CN114711227B

CN114711227B - Auxiliary agent and composition for improving compatibility of high-electrolyte system

Info

Publication number: CN114711227B
Application number: CN202210188352.9A
Authority: CN
Inventors: 秦敦忠
Original assignee: Jiangsu Sinvo Chemical Technology Co ltd
Current assignee: Jiangsu Sinvo Chemical Technology Co ltd
Priority date: 2022-02-28
Filing date: 2022-02-28
Publication date: 2023-06-20
Anticipated expiration: 2042-02-28
Also published as: CN114711227A

Abstract

The invention discloses an auxiliary agent for improving high electrolyte system compatibility and a composition thereof, wherein an alkoxy chain of the auxiliary agent can improve the dispersion capacity of the auxiliary agent in a system and the compatibility between preparations; the imide functional group of the pesticide adjuvant can increase the compatibility of the pesticide adjuvant with pesticide particles.

Description

Auxiliary agent and composition for improving compatibility of high-electrolyte system

Technical Field

The invention belongs to the field of pesticide auxiliaries, and particularly relates to an auxiliary and a composition for improving compatibility of a high-electrolyte system.

Background

Chemical fertilizers and pesticides are indispensable input products in agricultural production, salt impurities are often generated in the process of resynthesis of raw materials, and part of raw materials contain metal complexes. Or part of the original medicine exists in the form of salt, and has certain solubility in water, such as emamectin benzoate, glyphosate salt and the like. Or, the preparation has high water hardness or is mixed with inorganic salt fertilizer to form high salt system.

In a high-salt system, the presence of the electrolyte can reduce the energy efficiency of the nonionic surfactant of the dispersing agent, so that the nonionic surfactant is disabled, and the stability of the preparation is affected. After the inorganic salt is dissolved in water, water is gathered around the ions due to the electrical property between the ions, free water is reduced, so that the nonionic surfactant is easy to separate out from the water and lose effect, and salting out is caused.

For example, in recent years, glufosinate is often mixed with other selective herbicides such as quizalofop-p-ethyl and clethodim in order to improve the control effect. In order to facilitate the use of farmers and achieve the optimal control effect, the research on pesticide formulas of glufosinate and other herbicides compounded according to a certain preferred proportion has attracted wide attention of the industry. It is known that glufosinate exists in the form of organic salts, which have a high solubility in the aqueous phase, whereas other herbicides used in combination therewith mostly have a low solubility in water. However, the existence of glufosinate improves the electrolyte concentration of a formula system, but most of auxiliary agents are poor in salt tolerance, and the auxiliary agents can be separated out from the system, so that incompatibility of the formula is easily caused, and the problems of unstable formula such as layering, demulsification, crystallization and the like of the preparation are caused. In terms of auxiliary agents, the application is extremely wide in the aspect of the market, the addition of the auxiliary agents is not needed in almost all pesticide and fertilizer formulas, and various auxiliary agents have the characteristics of the auxiliary agents, and the vegetable oil-based auxiliary agents are taken as examples, are the synergistic agents with the highest development and utilization rate at present, and are mainly composed of vegetable oil and derivatives thereof, but due to the nature of the vegetable oil, other emulsifying agents are difficult to emulsify, and the problems of unstable formulas such as layering, crystallization and the like of the preparation are increased. 1. In the aspect, the blockage of a nozzle or a screen can be caused, the effectiveness of a product applied by spraying is reduced, the agricultural production cost is increased, the benefit is reduced, the quality of agricultural products is reduced, and the continuous yield increase of grains and the quality safety of the agricultural products are directly influenced; on the other hand, the use of continuously-increased pesticides brings about very serious problems for the environment, the agricultural grain and food residues.

Therefore, based on various pesticides or fertilizers containing auxiliary agents at present, one or more preparation products and/or other commonly used water-soluble fertilizer components are selected for combination or mixing in order to improve the use effect, so that the environment of a final system is often changed greatly, and the problems of influencing the stability of the mixed preparation, such as a high-electrolyte system and the like, are formed; continuing to develop corresponding adjuvant solutions, improving formulation stability, reducing or avoiding the generation of solid precipitates or phase separation, and preserving and increasing their complete biological efficacy is a technical problem to be solved in the art.

Disclosure of Invention

1. Problems to be solved

Aiming at the problems that the existing agricultural preparation products (such as pesticides and fertilizers) are poor in stability and easy to generate solid precipitates or phase separation and the like, the invention provides a compatible auxiliary agent and a compatible composition, which are particularly suitable for improving the compatibility of a high-electrolyte system;

meanwhile, the invention also provides a preparation method of the auxiliary agent and the composition.

2. Technical proposal

In order to solve the problems, the invention provides a compatible auxiliary agent, which has a general formula as (1) or (2):

wherein M is H ⁺ 、Na ⁺ 、K ⁺ Diethanolamine or triethanolamine;

wherein M is H ⁺ 、Na ⁺ 、K ⁺ Diethanolamine or triethanolamine.

A preparation method of a compatibility auxiliary agent comprises the following steps: (1) preparing a compatibility auxiliary agent intermediate B: in the environment of vegetable oil, the active polymerization monomer A is contacted and mixed with organic amine in a dropwise manner to carry out amination reaction; wherein,,

the active polymerization monomer A is maleic anhydride active polymerization monomer;

the organic amine is one or more of alkylene amine, polyether amine and alkanolamide;

the vegetable oil accounts for 30-70% of the total weight of the vegetable oil, the active polymerization monomer A and the organic amine;

the amount of the active polymerization monomer and the organic amine is calculated according to the mole number of anhydride and the mole number of primary amine groups, and the mole ratio of the anhydride to the primary amine groups is (1-2): 1, a step of;

(2) Preparing a compatibility auxiliary agent: allowing compatibility auxiliary intermediates B and P ₂ O ₅ Mixing by dripping, heating and aging, and hydrolyzing and neutralizing; or alternatively

Ethoxylation treatment is carried out on the compatibility auxiliary agent intermediate B, and then the compatibility auxiliary agent intermediate B is reacted with P ₂ O ₅ Mixing by dripping, heating and aging, and hydrolyzing and neutralizing;

Wherein, according to the mole number of alcohol amine hydroxyl groups and P ₂ O ₅ Calculated by mole number, the alcohol amine hydroxyl and P ₂ O ₅ The molar ratio is (3-1) 1;

the curing temperature is higher than P ₂ O ₅ The dripping operation temperature is raised by at least 30 ℃ but not higher than 70 ℃;

the operating temperature of the neutralization treatment is required to be lower than the operating temperature of curing, and the difference is not higher than 60 ℃.

Further, in step (1), the maleic anhydride living polymeric monomer of formula (i), including but not limited to formula (3):

wherein: the R is one or more of polyisobutylene residue, castor oil residue, soybean oil residue, olive oil residue, peanut oil residue, rapeseed oil residue, corn oil residue, sesame oil residue, cotton oil residue, rape oil residue, safflower oil residue, linseed oil residue, palm oil residue, grape seed oil residue, artemisia annua oil residue, pumpkin oil residue, core oil residue, borage seed oil residue, chickpea oil residue, almond oil residue, pistachio oil residue, almond oil residue, kunskia nut oil residue, avocado oil residue, sea buckthorn oil residue, hemp oil residue, hazelnut oil residue, evening primrose oil residue, wild rose oil residue, thistle oil residue, walnut oil residue, sunflower oil residue, jatropha seed oil residue, swill-cooked dirty oil residue;

When R is polyisobutene residue, the molecular weight of the polyisobutene is 600-2300.

Further, in the step (1), the alkanolamine includes one or both of monoethanolamine and monoisopropanolamine;

the alkylene amine comprises one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, aminopropylmorpholine and aminoethylpiperazine; preferably tetraethylenepentamine;

the polyetheramine comprises one or more of monofunctional polyetheramine (polyether monoamine structure), difunctional polyetheramine (polyether diamine structure), trifunctional polyetheramine (polyether triamine structure), tetrafunctional polyetheramine (polyether tetramine structure) and polyfunctional polyetheramine; wherein the polyether monoamine has a structural general formula (4) as follows:

wherein R is C1-C57 straight chain or branched chain alkyl, phenyl, unsaturated hydrocarbon chain, polymerized glyceryl, saccharose group or sorbitan group; r1, R2, R3 independently of one another denote H, CH ₃ Or CH (CH) ₂ CH ₃ The method comprises the steps of carrying out a first treatment on the surface of the n1, n2, n3 independently of each other represent an integer of 0 to 35; the sum of n1, n2 and n3 is not less than 2, and n is an integer of 1 to 8;

the polyether diamine has a general formula (5) as follows:

wherein R is ₄ ，R ₅ ，R ₆ Represent H, CH independently of each other ₃ Or CH (CH) ₂ CH ₃ The method comprises the steps of carrying out a first treatment on the surface of the n4, n5, n6 independently of each other represent an integer of 0 to 35; the sum of n4, n5, n6 is not less than 2;

the polyether triamine has a general formula (6) as follows:

wherein R is ₄ ，R ₅ ，R ₆ ，R ₇ Represent H, CH independently of each other ₃ Or CH (CH) ₂ CH ₃ The method comprises the steps of carrying out a first treatment on the surface of the n4, n5, n6, n8 independently represent an integer of 1 to 100; n7 is an integer of 0 or 1;

the polyether tetramine has a general formula (7) as follows:

wherein R is ₈ Representation H, CH ₃ Or CH (CH) ₂ CH ₃ ；R ₆ Representation ofC1-C5 alkyl; n6 independently represents an integer of 20 to 55.

Further, in the step (1), the specific contact mode between the active polymerization monomer and the organic amine is any one of the following modes:

firstly, mixing an active polymerization monomer and vegetable oil in a contact way, and then, adding the organic amine in a dropwise manner;

the temperature in the dropping process is 60-65 ℃, and the dropping time is 0.5-3 hours;

vacuum degassing and amination are carried out after the dripping is finished, the temperature is 120-160 ℃ and the time is 2-7 hours;

or firstly, contacting and mixing the organic amine with vegetable oil, and then, adding the active polymerization monomer in a dropwise manner;

and (3) after the dripping is finished, vacuum degassing and amination are carried out, the temperature is 120-160 ℃, and the time is 2-7 hours.

Further, in step (1), the general formula of the compatibility auxiliary intermediate B includes, but is not limited to, general formulas (8) and (6):

wherein R is ₁₀ Represents a monoethanolamine or monoisopropanolamine residue.

Wherein R is ₁₁ Represents an alkylene amine, polyether amine residue.

Further, in the step (1), the vegetable oil may be one or more of soybean oil, rapeseed oil, palm oil, olive oil, coconut oil, orange peel oil, citronella oil, and turpentine.

Further, in the step (2), the general formula of the compatible auxiliary agent is shown as (10) or (11):

wherein M is H ⁺ 、Na ⁺ 、K ⁺ Diethanolamine or triethanolamine;

wherein M is H ⁺ 、Na ⁺ 、K ⁺ Diethanolamine or triethanolamine.

Further, in the step (2), P is performed ₂ O ₅ Specific conditions for dripping are as follows: the dripping temperature is 20-40 ℃ and the dripping time is about 1.5h;

the specific conditions of the heating and curing treatment are as follows: heating to 78-82 ℃ and treating for 3.5-4.5 h;

the specific conditions of the hydrolysis and neutralization treatment are as follows: adding 1-1.5% of deionized water according to weight percentage, wherein the adding time is 20-30 min, and hydrolyzing for 1-1.5 h after the adding is completed, wherein the hydrolysis temperature is 75-80 ℃; then cooling to 60-70 ℃, adding a neutralizing reagent, and neutralizing; and (5) dehydrating for 30-40 min after the neutralization is finished, and obtaining the compatibility auxiliary agent after the dehydration is finished.

In the step (2), ethoxylation treatment is carried out on the compatible auxiliary agent intermediate B by using ethylene oxide, wherein the ratio of the addition mole number of the ethylene oxide to the mole number of active hydrogen in the compatible auxiliary agent intermediate B is (1-4): 1.

Further, in step (2), after ethoxylation treatment is performed on the compatible auxiliary agent intermediate B, the general structure includes, but is not limited to, general formulas (12) and (13):

wherein R is ₁₂ Are polyetheramine residues.

Wherein m is an integer of 0 to 3.

Further, in the step (2), the compatibility auxiliary intermediate B is subjected to ethoxylation treatment and then is subjected to P ₂ O ₅ The structural general formula after treatment includes but is not limited to general formulas (14) and (15):

wherein M is H ⁺ 、Na ⁺ 、K ⁺ One of diethanolamine or triethanolamine or a combination thereof.

Wherein M is an integer of 0 to 3, M is H ⁺ 、Na ⁺ 、K ⁺ One of diethanolamine or triethanolamine or a combination thereof.

A composition comprising any one of the above compatibility aids or a compatibility aid prepared by any one of the above methods, the compatibility aid being 40 to 70 parts; 30-60 parts of composite auxiliary agent; preferably, the formulation of the composition is: 55-70 parts of compatibility auxiliary agent and 30-45 parts of composite auxiliary agent;

The composite auxiliary agent comprises anionic surfactant, alcohol ether glycoside and alkyl glycoside, wherein the mass ratio of the anionic surfactant to the alcohol ether glycoside to the alkyl glycoside is (2-6), and the mass ratio of the alcohol ether glycoside to the alkyl glycoside is (1-5), and the mass ratio of the alcohol ether glycoside to the alkyl glycoside is (6-16).

Further, the anionic surfactant can be one or more of alcohol ether sulfosuccinic acid monoester disodium salt, sodium dodecyl sulfate, sodium alkylbenzenesulfonate, calcium alkylbenzenesulfonate, sodium fatty alcohol polyoxyethylene ether sulfate and the like.

Further, the alkyl glycoside (abbreviated as APG) contains water in an amount of 50% by weight, and the alkyl glycoside includes one or more of APG0810, APG0814, APG1214, APG0816, APG1216, APG1618, and the like.

Further, the alcohol ether glycoside comprises 50% wt. of water, and the alcohol ether glycoside comprises one or more of isooctyl alcohol ether (3 EO) ether glycoside, isooctyl alcohol ether (5 EO) ether glycoside, C12-14 alcohol ether (5 EO) glycoside, isomeric 13 alcohol ether (5 EO) glycoside, C12-14 alcohol ether (3 EO) glycoside, decyl alcohol ether (5 EO) glycoside, isomeric 13 alcohol ether (3 EO) glycoside and the substance of formula (16);

in which R is ₁₄ Alkyl having 7 to 21 carbon atoms, saturated or unsaturated, straight or branched, or mixtures thereof, preferably isooctyl, decyl, C12-14 alkyl, isomeric 13 alkyl; r is R ₁₅ Is a polyether chain residue, n11 is any integer from 0 to 5; n12 is 1.1 to 3, preferably 1.4 to 1.6.

Further, the composition is prepared by the following method: 1) 30-60 parts of the compatible auxiliary agent and the composite auxiliary agent are added under the condition of 60-70 ℃; 2) Stirring for 30min to obtain the composition

3. Advantageous effects

Compared with the prior art, the invention has the beneficial effects that:

1) The compatibility auxiliary agent and the composition thereof provided by the invention have the alkoxy chain which can improve the dispersion capacity in a system and the compatibility between preparations; the imide functional group of the pesticide adjuvant can increase the compatibility of the pesticide adjuvant to pesticide particles; the polyethylene polyamine chain segment increases the cationic density of the whole system and improves the salt tolerance of the system, and the phosphate group of the polyethylene polyamine chain segment can increase the chelation effect on metal ions, so that the salt tolerance of the whole system and the deposition amount of the medical fertilizer on a target are improved, the application effect under a high-electrolysis system is facilitated, and the phenomena of precipitation, flocculation, particle size increase and the like caused by the addition of the water-soluble fertilizer are reduced and reduced.

1) The preparation method of the compatibility auxiliary agent provided by the invention comprises the steps of utilizing maleic anhydride vegetable oil active polymerization monomer, then dropwise adding one or a mixture of alkylene amine and polyether amine to carry out amination reaction on the maleic anhydride vegetable oil Preparing into a compatible auxiliary intermediate, and then utilizing P ₂ O ₅ Processing the mixture to obtain a compatibility auxiliary agent; the introduction of the alkoxy chain improves the dispersibility in water and compatibility among preparations; the introduction of the imide functional group increases the compatibility of the auxiliary agent to pesticide particles; the polyethylene polyamine chain segment increases the cation density of the whole system and improves the salt tolerance of the system, and simultaneously, the introduction of the phosphate group increases the chelation to metal ions, improves the salt tolerance of the whole system and the deposition amount of the medical fertilizer on a target, is beneficial to the application effect under a high-electrolysis system, and reduces the generation of the phenomena of precipitation, flocculation, particle size increase and the like caused by the addition of the water-soluble fertilizer.

Detailed Description

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.

In the present invention, the specific conditions are not specified in the examples, and the process is carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.

The term "about" as used herein is used to provide the flexibility and inaccuracy associated with a given term, metric or value. The degree of flexibility of a particular variable can be readily determined by one skilled in the art.

Drawings

FIG. 1 shows results of a tank mix compatible stability overall stability index (TSI) determination of the product 1D, 8D product, the commercial adjuvants Atlox4616 and Agrilan1028 for the components of the flying guard package in preparation of the composition.

Compatible auxiliary intermediate B preparation example 1:

adding 18.6g of tetraethylenepentamine and 20g of soybean oil into a four-necked flask, heating and dropwise adding 100g of polyisobutylene succinic anhydride (R is a polyisobutene residue and M=600), wherein the dropwise adding temperature is 60-65 ℃ and the dropwise adding time is 0.5-3 h; after the dripping is finished, the vacuum degassing amination temperature is 120-160 ℃, the dehydration amination time is 2-7 hours, and the mono-polyisobutylene succinimide compatible auxiliary agent intermediate 1B is obtained.

Ethoxylation compatible auxiliary intermediate B preparation example 1:

100g of the mono-polyisobutylene succinimide compatible adjuvant intermediate 1B was added to the ethoxylation reactor. Replacing nitrogen for 3 times, heating to 80-150 ℃, feeding 18.6g of ethylene oxide, curing for 1-1.5 h at the temperature of 60-130 ℃ after the ethylene oxide is fed, cooling to 60-70 ℃ and discharging to obtain the ethoxylation mono-polyisobutene succinimide compatible auxiliary agent intermediate.

Compatible auxiliary preparation example 1:

100g of ethoxylated mono-polyisobutylene succinimide compatible auxiliary agent intermediate 1B is added into a four-necked flask, and 18g of P is added dropwise ₂ O ₅ Carrying out phosphoric acid esterification, dropwise adding at the esterification temperature of 20-40 ℃ for about 1.5h; after the dripping is finished, the temperature is raised to 78-82 ℃ for curing for 3.5-4.5 hours, then deionized water accounting for 1-1.5% of the total mass is dripped for hydrolysis, deionized water is dripped for 20-30 minutes for 1-1.5 hours, the hydrolysis temperature is 75-80 ℃, and a neutralizing reagent is added for neutralization after the temperature is reduced to 60-70 ℃. And (3) dehydrating for 30-40 min after neutralization, and discharging after dehydration to obtain the compatible auxiliary agent 1C.

Composition preparation example 1:

under the condition of 60-70 ℃, adding: the compatibility auxiliary 1C 70 weight portions, alcohol ether (3 EO) sulfosuccinic acid monoester disodium salt 6 weight portions, isooctyl alcohol ether (3 EO) 3 weight portions, APG0810 18 weight portions, and stirring for 30min to obtain the compatibility auxiliary composition 1D.

Compatible auxiliary intermediate B preparation example 2:

adding 10.5g of diethylenetriamine and 20g of soybean oil into a four-necked flask, heating and dropwise adding 100g of rapeseed oil-based succinic anhydride (R is soybean oil residue and M=880), wherein the dropwise adding temperature is 60-65 ℃ and the dropwise adding time is 0.5-3 h; after the dripping is finished, the vacuum degassing amination temperature is 120-160 ℃, the dehydration amination time is 2-7 hours, and the single rapeseed oil-based succinimide compatible auxiliary agent intermediate 2B is obtained.

Ethoxylation compatible auxiliary intermediate B preparation example 2:

100g of single rapeseed oil based succinimide compatible adjuvant intermediate 2B was added to an ethoxylation reactor. Replacing nitrogen for 3 times, heating to 80-150 ℃, feeding 12.4g of ethylene oxide, curing for 1-1.5 h at the temperature of 60-130 ℃ after the ethylene oxide is fed, cooling to 60-70 ℃ and discharging to obtain the ethoxylated single rapeseed oil-based succinimide compatible auxiliary intermediate 2B.

Compatible auxiliary preparation example 2:

100g of ethoxylated single rapeseed oil based succinimide compatible auxiliary agent intermediate 2B is added into a four-necked flask, and 11.8g P is added dropwise ₂ O ₅ Carrying out phosphoric acid esterification, dropwise adding at the esterification temperature of 20-40 ℃ for about 1.5h; after the dripping is finished, the temperature is raised to 78-82 ℃ for curing for 3.5-4.5 hours, then deionized water accounting for 1-1.5% of the total mass is dripped for hydrolysis, deionized water is dripped for 20-30 minutes for 1-1.5 hours, the hydrolysis temperature is 75-80 ℃, and a neutralizing reagent is added for neutralization after the temperature is reduced to 60-70 ℃. And (5) dehydrating for 30-40 min after neutralization, and discharging after dehydration to obtain the compatible auxiliary agent 2C.

Composition preparation example 2:

under the condition of 60-70 ℃, adding: 50 parts by weight of the compatible auxiliary agent 2C; 12 parts by weight of fatty alcohol polyoxyethylene ether sodium sulfate, 6 parts by weight of decyl alcohol ether (5 EO) glucoside and 1214 32 parts by weight of APG are stirred for 30min, so that the compatible auxiliary composition 2D is obtained.

Compatible auxiliary intermediate B preparation example 3:

adding 13.2g of triethylene tetramine and 20g of soybean oil into a four-necked flask, heating and dripping 100g of soybean oil-based succinic anhydride (R is soybean oil residue, M=880), wherein the dripping temperature is 60-65 ℃, and the dripping time is 0.5-3 hours; after the dripping is finished, the vacuum degassing amination temperature is 120-160 ℃, the dehydration amination time is 2-7 hours, and the single soybean oil-based succinimide compatible auxiliary agent intermediate 3B is obtained.

Ethoxylation compatible auxiliary intermediate B preparation example 3:

100g of single soybean oil-based succinimide compatible adjuvant intermediate 3B was added to the ethoxylation reactor. Replacing nitrogen for 3 times, heating to 80-150 ℃, feeding 15.6g of ethylene oxide, curing for 1-1.5 h at the temperature of 60-130 ℃ after the ethylene oxide is fed, cooling to 60-70 ℃ and discharging to obtain the ethoxylated single soybean oil-based succinimide compatible auxiliary agent intermediate 3B.

Compatible auxiliary agent preparation example 3:

100g of ethoxylated single rapeseed oil based succinimide compatible auxiliary agent intermediate 3B is added into a four-necked flask, and 11.8g P is added dropwise ₂ O ₅ Carrying out phosphoric acid esterification, dropwise adding at the esterification temperature of 20-40 ℃ for about 1.5h; after the dripping is finished, the temperature is raised to 78-82 ℃ for curing for 3.5-4.5 hours, then deionized water accounting for 1-1.5% of the total mass is dripped for hydrolysis, deionized water is dripped for 20-30 minutes for 1-1.5 hours, the hydrolysis temperature is 75-80 ℃, and a neutralizing reagent is added for neutralization after the temperature is reduced to 60-70 ℃. And (3) dehydrating for 30-40 min after neutralization, and discharging after dehydration to obtain the compatible auxiliary agent 3C.

Composition preparation example 3:

adding 50 parts of the compatible auxiliary agent 3C at 60-70 ℃; 12 parts of sodium dodecyl sulfate, 6 parts of isomeric 13 alcohol ether (3 EO) glycoside and 32 parts of APG0814, and stirring for 30min to obtain the compatible auxiliary agent composition 3D.

Compatible auxiliary intermediate B preparation 4:

adding 16.3g of tetraethylenepentamine and 20g of soybean oil into a four-necked flask, heating and dripping 100g of soybean oil-based succinic anhydride (R is soybean oil residue, M=880), wherein the dripping temperature is 60-65 ℃ and the dripping time is 0.5-3 h; after the dripping is finished, the vacuum degassing amination temperature is 120-160 ℃, the dehydration amination time is 2-7 hours, and the single soybean oil-based succinimide compatible auxiliary agent intermediate 4B is obtained.

Ethoxylation compatible auxiliary intermediate B preparation example 4:

100g of single soybean oil-based succinimide compatible adjuvant intermediate 4B was added to the ethoxylation reactor. Replacing nitrogen for 3 times, heating to 80-150 ℃, feeding 16.1g of ethylene oxide, curing for 1-1.5 h at the temperature of 60-130 ℃ after the ethylene oxide is fed, cooling to 60-70 ℃ and discharging to obtain the ethoxylated soybean oil-based succinimide compatible auxiliary agent intermediate 3B.

Compatible auxiliary agent preparation example 4:

100g of ethoxylated monomerAdding the soybean oil-based succinimide compatible auxiliary agent intermediate 4B into a four-necked flask, and dropwise adding 5.1gP ₂ O ₅ Carrying out phosphoric acid esterification, dropwise adding at the esterification temperature of 20-40 ℃ for about 1.5h; after the dripping is finished, the temperature is raised to 78-82 ℃ for curing for 3.5-4.5 hours, then deionized water accounting for 1-1.5% of the total mass is dripped for hydrolysis, deionized water is dripped for 20-30 minutes for 1-1.5 hours, the hydrolysis temperature is 75-80 ℃, and a neutralizing reagent is added for neutralization after the temperature is reduced to 60-70 ℃. And (5) dehydrating for 30-40 min after neutralization, and discharging after dehydration to obtain the compatible auxiliary agent 4C.

Composition preparation 4:

under the condition of 60-70 ℃, adding: 60 parts by weight of the compatible auxiliary agent 4C; 12 parts by weight of alcohol ether sulfosuccinic acid monoester disodium salt, 8 parts by weight of decyl alcohol ether (5 EO) glucoside and 0810 20 parts by weight of APG are stirred for 30 minutes, so that the compatible auxiliary composition 4D is obtained.

Compatible auxiliary intermediate B preparation 5:

adding 16.3g of tetraethylenepentamine and 20g of soybean oil into a four-necked flask, heating and dripping 100g of soybean oil-based succinic anhydride (R is soybean oil residue, M=880), wherein the dripping temperature is 60-65 ℃ and the dripping time is 0.5-3 h; after the dripping is finished, the vacuum degassing amination temperature is 120-160 ℃, the dehydration amination time is 2-7 hours, and the single soybean oil-based succinimide compatible auxiliary agent intermediate 5B is obtained.

Compatible auxiliary agent preparation example 5:

100g of single soybean oil-based succinimide compatible adjuvant intermediate 4B was added to the ethoxylation reactor. Replacing nitrogen for 3 times, heating to 80-150 ℃, feeding 16.1g of ethylene oxide, curing for 1-1.5 h at the temperature of 60-130 ℃ after the ethylene oxide is fed, cooling to 60-70 ℃ and discharging to obtain the ethoxylated soybean oil-based succinimide compatible auxiliary agent intermediate 5C.

Composition preparation 5:

60 parts of the compatible auxiliary agent 5C is added under the condition of 60-70 ℃; 12 parts of alcohol ether sulfosuccinic acid monoester disodium salt, 8 parts of C12-14 alcohol ether (5 EO) glycoside and 20 parts of APG0814, and stirring for 30min to obtain the compatible auxiliary agent composition 5D.

Compatible auxiliary intermediate B preparation example 6:

adding 11.2g of triethylene tetramine and 20g of soybean oil into a four-necked flask, heating and dropwise adding 100g of polyisobutylene succinic anhydride (R is a polyisobutene residue and M=1200), wherein the dropwise adding temperature is 60-65 ℃ and the dropwise adding time is 0.5-3 h; after the dripping is finished, the vacuum degassing amination temperature is 120-160 ℃, the dehydration amination time is 2-7 hours, and the mono-polyisobutylene succinimide compatible auxiliary agent intermediate 6B is obtained.

Ethoxylation compatible auxiliary intermediate B preparation example 6:

100g of the mono-polyisobutylene succinimide compatible adjuvant intermediate 1B was added to the ethoxylation reactor. Replacing nitrogen for 3 times, heating to 80-150 ℃, feeding 12.3g of ethylene oxide, curing for 1-1.5 h at the temperature of 60-130 ℃ after the ethylene oxide is fed, cooling to 60-70 ℃ and discharging to obtain the ethoxylation mono-polyisobutene succinimide compatible auxiliary agent intermediate 6B.

Compatible auxiliary agent preparation example 6:

100g of ethoxylated mono-polyisobutylene succinimide compatible auxiliary intermediate 6B is added into a four-necked flask, and 4.6g P is added dropwise ₂ O ₅ Carrying out phosphoric acid esterification, dropwise adding at the esterification temperature of 20-40 ℃ for about 1.5h; after the dripping is finished, the temperature is raised to 78-82 ℃ for curing for 3.5-4.5 hours, then deionized water accounting for 1-1.5% of the total mass is dripped for hydrolysis, deionized water is dripped for 20-30 minutes for 1-1.5 hours, the hydrolysis temperature is 75-80 ℃, and a neutralizing reagent is added for neutralization after the temperature is reduced to 60-70 ℃. Dehydrating for 30-40 min after neutralization, discharging to obtain compatible auxiliary agent 6C

Composition preparation example 6:

under the condition of 60-70 ℃, adding: 50 parts by weight of the compatible auxiliary agent 6C; 12 parts by weight of sodium alkylbenzenesulfonate, 10 parts by weight of isomeric 13 alcohol ether (5 EO) glycoside and 0814 28 parts by weight of APG, and stirring for 30min to obtain a compatible auxiliary composition 6D.

Compatible auxiliary intermediate B preparation 7: ( Polyether diamine, MA: amine 1:1, m=100, bis-monophosphate )

Adding 20.4g of polyoxyethylene ether diamine (M=200), 20g of soybean oil into a four-neck flask, heating and dripping 100g of soybean oil-based succinic anhydride (R is soybean oil residue, M=880), wherein the dripping temperature is 60-65 ℃, and the dripping time is 0.5-3 hours; after the dripping is finished, the vacuum degassing amination temperature is 120-160 ℃, the dehydration amination time is 2-7 hours, and the single soybean oil-based succinimide compatible auxiliary agent intermediate 7B is obtained.

Ethoxylation compatible auxiliary intermediate B preparation example 7:

100g of the single soybean oil-based succinimide compatible adjuvant intermediate 7B was added to the ethoxylation reactor. Replacing nitrogen for 3 times, heating to 80-150 ℃, feeding 7.5g of ethylene oxide, curing for 1-1.5 h at the temperature of 60-130 ℃ after the ethylene oxide is fed, and discharging at the temperature of 60-70 ℃ to obtain the ethoxylated soybean oil-based succinimide compatible auxiliary agent intermediate 7B.

Compatible auxiliary preparation example 7:

100g of ethoxylated single soybean oil-based succinimide compatible auxiliary agent intermediate 7B is added into a four-neck flask, and 20gP is added dropwise ₂ O ₅ Carrying out phosphoric acid esterification, dropwise adding at the esterification temperature of 20-40 ℃ for about 1.5h; after the dripping is finished, the temperature is raised to 78-82 ℃ for curing for 3.5-4.5 hours, then deionized water accounting for 1-1.5% of the total mass is dripped for hydrolysis, deionized water is dripped for 20-30 minutes for 1-1.5 hours, the hydrolysis temperature is 75-80 ℃, and a neutralizing reagent is added for neutralization after the temperature is reduced to 60-70 ℃. Dehydrating for 30-40 min after neutralization, discharging to obtain compatible auxiliary agent 7C

Composition preparation example 7:

under the condition of 60-70 ℃, adding: 7C 70 parts of the compatible auxiliary agent; 6 parts by weight of disodium alcohol ether sulfosuccinate monoester, 3 parts by weight of decyl alcohol ether (3 EO), 0814 18 parts by weight of APG and stirring for 30min to obtain a compatible auxiliary composition 7D.

Preparation example 8 of compatible auxiliary intermediate B

16.1g of polyoxyethylene ether diamine (M=400), 20g of soybean oil are added into a four-necked flask, 100g of poly (isobutenyl) amber anhydride (R is polyisobutene residue, M=2000) is dripped at 60-65 ℃ for 0.5-3 h; after the dripping is finished, the vacuum degassing amination temperature is 120-160 ℃, the dehydration amination time is 2-7 hours, and the mono-poly-isobutyl succinimide compatible auxiliary agent intermediate 8B is obtained.

Ethoxylation compatible auxiliary intermediate B preparation example 8:

100g of the monopolyisobutenyl succinimide compatible adjuvant intermediate 8B was added to the ethoxylation reactor. 3 times of nitrogen replacement are adopted, the temperature is raised to 80-150 ℃, 3.5g of ethylene oxide is added, the temperature is controlled to be 60-130 ℃ for curing for 1-1.5 h after the ethylene oxide is fed, the temperature is reduced to be 60-70 ℃ for discharging, and the ethoxylation single polyisobutenyl succinimide compatible auxiliary agent intermediate 8B is obtained.

Compatible auxiliary agent preparation example 8:

100g of an ethoxylated mono-polyisobutenyl succinimide compatible adjuvant intermediate 8B was added to a four-necked flask and 11g of P was added dropwise ₂ O ₅ Carrying out phosphoric acid esterification, dropwise adding at the esterification temperature of 20-40 ℃ for about 1.5h; after the dripping is finished, the temperature is raised to 78-82 ℃ for curing for 3.5-4.5 hours, then deionized water accounting for 1-1.5% of the total mass is dripped for hydrolysis, deionized water is dripped for 20-30 minutes for 1-1.5 hours, the hydrolysis temperature is 75-80 ℃, and a neutralizing reagent is added for neutralization after the temperature is reduced to 60-70 ℃. Dehydrating for 30-40 min after neutralization, discharging to obtain compatible auxiliary agent 8C

Composition preparation 8:

under the condition of 60-70 ℃, adding: 8C70 parts of the compatible auxiliary agent; 6 parts by weight of fatty alcohol polyoxyethylene ether sodium sulfate, 3 parts by weight of isomeric 13 alcohol ether (5 EO) and 0810 18 parts by weight of APG are stirred for 30min to obtain a compatible auxiliary composition, and stirred for 30min to obtain a compatible auxiliary composition 8D.

Compatible auxiliary intermediate B preparation example 9:

adding 57g of polyether diamine ED-600 (M=600), 20g of soybean oil into a four-necked flask, heating and dripping 100g of poly (isobutenyl) amber anhydride (R is polyisobutene residue, M=600), wherein the dripping temperature is 60-65 ℃, and the dripping time is 0.5-3 h; after the dripping is finished, the vacuum degassing amination temperature is 120-160 ℃, the dehydration amination time is 2-7 hours, and the mono-polyisobutenyl succinimide compatible auxiliary agent intermediate 6B is obtained.

Ethoxylation-compatible auxiliary intermediate B preparation example 9:

100g of the monopolyisobutenyl succinimide compatible adjuvant intermediate 6B was added to the ethoxylation reactor. Replacing nitrogen for 3 times, heating to 80-150 ℃, feeding 5.6g of ethylene oxide, curing for 1-1.5 h at the temperature of 60-130 ℃ after the ethylene oxide is fed, cooling to 60-70 ℃ and discharging to obtain the ethoxylation single polyisobutenyl succinimide compatible auxiliary agent intermediate 6B.

Compatible auxiliary preparation example 9:

100g of ethoxylated mono-polyisobutenyl succinimide compatible adjuvant intermediate 6B was added to a four-necked flask and 17g of P was added dropwise ₂ O ₅ Carrying out phosphoric acid esterification, dropwise adding at the esterification temperature of 20-40 ℃ for about 1.5h; after the dripping is finished, the temperature is raised to 78-82 ℃ for curing for 3.5-4.5 hours, then deionized water accounting for 1-1.5% of the total mass is dripped for hydrolysis, deionized water is dripped for 20-30 minutes for 1-1.5 hours, the hydrolysis temperature is 75-80 ℃, and a neutralizing reagent is added for neutralization after the temperature is reduced to 60-70 ℃. Dehydrating for 30-40 min after neutralization, discharging to obtain compatible auxiliary agent 6C

Composition preparation example 9:

under the condition of 60-70 ℃, adding: 70 parts by weight of the compatible auxiliary 6C; 12 parts by weight of alcohol ether sulfosuccinic acid monoester disodium salt, 6 parts by weight of isomeric 13 alcohol ether (5 EO) and 6 parts by weight of APG0810, stirring for 30min to obtain a compatible auxiliary composition, and stirring for 30min to obtain the compatible auxiliary composition 6D.

Compatible auxiliary intermediate B preparation 10:

Ethoxylation-compatible adjuvant intermediate B preparation 10:

100g of the monopolyisobutenyl succinimide compatible adjuvant intermediate 6B was added to the ethoxylation reactor. Replacing nitrogen for 3 times, heating to 80-150 ℃, feeding 5.6g of ethylene oxide, curing for 1-1.5 h at the temperature of 60-130 ℃ after the ethylene oxide is fed, cooling to 60-70 ℃ and discharging to obtain the intermediate 10C of the ethoxylation single polyisobutenyl succinimide compatible auxiliary agent.

Composition preparation 10:

under the condition of 60-70 ℃, adding: 70 parts by weight of the compatible auxiliary 10C, 12 parts by weight of alcohol ether sulfosuccinic acid monoester disodium salt, 6 parts by weight of decyl alcohol ether (3 EO) and 6 parts by weight of APG0814, stirring for 30min to obtain a compatible auxiliary composition, and stirring for 30min to obtain a compatible auxiliary composition 10D.

The products 1D-10D prepared by the products 1D-10D in the preparation examples of the composition have the properties of the commercial additives Atlox4616 and Agrilan1028 and the technical effects of the products in the pesticide preparation field.

Performance verification experiment 1

Balance surface tension: the products 1D to 10D of the inventive compositions preparation examples 1 to 10 and the comparative commercial auxiliaries Atlox4616, agrilan1028 were diluted to 1% by mass of aqueous auxiliaries and then measured at 25.0℃at 20.1℃using a Kruss model K10ST tensiometer equipped with Wilhelmy plates.

Spreading area the products 1D-10D of the compositions preparation examples 1-10 and the commercial auxiliaries Atlox4616 and Agrilan1028 were diluted into 0.05% by mass of aqueous auxiliary solution, and then 20. Mu.l of aqueous solution was respectively dropped onto a plastic glass plate with data cells by a pipette to measure the spreading area.

The retention amount is that fresh and clean rice leaves with a certain area (S) are sheared, the mass (m 0) of the leaves or the base material is weighed by an FA2204 electronic balance, the leaves or the base material is clamped by forceps and vertically placed into the prepared liquid medicine to be soaked for 10 seconds, the liquid medicine is taken out, the mass (m 1) is weighed again when no liquid drops fall, the maximum retention amount (RM) of the liquid medicine is calculated according to a formula (1), the process is repeated for 5 times, and the average value is obtained. And simultaneously performing a blank test. The retention was calculated as follows: RM (mg/cm) ² )＝((m1～m0)/(2×S))×1000

Wherein RM represents a retention amount (mg/cm) ² )；

m1 represents the mass of a rice leaf or a base material dipped with the medicine liquid, and g;

m0 represents the mass of fresh clean rice leaves or substrate, g;

s represents the area of rice leaf, cm ² ；

The results are shown in Table 1 below.

Table 1 Properties of products 1D to 10D prepared from the compositions preparation examples 1 to 10 and commercially available additives Atlox4616 and Agrilan1028

From the data in table 1 above, it can be seen that:

Compared with the commercial additives Atlox4616 and Agrilan1028, the composition products of the products 1D-10D in the preparation examples 1-10 have lower equilibrium surface tension, excellent spreadability and higher retention, are favorable for the penetration and spreading of the preparation on a target and are favorable for the retention of the preparation on the target, so that the utilization rate of the preparation is increased, and the use amount of the pesticide is reduced or reduced.

2. Impact of inventive embodiments on flight-control package stability

The combination of cotton field defoliant package and the common flying prevention package of two diseases and two insects in paddy fields is selected as a standard, and the combination products in the products 1D and 7D in the preparation example of the combination and the commercial additives Atlox4616 and Agrilan1028 are selected for evaluating the compatibility stability of the flying prevention package.

The pesticide formulation and dilution ratio contained in the rice flight preventive package are shown in table 2:

table 2 pesticide formulation and dilution thereof contained in rice flight protection package

Based on the flying-prevention package, the composition products in the products 1D and 7D in the preparation example of the composition and the commercial additives Atlox4616 and Agrilan1028 are respectively added, and a multiple light stability analyzer is adopted to measure the integral stability index (TSI) of the barrel mixing compatibility of the components of the flying-prevention package by the composition products in the products 1D and 7D in the preparation example of the salt-tolerant barrel mixing compatibility agent composition at the flying-prevention dilution concentration, the commercial additives Atlox4616 and Agrilan 1028;

The test result for 30min is shown in figure 1, 1D and 7D of 30% diuron and thidiazuron OD+3X hard water are respectively added, and the stability index ranking within 30min is 7D < 1D < Agrilan1028 < Atlox4616 when commercial additives Atlox4616 and Agrilan1028 are respectively tested;

5% avermectin EC+30% oxime tebuconazole SC+25% pymetrozine dry powder SC+monopotassium phosphate+3X hard water is respectively added with 1D and 7D, and commercial additives Atlox4616 and Agrilan1028, and the stability index sequencing is 7D < 1D < Atlox4616 < Agrilan1028 within 30 minutes;

the above description demonstrates that the composition products 1D and 7D in the products 1D, 7D of the composition preparation have better compatibility stability at the fly concentration.

3. Drug fertilizer compatibility tank mix stability experiment

The medicament comprises 25% of pymetrozine suspending agent, 20% of fosthiazate aqueous emulsion, 430g/L of tebuconazole suspending agent, 25g/L of lambda-cyhalothrin emulsifiable concentrate, 80% of mancozeb wettable powder and 5% of diethyl aminoethyl hexanoate soluble liquid.

The products 1D-10D of the preparation examples 1-10 of the composition of the invention and the commercial auxiliary agent Atlox4616 and Agrilan1028 are respectively subjected to dilution with 5 times of hard water according to the dilution factors shown in Table 3 and are prepared into tank mixed liquid medicine with medicaments; placing the barrel mixed liquid medicine in a 100ml pointed bottom measuring cylinder with a plug, standing for 1h, and observing whether the floating paste is precipitated or not: and (5) marking the paste as qualified without the precipitation of the paste, otherwise, marking the paste as unqualified.

The specific results are shown in Table 3.

Table 3 experiment of the compatibility of the pesticide and fertilizer in tank mix stability

From the data in table 3 it is evident that:

the 1D-10D composite products in the preparation examples 1-10 of the composition have good compatibility with 25% pymetrozine suspending agent, 20% fosthiazate aqueous emulsion, 430g/L tebuconazole suspending agent, 25g/L high-efficiency cyhalothrin emulsifiable concentrate, 80% mancozeb wettable powder and 5% diethyl aminoethyl hexanoate soluble liquid under the condition of 5 times hard water;

the dosage forms of the commercial additives Atlox4616 and Agrilan1028 with qualified barrel mixing stability are less than the synthetic additive of the invention.

4. Water-soluble fertilizer compatibility tank mixing stability experiment

The water-soluble fertilizer comprises a medium element water-soluble fertilizer calcium-soluble fertilizer (calcium and magnesium are more than 170g/l, and N is more than 150 g/l), a high-potassium water-soluble fertilizer fruit-metadox (10-08-40+TE), a high-phosphorus water-soluble fertilizer country Peters No. 2 (10-30-20+2MgO+TE), a high-phosphorus water-soluble fertilizer country Peters No. 15 (6-40-25+TE), and a Bayer Wo medium element water-soluble fertilizer (calcium, magnesium, copper, iron and zinc fertilizer).

The testing method comprises the following steps: respectively testing the products 1D-10D of the preparation examples 1-10 of the composition, respectively adding 8-17.5% of bifenthrin suspending agent (SC) into the commercial additives Atlox4616 and Agrilan1028, respectively diluting the water-soluble fertilizer with 5 times of hard water according to the dilution ratio shown in Table 4, and preparing the diluted water-soluble fertilizer and 17.5% of bifenthrin SC into a tank-mixed liquid medicine with a water-soluble fertilizer sample; placing the barrel mixed liquid medicine into a 100ml pointed-bottom measuring cylinder with a plug, standing for 3 hours to observe whether the floating paste is precipitated or not, and using +to represent the micro precipitation amount, wherein:

The precipitation amount is less than++ and is qualified;

precipitation exceeding++ represents failure.

The specific results are shown in Table 4.

Table 4 experiment of compatibility of Water-soluble fertilizers in tank mix stability

From the data in table 4 it is evident that:

the products 1D-10D of the preparation examples 1-10 of the composition of the invention and the auxiliary agents prepared by the commercial auxiliary agents Atlox4616 and Agrilan1028 are added into 17.5% bifenthrin SC, and the mixture is diluted 200 times with medium element water-soluble fertilizer calcium fermi, high-potassium water-soluble fertilizer fruit metadox, high-phosphorus water-soluble fertilizer beauty Peters No. 2, high-phosphorus water-soluble fertilizer beauty Peters No. 15 and Bayer Wo medium element water-soluble fertilizer under the condition of 5 times hard water to have good stability and compatibility within 3 hours; and other commercially available auxiliary agents Atlox4616 and Agrilan1028 have the advantages that the dosage forms with stable barrel mixing and qualified compatibility are smaller than the auxiliary agents synthesized by the invention, and the 1D and 7D effects are optimal.

5. Field efficiency test

The field efficacy test of 20% dinotefuran SC (water suspension agent) 2-3 generation rice planthoppers mainly comprises brown planthoppers (Nilaparvatalugens Stal). Rice sheath blight (Rhizoctonia solani K uln) in the tillering stage to the yellow ripe stage is prevented and treated by 45% tebuconazole prochloraz EW (emulsion in water), and rice stem ear pest (Magnaporthe grisea 9 Hebert) Barrnov. In order to increase the yield and income of crops and reduce the comprehensive application cost, various foliar fertilizers or water-soluble fertilizers can be added in the flying prevention for use. The problem that the pesticide diluent is flocculated and precipitated in the high-electrolyte water-soluble fertilizer diluent is invalid often occurs when the auxiliary agent is not used.

In the test, a combined package of 20% dinotefuran SC+45% tebuconazole prochloraz EW, which is compared with commercial additives such as 1D and 7D, agrilan1028 and the like, is adopted, diluted according to the dilution factors shown in Table 5, and is prepared into a tank-mixed liquid medicine with high-potassium type water-soluble fertilizer fruit-metadox, high-phosphorus type water-soluble fertilizer metastine No. 2 and Bayer Wo secondary element water-soluble fertilizer.

The results of the drug effect are shown in the following table 5:

TABLE 5 field control experiments

Sequence number	Barrel mixing combination	Dilution factor	3d control effect (%)
				1#	20% dinotefuran SC+45% tebuconazole prochloraz EW	40×+40×+100×	68.48
2	1#+1D	40×+40×+100×	68.61
				3	1# +1D+ Wo Sheng	40×+40×+100×+25×	68.17
4	1# +1D+ Guomeduo	40×+40×+100×+25×	68.87
				5	1# +1D+Peters No. 2	40×+40×+100×+25×	66.46
6	1#+7D	40×+40×+100×	66.68
				7	1# +7d+ Wo Sheng	40×+40×+100×+25×	68.78
8	1# +7D+ Guomeduo	40×+40×+100×+25×	68.64
				6	1# +7D+Peters No. 2	40×+40×+100×+25×	68.22
10	1#+Atlox4616	40×+40×+100×	68.21
				11	1# +Atlox4616+ Wo Sheng	40×+40×+100×+25×	65.87
12	1# +Atlox4616+ Guomeduo	40×+40×+100×+25×	75.42
				13	1# +Atlox4616+Peters No. 2	40×+40×+100×+25×	66.65
14	1#+Agrilan1028	40×+40×+100×	68.17
				15	1# + Agrilan1028+ Wo Sheng	40×+40×+100×+25×	72.18
16	1# +agrilan1028+ fruit metoprolol	40×+40×+100×+25×	65.84
				17	1# +Agrilan1028+Peters No. 2	40×+40×+100×+25×	61.55
18	CK

From the data in table 5 it is evident that:

the composition products in the products 1D and 7D in the preparation example of the preferred composition can improve the product control effect compared with the independent use of commercial additives Atlox4616 and Agrilan1028, mainly because the cationic density of the whole system is increased by containing quaternary ammonium salt in the 1D and 7D compositions, the deposition on a drug target is facilitated, the pesticide utilization rate is improved, and the control effect of the preferred 1D and 7D compositions is slightly higher than the synergistic effect of the independent use of the preparation when the water-soluble fertilizer of a high-salt system, the water-soluble fertilizer of high-potassium type, the water-soluble fertilizer of high-phosphorus type, peters No. 2 of water-soluble fertilizer state and Bayer Wo Sheng are added, and the control effect is far higher than that of the commercial additives Atlox4616 and Agrilan1028.

6. Field fertilizer efficiency test

Field fertilizer efficiency test-based on indoor green test, tank mix was performed and tested using the composition products prepared in examples 1 to 5.

6.1, respectively mixing the composition products 1D-5D prepared in examples 1-5, the auxiliary agent Atlox4616 and Agrilan1028 with a fertilizer in a barrel, spraying rice leaves in the field for 72h, and taking the leaves for indoor measurement. And comparing and detecting the fertilizer with the same fertilizer.

Pretreatment of test, namely setting a treatment concentration for the test composition product to assist in absorbing, conducting and transporting fertilizer, wherein the treatment concentration of the test composition product is 100ml/hm < 2 > and 200ml/hm < 2 > of fertilizer, and repeating each treatment for 3 times, and the cell area is 20m ² . And (3) comparing the high-phosphorus water-soluble fertilizer American Peters No. 2 (10-30-20+2MgO+TE) foliar fertilizer with blank clear water for test.

The test method comprises the steps of spraying leaf surfaces for 72 hours, sampling 3 points in each cell, mixing and carrying back to the room for measurement.

The core principle is that the plant leaves are ground by using acetone or ethanol solution to extract chlorophyll, the optical density values under different wavelengths are measured, and the chlorophyll is calculated. Cutting a plurality of leaves of the rice flag leaves randomly, cutting the leaves into pieces and removing major veins, weighing 0.5g of the leaves, adding 20ml of 65% ethanol solution for soaking, extracting for 24-36 h at dark room temperature, diluting the extracting solution by a certain multiple (according to the situation), and then using an ultraviolet spectrophotometer to respectively conduct colorimetry at 665nm, 646nm and 470 nm. Based on the OD value of each wavelength, the concentrations of chlorophyll a, b and carotenoids (mg.L) ^-1 ) (denoted as C respectively) _a 、C _b 、C _x.c ) The content (mg/g fresh weight) of each pigment was calculated from the obtained concentration. The specific measurement results are shown in Table 8.

C _a ＝13.65×D ₆₆₅ -6.88×D ₆₄₆

C _b ＝24.66×D ₆₄₆ -7.32×D ₆₆₅

In the formula C _a Represents chlorophyll a concentration;

D ₆₆₅ representing absorbance values at 665nm wavelength;

D ₆₄₆ represents absorbance values at 646nm wavelength;

D ₄₇₀ representing absorbance values at 470nm wavelength;

C _b represents chlorophyll b concentration;

C _x.c represents carotenoid concentration.

6.2, respectively mixing the composition products 1D-5D prepared by the compositions 1-5, the auxiliary agent Atlox4616 and Agrilan1028 with a fertilizer in a barrel, spraying potato plants 7D in the field, and taking leaves for indoor measurement. And comparing and detecting the same fertilizer.

Pretreatment of test, namely setting a treatment concentration for the test composition product to assist in absorbing, conducting and transporting fertilizer, wherein the treatment concentration of the test composition product is 100ml/hm < 2 > and 200ml/hm < 2 > of fertilizer, and repeating each treatment for 3 times, and the cell area is 20m ² . And (3) comparing the high-potassium water-soluble fertilizer fruit-metadol (10-08-40+TE) foliar fertilizer with a blank clear water test.

The test method comprises the steps of 7d after foliar spraying, sampling 3 points in each cell, mixing and carrying back to the room for measurement.

And (3) measuring the content of reducing sugar, namely preparing glucose standard solutions with different concentration gradients, and drawing a glucose concentration-absorbance standard curve. Accurately weighing 0.5g of potato tuber sample, grinding with a small amount of distilled water to obtain homogenate, adding distilled water to constant volume of 50ml, shaking, placing in a constant temperature water bath at 50deg.C for 10min, leaching reducing sugar, transferring into a centrifuge tube, centrifuging at 4000r/min for 10min, and collecting supernatant. 2.0ml of the test solution and 1.5ml of 3, 5-dinitrosalicylic acid (DNS) were added as a color reagent to the test tube. After shaking up, the mixture was incubated in a boiling water bath for 5min, cooled to room temperature, and the volume was set to 25ml, and colorimetry was performed at 540 nm. And calculating the content of the reducing sugar in the sample by using a glucose concentration-absorbance standard curve.

Reducing sugar (in glucose)% =c×v/(m×1000) ×100

Total sugar (in glucose)% =c×v/(m×1000) ×dilution x 0.6×100

Wherein C represents the concentration of reducing sugar or total sugar extract, mg/ml

V represents total volume of reducing sugar or total sugar extract, ml

m represents the weight of the sample, g

1000 represents the coefficient of mg converted into g.

The specific measurement results are shown in Table 6.

Table 6 reducing sugar content in each sample

Glucose concentration (mg/ml)	0	0.1	0.2	0.3	0.4	0.5	0.6
								OD	0	0.065	0.147	0.281	0.383	0.460	0.574

6.3, respectively mixing the composition products 1D-5D prepared in examples 1-5, an auxiliary agent Atlox4616 and Agrilan1028 into a fertilizer in a barrel, spraying soybean plants in the field for 7D, and taking seeds for indoor measurement. And comparing and detecting the fertilizer with the same fertilizer.

Test treatment, namely, setting a treatment concentration for the test composition product to assist in absorbing, conducting and transporting the fertilizer, wherein the treatment concentration for the test composition product is 100ml/hm < 2 > and 200ml/hm < 2 > of the fertilizer, and repeating each treatment for 3 times, and the cell area is 20m ² . The contrast medium element water-soluble fertilizer Calmete (calcium+magnesium > 170g/l, N > 150 g/l) foliar fertilizer and blank clear water test.

And (3) measuring soluble proteins, namely preparing bovine serum albumin standard solutions with different concentration gradients, and drawing a protein concentration-absorbance standard curve. Accurately weighing 0.5g of soybean seed sample, adding 2ml of distilled water, grinding into homogenate, then flushing a mortar with 6nl of distilled water, collecting the washing liquid in the same centrifuge tube, centrifuging for 10min at 4000r/min, taking the supernatant, adding the supernatant into a volumetric flask, fixing the volume to 10ml with distilled water, shaking uniformly, and then measuring. Sucking 0.1ml of sample extract, placing into test tubes with plugs (each sample is repeated for 2 times), adding 5ml of coomassie brilliant blue G-250 solution, stirring for 30min, mixing thoroughly, standing for 2min, comparing colors at 565nm, and checking protein content in the sample by using standard curve.

Wherein C represents the value of the standard curve (μg);

V _t represents total volume (ml) of the extract;

W _f represents the fresh weight (g) of the sample;

V _s the amount of sample (ml) to be added at the time of measurement was shown.

The specific measurement results are shown in Table 7.

TABLE 7 protein content in each sample

6.4, respectively and barrelled and mixed with a fertilizer by using the composition products 1D-5D prepared in examples 1-5, the auxiliary agent Atlox4616 and Agrilan1028, and spraying rice plants in the field three times in the tillering stage, the booting stage and the scion alignment stage of the rice until the rice is harvested, and selecting cobs in the field for measurement. And comparing and detecting the fertilizer with the same fertilizer.

Test treatment, namely, setting a treatment concentration for the test composition product to exert the effect of increasing yield on auxiliary fertilizer, wherein the treatment concentration of the test composition product is 100ml/hm2 and 200ml/hm2 of fertilizer, and repeating each treatment for 3 times, and the cell area is 20m ² . And (3) comparing the Bayer Wo secondary element water-soluble fertilizer (calcium-magnesium-copper-iron-zinc fertilizer) with a foliar fertilizer and a blank clear water test.

The test method is that before harvesting rice, the cob is selected in the field for measurement.

Measurement of thousand grain weight of Rice sampling and measurement are carried out according to GBT5516-2018 method for measuring thousand grain weight of grains and beans. The specific measurement results are shown in Table 8.

6.5, respectively mixing the composition products 1D-5D prepared in the examples 1-5, the auxiliary agent Atlox4616 and Agrilan1028 (1 # to 7 #) with a fertilizer in a barrel, spraying the citrus leaves in the field continuously for 3 times every 10D in the citrus fruit swelling period until the citrus fruit matures, and randomly selecting fruits for measurement. And comparing and detecting the fertilizer with the same fertilizer.

Test treatment, namely setting a treatment concentration for the test composition product to exert the effect of increasing yield on auxiliary fertilizers, wherein the treatment concentration of the test composition product is 100ml/hm < 2 > and 200ml/hm < 2 > of the fertilizer, and repeating each treatment for 3 times, so that the cell area is 20 plants. And (3) comparing the high-potassium water-soluble fertilizer fruit-metadol (10-08-40+TE) foliar fertilizer with a blank clear water test.

The test method is that the ripe period of citrus fruits is measured by randomly selecting fruits.

And (3) measuring sugar degree of citrus fruits by adopting a fruit sugar degree rapid measuring instrument. The specific measurement results are shown in Table 8.

The results are visually determined from tables 8.1 to 6.5

As can be seen from table 8:

the composition product assists plants to promote trace element absorption, transportation and conduction.

The results of the field fertilizer efficiency test and the indoor measurement show that the foliar fertilizer dosage and the treatment of the barrel mixed composition product are obviously superior to the foliar fertilizer of 200ml/hm2 alone in terms of the absorption of liquid fertilizer elements by plants. The foliar fertilizer tank-mixed composition product has obvious synergistic effect, and meanwhile, the foliar fertilizer tank-mixed composition product can obviously increase the absorption and transportation conduction of plants to elements. The foliar fertilizer tank-mixed composition product has obvious synergism, can increase absorption and transportation conduction of elements by plants, and has good application value in agricultural application.

From the above test cases, it is clear that the inventive composition products give a higher synergistic effect and that the amount of the composition is substantially reduced compared to the amount of the active compound alone, i.e. the activity of the composition is greater than the activity of the individual components.

More specifically, although exemplary embodiments of the present invention have been described herein, the present invention is not limited to these embodiments, but includes any and all embodiments that have been modified, omitted, e.g., combined, adapted, and/or substituted between the various embodiments, as would be recognized by those skilled in the art in light of the foregoing detailed description. The limitations in the claims are to be interpreted broadly based on the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, definitions, will control. Where a mass, concentration, temperature, time, or other value or parameter is expressed as a range, preferred range, or as a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1 to 50 should be understood to include any number, combination of numbers, or subranges of numbers selected from 1, 2, 3, 4, 5, 6, 7, 8, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 16, 20, 21, 22, 23, 24, 25, 26, 27, 28, 26, 30, 31, 32, 33, 34, 35, 36, 37, 38, 36, 40, 41, 42, 43, 44, 45, 46, 47, 48, 46, or 50, and all fractional values between the foregoing integers, such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.6. Regarding sub-ranges, specifically considered are "nested sub-ranges" that extend from any end point within the range. For example, the nested subranges of exemplary ranges 1 to 50 can include 1 to 10, 1 to 20, 1 to 30, and 1 to 40 in one direction, or 50 to 40, 50 to 30, 50 to 20, and 50 to 10 in another direction.

Claims

1. An auxiliary agent for improving compatibility of a high electrolyte system, which is characterized in that: the general formula of the auxiliary agent is as (1) or (2):

（1）

wherein M is H ⁺ 、Na ⁺ 、K ⁺ Diethanolamine or triethanolamine;

（2）

wherein M is H ⁺ 、Na ⁺ 、K ⁺ Diethanolamine or triethanolamine;

r is one or more of polyisobutylene residue, castor oil residue, soybean oil residue, olive oil residue, peanut oil residue, seed oil residue, corn oil residue, sesame oil residue, cotton oil residue, canola oil residue, safflower oil residue, linseed oil residue, palm oil residue, grape seed oil residue, artemisia annua oil residue, pumpkin oil residue, core oil residue, borage seed oil residue, wood germ oil residue, almond oil residue, pistachio oil residue, almond oil residue, quebracho nut oil residue, avocado oil residue, sea buckthorn oil residue, hemp oil residue, hazelnut oil residue, evening primrose oil residue, wild rose oil residue, thistle oil residue, walnut oil residue, sunflower oil residue, jatropha seed oil residue, and swill-cooked dirty oil residue;

when the R is a polyisobutene residue, the molecular weight of the polyisobutene residue is 600-2300;

R ₁₀ represents one or more of monoethanolamine, monoisopropanolamine residues, alkylene amines or polyetheramine residues.

2. The method for preparing the auxiliary agent for improving the compatibility of the high electrolyte system according to claim 1, wherein the method comprises the following steps: comprising the following steps:

(1) Preparing a compatibility auxiliary agent intermediate B: in the environment of vegetable oil, the active polymerization monomer A is contacted and mixed with organic amine in a dropwise manner to carry out amination reaction; wherein,,

3. The method for preparing the auxiliary agent for improving the compatibility of the high electrolyte system according to claim 2, wherein the method comprises the following steps: in step (1), the maleic anhydride living polymeric monomer of formula (la), including but not limited to formula (3):

（3）

wherein:

the R is one or more of polyisobutylene residue, castor oil residue, soybean oil residue, olive oil residue, peanut oil residue, rapeseed oil residue, corn oil residue, sesame oil residue, cotton oil residue, rape oil residue, safflower oil residue, linseed oil residue, palm oil residue, grape seed oil residue, artemisia annua oil residue, pumpkin oil residue, core oil residue, borage seed oil residue, chickpea oil residue, almond oil residue, pistachio oil residue, almond oil residue, kunskia nut oil residue, avocado oil residue, sea buckthorn oil residue, hemp oil residue, hazelnut oil residue, evening primrose oil residue, wild rose oil residue, thistle oil residue, walnut oil residue, sunflower oil residue, jatropha seed oil residue, swill-cooked dirty oil residue;

When R is a polyisobutene residue, the molecular weight of the polyisobutene residue is 600-2300.

4. The method for preparing the auxiliary agent for improving the compatibility of the high electrolyte system according to claim 2, wherein the method comprises the following steps: the specific contact mode of the active polymerization monomer and the organic amine is any one of the following:

the temperature in the dripping process is 60-95 ℃, and the dripping time is 0.5-3 hours;

after the dripping is finished, vacuum degassing and amination are carried out, the temperature is 120-160 ℃, and the time is 2-7 hours;

and (3) after the dripping is finished, carrying out vacuum degassing amination, wherein the temperature is 120-160 ℃ and the time is 2-7 hours.

5. The method for preparing the auxiliary agent for improving the compatibility of the high electrolyte system according to claim 2, wherein the method comprises the following steps: in step (1), the general formula of the compatibility auxiliary intermediate B includes, but is not limited to, general formulas (8) and (9):

（8）

wherein R is ₁₀ Represents a monoethanolamine and monoisopropanolamine residue;

（9）

Wherein R is ₁₁ Represents an alkylene amine, polyether amine residue.

6. The method for preparing the auxiliary agent for improving the compatibility of the high electrolyte system according to any one of claims 2 to 5, which is characterized in that: in the step (2), P is performed ₂ O ₅ Specific conditions for dripping are as follows: the dripping temperature is 20-40 ℃, and the dripping time is about 1.5 hours;

the specific conditions of the heating and curing treatment are as follows: heating to 78-82 ℃ and treating for 3.5-4.5 hours;

the specific conditions of the hydrolysis and neutralization treatment are as follows: adding 1-1.5% of deionized water according to weight percentage, wherein the adding time is 20-30 min, and hydrolyzing for 1-1.5 h after the adding is completed, wherein the hydrolysis temperature is 75-80 ℃; then cooling to 60-70 ℃, adding a neutralizing reagent, and neutralizing; and (5) dehydrating for 30-40 min after neutralization, and obtaining the compatibility auxiliary agent after dehydrating.

7. The method for preparing the auxiliary agent for improving the compatibility of the high electrolyte system according to claim 6, wherein the method comprises the following steps: and ethoxylation treatment is carried out on the compatible auxiliary agent intermediate B by using ethylene oxide, wherein the ratio of the number of added moles of the ethylene oxide to the number of moles of active hydrogen in the compatible auxiliary agent intermediate B is (1-4): 1.

8. The method for preparing the auxiliary agent for improving the compatibility of the high electrolyte system according to claim 7, wherein the method comprises the following steps: ethoxylation of the compatibility auxiliary intermediate B shown in the general formula (9) and then treatment by P ₂ O ₅ The structural general formula after treatment includes but is not limited to general formulas (14) and (15):

（14）

wherein M is H ⁺ 、Na ⁺ 、K ⁺ One of diethanolamine or triethanolamine or a combination thereof; r is R ₁₂ Represents an alkylene amine, polyether amine residue;

（15）

9. An adjuvant composition characterized in that: comprising the following steps:

40-70 parts of a compatibility auxiliary agent, wherein the compatibility auxiliary agent is an auxiliary agent in claim 1 or an auxiliary agent prepared by any one of the methods in claims 2-8;

the composite auxiliary agent comprises 30-60 parts of anionic surfactant, alcohol ether glycoside solution and alkyl glycoside alcohol ether glycoside solution, wherein the mass ratio of the anionic surfactant to the alcohol ether glycoside solution to the alkyl glycoside alcohol ether glycoside solution is (2-6) (1-5) (9-16).