WO2014101149A1 - Pesticide solvent and preparation method and applications thereof - Google Patents

Abstract

A pesticide solvent and a preparation method and applications thereof. The pesticide solvent comprises an unsaturated ester-amide expressed by a structural formula R'OCOCH=CH(CH₂)_nCON(R₁R₂), wherein n=0-8, and R' refers to an alkyl of C₁-C₆; and R₁ and R₂ respectively refer to alkyls of C₁-C₆ or nitrogen heterocycles formed by alkyls of C₁-C₆ and N. The unsaturated ester-amide of the pesticide solvent contains both ester functional groups and amide functional groups, and therefore, has a strong dissolving capacity; and the unsaturated ester-amide is of non-toxicity or low-toxicity, and can be widely applied to various pesticide preparations or prepared pesticide tank-mixing aids.

Description

Pesticide solvent and preparation method and application thereof Technical field

 The invention relates to the technical field of pesticides, in particular to a pesticide solvent and a preparation method and application thereof.

Background technique

 Environmentally friendly, safe, Efficient biological, biomimetic or bio-sourced pesticides have gradually become an important trend in the development of the current pesticide industry. In recent years, China has made great progress in the development and application of biological and biomimetic pesticides. Abamectin, emamectin formate (referred to as: avidin), Bacillus thuringiensis, new Biological biomimetic pesticide compounds such as nicotine analogues, pyrethroids and insect growth regulators have been successfully industrialized in China, and their crude drug production and export volume are among the highest in the world.

 However, the level of formulation development and industrialization of pesticides in China is still in a low-level stage, and most pesticide preparations are still traditional emulsifiable concentrates (% of the ratio). 40%-50% or so) or powder, hundreds of thousands of tons of contaminated solution per year / Auxiliaries are discharged into the agro-ecological environment with pesticide products, and become the most important source of pollution for the atmosphere, soil and food. Take the avermectin, the largest bio-pesticide variety in China, for example. Most of its registered products are emulsifiable concentrates. 80 More than % is a 'triphenyl' type light aromatic hydrocarbon organic solvent. These solvents are not only highly polluting, but also have high energy consumption, and have different degrees of toxic effects on humans and animals. For example, toluene enters the body and causes serious damage to the nervous system; Xylene can cause loss of appetite, nausea, vomiting and abdominal pain, sometimes causing reversible damage of liver and kidney Long-term exposure can cause nervous system dysfunction; long-term exposure to benzene can cause bone marrow and genetic damage, white blood cells, thrombocytopenia, whole blood cell reduction and aplastic anemia, and even leukemia. International Cancer Research Center (IARC) Benzene has been identified as a Class I carcinogen. The poisoning problem of the solubilizer/auxiliaries eclipses the 'biological' characteristics of biological pesticides. Therefore, only environmentally friendly / Bio-sourced pesticides produced by auxiliaries are truly green products, and solving this problem is one of the most important and urgent issues in the current research and development of pesticides.

The traditional light aromatic non-environmental solvent substitutes appearing on the market are summarized as follows: plant-derived green solvents (vegetable oils and their modified vegetable oils, epoxidized soybean oil, pine oil, jatropha oil, biodiesel, etc.), petroleum / Coal tar cracking solvents (solvent oil, mineral oil, liquid paraffin oil, kerosene, naphtha, etc.) and synthetic green solvent products (carbonate, dibasic acid ester DBE, amide, etc.). Each of these three types of solvents has advantages and disadvantages: petroleum / Coal tar cracking solvent, belonging to substituted aromatic hydrocarbon or polycyclic aromatic hydrocarbon. This type of solvent generally has a high flash point, is generally soluble in pesticides, and is slowly degraded in the natural environment, and has certain ecological risks. Synthetic solvents are 'tailor-made' for pesticide formulations. They are excellent in performance and easy to degrade, but the production cost is relatively high. The production cost of some solvents even exceeds that of active ingredients (pesticide). Domestic applications are very limited. The plant-derived green solvent attracts attention because it is derived from plants, is environmentally friendly, and is easily degraded. Plant-derived pesticide solvents are the current research hotspots, and hundreds of companies in the country are studying plant-derived pesticide solvents. However, the biggest deficiency of plant-derived solvents is the compatibility of the active ingredients of the pesticides and their own stability problems. Plant-derived solvents tend to dissolve only one type or series of pesticides, while other pesticides have low solubility and are not as universal as light aromatic hydrocarbon solvents. Plant-derived solvents greatly limit their use in pesticide formulations due to their 'bottleneck' problem of poor compatibility with pesticides.

At present, experts have analyzed that dibasic acid esters and dialkylamide solvents are easily degraded, and after good application in agrochemical products, the synthesis methods of some ester amide compounds and their application in different fields are summarized. A new method for synthesizing ester amides and the use of ester amides in phytosanitary preparations have been proposed.

The ester amide compound is characterized by containing both an ester functional group and an amide functional group in the same molecule. Fatty acid ester compounds are a class of non-toxic, harmless and easily degradable compounds, while dialkyl fatty acid amides are also characterized by low toxicity and easy degradation. The ester amide compound has similar characteristics, and in addition, it has much better solubility to various pesticides than plant-derived pesticide solvents (such as methyl oleate, biodiesel, etc.). However, current ester amide compounds are generally difficult to synthesize and costly.

technical problem

In view of this, it provides a pesticide with good solubility, safety, environmental protection, easy degradation, no pollution, easy synthesis, and low cost. Pesticide solvent and preparation method and application thereof.

Technical solution

 A pesticide solvent comprising an unsaturated ester amide represented by the formula (1):

R'OCOCH=CH(CH ₂ ) _n CON(R ₁ R ₂ ) ------------- (1) ;

Wherein the value of n is from 0 to 8, and R' is a C ₁ -C ₆ hydrocarbon group; and R ₁ and R ₂ are each a C ₁ -C ₆ hydrocarbon group or together with N form a nitrogen heterocycle.

The invention relates to a method for preparing a pesticide solvent, which comprises the following steps: synthesizing an unsaturated dibasic anhydride with a secondary amine and a lower carbon chain, respectively, and performing a one-step esterification reaction to synthesize a structural formula represented as R′OCOCH=CH(CH ₂ ) _n CO An unsaturated ester amide of -N(R ₁ R ₂ ), the pesticide solvent is obtained.

 And, the above pesticide solvent is used for a pesticide preparation or a pesticide tank mixing auxiliary.

Beneficial effect

 Using unsaturated ester amide as a pesticide solvent, first of all, Since the ester amide compound has both an ester functional group and an amide functional group, it exhibits superior solvency. Secondly, the synthesis of the unsaturated ester amide is achieved by an amine hydrolysis and a one-step esterification reaction of the secondary carboxylic acid and the lower carbon chain alcohol, respectively, to simplify the synthesis route, and the synthesis is simple and convenient. Unsaturated ester amides also have the advantage that a series of 'triphenyl' solvents are not available, such as non-toxic or low toxicity, and easy to degrade. Moreover, the synthetic raw materials are abundant in source and low in cost, and for example, low-priced divalent acid anhydrides such as maleic anhydride and fumaric anhydride are used. In addition, the unsaturated ester amide is easy to synthesize and has low production cost. The pesticide solvent or the solvent solvent thereof can be used as a co-solvent to form a new solvent system, which can completely replace the light aromatic hydrocarbon organic solvent.

DRAWINGS

 Fig. 1 is an unsaturated ester amide represented by the structural formula (1) in a pesticide solvent according to an embodiment of the present invention.

Embodiments of the invention

 The present invention will be further described in detail below with reference to the embodiments and the accompanying drawings.

 The present invention provides a pesticide solvent comprising the unsaturated ester amide represented by the formula (1):

R'OCOCH=CH(CH ₂ ) _n CON(R ₁ R ₂ ) ------------- (1) ;

Wherein the value of n is from 0 to 8, and R' is a C ₁ -C ₆ hydrocarbon group; R ₁ and R ₂ are each a C ₁ -C ₆ hydrocarbon group or together with N form a nitrogen heterocycle. The structural form (1) is shown in Figure 1.

 Embodiment of the present invention The unsaturated ester amide molecule has an unsaturated bond structure, that is, a double bond structure, which is mainly different from the saturated ester amide. The unsaturated bond forms a conjugation if it is adjacent to the carbonyl group, forming a delocalized π bond. Both ends of the main chain of the present embodiment have a carbonyl group, and therefore, The unsaturated bond in the unsaturated ester amide molecule of the embodiment of the present invention and the carbonyl group at both ends can form a delocalized π bond. and And the closer the unsaturated bond is to the carbonyl group, the greater the degree of conjugation. Since most of the pesticide molecules are electron-rich large π bond structures containing a similar benzene ring. The conjugated structure of the unsaturated ester amide of the examples of the present invention will have better compatibility with pesticides. Thus, preferably, in the unsaturated ester amide molecule of the present embodiment The value of n is further from 0 to 4, preferably 0 or 1, and the value of n is more preferably 0. When the value of n is 0, both the double bond and the two carbonyl groups form a typical conjugated structure, forming a large delocalization. The π bond has excellent compatibility with pesticides.

R' is a C ₁ -C ₆ hydrocarbon group, and may be, for example but not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group or the like.

The -N(R ₁ R ₂ ) functional group in the structural formula (1) is preferably any one of a dimethylamino group, a diethylamino group, a methylethylamino group, a pyrrolyl group, a tetrahydropyrrolyl group, and a piperidinyl group.

 Embodiment of the present invention The unsaturated ester amide is synthesized by subjecting an unsaturated divalent acid anhydride to an amine hydrolysis or an esterification reaction with a secondary amine or a lower carbon chain alcohol, respectively. Some of the existing ester amide pesticide solvents are generally synthesized by reacting a saturated divalent anhydride with an alcohol to form an ester, and another unreacted carboxyl group is then reacted with a secondary amine to form an amide, thereby synthesizing the ester amide. Such a synthetic route is not advantageous because the alcoholysis of the acid anhydride is relatively easy to occur, but the carboxylic acid is difficult to form an amide. The direct reaction requires a higher reaction temperature, a longer reaction time, or an indirect conversion to an acid chloride to form an amide. This is more complicated, and acid is generated during the reaction, which is highly resistant to corrosion. In the process of producing the ester amide, the unsaturated ester amide of the present embodiment exchanges the order of the amide formation and the ester formation, and firstly, the acid anhydride and the secondary amine are first subjected to amine hydrolysis to form an amide (the amine hydrolysis reaction of the acid anhydride is easy to occur). Another ester which has not reacted is esterified with an alcohol. The esterification reaction here can be carried out in one step, and the reaction conditions are mild, which is advantageous for industrial production.

The preparation method of the above pesticide solvent is described below. The method comprises the following steps: synthesizing the unsaturated divalent anhydride with the secondary amine and the lower alcohol chain, and synthesizing the structural formula into R'OCOCH=CH(CH ₂ ). An unsaturated ester amide of _n CON(R ₁ R ₂ ), the pesticide solvent is obtained.

Specifically, the process is carried out in two steps, one being an amine hydrolysis reaction process and the other being a one-step esterification reaction process. During the amination reaction, a stoichiometric amount of an unsaturated dibasic acid anhydride (for example, one equivalent) is dissolved in ethyl acetate and placed in a three-necked flask, and stirred to form a homogeneous solution to form an unsaturated dibasic anhydride solution. Then, a secondary amine (for example, one equivalent) is dissolved in a certain amount of ethyl acetate and slowly added dropwise to the above unsaturated dibasic anhydride solution (if the secondary amine is a gas, it is directly introduced into the solution of the unsaturated dibasic anhydride) . After the completion of the dropwise addition, the reaction was continued for 30 to 60 minutes, and the amination reaction was completed. After distilling off the excess solvent, lower chain alcohol is added (three equivalents), and a catalyst (1% equiv, with respect to the unsaturated anhydride divalent), the reaction at a temperature of 100 ~ 120 ^o C for 4 hours. After cooling to room temperature, the catalyst was removed by suction filtration, and the excess alcohol was removed by rotary evaporation to obtain the corresponding unsaturated ester amide pesticide solvent. The catalyst is selected from p-toluenesulfonic acid. The final purified product has a total yield of more than 85% and an unsaturated ester amide content of more than 90%. Thus, the mass percentage of the unsaturated ester amide in the pesticidal solvent is 90% or more, preferably 97% or more.

In the raw materials of the above preparation method, the structural formula of the unsaturated divalent anhydride can be expressed as: -COCH=CH(CH ₂ ) _n -COO- (wherein the first two bonds are joined), and the secondary amine is represented as R ₁ NHR ₂ . Specifically, the unsaturated divalent anhydride is selected from unsaturated divalent anhydrides having a carbon chain of 4 to 12, that is, the value of n is 0-8; preferably, the C ₄ -C ₆ unsaturated divalent anhydride, that is, the value of n 0-4 is more preferably maleic anhydride, fumaric anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, glutaconic anhydride or the like. This embodiment is preferably maleic anhydride or fumaric anhydride, i.e., the value of n is zero. The secondary amine is selected from a secondary amine having an average carbon number of C ₁ - C ₆ , and preferably any one of dimethylamine, diethylamine, methylethylamine, pyrrole, tetrahydropyrrole, and piperidine. The lower chain alcohol (R'OH) is an alcohol having six or less carbon atoms, preferably methanol or ethanol. The esterification reaction here is carried out in one step, and the temperature is in the range of 100 to 120 ^o C, so the reaction conditions are mild, easy to implement, and high-temperature equipment is not required, which is advantageous for industrial production. In the one-step esterification reaction, corrosive by-products such as acid are not generated, and the entire method is environmentally friendly. The prepared pesticide solvent is non-toxic or low-toxic, safe and environmentally friendly.

 In addition, it should be noted that in the embodiment of the present invention The meaning of 'solvent' in a pesticide solvent includes a solvent which is a main dissolution, that is, a solvent in a usual sense, and also acts as a co-solvent, and synergizes with other solvent components to dissolve or assist dissolution.

The pesticide solvent of the embodiment of the invention can be used for a pesticide preparation or a pesticide tank mixing auxiliary. When used in a pesticide formulation, it includes a pesticide solvent as described above and a mass percentage of 1-20%. Surfactant (the ratio of surfactant to total pesticide formulation), the mass percentage of pesticide solvent is preferably 4-95% . The surfactant is a mixture of one or more of an agricultural surfactant or a daily surfactant, preferably a fatty alcohol polyoxyethylene ether, EO/PO The block copolymer and its phosphate ester, castor oil polyoxyethylene ether, Tween, alkyl sulfonate, alkyl sulfate, these surfactants have superior effects. Types of pesticide formulations include, but are not limited to, emulsifiable concentrates, oils, oil suspensions, microemulsions, aqueous emulsions or ultra low sprays.

The pesticide preparation may be used in the above manner, and the pesticide solvent may be used together with the surfactant, and may also be used in combination with other adjuvants or components, for example, to assist the use of the fatty acid methyl ester of Jatropha oil, and is not limited thereto. Types of pesticide formulations include, but are not limited to, emulsifiable concentrates, oils, oil suspensions, microemulsions, aqueous emulsions or ultra low sprays. In addition, the above-mentioned pesticide preparation generally refers to a pesticide processed product containing an active ingredient of a pesticide, and the pesticide tank mixing aid generally means that the pesticide active ingredient is not contained, and the pesticide preparation is mixed with the pesticide preparation in a spray tank or a medicine barrel to improve or improve the pesticide. Spray auxiliaries for use, sometimes called spray auxiliaries

When applied to a pesticide tank mixing additive, it is preferably used as a spray aid, and the spray aid is mixed with a pesticide tank to promote mutual dissolution and uniform mixing between the components. Pesticide 'tank mix' is a commonly used method of mixing pesticides, that is, a pesticide preparation factory produces a single agent that can be used for tank mixing. According to the barrel mixing method, two or more types are used according to the label description when applying in the field. Different pesticides are proportioned by motorized device or manual dispensing or directly into the storage tank of the application tractor to form a mixed drug solution.

Hereinafter, the above-mentioned pesticide solvent, preparation method and application will be exemplified by specific experimental examples, and corresponding application experiments are carried out to examine the effects.

 Example 1

98 g of maleic anhydride dissolved in 100 ml of ethyl acetate was added to a 500 ml three-necked flask equipped with a reflux condenser, and 73 g of diethylamine dissolved in 50 ml of ethyl acetate was slowly added dropwise to the above-mentioned Malay through a constant pressure dropping funnel. In the solution of an acid anhydride . After the dropwise addition of diethylamine to control the temperature 50 ^o C for 2 h, removed by rotary evaporation of ethyl acrylate. Methanol was then added 102 g (3eq, eq refers to equivalents), and 1% p-toluenesulfonic acid (relative to the amount of substance of maleic anhydride), the temperature was raised to 100 ^o C for 4 hours the reaction was monitored by thin layers chromatography end. After dropping to room temperature, excess methanol was removed by rotary evaporation, and the catalyst was neutralized to obtain a solvent of a brown ester having a viscosity of an unsaturated ester amide in a yield of 94%.

 Example 2

 The same as in Example 1, except that maleic anhydride was replaced with fumaric anhydride and diethylamine was replaced with tetrahydropyrrole.

 Example 3

 The same as in Example 1, except that 102 g of methanol was changed to 130 g of ethanol during esterification.

 Example 4

 Same as in Example 1, except that 98 g of maleic anhydride was replaced by 114 g of glutaconic anhydride, and 102 g of methanol was replaced by esterification. 180 grams of isopropyl alcohol.

 Example 5

98 g of maleic anhydride was dissolved in 50 mL of ethyl acetate and added to a three-necked flask equipped with a reflux condenser, and dimethylamine gas (1.2 eq) was slowly introduced. After dimethylamine gas through controlling the temperature 50 ^o C after 2 hours of reaction, ethyl acetate was distilled. Methanol was then added 102 g (3eq), (the amount of maleic anhydride equivalent substance) 1% p-toluenesulfonic acid was added while the temperature was raised to 100 ^o C for 4 hours the end of the reaction was monitored by TLC. After dropping to room temperature, excess methanol was removed by rotary evaporation, and the catalyst was neutralized to obtain a solvent of a brown ester having a viscosity of an unsaturated ester amide in a yield of 95%.

 Example 6

 The same as in Example 5 except that 98 g of maleic anhydride was replaced with 128 g of citric anhydride.

 Example 7

 The same as in Example 5 except that maleic anhydride was replaced with fumaric anhydride, and methanol was exchanged for 222 g of n-butanol during esterification.

 Example 8

 The same as in Example 5 except that the dimethylamine gas fed was replaced with methylethylamine.

 Example 9

 The same as in Example 5 except that maleic anhydride was replaced with 126 g of 2-hexenedioic anhydride.

 Example 10

 The same as in Example 5 except that maleic anhydride was replaced with 210 g of 2-myrcene dianhydride.

A series of physicochemical properties (such as density, surface tension, boiling point, vapor pressure, dynamic viscosity, freezing point, flash point, etc.) of the synthetic solvent of Example 1 were determined and carried out with methyl sulphate methyl ester and xylene. Comparison, the data is listed in Table 1. Medium.

Table 1 Physical and chemical properties of new pesticide solvents and methyl ketone and xylene Physical and chemical properties (units) Jatropha oil methyl ester Xylene Example 1 Molecular weight (g/mol) 293 106 157 Density (g/ml, 20 ^o C) 0.912 0.864 1.058 Surface tension (dyne/cm) 30.90 31.23 16.16 Boiling point ( ^o C) >200 144.4 >200 Steam pressure (mmHg) 10 9.98 (32 ^o C) 14.2 Dynamic viscosity (mm ² /s, 40 ^o C) 5.384 1.065 186.24 Freezing point ( ^o C) -9.0 -25.5 -22.0 Flash point ( ^o C) 279 30 >200 Solubility in water Layering Slightly soluble Soluble

It can be seen from the results in Table 1: The boiling point and flash point of the synthesized unsaturated ester amide solvent are very high, above 200 ^o C, indicating that the production and storage of this solvent is safe; the freezing point is as low as -22 ^o C, indicating that its stability at low temperatures is guaranteed. The surface tension value is 16.16 dyne/cm, which is equivalent to half of xylene or jatropha methyl ester. In general, the smaller the surface tension, the smaller the contact angle, that is, the lower the surface energy, the greater the adhesion; the larger the surface tension, the larger the contact angle, that is, the higher the surface energy, the smaller the adhesion. The adhesion can also be directly explained by another data, the dynamic viscosity, which has a dynamic viscosity of 186.24 mm ² /s, which is much larger than that of xylene and jatropha oil methyl ester. In pesticide products, if the surface tension of the solvent is small and the dynamic viscosity is large, it will help the pesticide active ingredient to adhere to the plant leaf surface to increase the efficacy. Another feature of this type of synthetic unsaturated ester amide solvent is its water solubility. It is miscible with water in any proportion and is miscible with most organic solvents. It is very convenient to use it as a solvent to prepare aqueous emulsions, microemulsions, water agents, water suspension agents and the like.

An experimental example of the solubility of a solvent of the present invention on a pesticide. Using the pesticide solvent synthesized in Example 5, fourteen kinds of pesticides were selected at room temperature (25 ^o C) (such as chlorpyrifos, cyhalothrin, quizalofop, 哒螨灵, 甲维盐, etc.) ). These fourteen kinds of original drugs cover insecticides, fungicides, herbicides, acaricides, etc., and there are pyrethroids, organophosphorus, macrolides, triazoles, ureas, etc. from the categories. These pesticides are used in large quantities at present and are representative. Table 2 also lists xylene, jatropha methyl ester, ND60 (a rosin-based vegetable oil, Shenzhen Noppin Agrochemical Co., Ltd.), ND60+ (ND60 added 10% of the synthesized unsaturated ester amide used in Example 5) Cosolvent) The solubility of these fourteen pesticides at room temperature.

From the data results of Table 2, we can see that the solvent synthesized by Example 5 is optimal in the solubility of the solvents to be compared. It is not only better than the traditional vegetable oil solvent - jatropha oil methyl ester or turpentine vegetable oil (ND60). Compared with the traditional light aromatic solvent xylene, the solubility of various pesticides has a considerable or more obvious advantage (except for dibutyl ether urea). The solvent synthesized in Example 5 is not only soluble in chlorpyrifos or pyrethroids (halothrin, fenpropathrin, etc.), but also in the organic solvent, which is usually soluble in organic solvents, and is also suitable for phenylbutyltin. , triazole tin, a vitamin salt, avermectin, which is usually difficult to dissolve, the solubility of the original drug is far better than xylene.

Table 2, solubility of 14 kinds of original drugs in the solvent of the present invention and comparative solvent ^a Original drug Xylene Jatropha methyl ester ND60 ^b ND60+ ^c Example 5 Chlorpyrifos >1.500 2.128 4.000 >2.450 >1.850 Lacy-cyhalothrin 0.800 1.060 2.060 >2.450 >1.050 Quinoxaline 0.300 0.135 0.320 0.400 0.420 Ling 0.390 0.119 0.313 0.380 0.320 Emamectin benzoate ≤0.050 ≤0.050 0.580 0.680 0.670 Phenyltin 0.030 ≤0.050 ≤0.050 0.250 0.120 Triazole tin 0.010 ≤0.050 0.182 0.200 0.220 Beta-cypermethrin 0.300 0.191 0.408 0.404 0.450 Bifenthrin 0.800 0.301 0.520 0.932 0.900 Difenoconazole 0.400 0.123 0.545 0.560 0.570 Avermectin ≤0.050 ≤0.050 ≤0.050 0.230 0.112 Pendimethalin 1.120 0.295 0.870 1.223 1.250 Dibutyl ether urea 0.200 ≤0.050 0.122 0.120 <0.100 Cypermethrin 0.660 0.334 4.000 >2.450 0.680 ^{a. The} measurement temperature is 25 ^o C in units of g/g. ND60 ^b. is the rosin-based vegetable oil solvent of Shenzhen Noppin Agrochemical Co., Ltd. ND60+ ^c. 10% of the unsaturated ester amide synthesized in Example 5 was added as a co-solvent for the ND60 solvent.

Therefore, the unsaturated ester amide solvent synthesized by the present invention is a kind of pesticide solvent which is excellent in performance. Not only that, but when it is used as a co-solvent, its solubilization effect is also very obvious. Compare Table 2 with ND60 and ND60+ We can find that when 10% of the above unsaturated ester amide is added as a co-solvent in ND60, the solubility of phenbutyltin, avermectin and pendimethalin is significantly improved.

The following are examples of the use of the unsaturated ester amide pesticide solvent for the pesticide preparation and the tank mixing aid in the examples of the present invention, but the present invention is by no means limited to these examples, and the following contents are all by mass.

 Application Example 11

 In the reaction kettle, 500 kg of the pesticide solvent of Example 1 was added, stirred, and then added triazophos 400 kg, alkylphenol ethoxylate 30 kg, castor oil polyoxyethylene ether 20 kg, fatty alcohol polyoxyethylene ether 20 kg, 30 kg of calcium dodecylbenzenesulfonate, stirred to dissolve, that is, 40% triazophos EC.

 Application Example 12

 In the reaction kettle, 800 kg of the pesticide solvent of Example 4 was added, stirred, and then bifenthrin 100 kg, alkylphenol ethoxylate was added. 50 kg, 50 kg of calcium dodecylbenzenesulfonate, stirred and dissolved, that is, 10% bifenthrin EC.

 Application Example 13

 In the reaction kettle, add 850 kg of the pesticide solvent of Example 3, stir, add fipronil 50 kg in sequence, and castor oil polyoxyethylene ether. 30 kg, 30 kg of fatty alcohol polyoxyethylene ether, 40 kg of calcium lauryl sulfonate, stirred and dissolved, that is, 5% fipronil emulsifiable concentrate.

 Example 14

 The pesticide solvent obtained in Example 3 was added to the reaction vessel at 902 kg, and avermectin 18 kg and castor oil polyoxyethylene ether were sequentially added. 15 kg, Tween 25 kg, and dodecyl sulfate 40 kg, evenly mixed to obtain 1.8% avermectin EC 1000 kg.

 Application Example 15

 75 kg of the pesticide solvent obtained in Example 5 was added to the reaction vessel, followed by the addition of lambda-cyhalothrin 25 kg, chlorpyrifos 125 Kilograms, EO/PO block copolymer phosphate 65 kg, alkylphenol formaldehyde resin polyoxyethylene ether 25.5 kg, calcium dodecylbenzenesulfonate 42.5 kg, isopropanol 30 In kilograms, mix well and add 612 kg of water. After mixing, make 15% cyhalothrin chlorpyrifos microemulsion 1000 kg.

 Application Example 16

 The pesticide solvent obtained in Example 5 was 885 kg, and the amifostatin formate 10 kg, castor oil polyoxyethylene ether 20 Kilograms, EO/PO block copolymer 15 kg, fatty alcohol polyoxyethylene ether 25 kg, calcium dodecylbenzenesulfonate 45 kg, added in order to obtain 1.0% Emamectin formate emulsifiable concentrate 1000 kg.

 Application Example 17

 The pesticide solvent obtained in Example 3 was 100 kg, and then propiconazole 200 kg, ethylene glycol 20 was sequentially added. Kilogram, alkylphenol ethoxylate phosphate 30 kg, EO/PO polyoxyethylene ether block copolymer 20 kg, mix well, add 620 kg of water and 10 kg of polyvinyl alcohol, mix evenly, speed 5000 rpm / high speed shear emulsification, that is, 1000 kg of 20% propiconazole water emulsion.

 Application Example 18

 200 kg of atrazine, 60 kg of gaseous silica, and 660 kg of pesticide solvent of Example 5 were added to the grinding kettle. C12-C14 alcohol polyoxyethylene ether 30 kg, sorbitan polyoxyethylene ether 20 kg, lignin sulfonate 30 kg, sanded, it is 1000 kg 20% Indigo oil suspension.

 Application Example 19

 Add 250 kg of phoxim and 40 kg of ethylene glycol to the reaction kettle. Example 6 Pitrate source pesticide solvent 650 Kilogram, alkylphenol ethoxylate 50 kg, alkylphenol polyoxyethylene ether phosphate 10 kg, stirred and dissolved, that is, 1000 kg 25% phoxim oil for ultra-low volume spray.

 Application Example 20

 Adding an unsaturated ester amide solvent to the reactor (Example 5) 850 kg, C12-C14 alcohol ethoxylate 60 Kilograms, propylene oxide / ethylene oxide block copolymer 40 kg, ethoxylated alkyl phosphate 50 kg, evenly stirred, that is, 1000 kg of pesticide tank mixing aid.

 Application Example 21

 The reaction vessel was charged with an unsaturated ester amide solvent (Example 5) 900 kg, N-octylpyrrolidone 30 kg, 20 kg of C12-C14 alcohol polyoxyethylene ether, 20 kg of sorbitan polyoxyethylene ether, 30 kg of ethoxylated alkylate, and evenly stirred, that is, 1000 kg of pesticide tank mixing aid.

 Application Example 22

 In the reactor, 250 kg of rice bran, 100 kg of Jatropha oil, and Example 2 solvent 590 were added. Kilograms, fatty alcohol polyoxyethylene ether 60 kg, stirred and dissolved, that is, 25% of rice peony oil for ultra-low volume spray.

 Application Example 23

 Add 550 kg of ND60+ solvent to the reaction kettle, stir, add flurazepam 350 kg, and castor oil polyoxyethylene ether. 25 kg, rosin glyceride ethoxylate 25 kg, calcium dodecyl sulfonate 50 kg, stir to dissolve, that is, 35% flurazepam emulsifiable concentrate 1000 kg.

The pesticide solvent involved in the invention can be well formulated with various pesticides into pesticide products of various dosage forms, and the effect is better than that of the main agent of 'triphenylenes'. The following are the experimental results comparing the effects of different formulations of medicaments.

 The efficacy of 40% triazophos EC on the third instar larvae of Chilo suppressalis was determined by rice straw impregnation method. The test results are shown in Table 3:

Table 3 Results of different formulations of 40% triazophos EC on the larvae of the third instar larvae Test reagent (solvent) Drug concentration (times) Number of test heads (head) Number of deaths (head) Corrected mortality (%) 40% triazophos EC (Application Example 11) 500 80 72 90.00 40% triazophos EC (Application Example 11) 1000 80 62 77.50 40% triazophos EC (Application Example 11) 2000 80 55 68.75 40% triazophos EC (xylene) 500 80 60 75.00 40% triazophos EC (xylene) 1000 80 52 65.00 40% triazophos EC (xylene) 2000 80 43 53.75 blank Tap water 80 3 -

 In indoor potting, the effect of 35% piracetin emulsifiable concentrate on the control of different formulations on the three-leaf stage sedge was determined by weighing method. The test results are shown in Table 4. :

Table 4, 35% flurazepam emulsifiable concentrate different formulas for trifoliate valerian control Test reagent Concentration of drug (times) Valerian fresh weight (g) Valerian fresh weight control (%) 35% flurazepam emulsifiable concentrate (Application Example 23) 1500 10.8 90.43 35% flurazepam emulsifiable concentrate (Application Example 23) 3000 21.6 80.85 35% flurazepam emulsifiable concentrate (Application Example 23) 4500 35.5 68.53 35% flurazepam emulsifiable concentrate (xylene is the main solvent) 1500 28.7 74.56 35% flurazepam emulsifiable concentrate (xylene is the main solvent) 3000 37.3 66.93 35% flurazepam emulsifiable concentrate (xylene is the main solvent) 4500 50.1 55.60 blank Tap water 112.8 -

 From Table 3 and Table 4, we can easily find that the pesticide solvent involved in the present invention is 40% triazophos EC, 35%. The piracetin emulsifiable concentrate has a certain synergistic effect.

The unsaturated ester amide solvent according to the embodiment of the invention has the following advantages compared with the aromatic non-environmental organic solvent: 1. Low toxicity, harmless and easy to degrade; 2. High flash point (generally higher than 100 ^o C, xylene) It is 30 ^o C), convenient for storage and transportation, safe and reliable. 3. It has good solubility to pesticides and wide applicability. The solubility of certain pesticides far exceeds that of aromatic solvents.

Compared with the traditional vegetable oil solvent, the unsaturated ester amide pesticide solvent of the invention has the following advantages: 1. The solubility of the pesticide is greatly improved compared with the traditional vegetable oil solvent, and is equivalent to the light aromatic hydrocarbon solvent; 2. Wide application range. Various types of pesticides can be used, and can be used in pesticides, oils, oil suspensions, microemulsions, water emulsions and other pesticide preparations and tank mixing aids; 3, good stability, temperature reduced to -20 ^o C, state Still able to maintain, there will be no phenomenon of low temperature solidification, stratification, crystallization.

In addition, compared with synthetic pesticides, the production cost is low, and the raw materials used are very low in price. For example, some unsaturated dibasic acid anhydrides such as maleic anhydride and fumaric anhydride are used at low prices, and the reaction conditions are mild, and are suitable for mass production. . And it can be used as a pesticide solvent or co-solvent in the pesticide preparation according to different needs.

The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. Within the scope.

Claims (10)

 A pesticide solvent comprising an unsaturated ester amide represented by the formula (1): R'OCOCH=CH(CH ₂ ) _n CON(R ₁ R ₂ ) ------------- (1) ; Wherein the value of n is from 0 to 8, and R' is a C ₁ -C ₆ hydrocarbon group; and R ₁ and R ₂ are each a C ₁ -C ₆ hydrocarbon group or together with N form a nitrogen heterocycle. The pesticide solvent according to claim 1, wherein the value of n is from 0 to 4. The pesticide solvent according to claim 1, wherein the value of n is 0 or 1. The pesticide solvent according to claim 1, wherein the value of n is zero. Claims 1 The pesticide solvent is characterized in that the unsaturated ester amide is synthesized by an amine hydrolysis and an esterification reaction of an unsaturated divalent acid anhydride with a secondary amine or a lower carbon chain alcohol, respectively. The pesticide solvent according to claim 1, wherein the -N(R ₁ R ₂ ) functional group in the formula is a dimethylamino group, a diethylamino group, a methylethylamino group, a pyrrolyl group or a tetrahydropyrrole group. Any one of piperidinyl groups. A method for preparing a pesticide solvent according to any one of claims 1 to 6, wherein the method comprises the steps of: subjecting an unsaturated divalent acid anhydride to a secondary amine and a lower carbon chain alcohol, respectively, to form an amine solution, a one-step ester The chemical reaction synthesis formula is represented by an unsaturated ester amide of R'OCOCH=CH(CH ₂ ) _n CON(R ₁ R ₂ ), and the pesticide solvent is obtained. The method for preparing a pesticide solvent according to claim 7, wherein the unsaturated divalent acid anhydride is maleic anhydride, fumaric anhydride, citraconic anhydride, 2,3- Dimethyl maleic anhydride or glutaconic anhydride. Claim 7 The method for producing a pesticide solvent, wherein the secondary amine is any one of dimethylamine, diethylamine, methylethylamine, pyrrole, tetrahydropyrrole, and piperidine. The pesticide solvent according to any one of claims 1 to 6 for use in a pesticide preparation or a pesticide tank mixing aid.

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