyl clofopyralid nano oil suspension comprises the steps of uniformly mixing the mixture and high-intensity sand grinding for 4.5 hours to obtain the product; the mixture comprises the following components:

[0097]

[0098] Stability test

[0099] Cold and hot storage stability test

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

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

[0102] Table 2

[0103]

[0104] Note: Decomposition rate of cold and hot storage comparison = (content of the component to be detected in the cold storage sample - content of the component to be detected in the hot storage sample) / content of the component to be detected in the cold storage sample * 100%; the cold storage samples were stored at 0℃ for 14 days, and the hot storage samples were stored at 54℃ for 14 days before testing.

[0105] As shown in Table 2, the components of the product in Example 3a are sufficiently stable after the cold and hot storage tests and are all qualified, while the clofopyralid 2-ethylhexyl ester in the products in Example 3b and Example 3c are both unqualified.

[0106] Example 4

[0107] Example 4a

[0108] The preparation method of 40% glufosinate-ammonium·clofopyralid 2-ethylhexyl nano oil suspension comprises the steps of uniformly mixing the mixture and sand-milling the mixture for 2.5 hours to obtain the product. The mixture is composed of the following components:

[0109]

[0110]

[0111] The 40% glufosinate-ammonium-clofopyralid 2-ethylhexyl nano oil suspension contains 10% by weight of clofopyralid 2-ethylhexyl he ...

[0112] Example 4b

[0113] The preparation method of 40% glufosinate-ammonium·clofopyralid 2-ethylhexyl nano oil suspension comprises the steps of uniformly mixing the mixture and sand-milling the mixture for 2.5 hours to obtain the product. The mixture is composed of the following components:

[0114]

[0115] Example 4c

[0116] The preparation method of 40% glufosinate-isooctyl clofopyralid nano oil suspension comprises the steps of uniformly mixing the mixture and high-intensity sand grinding for 4.5 hours to obtain the product, wherein the mixture comprises the following components:

[0117]

[0118] Stability test of the above embodiment

[0119] Cold and hot storage stability test

[0120] The products of Examples 4a-4c were subjected to cold and hot storage tests simultaneously to compare their stability.

[0121] The experimental samples were packaged in 6 ampoules, 2 of which were stored in a 54°C constant temperature oven, 2 were stored in a 0°C refrigerator, and 2 were placed at room temperature. After 14 days, the decomposition rates of the cold-stored and hot-stored samples were measured. The experimental results are shown in Table 3.

[0122] Table 3

[0123]

[0124] Note: Decomposition rate of cold and hot storage comparison = (content of the component to be detected in the cold storage sample - content of the component to be detected in the hot storage sample) / content of the component to be detected in the cold storage sample * 100%; the cold storage samples were stored at 0℃ for 14 days, and the hot storage samples were stored at 54℃ for 14 days before testing.

[0125] As shown in Table 3, the components of the product in Example 4a are sufficiently stable after the cold and hot storage tests and are all qualified, while the clofopyralid 2-ethylhexyl ester of the products in Example 4b and Example 4c are both unqualified.

[0126] Example 5

[0127] Example 5a

[0128] The preparation method of 50% glufosinate-ammonium·clofopyralid 2-ethylhexyl nano oil suspension comprises: uniformly mixing the above mixture and sand-milling for 2.5 hours to obtain the product; the mixture is composed of the following components:

[0129]

[0130] The 50% glufosinate-ammonium-clofopyralid 2-ethylhexyl nano oil suspension contains 10% by weight of clofopyralid 2-ethylhexyl based on 100% purity.

[0131] Example 5b

[0132] The preparation method of 50% glufosinate-ammonium·clofopyralid 2-ethylhexyl nano oil suspension comprises: uniformly mixing the above mixture and sand-milling for 2.5 hours to obtain the product; the mixture is composed of the following components:

[0133]

[0134] Example 5c

[0135] The preparation method of 50% glufosinate-ammonium·clofopyralid 2-ethylhexyl nano oil suspension comprises: uniformly mixing the above mixture, grinding with high-strength sand for 4.5 hours to obtain the product; the mixture is composed of the following components:

[0136]

[0137] Stability test of the above embodiment

[0138] Cold and hot storage stability test

[0139] The products of Examples 5a-5c were subjected to cold and hot storage tests simultaneously to compare their stability.

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

[0141] Table 4

[0142]

[0143]

[0144] Note: Decomposition rate of cold and hot storage comparison = (content of the component to be detected in the cold storage sample - content of the component to be detected in the hot storage sample) / content of the component to be detected in the cold storage sample * 100%; the cold storage samples were stored at 0℃ for 14 days, and the hot storage samples were stored at 54℃ for 14 days before testing.

[0145] As shown in Table 4, the components of the product in Example 5a are sufficiently stable after the cold and hot storage tests and are all qualified; while the clofopyralid 2-ethylhexyl ester in the products of Example 5b and Example 5c are both unqualified.

[0146] Example 6

[0147] Example 6a

[0148] The method for preparing 33% glufosinate-ammonium·safensulfuron nano oil suspension comprises: uniformly mixing the mixture and sand-milling for 2.5 hours to obtain the product, wherein the mixture comprises the following components:

[0149]

[0150] The 33% glufosinate-ammonium saflufenacil nano oil suspension contains 3% saflufenacil by weight based on a purity of 100%.

[0151] Example 6b

[0152] The method for preparing 33% glufosinate-ammonium·safensulfuron nano oil suspension comprises: uniformly mixing the mixture and sand-milling for 2.5 hours to obtain the product, wherein the mixture comprises the following components:

[0153]

[0154] Example 6c

[0155] The method for preparing 33% glufosinate-ammonium·safensulfuron nano oil suspension comprises: uniformly mixing the mixture, and high-intensity sand grinding for 4.5 hours to obtain the product, wherein the mixture is composed of the following components:

[0156]

[0157] Stability test of the above embodiment

[0158] Cold and hot storage stability test

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

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

[0161] Table 5

[0162]

[0163] Note: Decomposition rate of cold and hot storage comparison = (content of the component to be detected in the cold storage sample - content of the component to be detected in the hot storage sample) / content of the component to be detected in the cold storage sample * 100%; the cold storage samples were stored at 0℃ for 14 days, and the hot storage samples were stored at 54℃ for 14 days before testing.

[0164] It can be seen from Table 5 that the components of the product in Example 6a are sufficiently stable after the cold and hot storage tests and are all qualified; while the saflufenacil in the products of Example 6b and Example 6c are both unqualified.

[0165] Example 7

[0166] Example 7a

[0167] The preparation method of 27% glufosinate-ammonium·safensulfuron nano oil suspension comprises: uniformly mixing the mixture and sand-milling for 2.5 hours to obtain the product, wherein the mixture consists of the following components:

[0168]

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

[0170] Example 7b

[0171] The preparation method of 27% glufosinate-ammonium·safensulfuron nano oil suspension comprises: uniformly mixing the mixture and sand-milling for 2.5 hours to obtain the product, wherein the mixture consists of the following components:

[0172]

[0173] Example 7c

[0174] The preparation method of 27% glufosinate-ammonium·safensulfuron nano oil suspension comprises: uniformly mixing the mixture, and high-intensity sand grinding for 4.5 hours to obtain the product, wherein the mixture consists of the following components:

[0175]

[0176]

[0177] Stability test of the above embodiment

[0178] Cold and hot storage stability test

[0179] The products of Examples 7a-7c were subjected to cold and hot storage tests simultaneously to compare their stability.

[0180] The experimental samples were packaged in 6 ampoules, 2 of which were stored in a 54°C constant temperature oven, 2 were stored in a 0°C refrigerator, and 2 were placed at room temperature. After 14 days, the decomposition rates of the cold-stored and hot-stored samples were measured. The experimental results are shown in Table 6.

[0181] Table 6

[0182]

[0183] Note: Decomposition rate of cold and hot storage comparison = (content of the component to be detected in the cold storage sample - content of the component to be detected in the hot storage sample) / content of the component to be detected in the cold storage sample * 100%; the cold storage samples were stored at 0℃ for 14 days, and the hot storage samples were stored at 54℃ for 14 days before testing.

[0184] It can be seen from Table 6 that the components of the product in Example 7a are sufficiently stable after the cold and hot storage tests and are all qualified; while the saflufenacil in the products of Example 7b and Example 7c are both unqualified.

[0185] Example 8

[0186] Example 8a

[0187] The preparation method of 43% glufosinate-ammonium·safensulfuron nano oil suspension comprises: uniformly mixing the mixture and sand-milling for 2.5 hours to obtain the product, wherein the mixture consists of the following components:

[0188]

[0189]

[0190] The 43% glufosinate-ammonium saflufenacil nano oil suspension contains saflufenacil in an amount of 3% by weight based on a purity of 100%.

[0191] Example 8b

[0192] Example 8a

[0193] The preparation method of 43% glufosinate-ammonium·safensulfuron nano oil suspension comprises: uniformly mixing the mixture and sand-milling for 2.5 hours to obtain the product, wherein the mixture consists of the following components:

[0194]

[0195] Example 8c

[0196] The preparation method of 43% glufosinate-ammonium·safensulfuron nano oil suspension comprises: uniformly mixing the mixture, and high-intensity sand grinding for 4.5 hours to obtain the product, wherein the mixture consists of the following components:

[0197]

[0198] Stability test of the above embodiment

[0199] Cold and hot storage stability test

[0200] Examples 8a-8c were subjected to cold and hot storage experiments simultaneously to compare the stability.

[0201] The experimental samples were packaged in 6 ampoules, 2 of which were stored in a 54°C constant temperature oven, 2 were stored in a 0°C refrigerator, and 2 were placed at room temperature. After 14 days, the decomposition rates of the cold-stored and hot-stored samples were measured. The experimental results are shown in Table 7.

[0202] Table 7

[0203]

[0204] Note: Decomposition rate of cold and hot storage comparison = (content of the component to be detected in the cold storage sample - content of the component to be detected in the hot storage sample) / content of the component to be detected in the cold storage sample * 100%; the cold storage samples were stored at 0℃ for 14 days, and the hot storage samples were stored at 54℃ for 14 days before testing.

[0205] It can be seen from Table 7 that the components of the product in Example 8a are sufficiently stable after the cold and hot storage tests and are all qualified; while the saflufenacil in the products of Example 8b and Example 8c are both unqualified.

[0206] 2. Field efficacy test

[0207] 1. Efficacy test using the products of Examples 6a-6c

[0208] 1.1 Test site location

[0209] Nopoxin test base in Jingzhou City, Hubei Province.

[0210] 1.2 Experimental crops

[0211] Non-arable land.

[0212] 1.3 Test target situation

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

[0214] 1.4 Meteorological data

[0215] The pesticide was applied once on June 6, 2020. The weather was sunny on the day of application, with a wind force of level 2 and an average temperature of 28.5℃.

[0216] 1.5 Experimental design and arrangement

[0217] 1.5.1 Dosage and number of medicines

[0218] See Table 8.

[0219] Table 8

[0220]

[0221] 1.5.2 Community 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 Plot area and repetition

[0225] The plot area is 30 square meters and the shape is rectangular (10m×3m);

[0226] Number of repetitions: 4 repetitions.

[0227] 1.5.4 Application method

[0228] 1.5.4.1 Period and method of use

[0229] During the peak growth period of weeds, spray the stems and leaves.

[0230] 1.5.4.2 Application equipment

[0231] The spraying equipment is MATABI SUPER GREEN-16 backpack manual sprayer. 1.5.4.3 Application time and frequency

[0232] The test was conducted on June 6, 2020, with one application of the pesticide.

[0233] 1.5.4.4 Water consumption

[0234] Each treatment agent was sprayed with water at a rate of 750 liters per hectare.

[0235] 1.5.4.5 Walking speed during application

[0236] 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.

[0237] 1.5.4.6 Survey methods, time and frequency

[0238] 1.5.4.6.1 Methods for investigating the efficacy of weeds

[0239] A total of 2 surveys were conducted. Survey time: 1) Weed count survey 15 days after treatment; 2) Weed count and fresh weight survey 30 days after treatment. The absolute value (number measurement) survey method and the diagonal 4-point sampling method were used. Four sample plots were taken in each plot, each with an area of ​​0.25 m2, and the weed poisoning symptoms, types and quantities were recorded respectively.

[0240] 1.5.4.6.2 Calculation method

[0241] The test was carried out in accordance with GB / T 17980.51-2000 Guidelines for Field Efficacy Tests of Pesticides (I) Herbicides for Control of Weeds in Non-arable Land.

[0242] Calculation method of control effect:

[0243]

[0244] The Duncan new multiple range method in DPS statistical analysis software was used to perform significance analysis of the differences. The same lowercase letters in the analysis results indicate that the differences were not significant at the 5% level.

[0245] 1.6 Weed control effect

[0246] Table 10 Average weed control effect (%) on non-cultivated land - 15 days after application

[0247]

[0248]

[0249] Table 11 Average weed control effect (%) on non-cultivated land—30 days after application

[0250]

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

[0252]

[0253] Table 13 Summary of the results of Examples 6a-6c in preventing weeds in non-cultivated land

[0254]

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

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

[0257] 2. Efficacy test using the products of Examples 2a-2c

[0258] 1.1 Test site location

[0259] Nopoxin Experimental Base in Jingzhou City.

[0260] 1.2 Experimental crops

[0261] Non-arable 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 data

[0265] The pesticide was applied once on June 6, 2020. The weather was sunny on the day of application, with a wind force of level 2 and an average temperature of 28.5℃.

[0266] 2. Experimental Design and Arrangement

[0267] 2.1 Dosage and number of medicines

[0268] Table 14 Test design of test drugs

[0269]

[0270] 2.2 Community Arrangement

[0271] 2.2.1 Cell Arrangement

[0272] Table 15 Random 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] The plot area is 30 square meters and the shape is rectangular (10m×3m);

[0276] Number of repetitions: 4 repetitions.

[0277] 2.3 Application method

[0278] 2.3.1 Period and method of use

[0279] During the peak growth period of weeds, spray the stems and leaves.

[0280] 2.3.2 Application equipment

[0281] The spraying equipment is MATABI SUPER GREEN-16 backpack manual sprayer.

[0282] 2.3.3 Application time and frequency

[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 application

[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 weeds

[0290] A total of 2 surveys were conducted. Survey time: 1) Weed count survey 15 days after treatment; 2) Weed count and fresh weight survey 30 days after treatment. The absolute value (number measurement) survey method and the diagonal 4-point sampling method were used. Four sample plots were taken in each plot, each with an area of ​​0.25 m2, and the weed poisoning symptoms, types and quantities were recorded respectively.

[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) Herbicides for Control of Weeds in Non-arable Land.

[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 the 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 weed control effect (%) on non-cultivated land - 15 days after application

[0298]

[0299] Table 17 Average weed control effect (%) on 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 efficacy results of controlling weeds in non-cultivated land

[0304]

[0305]

[0306] Note: The same lowercase letters after the numbers indicate no significant difference at the 0.05 level.

[0307] From Tables 14 to 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 sustained and stable drug effect 30 days after medication, and the total plant control effect 30 days after medication can still reach 95.37%, and the total fresh weight control effect 30 days after medication can still reach 98.37%. Therefore, the product of Example 2a has good physical and chemical stability and good drug utilization rate.

[0308] In summary, the nano lipid carrier composition of the embodiment of the present application uses an aqueous coating agent to wrap the oily herbicide into individual oily herbicide nanoparticles with an aqueous coating, and encapsulates the herbicide in the nanoparticle core, which can not only improve the physicochemical stability of the oil suspension prepared by the compound composition with glufosinate ammonium, but also increase the stability of the embedded components during the drug delivery process, thereby improving the utilization of the drug.

[0309] Compared with related technologies, the nanolipid carriers and pesticide preparations such as oil suspensions made based on the nanolipid carrier composition have better affinity for plant leaves and weed tissues, are more conducive to targeted transport, and thus improve the absorption rate of weed tissues; in addition, due to the effect of the nanolipid carriers, the biochemical degradation and metabolism of the pesticide products under the surface of the leaves are slowed down, the storage stability is greatly improved, and the efficacy period is extended, so that the products based on the nanolipid carriers have better efficacy and drug utilization.

[0310] The above are only preferred embodiments of the present application and are not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A nano lipid carrier composition, characterized in that: The invention 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.

2. The nano lipid carrier composition according to claim 1, characterized in that: The oily herbicidal compound includes one or more of clofopyralid and saflufenacil; and / or, 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 nano lipid carrier composition 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. A method for preparing a nano lipid carrier, characterized in that: include: Mixing the oily herbicide compound and the oily solvent in the nanolipid carrier composition according to any one of claims 1 to 3 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 method for preparing the nano lipid carrier 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 the oily herbicide and the aqueous coating agent are mixed, the mixed solution is emulsified by stirring, oscillating or high shearing at -5°C to 2°C, and then ultrasonically micronized, stirred and dried to obtain a nano lipid carrier.

6. Use of a nanolipid carrier obtained by using the nanolipid carrier composition according to any one of claims 1 to 3 or a nanolipid carrier obtained by using the preparation method according to any one of claims 4 to 5 for preparing a pesticide formulation.

7. Oil suspension, characterized in that, include: A first herbicide and a nanolipid carrier obtained by using the nanolipid carrier composition as described in any one of claims 1 to 3 or a nanolipid carrier obtained by using the preparation method as described in any one of claims 4 to 5.

8. The oil suspension according to claim 7, characterized in that: The first herbicide includes one or more of glufosinate-ammonium and fluazifop-ethyl; and / or, the oil suspension further includes the following components in parts by weight: 1 to 10 parts of a surfactant, 1 to 5 parts of an adjuvant and 1 to 80 parts of an oily carrier.

9. The oil suspension according to claim 8, 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.

10. A method for preparing the oil suspension according to any one of claims 7 to 9, characterized in that: include: The components for preparing the oil suspension are mixed and ground to obtain the oil suspension.

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