CN110476959B - Insecticidal composition containing chlorpyrifos and dinotefuran - Google Patents

Abstract

The invention provides a chlorpyrifos and dinotefuran-containing insecticidal composition, which comprises the following components: (a) a dispersed oil phase comprising: an oil phase in which chlorpyrifos is dissolved; and (b) a continuous phase comprising: wherein a continuous phase of dinotefuran is suspended, the solubility of the continuous phase relative to dinotefuran being < 10 g/kg; the invention also provides a preparation method of the insecticidal composition. The insecticidal composition provided by the invention can be used for preventing or controlling pests. The preparation of the insecticidal composition containing chlorpyrifos and dinotefuran shows no caking in a low-temperature stability test, shows no increase of particle size in an accelerated stability test, does not have crystallization and precipitation, does not form ointment, and has important application value.

Description

Insecticidal composition containing chlorpyrifos and dinotefuran

The application is a divisional application with application number 201510671080.8, application date 2015 10-16 and invention name 'an insecticidal composition containing chlorpyrifos and dinotefuran'.

Technical Field

The invention belongs to the field of pesticides, and particularly relates to an insecticidal composition containing chlorpyrifos and dinotefuran and a preparation method thereof.

Background

Chlorpyrifos is a broad-spectrum organophosphorus insecticide, has the action mechanism of inhibiting acetylcholinesterase, has three action modes of contact poisoning, stomach poisoning and fumigation, has a wide insecticidal spectrum and low toxicity, is one of main insecticides for preventing and treating insect pests of grains, fruit trees, vegetables and other economic crops, and is safe for users.

Chemical name of Chlorpyrifos (Chlorpyrifos): o, O-diethyl-O- (3,5, 6-trichloro-2-pyridyl) phosphorothioate. Chlorpyrifos belongs to a phosphorothioate broad-spectrum pesticide and has the effects of contact poisoning, stomach poisoning and fumigation. The chlorpyrifos can be widely applied to control of various pests and mites such as snout moth's larva, leaf roller, armyworm, scale insect, aphid, cotton bollworm and the like on crops such as rice, cotton, fruit trees, tea leaves, wheat, sugarcane and the like. The chlorpyrifos has relatively low toxicity, has the effects of contact poisoning, stomach poisoning, fumigation and the like on pests, and can also treat mites. In recent years, the country speeds up the pace of eliminating high-toxicity pesticides, and chlorpyrifos has become one of the alternatives of high-toxicity organophosphorus insecticides. At present, the emulsified oil is mainly processed into missible oil for use in China. Chlorpyrifos can also be processed into solid preparation for use. The processed solid preparation can be powder or granule. Chlorpyrifos can also be processed into environmentally friendly suspending agents for use.

However, in the water-dispersed formulation, the particle size of solid formulations such as Wettable Powder (WP) and water-dispersible granule (WG) and liquid formulations such as suspending agent (SC) and microcapsule suspending agent (CS) have a great influence on the stability and suspension rate of the formulation. In order to obtain very small particle sizes (2-20um), various types of comminution are necessary. However, since the melting point of the low-melting active substance is low, not exceeding 90 ℃, it is difficult to directly pulverize the solid low-melting insecticide because the active substance is easily melted or softened during the pulverization. Low temperature pulverization may solve this problem, but the additional increase in production cost makes the method not widely applicable, and also causes problems in storage stability and suspension ratio because the particle size obtained by pulverization using the method does not satisfy the demand.

Organophosphorus insecticides are relatively unstable compounds, particularly susceptible to decomposition under conditions of excessively high or low pH. Furthermore, organophosphorus compounds are susceptible to hydrolysis in the presence of water. It is known from the known art that the chemical stability of solid compositions of organic phosphorus can be increased by the addition of substances which reduce the chemical degradation of the active substances.

US4380537A, US5140019A, US5165934A and US5260312A all disclose techniques for loading organic phosphorus on some solid support, such as clay. In particular, US4380537A discloses a solid composition containing an organophosphorus insecticide, for example chlorpyrifos, loaded on a clay, such as montmorillonite or attapulgite, with 0.5% to 10% lactone as a stabilizer. Other substances as stabilizers for organic phosphorus are polyethylene glycol and polypropylene glycol. However, clay-based solid compositions with the addition of stabilizers are not always satisfactory. For example, a 15% chlorpyrifos solid composition with clay as carrier and 4.5% dipropylene glycol as a stabilizer. After the solid composition is stored at a relatively low temperature, the caking phenomenon of the preparation occurs, and the agricultural use is seriously influenced. So far, no good method is available for solving the problem of low-temperature caking of the solid composition of chlorpyrifos.

On the other hand, a solid composition of chlorpyrifos has a problem of easy crystallization after hot storage because of its low melting point (42 ℃ to 43.5 ℃). The active component is easy to crystallize and separate out from the preparation after thermal storage, and when the pesticide is sprayed for use, a filter and a nozzle are blocked due to crystallization and separation of the active component, so that inconvenience is brought to agricultural application, and the pesticide effect is influenced. Because of these technical difficulties, water-dispersible formulations of chlorpyrifos, either solid or liquid, have not been widely used. Therefore, solving these technical problems is an urgent need for widespread application of chlorpyrifos.

Dinotefuran (Dinotefuran) is a third generation of a nicotinic insecticide developed by mitsui chemical company, japan. Dinotefuran has a wide insecticidal spectrum, has excellent systemic osmosis effect, and shows high insecticidal activity at a very low dosage. Dinotefuran is very safe to mammals, birds and aquatic organisms, has no phytotoxicity to crops, and can be used for various crops such as rice, fruit trees, vegetables and the like. The melting point of dinotefuran is 107.5 ℃. The solubility of the compound is 40g/L of water, and the compound is difficult to dissolve in organic solvents such as cyclohexane, xylene and the like.

CN101978832A discloses an insecticidal composition containing dinotefuran and chlorpyrifos. The dinotefuran and the chlorpyrifos can generate good synergistic effect after being compounded. The insecticidal composition containing dinotefuran and chlorpyrifos can be prepared into wettable powder and suspending emulsion.

CN103444772A discloses a dinotefuran-containing pesticide, the effective components of which are dinotefuran and chlorpyrifos, the mass ratio of the dinotefuran to the chlorpyrifos is 1:50-50:1, and the dinotefuran-and chlorpyrifos-containing pesticide composition can be prepared into microemulsion.

CN102415408A discloses a composite insecticidal composition containing dinotefuran and chlorpyrifos, wherein the weight ratio of dinotefuran to chlorpyrifos is 0.1-80: 0.5-80. The insecticidal composition containing dinotefuran and chlorpyrifos can be prepared into missible oil, a suspending agent, an aqueous emulsion, wettable powder, a microemulsion or water dispersible granules.

CN102057941A discloses an insecticidal composition compounded by dinotefuran and one or more of abamectin, bifenthrin, chlorpyrifos and isoprocarb, the effective components of which are A and B, wherein A is dinotefuran, and B is one or more selected from abamectin, bifenthrin, chlorpyrifos and isoprocarb. The insecticidal composition can be prepared into missible oil, wettable powder, microemulsion, aqueous emulsion, aqueous suspension or water dispersible granules.

Due to the low melting point of chlorpyrifos, the high water solubility and the low oil solubility of dinotefuran, it is not easy to formulate chlorpyrifos and dinotefuran into a formulation in the form of a single composition.

Dinotefuran is not suitable for preparing aqueous suspension, high-content emulsion, microemulsion and other dosage forms because of high water solubility and low oil solubility. The chlorpyrifos has low melting point (42.5-43 ℃) and is not easy to be processed into suspending agents, wettable powder, water dispersible granules and other formulations.

The composition of the chlorpyrifos and the dinotefuran is prepared into wettable powder, water dispersible granules, water suspending agents, oil suspending agents and suspending emulsions, the products are easy to generate agglomeration and creaming phenomena after thermal storage, and active components are easy to crystallize and separate out from the preparation.

The composition of the chlorpyrifos and the dinotefuran is prepared into missible oil, microemulsion, aqueous emulsion and other dosage forms, and the dinotefuran is easy to separate out crystals from the water spray liquid to block a spray head due to the high solubility of the dinotefuran in water; meanwhile, due to the small oil solubility of dinotefuran, the dinotefuran is difficult to prepare into high-content missible oil, microemulsion or emulsion in water products.

Disclosure of Invention

In order to solve the above technical problems, it is an object of the present invention to provide a stable chlorpyrifos and dinotefuran-containing pesticidal composition which is physicochemically stable, has good emulsion/dispersion properties, and is also stable in the conventional tests of accelerated stability and low temperature stability representing 2 years storage stability.

The invention provides a stable chlorpyrifos and dinotefuran-containing insecticidal composition, which comprises dinotefuran suspended in a continuous phase and chlorpyrifos dissolved in an oil phase in a molecular state, and improves the low-temperature fluidity and the heat storage stability of the chlorpyrifos and dinotefuran-containing insecticidal composition.

In one aspect, the invention provides a stable chlorpyrifos and dinotefuran-containing insecticidal composition, which comprises the following components:

(a) a dispersed oil phase comprising:

(i) an oil phase in which chlorpyrifos is dissolved; and

(b) a continuous phase comprising:

(ii) wherein a continuous phase of dinotefuran is suspended, said continuous phase having a solubility of < 10g/kg relative to dinotefuran.

The oil phase (component (a)) may contain one or more solvents in which the chlorpyrifos is dissolved in a molecular state. Preferably, the oil phase may further comprise one or more surfactants. Particularly preferred surfactants are selected from nonionic surfactants of the fatty alcohol and/or castor oil type, ionic surfactants of the alkylnaphthalenesulfonate type.

The continuous phase (component (b)) may contain one or more solvents in which the dinotefuran is suspended as fine particles. Preferably, the continuous phase may further comprise one or more dispersants. Particularly preferred dispersants are selected from one or more of alkyl sulfonates, lignosulfonates, naphthalene sulfonates, fatty alcohol-polyoxyethylene ethers, nonylphenol polyoxyethylene ether phosphate esters, methacrylic acid-methacrylate-polyethylene glycol graft copolymers, tristyrylphenol polyoxyethylene ethers, propylene glycol/ethylene glycol block copolymers.

The solvent of the oil phase may be the same or different from the solvent of the continuous phase. Preferably, the solvent of the oil phase is the same as the solvent of the continuous phase.

The solvent is preferably a mineral oil, a mixture of naphtha heavy solvents and/or isoparaffin oils, a mixture of natural vegetable oils, hydrogenated or epoxidized or alkylated vegetable oils.

In the stable chlorpyrifos-dinotefuran-containing insecticidal composition, the weight ratio of the chlorpyrifos to the dinotefuran is 50:1-1:50, preferably 25:1-1:25, further preferably 10:1-1:10, and further preferably 5:1-1: 5.

In the stable chlorpyrifos and dinotefuran-containing insecticidal composition, the content of the chlorpyrifos and the dinotefuran accounts for 10 wt% -80 wt%, preferably 10 wt% -60 wt%, further preferably 15 wt% -55 wt%, and further preferably 20 wt% -40 wt% of the insecticidal composition.

In the stable chlorpyrifos and dinotefuran-containing insecticidal composition, the content of chlorpyrifos is 8-50 wt% of the insecticidal composition, and the content of dinotefuran is 2-30 wt% of the insecticidal composition. Wherein "wt%" means "weight percent content".

In another aspect, the present invention provides a method for preparing the stable chlorpyrifos and dinotefuran-containing insecticidal composition, which comprises the following steps:

step 1: providing an oil phase of chlorpyrifos; chlorpyrifos is present in a molecular state in the oil phase;

step 2: providing a continuous phase of dinotefuran; dinotefuran is suspended as fine particles in the continuous phase;

and step 3: mixing the oil phase prepared in the step 1 and the continuous phase prepared in the step 2.

The invention discloses application of a stable chlorpyrifos and dinotefuran-containing insecticidal composition to prevention or control of pests.

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

(1) the stable chlorpyrifos and dinotefuran-containing insecticidal composition provided by the invention shows no caking in a low-temperature stability test, shows no grain size increase, no crystallization and no creaming in an accelerated stability test after a diluent of a preparation prepared from the composition is placed at room temperature for 24 hours.

(2) After the stable chlorpyrifos and dinotefuran-containing insecticidal composition provided by the invention is placed at room temperature for 24 hours, no crystal is precipitated in the sample water diluent before and after thermal storage in the test of the stability of the water diluent, and the stability of the water diluent is good.

Detailed Description

An object of the present invention is to provide a stable insecticidal composition containing chlorpyrifos and dinotefuran.

Since chlorpyrifos and dinotefuran are chemically and biologically different and more importantly are physicochemically different (different solubility properties, vapour pressure, melting point, etc.), the formulation of chlorpyrifos and dinotefuran together is clearly not so simple. The main difficulty is to prepare a formulation that provides a stable insecticidal composition containing chlorpyrifos and dinotefuran. It needs to show no caking in the test of low-temperature stability, no grain size increase in the test of accelerated stability, no crystal precipitation and no creaming.

The invention provides a stable chlorpyrifos and dinotefuran-containing insecticidal composition, which comprises dinotefuran suspended in a continuous phase and chlorpyrifos dissolved in an oil phase in a molecular state.

In one aspect, the invention provides a stable chlorpyrifos and dinotefuran-containing insecticidal composition, which comprises the following components:

(a) a dispersed oil phase comprising:

(i) an oil phase in which chlorpyrifos is dissolved; and

(b) a continuous phase comprising:

(ii) wherein a continuous phase of dinotefuran is suspended, said continuous phase having a solubility of < 10g/kg relative to dinotefuran.

The oil phase (component (a)) may contain one or more solvents in which the chlorpyrifos is dissolved in a molecular state.

The continuous phase (component (b)) may contain one or more solvents in which the dinotefuran is suspended as fine particles.

The solvent of the oil phase may be the same or different from the solvent of the continuous phase. Preferably, the solvent of the oil phase is the same as the solvent of the continuous phase.

The solvent is preferably a mineral oil, a mixture of naphtha heavy solvents and/or isoparaffin oils, a mixture of natural vegetable oils, hydrogenated or epoxidized or alkylated vegetable oils.

When the oil is vegetable oil, preferably soybean oil, corn oil, cottonseed oil, sunflower oil, rice bran oil, olive oil, linseed oil, palm oil and coconut oil; and any saponified and/or alkylated (preferably methylated or ethylated) form of said oil.

In the stable chlorpyrifos and dinotefuran-containing insecticidal composition, chlorpyrifos is dissolved in a molecular state in the solvent, and dinotefuran is suspended in the solvent in a state of fine particles.

The preferred oil phase (component (a)) also requires the addition of a surfactant for the purpose of emulsifying the oil phase into water prior to field application. The selected emulsifier needs to have wetting activity while providing a good emulsion. Among the many surfactants available are especially ethoxylated and/or propoxylated C12-C20 alcohols of the type. Particularly effective are 2 to 45 moles of propoxylated or ethoxylated/propoxylated fatty alcohols. Nonionic surfactants of the fatty alcohol and castor oil type are preferred.

Anionic surfactants are also preferred herein. Ionic emulsifiers of the alkylnaphthalenesulfonate type, preferably in the form of calcium or sodium salts, may also be ethanolamine or ammonium salts. Calcium dodecylbenzenesulfonate or the corresponding sodium salt is preferred.

In general for hydrophobic and water-insoluble pesticidally active ingredients, due to the hydrophobicity of the active ingredient, it is necessary to add a suitable dispersing agent to the formulation in order to obtain a homogeneous aqueous dispersion when it is used in dilution. Furthermore, the resulting homogeneous aqueous dispersion must remain stable over time, at least stable during normal spray application, and any settling, flocculation can lead to uneven, ineffective application, and clogging of the spray equipment. It is therefore necessary to find suitable dispersants to obtain readily dispersible, homogeneous dilutions while maintaining stability of aqueous dilutions during spraying. The continuous phase (component (b)) may therefore further comprise one or more dispersants. Particularly preferred dispersants are selected from: one or more of alkyl sulfonate, lignosulfonate, naphthalene sulfonate, fatty alcohol-polyoxyethylene ether, nonylphenol polyoxyethylene ether phosphate, methacrylic acid-methacrylate-polyethylene glycol graft copolymer, tristyrylphenol polyoxyethylene ether and propylene glycol/ethylene glycol block copolymer.

The stable chlorpyrifos and dinotefuran-containing insecticidal composition can also contain a functional auxiliary agent. The functional auxiliary agent is one or more of emulsifying dispersant, viscosity regulator, anti-freezing agent, biocide, defoaming agent and capsule wall material; the emulsifying dispersant is one or more of alkyl sulfonate, lignosulfonate, naphthalenesulfonate, fatty alcohol-polyoxyethylene ether and nonylphenol polyoxyethylene ether phosphate; the viscosity regulator is one or more of fumed silica, polyvinyl alcohol, bentonite, xanthan gum, cellulose ether and its derivatives, and polyvinyl alcohol; the antifreeze agent is selected from ethylene glycol, propylene glycol, glycerol, isopropanol or urea; the biocide is selected from potassium sorbate, sodium benzoate, formaldehyde or isothiazolinone; the defoaming agent is selected from organosilicon or low-carbon alcohol defoaming agents; the wall material is polyurea resin prepared by the interfacial polymerization reaction of isocyanate and polyamine aqueous solution.

In the stable chlorpyrifos-dinotefuran-containing insecticidal composition, the weight ratio of the chlorpyrifos to the dinotefuran is 50:1-1:50, preferably 25:1-1:25, further preferably 10:1-1:10, and further preferably 5:1-1: 5.

The weight ratio of chlorpyrifos and dinotefuran in the invention is 50:1-1:50, for example, 50:1, 50:2, 50:3, 50:5, 50:6, 50:8, 50:10, 50:15, 50:20, 50:25, 50:28, 50:30, 50:35, 50:40, 50:45, 50:50, 1:2, 1:5, 1:10, 1:15, 1:18, 1:20, 1:22, 1:25, 1:28, 1:30, 1:35, 1:40, 1:45, 1: 50.

In the stable chlorpyrifos and dinotefuran-containing insecticidal composition, the content of the chlorpyrifos and the dinotefuran accounts for 10 wt% -80 wt%, preferably 10 wt% -60 wt%, further preferably 15 wt% -55 wt%, and more preferably 20 wt% -40 wt% of the insecticidal composition. Wherein "wt%" means "weight percent content".

The content of chlorpyrifos and dinotefuran in the present invention is 10 wt% to 80 wt% of the pesticidal composition, and may be, for example, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%.

In the stable chlorpyrifos-and-dinotefuran-containing insecticidal composition, the content of chlorpyrifos accounts for 8-50 wt% of the insecticidal composition, and the content of dinotefuran accounts for 2-30 wt% of the insecticidal composition. Wherein "wt%" means "weight percent content".

The content of chlorpyrifos in the present invention is 8 wt% to 50 wt% of the pesticidal composition, and may be, for example, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, 32 wt%, 35 wt%, 40 wt%, 45 wt%, 48 wt%, 50 wt%.

The dinotefuran is present in an amount of 2 wt% to 30 wt% of the pesticidal composition, and may be, for example, 2 wt%, 3 wt%, 5 wt%, 6 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%.

The stable chlorpyrifos and dinotefuran-containing insecticidal compositions of the present invention may be prepared in a known manner and using techniques known to those skilled in the art.

The invention provides a method for preparing the stable chlorpyrifos and dinotefuran-containing insecticidal composition, which comprises the following steps:

step 1: providing an oil phase of chlorpyrifos; chlorpyrifos exists in a molecular state in the oil phase;

and 2, step: providing a continuous phase of dinotefuran; dinotefuran is suspended as fine particles in the continuous phase;

and 3, step 3: mixing the oil phase prepared in the step 1 and the continuous phase prepared in the step 2.

The stable preparation of the insecticidal composition containing chlorpyrifos and dinotefuran prepared according to the invention can be kept stable even if stored under high temperature or cold conditions, and no crystal growth is found. If diluted with water, the preparation can be converted into a homogeneous spray without the spray nozzles becoming clogged as a result of crystallization of the active ingredient present in the spray.

The stable insecticidal compositions according to the invention containing chlorpyrifos and dinotefuran are applied in a particularly advantageous manner to plants and/or their growing areas. The research shows that compared with the same active ingredients in the same type of traditional preparation, the insecticidal composition of the invention has better biological activity.

The stable chlorpyrifos and dinotefuran-containing insecticidal composition has good plant compatibility and favorable constant temperature animal toxicity, and is suitable for controlling harmful organisms, preferably arthropods and nematodes, especially insects and mites, encountered in agriculture, forestry, protection of stored products and materials, and sanitation. They are generally active against sensitive and resistant species and active against all or a single developmental stage.

The invention discloses an application of a stable chlorpyrifos and dinotefuran-containing insecticidal composition in preventing or controlling pests.

The term "pest" is used herein to mean any organism that can cause loss of the normal state of a plant. The method comprises the following steps:

lepidopteran pests include, for example: chilo suppressalis (chilopodes) (walker), tryporyza incertulas (walker), ostrinia nubilalis (ostrinia nubilalis), ostrinia nubilalis (pachilioxustifolia), phaeriana leucoptera (Pierilispora), Orthosiphon aristatus (paraguatta), Trichophyta leucoptera (Papilifera), Pieris alba (Pierirasrucaria), Plectria recti (paraguata), Trichophyta rostiana (malacosoma neosticea), Lymantria dispar (Lymantria dispar), Hypoglossa americana (hylophia dispar), Trichoplusia orientalis (eupolyphaga), Trichoplusia nigra (Spodoptera), Spodoptera fructicola (Spodoptera), Spodoptera litura (Spodopterocarpus litura), Spodopterocarpus androgynia (Spodopterocarpus lucilia), Spodoptera (Spodopterocarpus punctifera), Spodoptera fructicola (Spodoptera), Spodoptera (Spodopterocarpus nipona), Spodoptera fructicola (Spodoptera), Spodoptera (Spodoptera fructicola), Spodoptera (Spodoptera), Spodoptera (Spodoptera fructicola), Spodoptera (Spodoptera), Sphaerothecoides), Spodoptera (Sphaerotheca (Spodoptera), Sphaerothecoides (Sphaemangifera (Spodoptera (Sphaerothecoides), Sphaerotroemia indica), Sphaemangifera (Spodoptera), Sphaemangifera (Sphaemangifera), Sphaemangifera (Sphaemangifera), Sphaemangifera (Sphaemangifera) and Sphaemangifera (Sphaemangifera) Sphaemangifera (Sphaemangifera), Sphaemangifera (Sphaemangifera), Sphaemangifera) and Sphaemangifera), Sphaemangifera) Sphaemangifera (Sphaemangifera) Sphaemangifera (Sphaemangifera), Sphaemangifera) and Sphaemangifera (Sphaemangifera) and Sphaemangifera) Sphaemangifer.

Coleopteran pests include, for example: rice elephants (sinophilius oryzae eines), corn elephants (s. zeamais), grain elephants (s. granaria), gibbon ape beetles (cabbagageleaf beetles), ape leaf beetles (Daikon leaf beetles), flea beetles (flambette), grape flea beetles (altiachalybla), curly striped flea beetles (phyllotritala), cucumber flea beetles (epixcucuumeris), tobacco flea beetles (ehirtiphennis), eggplant flea beetles (e.fuscula), yellow datura (aulachorandica (gemlin), mustard leaf beetles (Phaedon cochleariae), and the like.

Dipteran pests include, for example: rice plant fly (agromozaoryza), barley water fly (hydralligriseola), gerbera camomilla (liriomyzatrifolii), pea leaf fly (chromoniahorticola), tomato leaf fly (liriomyzabryoniae), gray fly (delactatura), green onion fly (delavata) mediterranean fly (ceratitis capitata wiedman), apple fly (rhagoletisponella), cherry fly (r.

Hemipteran pests include, for example: stinkbug (megatiptattia), lygus lucorum (eurydemarrusum), lygus major (eusaroriscelewisi), lygus alba (eusaroriscapus), lygus lucorum (nezaraviridae), lygus stephani (plantasila), harlequin (harymorphhamista), lygus lucorum (clethosturger), lygus lineolatus (leptospiricus), lygus lucorum (leptospiriginensis), lygus giraldii (stephanicidula), lygus lucorum (trichotyrosomes).

Homopteran pests include, for example: leafhopper black (nonphytttixcinceps), laodelphax striatellus (laodelphax striatellus), brown rice planthopper (nilaparvatalens), white back planthopper (sogatella furcifera), pear psylla (psyllium), diaphorina citri (diaphorinatacaci), bemisia tabaci (bemisia tabaci), aphid (homoptera), and cotton aphid (eriomonangium malignatum).

Membranous (hymenoptera) pests include, for example: oak leaf wasps (athaliarasaoruficornis), Rosemaria multiflora (Argepagana), Formica japonica (Formica japonica), and Licardium kawakamii (dryocsumuriphilus).

Pests of the order thysanoptera, for example thrips (haplothrips chinensis priesner).

Pests of the class Arachnida (Arachnida), such as Tetranychus citri (pannychus citri), Tetranychus ulmi (pannychus ulmi), Tetranychus urticae (tetranychus urticae), Tetranychus hawthorn (tetranychus vinnensis), Tetranychus stipulus (oligonychus undalis), Tetranychus citrifolia (eotranychus kankiss), Brevicia purpurascens (brevipopus phoenicis), Medicago sativa (Bryopiabia praetiosa), Tetranychus tritici (aci tulipara), Vitis vinifera (vitis vinifera), Phytophagus sinensis (caerulus carinatus), Phytophagus theophyllus (Polygonatum), Phytophagus longipes (Rhizophora), and the like.

From the order of the Anoplura, Phthiraptera, for example, the animal louse genus (Damalinia spp.).

Blood louse (Haematopinus spp.), pediculosis (Linoganthus spp.), pediculosis (Pediculus spp.), and pediculosis (Trichoderma spp.).

Isopoda (Isopoda), for example, Gardenia jasminoides Ellis (Oniscus asellus), Armadillium vulgare (Armadillidium vulgare), Armadillidium globosum (Porcellio scaber).

From the order of the Diplopoda (Diplopoda), for example, Blaniulus guttulatus.

From the order of the Diplopoda (Chilopoda), for example, Geophilus carpopophagus Scutigera spp.

The synthetic mesh (Symphyla), for example, white pine worm (Scutigerella immaculata).

From the order of the Thysanura, for example, Chlamydomonas (Lepisma saccharana).

From the order of the Collelmola (Collelmbola), for example, Onychiurus armatus (Onychiurus armatus).

Orthoptera (Orthoptera), for example, cricket (Acheta domesticus), Phillidium species (Gryllotalpa spp.), Asiatic migratory locusts (Locusta migratoria ioids), Black locusts species (Melanoplus pp), desert locusts (Schistocercagregaria).

From the order of the Blattaria (Blattaria), for example, Blatta orientalis (Blatta orientalis), Periplaneta americana (Periplaneta americana), Blattella maderae (Leucophaea maderae), Blattella germanica (Blattella germanica).

From the Dermaptera (Dermaptera), for example, Forficula auricularia (Forficula auricularia).

From the order of the Isoptera (isoptera), for example, the Reticulitermes spp.

Representative organisms of the class Nematoda (Nematoda) are nematodes selected from root-knot nematodes, cyst-forming nematodes, stalk nematodes and leaf nematodes. Preferred are soybean cyst nematode (Heterodera), potato nematode (Golbodera rostochiensis), Meloidogyne incognita (Meloidogyne incognita), and the like, among the nematodes of the order Lanciformes (dorylaimida), and the like, among the species Leptotertagia sp.

All plants and plant parts can be treated according to the invention. By "plant" is herein understood all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants are plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or by combinations of these methods, including the transgenic plants, also including plant varieties which can be protected or not protected by plant breeders' rights. Plant parts are to be understood as meaning all parts and organs of the plant above and below the ground, such as shoots, leaves, flowers and roots, examples which may be mentioned being leaves, needles, leaves, stems, flowers, fruit bodies, fruits and seeds, and also roots, tubers and rhizomes. The plant parts also include harvests and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, shoots and seeds.

It is emphasized that the stable chlorpyrifos and dinotefuran-containing insecticidal composition of the present invention is particularly advantageous for use in, for example, the following plants: cereals such as wheat, oats, barley, spelt, triticale and rye, but also maize, sorghum and millet, rice, sugarcane, soybean, sunflower, potato, cotton, oilseed rape (rape), canola, tobacco, sugar beet, fodder beet, asparagus, hop and fruit plants (including pomes such as apple and pear, stone fruits such as peach, nectarine, cherry, plum, apricot, citrus fruits such as orange, grape cypress, lime, pistachio, kumquat, citrus and samomo mandarin, nuts such as avocado, almond, walnut and pecan, tropical fruits such as mango, papaya, pineapple, date and banana, and grapes) and vegetables (including leafy vegetables such as endive, fennel, leafy lettuce, swiss beet, spinach and chicory, broccoli, lettuce, black wheat and rye, corn, sorghum, maize, rape, maize, rape, maize, rape, maize, rape, maize (maize, maize (maize, maize (maize, lettuce leaves, Brassica oleracea (L.) convar. acephalavar. sabellica L. (savoy cabbage, kale), kohlrabi, brussel sprouts, red cabbage, white cabbage and savoy cabbage, fruit vegetables such as eggplant, cucumber, pepper, edible pumpkin, tomato, zucchini and sweet corn, root vegetables such as celeriac, rape, carrot including yellow varieties, wild radish vegetables including Ranus sativus var.niger and Ranus sativus var.radiacula, sugar beet, celery, plants such as peas and soybeans, and allium vegetables such as leeks and leguminous onions).

The treatment of plants and plant parts with the stabilized insecticidal compositions containing chlorpyrifos and dinotefuran according to the invention is carried out directly or by treating their environment, habitat or storage space by customary treatment methods, for example by pouring (dipping), drip irrigation, spraying, evaporation, atomization, broadcasting, coating or the like.

The active ingredients can also enter the interior of the plant through the root system (systemic action). Examples of the method of applying the chemical to the soil include a method of directly applying the liquid chemical to the roots of plants or rice seedlings for raising seedlings, with or without diluting the liquid chemical in water.

The insecticidal compositions of the invention are also suitable for protecting propagation material of plants, such as seeds, fruits, tubers or kernels, or plant cuttings, against pests, in particular insects and mites. The propagation material may be treated with the composition before application, for example dressing the seed before sowing. The active ingredient may also be applied to the kernel (coating) by soaking the kernel in a liquid composition or coating the kernel with a solid composition. The composition may also be applied to the application site when the propagation material is applied during sowing, for example in a seed sowing trench.

Formulation examples

Example 1:

the insecticidal composition is prepared by the following steps:

step 1: mixing chlorpyrifos and Emulsogen ^TM EL360、RHODACAL ^TM 70/B-C dissolved in SOLVESSO ^TM 100, obtaining oil phase containing chlorpyrifos;

step 2: mixing dinotefuran, methyl oleate and Morwet ^TM D425、Breakthru ^TM AF9902 is mixed according to a proportion, and after being uniformly stirred, the mixture is ground by a horizontal stirring ball mill to obtain a continuous phase containing dinotefuran; d50 is controlled to be not more than 3 microns, d90 is controlled to be not more than 6 microns;

and step 3: and (3) under the condition of continuous stirring, adding the oil phase containing the chlorpyrifos obtained in the step (1) into the continuous phase containing the dinotefuran obtained in the step (2), and adding the viscosity regulator fumed silica during the stirring process.

Example 2:

the insecticidal composition is prepared by the following steps:

step 1: mixing chlorpyrifos and Emulsogen ^TM EL360、RHODACAL ^TM Dissolving 70/B-C in part of methyl oleate to obtain an oil phase containing chlorpyrifos;

step 2: dinotefuran, the balance of methyl oleate and Morwet T ^M D425、Breakthru ^TM AF9902 is mixed according to a proportion, and after being uniformly stirred, the mixture is ground by a horizontal stirring ball mill to obtain a continuous phase containing dinotefuran; d50 is controlled to be not more than 3 microns, d90 is controlled to be not more than 6 microns;

and step 3: and (3) adding the oil phase containing the chlorpyrifos obtained in the step (1) into the continuous phase containing the dinotefuran obtained in the step (2) under continuous stirring, and adding the viscosity regulator fumed silica in the stirring process.

Comparative example 1: 36% Chlorpyrifos + 4% dinotefuran aqueous Suspension (SC)

After the components are uniformly stirred, grinding the components by using a horizontal stirring ball mill to obtain a continuous phase containing chlorpyrifos and dinotefuran; d50 is controlled to be not more than 3 microns, and d90 is controlled to be not more than 6 microns.

Comparative example 2: 36% Chlorpyrifos + 4% dinotefuran Emulsifiable Concentrate (EC)

Chlorpyrifos	36％
		Dinotefuran	4％
Emulsogen TM EL360	5％
		RHODACAL TM 70/B-C	5％
N-methyl pyrrolidone	Make up to 100%

The components are stirred evenly to obtain a clear and transparent phase.

Comparative example 3: 36% Chlorpyrifos + 4% dinotefuran Wettable Powder (WP)

According to the conventional processing process of wettable powder, the traditional Chinese medicines in the jet mill are melted and agglomerated and cannot be processed normally.

Comparative example 4: 36% chlorpyrifos and 4% dinotefuran Water Dispersible Granule (WDG)

Chlorpyrifos	36％
		Dinotefuran	4％
Morwet D425	3％
		Disintegrating agent	2％
Fumed silica	3％
		Corn starch	Make up to 100%

According to the conventional water dispersible granule processing process, the traditional Chinese medicines in the jet mill are melted and agglomerated and cannot be processed normally.

Heat storage stability test

The samples prepared in examples 1-2 and comparative examples 1-4 were tested for heat storage stability. The heat storage stability was carried out in an oven at 54 ℃. After heat-storage in an oven at 54 ℃ for 14 days, the samples were removed from the oven. After cooling to room temperature, the test article was poured out. The test article was passed directly through a 325 mesh screen. Note that the particles left on the screen were observed. If the granules are hard, the granules are rinsed with water to remove the surface coating of the granules, and if a clear crystal form can be observed, the granules are crystals of chlorpyrifos and/or dinotefuran, observed with a 10X magnifying glass. The results of the 14-day heat storage are shown in the following table.

Stability test of Water dilution

The samples prepared in examples 1-2 and comparative examples 1-4, before and after heat storage, were used to test the stability of the aqueous dilution.

The prepared sample was diluted 200-fold with hard water (CIPAC standard water D, 342ppm), and the presence or absence of crystal formation in the dilution was observed after the dilution was left at room temperature for 24 hours.

If the samples after heat storage have the phenomena of particle aggregation, crystal precipitation and creaming, the stability of the dilution of the samples after heat storage is not tested.

The heat storage stability test result shows that the stable chlorpyrifos and dinotefuran-containing insecticidal composition has the advantages that the phenomena of particle aggregation, crystal precipitation, creaming and the like do not occur in a sample after heat storage, and the sample has good heat storage stability.

The stability test result of the water diluent shows that the stable insecticidal composition containing chlorpyrifos and dinotefuran does not precipitate crystals in the sample water diluent before and after thermal storage, and the stability of the water diluent is good.

The applicant states that the present invention is illustrated by the above examples of the process of the present invention, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (6)

1. The insecticidal composition containing chlorpyrifos and dinotefuran is characterized by comprising the following components:

(a) a dispersed oil phase comprising:

(i) an oil phase in which chlorpyrifos is dissolved; and

(b) a continuous phase comprising:

(ii) wherein a continuous phase of dinotefuran is suspended, the solubility of the continuous phase relative to dinotefuran being < 10 g/kg;

the oil phase contains one or at least two solvents, and chlorpyrifos is dissolved in the solvents in a molecular state; the solvent in the oil phase is selected from the group consisting of mixtures of isoparaffin oils, mineral oils, naphtha heavy solvents, natural vegetable oils, hydrogenated or epoxidized or alkylated vegetable oils;

the continuous phase contains one or at least two solvents in which dinotefuran is suspended as fine particles; the solvent in the continuous phase is selected from the group consisting of mixtures of isoparaffin oils, mineral oils, heavy naphtha solvents, natural vegetable oils, hydrogenated or epoxidized or alkylated vegetable oils;

the solvent in the oil phase and the solvent in the continuous phase are the same or different;

the content of the chlorpyrifos accounts for 28-40 wt% of the insecticidal composition, and the content of the dinotefuran accounts for 2-10 wt% of the insecticidal composition;

the oil phase further comprises one or at least two surfactants;

the continuous phase further comprises one or at least two dispersants;

the insecticidal composition also comprises an antifoaming agent and a viscosity regulator;

the viscosity regulator is at least one of fumed silica, bentonite, xanthan gum, cellulose ether and derivatives thereof, and polyvinyl alcohol; the defoaming agent is an organic silicon or low-carbon alcohol defoaming agent.

2. The insecticidal composition according to claim 1, wherein the weight ratio of chlorpyrifos and dinotefuran is 50:1-50: 10.

3. The insecticidal composition according to claim 1, wherein the chlorpyrifos and dinotefuran are present in an amount of 30 wt% to 50 wt% of the insecticidal composition.

4. The insecticidal composition according to claim 3, wherein the chlorpyrifos and dinotefuran are present in an amount of 40 wt% of the insecticidal composition.

5. Use of the pesticidal composition according to claim 1 for preventing or controlling pests.

6. A process for preparing the pesticidal composition of claim 1, comprising the steps of:

step 1: providing an oil phase of chlorpyrifos; chlorpyrifos is present in a molecular state in the oil phase;

step 2: providing a continuous phase of dinotefuran; dinotefuran is suspended as fine particles in the continuous phase;

and step 3: mixing the oil phase prepared in the step 1 and the continuous phase prepared in the step 2.