CN110845717B - Viscoelastic auxiliary agent and composition, preparation method and application thereof - Google Patents

Viscoelastic auxiliary agent and composition, preparation method and application thereof Download PDF

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CN110845717B
CN110845717B CN201911202527.1A CN201911202527A CN110845717B CN 110845717 B CN110845717 B CN 110845717B CN 201911202527 A CN201911202527 A CN 201911202527A CN 110845717 B CN110845717 B CN 110845717B
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viscoelastic
acid
auxiliary agent
fatty acid
adjuvant
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CN110845717A (en
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王磊
曹雄飞
宋文勇
沈姣姣
秦敦忠
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Jiangsu Sinvo Chemical Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2633—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen the other compounds containing amide groups
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/24—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients to enhance the sticking of the active ingredients
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/324—Polymers modified by chemical after-treatment with inorganic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements

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Abstract

The invention provides a viscoelastic auxiliary agent, a composition thereof, a preparation method and application, wherein the preparation method comprises the following steps: (1) under the action of an acid catalyst, polyethylene polyamine is dripped into dimer acid, and after curing reaction, the dimer acid is blocked by fatty acid or fatty acid ester to obtain A; (2) adding an alkaline catalyst into the A, then adding an epoxy compound for curing reaction, adding a neutralizing agent for adjusting the pH value, adding an acid catalyst and fatty acid or fatty acid ester, and carrying out esterification modification to obtain a modified polyethylene polyamine alkoxy ester compound B; (3) and carrying out cationization reaction on the B under the action of a cationization reagent aqueous solution to obtain the viscoelastic auxiliary agent. The viscoelastic auxiliary composition provided by the invention can obviously reduce the rebound and rolling of pesticide preparation droplets on a target, and improve the retention, spreading and utilization rate of pesticides.

Description

Viscoelastic auxiliary agent and composition, preparation method and application thereof
Technical Field
The invention relates to the technical field of pesticide auxiliaries, in particular to a viscoelastic auxiliary, a composition thereof, a preparation method and application.
Background
The pesticide is used as an important agricultural production data in China, is widely used for preventing and controlling diseases, insects, grasses and pests which seriously harm production activities such as agriculture, forestry, herding, fishing and the like, and makes contribution to the national strategic problems of increasing the grain yield and the like without being worn out. However, the amount of the agricultural chemical solution used is often innovative. Research shows that the pesticide utilization rate is only 30% after pesticide application and spraying in China, and about 70% of liquid medicine enters ecological environment due to the fact that fog drops cannot effectively drip and adhere to the surface of a target to bounce, fall, gather and lose, so that most of pesticide active ingredients are lost, and further environmental pollution and resource waste are caused. The pesticide synergistic auxiliary is a general name of the auxiliary used in spraying method application or similar application technologies, and the viscosity, deposition amount, wetting and spreading performance of pesticide droplets on the surface of a target can be obviously improved by properly adding the pesticide synergistic auxiliary. The wetting quality of the surface of the blade is changed, the impact spreading behavior of liquid drops on the surfaces of the super-hydrophobic and hydrophobic blades is promoted, the volume particle size of the fog drops is increased, the atomization state in spraying is effectively controlled, the drifting and flying of the pesticide liquid are reduced, the effective utilization rate of the pesticide can be improved, the loss and pollution of the pesticide liquid drops caused by the splashing on the surfaces of the super-hydrophobic blades are reduced, and the purpose of pesticide reduction can be achieved.
The earliest, simpler, binder adjuvants included fatty acids and their salts, mineral oils and drying oils (such as tung oil and linseed oil). More recent adhesive aids include latex polymers, polymeric terpenes, alkylphenol alkoxylates (such as nonylphenol ethoxylate condensate polymers), fatty acid derivatives, gums and polysaccharides. However, these currently used adhesive adjuvants have limited formulation capabilities, and alkylphenol alkoxylates, such as popular adhesive adjuvants based on nonylphenol ethoxylate condensate polymers, have been limited in various areas. The application with the patent publication No. CN108293987A discloses a composition for preventing liquid drops from rebounding and splashing on a super-hydrophobic surface and application thereof in pesticides, wherein the composition can effectively reduce the damage of pesticide liquid drops caused by splashing on the surface of a super-hydrophobic bladeAnd the dosage and the frequency of pesticide spraying are effectively reduced, and the pollution of the pesticide to the environment can be reduced. However, the composition uses polyoxyethylene ether with the molecular weight of 100-500 ten thousand, the substance is difficult to dissolve and the ethoxy chain is easy to break in water to cause the failure of the surfactant, and meanwhile, the polyoxyethylene trisiloxane or the modified product thereof in the composition is easy to hydrolyze in water to cause the failure of the composition, thereby limiting the use of the composition. Patent publication No. CN108293987A discloses a composition for preventing water droplet bounce and splash on superhydrophobic surfaces, combining the advantages of low dynamic surface tension, low equilibrium surface tension, and polymeric viscosity and thixotropic materials, to solve the problem of ejection and splash of aqueous solutions on superhydrophobic surfaces. However, the application range of the composition is limited by the use of nonylphenol oxyethylene and 400-ten-thousand polyethylene glycol or polyoxyethylene ether with the molecular weight of 200-. Application No. US10015960 discloses a polyamide and polyimide adhesion promoter that is a polyetheramide or polyetherimide formed by reacting a polyether polyamine with a polyfunctional monomer. The polyfunctional monomer can be polybasic acid, difunctional acyl halide, anhydride, poly (anhydride) and mixtures thereof, can be used in agrochemical compositions, but the raw material polyetheramine preparation process is complicated, and in particular requires a special high efficiency catalyst to increase NH3Otherwise NH is easily caused3The waste of polluted air.
Based on the defects of the prior art, the invention of a novel fog drop viscoelastic auxiliary agent which can obviously reduce the rebound and the rolling of the fog drops of the pesticide preparation on a target and improve the retention, the spreading and the utilization rate of the pesticide is needed to expand the application range.
Disclosure of Invention
1. Problems to be solved
The viscoelastic auxiliary agent is prepared by amidating polyethylene polyamine and dimer acid, then carrying out end capping on the amidated polyethylene polyamine and dimer acid by using fatty acid, carrying out alkoxylation and esterification modification in a side chain, and finally carrying out cationization reaction on amine. The composition prepared by the invention is added into an aqueous spraying solution or a mixture, so that the rebound and the rolling of the pesticide preparation droplets on a target can be reduced, the retention, the spreading and the utilization rate of the pesticide are improved, the preparation method is simple, the performance of the auxiliary agent is excellent, and the application value is wide.
2. Technical scheme
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a viscoelastic auxiliary agent, which comprises the following steps:
(1) under the action of an acid catalyst, polyethylene polyamine is dripped into dimer acid, and after curing reaction, the dimer acid is blocked by fatty acid or fatty acid ester to obtain A;
(2) adding an alkaline catalyst into the A, then adding an epoxy compound for curing reaction, adding a neutralizing agent for adjusting the pH value, and then adding an acid catalyst and fatty acid or fatty acid ester for esterification reaction to obtain a modified polyethylene polyamine alkoxy ester compound B;
(3) and (3) carrying out cationization reaction on the modified polyethylene polyamine alkoxy ester compound B under the action of a cationization reagent aqueous solution to obtain the viscoelastic auxiliary agent C.
The viscoelastic auxiliary agent prepared by the invention is prepared by amidating polyethylene polyamine and dimer acid, then carrying out end capping on the amidated polyethylene polyamine and dimer acid by using fatty acid or fatty acid ester, carrying out alkoxylation and esterification modification in a side chain, and finally carrying out amine cationic reaction. The cationic surfactant has the characteristics of a cationic surfactant, is beneficial to improving the deposition amount of the liquid medicine on a target and reducing the loss of the liquid medicine, and the dimer acid and the fatty acid contained in the auxiliary agent are similar to main components of plant leaf surfaces, are good in compatibility and strong in affinity, and further enhance the retention and conduction of the liquid medicine; and the auxiliary agent simultaneously contains an alkoxylated chain, so that the compatibility between the auxiliary agent and different preparations is improved, and the physical stability of the mixed liquid medicine can be improved.
The viscoelastic auxiliary agent obtained by the preparation method of the viscoelastic auxiliary agent has better molecular structure regularity, and can reduce the generation of byproducts: under the action of an acid catalyst, polyethylene polyamine is dripped into dimer acid to carry out amidation reaction, so that the reaction process is prevented from being influenced by side reaction caused by excessive polyethylene polyamine; under the action of an acidic catalyst, the esterification end capping reaction is facilitated to be carried out, after the second-step alkoxylation reaction is carried out to obtain an R-OH compound, the esterification modification is carried out, and finally the cationization reaction is carried out to obtain the product. The whole process is simple and the yield is high.
As a further improvement of the invention, the step (1) specifically comprises the following steps:
(a) firstly, adding an acid catalyst and dimer acid into a reaction kettle, then replacing air in the reaction kettle with nitrogen, and raising the temperature to 140-;
(b) then adding polyethylene polyamine dropwise, introducing nitrogen gas slightly for dehydration, controlling the dropping temperature to be 140-;
(c) after the curing is finished, adding fatty acid or fatty acid ester, controlling the temperature to be 140-; and finally, vacuumizing at the temperature of 80-85 ℃ to remove volatile components, thus obtaining the A.
As a further improvement of the invention, the acidic catalyst comprises one or more of zinc acetate, methanesulfonic acid, p-toluenesulfonic acid, zirconium naphthenate, dibutyl tin dilaurate, stannous chloride, tin octoate, tetrapropyl titanate or tetrabutyl titanate.
According to the invention, nitrogen is firstly introduced to replace air in the reaction kettle, so that the side reaction can be reduced, the feeding mode of dripping polyethylene polyamine is adopted, the concentration of the polyethylene polyamine in the whole system is controlled within a certain range, the regularity of the obtained molecular structure is better under the condition of excessive concentration of dimer acid, and the generation of byproducts can be reduced. The introduction of the dimer acid and the fatty acid not only regulates the high viscosity of the system, but also improves the affinity and compatibility of the auxiliary agent and the leaf surface and is beneficial to the retention and conduction of the liquid medicine, and the structures of the dimer acid and the fatty acid are similar to the main components of the leaf surface.
As a further improvement of the invention, the general formula of A in the step (1) is as follows:
Figure GDA0003478517540000031
wherein n is an integer of 1-10, R is a dimer acid residue, and the dimer acid is derived from C36 dimer fatty acid (HONGTAI), UNIDYMETM14 and UNIDYMETM18, R1 is a fatty acid residue, and the source of R1 is a straight or branched chain, saturated or unsaturated alkane carboxylic acid having from C1 to C22 or fatty acid methyl ester such as caproic acid, caprylic acid, capric acid, undecanoic acid, palmitic acid, coconut oil acid, lauric acid, and stearic acid, methyl oleate, methyl stearate, and the like. Unsaturated fatty acids such as tall oil acid, ricinoleic acid, linoleic acid and the like are also possible, preferably R1 is oleic acid, stearic acid, palmitic acid, and n1 and n2 are all any integer from 0 to 5.
As a further improvement of the invention, the epoxy compound comprises ethylene oxide, propylene oxide or butylene oxide. The polyethylene polyamine is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine or pentaethylene hexamine.
As a further improvement of the invention, the basic catalyst comprises one or more of metal potassium, metal sodium, potassium methoxide, sodium methoxide, potassium hydroxide and sodium hydroxide, and the ratio of the basic catalyst to the total mass of the alkoxy compound is (0.1-0.8): 100.
as a further improvement of the present invention, the step (2) specifically comprises the following steps:
s1, adding the A obtained in the step (1) into a reaction kettle, replacing the A with nitrogen for 3 times, raising the temperature to 115-130 ℃, introducing a certain amount of alkoxy compound, introducing nitrogen to ensure that the pressure is 0.15-0.35MPa, curing the mixture for 1-3 hours at 115-130 ℃, and finishing the reaction after the pressure is kept unchanged. And (3) vacuumizing at 80-85 ℃ to remove volatile components to obtain the modified polyethylene polyamine alkoxy compound intermediate.
S2, adding the modified polyethylene polyamine alkoxy compound intermediate obtained in the step (1) and a certain amount of basic catalyst into a reaction kettle, replacing the mixture with nitrogen for three times, heating to 100-160 ℃, removing water within a certain time to ensure that the water content of the material in the reaction kettle is less than 0.05 percent, heating to 115-160 ℃, and adding corresponding alkoxy compound in batches according to the structural requirements.
The feeding temperature is controlled at 160 ℃ and the maximum feeding pressure is less than 0.35 MPa; and (5) finishing feeding. Curing at the temperature of between 120 and 160 ℃, and introducing nitrogen to keep the pressure at 0.15-0.25MPa when the curing pressure is close to 0.02 MPa. When the pressure in the reaction kettle is kept constant, the reaction is finished, and the curing time is required to be about 1-3 h. Vacuumizing at 135 ℃ of 120-; when the conversion rate of the fatty acid or the fatty acid ester reaches more than 97 percent, the modified polyethylene polyamine alkoxy ester compound B is obtained.
The beneficial effects of the preferred technical scheme are as follows: the nitrogen is used for thoroughly replacing the air in the reaction kettle and the material, so that the danger can be avoided, and the byproduct production can be reduced; the dehydration treatment can remove water in the materials, so that active hydrogen in the water is prevented from influencing the reaction of alkoxy compounds, and the increase of by-products in the product is avoided; the invention controls the feeding temperature to be lower, and can avoid the phenomenon that the reaction rate is too high due to the overhigh concentration of the catalyst in the initial material; the reaction rate can be ensured along with the temperature rise of the reaction; the pressure is controlled within a controllable range, so that the safety production can be ensured. The introduction of an alkoxylated chain into the viscoelastic auxiliary agent increases the compatibility among preparations, adjusts the viscosity of a system, has a structure similar to that of main components of the leaf surface, increases the affinity of the auxiliary agent and the leaf surface, and is beneficial to the conduction and absorption of liquid medicine.
As a further improvement of the invention, the structural formula of the modified polyethylene polyamine alkoxy ester compound B is as follows:
Figure GDA0003478517540000051
in the formula, xY and z are respectively an integer of 0-30, the sum of x, y and z is an integer more than 0, a, b and c are one of oxyethylene (EO), oxypropylene (PO) and oxybutylene (BO), R is a dimer acid residue, and1is a fatty acid residue, R2Is one of H and fatty acid residue, wherein n1 and n2 are any integer from 1 to 5, and n is an integer from 1 to 10.
As a further improvement of the present invention, the step (3) is specifically: firstly, adding a modified polyethylene polyamine alkoxy ester compound B into a container, and adding a certain amount of water as a solvent, wherein the addition amount of the water is 20-70% of the mass of the modified polyethylene polyamine polyether fatty acid ester. And (3) dripping a cationization reagent aqueous solution at 70-80 ℃, and dehydrating after refluxing reaction for 6-8h to obtain the viscoelastic auxiliary agent C.
As a further improvement of the invention, the cationizing agent comprises formic acid, acetic acid, phosphoric acid, citric acid, alkyl halide with 1-5 carbon atoms (such as methyl chloride and ethyl chloride), halohydrin with 1-5 carbon atoms (such as ethyl chloride) or halocarboxylate with 2-5 carbon atoms.
In a further aspect of the present invention, the cationizing agent is preferably an aqueous solution of sodium chloroacetate or an aqueous solution of hydrogen peroxide. According to the invention, the cationization auxiliary agent is prepared by dripping the cationization reagent, so that the electrostatic adsorption effect between the amino group as an anchor group and the target is enhanced, the coalescence loss and rebound of liquid drops are weakened, and the retention and deposition of the liquid medicine are improved.
The viscoelastic auxiliary agent C prepared by the preparation method has a structure of a general formula (1) or (2):
Figure GDA0003478517540000061
x, y and z are integers including 0-30, the sum of x, y and z is an integer more than 0, a, b and c are one of oxyethylene (EO), oxypropylene (PO) and oxybutylene (BO), R is a dimer acid residue, and the total content of the two or more of the three1Is a fatty acid residue, R2Is one of H and fatty acid residue, the n1,n2 is any integer of 1-5, and n is an integer of 1-10.
As a further improvement, the invention provides a viscoelastic adjuvant composition comprising a silicone adjuvant, a sodium sulfosuccinate diester salt system and the viscoelastic adjuvant.
As a further improvement of the invention, the viscoelastic adhesive comprises, by mass, 0-20% of an organosilicon additive, 10-50% of a sodium sulfosuccinate diester system and 30-90% of a viscoelastic additive.
As a further improvement of the present invention, the preparation method of the viscoelastic auxiliary composition comprises the following steps:
(a) respectively weighing the organic silicon additive, the sulfosuccinic acid diester sodium salt system and the viscoelastic additive;
(b) stirring for 30min at the temperature of 60-70 ℃ to obtain the viscoelastic auxiliary agent composition.
As a further improvement of the invention, the silicone auxiliary is predominantly polyoxyethylene trisiloxane or a modified product thereof, preferably Silwet408, Silwet77 and SP-408, SP-4078, SP-4030, SP-4086, SP-4026 from Sinvo, from Michem.
In a further improvement of the invention, the two lipophilic chain groups in the sodium sulfosuccinate are linear alkanes having 4-18 carbon atoms or isomers thereof, preferably any one or combination of sodium sulfosuccinate systems using methyl oleate, butanol, isooctanol and propane as solvents by Eliter and Sinvo company.
Therefore, the composition prepared by the viscoelastic auxiliary agent has excellent dynamic surface tension and spreading and penetrating capabilities. Through the addition of the composition, the wettability of the surfaces of the leaves is changed in the process of impacting the pesticide liquid drops with the surfaces of the plant leaves, the impacting and spreading behavior of the liquid drops on the surfaces of the super-hydrophobic and hydrophobic leaves is promoted, the loss and pollution of the pesticide liquid drops caused by splashing on the surfaces of the super-hydrophobic leaves are reduced, the pesticide utilization rate is improved, and the pollution of pesticides to the environment can be reduced.
As a further improvement of the invention, the viscoelastic auxiliary composition is used as a mist viscoelastic pesticide auxiliary.
3. Advantageous effects
(1) The viscoelastic auxiliary agent is a water-based polymer auxiliary agent which takes cationized amino as an anchoring point, amido as a main chain and alkoxy as a solvation chain, the anchoring group and the amido are adsorbed on a target in a single-point adsorption or multi-point anchoring mode through the interaction of ionic bonds, covalent bonds, hydrogen bonds, van der waals force and the like, the deposition amount of liquid medicine on the target is improved, the liquid medicine loss and droplet rebound are reduced, dimer acid and fatty acid are similar to main components of plant leaf surfaces in structure, the dimer acid and the fatty acid have affinity with the plant leaf surfaces, and the dimer acid and the fatty acid are easy to dissolve and permeate into plant bodies.
(2) The viscoelastic auxiliary composition contains an alkoxylated chain, improves the compatibility between preparations and the physical stability between mixed liquid medicines, has good water dispersion, and is convenient and quick to use; the viscoelastic auxiliary composition has a plurality of cation centers, low dynamic surface tension and spreading and penetrating capability, and the liquid medicine added with the viscoelastic auxiliary composition enhances the electrostatic adsorption effect, weakens the coalescence loss and rebound of liquid drops and improves the retention and deposition of the liquid medicine at the moment of contacting with a target.
(3) According to the viscoelastic auxiliary agent composition, the organic silicon with good spreading and permeability and the sulfosuccinic acid diester sodium salt system with low dynamic surface tension are introduced, so that the spreading of the liquid medicine on a target is improved, the pinning effect of the liquid medicine on the target is increased, and the rebound loss of fog drops is reduced.
Drawings
FIG. 1 is a graph of the dynamic surface tension change values for an adjuvant composition of an example;
FIG. 2 is a graphic comparison of the viscoelastic properties of medical fluids captured using high speed photographic techniques in catapult and sputter experiments conducted with the adjuvant compositions of the examples.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment of the invention discloses a fog drop viscoelastic water-based polymer additive and a composition thereof, and the preparation method specifically comprises the following steps: (1) adding 2.75g of methanesulfonic acid and 561g of dimer acid (HONGTAI) into a reaction kettle, replacing 3 times by nitrogen, raising the temperature to 140-.
(2) 189g of A1 obtained in the step (1) is added into the reaction kettle, nitrogen is used for replacing for 3 times, the temperature is raised to 115-fold 130 ℃, 13.9g of ethylene oxide is introduced, nitrogen is introduced to ensure that the pressure is 0.15-0.35MPa, the aging is carried out for 1-3h at 115-fold 130 ℃, and the reaction is finished after the pressure is kept unchanged. And (3) vacuumizing at 80-85 ℃ to remove volatile components to obtain a modified polyethylene polyamine ethoxylate B1 intermediate.
(3) Adding 1.5g of NaOH into the modified polyethylene polyamine ethoxylate B1 intermediate obtained in the step (2), replacing the NaOH with nitrogen for three times, heating to the temperature of 100-; and (5) finishing feeding. Curing at the temperature of between 120 and 160 ℃, and introducing nitrogen to keep the pressure at 0.15-0.25MPa when the curing pressure is close to 0.02 MPa. When the pressure in the reaction kettle is kept unchanged, the reaction is finished; the curing time is about 1-3 h. Vacuumizing at 135 ℃ of 120 ℃ for 0.5-1h, cooling to 70-80 ℃, adding a neutralizing agent, and adjusting the pH value to 5-7. Adding 84.6g of oleic acid and 2g of p-toluenesulfonic acid, controlling the temperature at 185 ℃, slightly introducing nitrogen for dehydration, and curing for 5-7h, wherein when the collected water is about 5g, the acid value is detected to be less than 0.9 mgKOH/g; the product was obtained and marked B1.
(4) Adding 54g of B into a four-neck flask, adding 45g of water at 70-80 ℃, dropwise adding 7.5g of 50% sodium chloroacetate aqueous solution, reacting for 6-8h at 70-80 ℃, and removing the aqueous solution after the reaction is finished to obtain the water-based polymer additive C1.
30g of sample C1, 20g of organosilicon assistant SP-408 and 50g of diisooctyl sulfosuccinate sodium salt system (methyl oleate system) were weighed out. The resulting mixture was thoroughly mixed and stirred at 70 ℃ for 30min to give a viscoelastic auxiliary composition having a transparent appearance, sample D1.
Example 2
The embodiment of the invention discloses a fog drop viscoelastic water-based polymer additive and a composition thereof, and the preparation method specifically comprises the following steps:
(1) to the reaction vessel were added 3.1g of p-toluenesulfonic acid and 561g of dimer acid (UNIDYME)TM14) Replacing 3 times by nitrogen, raising the temperature to 140-160 ℃, dropwise adding 347g of pentaethylenehexamine, slightly introducing nitrogen for dehydration, simultaneously controlling the dropwise adding temperature to 180-190 ℃, carrying out the dropwise adding time for 2.5-3h, after the dropwise adding is finished, controlling the temperature to 180-190 ℃ for curing reaction, wherein the curing time is 4-6h, when the collected water is about 36g, detecting the acid value to be less than 1.8mgKOH/g, adding 216g of oleic acid, controlling the temperature to be 180-195 ℃, slightly introducing nitrogen for dehydration, carrying out the curing time for 5-7h, when the collected water is about 18g, detecting the acid value to be less than 1.2mgKOH/g, finally vacuumizing to remove volatile components under the condition of 80-85 ℃ to obtain A2.
(2) 113.5g of A2 obtained in the step (1) is added into the reaction kettle, nitrogen is used for replacing for 3 times, the temperature is raised to 115-class 130 ℃, 27g of ethylene oxide is introduced, nitrogen is introduced to ensure that the pressure is 0.15-0.35MPa, the aging is carried out for 1-3h at 115-class 130 ℃, and the reaction is finished after the pressure is kept unchanged. And (3) vacuumizing at 80-85 ℃ to remove volatile components to obtain a modified polyethylene polyamine ethoxylate B2 intermediate.
(3) Adding 1.15g of KOH into the modified polyethylene polyamine ethoxylate B2 intermediate obtained in the step (2), replacing the KOH with nitrogen for three times, heating to the temperature of 100 ℃ and 135 ℃, removing water within a certain time to ensure that the water content of the material in the reaction kettle is less than 0.5%, heating to the temperature of 100 ℃ and 160 ℃, introducing 175gEO, controlling the feeding temperature to be 100 ℃ and 160 ℃, and controlling the maximum feeding pressure to be less than 0.35 MPa; and (5) finishing feeding. Curing at the temperature of between 120 and 160 ℃, and introducing nitrogen to keep the pressure at 0.15-0.25MPa when the curing pressure is close to 0.02 MPa. When the pressure in the reaction kettle is kept unchanged, the reaction is finished; the curing time is about 1-3 h. Vacuumizing at 135 ℃ of 120 ℃ for 0.5-1h, cooling to 70-80 ℃, adding a neutralizing agent, and adjusting the pH value to 5-7. Adding 84g of oleic acid and 3.52g of p-toluenesulfonic acid, controlling the temperature at 185 ℃, slightly introducing nitrogen for dehydration, and curing for 5-7h, wherein when the collected water is about 5g, the acid value is detected to be less than 1.2 mgKOH/g; the product was obtained and marked B2.
(4) Adding 80g of B2 into a four-neck flask, adding 300g of water, dropwise adding 10.8g of 37.5% aqueous hydrogen peroxide solution, reacting at 70-80 ℃ for 6-8h, and removing the aqueous solution after the reaction is finished to obtain the high-viscosity low-viscosity fog-drop viscoelastic water-based polymer additive C2.
Example C2 sample 35g, 15g of the silicone additive Silwet77, 50g of the diisooctyl sulfosuccinate sodium salt system (butanol as system) were weighed out. The resulting mixture was thoroughly mixed and stirred at 70 ℃ for 30min to give a viscoelastic auxiliary composition having a transparent appearance, sample D2.
Example 3
The embodiment of the invention discloses a fog drop viscoelastic water-based polymer additive and a composition thereof, and the preparation method specifically comprises the following steps:
(1) to the reaction vessel, 7.5g of p-toluenesulfonic acid and 561g of dimer acid (UNIDYME) were addedTM18) Replacing 3 times by nitrogen, raising the temperature to 140-160 ℃, dropwise adding 138g of diethylenetriamine, slightly introducing nitrogen for dehydration, simultaneously controlling the dropwise adding temperature to 180-190 ℃, carrying out the dropwise adding time for 2.5-3h, after the dropwise adding is finished, controlling the temperature to 180-190 ℃ for curing reaction, wherein the curing time is 4-6h, when the collected water is about 35g, detecting that the acid value is less than 4mgKOH/g, adding 228g of coconut oil acid, controlling the temperature to 180-195 ℃, slightly introducing nitrogen for dehydration, the curing time is 5-7h, when the collected water is about 11g, detecting that the acid value is less than 0.8mgKOH/g, finally vacuumizing for removing volatile components at the temperature of 80-85 DEGThus, A3 was obtained.
(2) Adding 132g of A3 obtained in the step (1) into a reaction kettle, replacing the mixture with nitrogen for 3 times, raising the temperature to 115-130 ℃, introducing 12gPO, introducing nitrogen to ensure that the pressure is 0.15-0.35MPa, curing the mixture for 1-3 hours at 115-130 ℃, and finishing the reaction after the pressure is kept unchanged. And (3) vacuumizing at 80-85 ℃ to remove volatile components to obtain a modified polyethylene polyamine ethoxylate B3 intermediate.
(3) Adding 1.2g of KOH into the modified polyethylene polyamine ethoxylate B3 intermediate obtained in the step (2), replacing the KOH with nitrogen for three times, heating to the temperature of 100 ℃ and 135 ℃, removing water within a certain time to ensure that the water content of the material in the reaction kettle is less than 0.5 percent, heating to the temperature of 100 ℃ and 160 ℃, introducing 106gEO, controlling the feeding temperature to be 100 ℃ and 160 ℃, and controlling the maximum feeding pressure to be less than 0.35 MPa; and (5) finishing feeding. Curing at the temperature of between 120 and 160 ℃, and introducing nitrogen to keep the pressure at 0.15-0.25MPa when the curing pressure is close to 0.02 MPa. When the pressure in the reaction kettle is kept unchanged, the reaction is finished; the curing time is about 1-3 h. Vacuumizing for 0.5-1h at 135 ℃ of 120-; the product was obtained and marked B3.
(4) 117g of B3 is added into a four-neck flask, 240g of water is added, 7.5g of 37.5 percent aqueous hydrogen peroxide is added dropwise, the mixture reacts for 6 to 8 hours at the temperature of between 70 and 80 ℃, and after the reaction is finished, the aqueous solution is removed, so that the high-viscosity low-viscosity fog-drop viscoelastic water-based polymer additive C3 is obtained.
Sample C3 (60 g), silicone adjuvant SP-4078 (10 g), and diisooctyl sulfosuccinate sodium salt system (isooctanol as system) were weighed. The resulting mixture was thoroughly mixed and stirred at 70 ℃ for 30min to give a viscoelastic auxiliary composition having a transparent appearance, sample D3.
Example 4
The embodiment of the invention discloses a fog drop viscoelastic water-based polymer additive and a composition thereof, and the preparation method specifically comprises the following steps:
(1) adding 5.6g of p-toluenesulfonic acid and 561g of dimer acid (HONGTAI) into a reaction kettle, replacing 3 times with nitrogen, raising the temperature to 140-.
(2) 215g of A4 obtained in the step (1) is added into the reaction kettle, nitrogen is used for replacing for 3 times, the temperature is raised to 115-130 ℃, 53gPO is introduced, nitrogen is introduced to ensure that the pressure is 0.15-0.35MPa, the aging is carried out for 1-3h at 115-130 ℃, and the reaction is finished after the pressure is kept unchanged. And (3) vacuumizing at 80-85 ℃ to remove volatile components to obtain a modified polyethylene polyamine ethoxylate B4 intermediate.
(3) Adding 1.9g of KOH into the modified polyethylene polyamine ethoxylate B4 intermediate obtained in the step (2), replacing the KOH with nitrogen for three times, heating to the temperature of 100 ℃ and 135 ℃, removing water within a certain time to ensure that the water content of the material in the reaction kettle is less than 0.5%, heating to the temperature of 100 ℃ and 160 ℃, introducing 396gEO, controlling the feeding temperature to be 100 ℃ and 160 ℃, and controlling the maximum feeding pressure to be less than 0.35 MPa; and (5) finishing feeding. Curing at the temperature of between 120 and 160 ℃, and introducing nitrogen to keep the pressure at 0.15-0.25MPa when the curing pressure is close to 0.02 MPa. When the pressure in the reaction kettle is kept unchanged, the reaction is finished; the curing time is about 1-3 h. Vacuumizing at 135 ℃ of 120 ℃ for 0.5-1h, cooling to 70-80 ℃, adding a neutralizing agent, and adjusting the pH value to 5-7. Adding 141g of oleic acid and 6.4g of p-toluenesulfonic acid, controlling the temperature at 185 ℃, slightly introducing nitrogen for dehydration, and curing for 5-7h, wherein when the collected water is about 9g, the acid value is detected to be less than 1 mgKOH/g; the product was obtained and marked B4.
(4) Adding 80g of B4 into a four-neck flask, adding 100g of water, dropwise adding 9g of 37.5% aqueous hydrogen peroxide solution, reacting at 70-80 ℃ for 6-8h, and removing the aqueous solution after the reaction is finished to obtain the high-viscosity low-viscosity fog-drop viscoelastic water-based polymer additive C4.
Sample 80g of example C4, 7g of organosilicon assistant SP-4030, 13g of diisooctyl sulfosuccinate sodium salt system (in the isooctanol system) were weighed out. The resulting mixture was thoroughly mixed and stirred at 70 ℃ for 30min to give a viscoelastic auxiliary composition having a transparent appearance, sample D4.
Example 5
The embodiment of the invention discloses a fog drop viscoelastic water-based polymer additive and a composition thereof, and the preparation method specifically comprises the following steps:
(1) 3.8g of p-toluenesulfonic acid and 281g of dimer acid (HONGTAI) are added into a reaction kettle, nitrogen is used for replacing for 3 times, the temperature is raised to 140-160 ℃, 189g of tetraethylenepentamine is dripped, nitrogen is slightly introduced for dehydration, the dripping temperature is controlled to 180-190 ℃, the dripping time is carried out for 2.5-3h, after the dripping is finished, the temperature is controlled to 180-190 ℃ for curing reaction, the curing time is 4-6h, when the collected water content is about 18g, the acid value is detected to be less than 1.8mgKOH/g, 282g of oleic acid is added, the temperature is controlled to 180-195 ℃, nitrogen is slightly introduced for dehydration, the curing time is 5-7h, when the collected water content is about 18g, the acid value is detected to be less than 2.3mgKOH/g, and finally the volatile component is removed by vacuum pumping at the temperature of 80-85 ℃ to obtain A5.
(2) Adding 143g of A5 obtained in the step (1) into the reaction kettle, replacing the mixture with nitrogen for 3 times, raising the temperature to 115-130 ℃, introducing 35gPO, introducing nitrogen to ensure that the pressure is 0.15-0.35MPa, curing the mixture for 1-3h at 115-130 ℃, and finishing the reaction after the pressure is kept unchanged. And (3) vacuumizing at 80-85 ℃ to remove volatile components to obtain a modified polyethylene polyamine ethoxylate B5 intermediate.
(3) Adding 1.3g of KOH into the modified polyethylene polyamine ethoxylate B5 intermediate obtained in the step (2), replacing the KOH with nitrogen for three times, heating to the temperature of 100 ℃ and 135 ℃, removing water within a certain time to ensure that the water content of the material in the reaction kettle is less than 0.5 percent, heating to the temperature of 100 ℃ and 160 ℃, introducing 264gEO, controlling the feeding temperature to be 100 ℃ and 160 ℃, and controlling the maximum feeding pressure to be less than 0.35 MPa; and (5) finishing feeding. Curing at the temperature of between 120 and 160 ℃, and introducing nitrogen to keep the pressure at 0.15-0.25MPa when the curing pressure is close to 0.02 MPa. When the pressure in the reaction kettle is kept unchanged, the reaction is finished; the curing time is about 1-3 h. Vacuumizing at 135 ℃ of 120 ℃ for 0.5-1h, cooling to 70-80 ℃, adding a neutralizing agent, and adjusting the pH value to 5-7. Adding 56.8g of stearic acid and 4.1g of p-toluenesulfonic acid, controlling the temperature at 185 ℃, slightly introducing nitrogen for dehydration, wherein the curing time is 5-7h, and when about 9g of water is collected and the acid value is detected to be less than 0.6 mgKOH/g; the product was obtained and marked B5.
(4) 99g of B5 is added into a four-neck flask, 130g of water is added, 10.8g of 37.5% aqueous hydrogen peroxide solution is added dropwise, the mixture reacts for 6 to 8 hours at 70 to 80 ℃, and after the reaction is finished, the aqueous solution is removed to obtain the high-viscosity low-viscosity fog-drop viscoelastic water-based polymer additive C5.
A sample of C5 was weighed out as 88g, 2g of the organosilicon assistant SP-4030 and 10g of the diisooctyl sulfosuccinate sodium salt system (butanol system). The resulting mixture was thoroughly mixed and stirred at 70 ℃ for 30min to give a viscoelastic auxiliary composition having a transparent appearance, sample D5.
Experiments carried out by the embodiment prove the technical effects of the auxiliary agent composition prepared in the embodiments 1 to 5 of the invention. Firstly, performance characterization: the contact angle, viscosity, flow sustaining rate and dynamic surface tension of examples 1 to 5 of the present invention were measured, respectively.
1. Contact angle
The compositions of examples 1 to 5 were diluted to 0.2% by mass of an aqueous solution, and then the contact angles were measured, respectively, as shown in table 1 below.
2. Viscosity of the oil
The viscosities of the adjuvant compositions prepared in examples 1 to 5 of the present invention were measured using a spindle, and the viscosities of the pure samples were measured on a TA ARG2 rheometer from TA Instruments, with the results shown in Table 1 below.
3. Balancing surface tension
The auxiliary composition prepared in the embodiments 1 to 5 of the present invention is diluted to 0.1% by mass of an auxiliary aqueous solution, and then the surface tension measurement is performed at 25.0 ℃ ± 0.1 ℃ by using a Kruss model K10ST tensiometer equipped with a Wilhelmy plate, and the results are shown in the following table 1.
4. Dynamic surface tension
The auxiliary composition prepared in the embodiments 1-5 of the invention is diluted into an auxiliary aqueous solution with the mass percent of 0.1%, then the dynamic surface tension is measured at 25.0 +/-0.1 ℃ by using a Bubble pressure tensiometer-BP100, the dynamic surface tension value is selected to be 0-50000ms, and the performance characterization results of the auxiliary composition in the embodiments are shown in the following table 1.
TABLE 1 characterization of the Properties of the adjuvant compositions of examples 1-5
Figure GDA0003478517540000131
From the data in table 1 above, it can be seen that: the auxiliary agent compositions of embodiments 1-5 of the invention all have lower contact angles, are beneficial to spreading of the preparation on the target, can avoid loss due to smaller contact angles, and are beneficial to retention of the preparation on the target; the cloud point of the auxiliary agent composition prepared in the embodiments 1-5 is less than 10 ℃, a uniform and stable emulsion is easily formed in cold water, and the compatibility and the stability among preparations are improved by combining linear water-soluble cation, oily (hydrophobic), hydrophilic compatible nonionic and optional anionic functionality; the auxiliary agent composition prepared in the embodiments 1 to 5 of the invention shows high viscosity and has good rheological efficiency.
FIG. 1 is a graph showing the dynamic surface tension change values of the adjuvant compositions of the examples, as can be seen from FIG. 1, the initial values of the dynamic surface tensions of the adjuvant compositions of examples 1-4 are low, and the dynamic surface tension changes faster with time, the dynamic surface tension value of 50000ms is not reduced to a low value, and the liquid medicine is not excessively spread due to too low surface tension to cause loss. On the other hand, the auxiliary composition D5 in example 5 had a high initial dynamic surface tension value, a low dynamic surface tension change with time, and a low dynamic surface tension value of 50000ms, and although the spreading of the drug solution was good, the effect of increasing the retention of the drug solution on the target surface was not as good as that of the auxiliary compositions in examples 1 to 4. The change speed of the dynamic surface tension value can also reflect that the auxiliary agent compositions prepared in the embodiments 1 to 5 have better capability of migrating at the liquid medicine interface, and are suitable for being used as a synergistic auxiliary agent for adjusting the liquid medicine interfacial force in the pesticide liquid medicine spraying process.
Second, ejection and sputtering experiment of assistant composition
The test simulates generation of liquid drops with the diameter of more than 300 microns, impacts the surface of a target at a certain initial speed, measures the time from the moment when the impact of the liquid drops is 0 to the occurrence of the maximum spreading area, and records the time when the liquid medicine is withdrawn to the highest point. The whole impact process is shown in figure 2 by using the picture pair of viscoelastic properties of the liquid medicine captured by the high-speed photographic technology. The results show that: the time for the auxiliary compositions D1-D4 of examples 1-4 to reach the maximum spreading area and the maximum withdrawing position on the target surface is longer than that of the auxiliary composition D5 of example 5, which indicates that the rheological viscosity of the liquid medicine on the target surface is greatly different, and the viscoelasticity of the liquid medicine is a result of the combined action of the dynamic surface tension change value and the rheological viscosity of the liquid medicine. Therefore, the examination further shows that the auxiliary agent compositions of examples 1-5 all have excellent viscoelastic properties.
Third, experiment of influence of adjuvant composition on liquid medicine retention
Medicament: 30% thiamethoxam suspension
The test method comprises the following steps: the auxiliary compositions prepared in examples 1 to 5 were diluted 400 ×, 300 ×, and 200 × respectively, and the reagents were diluted 2500 × respectively. The preparation method comprises preparing 10 × adjuvant diluent, preparing 150 × medicinal diluent, stirring, mixing with 3 times, 2 times and 1 time of clear water, and stirring. Then, get
Figure GDA0003478517540000141
Placing the culture dish on a ten-thousandth balance, and adopting
Figure GDA0003478517540000142
A hole puncher cutting about 2cm2Weighing and recording the mass of the round plant leaves, clamping the leaves with a sharp-nose forceps, dipping the prepared liquid medicine to be measured, repeatedly soaking for 10s, suspending and standing for 10s, and placing the leaves in a culture dish to weigh the mass of the liquid medicine held by the leaves. The effect of the auxiliary agents of the examples on the retention of the drug solution is shown in Table 2.
TABLE 2 EXAMPLES 1-5 comparison of Effect of adjuvants on drug solution Retention
Figure GDA0003478517540000151
As is apparent from the experimental results in table 2: the aid compositions obtained in examples 1 to 5 all contribute to the increase of the formulation retention; compared with the assistant compositions of examples 1 to 4, the assistant composition of example 5 has a lower content density of amine groups in the initiator for condensation of tetraethylenepentamine and dimer acid, and has fewer cation multi-adsorption centers formed when cationization is performed on the amine groups. Therefore, the auxiliary agent composition of example 5 has less retention and deposition effect on the chemical solution than the auxiliary agent compositions of examples 1 to 4.
Fourth, field control experiment
(1) Control subject 1: myzus avenae; test work: wheat; medicament: 5% acetamiprid soluble liquid; the test method comprises the following steps: after wheat jointing, the field surveys the plots with about 1000 insect population per hundred plants to carry out the test. The adjuvant compositions obtained in the examples were diluted at 500X and the dosage forms were diluted at 200X. The two-stage dilution method includes preparing 50 times of adjuvant diluent, preparing 5 times of medicament diluent, mixing the two solutions after fully stirring to obtain a mixed solution, adding 9 times of clear water, and stirring uniformly. An electric knapsack sprayer with the model of 20FT, a conical nozzle, the volume of 15L and the spraying pressure of 0.25 MPa-0.4 MPa is adopted, random block plots are uniformly sprayed, a group without the addition of an auxiliary agent composition and a clear water control group are arranged, and the number of insect population is respectively investigated at 1d, 3d, 7d and 14d after the pesticide is applied. The results of comparing the synergistic effect of the adjuvant compositions on pesticides obtained in the examples are shown in table 3.
Table 3 comparative results of the synergistic effects of the adjuvants on pesticides
Figure GDA0003478517540000161
(2) Control object 2: prodenia litura; test work: soybean; medicament: 20% dinotefuran suspending agent; the test method comprises the following steps: in the middle and later growth period of soybean, the insect population is collected by a black light lamp in an investigation way, and the prevention and treatment test can be carried out at a rate of 30-50 heads/d. The adjuvant compositions obtained in the examples were diluted at 1500X and the dosage forms were diluted at 1500X. The two-stage dilution method includes preparing 150 times of adjuvant diluent, preparing 150 times of medicament diluent, mixing the two solutions after fully stirring to obtain a mixed solution, adding 9 times of clear water, and stirring uniformly. An electric knapsack sprayer with the model of 20FT, a conical nozzle, the volume of 15L and the spraying pressure of 0.25 MPa-0.4 MPa is adopted, random block plots are uniformly sprayed, a group without the addition of an auxiliary agent composition and a clear water control group are arranged, and the number of insect population is respectively investigated at 1d, 3d, 7d and 14d after the pesticide is applied. The results of the synergistic effect of the adjuvant composition on pesticides obtained in the examples are shown in table 4.
Table 4 comparative results of the synergistic effects of the adjuvants on pesticides
Figure GDA0003478517540000162
(3) Control object 3: tetranychus urticae; test work: muskmelon (protected land); medicament: 11% of abamectin and etoxazole suspending agent; the test method comprises the following steps: after the melons are fruited, the insect population is investigated for about 200 heads/leaf of land blocks to carry out the test. The adjuvant compositions obtained in the examples were diluted at 400X and the formulations were diluted at 3000X. The two-stage dilution method includes preparing diluent of 40 times the assistant, preparing diluent of 300 times the medicine, mixing the two after stirring to obtain mixed liquid, adding 9 times of clear water, and stirring. An electric knapsack sprayer with the model of 20FT, a conical nozzle, the volume of 15L and the spraying pressure of 0.25 MPa-0.4 MPa is adopted, random block plots are uniformly sprayed, a group without the addition of an auxiliary agent composition and a clear water control group are arranged, and the number of insect population is respectively investigated at 1d, 3d, 7d and 14d after the pesticide is applied. The results of comparing the synergistic effect of the adjuvant compositions obtained in the examples on pesticides are shown in table 5.
Table 5 results of the synergistic effect of the adjuvant on the pesticide obtained in the example
Figure GDA0003478517540000171
From the experimental results in tables 3-5, it is evident that: the auxiliary agent compositions prepared by the methods of examples 1-5 all have obvious pesticide synergistic effect.

Claims (10)

1. A preparation method of a viscoelastic auxiliary agent is characterized by comprising the following steps: the method comprises the following steps:
(1) under the action of an acid catalyst, polyethylene polyamine is dripped into dimer acid, and after curing reaction, the dimer acid is blocked by fatty acid to obtain A;
(2) adding an alkaline catalyst into the A, then adding an epoxy compound for curing reaction, then adding a neutralizing agent for regulating the pH value, and then adding the acidic catalyst and fatty acid or fatty acid ester for esterification reaction to obtain a modified polyethylene polyamine alkoxy ester compound B;
(3) and carrying out cationization reaction on the modified polyethylene polyamine alkoxy ester compound B under the action of a cationization reagent aqueous solution to obtain the viscoelastic auxiliary agent.
2. A method of preparing a viscoelastic adjuvant according to claim 1, characterized in that: the general formula of the modified polyethylene polyamine alkoxy ester compound B is as follows:
Figure FDA0003478517530000011
wherein x, y and z are integers including 0-30 and the sum of x, y and z is an integer more than 0, a, b and c are one of oxyethylene, oxypropylene and oxybutylene, R is a dimer acid residue, and R is a dimer acid residue1Is a fatty acid residue, R2Is one of H and fatty acid residue, wherein n1 and n2 are any integer from 1 to 5, and n is an integer from 1 to 10.
3. A method of preparing a viscoelastic adjuvant according to claim 2, characterized in that: the compound formula of A is:
Figure FDA0003478517530000012
in the formula, n is any integer of 1-10, R is a dimer acid residue, R1 is a fatty acid residue, and n1 and n2 are both any integer of 1-5.
4. A method for producing a viscoelastic auxiliary according to claim 2 or 3, characterized in that: the epoxy compound comprises ethylene oxide, propylene oxide or butylene oxide; the polyethylene polyamine is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine or pentaethylene hexamine.
5. A viscoelastic additive, characterized by: the viscoelastic auxiliary agent is prepared by the preparation method of the viscoelastic auxiliary agent as set forth in any one of claims 1-4.
6. A viscoelastic adjuvant composition characterized by: comprising the viscoelastic adjuvant, the silicone adjuvant, and the sodium sulfosuccinate diester system of claim 5.
7. A viscoelastic adjuvant composition as set forth in claim 6, wherein: the cationizing agent comprises any one of formic acid, acetic acid, phosphoric acid, citric acid, alkyl halide with 1-5 carbon atoms, halohydrin with 1-5 carbon atoms or halogenated carboxylate with 2-5 carbon atoms.
8. A viscoelastic adjuvant composition as set forth in claim 7, wherein: the organic silicon coating comprises 0-20% of organic silicon auxiliary agent by mass percent, wherein the organic silicon auxiliary agent does not comprise 0%; 10-50% of a sodium sulfosuccinate diester system and 30-90% of the viscoelastic auxiliary agent.
9. A method of making a viscoelastic adjuvant composition as set forth in claim 6, characterized in that: the method comprises the following steps:
(a) respectively weighing the organic silicon assistant, the sodium sulfosuccinate diester system and the viscoelastic assistant;
(b) stirring under heating to obtain the viscoelastic auxiliary composition.
10. Use of a viscoelastic adjuvant as set forth in claim 5 or a viscoelastic adjuvant composition as set forth in claim 6 in a pesticidal adjuvant.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4737160A (en) * 1984-11-02 1988-04-12 Phillips Petroleum Company Reaction products of amido-amine and epoxide useful as fuel additives
CN103113556A (en) * 2013-03-10 2013-05-22 山东轻工业学院 Preparation method of curing agent suitable for epoxy resin base microporous ceramic molding die
CN105085906A (en) * 2015-08-17 2015-11-25 广东省造纸研究所 Preparation method of papermaking wet strength agent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4737160A (en) * 1984-11-02 1988-04-12 Phillips Petroleum Company Reaction products of amido-amine and epoxide useful as fuel additives
CN103113556A (en) * 2013-03-10 2013-05-22 山东轻工业学院 Preparation method of curing agent suitable for epoxy resin base microporous ceramic molding die
CN105085906A (en) * 2015-08-17 2015-11-25 广东省造纸研究所 Preparation method of papermaking wet strength agent

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