GB2585502A

GB2585502A - Miscible nano-sized pesticide suspension

Info

Publication number: GB2585502A
Application number: GB2010112.7A
Authority: GB
Inventors: Zhang Ziyong; Liang Bing
Original assignee: Individual
Current assignee: Individual
Priority date: 2018-12-28
Filing date: 2019-09-04
Publication date: 2021-01-13
Anticipated expiration: 2039-09-04
Also published as: GB2587264A; GB202010113D0; WO2020136451A1; GB2587264B; GB2585502B; WO2020136450A1; GB202010112D0

Abstract

The present invention relates to the technical field of pesticides. Disclosed are a miscible nano-sized pesticide suspension and a method of preparing a nano-sized pesticide suspension. The miscible nano-sized pesticide suspension is an aqueous dispersion formed by adding a miscible solution of active compound dropwise into an aqueous compounding agent, and has nano-sized crystals and miscelles having an enhanced solubility present therein at the same time.

Description

MISCIBLE NANOSUSPENSION

Technical Field

The present invention relates to the technical field of pesticides, and in particular, to a miscible nanopesticide suspension and a preparation method of the nanopesticide suspension.

Prior Art

On April 1, 2019, the International Union of Pure and Applied Chemistry (IUPAC) announced the top ten chemical inventions that would change the world, with "nanopesticides" topping the list, on the occasion of its 100th anniversary and the 150th mmiversary of the publication of the Mendeleev's Periodic Table of Elements. These emerging technologies were representative one selected by five authoritative experts recruited by IUPAC from the industry and academia from a series of nominations submitted by chemists all over the world, represent the cutting-edge trend of the development of technologies in the international chemical field, have the potential to become a major chemical breakthrough in the 21" century, and might change the world to make the Earth more sustainable.

Considering the continuous growth of the world population, nanopesticides is the top-ranking emerging technology. The world population is predicted to be close to 10 billion by 2050. In order to feed a large population, a significant increase in agricultural production is required and the environmental impact caused by land use needs to be minimized, including reducing pesticide pollution, reducing water consumption, and reducing the population size. Nanopesticides and their delivery systems will be good tools to address the main problems of traditional pesticides, including envirmunental pollution, the accumulation of the pesticides in organisms, and the significant increase in pest resistance. Nanopesticides are small in particle size and targets have better absorbability, and while it cannot be said to be the only path to sustainable agricultural development, it is certain that they have less impact on the ecological environment and human health.

Nanometre (nm), also known as mill imicron, is a unit of length. 1 nm is one billionth of a meter (10-9 m) or one millionth of a millimeter (10' mm). Simply put, the nanopesticides refer to pesticide preparations in which the particle size of active ingredients of pesticides is at a nanoscale level. The nanoscale level usually covers a range of several to several hundred MITIOMCITCS. it is generally believed that nanopesticide terms can be used to describe any of the following pesticide preparations including: (1) preparations with active ingredient particles being in the nano-size range, generally several to several hundred mmometres, (2) preparations forming substances with specified "nano" as a prefix, such as nanocrystals, nanohybrids, nanocomposites, nffitoparticles, and nanocapsules; and (3) preparations with novel features related to small-size particles, such as a giant surface area and an excellent control effect.

It has been found in studies that the efficacy of the pesticide preparations is related to the particle size, surface area and dispersion of finally fornted particles of the active ingredients in a pesticide dosage Ionia and after spraying. The smaller the particle size of pesticides, the larger the surface area, the more uniform the dispersion on leaf surfaces of crops and the wider the area of contact to biological targets, and the fuller the play of the pesticide effect.

Therefore, the most effective way to make the pesticide dosage form efficient is to reduce the particle size of the active ingredients of the pesticides as much as possible. It has been calculated that when the particle size of the active ingredients in the pesticide preparations is reduced from the existing micron size to a corresponding nano-size, the size is reduced by three orders of magnitude, the number of pesticide particles of the same mass increases by 1 billion times, and the surface area increases by a thousand times, so that the pesticide particles can more fully make contact with the targets to play a better preventive role and significantly improve the effectiveness of the pesticides. In this way, to achieve the same effect on pest control, the use amount of the pesticides can be obviously reduced compared with traditional pesticide preparations, so as to achieve the purposes of reducing the use amount and controlling hazards of the pesticides and to reduce the impact of application of the pesticides on the ecological environment. This is the primary cause of the development of nanopesticides.

Can all pesticides be prepared into nanopesticides? This starts with the dissolving property of the pesticides in water. Because the pesticides are mostly sprayed with water as a dispersion medium, according to the dissolving property in water, the pesticides can be roughly divided into three categories: one is pesticides soluble in water, and the number of such pesticide varieties is small, about 8%; the second is pesticides hard to dissolve or insoluble in water but soluble in a certain organic solvent, and such pesticide varieties are about 50%; and the third is pesticides insoluble in both water and organic solvents, which are close to 20%. The remaining pesticides are not clear in properties, or are bio-living and gas-type pesticides. The pesticides soluble in water are single-molecule dispersion in water and belong to true solutions. Since most pesticides are small-molecular organic compounds, the molecular size is generally less than 1 nanometre. Because the molecular size is smaller than the nano-size, this part of pesticides solhble in water does not need to be prepared into nanopesticides. It can be seen that the nanopesticides are for water-insoluble pesticide varieties, and because the pesticides cannot be dissolved in water and can only gather, it is hoped that their aggregates in water are dispersed in a size as small as possible, namely the nano-size, from a few nanometres to dozens and hundreds of nanometres, and this is the nanopesticides. In this way, not all the pesticides need to be made into nanopesticides, such as the water-soluble pesticides. Another thing is that not all the pesticides can be made into nanopesticides. At present, only the pesticide varieties that are insoluble in water but soluble in the organic solvents are possible to be prepared into nanopesticides by dispersion, precipitation, loading and so on, according to their dissolving property and dissolving conditions in the solvents.

This class of pesticides accounts for about half of all pesticide varieties and is also covered by the present invention. For the third type of pesticide varieties that are neither soluble in water nor the organic solvents, they are dispersed into nano-size aggregates usually by being crushed and ground by mechanical force. According to the existing technical level, it is almost impossible 1.0 disperse them all hi this way into the nano-size, so it is difficult for such pesticide varieties to be prepared into nanopesticides.

Compared with the traditional pesticide preparations, nanopesticides have four obvious advantages: first, the pesticide effect is improved. Because of the small particle size of the active ingredients, for pesticides with the same mass, the more particles, the larger area of contact to crop targets, so the same plant protection effect can be achieved even if the use amount of the pesticides is significantly reduced. Second, preparation of pesticide is stable. The smaller the particle size of nanopesticides dispersed in water, the better the transparency of the preparations, and apparent water solution and thermodynamic stability are achieved. Through property control, no pesticide precipitation or sedimentation occurs after dilution by water, so that the use of the pesticides is more efficient and convenient. Third, environmental protection is achieved. Through the existing technology, nanopesticides can be developed into environment-friendly preparations which take water as a dispersion medium and take natural substances or derivatives thereof as additives and do not use highly toxic benzene solvents and additives, so that the problem of agricultural non-point source pollution caused by pesticide application is fundamentally solved. Fourth, manufacturing is safe. The original purpose of the study of nanopesticides is to improve the pesticide effect of pesticides and reduce the use amount of the pesticides. In this process, no highly toxic organic solvents or additives are used, and water replaces or partially replaces the organic solvents. All of these initiatives not only indicate high efficiency and environmental friendliness of nanopesticides, but also show that production, storage, transportation, and operations are safer than those of traditional pesticide dosage forms such as emulsifiable concentrates. Because of this nanopesticides have become the world's competing research and development hot field.

Current nanopesticides can be divided into three major types: The First type is nanopesticides with improved apparent solubility. The purpose of this type of nanopesticide preparations is to improve the apparent solubility of the active ingredients of water-insoluble pesticides. When the particle size of the pesticides dispersed in water is less than a quarter of the visible wavelength (400 to 760 nm), incident light does not produce serious refraction or reflection, and a solution shows the apparent water solubility and transparent appearance, thereby improving the apparent solubility of nanopesticides in water.

This type of nanopesticides includes: micro-emulsions, nano-emulsions, nanodispersions, etc. The second type is nanopesticides with nanopesticide particles protected and given slow-release or controlled-release performance. The original intention of developing sustained-release or controlled-release preparations mainly aims at the problem that active ingredients of pesticides are degraded too early or deviate from targets, as well as for the case of active ingredients with low-water solubility. People recognized that most of active ingredients of pesticides are affected by environmental factors (ultraviolet rays, oxygen, and heat) after spraying, and will degrade or decompose, thereby affecting the pesticide effect. In order to achieve the slow-release or controlled-release of the pesticides, it is necessmy to protect the active ingredients from premature decomposition. The way to protect the active ingredients is the use of carrier substances. The carrier substances are divided into soft carriers (polymers and solid lipids) and hard carriers (porous hollow nano-SiO2, laminated bimetallic hydroxides (LDH), and clay). According to the different types of the carrier substances, this type of nanopesticides includes nanopesticide microspheres, nanopesticide gels, nanopesticide fibers, nanopesticide lipids, nanopesticide hollow porous SiO2, nanopesticide LDH, nanopesticide clay, etc. The third type is nano-metallic or nano-metallic oxide pesticide preparations. Nano-metals such as silver (Ag) and nano-oxides such as titanium dioxide (TiO2) are typical inorganic substances, each with respective special properties. They are either individual, or combined with pesticide tuumparticles, to form the nano-metallic or nano-metallic oxide pesticide preparations. Ag has a well-known antibacterial property. Nano-Ag can significantly inhibit the growth of plant pathogens in a dose-dependent way. Nano-TiO2 is known as a photocatalyst, which can catalytically decompose organic matter under the action of ultraviolet rays. This type of mmopesticide preparations includes two types: one is nano-metallic and Imo-metallic oxides used individually, and the other is nanopesticides with combined use of active ingredients of pesticides and the nano-metallic and nano-metallic oxides.

The development of nanopesticides is to apply nanopesticides in agricultural production, specifically, is to improve the pesticide effect of the pesticides, reduce the use amount of the pesticides, and reduce the impact on the ecological environment. However, there are some problems in the research and development of nanopesticides, including: (1) lack of common technology research, specifically, most research and development is isolated and divergent research and exploration, usually for nanopesticide preparation and characterization for a certain pesticide variety; (2) lack of the research direction and general thinking and design of developing nanopesticides, and nonsystematic and shallow research; (3) lack of knowledge of relevant i nterdi sc ipl i nes, specifically, some studies have deviations without self-acknowledgement; and (4) lack of practicality, specifically, most researches are only limited to laboratory results, making it difficult for industrialization and commercialization of nanopesticides. The latter mainly involves the difficulty of a ntmopesticide preparation method, control over a process operation flow, property control of nanopesticides, and easy availability and cost performance of additives.

It should be noted that nanopesticides do not imply that they are inherently environmentally friendly. The environmental-friendly nanopesticides can be obtained only by establishing a green and environmental protection concept in the research and development process, not using highly toxic benzene solvents or toxic additives such as nonylphenol polyoxyethylene ether feminization agents, and not using highly toxic benzene solvents.

Summary of Invention I. Terminology notes

The present invention relates to a number of specialized terms. Among these specialized terms, sonic are specialized terms well known to those skilled in the art, while others are specifically labeled for some components and obtained intermediate products for the purpose of convenient description in the present invention, representing only the specified meanings. The description of some terms can be found in Table-1.

Table-1 Technical term and description of the invention

N2 Technical term Description

1 Mixed solvent An organic solvent for dissolving pesticides in the present invention, including a solvent soluble in water and a solvent insoluble in water, and a mixture composed of the two in proportion becomes a mixed solvent.

In the present invention, a specific mixed solvent s represented by the character Ai 0 = 1, 2, 3.4.

2 Miscible pesticide raw solution A solution formed by dissolving raw pesticides in a mixed solvent.

In the present invention, a specific miscible pesticide raw solution is represented by the character Bi (i = 1, 2, 3...).

3 Anionic additive That is, an anionic surfactant, usually composed of acid radicals of 8 to 18 carbon hydrocarbon groups and metal ions. Types of the acid radicals include carboxylic acid, sulfonic acid, sulfuric acid, and phosphoric acid.

4 Nonionic additive That is, a nonionic surfactant, usually composed of polyoxyethylene (or/and polyoxypropylene) chains with different lengths and different hydrocarbon groups, as well as polysaccharide and polyoxyethylene ether structures.

Small molecule additives Mixed additives composed of anionic additives and nonionic additives.

6 Polymer a di es It is composed of water-soluble polymers, which are divided into natural polymers and synthetic polymers.

7 Mixed additives Mixed additives compounded proportionally by anion additives, nonionic additives and polymer additives.

8 Mixed additive aqueous solution An aqueous solution formed by dissolving mixed additives (polymer additives and small molecule additives) in water in sequence respectively.

The aqueous solution formed by dissolving the polymer additives in water s called a polymer aqueous solution.

In the present invention, a specific polymer aqueous solution is represented by the character Ci (i = 1, 2, 3...).

In the present invention, a specific mixed additive aqueous solution is represented by the character Di (i = 1, 2, 3...).

9 Miscible Also known as a miscible nanopestici de suspension, an aqueous dispersion in which nanocrystal and solubilized micelles coexist formed by dropwise adding a miscible pesticide raw solution to a mixed additive aqueous solution under stirring.

nanosuspension In the present invention, a specific miscible nanosuspension is represented by the character Ei (i = 1, 2, 3...).

Nanosuspens on Also known as a nanopesticide suspension, a nanopesticide aqueous dispersion finally formed after some solvents are recovered by vacuum distillation based on a miscible nanosuspeasion In the present invention, a specific nanosuspension is represented by the character Fi (i = 1, 2, 3...).

Also known as nanopesticide solid powder, a nanopesticide powder solid finally formed after some solvents are recovered by spray drying based on a miscible 11 Nano solid powder nanosuspension.

In the present invention, a specific nano solid powder is represented by the character Gi (i= 1, 2, 3...).

The system refers to a whole formed by combination and processing of required 12 System substances by the above components in accordance with a particular procedure and method.

II. Objectives of the present invention The present invention is firstly directed to overcome the defects in the prior art and provide a novel environmental-friendly miscible nanopesticide suspension, a nanopesticide suspension and nanopesticide solid powder. The miscible nanosuspension, the nanosuspension and the nano powder have the characteristics better than existing emulsifiable concentrates, suspensions, emulsion in water, wettable powder, dispersible granules, water dispersible granules and other dosage forms: (1) particles of a pesticide are dispersed in a nano-size, which is 2 to 3 orders of magnitude smaller than a micron size of particles of existing pesticide dosage forms, and thus pesticide active ingredients with the same mass have more particles and a larger specific surface area, which is more conductive to improving the pesticide effect; (2) no highly toxic benzene solvent or toxic additive is used, natural products and derivatives thereof are selected as a green additive, and a low-toxic solvent is selected and is recovered; (3) the miscible nanosuspension, the nanosuspension and the nano powder are stable in property with property indexes meeting national related regulations; and (4) a technology of the present invention is relatively not complex, which is conductive to industrialization of nanopesticides.

The present invention is further directed to provide a preparation method of the environmental-friendly miscible nanosuspension, the nanosuspension and the nano solid powder.

The difference between the nanosuspension and an existing suspension is that, except that the particle size of the pesticide active ingredients is smaller by 2 to 3 orders of magnitude, their preparation processes are also different. Preparation of a traditional suspension requires primary crushing by a high-speed shear before transferring into a continuous sander for grinding with additives. Therefore, the preparation of the traditional suspension needs to purchase a corresponding high-speed crusher, a grinder and other mechanical equipment, and preparation operations need to go through different processes. In addition, preparation properties are different. Because the particle size of particles of the existing suspension is in the micron level or above and can refract and reflect visible light, it is not transparent, and it is prone to being gathered and precipitated; while the particles of the miscible nanosuspension and the nanosuspension are less than a quarter of the wavelength of the visible light and do not produce serious refraction and reflection, so a preparation is transparent and stable. The method and process for preparing the miscible nanosuspension and the nanosuspension have the following remarkable advantages: (1) the adopted equipment is simple. Only a stirring kettle with controllable stirring speed, provided with a reflux condenser and capable of performing a vacuum distillation operation under a heating condition is required. (2) Operations are not complex, including controlling a dropping speed, heating and pressure-reduced recovery of solvents. (3) A preparing process is green and energy-saving. In the preparation process, although a certain amount of organic solvents are used, the organic solvents are low-toxic and can be recovered through a subsequent operation link. (4) A universal preparation method is provided. The present invention provides a universal and effective method for preparing the miscible nanosuspension, the nanosuspension and the nano solid powder for numerous pesticide varieties.

DI Composition of miscible nanopesticide suspension 1. Component selection of miscible nanopesticide suspension (1) Mixed solvents miscible with pesticides The first step of the present invention is to select a mixed solvent capable of being miscible with pesticides. The mixed solvent is formed by mixing at least two solvents according to a certain Selecting principles include: (1) the dissolving property to the pesticides should be as good as possible, so that a use amount of the solvent is not too large; (2) a boiling point of the solvent should not be too high, so that recovery is facilitated; (3) toxicity should be as low as possible, namely, a low-toxic solvent shall be selected when there are many solvents to be selected; (4) in the mixed solvent, each solvent is:Thk to dissolve raw pesticides, including two types: one is a solvent soluble in water, and the other is a solvent insoluble in water; and (5) the mixed solvent should include one solvent soluble in water and;u: iia one solvent insoluble in water.

There are many types of organic solvents. According to different structural types, the organic solvents arc mainly divided into a benzene solvent, an alkane solvent, a ketones solvent, an esters solvent, an alcohols solvent, an oils solvent, etc. The present invention mainly aims at pesticide varieties insoluble in water but soluble in the organic solvents.

In existing pesticide manuals and literatures, physical properties of pesticide varieties are generally listed, including the dissolving property in some solvents, but the information is not complete. The dissolving property of these solvents can be used for selection of the solvents and the mixed solvents used in the present invention. For example, some important pesticide active ingredients are listed in Table-2, including solvents optionally used for a bactericide, an insecticide and a herbicide, units of data in brackets are g/L, namely grams of the pesticide active ingredients soluble in each liter, while data of solvents without brackets are not quite clear, and this is for reference of selecting the Mixed solvents. The method of the present invention only uses this as an example, but is not limited to the table, the pesticide varieties listed in the table and types of solvents dissolving the pesticide varieties. In the dissolving property data of the pesticide active ingredients provided in Table-2, selection of the mixed solvents also has the following empirical laws: 1. In the dissolving property data of the pesticides, acetone (soluble in water) appears the most frequently, and a ketone solvent insoluble in water compounded with the acetone includes cyclohexanone, methyl ethyl ketone, acetophenone and their derivatives, with the solubility similar to the acetone.

2. In selection of methanol, ethanol, isopropanol, acetonitrile and tetrahydrofuran solvents soluble in water, in the solvents insoluble in water compounded with the above solvents, except the ketones solvent, ethyl acetate insoluble in water has low toxicity and low boiling point, thereby being an optional esters solvent, and propyl acetate, isopropyl acetate, etc., which are homologous to the ethyl acetate, have the solubility similar to it.

3. Selection principles: relatively high solubility (reducing the use amount of the solvents), low toxicity, relatively low price, low boiling point (facilitating recovery), and so on Table-2 Optional mixed solvent for certain different types of important pesticide varieties No. Mixed solvents Pesticide varieties Soluble hi water (g/L) Insoluble in water but soluble in solvents (g/L) Bactericide 1 Fenpyrafamine meth anol methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate (250), propyl acetate, isopropyl acetate acetone (250)0, ) 2 Metrafenone acetone (403), acetonitrile (165) methyl ethyl ketone, cyclohexanone, methyl cl),clohexanone, acetophenone, ethyl acetate (261), propyl acetate, isopropyl acetate, dichloromethane (1950), toluene (363) methanol (26.1) id methyl sulfoxide (940), acetone dichloromethane (1380), chloroform (1280), ethyl acetate, methyl ethyl ketone, cyclohexanone 3 Metominostrobm 4 Quinoxyfen acetone (116) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (179), isopropyl acetate, dichloromethmie (589), toluene (272) Peinhiopynid methanol (402), acetone (557) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (179), isopropyl acetate 6 Pyraclostrobi n acetone (500), isopropanol (30), methanol (100), acetonitrile (500) methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate (500), propyl acetate, isopropyl acetate, dichloromethane (500), toluene (500) 7 Isopyrazam acetone (314), methanol (119) methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate (179), propyl acetate, isopropyl acetate, dichloromethane (330) 8 Prothioconazole acetone (250), dimethyl sulfoxide (126), acetonitrile methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate (250), propyl acetate, isopropyl acetate, dichloromethane (88) (69), n_octanol (87), isopropanol (58) 9 Proqui nazid acetone (250), dimethyl formamide (250), n-octanol (250) cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate (250), propyl acetate.

isopropyl acetate, Isopropyl dichloromethane (250), n-hexane (250) Boscalid acetone (100), methanol (50) methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate (250), propyl acetate, isopropyl acetate 11 Picoxystrobin acetone (250), methanol (96), methyl ethyl ketone, cyclohexanone, methyl cYclohexanone, acetophenone, ethyl acetate (250), ' propyl acetate, isopropyl acetate, xylem (250), dicliloroethane (250) 12 Famoxadone acetone (274), acetonitrile methyl ethyl ketone, cyclohexanone, methyl (125) cyclohexanone, acetophenone, ethyl acetate (125), propyl acetate, isopropyl acetate, dichloromethane (239) 13 Fluopicolide acetone (74.7), dimethyl sulfoxide (183) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (37.7), dichloromethane (126) 14 Fluopymin acetone (250), dimethyl sulfoxide (250), methanol (250) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (250), dichloromethane (250) Fluazinam acetone (853), methanol (192) methyl ethyl ketone, eyclohexanone, acetophenone, ethyl acetate (722), dichloromethane (675), toluene (451) 16 Triflumizole acetone (1440), methanol (496) cyclohexanone, acetophenone, ethyl acetate, dichloromethane (675), toluene (639) 17 Oxathiapiprol in acetone (162) methyl ethyl ketone, cyclohexanone, acetophenone, dichloromethane (352) 18 Flutolanil acetone (606), acetonitrile (333), methanol (322) methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate (364), propyl acetate, isopropyl acetate, dichloromethane (377) 19 Sedaxane acetone (410), methanol (110). methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate (200), propyl acetate, isopropyl acetate, dichloromethane (500) Penflufen acetone (139). methanol (126), dimethyl sulfoxide methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate (96), propyl acetate, isopropyl acetate, dichloromethane (250) (126) 21 Fludioxoni I acetone (190), methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (200) 22 Silthiopham acetone (250), methanol (250) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (250), xylene (250), dichloromethane (250) 23 Cyproconazole acetone (360), ethanol (230), methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (240), dichloromethane (430), xylene (120), toluene (100) ) methanol (410), dimethyl sulfoxide (180), oetanol (100) 24 Cyflufenamid acetone (920), acetonitrile (943), methanol (653), ethanol (500) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (808), isopropyl acetate, dichloromethime (902), xylene (658), Fenbuconazole acetone (250) methanol (60.9) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (132), dichloroethane (250) 26 Metalaxyl-m miscible with acetone. methanol, and n-octanol miscible with methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dichloromethane, toluene, etc. 27 Bixafen acetone (250) methyl ethyl ketone, cyclohexanone, acctophcnone, dichloromethane (102) 28 Fenamidone acetone (250), acetonitrile (86) methyl ethyl ketone, cyclohexanone, acetophenone, dichloromethane (330) 29 Kresoxim-methyl acetone (217) methyl ethyl ketone, cyclohexanone, acctophcnone, ethyl acetate (123), dicliloromethane (939) Cyprodinil acetone (610), ethanol (160), n-ocianol (140) methyl ethyl ketone, cyclohexanone, acctophcnone, toluene (440) 31 Mandipropamid acetone (300), methanol (66) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (120), dichloromethane (400) 32 Tetniconazole easily soluble in acetone and methanol methyl ethyl ketone, cyclohexanone, acctophcnone, easily soluble in dick loroellume 33 Triflox-ystrobin acetone (500), methanol (76) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (500), dichloromethmle (500) 34 Penconazole acetone (770), ethanol (730), n-octanol (400) methyl ethyl ketone, cyclohexanone, acetophenone, toluene (610) Probenazole easily soluble in acetone and dimethyl formamide methyl ethyl ketone, cyclohexanone, acetophenone, easily soluble in chloroform 36 Solatenol acetone (350) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (190), dichloromethime (450), 36 Metconazole acetone (363), methanol (403), isopropanol (231) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (260), di chloromethane (481), toluene (103) 37 Ipconazole acetone (570), methanol (680), n-octanol (230), methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (430), dichloromethane (580), dichloroethane (420), toluene (160), xylene (150) Insecticide 38 Tebufenpyrad acetone (819), methanol methyl ethyl ketone, cyclohexanone, methyl ethyl (818), acetonitrile (785) ketone, acetophenone, dichloromethane (1044), toluene (772), hexane (255) 39 Cyllumetofen acetone (500), methanol (100) methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetophenone, ethyl acetate (500), toluene (500) Pyridalyl acetone, acetonitrile, n-octanol, dimethyl fommmide (>1000), methanol (>500) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, tricliloromethane, toluene, hexane (>1000) 41 Fluensulfone acetone (350), methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (351), dichloromethane (306) 42 Efficient cyhalothrin acetone, methanol (>500) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (>500) 43 B ife mini n acetone methyl ethyl ketone, cyclohexanone, acetophenone, chloroform, dichloromethane, toluene, diethyl ether 44 Spnotetramat acetone (120), dimethyl sulfoxide (300), ethanol (44) methyl ethyl ketone, cyclohexanone, acetophenone, dichloromethane (>600), ethyl acetate (67) Spi rod i clofen acetone, acetonitrile (>250) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dichloromethane, xylem (>250) 46 Metaflumizone acetone (153), acetonitrile (63) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (169), dichloromethane (98) 47 Lufenuron acetone (460), methanol (52) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (330), 48 [taxa:401e acetone (300), methyl ethyl ketone, cyclohexanone (500), acetophenone, ethyl acetate (250), tetrahydrofuran (750), methanol (90) 49 I ndoxaca rb acetone (>250), methanol (103), acetonitrile (139) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate Tolfenpyrad acetone (368), methanol (59) methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetophenone, ethyl acetate (339), toluene (366) 51 Fenpyroximate acetone (150), methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (201), chloroform (1197), toluene (268) letrahydrofuran (737) 52 Pyriproxyfen acetone, methanol (200) methyl ethyl ketone, cyclohexanone, methyl ethyl ketone. acetophenone, ethyl acetate, xylem (500) Herbicide 53 Amicarbazone acetone, acetonitrile (>210), isopropanol (110), dimethyl sulfoxide (250) methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetophenone, ethyl acetate (140), dichloromethane (>250) 54 Saflufenacil acetone (275), methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (65.5) tetrahydrofuran (362), acetonitrile (194) Oxadiargy I acetone (250), acmonitrile (94.6) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (121), dichloromethane (>500) 56 Metamifop acetone, methanol (>250) methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (>250), dichlorocthanc (>250) 57 Flurtamone acetone (350), methanol (199), methyl ethyl ketone, cyclohexanone, acetophenone, dichloromethane (358) 58 Tefinyltnone acetone (300) methyl ethyl ketone, cyclohexanone, acetophenone 59 Picolinafen acetone (557), methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate (464), dicldoroethane (764) Flufenacet acetone (>200), isopropanol (170), dimethyl fonnamide (>200) methyl ethyl ketone, cyclohexanone, acetophenone, toluene, dichloromethane (>200) 61 S-meto lac hlor easily soluble in acetone and methanol easily soluble in methyl ethyl ketone, cyclohexanone, ethyl acetate, dichloromethane, toluene and n-hexane 62 Pyriminobac-in acetone ((Erni, (Z)584), methanol ((E)14.6, (Z)140) methyl ethyl ketone, cyclohexanone, ethyl acetate ((E)45, (Z)1370), dichloromethane ((E)510, (Z) 3110) 63 Eluthiacet-methyl acetone (101) acetonitrile methyl ethyl ketone, cyclohexanone, acetophenone, dichloromethane (531), ethyl acetate (73) (68) 64 Cyhalofop-butyl acetone, methanol (>250) methyl ethyl ketone, ethyl acetate, dichloroethane (>250) Propytamide acetone, methanol, methyl ethyl ketone, cycloheximone, methyl ethyl ketone (200) isopropanol (200), dimethyl sulfoxide (330) 66 Ac ifluorfen acetone (600), ethanol (500) methyl ethyl ketone, cyclohexanone, acetophenone, methyl ethyl ketone 67 Trichlopyr acetone (581) met methyl ethyl ketone, cyclohexanone, methanol methyl (665) methyl ethyl ketone, ethyl acetate (271) 68 Flontsulam acetone (123), acetonitrile (72) methyl ethyl ketone, cyclohexanone, acetophenone, methyl ethyl ketone 69 Pyracionil acetone (500) methyl ethyl ketone, cyclohexanonc, acetophenone, methyl ethyl ketone Et hofumesate acetone (400), ethanol (100) methyl ethyl ketone, cyclohexanone, acetophenone, methyl ethyl ketone, trichlommethane (400) 71 Oxyfluorfen acetone (700), methyl ethyl ketone, cyclohexanone, acetophenone, methyl ethyl ketone, isophorone (600) 72 Isoxaflutole acetone (293) methyl ethyl ketone, cyclohexanone, acetophenone, methyl ethyl ketone, ethyl acetate (142), dichlommethmie (346) 73 Pinoxaden acetone (250), meth anol (260), octane! (140) methyl ethyl ketone, cyclohexanone, acetophenone, methyl ethyl ketone, ethyl acetate (130), dichloromethane (>500) (2) Mixed additives The miscible nanopesticide suspension and the nanopesticide suspension prepared in the present invention also need mixed additives (systems) in addition to the use of the mixed solvents. The mixed additives include small molecule additives and polymer additives. Their components and functions are described below.

1. Small molecule additives The small molecule additives all belong to surfactants, and mainly include an anionic surfactant and a nonionic surfactant.

Molecules of the anionic surfactant are composed of hydrophilic polar groups and hydrophobic hydrocarbon groups. The anionic surfactant is dissociated into an ion state in an aqueous solution to form acid radical groups containing negative charges and metal ions containing positive charges around the acid radical groups. From the chemical structure, it may be carboxylate, sulfonate, sulfate or phosphate formed by straight-chain or branched-chain hydrocarbon groups (including alkanes and olefins) with 8 to 18 carbon atoms, or cmboxylate, sulfonate, sulfate or phosphate formed by the straight-chain or branched-chain hydrocarbon groups (including alkanes and olefins) with 8 to 18 carbon atoms and aryl groups. Considering environmental-friendly performance, the order of environmental-friendly performance from good to poor is as follows: various salts of straight-chain hydrocarbon groups > various salts of branched-chain hydrocarbon groups > various salts of the awl groups.

These anionic surfactants all have the properties of reducing surface tension, emulsifying and sohibi fixing. They are characterized by three property indexes: the first one is critical micelle concentration (CMC), i.e. the minimum emulsifier concentration that fonus a micelle. The lower a CMC value, the lower the concentration of the micelle formed by the anionic surfactants, and the higher the activity. The so-called micelle is that the anionic surfactants are dissolved in water in a single molecule dispersion state under the CMC, when the CMC is exceeded, molecules are concentrated, a plurality of anionic surfactant molecules are concentrated in a lowest energy state, hydrophilic polar groups face toward a water phase, while hydrophobic non-polar groups (tipophilic groups) are concentrated to form a spherical micelle with the diameter of several nanometres, and a schematic diagram of the morphological structure is as shown in FIG. 1. When the concentration of the anionic surfactants is higher, in addition to the spherical micelle, a rod-like micelle may also be formed. No matter the spherical micelle or the rodlike micelle, the hydrophilic groups such as carboxylate, sulfonate, sulfate or phosphate are located outside, while the lipophilic hydrocarbon groups are located inside, and according to the principle of like dissolves like, a hydrophobic and lipophilic environment can accommodate pesticides insoluble in water or solutions of hydrophobic solvents thereof When the CMC of the anionic surfactants is examined, generally is that the lower the value, the higher the activity. The second one is Krafft temperature, which is a temperature when the anionic surfactants form the micelle, and also a temperature of three-phase equilibrium of a molecule dissolution state, the micelle and gel. Above the temperature, the solubility of the anionic surfactants is sharply increased to form the micelle. Under the temperature, the anionic surfactants are precipitated in the form of gel. Therefore, the lower the temperature, the lower the temperature of forming the micelle in water or precipitating the gel, and the wider a temperature range used. The third one is hydrophilic-lipophilic balance (HLB). Surfactants are all composed of hydrophilic and lipophilic groups, the hydrophilic and I ipophilic tendency of whole molecules is measured by the HLB value which is an important basis for reasonably selecting the surfactants. Regulations of relative standards of the HLB value of the surfactants at present are as follows: the HLB of paraffin is 0, the HLB of oleic acid is 1, the HLB of potassium oleate is 20, and the HLB of sodium lauiyl sulfate is 40. The hydrophilicity is enhanced from low to high from 1 to 40. Generally, the lipophi Hefty is good when the HLB is less than 10, and the hydrophilicity is good when the HLB is greater than 10. The application of the surfactants may be inferred according to the HLB value. HLB value ranges of the surfactants required for various applications are listed in

Table-3.

Besides the anionic surfactant, the small molecule additives further require the use of the nonionic surfactant. This kind of surfactant is called the nonionic surfactant because it is not disassociated into an ion state in an aqueous solution, but exists in the solution in a molecule or micelle-cluster state. Its lipophi lie group is generally a hydrocarbon chain or a polyoxypropylene chain, and a hydrophilic part is polyoxyethylene, a hydroxyl group or ether group, an amide group and the like. Most nonionic surfactant products are in a liquid state or paste state, which is different from the anionic surfactant. According to different structures of its hydrophilic groups, the nonionic surfactant mainly includes a polyoxyethylene nonionic surfactant, a polyol pseudo-ionic surfactant and au alleylolamide nonionic surfactant. Among them, the polyoxyethylene nonionic surfactant is the most important kind of nonionic surfactant, and especially that polyoxyethylene ether of fatty alcohol has many varieties and large production. The property of this kind of nonionic surfactant not only depends on a hydrophobic group, but also has a large relationship with the length of a polyoxycthylene ether chain. A plurality of nonionic surfactant molecules in water fonn a spherical micelle-cluster above the CMC, a morphological structure of the micelle-cluster is similar to that of the micelle, hydrophilic polyoxyethylene chains are located outside and face a water phase, lipophilic hydrocarbyl structures are located inside, and the micelle-cluster has a slightly Larger size than the micelle, as shown in FIG. 3.

Table-3 HLB value ranges of surfachmts and approximate applications thereof HLB value ranges Applications 1-3 Deforuning agent 3-6 Water/oil (W/O) emulsifier 7-9 Wetting agent 8-18 Oil/water (0/W) emulsifier 13-15 Detergent 14-18 Solubilizer Biodegradation of the nonionic surfactant includes two parts, i.e., a hydrocarbon chain and a polyoxyethylene chain. In the hydrocarbon chain part, it is still that a straight chain is easier to degrade than a branched chain, and the hydrocarbon chain containing an aryl group is more difficult to degrade than the one containing a fatty group.

The longer the polyoxyethylene chain is, the poorer the degradability is. In alkylphenol ethoxylates, especially nonylphenol polyoxyethylene ether, phenol ether is degraded, and then nonyl phenol is generated. The nonyl phenol is verified as a substance with feminization toxicity, and will feminize aquatic organisms when entering the environment, especially water bodies. Mankind who eat feminized aquatic organisms will suffer infertility, so this kind of nonionic surfactant has been forbidden despite its good emulsification property.

The nonionic surfactant is characterized by a cloud point and the HLB value. After a transparent aqueous solution of the nonionic surfactant is slowly heated to a certain temperature, the solution will be cloudy, representing that the surfactant starts to be precipitated. The lowest temperature enabling the solution to be cloudy is called a "cloud point", which is a temperature at which the aqueous solution has phase separation along with the increasing temperature. In a homolog of the nonionic surfactant with the same lipophihc group, the longer the polyoxyethylene chain is, the higher hydrophilicity is, and the higher the cloud point is. Considering practicability, if a system needs a heating process, the cloud point of an adopted nonionic surfactant needs to be considered, otherwise, the stability of the system would be damaged by the cloud point.

The HLB value of the nonionic surfactant is the same as that of the anionic surfactant in description, which is also a qualitative characterization of hydrophilic and lipophilic properties. The El LB value of the surfactant may be obtained via various methods such as assay determination and calculation, and may also be searched from manuals and literatures. A range of the HLB value may be roughly estimated according to a dissolved state of the surfactant in water. For example, a rapid method for estimating the range of the HLB value of the surfactant is listed in Table-4.

Table-4 Ranges of HLB value estimated according to dissolved state of surfactant n Ovate Dissolving property in water 111.13 Dissolving property in water HLB Not dispersed 1-4 Stable milky dispersion 8-10 Not well dispersed 3-6 Translucent to transparent dispersion 10-13 Milky after violent oscillation 6-8 Transparent solution > 13 The small molecule additives used in the present invention are composed of at least one anionic surfactant and at least one nonionic surfactant, so that the micelles and the micelle-clusters with a solubilization property are formed in an aqueous solution. Therefore, selection principles of the small nolecule additives are as follows: first, considering the stability of the system, the krafft temperature of the anionic surfactant should be as low as possible, most preferably close to 0°C; second, the cloud point temperature of the nonionic surfactant should be higher than 60°C as far as possible, so as to prevent a heating temperature from exceeding the cloud point temperature when solvents arc recovered with reduced pressure; and third, a miscible pesticide raw solution of the mixed solvent for dissolving the pesticide active ingredients should realize nano-size solubilization in the micelles and the micelle-clusters, and the HLB value of the small molecule additives should be 13 or above, and most preferably 14 or above. This is because that the solution is transparent at the moment, while transparency indicates that the particle size of the pesticides is smaller than one quarter of the wavelength of visible light, namely 100 tun or below.

2. Polymer additives The polymer additives are also polymer surfactants, which usually refer to substances having surface activity and with relative molecular mass being greater than lff 000. Compared with the small molecule surfactants, the polymer surfactants are not Whin surface tension lowering capability, but have some other special properties such as dispersion, suspension and viscosity increase. According to sources, the polymer surfactants may be divided into natural polymers and derivatives thereof, and synthetic polymers. The polymer surfactants have hydrophobic main chains and suspended hydrophilic functional groups such as a hydroxyl group, a carboxyl group, a carboxymethyl group, a suffonic group, a sulfate group, a phosphate group and an amino group, thereby being water-soluble polymers. Water-soluble natural polymers and derivatives thereof include starch, dextrin and various derivatives, water-soluble starch, oxidized starch, carboxymethyl starch, modified starch, celluloses and derivatives thereof, carboxymethyl celluloses, hydroxyethyl hydroxypropyl celluloses, carboxymethyl chnosan, modified guar, tea saponin, water-soluble!tunic acid, sodium lignin sulfonate, etc. Water-soluble synthetic polymers include polyvinyl alcohol, polyacrylic acid, polyactylamide, a polystyrene-maleic anhydride copolymer, polyvinyl pyrrolidone, etc. Since main chains of the water-soluble synthetic polymers are mostly carbon chains and are not easy to biodegrade, considering environmental friendliness, the water-soluble natural polymers and derivatives thereof should be selected as far as possible so as to minimize the impact on the ecological environment.

The reason for the present invention to choose the polymer additives is to use the effects of dispersion, suspension, etc. of the water-soluble polymers in the aqueous solution. A water-soluble polymer with relative molecular mass of tens of thousands and hundreds of thousands is usually of a linear polymer chain structure, and can be dissolved in water. When linear polymers are dissolved in water, a length-diameter ratio of the linear polymers is very large, but the linear polymers do not present a straight linear state, but present a curved state due to the flexibility of a molecular chain, that is, a morphological structure of a "random coil", see FIG. 5. Hydrophilic groups in the random coil face towards a water phase as far as possible, while lipophilic chain structures are curved inside the random coil. A size of the random coil depends on the relative molecular mass and a concentration of the polymer additives, as well as an aggregation structure of the polymers. A volume of the random coil formed by a single molecule is large if the molecular mass is huge. When the concentration of the water-soluble polymers is relatively high, random coils formed by different molecules will be aggregated, so that the volume is relatively large. Generally, when the molecular mass of the water-soluble polymers is tens of thousands and hundreds of thousands, the formed random coil usually has a size of tens to hundreds nanometres. If pesticide nanocrystals are generated in the system, according to the principle that like dissolves like, lipophilic nanocrystals tend to enter a lipophilic random coil to be doped in different portions of the random coil. When the pesticide nanocrystals have a small size, a plurality of nanocrystals may be dispersed in the random coil. Actually, the water-soluble polymer additives may act on the generated nanocrystals as a dispersant and a stabilizer, which is also the principle utilized by traditional pesticide suspensions, but their pesticide particles have a micron size, and since micron particles are relatively large in size and have a relatively high gravity action, the stability of the suspensions has relatively high uncertainty:. When the particle size of the pesticide is lowered by 2 to 3 orders of magnitude, the gravity action of the particles will be much lower, a same water-soluble polymer surfactant may obtain a more stable suspension and dispersion system, and apparent water solubility and transparent appearance are realized.

2. Component proportion of miscible nanopesticide suspension The miscible nanopesticide suspension and the nanopesticide suspension of the present invention include the following components: pesticide active ingredients, solvents (including the solvents soluble in water and the solvents insoluble in water), additives (including the small molecule anionic additives, the small molecule nonionic additives and the polymer additives) and water. By further conclusion, the system includes three components: the first one is a miscible pesticide raw solution (raw pesticides ± solvent S1 + solvent 52 second one is the mixed additives (s ma 11 molecule anionic additives+small molecule nonionic additives + poly me r additives), and the third one is water.

In an ideal case, a mass ratio of the three components is: The miscible pesticide raw solution: the mixed additives: water is approximately equal to 35%:25%:40% and approximately equal to 0.875:0.625:1. That is, the mass of the miscible pesticide raw solution and the mass of the mixed additives are about 0.875 and 0.625 time the mass of the water respectively.

After further combination, the system only includes two components, namely the miscible pesticide raw solution and a mixed additive aqueous solution, and a ratio of the two is about: The miscible pesticide raw solution: the mixed additive aqueous solution is approximately equal to 35%:65% and approximately equal to 7:13 A proportion relationship between the components is discussed as follows: (1) It is determined that a mass percentage of the miscible pesticide raw solution is about 35%. Reasons are analyzed as follows: the miscible pesticide raw solution includes mass of raw pesticide active ingredients and mass of the mixed solvent. There are two different representing methods for the content of the raw pesticide active ingredients: one is a mass percentage, %, and the other is volume mass, g/L. The former is frequently used, and the present invention also uses the mass percentage to represent the mass of the components. In traditional pesticide preparations, although pesticides are different in activity and use amount, manufacturers always like to pursuit a high active ingredient content of the pesticides when preparing the pesticide preparations. The high content can reduce a volume of packages and the transportation cost, but a relatively low additive content will affect the dispersion property of liquid pesticides after the pesticide preparations arc diluted with water as well as the control effect over pests. Actually, each pesticide variety should have respective suitable active ingredient content according to the activity and different physical dissolving properties of the pesticides. In the present invention, a miscible nanopesticide suspension and a mmopesticide suspension (nanodispersion) of a certain pesticide are prepared according to its solubility in a certain solvent system (Sti, St2... St), and considering that the use amount of a solvent has an approximate upper limit, e.g., 30%, the final content of pesticide active ingredients in a preparation is determined. For example, for the No. 4 bactericide, quinoxyfen, its solubility in acetone is 116 g/L. That is, 10 g of the acetone (a solvent soluble in water) can dissolve about 1.16 g of a pesticide active ingredient, while a homologous solvent insoluble in water, such as methyl ethyl ketone and cyclohexanone, has similar solubility. Therefore, if 30 g of a solvent is used, 3.48 g of an active ingredient can be dissolved. Due to the fact that a saturated solution is prone to precipitating solute and the miscible pesticide raw solution cannot be prepared into a saturated state, the mass percentage of the raw pesticide active ingredients in the miscible pesticide raw solution may be determined to be 3.3%. In the system components, the miscible pesticide raw solution is 3.3%, while other components are the mixed additives and water. In the later period of preparing the preparation, die solvents are recovered through vacuum distillation Assuming that all the used solvents are recovered, in addition, part of water is evaporated as an azeotrope composition, and the final content of the active ingredients may reach about 5%. Although the use amount of the solvents may further be increased to dissolve more pesticide active ingredients, this certainly will reduce the proportions of the use amount of the mixed additives and water, and thus the uniformity and stability of generated pesticide nanocrystals may be affected. Accordingly, the upper limit of the miscible pesticide raw solution is set as 35%. Although the preparation may also be prepared with a content slightly higher than 35% the proportions of other components will be obviously affected if the content is too high. Since the mass percentage of the miscible pesticide raw solution is 35%, an upper limit of a mass percentage of the mixed solvent is about 30%. Vice versa, expected solubility of the raw pesticides may be checked, and accordingly the variety of the raw pesticides and the mixed solvent are selected. The above example is on the basis that the raw pesticide solubility is about 100 g/L. When the solubility of the raw pesticides to a certain mixed solvent is greater than 100 g/L, the mass of a used solvent may be less than 30%, the mass percentage of the raw pesticide active ingredients may be properly increased to 3% to 12%, therefore, the sum of the mixed solvent and the raw pesticides (namely the miscible pesticide raw solution) is approximately 35%, while the proportions of other components in the system are selected from remaining mass percentages. On the contrary, when the solubility of the raw pesticides to a certain mixed solvent is less than 100 g/L, a target product with lower active ingredient content can only be obtained.

Therefore, in the miscible pesticide raw solution, the mass percentage of the active ingredients, Wa t.%, is set in a range from 3% to 12%. Theoretically, it is equal to the sum of a product of multiplying a mass percentage Si% of a solvent Si and solubility St' of raw pesticides in the solvent, a product of multiplying a mass percentage S2% of a solvent St and solubility St2 of the raw pesticides in the solvent, and so on, as shown in the following formula: % = SID/0-+ S2%*St2+ Rules of optimally selecting the mixed solvent are summarized in Table-5. Table-5 Mixed solvent optimal selection rules

Level Property Description

1 Solubility The solubility of the mixed solvent is a key problem related to whether alternative pesticides can be prepared into the described miscible nanopesticide suspension and nanopesticide suspension, as well as the content of the active ingredients, thereby being a principle that is firstly considered for selecting the mixed solvent.

2 Boiling point The boiling point of component solvents in the mixed solvent is related to the recovery difficulty and recovery degree of the solvents. When the boiling points of the solvent soluble in water and the solvent insoluble in water are relatively low, e.g., 50 to 70°C, it is conductive to recovering the solvents through vacuum distillation under 60°C.

3 Toxicity The toxicity of the selected solvents firstly relates to safety in a preparation process and the influence on physical health of operators, and secondly relates to the impact on the ecological environment by part of the solvents that may not be completely recovered.

4 Proportion The proportion of the solvent soluble in water to the solvent insoluble in water depends on a mass percentage of dissolved raw pesticides by the mixed solvent in total, but the ratio of the two is generally about 1:2. Therefore, when the miscible pesticide raw solution is dropwise added into the mixed additive aqueous solution, about 1/3 of the raw pesticides dissolved by the solvents are precipitated to form nanoctystals, and the remaining 2/3 of the raw pesticides dissolved by the solvents arc gradually turned into the nanocrystals in the following vacuum distillation process for solvent recovery.

(2) It is determined that a component proportion of the mixed additives is about 25%. Reasons are analyzed as follows: the mixed additives include the small molecule additives and the polymer additives. The use amount of the small molecule additives is discussed first. The small molecule additives include the anionic surfactant and the nonionic surfactant. Selection of the types should consider different factors. For the anionic surfactant, factors to be considered include: the chemical structure, the CMC, the krafft temperature and the HLB value. For the nonionic surfactant, factors to be considered include: the chemical structure, the CMC value, the cloud point temperature and the HLB value. The two have common points in: 1. the chemical structure. Considering environmental friendliness, biodegradable surfactants am selected. 2. The CMC value. Considering the activity of the surfactants, varieties with low CMC value Me are selected to reduce the use amount. 3. The HLB value. Considering features of the surfactants and generation of a transparent solution (whether the solution is transparent relates to whether particles are in a nano-size), and surfactant varieties with the HLB value greater than 13 are selected. The two are different in that: the krafft temperature of the anionic surfactant is a temperature of three-phase balance of a molecule dissolution state, micelles and gel, when the temperature is lower than the krafft temperature, the surfactant will be precipitated in a gel form, so the krafft temperature should be as low as possible, e.g., close to 0°C, so that low-temperature storage is achieved. The cloud point temperature of the nonionic surfactant is a temperature at which an aqueous solution of the surfactant has phase separation along with the increasing temperature. The cloud point temperature should be high, most preferably >60°C due to the fact that the temperature needs to be raised in the later period of the preparation process to perform vacuum distillation for recycling the solvents, while avacuum distillation temperature needs to be lower than the cloud point temperature of the nonionic surfactant, otherwise the nonionic surfactant would be aggregated and precipitated from water, and the stability of the system would be damaged.

The component proportion of the small molecule additives is analyzed as follows: the small molecule additives include the anionic surfactant and the nonionic surfactant, which form the micelles or the micelle-clusters in water respectively afterbeing dissolved in water, see FIG. I and FIG. 3. When the miscible pesticide raw solution is dropped into an aqueous solution of the small molecule additives, the micelles or the micelle-clusters play roles in dispersing, solubilizing and stabilizing pesticide solution liquid drops. The miscible pesticide raw solution liquid drops contain organic solvents soluble in water and insoluble in water, after entering the aqueous solution of the small molecule additives, the solvent soluble hi water is miscible with water immediately and enters at water phase, the part of pesticides dissolved by the solvent will be precipitated from water, and a precipitation speed of pesticide crystals is controllable if a dropping speed of the miscible pesticide raw solution and a system stirring speed are controllable and the quantity of the solvent soluble in water is proper. Therefore, under the condition that a system solution is controlled to be transparent, the size of pesticide particles is controlled to be 100 tun or below. The remaining pesticide solution insoluble in waterbelongs to an oil phase in the system and cannot be mutually soluble with water, but according to the principle that like dissolves like, the oil-soluble pesticide solution may enter the micelles and the micelle-clusters formed by the small molecule additives to form solubilized micelles (see FIG. 2) and solubilized micelle-clusters (see FIG. 4). When volumes of the solubi li zed micelles and the solubilized Mkt I lc-clusters are small enough and smaller than 100 run, the system is clear and transparent. Since the solubilized micelles and the solubi liven micelle-clusters formed by this pan of raw pesticide solution are small in size, the solution is thermodynamically stable. To achieve this goal, a large number of micelles and micelle-clusters are needed, while a large number of small molecule surfactants are required for forming the large number of micelles and micelle-clusters. The mass percentage of the small molecule additives meeting this requirement should be 20% or above. There is no strict ratio of the anionic surfactant to the nonionic surfactant, except that the form and quantity of the micelles and the micelle-clusters formed by the two are different, but the HLB value jointly formed by them needs to be controlled to be 13 or above to gtmrantee generation of an 0/W emulsion. After comprehensive consideration, optimal selection principles of the small molecule additives are summarized in Table-6.

Table-6 Small molecule additive optimal selection principles Level Index Anionic additives Nonionic additives 1 Characteristic temperature Krafft temperature, as low as possible, as low as 0°C being conductive to low-temperature storage Cloud point temperature, as high as possible, being conductive to temperature control during vacuum distillation for solvent recovery 2 Chemical structure Catboxylate, sulfonate, sulfate or phosphate containing straight-chain or branched-chain hydrocarbon groups (alkalies and olefins) with 8 to 18 carbon atoms or (and) aryl groups Polyoxyethylene ether with hydrocarbon groups (alkalies and olefins) or (and) aryl groups, and with polyol Environmental friendliness Degradation difficulty: straight-chain hydrocarbyl salts > branched-chain hydrocarbyl salts > and salts Degradation difficulty!: straight-chain hydrocarbyl polyoxyethylene ether > branched-chain hydrocarbyl polyoxyethylene ether > aryl polyoxyethylene ether Water quality (resistance to standard hard water) Non-resistant to bard water Resistant to hard water HLB Usually greater than 13 Depending on the length of a polyoxyethylene chain, preferably >13 6 Micro morphology Micelles, solubilization property depending on use amount of additives Micelle-clusters, solubilization property depending on use amount of additives Component proportion of the polymer additives. The polymer additives need to be water-soluble, including the natural polymers and the synthetic polymers. Selection principles include: 1. properties shall be environmental-friendly. Considering the aspects of facilitating biodegradation and safety of degradation products, the natural water-soluble polymers and the derivatives thereof are preferably selected. The synthetic water-soluble polymers may also be selected if they have good properties and small impact on the environment. 2. The dissolving property shall be good. Different from small molecule dissolution, in polymer dissolution, a dissolution process often has a swelling stage, polymer dissolution is more difficult that small molecule dissolution and some polymers require long time. Their dissolving properties are affected by varieties, aggregation structures and relative molecular mass of the polymers. However, considering production, it is hoped that the dissolution process will not affect a production process, that is, the easier and the quicker dissolution, the better. 3. Cost performance shall be good. Relatively cheap varieties are selected as far as possible on the premise of meeting using properties.

To determine the component proportion of the polymer additives, the purpose of adding the polymer additives should be firstly considered. As described above, the water-soluble polymer additives generate random coils in 1 5 water after being dissolved in water. When the miscible pesticide raw solution is dropwise added into the mixed additive aqueous solution where the small molecule additives and the polymer additives are dissolved with a controllable speed under a mining condition, the solvent soluble in water in the mixed solvent is miscible with water, and the part of pesticides dissolving the solvent soluble in water is precipitated from the solution in a crystal form. By controlling a dropping speed and a stirring speed of the system, a precipitation speed of pesticide crystals and the size of the crystals may be controlled. The precipitated pesticide crystals are lipophilic (hydrophobic), thus will be diffused to hydrophobic interiors of the random coils formed by the polymer additives, and due to the small size of the crystals (keeping the system transparent indicates smaller than 100 mu), the crystals will be dispersed into the random coils formed by the polymer additives suspending in water, see FIG. 6. Accordingly, the polymer additives play roles in suspending, dispersing and stabilizing the generated nanopesticide crystals in fact. Due to large relative molecular mass of the water-soluble polymers, the viscosity of the aqueous solution is much higher than the viscosity of small molecules of the same concentration, which is a basic characteristic of the polymer solution. In order to both suspending the nanocrystals and keeping the viscosity of the system slightly higher than that of a microemulsion, for example, 300 to 500 inPa.s, the mass percentage of the polymer additives should be controlled to be about 5%.

The mixed additives are composed of the small molecule additives (20%) and the polymer additives (5%), so the total mass percentage of the two is about 25%.

After comprehensive consideration, optimal selection principles of the polymer additives are shown in Table-Table-7 Levels and properties of polymer additive selection

Level Index Description

1 Degradation Preferably select biodegradable water-soluble polymer additives, being conductive to protecting ecological environment 2 Dissolution Preferably select polymer additives with good solubility and fast dissolution in water, being conductive to accelerating a preparation process Cost Preferably select polymer additives with low cost to improve cost performance of products 4 Viscosity System viscosity depends on varieties, molecular mass and use amount of polymer additives, and suitable viscosity is conductive to improving stability of products (3) A remaining component is water. The mass percentage of water is about 40%. Water is a dispersion medium, playing a role in maintaining dispersion and stability of all the components in the system, so the proportion of water in the components is also quite important. If the proportion of water is too large and the proportions of the active ingredients and other components in the system are relatively small, it is not conductive to obtaining nanopestici des with high content of the active ingredients. If the proportion of water is relatively small, the system viscosity is relatively high, it is not conductive to generation, dispersion and stability of the nanopesticide crystals. A suitable proportion of water is necessary for preparing the nanopesticide suspension. Generally, the mass percentage of water should be about 40%.

The mass percentages of the components, the combined three components and the combined two components of the miscible nanopesticide suspension of the present invention are shown in Table-8 and Table-9.

Table-8 Mass percentages of components of miscible nanopesticide suspensio (ideal condition) Component Proportion of each Proportion of combined Proportion of combined component (%) three components (%) two components (%) Active ingredients (raw pesticides) 3-12 35+3 35+3 Miscible pesticide raw Miscible pesticide raw Mixed solvent (Ai) 23-32 solution (Bi) solution (Bi) Small molecule additives 16-21 25±2 65±3 Mixed additives Mixed additive aqueous solution (Di) Polymer additives 3-6 Water 40±2 40±2 Table-9 Mass percentages of components of miscible nanopesticide suspension (acceptable condition) Component Proportion of each Proportion of combined Proportion of combined component (%) three components (%) two components (%) Active ingredients (raw pesticides) 3-18 35±5 35±5 Miscible pesticide raw Miscible pesticide raw solution (Bi) solution (Bi) Mixed solvent (Ai) 17-32 Small molecule additives 12-22 25±3 65±5 Mixed additives Mixed additive aqueous solution (Di) Polymer additives 2-7 Water 40±5 40±5 IV. Preparation of nanopesticide suspension and formation of nanopesticide crystals 1. Preparation of mixed solvent and miscible pesticide raw solution A solvent system capable of dissolving pesticides is selected according to varieties of the pesticides, and the solvent system includes a water-soluble/water-insoluble mixed solvent system, including at least one solvent soluble in water and at least one solvent insoluble in water. The use amount of the pesticide active ingredients and the use amount of the mixed solvent (in mass percentage) are determined according to the solubility in Table-2.

The method is not limited to the pesticide varieties and solvent types collected in Table-2.

Solvents with the determined mass percentages, including the solvent soluble in water and the solvent insoluble in water, are added into a container provided with a reflux condenser, and are properly stirred to be prepared into the mixed solvent. The pesticide active ingredients with the determined mass percentages arc added into the above generated mixed solvent, and are properly stirred and dissolved to obtain the miscible pesticide raw solution in which the pesticide active ingredients are miscible. The pesticide active ingredients are dispersed in the miscible pesticide raw solution in a single-molecule fonn, and a true solution is generated and is transparent and stable.

2. Preparation of mixed additive aqueous solution The additives include the small molecule additives and the polymer additives, and the small molecule additives further include the anionic surfactant and the nonionic surfactant. Since the polymer additives arc relatively hard to dissolve, when being prepared, the mixed additive aqueous solution is finally obtained by firstly dissolving the polymer additives and then dissolving the small molecule additives. A preparation process is as follows: Water with the determined mass percentage is added into a container which is provided with stirring and reflux condensers and capable of performing heating and vacuum distillation, one or several polymer additives with the determined mass percentages are added under stirring, and static swelling is performed if necessary. After a certain period (several hours or one day), full swelling is achieved, and stirring is started until complete dissolution, so that a transparent polymer aqueous solution is generated. One or several small molecule additives with the determined mass percentages are added into the transparent polymer aqueous solution, and are stirred and dissolved to obtain the mixed additive aqueous solution. The mixed additive aqueous solution is transparent in appearance and stable. The mixed additive aqueous solution contains the small molecule additives and the polymer additives which form the micelles and the micelle-clusters in water, and the polymer additives form the random coils in water. Schematic diagrams of micro morphologies of the various additives in water are as shown in FIG. 7.

3. Generation of pesticide nanocrystals --preparation of miscible nanopesticide suspension In the system of the above prepared mixed additive aqueous solution, the miscible pesticide raw solution is dropwise added into the mixed additive aqueous solution under the condition that a stirring speed is controllable. By controlling dropping speed and stirring speed, the nanopesticide crystals, namely the miscible nanopesticide suspension is generated. If solvent recovery is not considered, the miscible nanopesticide suspension may also be used as nanopesticides.

A principle of generating the nanopesticide crystals is analyzed as follows: the miscible pesticide raw solution contains the solvents mutually soluble with water, for example, optional solvents include acetone, methanol, tetrahydrofuran, acetonitrile, etc. When the solution is dropwise added into a water phase, the solvent soluble in water is mutually soluble with water quickly and enters the water phase, and only a raw pesticide solution insoluble in water is left in the aqueous solution. Since the quantity of the solvent for dissolving the raw pesticides in the solution is reduced and the solvent is not enough to dissolve the original raw pesticides, part of the raw pesticides is precipitated from water. By controlling the dropping speed of the miscible pesticide raw solution and the stirring speed, the particle size of the uniformly precipitated raw pesticides may be controlled. The added solvent insoluble in water with the proportion actually plays an important role in controlling a precipitation speed of the raw pesticides, so the situation that the raw pesticides are precipitated too fast and thus forming large-size crystal aggregation is avoided. Accordingly, a ratio of the solvent soluble in water ° the solvent insoluble in water is also an important influence factor for controlling the precipitation speed of the pesticide nanocrystals. The raw pesticides are different in chemical structure and different in physical property and dissolving property, mixing ratios of the two or more selected solvents are also different, a mass ratio of the solvents is generally about 1:2, but it is better to be determined through experiments and proper adjustment.

The generated nanocrystals cannot stably exist in water. Due to the action of self-gravity, the crystals will aggregate and grow when being static, and consequently the crystals are precipitated out in a form of large-size crystals. To prevent this phenomenon, the polymer additives added into the system play roles in dispersion and stabilization. The water-soluble polymers exist in the morphological structure of random coils. Each random coil is of a loose spherical structure spontaneously fonned by water-soluble polymer chains, lipophilic and hydrophobic molecule main chains are aggregated inside, and hydrophilic polar groups are located outside. At the moment, when the system generates the pesticide nanocrystals, according to the principle that "like dissolves like", these lipophilic and hydrophobic nanopesticide crystals will spontaneously enter the random coils to be loaded by the random coils, sec FIG. 3b. The random coils play roles in suspending, dispersing, stabilizing and protecting the nanopesticide crystals. The random coils are evenly dispersed in the water phase, so that the mumpesticide crystals evenly dispersed in the random coils are also evenly dispersed in the water phase. When the size of the pesticide nanocrystals is 100 MB or below, the system looks clear and transparent.

Only the solvent insoluble in water remains in the miscible pesticide raw solution. Liquid drops of the raw pesticide solution are also lipophilic and have a much larger volume relative to the micelles, the micelle-clusters and the random coils. The liquid drops best go to the micelles and the micelle-clusters. According to the principle that "like dissolves like", they can quickly and spontaneously enter the micelles and the micelle-clusters to become the solubilized micelles and the solubilized micelle-clusters. As long as there are sufficient micelles and micelle-clusters, the remaining miscible pesticide raw solution can be solubilized and kept in the size of 100 nm or below, so that the system still looks clear and transparent.

Therefore, when the miscible pesticide raw solution is dropwise added into the aqueous solution containing the small molecule additives and the polymer additives continuously, the nanopesticide crystals are continuously generated and continuously enter the random coils formed by the polymer additives, and the remaining miscible pesticide raw solution continuously enters the micelles and the micelle-clusters until the miscible pesticide raw solution is completely dropwise added. It is not excluded that the generated nanopesticide crystals may also enter the micelles and the micelle-clusters to be dissolved and it is also not excluded that the remaining miscible pesticide raw solution may enter the random coils. However, from the stability analysis of the system, the before-mentioned dispersion condition should be the energy-minimum state. Schematic diagrams of forms of the nanopesticide crystals and various particles in the miscible pesticide raw solution are as shown in FIG. 8 4. Control over dropping speed and stirring speed 1 5 It should be noted that in the process of generating the nanopesticide crystals, the dropping speed of the miscible pesticide raw solution and the stirring speed for entering the mixed additive aqueous solution relate to the quantity of the solution entering the water phase in unit time and dispersion uniformity and are important factors affecting the size of the generated nanopesticide crystals. As for the dropping speed, if the goal is that the size of the precipitated nanopesticide crystals is smaller than 100 mu, whether the system is clear and transparent is a criterion. Its theoretical basis is that when the particle size is less than one quarter of the wavelength of the visible light, no serious refraction or reflection is produced, so the system is transparent. The wavelength of the visible light is 400 to 760 mu, so less than one quarter is 100 mu or below. Vice versa, if the system where the nanopesticide crystals are generated is clear and transparent, it indicates that the size of the generated crystals is smaller than 100 To achieve this goal, the following needs to be noticed: 1. the dropping speed of the miscible pesticide raw solution shall not be too fast. If the dropping speed is too fast, the pesticide crystals are generated faster, and when too many nanopesticide crystals are simultaneously generated in the water phase, the nanocrystals may be aggregated, so the crystals may be larger. If opalescence appears in the system, it indicates that the size of the crystals has been hundreds of mmometres, and if the opalescence is more and more serious and even the system is not transparent, it indicates that the size of the crystals has been close to or exceeded one micron. Accordingly, the dropping speed should keep the system transparent all the time. 2. A dropping way of the solution may also affect the size of the crystals. To obtain the uniform and small-size nanocrystals, the solution may be dropwise added in a more even dispersion way, such as single point dropping, multi-point dropping and spray dropping. When the liquid drops of the dropwisc-added miscible pesticide raw solution are smaller and more even, the speed of generating the nanopesticide crystals is more even, and thus aggregation of the crystals can be avoided and the obtained nanocrystals are smaller. 3. The stirring speed of the system shall be properly increased. The stirring speed of the system relates to a generation speed and a dispersion speed of the nanopesticide crystals generated in the water phase, and the faster the stirring, the faster the dispersion, the less likely to aggregate and collide among the crystals, and the more conductive to keeping dispersion of the small-size crystals. The stirring speed of the system should be greater than the stirring speed for dissolving the raw pesticides in the mixed solvent, and should also be greater than the stirring speed for dissolving the polymer additives and the small molecule additives in water. The stirring speed of the system is matched with the dropping speed of the miscible pesticide raw solution to obtain the small-size and unifoma nanopesticide crystals. After the miscible pesticide raw solution is completely dropwisc added, the miscible nanopesticide suspension has been obtained at the moment, and may also be used as a nanopesticide dosage form.

5. Recovery of solvents (heating and vacuum distillation) --preparation of nanopesticide suspension The miscible nanopesticide suspension obtained above further contains organic solvents with determined mass percentages. Pesticide active ingredients dissolved in this part of solvents do not exist in a nanocrystal way. For this reason, a final process is further required to complete this transformation.

The final preparation process of the present invention is vacuum distillation. Vacuum distillation is performed for the following purposes: 1. All the pesticide active ingredients are transformed to the form of the nanopesticide crystals, that is, all or most of the pesticide active ingredients in the system are transformed to the nanocrystals. 2. The organic solvents in the system are recovered to further improve environmental friendliness of the nanopesticide suspension. 3. The organic solvents are recovered by vacuum distillation to concentrate the miscible nanopesticide suspension, and the active ingredient content of the nanopesticide suspension may be increased.

The miscible nanopesticide suspension obtained above contains the organic solvents which include a solvent soluble in water and a solvent insoluble in water. The organic solvent soluble in water is miscible in the water phase. A solution, dissolving the active ingredients, of the solvent insoluble in water is sohibil ized in the micelles or the micelle-clusters. In a process of vacuum distillation, a solvent with a relatively low boiling point is firstly evaporated. For example, in an acetone/methyl ethyl ketone mixed solvent system, acetone is miscible with water and has a relatively low boiling point so as to be firstly evaporated, where the boiling point is 56.12°C. After the acetone is evaporated, an azeotrope of methyl ethyl ketone-water (at a composition ratio of 88.7/11.3) with a boiling point of 73.41°C starts to be evaporated. Since pesticide active ingredients are still dissolved in methyl ethyl ketone and exist in the micelles or the micelle-clusters, in a pressure reduction process, the pesticide active ingredients dissolved in the solvent are continuously precipitated to generate the pesticide nanoctystals along with evaporation and gradual decrease of the methyl ethyl ketone solvent. The pesticide mmocrystals may continue staying in the micelles or the micelle-clusters, and may also be precipitated from the micelles or the micelle-clusters to be transferred into the random coils formed by the polymer additives until all or most of the methyl ethyl ketone solvent is evaporated.

A solvent evaporation way depends on the boiling points of the solvents and the cloud point temperature of the nonionic surfactant The cloud point temperature of a commonly used nonionic surfactant is usually about 60°C, the boiling point of the acetone is lower than 60°C, so the acetone can be distillated under a normal pressure, while an azeotropic point of the methyl ethyl ketone-water is 74°C which exceeds the cloud point temperature, so the methyl ethyl ketone-water needs to be distillated under reduced pressure. Vacuum distillation of the organic solvents in the system will relate to types and boiling points of the organic solvents and whether the solvents can form an azeotrope with water, including the composition and boiling point of the azeotrope and a relation between the boiling point and pressure. In order to accelerate evaporation of the azeotrope, the system may be heated. There are some points needing to be noticed: 1. Azeotropes formed by different solvents and water are different in boiling point. Azeotropic points and compositions of azeotropes that may be fonned by some solvents involved in the present invention are collected in Table-10. During vacuum dishllahon, the solvents with low azeotropic points are firstly evaporated, and then the solvents with high azeotropic points are evaporated. According to the compositions of the azeotropes, the mass of water carried by the evaporated solvents with different mass percentages may be approximately worked out. Accordingly, the mass percentage of the pesticide active ingredients in the miscible nanopesticide suspension finally generated is further worked out. It should be noted that not all the organic solvents can be completely evaporated, and when a certain solvent has a relatively high boiling point, the solvent is very hard to evaporate, such as di methyl forma m ide and di methyl sulfoxide, so it should be cautious to select this kind of solvents.

2. Different solvents may form a ternary azeotrope with water.

3. The relations between boiling points of the azeotropes formed by different solvents and water and pressure are different. When the azeotropic point temperature is relatively high, the boiling point of the azeotropes can only be lowered under a reduced pressure condition. The system needs to be properly heated to achieve a boiling point temperature when the pressure is reduced to a certain vacuum degree.

4. A maximum temperature of system heating is limited. A system heating temperature needs to be lower than the cloud point temperature of the nonionic surfactant. Otherwise, since the temperature of the nonionic surfactant in the system is raised to the cloud point temperature or above, turbidity and aggregation will occur, and the stability of the system is damaged.

5. The content of the pesticide active ingredients before and after vacuum distillation changes. After vacuum distillation, the organic solvents in the system may be evaporated as far as possible, meanwhile, part of water is carried outside through the azeotropes, so the amiss percentage of the system changes, and the mass percentage of the pesticide active ingredients also changes. A formula (1) shows that the sum of mass percentages of all the components is 100%. A formula (2) is an expression of the mass percentage of the pesticide active ingredients before vacuum distillation. A formula (3) is an expression of the mass percentage of the pesticide active ingredients after vacuum distillation.

100% = W % = + Si% + S2% ± Adl% Ad2%+ W,% CO 1.1 W a (2) W.1.2% (3) Sz+ Ad, + Ada+ W,, = ajWAdy+Ad2+Ww2 In the formulas, Waif and Wa, 2 are respectively the mass percentages of the pesticide active ingredients before and after vacuum distillation, and Wit l<Wai.2; Wwi and Ww2 are respectively mass of water before and after vacuum distillation, and W., >Ww.

It can be seen that the content of the pesticide active ingredients is increased after vacuum distillation. Table-10 Compositions and boiling points of binary azeotropes of solvent-water (pressure being 101.3 kPa) Solvent Azeotropic point Mass Acetone 56.12 (no azeotrope) 100 Methanol 64.51 (no azeotrope) 100 Tetmhydroftwan 63.4 95 Ethanol 78.17 96.0 Acetonitrile 76.0 85.8 Methyl ethyl ketone 73.41 882 3-methyl-2-butanone 79 87.0 Cyclohexanone 95.0 384 Ethyl acetate 70.38 91.5 Propyl acetate 824 86.0 Isopropyl acetate 76.6 89.4 I sobuty I acetate 87.4 83.5 Ethyl propionate 81.2 90 Propyl propionate 88.9 77.0 Ethyl butyrate 87.9 78.5 Methyl isobutyratc 77.7 93.2 Toluene 84.1 80.4 Benzene 69.25 91.2 Dichloromethane 38.1 98.5 Chloroform 56.12 97.2 Carbon tetrachloride 66.0 95.9 V. Preparation process flowchart and notes Preparation process flows and notes of the miscible nanopesticide suspension and the nanopesticide suspension of the present invention arc summarized in Table-11.

Table-11 Preparation process flows and opera ion points of nanosuspension Sequence Preparation process Process flow Operation points mid description 1 Preparation of mixed solvent See FIG. 9 1. Mixing of a water-soluble solvent and a water-insoluble solvent 2. A mass ratio of the two is 1:2 to 1.5:1.5 2 Miscible pesticide raw solution See FIG. 10 Dissolving raw pesticides in a mixed solvent to obtain a miscible pesticide raw solution Preparation of mixed additive aqueous solution See FIG. 11 1. Polymer additives are hard to dissolve and are dissolved firstly; static swelling is perfomied if necessary 2. Small molecule additives are then added after the polymer additives are completely dissolved and a transparent polymer aqueous solution is formcd 4 Preparation of miscible nanosuspension-controlled dropping See FIG. 12 1. Dropping way (small-point, multi-point, spray) and dropping speed 2. Related to a stirring speed, a preferred stirring speed is 100 to 200 Muni 3. Matching marks of the two: transparent system, no sediment Preparation of nanosuspension- See FIG. 13 1. A vacuum distillation speed affects a generation speed of pesticide nanocrystals, and should not be too fast vacuum distillation 2. The higher a vacuum degree, the faster the solvent evaporation 3. Temperature rise is conductive to solvent evaporation,but a temperature shall not be higher than a cloud point temperature of a nonionic surfactant

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 Micelle

FIG. 2 Solubilized micelle FIG. 3 Micelle-cluster FIG. 4 Solubilized micelle-cluster FIG. 5 Random coil FIG. 6 Random coil loaded with nanomystals FIG. 7 Schematic diagram of micro morphologies of small molecule additives and polymer additives in water FIG. 8 Schematic diagram of micro distribution morphologies of pesticide nanocrystals and pesticide liquid globules insoluble in an aqueous solution FIG. 9 Preparation of a mixed solvent FIG. 10 Preparation of a miscible pesticide raw solution 1 5 FIG. 11 Preparation of a mixed additive aqueous solution FIG. 12 Preparation of a miscible nanosuspension FIG. 13 Preparation of a nanosuspension

DETAILED DESCRIPTION

Dosage forms in the present invention are illustrated in detail below through preferred embodiments. But the present invention is not merely limited to the following embodiments.

Various raw materials used in the embodiments are connuercially available. Embodiment 1: 8% prothioconazole nanosuspension Raw material proportions (mass percentage): Prothioconazole 6% (weight percentage, the same below) Sodium!amyl sulfate 4% Sodium oleate 6% AE015 5% A E020 7% Carboxymethyl starch 2% Tea sapo n n 3% Acetone 4% Methyl ethyl ketone 20% Water 43% The 8% prothioconazole nanosuspension is prepared by the following method (in terms of 100 kg of fed mate ri als): I. The acetone and the methyl ethyl ketone are mixed to be prepared into a mixed solvent which is recorded as a component Ai.

II. The prothioconazole is dissolved in the mixed solvent Ai to obtain a miscible pesticide raw solution which is recorded as a component Bt.

Ill. The carbonmethyl starch and the tea saponin are dissolved in the water to obtain a polymer additive aqueous solution which is recorded as a component Cu IV. The sodium lamyl sulfate, the sodium oleate, the AE015 and the AE020 arc dissolved in the component CI to obtain a mixed additive aqueous solution which is recorded as a component Di.

V. Under a proper stirring speed, the component Bi is slowly dropwise added into the component Di. The stirring speed and a dropping speed are matched to keep a system transparent and avoid sediments. After dropwise adding, a miscible nanopesticide suspension Ei is obtained.

VI. Vacuum distillation is performed to gradually reach a maximum vacuum degree of equipment. The system is gradually heated with a maximum temperature not higher than 55°C vacuum distillation is performed for 0.5 to 1 hour to obtain a nanopesticide suspension Ft, and the weight of the product is about 70 kg.

Further, the content of a prothioconazole active ingredient is measured, and water is supplemented until the content of the active ingredient is 8% to obtain a prothioconazole nanosuspension product (about 75 kg). The product is transparent in appearance, and it is predicted according to Tyndall phenomenon that a particle size of the pesticide active ingredient is 100 nm or below. The particle size and size distribution arc measured by a laser nanometre particle size analyzer.

Embodiment 2: 15% cyllufenamid nanosuspension Raw material proportions (mass percentage): Cyflufenamid 12% (weight percentage, the same below) Sodium hturyl sulfate 3% Sodium linoleate 5% Tween-40 8% AE020 6% Modified guar 2% Polyvinyl alcohol 2% Ethanol 7% Ethyl acetate 13% Water 42% The 15% cyflufenaruid mmosuspension is prepared by the following method (in terms of 100 kg of fed materials): I. The ethanol and the ethyl acetate are mixed to be prepared into a mixed solvent which is recorded as a component A2.

II. The cyflufenmaid is dissolved inthe mixed solvent A2 to obtain a miscible pesticide raw solution which is recorded as a component B2.

III. The polyvinyl alcohol and the modified guar are dissolved in the water to obtain a polymer additive aqueous solution which is recorded as a component IV. The sodium laurel sulfate, the sodium linoleate, the Tween-40 and the AE020 are dissolved in the component Cs to obtain a mixed additive aqueous solution which is recorded as a component D2.

V. Under a proper stirring speed, the component B2 is slowly dropwise added into the component D2. The stirring speed and a dropping speed are matched to keep a system transparent and avoid sediments. After dropwise adding, a miscible nanopesticide suspension E2 is obtained.

VI. Vacuum distillation is performed to gradually reach a maximum vacuum degree of equipment. The system is gradually heated with a maximum temperature not higher than 55°C, vacuum distillation is performed for 0.5 to 1 hour to obtain a nanopesticide suspension F2, and the weight of the product is about 78.5 kg.

Further, the content of a cyflufenzurid active ingredient is measured to be about 16%. The product is transparent in appearance, and it is predicted according to Tyndall phenomenon that a particle size of the pesticide active ingredient is 100 urn or below. The particle size and size distribution are measured by a laser nimometre particle size analyzer.

Embodiment 3: Preparation of 16% eyflumetofen nanosuspension Raw material proportions (mass percentage): Cyflumetofen 12% (Weight percentage, the same below) Sodium laurel ether sulfate 3% Sodium linoleate 4% Polyoxyethylene castor oil 4% Tween-80 5% Carboxymethyl cellulose 1% Sodium lignin sulfonate 2% Tea saponin 2% Acetone 5% Ethyl acetate 20% Water 42% The 16% eyflumelofen nanosuspension is prepared by the following method (in terms of 100 kg of fed materials): I. The acetone and the ethyl acetate are mixed to be prepared into a mixed solvent which is recorded as a component A3.

II. The cyflumetofen is dissolved in the mixed solvent A3 to obtain a miscible pesticide raw solution which is recorded as a component B. ITT. The carboxymethyl cellulose, the sodium lignin sulfonale and the tea saponin are dissolved in the water to obtain a polymer additive aqueous solution which is recorded as a component C3.

IV. The sodium lauryl ether sulfate, the sodium linoleate, the polyoxyethylene castor oil, and the Tween-80 are dissolved in the component C3 to obtain a mixed additive aqueous solution which is recorded as a component D3.

V. Under a proper stirring speed, the component B3 is slowly dropwise added into the component D3. The stirring speed and a dropping speed are matched to keep a system transparent and avoid sediments. After dropwise adding, a miscible nanopesticide suspension Ei is obtained.

VI. Vacuum distillation is performed to gradually reach a maximum vacuum degree of equipment. The system is gradually heated to 56°C, vacuum distillation is performed for 0.5 to 1 hour, the weight of a product is about '73 kg, and a nanopesticide suspension F3 is obtained.

Further, the content of a cyflumetofen active ingredient is measured, and water is supplemented until the active ingredient is 16% so as to obtain a cyfhunetofeniumopesticide suspension which is about 75 kg. The product is transparent in appearance, and it is predicted according to Tyndall phenomenon that a particle size of the pesticide active ingredient is 100 mu or below. The particle size and size distribution are measured by a laser nanometre particle size analyzer Embodiment 4: 18% tebufenpyrad nanosuspension Raw material proportions (mass percentage): Tchufenpyrad 14% (weigh( percentage, the same below) Sodium monododecyl phosphate 3% Sodium linoleate 5% AE020 5% Alkyl polyglycoside 6% Sodium ctuboxymethyl starch 2% Sodium carboxymethyl cellulose 1% Methanol 4% Methyl ethyl ketone 16% Water 44% The 18% tebufenpyrad nanosuspension is prepared by the following method (in terms of 100 kg of fed materials): I. The methanol and the methyl ethyl ketone are mixed to be prepared into a nixed solvent which is recorded as a component A4.

II. The tebufenpyrad is dissolved in the mixed solvent A4 to obtain a miscible pesticide raw solution which is recorded as a component. B4.

III. The sodium carboxymethyl starch and the sodium carboxymethyl cellulose are dissolved in the water to obtain a polymer additive aqueous solution which is recorded as a component C4.

IV. The sodium monododecyl phosphate, the sodium linoleate, the AE020 and the alkyl polyglycoside are dissolved in the component C4 to obtain a mixed additive aqueous solution which is recorded as a component D4.

V. Under a proper stirring speed, the component B4 is slowly dropwise added into the component D4. The stirring speed and a dropping speed are matched to keep a system transparent and avoid sediments. After dropwise adding, a miscible nanopesticide suspension ELL is obtained.

VI. Vacuum distillation is performed to gradually reach a maximum vacuum degree of equipment. The system is gradually heated with a maximum temperature not higher than 56°C_ vacuum distillation is performed for 0.5 to 1 hour to obtain a nanopesticide suspension F4, and the weight of the product is about 76.5 kg.

Further, the content of a tebufenpyrad active ingredient is measured, and water is supplemented until the content of the active ingredient is 18% so as to obtain a tebufenpyrad nanosuspension which is about 77 kg. The product is transparent in appearance, and it is predicted according to Tyndall phenomenon that a particle size of the pesticide active ingredient is 100 inn or below. The particle size and size distribution are measured by a laser nanometre particle size analyzer.

Embodiment 5: 10% cyhalofon-butyl nanosuspension Raw material proportions (mass percentage): Cy hal ofop-buty 7% (weight percentage, the same below) Sodium a-olefin sulfonate Sodium ricinoleate 4% Tween-80 4% Polyoxyethylene castor oil 6% Styrene-maleic anhydride copolymer 2% Sodium lignin sulfonate 2% Methanol 8% Ethyl acetate 20% Water 44% The 10% cyhalofop-butyl nanosuspension is prepared by the following method (in terms of 100 kg of fed materials): I. The methanol and the ethyl acetate are mixed to be prepared into a mixed solvent which is recorded as component A5.

II. The cy halMop-butyl is dissolved in the mixed solvent AS to obtain a miscible pesticide raw solution which is recorded as component B5.

III. The styrene-maleic anhydride copolymer and the sodium lignin sulfonate are dissolved in the water to obtain a polymer additive aqueous solution which is recorded as component CS.

IV. The sodium a-olefin sulfonate, the sodium ricinoleate, the Tween-80, and the polyoxyethylene castor oil are dissolved in the component Cs to obtain a mixed additive aqueous solution which is recorded as component D5.

V. Under a proper stirring speed, the component BS is slowly dropwise added into the component Ds. The stirring speed and a dropping speed are matched to keep a system transparent and avoid sediments. After dropwise adding, a miscible nanopesticide suspension Es is obtained.

VI. Vacuum distillation is performed to gradually reach a maximum vacuum degree of equipment. The system is gradually heated with a maximum temperature not higher than 55°C, vacuum distillation is performed for 0.5 to 1 hour to obtain a nanopesticide suspension Fs, and the weight of the product is about 69 kg.

Further, the content of a cyhalofop-butyl active ingredient is measured, and water is supplemented until the content of the active ingredient is 10% so as to obtain a cyhalorop-butyl nanosuspension which is about 70 kg. The product is transparent in appearance, and it is predicted according to Tyndall phenomenon that a particle size of the pesticide active ingredient is 100 mn or below. The particle size and size distribution are measured by a laser nanometre particle size analyzer.

Claims

Claims 1. A miscible nanosuspension, said miscible nanosuspension is an aqueous dispersion of coexisting nanocrystal and solubilized micelles, formed by dropwise adding a miscible pesticide raw solution into a mixed additive aqueous solution; said miscible pesticide raw solution is a solution formed by dissolving pesticide raw into a mixed solvent; said mixed additive aqueous solution is formed by dissolving polymer additives and small molecule additives into water in sequence, respectively; said mixed solvent is formed by mixing at least two kinds of solvent according to a certain mass percentage; said mixed solvent includes at least one solvent soluble in water and one solvent insoluble in water; each said solvent is able to dissolve pesticide raw.
2. A miscible nanosuspension according to claim 1, wherein sum total of mass percentage of said miscible pesticide raw solution and mass percentage of said mixed additive aqueous solution, in said miscible nanosuspension, is 100%; range of said mass percentage of said miscible pesticide raw solution is 35% ± 5%; range of said mass percentage of said mixed additive aqueous solution is 65% ± 5%; preferably, said range of said mass percentage of said miscible pesticide raw solution is 35% ± 3%, said range of said mass percentage of said mixed additive aqueous solution is 65% ± 3%.
3. A miscible nanosuspension according to claim 2, wherein range of mass percentage of said pesticide raw in said miscible pesticide raw solution is 3%-18%, range of mass percentage of said mixed solvent in said miscible pesticide raw solution is 17%-32%; preferably, said range of said mass percentage of said pesticide raw is 3%-12%, said range of said mass percentage of said mixed solvent is 23%-32%.
4. A miscible nanosuspension according to claim 2, wherein said polymer additives and said small molecule additives form a mixed addictive; range of mass percentage of said mixed addictive in said miscible nanosuspension is 22%-28%; range of mass percentage of said water in said miscible nanosuspension is 35% -45%; preferably, said range of mass percentage of said mixed addictive in said miscible nanosuspension is 23%-27%, said range of mass percentage of said water in said miscible nanosuspension is 38%-42%.
5. A miscible nanosuspension according to claim 4, wherein range of mass percentage of said small molecule additives in said miscible nanosuspension is 12%-22%, range of mass percentage of said polymer additives in said miscible nanosuspension is 2%-7%; preferably, said range of mass percentage of said small molecule additives in said miscible nanosuspension is 16%-21%, said range of mass percentage of said polymer additives in said miscible nanosuspension is 3%-6%.
6. A miscible nanosuspension according to any of claims 1 to 5, wherein HLB value of said small molecule additives is at least 13; preferably more than 14.
7. A miscible nanosuspension according to any of claims 1 to 5, wherein said small molecule additives include anionic additive and nonion additive.
8. A miscible nanosuspension according to claim 7, wherein said anionic additive is carboxylate, sulfonate, sulfate or phosphate constituted by straight-chain or branched-chain hydrocarbon groups with 8 to 18 carbon atoms.
9. A miscible nanosuspension according to claim 7, wherein said anionic additive is sodium, potassium or ammonium salt of carboxylic acid, sulfonic acid, sulfuric acid or phosphoric acid, constituted by straight-chain hydrocarbon groups with 8 to 18 carbon atoms.
10. A miscible nanosuspension according to claim 7, wherein said nonion additive is polyoxyethylene ether surfactant, polyol surfactant, or oxyethylene-oxypropylene polyether surfactant; the oxyethylene polyether surfactant does not include nonylphenol polyoxyethylene ether surfactant.
11. A miscible nanosuspension according to any of claims 1 to 5, wherein said polymer additives include water-soluble natural polymer, water-soluble natural polymer derivative or water-soluble synthetic polymer substance.
12. A miscible nanosuspension according to claim 11, wherein said water-soluble natural polymer, said water-soluble natural polymer derivative or said water-soluble synthetic polymer substance is readily-biodegradable substance.
13. A miscible nanosuspension according to any of claims 1 to 5, wherein said pesticide raw and said mixed solvent are selected from the following table: No. Pesticide varieties Mixed solvents Soluble in water (g/L) I Insoluble in water but soluble in solvents (g/L) * 1 Fenpyrazamine acetone, methanol methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone. ethyl acetate, propyl acetate, isopropyl acetate 2 Metrafenonc acetone, acetonthile methanol methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate. propyl acetate isopropyl acetate. dichloromethane toluene 3 Metominostrobin dimethyl sulfoxide, acetone dichloromethane. chlorofrom, ethyl acetate. methyl ethyl ketone, cyclohexanone 4 Quinoxvfen acetone methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, isopropyl acetate, dichloromethane toluene Penthiopyrad methanol. acetone methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, isopropyl acetate 6 Pyraelostrobin acetone, isopol, methanol methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate, propyl acetate, isopropyl acetate. dichloromethane, toluene ropan, acetonitri le Isopyrazam acetone, methanol methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate, propyl acetate, isopropyl acetate, dicliloromethane 8 Prolliloconazole acetone, dimethyl sulfoxide, acelonitrile, n-octanol, isopropanol methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate, propyl acetate, isopropyl acetate, dichloromethane 9 Pmquinazid acetone, w mide. n- cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate, propyl acetate, isopropyl acetate, dichloromethane, n-hexane dimell l forma -octanol Boscalid acetone, methanol methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone. ethyl acetate, propyl acetate, isopropyl acetate 11 Picoxy strobin acetone, methanol, methyl ethyl ketone. cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate, propyl acetate, isopropyl acetate, xylene, dichloroethane 12 Famoxadone acetone, acetonitrile methyl ethyl ketone, cyclohexanone, methyl c -clohexartone, acetophenone. ethyl acetate, propyl acetate, isopmpyl acetate, dichloromethane 13 Fluopicolide acetone, dimethyl sulfoxide methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dichloromethane 14 Fluopyram acetone, dimetlndsulfoxide, methanol methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dichloromethane Fluazinam acetone, methanol methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dichloromethane, toluene 16 Triflumizole acetone, methanol cyclohexanone, acetophenone, ethyl acetate, dichloromethane, toluene 17 Oxathiapiprolin acetone methyl ethyl ketone, cyclohexanone, acetophenone, dichloromethane 18 Flutolanil acetone, acetonitrile, methanol methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate, propyl acetate, isopropyl acetate, dichloromethane 19 Sedaxane acetone, methanol methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate, propyl acetate, isopropyl acetate, dichloromethane Penflufen acetone, methanol, dimethyl sulfoxide methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, acetophenone, ethyl acetate, propyl acetate, isopmpyl acetate, dichloromethane 21 Fludioxonil acetone methyl ethyl kctonc, cyclohexanone, acctophcnonc. ethyl acetate 22 Silthiopham acetone, methanol methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, xvlene, dichloromethane 23 Cyproconazole acetone, ethanol, methanol, dimethyl sulfoxide, octanol methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dichloromethane, xylem, toluene 24 Cyfhtlenamid acetone, acetonitrilenethanol, ethanol methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, isopropyl acetate, dichloromethane, xylene, Fenbuconazole acetone, methanol methyl ethyl kctonc, cyclohexanone, acetophenone, ethyl acetate dichloroethane 26 Nittalaxyl-m miscible with acetone, methanol, and n-octanol miscible with methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dichloromethanc, toluene, etc. 27 Bixafen acetone methyl ethyl ketone, cyclohexanone, acetophenone, dichloromethane (102) 28 Fenamidone acetone, acetonitrile methyl ethyl kctonc, cyclohexanone, acctophcnonc, dichloromethane 29 Kreson-methyl acetone methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dicliloromethane Cyprodinil acetone, ethanol, n-octanol methyl ethyl ketone, cyclohexanone, acctophcnonc. toluene 31 Mandipropamid acetone, methanol methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dichloromethane 32 Tetraconazole easily soluble in acetone and methanol methyl ethyl ketone, cyclohexanone,, acetophenone, easily soluble in dichloroethane 33 Trilloxystrobin acetone, methanol methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dichloromethane 34 Penconazole acetone, ethanol, n-octanol methyl ethyl kctonc, cyclohexanone, acctophcnonc, toluene Probcnazolc easily soluble in acetone and dimethyl formamide methyl ethyl ketone, cyclohexanone, acetophenone, easily soluble in chloroform 36 Solatenol acetone methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dicliloromethane, 36 Metconazole acetone, methanol, isopropanol methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dichloromethane, toluene 37 Ipconazole acetone, methanol, n-octanol, methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dichloromethane, dichloroethane, toluene, Wen° Insecticide 38 Tebufenpy and acetone, methanol, acetonitrile methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetophenone, dichloromcthanc, toluene, hexane 39 Cyflumetofen acetone, methanol methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetophenone, ethyl acetate, toluene Pyridalyl acetone, acetonibile, n-octanol, dimethyl formamidc, methanol methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, trichloromethanc, toluene, hexane 41 Fluensulfone acetone, methyl ethyl ketone, cyclohexanone, acetophenone, ell.1 acetate, dichloromethane 42 Efficient cyhaloflutin acetone, methanol methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate 43 Bifenthrin acetone methyl ethyl ketone, cyclohexanonc, acetophenone, chloroform, dichloromethane, toluene, diethyl ether 44 Spirotetramat acetone, dimethyl sulfoxide, ethanol methyl ethyl ketone, cyclohexanone, acetophenone, dichloromethane, ethyl acetate Spirodiclofen acetone, acetonitrile methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dichloromethane, xylem 46 Metaflumizone acetone, acetonibile methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dichloromethane 47 Lufenuron acetone, methanol methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, 48 Etoxazole acetone, tetrahydrofuran, methanol methyl ethyl ketone, cyclohexmlone, acetophenone, ethyl acetate, 49 Indoxacarb acetone, methanol, acetonitrile methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate Tolfenpy and acetone, methanol methyl ethyl ketone, cyclohexanonc, methyl ethyl ketone, acetophenone, ethyl acetate, toluene I Fenpyroximate acetone, tetrahydrofuran methyl ethyl keto, cyclohexanone, acetophenone, ethyl acetate, chloroform, toluene methanol methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetophenone, ethyl acetate, xylene Herbicide 53 Amicarbazone acetone, acetonitrile, methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetophenone, ethyl acetate, dichloromethane isopropanol, dimethyl sulfoxide 54 Saflufenacil acetone, tetrahydrofuran, acetonitrile methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate Oxadiargyl acetone, acetonitrile methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dichloromethane 56 Metamifop acetone, methanol methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate dichloroethanc 57 Fluitamone acetone, methanol methyl ethyl ketone, cyclohexanone, acetophenone, dichloromethane 58 TefunErione acetone metMlethvl ketone, cyclohexanone, acetophenone 59 Picolinafen acetone methyl ethyl ketone, cyclohexanone, acetophenone, ethyl acetate, dichlorocthane Flufenacet acetone, isopropanol, dimethyl formamide methyl ethyl ketone, cyclohexanom, acetophenone, toluene, dichloromethane 61 S-metolachlor easily soluble in acetone and methanol easily soluble in methyl ethyl ketone, cyclohexanone, ethyl acetate dichloromethane toluene and n-hexane 62 Pyriminobac-m acetone, methanol methyl ethyl ketone, cyclohexanone, ethyl acetate, dichloromethane 63 Eluthiacet-methyl acetone, acetonitrile methyl ethyl ketone, cyclohexanone, acetophenone, dichloromethane, ethyl acetate 64 Cyhatofop-butyl acetone, methanol methyl ethyl ketone, ethyl acetate, dicliloroethane Propyzamide acetone, methanol, isopmpanol, dimethyl sulfoxide methyl ethyl ketone, cyclohexanone, methyl ethyl ketone 66 Acifluorfen acetone, ethanol methyl ethyl ketone, cyclohexmlone, acetophenone, meth ethyl ketone 67 Trichlopyr acetone, methanol methyl ethyl ketone, cyclohexanone, acetophenone, methyl ethyl ketone, ethyl acetate 68 Florasulam acetone, acetonitrile methyl ethyl ketone, cyclohexanone, acetophenone, methyl ethyl ketone 69 Pyraclonil acetone methyl ethyl ketone, cyclohexanone, acetophenone, methyl ethyl ketone Ethofumesate acetone, ethanol methyl ethyl ketone, cyclohexanonc, acetophenone, methyl ethyl ketone, trichloromethane 71 Oxyfluorfen acetone methyl ethyl ketone, cyclohexanone, acetophenone, methyl ethyl ketone, isophomne 72 lsoxaflutole acetone methyl ethyl ketone, cyclohexanone, acetophenone, methyl ethyl ketone, ethyl acetate, dichloromethanc 73 Pinoxaden acetone, methanol, octanol methyl ethyl ketone, cyclohexanone, acetophenone, methyl ethyl ketone, ethyl acetate, dichloromethane