阅读说明：本技术 一种杀虫剂助剂及其制备方法和应用 (Insecticide additive and preparation method and application thereof ) 是由 陈维洪 彭静 李�昊 蒋殿君 黄雪萍 李树权 范小英 梁丽丽 邓晓珊 于 2020-05-14 设计创作，主要内容包括：本发明涉及农药助剂技术领域,具体涉及一种杀虫剂助剂及其制备方法和应用。一种杀虫剂助剂,按重量百分比计,至少包括以下组分：聚氧乙烯型非离子表面活性剂30-80％、阴离子表面活性剂5-20％、保湿剂10-20％、水补足100％。本发明提供的杀虫剂助剂为环保型助剂,生产过程无三废产生,制备原料均为低毒或无毒物质,易生物降解,对生态环境不造成危害；其次,该杀虫剂助剂主要用作水基性农药制剂的助剂,可大量减少农药制剂中有机溶剂的使用,绿色环保；另外,该杀虫剂助剂能显著降低药液的表面张力,润湿渗透性好,能高效渗透靶标,尤其对触杀型杀虫剂和内吸型杀虫剂增效作用明显。(The invention relates to the technical field of pesticide auxiliary agents, and particularly relates to an insecticide auxiliary agent and a preparation method and application thereof. The pesticide auxiliary agent at least comprises the following components in percentage by weight: 30-80% of polyoxyethylene type nonionic surfactant, 5-20% of anionic surfactant, 10-20% of humectant and water for supplementing 100%. The pesticide auxiliary agent provided by the invention is an environment-friendly auxiliary agent, no three wastes are generated in the production process, and the preparation raw materials are all low-toxicity or non-toxic substances, are easy to biodegrade and do not cause harm to the ecological environment; secondly, the pesticide auxiliary agent is mainly used as an auxiliary agent of a water-based pesticide preparation, so that the use of organic solvents in the pesticide preparation can be greatly reduced, and the pesticide auxiliary agent is green and environment-friendly; in addition, the pesticide adjuvant can obviously reduce the surface tension of the liquid medicine, has good wetting permeability, can efficiently permeate a target, and particularly has obvious synergistic effect on contact insecticides and systemic insecticides.)

1. The pesticide adjuvant is characterized by at least comprising the following components in percentage by weight: 30-80% of polyoxyethylene type nonionic surfactant, 5-20% of anionic surfactant, 10-20% of humectant and water for supplementing 100%.

2. The insecticide aid of claim 1, wherein said polyoxyethylene-type nonionic surfactant comprises isooctanol polyoxyethylene polyoxypropylene ether.

3. The insecticide aid of claim 2, wherein said polyoxyethylene ether type nonionic surfactant is a combination of fatty alcohol polyoxyethylene ether and isooctanol polyoxyethylene polyoxypropylene ether in a weight ratio of (0.5-1.5): 1.

4. The insecticide aid of claim 3, wherein the weight ratio of fatty alcohol-polyoxyethylene ether to isooctanol polyoxyethylene polyoxypropylene ether is 1: 1.

5. The insecticide aid of claim 1, wherein said anionic surface active agent is selected from at least one of salts of fatty acids, sulfonates, sulfates and phosphates.

6. The insecticide aid according to claim 5, wherein the anionic surfactant is a combination of fatty acid methyl ester sulfonate and fatty alcohol polyoxyethylene ether sulfate in a weight ratio of 1: (0.1-10).

7. The insecticide aid of claim 1, wherein said humectant is selected from at least one of propylene glycol, ethylene glycol, glycerin, butylene glycol, pentylene glycol, sodium lactate, hydroxyethyl urea, polyethylene glycol, and polypropylene glycol.

8. A process for the preparation of an insecticide adjuvant according to any of claims 1 to 7, characterized in that it comprises at least the following steps:

(1) adding water and a humectant into a reaction kettle, and heating to 30-70 ℃ while stirring;

(2) adding an anionic surfactant, and stirring until the mixture is uniformly mixed;

(3) adding polyoxyethylene ether type nonionic surfactant, stirring, and cooling to room temperature.

9. Use of an insecticide adjuvant according to any of claims 1 to 7 in a water-based pesticide.

10. The use of the pesticide adjuvant according to claim 9, wherein the water-based pesticide is in a form selected from one of a soluble solution, an aqueous emulsion and a microemulsion.

Technical Field

The invention relates to the technical field of pesticide auxiliary agents, and particularly relates to an insecticide auxiliary agent and a preparation method and application thereof.

Background

By "pesticide" is meant, in fact, a pesticide formulation that is sold as a commodity and can be used directly. The pesticide preparation consists of original pesticide and auxiliary agent, wherein the original pesticide is a functional active ingredient, the auxiliary agent is a general name of various auxiliary agents used in addition to the active ingredient in a chemical pesticide processing formulation, and the proportion of the organic solvent-containing auxiliary agent in the pesticide is usually as high as 80%. The assistant has no bioactivity but has synergistic effect, and can improve pesticide effect, reduce pesticide consumption, save cost and reduce environmental pollution caused by pesticide. The action mechanism of the auxiliary agent is different due to different types of the auxiliary agent. Pesticide adjuvants have evolved with advances in formulation processing and application techniques. With the increasing importance of our country on environmental protection, the traditional formulations such as emulsifiable concentrates and powders in the pesticide industry will be gradually limited, and then replaced by environment-friendly water-based formulations such as suspending agents, aqueous emulsions, soluble solutions and microemulsions. In the prior auxiliary industry, the aqueous emulsion is generally an auxiliary agent of the corresponding aqueous emulsion, and the microemulsion uses the corresponding microemulsion auxiliary agent, so that time and labor can be saved, and fewer universal auxiliary agent products are really available. The existing pesticide auxiliary agent has the defects of poor effect performance, immature process, large difference of each batch, extremely unstable performance, easy layering and crystallization when being compounded with pesticide and the like, and the normal use in the production and processing process of the pesticide is seriously influenced.

The basic guideline for the development of the pesticide industry in China is 'high efficiency, low toxicity and environmental protection', and because the proportion of the pesticide auxiliary agent containing the organic solvent in the pesticide is very large (generally 60-80 percent, and the height can reach 98 percent), the development of the environment-friendly green pesticide auxiliary agent is an important precondition for realizing the environmental protection of the pesticide. The green pesticide auxiliary agent is required to be as follows: the raw materials for preparation are low-toxic or non-toxic; the synthesized new compound has low toxicity or no toxicity; the preparation process is reasonable, and energy is saved; waste gas, waste water and waste residue are not generated in the production process; the final product has good biodegradability, namely the decomposition rate of the compound in soil is more than 80 percent after more than 90 days.

Aiming at the problems, the invention provides a green pesticide auxiliary agent which is suitable for water-based pesticides and has low toxicity, environmental protection, stable performance, strong wetting and penetrating capability and good compatibility with raw pesticides.

Disclosure of Invention

In order to solve the technical problem, the first aspect of the invention provides an insecticide adjuvant, which at least comprises the following components in percentage by weight: 30-80% of polyoxyethylene type nonionic surfactant, 5-20% of anionic surfactant, 10-20% of humectant and water for supplementing 100%.

In a preferred embodiment of the present invention, the polyoxyethylene-type nonionic surfactant comprises isooctanol polyoxyethylene polyoxypropylene ether.

As a preferable technical scheme of the invention, the polyoxyethylene ether type nonionic surfactant is a combination of fatty alcohol polyoxyethylene ether and isooctanol polyoxyethylene polyoxypropylene ether, and the weight ratio is (0.5-1.5): 1.

As a preferable technical scheme, the weight ratio of the fatty alcohol-polyoxyethylene ether to the isooctanol-polyoxyethylene-polyoxypropylene ether is 1: 1.

In a preferred embodiment of the present invention, the anionic surface activity is at least one selected from the group consisting of fatty acid salts, sulfonic acid salts, sulfuric acid ester salts, and phosphoric acid ester salts.

As a preferable technical scheme, the anionic surfactant is a combination of fatty acid methyl ester sulfonate and fatty alcohol-polyoxyethylene ether sulfate, and the weight ratio of the anionic surfactant to the fatty acid methyl ester sulfonate is 1: (0.1-10).

In a preferred embodiment of the present invention, the humectant is at least one selected from propylene glycol, ethylene glycol, glycerin, butylene glycol, pentylene glycol, sodium lactate, hydroxyethyl urea, polyethylene glycol, and polypropylene glycol.

The second aspect of the invention provides a preparation method of the pesticide adjuvant, which at least comprises the following steps:

(1) adding water and a humectant into a reaction kettle, and heating to 30-70 ℃ while stirring;

(2) adding an anionic surfactant, and stirring until the mixture is uniformly mixed;

(3) adding polyoxyethylene ether type nonionic surfactant, stirring, and cooling to room temperature.

The third aspect of the invention provides the application of the pesticide adjuvant in water-based pesticides.

As a preferable technical scheme of the invention, the formulation of the water-based pesticide is selected from one of soluble solution, aqueous emulsion and microemulsion.

Advantageous effects

(1) The pesticide adjuvant is an environment-friendly adjuvant, no three wastes are generated in the production process, and the preparation raw materials are low-toxicity or non-toxic substances, are easy to biodegrade and do not cause harm to the ecological environment.

(2) At present, when the pesticide is used in China, the missible oil still accounts for a large proportion, contains a large amount of organic solvents such as dimethylbenzene and the like, and is very easy to pollute the atmospheric environment, the water environment and the soil environment. The pesticide auxiliary agent is mainly used as an auxiliary agent of a water-based pesticide preparation, can greatly reduce the use of organic solvents in the pesticide preparation, and is green and environment-friendly.

(3) The pesticide adjuvant can obviously reduce the surface tension of the liquid medicine, has good wetting permeability, can efficiently permeate a target, and particularly has obvious synergistic effect on contact insecticides and systemic insecticides.

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.

In order to solve the technical problem, the first aspect of the invention provides an insecticide adjuvant, which at least comprises the following components in percentage by weight: 30-80% of polyoxyethylene type nonionic surfactant, 5-20% of anionic surfactant, 10-20% of humectant and water for supplementing 100%.

In a preferred embodiment, the pesticide adjuvant comprises the following components in percentage by weight: 45-65% of polyoxyethylene type nonionic surfactant, 6-15% of anionic surfactant, 10-16% of humectant and water for supplementing 100%.

In a more preferred embodiment, the insecticide adjuvant comprises at least the following components in percentage by weight: 60% of polyoxyethylene type nonionic surfactant, 10% of anionic surfactant, 10% of humectant and water, wherein the balance is 100%.

Polyoxyethylene type nonionic surfactant

The polyoxyethylene nonionic surfactant means that the melting point and hydrophobicity of the polyoxyethylene nonionic surfactant are increased correspondingly as the alkyl chain is generally increased, and the water solubility is increased as the number of units in the polyoxyethylene group is increased. When dissolved in water, the water molecules are hydrogen bonded to the oxygen atoms of the polyoxyethylene ether, and the hydrogen atoms of the water molecules are bonded to the "free electron pairs" of the ether-bonded oxygen atoms. The dissolution is accomplished by hydration with 1 (4-6) water molecules. In order to increase water solubility, a large number of ether linkage oxygen atoms must be present, and each oxygen atom can be combined with 4-6 water molecules. From the intermediate state, 4 to 6 water molecules are likely to be bonded to the oxygen atom of the ether only when the polyoxyethylene chain is in a zigzag arrangement. Such surfactants generally have lower foaming properties than ionic surfactants and are not sensitive to hard water.

In the present invention, the polyoxyethylene type nonionic surfactant includes isooctanol polyoxyethylene polyoxypropylene ether.

In a preferred embodiment, the polyoxyethylene ether type nonionic surfactant is a combination of fatty alcohol polyoxyethylene ether and isooctanol polyoxyethylene polyoxypropylene ether in a weight ratio of (0.5-1.5): 1.

In a more preferred embodiment, the fatty alcohol-polyoxyethylene ether and isooctanol polyoxyethylene polyoxypropylene ether are combined in a weight ratio of 1: 1.

Fatty alcohol polyoxyethylene ether

Fatty alcohol polyoxyethylene ethers, also known as polyoxyethylene fatty alcohol ethers. The variety with the fastest development and the largest dosage in the nonionic surfactant. Surfactants of this type are ethers of ethylene oxide ring-opening polymerized with fatty alcohols and are represented by the general formula: RO (CH)₂CH₂O)_nH, where n is the degree of polymerization, and the degree of polymerization and the type of fatty alcohol are different.

In the invention, the fatty alcohol polyoxyethylene ether is C7-C16 alcohol polyoxyethylene ether.

In a preferred embodiment, the fatty alcohol-polyoxyethylene ether has a pH of 5 to 7.

In a preferred embodiment, the fatty alcohol-polyoxyethylene ether has an HLB value of 10 to 16.

In a more preferred embodiment, the fatty alcohol-polyoxyethylene ether has an HLB value of from 11 to 13.

HLB value: the surfactant is an amphiphilic molecule with a hydrophilic group and a lipophilic group, and the amount of the size and the force balance degree between the hydrophilic group and the lipophilic group in the surfactant molecule is defined as the hydrophilic-lipophilic balance value of the surfactant.

In the present invention, the source of the fatty alcohol-polyoxyethylene ether is not particularly limited, and may be one of the types JFC-2, JFC-3, JFC-4, 1005, 1305, AEO-9, AEO-15, O-15 and O-20, available from Wuhanji and Changchang materials Ltd; JFC-2, 1005, 1305 and O-20 are preferred.

Isooctanol polyoxyethylene polyoxypropylene ether

In a preferred embodiment, the isooctanol polyoxyethylene polyoxypropylene has an HLB value of from 8 to 13.

In a more preferred embodiment, the isooctanol polyoxyethylene polyoxypropylene ether has an HLB value of 12.5.

In the present invention, the source of the isooctanol polyoxyethylene polyoxypropylene ether is not particularly limited, and Jiangsu Haian petrochemical plant, models EH-3, EH-6 and EH-9, etc. may be mentioned; EH-9 is preferred.

Anionic surfactants

Anionic surfactants are the most well developed, largest yielding and most diverse class of surfactants. Anionic surfactants are classified according to the structure of their hydrophilic groups: sulfonates and sulfate salts are currently the major class of anionic surfactants. The various functions of surfactants are mainly manifested in changing the surface, liquid-liquid interface and liquid-solid interface properties of liquids, of which the surface (interfacial) properties of liquids are most important.

In the present invention, the anionic surface activity is at least one selected from the group consisting of fatty acid salts, sulfonic acid salts, sulfuric acid ester salts and phosphoric acid ester salts.

In a preferred embodiment, the anionic surfactant is a combination of fatty acid methyl ester sulfonate and fatty alcohol polyoxyethylene ether sulfate, and the weight ratio is 1: (0.1-10).

In a preferred embodiment, the anionic surfactant is a combination of fatty acid methyl ester sulfonate and fatty alcohol polyoxyethylene ether sulfate, and the weight ratio is 1: (0.8-8).

In a more preferred embodiment, the anionic surfactant is a combination of fatty acid methyl ester sulfonate and fatty alcohol polyoxyethylene ether sulfate in a weight ratio of 1: 1.

In a preferred embodiment, the fatty acid methyl ester sulfonate is sodium fatty acid methyl ester sulfonate; the fatty alcohol-polyoxyethylene ether sulfate is fatty alcohol-polyoxyethylene ether sodium sulfate.

In the invention, the sources of the sodium fatty acid methyl ester sulfonate and the sodium fatty alcohol-polyoxyethylene ether sulfate are not particularly limited, and the sodium fatty acid methyl ester sulfonate and the sodium fatty alcohol-polyoxyethylene ether sulfate are commercially available and are suitable for the invention.

Moisture-retaining agent

In the present invention, the humectant is at least one selected from the group consisting of propylene glycol, ethylene glycol, glycerin, butylene glycol, pentylene glycol, sodium lactate, hydroxyethyl urea, polyethylene glycol, and polypropylene glycol.

In a preferred embodiment, the humectant is selected from at least one of propylene glycol, ethylene glycol, glycerin.

Water (W)

In the present invention, the water is not particularly limited, and tap water, deionized water, distilled water, and the like can be mentioned.

In a preferred embodiment, the water is deionized water.

The second aspect of the invention provides a preparation method of the pesticide adjuvant, which at least comprises the following steps:

(1) adding water and a humectant into a reaction kettle, and heating to 30-70 ℃ while stirring;

(2) adding an anionic surfactant, and stirring until the mixture is uniformly mixed;

(3) adding polyoxyethylene ether type nonionic surfactant, stirring, and cooling to room temperature.

The third aspect of the invention provides the application of the pesticide adjuvant in water-based pesticides.

In a preferred embodiment, the formulation of the water-based pesticide is selected from one of a soluble agent, an aqueous emulsion, and a microemulsion.

The pesticide adjuvant provided by the invention can obviously reduce the surface tension of pesticide liquid, has good wetting permeability, can efficiently permeate a target, effectively improves the utilization rate of a raw pesticide, and particularly has obvious synergistic effect on a contact insecticide and a systemic insecticide. The inventor believes that the possible reason is that the auxiliary agent can enable the pesticide solution to rapidly penetrate through the epidermis of pests to permeate into the body, so that the pests are poisoned or killed; or the pesticide liquid is absorbed into the plant body through the leaves, stems, roots or seeds of the plant, and is dredged, diffused and retained in the plant body, so that the pests are poisoned and killed when the pests stab the juice of the toxic plant or eat the tissues of the toxic plant. In addition, the invention solves the problems of layering, flocculation, coalescence, crystal growth and the like of the water-based pesticide in the using and storing processes through reasonable proportioning, particularly when isooctanol polyoxyethylene polyoxypropylene ether and an anionic surfactant are compounded and applied to the water-based pesticide, the long chain of the hydrophilic framework can form irreversible and full coating on the active ingredient particles of the pesticide, and the charges carried by the anionic surfactant can form effective charge layer repulsion effect, thereby effectively preventing the agglomeration and sedimentation among the particles, improving the stability of the preparation, reducing the surface tension of the preparation, and improving the acid and alkali resistance, the adhesion and the wetting permeability.

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.

In addition, the starting materials used are all commercially available, unless otherwise specified.