WO2019033917A1

WO2019033917A1 - An oil-based suspension, a preparation method therefor and the use thereof

Info

Publication number: WO2019033917A1
Application number: PCT/CN2018/097413
Authority: WO
Inventors: Yifan Wu
Original assignee: Jiangsu Rotam Chemistry Co., Ltd.
Priority date: 2017-08-14
Filing date: 2018-07-27
Publication date: 2019-02-21
Also published as: TWI778114B; CN107484767A; AR112232A1; TW201909742A

Abstract

Disclosed are an oil-based suspension, a preparation method therefor and the use thereof. Said oil-based suspension comprises the following components: Component A: at least one spirotetramat active substance which is a solid at room temperature; Component B: at least one fatty acid ester of general formula R 1-COO-R 2 and/or R 1-COO-R 2-OOC-R 1; Component C: at least one non-ionic surfactant and/or at least one anionic surfactant; and Component D: optionally one or at least two additives selected from an emulsifier, a defoaming agent, a preservative, an antioxidant, a colourant and an inert filling material. The oil-based suspension prepared by the present invention effectively resolves the problem of particle size increase of spirotetramat during storage, greatly inhibits the particle size of suspended spirotetramat particles from increasing, increases the activity of spirotetramat, obtains a higher activity compared with conventional formulations, and reduces the use amount of spirotetramat.

Description

AN OIL-BASED SUSPENSION, A PREPARATION METHOD THEREFOR AND THE USE THEREOF

Technical Field

The present invention belongs to the field of pesticides, and relates to an oil-based suspension, a preparation method therefor and the use thereof.

Background Art

Spirotetramat is a tetronic acid-based compound developed by Bayer Corporation and is one of the modern insecticides with two-way systemic transport properties to date. The compound can move upwards and downwards throughout the plant in vivo and reach the foliage and bark so as to control, for example, pests on the inner leaves of lettuce and cabbage and the barks of fruit trees. This unique systemic property can protect new stems, leaves and roots, and prevent pest eggs and larvae from growing. Another characteristic thereof is that it has a long effect lasting period and can provide an effective control for up to 8 weeks.

Because spirotetramat has two-way systemic transport properties, preparing spirotetramat as an oil-based suspension is the best choice. It has been known that many types of anhydrous suspension concentrates of active agrochemical substances are disclosed. For example, EP 0, 789, 999 describes a formulation of this type, which further contains a hydrophobized aluminium silicate thickening agent in addition to an active substance and an oil. The stability of this formulation is good, but the disadvantage thereof is that the thickening agent is necessary, which can make the production process more complicated and the processing cost and the energy consumption increase.

In addition, US 6,165,940 discloses an anhydrous suspension concentrate, wherein an organic solvent is present in addition to an active ingredient, a penetrating agent and a surfactant, and suitable solvents include liquid paraffin or vegetable oils and fats. However, the anhydrous suspension concentrate has a serious risk of particle size increase during storage.

CN 100,435,637 C discloses an oil-based suspension concentrate, wherein in addition to an active agrochemical substance that is a solid at room temperature, an alkanol alkoxylate and non-ionic and/or anionic surfactants, a vegetable oil or a mineral oil is also used, and there is also a serious risk of particle size increase.

CN 100,548,124 C discloses an oil-based suspension, wherein in addition to the inclusion of an active substance with a structure of formula I, a penetrating agent and non-ionic and/or anionic surfactants, a vegetable oil is also used, and there is also a serious risk of particle size increase.

Summary of the Invention

In view of the deficiencies of the prior art, an object of the present invention is to provide an oil-based suspension, a preparation method therefor and the use thereof.

In order to achieve this object, the following technical solution is used in the present invention:

in one aspect, the present invention provides an oil-based suspension comprising the following components:

Component A: at least one spirotetramat active substance which is a solid at room temperature;

Component B: at least one fatty acid ester of general formula R ₁-COO-R ₂ and/or R ₁-COO-R ₂-OOC-R ₁, wherein R ₁ is an alkyl and/or alkenyl group having 10-25 carbon atoms, and R ₂ is an alkyl group having 1-10 carbon atoms;

Component C: at least one non-ionic surfactant and/or at least one anionic surfactant; and

Component D: optionally one or at least two additives selected from an emulsifier, a defoaming agent, a preservative, an antioxidant, a colourant and an inert filling material.

In the present invention, the specific selection of the components of an oil-based suspension, particularly the choice to use a fatty acid ester component, makes the oil-based suspension capable of effectively resolve the problem of particle size increase of spirotetramat during storage, greatly inhibits the particle size of suspended spirotetramat particles from increasing, and improves the stability of the formulation and the effect of spirotetramat.

In the present invention, said oil-based suspension does not contain any thickening agent (such as a vegetable oil or a mineral oil) but can exhibit excellent stability, and in particular can improve the stability of a formulation containing the spirotetramat active substance.

Preferably, said oil-based suspension comprises the following components in weight percentage: 0.1-30%of Component A, 20-90%of Component B, 1-30%of Component C and 0-40 of Component D.

In the present invention, by the mutual cooperation of these components in specific amounts, the components of the oil-based suspension achieve a better cooperation condition, effectively resolving the problem of particle size increase of spirotetramat during storage, inhibiting the particle size of suspended spirotetramat particles from increasing and improving the stability of the formulation.

Preferably, said fatty acid ester in said oil-based suspension is preferably an ester of general formula R ₁-COO-R ₂ and/or R ₁-COO-R ₂-OOC-R ₁, wherein R ₁ is a linear or branched alkyl and/or alkenyl group having 10-25 carbon atoms, and R ₂ is a linear or branched alkyl group having 1-10 carbon atoms. An ester corresponding to the above-mentioned structure is usually a C ₁₀-C ₂₅ fatty acid ester formed from a C ₁-C ₁₀ alkyl monohydric alcohol or dihydric alcohol and a fatty acid. Said C ₁-C ₁₀ alkyl monohydric alcohol or dihydric alcohol may be methanol, ethanol, propanol, butanol, pentanol, hexanol, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol or hexylene glycol, etc. Said fatty acid is preferably a fatty acid having an even number of carbon atoms, and may be, for example, decanoic acid, erucic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid or arachidic acid, etc.

Preferably, in said Component B, R ₁ is an alkyl group and/or alkenyl group having 12-20 carbon atoms, e.g., 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, and is further preferably an alkyl group and/or alkenyl group having 12-18 carbon atoms; and R ₂ is an alkyl group having 2-8 carbon atoms, e.g., 2, 3, 5, 6, 7 or 8 carbon atoms, and is further preferably an alkyl group having 2-6 carbon atoms.

Preferably, said alkyl group is a linear or branched alkyl group.

Preferably, in said oil-based suspension, said component B is any one of or a combination of at least two of ethyl oleate, butyl oleate, hexyl laurate, ethylene palmitate or pentylene linoleate.

Preferably, said non-ionic surfactant is selected from any one of or a combination of at least two of an ethylene oxide-propylene oxide block copolymer, a fatty alcohol polyoxyethylene ether, a polymerization reaction product of a fatty alcohol and ethylene oxide and/or propylene oxide, a copolymer of methacrylic acid and a methacrylate, an alkyl glycoside, a polyvinyl alcohol, polyvinylpyrrolidone, an alkyl ethoxylate, an alkyl aryl ethoxylate, and a mixture of polyoxyethylene sorbitan monolaurate and a part of polyoxyethylene disorbitan monolaurate (Tween series) .

Preferably, said anionic surfactant is selected from any one of or a combination of at least two of a lignosulphonate (Borresperse NA) , a succinate sulphonate, a naphthalenesulphonate formaldehyde condensate, a sulphate of tristyryl ethoxylate, and a phosphate or polycarboxylate of tristyryl ethoxylate.

Preferably, said emulsifier is any one of or a combination of at least two of a reaction product of an alkyl phenol with ethylene oxide and/or propylene oxide, an ethoxylated nonyl phenol, a castor oil ethoxylate, a mixture of polyalkoxylated alcohols (Atlox 4894) , an alkyl calcium salt, a calcium alkylbenzene sulphonate salt, a sorbitan derivative or a polyethylene oxide-sorbitan fatty acid ester.

In the present invention, suitable defoaming agents include all substances commonly used for this purpose in agrochemical compositions, and preferably, said defoaming agent is a silicone defoaming agent, preferably a siloxane defoaming agent.

In the present invention, suitable preservatives include all substances commonly used for this purpose in agrochemical compositions, and preferably, said preservative is selected from Proxel series and/or Nipacide series preservatives.

In the present invention, suitable antioxidants include all substances commonly used for this purpose in agrochemical compositions, and preferably, said antioxidant is 2, 6-di-tert-butyl-4-methylphenol.

In the present invention, suitable colourants include all substances commonly used for this purpose in agrochemical compositions, and preferably, said colourant is any one of or a combination of at least two of titanium dioxide, zinc oxide, a blue pigment, or Pigment Red BBN (i.e., Light Fast Scarlet BBN) .

In the present invention, suitable inert materials include all substances commonly used for this purpose but not as thickening agents in agrochemical compositions, and preferably, said inert filling material is any one of or a combination of at least two of urea, a silicate, a sulphate or an oxide.

Preferably, said oxide is a metal oxide and/or a non-metal oxide.

In the present invention, the amounts of said Component A, Component B, Component C and Component D can be within wider ranges.

In the present invention, the weight percentage of Component A in said oil-based suspension is 0.1-30%, for example, 0.1%, 0.8%, 2%, 5%, 6.9%, 8.4%, 9.6%, 12.9%, 15%, 17%, 19.6%, 21.3%, 25%, 27.8%or 30%, preferably 5-25%.

In the present invention, the weight percentage of Component B in said oil-based suspension is 20-90%, for example, 20%, 25%, 32%, 40%, 50%, 55%, 60%, 68%, 72%, 80%, 85%or 90%, preferably 40-80%.

In the present invention, by using any one of or a combination of at least two of esters in said Component B, the use of traditional vegetable oils is avoided, and when the content of said Component B is preferably in the range of 40-80%, the risk of particle size increase can be more effectively reduced, overcoming the problems encountered in the storage process.

In the present invention, the weight percentage of Component C in said oil-based suspension is 1-30%, for example, 1%, 2%, 5%, 7%, 8.6%, 10.4%, 12%, 14%, 15%, 16.4%, 17.9%, 19%, 21%, 23.1%, 25%, 28%or 30%, preferably 2-20%.

In the present invention, the weight percentage of Component D in said oil-based suspension is 0-40%, for example, 0%, 2%, 5%, 7%, 9.6%, 11.4%, 13%, 16%, 17.4%, 20%, 25%, 27%, 30%, 34%, 37%or 40%, preferably 0-30%.

In another aspect, the present invention provides a method for preparing said oil-based suspension, the preparation method involving: stirring and mixing said Component A, Component B, Component C and Component D and grinding same to obtain said oil-based suspension, wherein the order of mixing these components with each other is arbitrary.

In the present invention, these components are mixed with each other in any order, achieving the effects of a simple preparation process and a reduction in processing costs.

Preferably, said grinding is carried out at 10-50℃, for example, 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, 45℃ or 50℃, preferably 15-40℃.

In the present invention, the grinding temperature conditions are mild, which reduces the energy consumption in the production process and reduces production costs.

Preferably, said grinding is carried out such that the solid particles in said oil-based suspension are ground to an average size of less than 10 μm, e.g., 0.4 μm, 0.8 μm, 1 μm, 2 μm, 3.4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm, preferably 1-5 μm.

In the present invention, the average size of the solid particles in said oil-based suspension are less than 10 μm, where said oil-based suspension is placed under normal temperature storage and/or hot storage conditions, the particle size changes little, increases relatively slow, and remains stable for a relatively long time.

In another aspect, the present invention provides a liquid spray comprising the oil-based suspension as described above.

In the present invention, by diluting with water, the oil-based suspension of the present invention can be converted into a homogeneous liquid spray. The liquid spray is applied by a conventional method, for example, by spraying, injection, dropping or pouring.

The oil-based suspension of the present invention, when the concentrate thereof is diluted with water, has neither obvious emulsion layering nor destructive flocculation effect, and has very good physical and chemical properties.

In another aspect, the present invention provides the use of the oil-based suspension as described above for application to a plant and/or the growing environment thereof.

When applied to a plant, the oil-based suspension of the present invention can be absorbed by the plant, the penetration of the oil-based suspension at the application site of the plant is enhanced, the application efficiency is improved, the bioavailability of the spirotetramat active substance is enhanced, and the amount thereof is reduced.

In another aspect, the present invention provides the use of the oil-based suspension as described above for the control of insects.

The oil-based suspension of the present invention has a good stability, can improve the activity of the active ingredient spirotetramat, and improve the control effect on insects.

Preferably, said insects to be controlled are any one of or at least two of lepidoptera pests, diptera pests, hemiptera pests or homoptera pests.

Lepidoptera pests are, for example, Earias insulana, Pieris rapae Linnaeus, Herpetogramma licarsisalis Walker, Spodoptera fugiperda, Spodoptera frugiperda, Rachiplusia nu, Pseudoplusia includens, Sesamia inferens, Cnaphalocrocis medinalis Guenee, Maruca testulalis, Cirphisunipuncta, Tuta absoluta, Trichoplusia ni, Sesamianonagrioides, Trichoplusia ni, Anticarsia gemmatalis, Grapholitha molesta, Phthorimaea operculella, Sitotroga cerealella, Earias vittella Fabricius, Adoxophyes orana, Pectinophoragossypiella Saunders, Heliothis armigera, Alabama argi llacea, Lymantria monacha, Cydia pomonella, Pandemis heparana, Lobesia botrana, Sparganothis pilleriana, Endopiza vriteana Clemens, Scirpophaga incertulas, Spodopteraexigua Hübner, Spodopteraritura, Ephestia elutella, Heliothis virescens, Epinotia aporema, Tineola bisselliella, Plodiainterpunctella and Ostrinianubilalis Hübner.

Diptera pests are, for example, Aedes aegypti, Liriomyza brassicae, Sarcophaga haemorrhoidalis, Glossina morsi tans, Phorbia antiqua, Ceratitis capitata, Delia radicum, Dacuscucurbi tae, Tabanus lineola, Calliphora vricina, Psila rosae, Bactrocera dorsalis, Culicoides furens, Aedes vexans, Rhagoletis mendax, Chrysomya spp., Chrysops discalis, Phorbia brassicae, Si todiplosis mosellana, Liriomyza trifolii, Rhagoletis pomonella, Hippelates, Bactrocera zonata, Pegomya hysocyami, Pegomya betae, Lucilia cuprina and Culexquinquefasciatus.

Hemiptera and homoptera pests are, for example, Sogatellafurcifera Horvrath, Trialeurodes vaporariorum, Ieryapurchasi Maskell, Iceryapurchasi, Aphis glycines, Nilaparvata lugens, Nilaparvrata lugens, Brevicoryne brassicae, Bemisia tabaci, Diaphorina citri, Nephotettix nigropictus, Ceroplastesrubens, Aonidiella aurantii, Laodelphax striatellus, Aphis craccivrora Koch, Macrosiphum avenae, Aphis pomi, Psylla mali, Brachycaudus persicae, Myzuspersicae Sulzer, Acyrthisiphon pisum Harris, Trialeurodes vaporariorum, Bemisia tabaci Gennadius, Empoasca spp., Peregrinus maidis, Peregrinus maidis Ashmead, Rhopalosiphum maidis and Sogatodes orizicola Muir.

The oil-based concentrate of the present invention is particularly suitable for the control of Bemisia tabaci Gennadius, plant hoppers, aphids, scale insects, thrips, Cnaphalocrocis medinalis Guenee, Scirpophaga incertulas, red spiders, Spodopteraritura, cabbage caterpillar, diamondback moth, Spodopteraexigua Hübner, Phyllotreta vittata or Empoasca pirisuga Matumura. It is further particularly suitable for the control of Bemisia tabaci Gennadius and/or plant hoppers.

Compared with the prior art, the present invention has the following beneficial effects:

(1) the oil-based suspension of the present invention can effectively control the increase of the particle size of spirotetramat during storage, resolving the problem of the increase of the particle size of suspended spirotetramat particles and improving the long-term storage stability of the oil-based suspension, as compared with the existing compositions having similar compositions.

(2) The oil-based suspension of the present invention overcomes the constraints of conventional conditions, does not contain any thickening agent, exhibits excellent stability, and is particularly suitable for the enhancement of the stability of formulations containing the spirotetramat active substance.

(3) The oil-based suspension of the present invention, when the concentrate thereof is diluted with water, has neither obvious emulsion layering nor destructive flocculation effect, and has very good physical and chemical properties.

(4) The oil-based suspension of the present invention improves the biological activity of spirotetramat and has a higher activity compared with conventional formulations, which can thus reduce the use amount of spirotetramat, enhance the bioavailability of the spirotetramat active substance and reduce costs, and has a good control effect on Bemisia tabaci Gennadius; after 25 days of high concentration administration, the control effect on adult plant hoppers can reach 95%or more, and the control effect on plant hopper nymphs can reach 85%or more.

(5) The preparation method of the invention is simple and easy to operate, and is advantageous for industrial scale production, reducing production costs.

Detailed Description of the Drawings

The technical solution of the present invention is further described below by way of specific examples. It will be clear to a person skilled in the art that said examples merely aid in the understanding of the present invention and should not be taken as a particular limitation on the present invention. The substances used in the following examples would be obtained by a person skilled in the art via conventional channels.

Example 1

In this example, the oil-based suspension comprised the following components:

The preparation method was as follows: the above substances were mixed in any order under stirring at room temperature, and uniformly stirred to obtain a suspension, and the suspension was subjected to primary coarse grinding and secondary fine grinding in a sand mill at 45 degrees Celsius to obtain an oil-based suspension having an average particle size of suspended particles of less than 3 μm.

Comparative Example 1

In this comparative example, the oil-based suspension comprised the following components:

Example 2-7 and Comparative Example 2-7 were prepared according to the above method with the same settings, and the components thereof and the amounts thereof were as shown in Table 1.

Table 1

The samples prepared in Examples 1-7 and the samples of Comparative Examples 1-7 as mentioned above were tested for particle size increase comparison during long-term storage. Test method: the above-mentioned 7 samples were placed in an oven at 54℃ for 14 days and 28 days, the particle sizes before and after the storage were tested using a Malvern particle size analyser, and the specific experimental results were as shown in Table 2 below:

Table 2

The experimental data in Table 2 showed that the spirotetramat-in-oil suspension of the present invention effectively controlled the rate of increase of granules after long-term storage of the suspended particles and improved the stability of the oil-based suspension.

Application Example 1

In this application example, the samples prepared in Examples 1-7 above and Comparative Examples 1-7 above were subjected to a bioactivity test, and the method was as follows:

Test object: White plant hopper on eggplant

The examples of Examples 1-7 and Comparative Examples 1-7 as mentioned above were tested using a spray method in an eggplant planting area, wherein the application was carried out at the peak of young insects, both sides were sprayed uniformly, and each was repeatedly treated 3 times.

Adult investigation: five eggplant trees were labelled in each area, two large branches were labelled in each plant, and when the adults were not active in the early morning, the number of adults on the large branches were investigated.

Nymph investigation: three leaves were collected from the top, middle and bottom of each of five unlabelled eggplant trees, i.e., 15 leaves in total, and the numbers of nymphs on these 15 leaves were recorded respectively.

The numbers of adults and nymphs on the plants after 7, 14 and 30 days after application were investigated.

Efficacy calculation method:

The results of the control effect on adult white plant hoppers were as shown in Table 3:

Table 3

Table 3 showed that the spirotetramat oil-based concentrate of the present invention had an excellent control effect on adult white plant hoppers, and the control effect on adult white plant hoppers after 25 days of a high dose application can reach over 95%.

The control effect on nymph white plant hoppers were as shown in Table 4

Table 4

Table 4 indicated that the spirotetramat oil-based concentrate of the present invention had an excellent control effect on nymph white plant hoppers, and the control effect thereof on nymph plant hoppers after 25 days after a high dose application can reach over 85%.

The applicant states that the oil-based suspension, the preparation method therefor and the use thereof of the present invention are illustrated by way of the above-mentioned examples, but the present invention is not limited to the above-mentioned examples, i.e. not meaning that the present invention has to be implemented depending on the above-mentioned examples. It will be clear to a person skilled in the art that any improvements to the present invention, equivalent replacements of the raw materials of the product and the addition of auxiliary ingredients, the selection of specific manners, etc., in the present invention all fall within the scope of protection and the scope of disclosure of the present invention.

Claims

An oil-based suspension, characterized in that said oil-based suspension comprises the following components:

Component A: at least one spirotetramat active substance which is a solid at room temperature;

Component B: at least one fatty acid ester of general formula R ₁-COO-R ₂ and/or R ₁-COO-R ₂-OOC-R ₁, wherein R ₁ is an alkyl and/or alkenyl group having 10-25 carbon atoms, and R ₂ is an alkyl group having 1-10 carbon atoms;

Component C: at least one non-ionic surfactant and/or at least one anionic surfactant; and

Component D: optionally one or at least two additives selected from an emulsifier, a defoaming agent, a preservative, an antioxidant, a colourant and an inert filling material.
The oil-based suspension according to claim 1, characterized in that the oil-based suspension comprises the following components in weight percentage: 0.1-30%of Component A, 20-90%of Component B, 1-30%of Component C, and 0-40%of Component D.
The oil-based suspension according to claim 1 or 2, characterized in that in said Component B, R ₁ is an alkyl group and/or alkenyl group having 12-20 carbon atoms, preferably an alkyl group and/or alkenyl group having 12-18 carbon atoms; R ₂ is an alkyl group having 2-8 carbon atoms, preferably an alkyl group having 2-6 carbon atoms; and

preferably, said alkyl group is a linear or branched alkyl group.
The oil-based suspension according to any one of claims 1-3, characterized in that said component B is any one of or a combination of at least two of ethyl oleate, butyl oleate, hexyl laurate, ethylene palmitate or pentylene linoleate.
The oil-based suspension according to any one of claims 1-4, characterized in that said non-ionic surfactant is selected from any one of or a combination of at least two of a copolymer of methacrylic acid and a methacrylate, a polymer of a fatty alcohol and ethylene oxide and/or propylene oxide, an ethylene oxide-propylene oxide block copolymer, a fatty alcohol polyoxyethylene ether, an alkyl glycoside, a polyvinyl alcohol, polyvinylpyrrolidone, an alkyl ethoxylate, an alkyl aryl ethoxylate or Tween;

preferably, said anionic surfactant is selected from any one of or a combination of at least two of a lignosulphonate, a succinate sulphonate, a naphthalenesulphonate formaldehyde condensate, a sulphate of tristyryl ethoxylate, and a phosphate or polycarboxylate of tristyryl ethoxylate.
The oil-based suspension according to any one of claims 1-5, characterized in that the weight percentage of Component A in said oil-based suspension is 5-25%;

preferably, the weight percentage of Component B in said oil-based suspension is 40-80%;

preferably, the weight percentage of Component C in said oil-based suspension is 2-20%; and

preferably, the weight percentage of Component D in said oil-based suspension is 0-30%.
A method for preparing the oil-based suspension according to any one of claims 1-6, characterized in that said preparation method involves: stirring, mixing and grinding said Component A, Component B, Component C and Component D to obtain said oil-based suspension;

preferably, said grinding is carried out at 10-50℃, preferably 15-40℃;

and preferably, said grinding is carried out such that the solid particles in said oil-based suspension are ground to an average size of less than 10 μm, preferably 1-5 μm.
A liquid spray, characterized in that said liquid spray comprises the oil-based suspension of any one of claims 1-6.
Use of the oil-based suspension according to any one of claims 1-6 for application to a plant and/or the growing environment thereof.
Use of the oil-based suspension according to any of the claims 1-6 for the control of insects;

wherein preferably, said insects to be controlled are any one of or at least two of lepidoptera pests, diptera pests, hemiptera pests or homoptera pests;

and preferably, said insects to be controlled are Bemisia tabaci Gennadius and/or plant hoppers.