CN111820221A

CN111820221A - Insecticidal composition containing flonicamid and pyridaben and application thereof

Info

Publication number: CN111820221A
Application number: CN202010862674.8A
Authority: CN
Inventors: 余徳勉; 王陈杰; 王丹斌; 张常庆; 万娜娜; 曹俊丽; 张钊
Original assignee: SHANGHAI YUELIAN CHEMICAL CO Ltd; Shanghai Yuelian Biotechnology Co ltd
Current assignee: SHANGHAI YUELIAN CHEMICAL CO Ltd; Shanghai Yuelian Biotechnology Co ltd
Priority date: 2020-08-25
Filing date: 2020-08-25
Publication date: 2020-10-27
Anticipated expiration: 2040-08-25
Also published as: CN111820221B

Abstract

The invention relates to the technical field of pesticides, and particularly relates to an insecticidal composition containing flonicamid and pyridaben and application thereof. The applicant provides an insecticidal composition which has good and high control effect on various plant pests such as tea lesser leafhopper, aphid and the like through synergistic effect by using flonicamid and pyridaben as active ingredients; and the applicant can prepare the insecticidal composition with higher active ingredient concentration by selecting proper wetting dispersant and thickener, improve grinding processability, reduce the increase of the particle size of the active ingredient in the storage process and reduce the phenomena of bubble generation and residue in the processing and diluting processes.

Description

Insecticidal composition containing flonicamid and pyridaben and application thereof

Technical Field

The invention relates to the technical field of pesticides, and particularly relates to an insecticidal composition containing flonicamid and pyridaben and application thereof.

Background

The pesticide can be used for preventing, eliminating or controlling insect pests which harm agriculture and forestry, and purposefully adjusting, controlling and influencing the metabolism, growth, development and propagation processes of plants and pests, has important significance for plant growth, and the problems of less insecticidal spectrum and insecticidal effect exist in a single pesticide, so that the compounding of various insecticidal active ingredients is a development trend.

Flonicamid (Flonicamid) is a novel pyridylamide insect growth regulator insecticide, aphids, whiteflies, pastures and bed bugs can be effectively controlled at a lower dose, Pyridaben (Pyridaben) is a broad-spectrum and contact acaricidal insecticide, has special effects on leaf mites, also has good control effects on rust mites, gall mites and tarsonchus tarda, has strong contact acaricidal properties, can improve pest control by compounding Flonicamid and Pyridaben, and plays a role in delaying resistance.

However, flonicamid and pyridaben have larger difference in structure and solubility, and the insecticidal composition prepared by compounding the two active ingredients, particularly the insecticidal composition with higher concentration has the problems of processing and stability.

Disclosure of Invention

In order to solve the problems, the invention provides a pesticidal composition containing flonicamid and pyridaben, which is prepared from the following raw materials in percentage by weight of 20-50 wt% of active ingredients, 1-10 wt% of wetting and dispersing agent, 0.2-0.5 wt% of thickening agent and the balance of water; the active ingredients comprise flonicamid and pyridaben in a weight ratio of (1-5): (1-5).

As a preferable technical scheme of the invention, the wetting dispersant comprises an anionic wetting dispersant and a nonionic wetting dispersant, and the weight ratio is (1.5-3): 1.

as a preferable technical scheme of the invention, the anion wetting dispersant comprises one or more of alkyl naphthalene sulfonate formaldehyde condensate, lignosulfonate, benzyl naphthalene sulfonate formaldehyde condensate and polystyryl phenol polyoxyethylene ether phosphate.

As a preferable technical scheme of the invention, the non-ionic wetting dispersant is selected from one or more of alkylaryl phenol polyoxyethylene ether condensate, fatty alcohol polyoxyethylene ether condensate and EO-PO block copolymer.

In a preferred embodiment of the present invention, the thickener is one or more selected from the group consisting of gum arabic, xanthan gum, carrageenan, zein, guar gum, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, polyvinyl acetate, and magnesium aluminum silicate.

As a preferred technical scheme of the present invention, the xanthan gum is modified xanthan gum, the modifier of the modified xanthan gum is 1, 2-alkylene oxide and sodium chloroacetate, and the molar ratio is 1: (1.5-2.5).

In a preferred embodiment of the present invention, the number of carbon atoms of the 1, 2-alkylene oxide is 3 to 7.

As a preferred technical scheme of the invention, the anion wetting dispersant also comprises sodium salt of styrene-acrylic acid copolymer.

As a preferable technical scheme, in the sodium salt of the styrene-acrylic acid copolymer, the weight percentage of acrylic acid in the styrene-acrylic acid copolymer is 10-30 wt%.

The second aspect of the invention provides application of the insecticidal composition containing flonicamid and pyridaben in controlling tea lesser leafhoppers and aphids.

Compared with the prior art, the invention has the following beneficial effects: the applicant provides an insecticidal composition which has good and high control effect on various plant pests such as tea lesser leafhopper, aphid and the like through synergistic effect by using flonicamid and pyridaben as active ingredients; and the applicant can prepare the insecticidal composition with higher active ingredient concentration by selecting proper wetting dispersant and thickener, improve grinding processability, reduce the increase of the particle size of the active ingredient in the storage process, reduce the phenomena of bubble generation and residue in the processing and diluting processes, and reduce the risk of layering or bottom forming of the product in the storage process.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.

The invention provides a pesticidal composition containing flonicamid and pyridaben, which comprises 20-50 wt% of active ingredients, 1-10 wt% of wetting and dispersing agent, 0.2-0.5 wt% of thickening agent and the balance of water.

In a preferred embodiment, the raw materials for preparing the insecticidal composition comprise 40 wt% of active ingredients, 6 wt% of wetting and dispersing agents, 0.37 wt% of thickening agents and the balance of water according to weight percentage.

Active ingredient

In one embodiment, the active ingredients comprise flonicamid and pyridaben in a weight ratio of (1-5): (1-5); further, the active ingredients of the invention comprise flonicamid and pyridaben in a weight ratio of 1: (1-5).

Flonicamid (Flonicamid) is a novel pyridine amide type insect growth regulator insecticide, and can effectively control aphids, whiteflies, herdsbugs and bed bugs at a lower dose; the insecticidal composition has unique action mechanism, has contact poisoning and stomach poisoning effects, also has good nerve effects and quick antifeedant effects, is effective by blocking the sucking effect of pests, stops sucking quickly after the pests take the insecticide, and finally dies by hunger, is effective to various piercing-sucking mouthpart pests, can permeate from roots to stems and leaves, but has relatively weak permeation effect from the leaves to the stems and roots, and has strong permeability, long persistence and good rain resistance in plants; resistance to other active ingredients, low sensitivity compared to existing insecticides such as neonicotinoid insecticides, no cross-resistance to traditional insecticides; in one embodiment, the flonicamid is available from shanxi huichi biotechnology limited.

Pyridaben (Pyridaben) is a broad-spectrum and contact-killing acaricidal insecticide, has special effect on spider mites, also has good control effect on rust mites, gall mites and tarsal mites, has strong contact killing property and no systemic conduction action, is effective on various growth periods (eggs, young nymphs and adult mites) of the mites, can be used for controlling various phytophagous harmful mites, has a continuously expanded insecticidal spectrum in recent years, has good control effect on pests such as tea lesser leafhoppers, thrips, aphids, phyllotreta and the like, and has no phytotoxicity on crops; in one embodiment, the pyridaben is purchased from Hubei Jiu Fenglong chemical Co. The applicant finds that by using synergistic effect of flonicamid and pyridaben, the insecticidal effect and insecticidal spectrum can be enlarged, and the insecticidal composition has good control effect on various plant pests, such as aphids, tea leafhoppers and the like.

Aphids are common pests of cruciferous vegetables, aphids harmful to cabbage mainly comprise myzus persicae (myzuspierica sulzer), aphids of radish (lipaphinerysimii kaltenbach) and aphids of cabbage (Brevicorynebrassicae L.), the two aphids are distributed almost all over the world and are commonly generated in China, the two aphids are frequently mixed on the cruciferous vegetables in the south of the river-Huai river basin, the aphids of cabbage are not as wide as the two aphids, but are sometimes dominant species in local areas such as Guizhou and Xinjiang. The damage of aphids to cabbage is generally caused by adult aphids, if aphids gather in the tender leaves and stems of cabbage and suck leaf juice, the leaves are curled and deformed, the plant grows slowly, moreover, the excreted honeydew can induce mildew and dirt disease to occur, the photosynthesis of the leaves is influenced, more importantly, various virus diseases can be transmitted, and finally, the serious yield reduction is caused.

Tea lesser leafhopper (empoasca flavescens fabricius) belongs to the family of hemiptera leafhopper, commonly known as flounder, leaf springtail and the like, and is a main pest in tea producing areas in China. The generation is about 8-12 generations in one year, the generations are serious alternately, adults live through the winter in the erigeron tea or weeds, and eggs are laid on tender tips of the tea in a growing season. Absorbing young leaf juice of young tips of tea trees by adults and nymphs, and consuming nutrients and water; the female is oviposited in young shoot tissue, hindering bud growth. The damaged tea tree internode is shortened, the bud leaves are withered and hardened, the leaf veins become red, the bud tips, the leaf tips and the leaf margins become red, brown and scorched, the bud tips grow slowly or stop, the new buds are reduced and even can not germinate, the new leaves are all scorched and fall off seriously, the bud heads drawn out in each tea season later are thin and small, the new tips are thin and short, the leaves are small and thick, the yield is greatly influenced, the quality of finished tea is also influenced, and the tea tree is more in fragments and has scorched dust and astringent taste. The tea garden with serious summer tea damage all the year around can ensure that summer tea is not harvested, and tea leafhoppers generally cause tea loss of 10-30 percent and are positioned at the head of tea plant diseases and insect pests. Besides tea trees, the weeds include peach, plum, pear, apple, camellia oleifera, soybean, broad bean, pea, fava bean, peanut, cruciferous vegetable, rice, wheat, cotton, tobacco, sugarcane, mulberry and various weeds.

Wetting and dispersing agent

In one embodiment, the wetting dispersant of the present invention comprises an anionic wetting dispersant and a nonionic wetting dispersant, wherein the weight ratio of (1.5-3): 1.

preferably, the anionic wetting and dispersing agent comprises one or more of alkyl naphthalene sulfonate formaldehyde condensate, lignosulfonate, benzyl naphthalene sulfonate formaldehyde condensate and polystyryl phenol polyoxyethylene ether phosphate; further, the anionic wetting dispersant comprises an alkyl naphthalene sulfonate formaldehyde condensate.

The alkyl naphthalene sulfonate formaldehyde condensate is a salt obtained by condensation polymerization of alkyl naphthalene sulfonic acid and formaldehyde, and has a large naphthyl structure and sulfonate ions, and the alkyl naphthalene sulfonate formaldehyde condensate is not particularly limited in the invention, and Morwet D-425 and Morwet D-400 of Acksonobel can be enumerated.

More preferably, the nonionic wetting dispersant of the present invention is selected from one or more of alkylaryl phenol polyoxyethylene ether condensate, fatty alcohol polyoxyethylene ether condensate, and EO-PO block copolymer; further, the non-ionic wetting dispersant is an EO-PO block copolymer; further, the weight average molecular weight of the EO-PO block copolymer is 2000-4000.

The weight average molecular weight is the molecular weight statistically averaged over the molecular weight.

The EO-PO block copolymer is a block copolymer obtained by connecting a polyoxyethylene chain segment with a polyoxypropylene chain segment at two ends, is easily soluble in organic solvents such as ethanol, isopropanol, toluene, mineral oil and the like, and is insensitive to hard water ions of calcium and magnesium ion machines in water; the EO-PO block copolymer of the present invention is not particularly limited, and examples thereof include Pluronic PRF series EO-PO block copolymers of Basff, such as RFE 1720, RFE 1740, RFE2035, RFE 2520, RFE2525 and RFE 3110.

The applicant finds that when the active ingredients are flonicamid and pyridaben which act synergistically, high insecticidal effect is achieved, but the large solubility and structural difference of flonicamid and pyridaben make the preparation process of the composition difficult, especially when the composition with high concentration is prepared, the viscosity of the material is rapidly increased under the action of high shear stress along with the grinding, so that the grinding is difficult and even impossible, and the applicant finds that by selecting proper anionic wetting dispersant and nonionic wetting dispersant to act together, the naphthalenesulfonic acid structure in the alkyl naphthalenesulfonate formaldehyde condensate with smaller molecules can be strongly adsorbed with the active ingredients to cover the periphery of the active ingredients, and the EO/PO block copolymer with higher molecular weight is distributed on the outer layer of the naphthalenesulfonic acid structure to obtain a stable adsorption layer, so that under the action of the grinding shear force, in the process that the adsorption layers among the active ingredient particles are close to each other, the mutual aggregation and viscosity increase of the active ingredients can be reduced under the action of compression resistance and electrostatic repulsion of polyoxyethylene chain segments among the adsorption layers.

Thickening agent

In one embodiment, the thickener of the present invention is selected from one or more of gum arabic, xanthan gum, carrageenan, zein, guar gum, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, polyvinyl acetate, magnesium aluminum silicate; further, the thickening agent comprises xanthan gum and magnesium aluminum silicate, and the weight ratio of the xanthan gum to the magnesium aluminum silicate is 1: (3 to 5)

Magnesium aluminum silicate is a white complex colloidal substance. The water content is less than 8%. Is nontoxic. Is tasteless. Is insoluble in water. Dispersing in water. The pH value is 7.5-9.5. The rheological property and the thixotropy are good. Has unique three-dimensional chain structure and special needle and rod crystal structure, and thus has unusual colloid and adsorption performance. The excellent thickening property, suspension property and colloid shaking melting property of the composite material are widely applied to the paint coating industry. Form an association network structure in a 'card palace' type in an aqueous medium. In one embodiment, the magnesium aluminum silicate is available from Nanjing Haimines New materials science and technology, Inc.

Xanthan gum (Xanthan gum), also known as Xanthan gum, is a microbial extracellular polysaccharide with wide action produced by Xanthomonas campestris (Xanthomonas campestris) by fermentation engineering with carbohydrate as main raw material (such as corn starch). The microbial polysaccharide has unique rheological property, good water solubility, stability to heat and acid and alkali, and good compatibility with various salts, can be widely applied to more than 20 industries such as food, petroleum, medicine and the like as a thickening agent, a suspending agent, an emulsifying agent and a stabilizing agent, and is the microbial polysaccharide which has the largest production scale and extremely wide application in the world at present; in one embodiment, the xanthan gum is available from jabotian biotechnology limited, Jiangsu.

The applicant finds that thixotropic property can be generated in the grinding process by adding the thickening agent and utilizing the xanthan gum and magnesium aluminum silicate in the thickening agent to form a spatial three-dimensional structure with water, so that the damage of the whole three-dimensional structure and the reformation of a small part of the three-dimensional structure are caused, the increase of the viscosity in the grinding process is further reduced, and the grinding processability is improved. Preferably, the thickener of the invention comprises xanthan gum and magnesium aluminum silicate in a weight ratio of 1: (3-5).

More preferably, the xanthan gum of the present invention is a modified xanthan gum, and the modifier of the modified xanthan gum is 1, 2-alkylene oxide and sodium chloroacetate, and the molar ratio is 1: (1.5-2.5).

More preferably, the number of carbon atoms of the 1, 2-alkylene oxide is 3 to 7. The 1, 2-alkylene oxide is not particularly limited, and 1, 2-propylene oxide, 1, 2-butylene oxide, 1, 2-pentylene oxide, 1, 2-hexylene oxide and 1, 2-heptylene oxide are listed.

Still more preferably, the modifier accounts for 2-3 wt% of the modified xanthan gum.

The modified xanthan gum of the present invention can be made or purchased by the manufacturer, and when made by the manufacturer, in one embodiment, the process for preparing the modified xanthan gum of the present invention comprises the steps of: adding xanthan gum into a solvent, adding strong base, mixing, dropwise adding a modifier, heating to 60-65 ℃, reacting for 5-6 h, washing, and drying to obtain the modified xanthan gum; the solvent is not particularly limited, and there may be exemplified ethanol, water, propanol and a mixture thereof; the invention does not limit the alkali specifically, plays the role of catalysis, and can be listed as potassium hydroxide and sodium hydroxide; in one embodiment, in the preparation method of the modified xanthan gum, the strong base accounts for 2-3 wt% of the xanthan gum

The applicant has surprisingly found that when using modified xanthan gum as a thickener, while further improving the grinding performance, the growth of crystallites, especially of pyridaben particles, during storage can be avoided, probably because pyridaben has a low solubility in water, when the concentration of active ingredient, such as pyridaben, is higher, the probability of intermolecular collisions increases significantly compared to lower concentrations, causing the growth of crystallites, especially at higher temperatures, the intermolecular forces of the wetting dispersant decrease, the stability of the adsorbed layer formed by the small molecule alkylnaphthalenesulfonate formaldehyde condensate and the low polarity EO/PO block copolymer decreases, causing intermolecular collisions of the active ingredient, especially of the low-soluble pyridaben, causing a rapid increase in particle size, thus affecting the stability of the insecticide and the composition.

By adding the modified xanthan gum, the hydroxyl on the surface of the xanthan gum is connected with hydrophilic groups such as alkylene oxide, acetate and the like, so that the xanthan gum is promoted to form a more compact and stronger three-dimensional structure with magnesium aluminum silicate, water and the like through hydrogen bonds, intermolecular action and the like, meanwhile, carboxyl grafted by the xanthan gum can also be strongly adsorbed with active ingredients and coact with an alkyl naphthalene sulfonate structure of small molecules, the exposure of the active ingredients, especially the active ingredients at high temperature, is reduced, and certain entanglement can be generated with an EO/PO chain by grafting the alkylene oxide with a certain chain length and utilizing an alkane chain and hydroxyl structure with a certain length, so that the stability of an adsorption layer is further promoted, and the increase of the particle size of the active ingredients is reduced.

And the applicant found that further increase in viscosity of the composition is easily caused due to the high branched structure and the action of the strong polar group after modification, but at the time of addition of a proper amount, the grinding is facilitated due to the participation of the modified xanthan gum in the adsorption layer, but when the content is large or the content of the modifier is added more, the grinding performance and the storage stability are adversely affected.

In one embodiment, the raw materials for preparing the insecticidal composition of the present invention further comprise an antifoaming agent.

Defoaming agent

The invention does not limit the defoamer specifically, including but not limited to C8-210 fatty alcohol compounds, epoxidized soybean oil, ethanol, silicone compounds, silicone defoamer, C10-C20 saturated fatty acid compounds; in one embodiment, the defoamer is a silicone defoamer, such as BYK024, BYK022, S-2354 of Longshida, SAG 1572 of My.

The applicant has found that the effect of the larger concentration and the addition of the modified xanthan gum causes the viscosity of the composition system to be relatively large, so that bubbles caused by air brought into the composition in the grinding process are difficult to eliminate, the foaming is serious, the defoaming is difficult, and a defoaming agent needs to be added in the process of adding hard water for dilution, but when the amount of the defoaming agent is too large, the compatibility and the stability of the composition are affected, so that the content of the defoaming agent needs to be controlled to be lower, and the defoaming effect is also affected. In one embodiment, the defoaming agent of the present invention accounts for 0 to 0.05 wt% of the insecticidal composition; furthermore, the defoaming agent accounts for 0.01-0.04 wt% of the insecticidal composition.

Preferably, the anionic wetting and dispersing agent of the present invention further comprises a sodium salt of a styrene-acrylic acid copolymer; further, the weight ratio of the sodium salt of the styrene-acrylic acid copolymer to the alkyl naphthalene sulfonate formaldehyde condensate is (0.5-1.5): 1.

the sodium salt of the styrene-acrylic acid copolymer of the present invention may be prepared or purchased by a manufacturer, is not particularly limited, and may be obtained by proton exchange of the styrene-acrylic acid copolymer under an alkaline condition, and in one embodiment, the preparation method of the sodium salt of the styrene-acrylic acid copolymer comprises the following steps: adding a styrene-acrylic acid copolymer into an alkaline solution for neutralization, washing and drying to obtain a sodium salt of the styrene-acrylic acid copolymer; further, the alkaline solution is a mixed solution of sodium hydroxide and methanol, and the weight ratio of the alkaline solution to the methanol is 1: (10-25); in one embodiment, the styrene-acrylic acid copolymer is purchased from Yuyaohuihong.

More preferably, in the sodium salt of the styrene-acrylic acid copolymer, the weight percentage of acrylic acid in the styrene-acrylic acid copolymer is 10-30 wt%; furthermore, in the sodium salt of the styrene-acrylic acid copolymer, the weight percentage of acrylic acid in the styrene-acrylic acid copolymer is 20-30 wt%.

Further preferably, the weight average molecular weight of the styrene-acrylic acid copolymer is 5000-10000; further, the weight average molecular weight of the styrene-acrylic acid copolymer is 7000-10000.

The applicant has found that by adding the sodium salt of a styrene-acrylic acid copolymer, a certain defoaming effect can be achieved, the elimination of air bubbles in the medium-high viscosity composition during grinding is promoted, and the problem of air bubbles under the condition of hard water dilution is reduced.

This is probably because, by adding a sodium salt of a styrene-acrylic acid copolymer in a certain weight percentage of acrylic acid, wherein the styrene segment can perform a conjugation with the active ingredient, the acrylic acid segment tends to be adsorbed at the air-water interface while the thickness of the adsorption layer is promoted to be increased, and the styrene segment with a higher proportion near the acrylic acid segment increases the hydrophobicity and can enter the inside of the bubble liquid film to form an oil bridge to promote the collapse of bubbles along with the intermolecular movement, and on the other hand, the acrylic acid segment with a certain content can generate a larger repulsive force with the carboxylate ions of the modified xanthan gum to increase the intermolecular distance, thereby avoiding the difficulty in eliminating bubbles due to an excessively high viscosity to a certain extent, promoting the elimination of bubbles in the milled composition, and avoiding the generation of more bubbles during the dilution process.

And the applicant found that when the acrylic acid content of the sodium salt of the styrene-acrylic acid copolymer added is higher or lower, there is a problem of solubility or stability easily, and particularly when the acrylic acid content is higher, the increase of bubbles is promoted rather due to good adsorption with the bubble liquid film.

In one embodiment, the pesticidal composition of the present invention further comprises an adjuvant.

Auxiliary agent

The invention is not particularly limited to the auxiliaries, and there may be mentioned, for example, preservatives, antifreeze agents and pH regulators.

Examples of the preservative include: parabens, sorbate, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-bromo-2-propane-1, 3-diol, 1, 2-benzisothiazolin-3-one, and the like, as long as they are known for the purpose, and one kind or two or more kinds thereof may be used alone or in any combination; in one embodiment, the preservative accounts for 0 to 0.1 wt% of the insecticidal composition.

Specific examples of the antifreeze include: water-soluble substances having a low molecular weight, such as urea and common salt; water-soluble polyhydric alcohols represented by propylene glycol, ethylene glycol, diethylene glycol, and glycerin; any known substance may be used for this purpose, and one kind or two or more kinds may be used alone or in any combination; in one embodiment, the antifreeze agent accounts for 0 to 6 wt% of the insecticidal composition.

Examples of the pH adjuster include: acidic substances represented by sulfuric acid and potassium dihydrogen phosphate; alkaline substances represented by sodium hydroxide and calcium carbonate; and a mixture of a weak acid and a conjugate base thereof, a mixture of a weak base and a conjugate acid thereof, and the like, which exert buffering capacity in an aqueous solution, may be used alone or in any combination of two or more; in one embodiment, the pH adjuster is 0 to 1 wt% of the pesticidal composition.

In one embodiment, the formulation of the insecticidal composition of the present invention is selected from one of a soluble agent, a suspending agent, and an aqueous agent; further, the dosage form of the insecticidal composition provided by the invention is a suspending agent.

The present invention is not further limited to the specific preparation method of the pesticidal composition, which is a technical method of wet milling well known in the art, and as an example, in one embodiment, the preparation method of the pesticidal composition of the present invention comprises the following steps: mixing the preparation raw materials of the insecticidal composition, shearing, sanding and filtering to obtain the insecticidal composition.

Applicants have found that when alkyl naphthalene sulfonate formaldehyde condensate, styrene-acrylic acid copolymer sodium salt is added as an anionic wetting dispersant and EO/PO block copolymer is added as a non-ionic wetting dispersant, wherein sulfonic acid groups, carboxylic acid groups, aryl groups, etc. in the anionic wetting dispersant can form stronger anchor points to form a firm three-dimensional adsorption layer, whereas EO/PO block copolymer with relatively small polarity is adsorbed on the outside of the adsorption layer, and the hydrophilic EO segments can freely spread in water to form a hydrated layer, when at higher temperature, because of more functions formed by different wetting dispersants, the anchor points and the hydrated layer can be maintained more stable, exposure and mutual collision of active ingredients can be reduced, thereby further reducing the increase of particle size during storage.

The invention provides an application of the insecticidal composition containing flonicamid and pyridaben in the second aspect, which is used for preventing and controlling tea lesser leafhopper and aphid.

Examples

The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.

A1: active ingredient

The active ingredient is pyridaben, Hubei Jiulong chemical Co.

A2: active ingredient

The active ingredient is flonicamid, Heicheng Biotech limited, Shaanxi.

B1: anionic wetting dispersants

The anionic wetting dispersant is an alkyl naphthalene sulfonate formaldehyde condensate, available from Morwet D-425 of Acrossobel.

B2: anionic wetting dispersants

The anionic wetting dispersant is an alkyl naphthalene sulfonate formaldehyde condensate, available from Morwet D-400 of Acrossobel.

B3: anionic wetting dispersants

The anionic wetting dispersant is a benzyl naphthalene sulfonate formaldehyde condensate, purchased from Hubei Jusheng science and technology Co.

B4: anionic wetting dispersants

The anion wetting dispersant is sodium salt of styrene-acrylic acid copolymer; the preparation method of the sodium salt of the styrene-acrylic acid copolymer comprises the following steps: adding a styrene-acrylic acid copolymer into an alkaline solution for neutralization, washing and drying to obtain a sodium salt of the styrene-acrylic acid copolymer; the alkaline solution is a mixed solution of sodium hydroxide and methanol, and the weight ratio of the alkaline solution to the methanol is 1: 20; the styrene-acrylic acid copolymer is purchased from Yuyao Hui hong (acrylic acid accounts for 30 wt% of the styrene-acrylic acid copolymer, and the weight-average molecular weight is 10000).

B5: anionic wetting dispersants

The anion wetting dispersant is sodium salt of styrene-acrylic acid copolymer; the preparation method of the sodium salt of the styrene-acrylic acid copolymer comprises the following steps: adding a styrene-acrylic acid copolymer into an alkaline solution for neutralization, washing and drying to obtain a sodium salt of the styrene-acrylic acid copolymer; the alkaline solution is a mixed solution of sodium hydroxide and methanol, and the weight ratio of the alkaline solution to the methanol is 1: 20; the styrene-acrylic acid copolymer is purchased from Yuyao Hui hong (acrylic acid accounts for 10 wt% of the styrene-acrylic acid copolymer, and the weight-average molecular weight is 10000).

B6: anionic wetting dispersants

The anion wetting dispersant is sodium salt of styrene-acrylic acid copolymer; the preparation method of the sodium salt of the styrene-acrylic acid copolymer comprises the following steps: adding a styrene-acrylic acid copolymer into an alkaline solution for neutralization, washing and drying to obtain a sodium salt of the styrene-acrylic acid copolymer; the alkaline solution is a mixed solution of sodium hydroxide and methanol, and the weight ratio of the alkaline solution to the methanol is 1: 20; the styrene-acrylic acid copolymer is purchased from Yuyao Hui hong (acrylic acid accounts for 50 wt% of the styrene-acrylic acid copolymer, and the weight-average molecular weight is 10000).

B7: anionic wetting dispersants

The anion wetting dispersant is sodium salt of styrene-acrylic acid copolymer; the preparation method of the sodium salt of the styrene-acrylic acid copolymer comprises the following steps: adding a styrene-acrylic acid copolymer into an alkaline solution for neutralization, washing and drying to obtain a sodium salt of the styrene-acrylic acid copolymer; the alkaline solution is a mixed solution of sodium hydroxide and methanol, and the weight ratio of the alkaline solution to the methanol is 1: 20; the styrene-acrylic acid copolymer is purchased from Yuyao Hui hong (acrylic acid accounts for 30 wt% of the styrene-acrylic acid copolymer, and the weight-average molecular weight is 5000).

B8: anionic wetting dispersants

The anion wetting dispersant is sodium salt of styrene-acrylic acid copolymer; the preparation method of the sodium salt of the styrene-acrylic acid copolymer comprises the following steps: adding a styrene-acrylic acid copolymer into an alkaline solution for neutralization, washing and drying to obtain a sodium salt of the styrene-acrylic acid copolymer; the alkaline solution is a mixed solution of sodium hydroxide and methanol, and the weight ratio of the alkaline solution to the methanol is 1: 20; the styrene-acrylic acid copolymer is purchased from Yuyao Huichun (acrylic acid accounts for 30 wt% of the styrene-acrylic acid copolymer, and the weight-average molecular weight is 20000).

C1: non-ionic wetting dispersants

The non-ionic wetting dispersant is an EO-PO block copolymer available from BASF as RFE 1740.

C2: non-ionic wetting dispersants

The non-ionic wetting dispersant is an EO-PO block copolymer available from BASF as RFE 2525.

C3: non-ionic wetting dispersants

The nonionic wetting dispersant is fatty alcohol-polyoxyethylene ether, which is purchased from AEO9 of Haian petrochemical plant of Jiangsu province.

D1: thickening agent

The thickener is magnesium aluminum silicate, and is purchased from Nanjing Haimines New Material science and technology Limited.

D2: thickening agent

The thickener is xanthan gum, and is purchased from Jiangsu Caosheng Biotech limited.

D3: thickening agent

The thickening agent is modified xanthan gum, the modifying agent of the modified xanthan gum is 1, 2-epoxy heptane and sodium chloroacetate, and the molar ratio is 1: 1.5; the modifier accounts for 2.5 wt% of the modified xanthan gum; the preparation method of the modified xanthan gum comprises the following steps: adding xanthan gum into a solvent, adding sodium hydroxide, mixing, dropwise adding a modifier, heating to 65 ℃, reacting for 6 hours, washing, and drying to obtain the modified xanthan gum; the solvent is ethanol and water, and the weight ratio is 2: 1, the weight percentage of sodium hydroxide in xanthan gum is 2.5 wt%.

D4: thickening agent

The thickening agent is modified xanthan gum, the modifying agent of the modified xanthan gum is 1, 2-epoxypropane and sodium chloroacetate, and the molar ratio is 1: 2.5; the modifier accounts for 2.5 wt% of the modified xanthan gum; the preparation method of the modified xanthan gum comprises the following steps: adding xanthan gum into a solvent, adding sodium hydroxide, mixing, dropwise adding a modifier, heating to 65 ℃, reacting for 6 hours, washing, and drying to obtain the modified xanthan gum; the solvent is ethanol and water, and the weight ratio is 2: 1, the weight percentage of sodium hydroxide in xanthan gum is 2.5 wt%.

D5: thickening agent

The thickening agent is modified xanthan gum, the modifying agent of the modified xanthan gum is 1, 2-butylene oxide and sodium chloroacetate, and the molar ratio is 1: 2; the modifier accounts for 2.5 wt% of the modified xanthan gum; the preparation method of the modified xanthan gum comprises the following steps: adding xanthan gum into a solvent, adding sodium hydroxide, mixing, dropwise adding a modifier, heating to 65 ℃, reacting for 6 hours, washing, and drying to obtain the modified xanthan gum; the solvent is ethanol and water, and the weight ratio is 2: 1, the weight percentage of sodium hydroxide in xanthan gum is 2.5 wt%.

D6: thickening agent

The thickening agent is modified xanthan gum, the modifying agent of the modified xanthan gum is 1, 2-butylene oxide and sodium chloroacetate, and the molar ratio is 1: 0.4; the modifier accounts for 2.5 wt% of the modified xanthan gum; the preparation method of the modified xanthan gum comprises the following steps: adding xanthan gum into a solvent, adding sodium hydroxide, mixing, dropwise adding a modifier, heating to 65 ℃, reacting for 6 hours, washing, and drying to obtain the modified xanthan gum; the solvent is ethanol and water, and the weight ratio is 2: 1, the weight percentage of sodium hydroxide in xanthan gum is 2.5 wt%.

D7: thickening agent

The thickening agent is modified xanthan gum, the modifying agent of the modified xanthan gum is 1, 2-butylene oxide and sodium chloroacetate, and the molar ratio is 1: 5; the modifier accounts for 2.5 wt% of the modified xanthan gum; the preparation method of the modified xanthan gum comprises the following steps: adding xanthan gum into a solvent, adding sodium hydroxide, mixing, dropwise adding a modifier, heating to 65 ℃, reacting for 6 hours, washing, and drying to obtain the modified xanthan gum; the solvent is ethanol and water, and the weight ratio is 2: 1, the weight percentage of sodium hydroxide in xanthan gum is 2.5 wt%.

D8: thickening agent

The thickening agent is modified xanthan gum, the modifying agent of the modified xanthan gum is 1, 2-epoxy decane and sodium chloroacetate, and the molar ratio is 1: 2; the modifier accounts for 2.5 wt% of the modified xanthan gum; the preparation method of the modified xanthan gum comprises the following steps: adding xanthan gum into a solvent, adding sodium hydroxide, mixing, dropwise adding a modifier, heating to 65 ℃, reacting for 6 hours, washing, and drying to obtain the modified xanthan gum; the solvent is ethanol and water, and the weight ratio is 2: 1, the weight percentage of sodium hydroxide in xanthan gum is 2.5 wt%.

D9: thickening agent

The thickening agent is modified xanthan gum, the modifying agent of the modified xanthan gum is 1, 2-butylene oxide and sodium chloroacetate, and the molar ratio is 1: 2; the modifier accounts for 3.5 wt% of the modified xanthan gum; the preparation method of the modified xanthan gum comprises the following steps: adding xanthan gum into a solvent, adding sodium hydroxide, mixing, dropwise adding a modifier, heating to 65 ℃, reacting for 6 hours, washing, and drying to obtain the modified xanthan gum; the solvent is ethanol and water, and the weight ratio is 2: 1, the weight percentage of sodium hydroxide in xanthan gum is 2.5 wt%.

E: defoaming agent

The antifoaming agent is Michem SAG 1572.

F: antifreezing agent

The antifreezing agent is propylene glycol.

G: preservative

The preservative is 1, 2-benzisothiazolin-3-one.

H: water (W)

TABLE 1

Attached table 1

Examples 1 to 17 provide the insecticidal compositions described above, prepared from the raw materials in the weight percentages shown in table 1.

Examples 1 to 17 also provide a method of preparing the insecticidal composition described above, comprising the steps of: mixing the preparation raw materials of the insecticidal composition, shearing, sanding and filtering to obtain the insecticidal composition.

Evaluation of Performance

The following experiments were performed as experimental groups provided in the examples.

1. And (3) testing toxicity: the toxicity tests of flonicamid and pyridaben with different proportions on tea lesser leafhopper and aphid are respectively tested by the plant protection institute of agricultural university of Anhui.

(1) Toxicity test of flonicamid and pyridaben on turnip aphids

a. Test treatment and mode

Dissolving flonicamid and pyridaben with acetone to prepare high-concentration mother liquor, diluting the mother liquor into a series of concentrations by 0.1% Tween 80 aqueous solution according to an equal ratio sequence, performing a preliminary experiment of flonicamid and pyridaben and different mixture ratios thereof, determining the experimental concentration range of each medicament on the basis, respectively setting 5 concentration gradients for each medicament according to the content of effective components, and using the corresponding organic solvent-containing aqueous solution without the medicament as a reference, wherein the specific concentration of each medicament is as follows:

b. measurement method

The test was carried out by the leaf dipping method. Collecting cabbage leaves which are not polluted by the pesticide, beating the cabbage leaves into round pieces with the diameter of 9cm, soaking the round pieces in each gradient pesticide liquid for 10s, taking out the round pieces, naturally drying the round pieces at room temperature, placing the round pieces in a culture dish with the diameter of 9cm and filled with wet filter paper, and inoculating the round pieces of aphids which are healthy, active and consistent in size. Treatment was repeated 4 times per concentration, with 30 replicates. After treatment, the mixture is placed in an artificial climate box with the temperature of (26 +/-1) DEG C, the photoperiod of 14h to 10h (light: dark), the light intensity of 2000lux and the relative humidity of (70 +/-5)% RH and is normally raised.

c. Statistical analysis

According to the concentration logarithm value of each medicament and the corresponding corrected mortality probability value, using DPS 13.5 statistical software to perform regression analysis, solving a regression equation of each medicament, and calculating LC50 and a 95% confidence limit thereof; calculating the co-toxicity coefficient (CTC) of the compound according to the Sun Yunpei, evaluating the combined action type of the compound, and expressing that the co-toxicity coefficient (CTC) of the compound is more than or equal to 120 as a synergistic action; CTC is less than or equal to 80, and the antagonism is shown; 80 < CTC < 120 showed additive effects. The results are shown in Table 2.

TABLE 2 indoor bioassay results of flonicamid, pyridaben and their mixed preparation on Aphis fabae

The test result shows that: the 2 single agents and the compound preparation thereof have better control effect on aphids, and the combined action is shown as additive or synergistic action.

(2) Toxicity test of flonicamid and pyridaben on tea lesser leafhoppers

a. Test treatment and mode

Dissolving flonicamid and pyridaben with a small amount of acetone, then preparing 1000mg/L mother liquor with 0.1% tween 80 aqueous solution, diluting the mother liquor with 0.1% tween 80 aqueous solution into 5 series concentrations according to an equal ratio sequence, performing preliminary experiments of flonicamid and pyridaben and different mixture ratios thereof, determining the experimental concentration range of each medicament on the basis, respectively setting 5 concentrations of each medicament according to the content of effective components, and using the corresponding organic solvent-containing aqueous solution without the medicament as a reference, wherein the specific concentration of each medicament is treated as follows:

b. measurement method

The test adopts an insect soaking method, fresh tea tree tender tips which are not contacted with any liquid medicine are cleaned by clear water and dried for standby. And (3) taking a clean glass bottle, injecting 1.5% agar with the thickness of 2cm into the bottom of the glass bottle, and inserting the dried tender tips of the tea trees on the agar for moisturizing. Putting nymphs in a refrigerator at 0-4 ℃ for about 5min, taking out when the nymphs are low, gently immersing the nymph-carrying nymph soaking cage in the liquid medicine, taking out after 10s, absorbing the redundant liquid medicine by using absorbent paper, carefully picking the nymphs of the tea lesser leafhoppers into cylindrical glass bottles by using a writing brush, sealing 30 heads in each glass bottle by using gauze, respectively marking, repeating the steps for 4 times at each concentration, and taking a 0.1% Tween 80 aqueous solution soaked with corresponding amount of acetone as a reference. Then placing into an artificial climate box with temperature of 26 + -1 deg.C, photoperiod of 16h 8h (light: dark), illumination intensity of 2000lux, and relative humidity of 70 + -5% RH, and normally feeding.

c. Statistical analysis

According to the concentration logarithm value of each medicament and the corresponding corrected mortality probability value, using DPS 13.5 statistical software to perform regression analysis, solving a regression equation of each medicament, and calculating LC50 and a 95% confidence limit thereof; calculating the co-toxicity coefficient (CTC) of the compound according to the Sun Yunpei, evaluating the combined action type of the compound, and expressing that the co-toxicity coefficient (CTC) of the compound is more than or equal to 120 as a synergistic action; CTC is less than or equal to 80, and the antagonism is shown; 80 < CTC < 120 showed additive effects. The results are shown in Table 3.

TABLE 3 indoor bioassay results of flonicamid, pyridaben and their mixed preparation on tea lesser leafhoppers

The 2 single agents and the compound preparation thereof have better control effect on the tea lesser leafhoppers, and the combined action is shown as additive or synergistic action.

2. Sanding processability: observe in the preparation process of the insecticidal composition that the embodiment provided, observe whether there is the increase of viscosity or even the unable condition of grinding in the sanding stage, wherein 1 level is that sanding in-process viscosity slightly increases, 2 levels are that sanding in-process viscosity increases generally, 3 levels are that sanding in-process viscosity increases more, 4 levels are that sanding in-process viscosity increases obviously, 5 levels are unable sanding, the result sees table 4.

TABLE 4 sanding workability

Examples	Stability of sanding
		1	Stage 2
2	Level 1
		3	Level 1
4	Stage 2
		5	Level 1
6	Grade 3
		7	4 stage
8	Grade 3
		9	4 stage
10	Grade 3
		12	Stage 2
13	4 stage
		17	Grade 5

3. Active ingredient particle size test: the average particle diameter d1 of pyridaben after the insecticidal compositions provided in the examples were respectively tested and compared with the average particle diameter d0 before heat storage at 54 ℃ for 7 days, 14 days and 21 days, and the particle diameter growth rate was calculated as (d1-d0)/d0 × 100%, and evaluated, wherein the particle diameter growth rate in the 1-stage was 5% or less, the particle diameter growth rate in the 2-stage was more than 5% and 10% or less, the particle diameter growth rate in the 3-stage was more than 10% and 20% or less, the particle diameter growth rate in the 4-stage was more than 20% and 30% or less, the particle diameter growth rate in the 5-stage was more than 30% and 40% or less, the particle diameter growth rate in the 6-stage was more than 40% and 50% or less, and the particle diameter growth rate in the 7-stage was more than.

TABLE 5 active ingredient particle size

4. Persistent foaming: the insecticidal compositions provided in the examples were tested for long-lasting foamability (mL after 1 min) according to GB/T28137-2011 and evaluated, wherein level 1 is a level of long-lasting foamability (mL after 1 min) of 30mL or less, level 2 is a level of long-lasting foamability (mL after 1 min) of 50mL or less, more than 30mL, level 3 is a level of long-lasting foamability (mL after 1 min) of 70mL or less, more than 50mL, level 4 is a level of long-lasting foamability (mL after 1 min) of 90mL or less, more than 80mL, and level 5 is a level of long-lasting foamability (mL after 1 min) of 90mL, with the results shown in table 6.

TABLE 6 Long-lasting foamability

5. Performance indexes are as follows: the insecticidal composition provided in example 5 was subjected to performance testing and found to meet the criteria, wherein the performance testing criteria are shown in table 7.

TABLE 7 Performance index

The test results in tables 2 to 7 show that the insecticidal composition provided by the invention has good insecticidal effect and good grinding processability, and the obtained composition has high stability, suspension rate, pourability and other properties, and in addition, when the low-temperature and thermal storage stability is respectively carried out according to the 'suspension preparation' in GB/T19137-; in addition, when the applicant performs a heat storage stability experiment, the mass fractions of pyridaben and flonicamid after heat storage are not less than 95% before storage, and the suspension rate, the pH value, the pourability, the wet sieve test and the lasting foamability meet the performance index requirements of Table 7.

The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims

1. The insecticidal composition containing flonicamid and pyridaben is characterized by comprising 20-50 wt% of active ingredients, 1-10 wt% of wetting dispersants, 0.2-0.5 wt% of thickening agents and the balance of water in percentage by weight; the active ingredients comprise flonicamid and pyridaben in a weight ratio of (1-5): (1-5).

2. The insecticidal composition containing flonicamid and pyridaben as claimed in claim 1, wherein the wetting dispersant comprises an anionic wetting dispersant and a nonionic wetting dispersant, and the weight ratio of the anionic wetting dispersant to the nonionic wetting dispersant is (1.5-3): 1.

3. the insecticidal composition containing flonicamid and pyridaben according to claim 2, wherein the anionic wetting dispersant comprises one or more of alkyl naphthalene sulfonate formaldehyde condensate, lignosulfonate, benzyl naphthalene sulfonate formaldehyde condensate and polystyrylphenol polyoxyethylene ether phosphate.

4. The insecticidal composition containing flonicamid and pyridaben as claimed in claim 2, wherein the non-ionic wetting dispersant is one or more selected from the group consisting of alkylaryl phenol polyoxyethylene ether condensate, fatty alcohol polyoxyethylene ether condensate and EO-PO block copolymer.

5. The insecticidal composition containing flonicamid and pyridaben according to claim 2, wherein the thickener is one or more selected from the group consisting of gum arabic, xanthan gum, carrageenan, mucin, guar gum, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, polyvinyl acetate, and magnesium aluminum silicate.

6. The insecticidal composition containing flonicamid and pyridaben as claimed in claim 5, wherein the xanthan gum is modified xanthan gum, the modifier of the modified xanthan gum is 1, 2-alkylene oxide and sodium chloroacetate, and the molar ratio is 1: (1.5-2.5).

7. The insecticidal composition containing flonicamid and pyridaben as claimed in claim 6, wherein the number of carbon atoms of the 1, 2-alkylene oxide is 3-7.

8. The insecticidal composition containing flonicamid and pyridaben as claimed in any one of claims 2 to 7, wherein the anionic wetting dispersant further comprises a sodium salt of a styrene-acrylic acid copolymer.

9. The insecticidal composition containing flonicamid and pyridaben as claimed in claim 8, wherein in the sodium salt of the styrene-acrylic acid copolymer, the weight percentage of acrylic acid in the styrene-acrylic acid copolymer is 10-30 wt%.

10. The application of the insecticidal composition containing flonicamid and pyridaben according to any one of claims 1 to 9 in prevention and treatment of tea lesser leafhopper and aphid.