CN113142198B - Pesticide adjuvant based on anion/cation in-situ precipitation and application method thereof - Google Patents

Pesticide adjuvant based on anion/cation in-situ precipitation and application method thereof Download PDF

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CN113142198B
CN113142198B CN202110437389.6A CN202110437389A CN113142198B CN 113142198 B CN113142198 B CN 113142198B CN 202110437389 A CN202110437389 A CN 202110437389A CN 113142198 B CN113142198 B CN 113142198B
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pesticide
solution component
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concentration
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CN113142198A (en
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陈兴江
唐军
杨颜
杨文龙
黄远胜
邹光进
柳强
陆宁
高贵
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Guizhou Institute of Tobacco Science
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/02Biocides, 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 liquids as carriers, diluents or solvents
    • A01N25/04Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A01N25/06Aerosols
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/24Biocides, 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
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/30Biocides, 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 characterised by the surfactants
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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Abstract

The invention discloses a pesticide adjuvant based on anion/cation in-situ precipitation, which comprises a cation solution component and an anion solution component, wherein the cation solution component is one or any combination of polyethylene imine, hydroxypropyl trimethyl ammonium chloride chitosan, chitosan or didodecyldimethyl-polyamine biquaternary ammonium salt, and the anion solution component is one or any combination of sodium hexametaphosphate, polyacrylic acid, sodium starch octenyl succinate, sodium dodecyl diphenyl ether disulfonate, sodium dodecyl benzene sulfonate or sodium hexadecyl sulfonate. The compatibility of the polycation and the anionic surfactant shows excellent performance of enhancing the adhesion of the pesticide, and can greatly improve the adhesion performance of the pesticide.

Description

Pesticide adjuvant based on anion/cation in-situ precipitation and application method thereof
Technical Field
The invention relates to a pesticide adjuvant based on anion/cation in-situ precipitation and an application method thereof, belonging to the technical field of pesticide adjuvants.
Background
The surface of the stem and leaf of the terrestrial plant is generally provided with a hydrophobic waxy layer, and the surface of the stem and leaf of the terrestrial plant is kept dry, the stress resistance is enhanced, and the harm of diseases and pests and the infection risk are reduced. However, the inherent defense structure of the plant (including crops) is also the main reason for the high-efficiency rebound of the water-system pesticide drops on the surfaces of stems and leaves, and even the self-cleaning degree of the blades can be achieved. Different terrestrial plants and surfactants will exhibit differentiated foliar spray retention characteristics, and some of the extenders with reduced droplet surface tension, and additives that can convert droplets of medicinal liquids into non-newtonian fluids have been successfully developed and applied. Common pesticide adjuvants include sodium alginate, gelatin, starch, organic silicon polymer, high molecular carboxylic acid, sulfonate, vegetable oil, etc. The dosage of the pesticide adjuvant is about 2-3 ten thousand tons in China, and the pesticide adjuvant plays an active role in reducing and enhancing the pesticide.
Calculated according to the utilization rate of the conventional pesticide about 10 percent, the utilization rate of the pesticide has about 90 percent of space which can be improved. The goals and implications of pesticide adjuvant/synergist development and application reside in this 90% of upgradable space. The non-point source pollution of the pesticide has the characteristics of wide range and incapability of centralized treatment, and the auxiliary agent and the synergist can effectively reduce the source emission of the pesticide, so the method is the most direct and effective treatment means. Sulfonate, organosilicon and essential oil single-phase spraying aids which are mainstream in the current market already show synergistic effect in field application and laboratory evaluation. However, the existing single-phase spraying aid still has the problem of poor adhesion effect.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a pesticide adjuvant based on anion/cation in-situ precipitation and an application method thereof, which can greatly improve the adhesion effect of pesticide so as to overcome the defects of the prior art.
The technical scheme of the invention is as follows: the pesticide auxiliary agent based on anion/cation in-situ precipitation comprises a cation solution component and an anion solution component, wherein the cation solution component is one or any combination of polyethylene imine, hydroxypropyl trimethyl ammonium chloride chitosan, chitosan or didodecyldimethyl-polyamine biquaternary ammonium salt, and the anion solution component is one or any combination of sodium hexametaphosphate, polyacrylic acid, sodium starch octenyl succinate, sodium dodecyl diphenyl ether disulfonate, sodium dodecyl benzene sulfonate or sodium hexadecylsulfonate.
Optionally, the pH value of the pesticide adjuvant is 4-6, and the concentration ratio of the cationic solution component to the anionic solution component is 3-1:1-3, wherein the concentration of the cation solution component is 0.1-0.3%, and the concentration of the anion solution component is 0.3-0.1%.
Optionally, the pH value of the pesticide adjuvant is 6, the cationic solution component is a 0.3% hydroxypropyl trimethyl ammonium chloride chitosan solution, and the anionic solution component is 0.1% sodium hexadecyl sulfonate.
Optionally, the pesticide adjuvant has a pH value of 5, the cationic solution component is a hydroxypropyl trimethyl ammonium chloride chitosan solution with a concentration of 0.1%, and the anionic solution component is sodium hexadecyl sulfonate with a concentration of 0.3%.
Optionally, the pH value of the pesticide adjuvant is 5, the cationic solution component is a polyethyleneimine solution with a concentration of 0.1%, and the anionic solution component is sodium dodecyl diphenyl ether disulfonate with a concentration of 0.1%.
Optionally, the pH value of the pesticide adjuvant is 5, the cationic solution component is hydroxypropyl trimethyl ammonium chloride chitosan with the concentration of 0.15% and the didodecyldimethyl-polyamine biquaternary ammonium salt with the concentration of 0.15%, and the anionic solution component is sodium dodecyl diphenyl ether disulfonate with the concentration of 0.3%.
The invention also provides an application method of the pesticide adjuvant based on anion/cation in-situ precipitation, which comprises the steps of dividing a pesticide solution to be sprayed into two parts, respectively adding the cation solution component and the anion solution component into the two parts of the pesticide solution, and spraying according to a sequential spraying mode or a staggered simultaneous spraying mode.
Among various pesticide adjuvant systems, a liquid medicine system with interface hydrophobic defects can be constructed to show superior high-adhesion potential of water-based pesticides. The system is initially related to the research of the oriented nano assembly of the laminated polymer appearing in the early stage, and then the idea of continuously spraying anions and cations to form an ultrathin membrane is added, so that a hydrophilic defect interface mediated liquid drop capturing and accumulating method is finally formed. In 2016, maher et al reported a new method for high-efficiency drug drop leaf surface attachment established by means of polymer anion and cation in-situ precipitation reaction, and the method can improve the attachment rate of an aqueous solution on the glass surface by more than 10 times. Similar to Maher and the like, researches on the preparation of high polymer materials by adopting an ion copolymerization method are not uncommon, and LPEI, PAA, chitosan (Chitosan, CS), alginic acid (Alginate, algA) and other natural and artificially synthesized charged high polymer materials are widely used for the development of nano-carriers and hydrogels. Based on the scientific cognition that the wax on the surface of the plant is an ester compound formed by polymerizing higher fatty acid and higher alcohol, the invention further forms a middle polar group through electrostatic assembly of an anionic surfactant and a cationic surfactant, and from the biobionics angle of alkane chain structures on two sides, the bionic structures are connected in series and crosslinked through electrostatic assembly between multi-anions and polycations, and a large hairbrush-shaped and crosslinked aggregate is formed based on in-situ precipitation reaction generated in the pesticide spraying process, the structural characteristics and the design principle of the invention are obviously different from those of a reticular structure formed by anionic-cationic-polymeric-ion crosslinking reported in the literature (as shown in figure 8).
The invention has the beneficial effects that: the compatibility of the polycation and the anionic surfactant shows excellent performance of enhancing the adhesion of the pesticide, and can greatly improve the adhesion performance of the pesticide. Combines the feasibility of the practical application of agricultural production, develops the spray pesticide adjuvant based on cheap and easily obtained charged molecules, and has outstanding practical application value.
In addition, the two-phase spraying system is used as a novel high-adhesion pesticide auxiliary agent system, can weaken liquid drop rebound caused by a hydrophobic structure on the surface of a plant in a targeted manner, can be used for single-phase dosing two-phase spraying, and greatly reduces the pesticide dosage under the condition of the same total water spraying amount.
Drawings
FIG. 1 is a schematic diagram of relative adhesion determination and spray method;
FIG. 2 is a microscope photograph of the invention after spraying;
fig. 3 is the relative attachment rates of CS, SS2, HACC with 6 anionic biphasic sprays, respectively, at pH = 5.0;
FIG. 4 is a graph showing the relative adhesion rate at an additive mass volume percent concentration of 0.1%;
FIG. 5 is a graph showing relative attachment rates for different concentration ratios of yin to yang;
FIG. 6 is a graph of the relative adhesion rates of preferred spray combinations at different pH;
FIG. 7 is a graph of the relative adhesion rates of preferred adjuvant combinations;
FIG. 8 is a schematic diagram of the structure of the present invention cross-linked polymer and the existing polymeric anion and cation cross-linked polymer.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments:
reagent and biomaterial
Polyethyleneimine (PEI, 99%), sodium hexametaphosphate (SHP, AR grade), polyacrylic acid (Polyacrylic acid, PAA,50% solid content) and Sodium dodecylbenzene sulfonate (LAS) are products of Mecanum biochemical science and technology Limited in Shanghai, and Starch Sodium octenyl succinate (SSOS, 99%) is a product of Michsandra chemical and technology Limited in Foshan city; hydroxypropyltrimethyl ammonium chloride Chitosan (Hydroxypropyl trimethyamine chloride Chitosan, HACC, viscosity 40-80mPa 2s, content 95%) is a product of beijing corporation, chitosan (Chitosan, CS, viscosity <200mPa 2s) is a product of hail chemical science and biochemical science, and sodium dodecyl diphenyl ether disulfonate (sodium dodecyl 4-dodecil-2, 4' -oxydibenzenesulfonate, MADs), didodecyldimethyl-polyamine-Bis-quaternary ammonium salt (Bis dodecil-polyamine-Bis quaternary ammonium salt, SS 2) and sodium hexadecylsulfonate (1-hexadecasimulinic acid sodium salt, SAS) are products of gazem organic research, experimental agents-Azoxystrobin, zaob 25%, saxatilic, saxatilin, sai, saiko corporation, gazem ethyl acetate, gardenia chemical industry, and gazem ethyl acetate, and its test agents are products of gazem organic research, and the saxatilis chromophoric reagent is a ethyl acetate, and the product of gazem ethyl acetate is a product of 18-ethyl acetate, the pharmaceutical chromatography, the gazem chemical company is a product of gazem ethyl acetate: sunfire (TM) C18, 25034.6mm,5um. The hydrophobic polytetrafluoroethylene membrane (PTFE) is a smooth surface filter membrane of the New Hinningde Filter New Material science and technology Limited company, the filter paper is a rapid qualitative filter paper of the Hangzhou emerging paper industry Limited company, and other reagents are all made in China and analyzed purely. The tested tobacco and loquat varieties are Yunyan 85 and Hangzhou local loquat, and the test samples are fresh mature leaves.
Adhesion effect evaluation method
And additionally dissolving gardenia blue pigment in the cation solution component to achieve the final concentration of 5 percent by mass. After spraying, the adhesion effect evaluation is carried out by adopting a relative adhesion rate determination method, namely the ratio of the polytetrafluoroethylene membrane (PTFE membrane) with the same size (2cm 32 cm) to the attachment amount of gardenia blue pigment on filter paper (calculated according to the light absorption value under 590nm of the equal volume of leaching liquor) is taken as a standard for judging the adhesion performance, and the high relative adhesion rate is the high adhesion performance. The calculation formula is as follows: relative attachment = PTFE membrane leach liquor absorbance/filter paper disc leach liquor absorbance.
Spray mode
The spraying mode adopts a two-phase spraying method, anions SHP, PAA, SSOS, LAS and SAS are respectively phase A, and cations PEI, HACC, CS and SS2 are respectively phase B. A. The spray of phase B was tested in two ways, spray one after the other (labeled ST) and spray at 45 ℃ angle simultaneously (labeled BS), with the control group of phase B single spray labeled SN and the spray method schematically shown in FIG. 1.
Example 1
The pesticide adjuvant comprises a cationic solution component and an anionic solution component, wherein the pH value of the pesticide adjuvant is 6, the cationic solution component is a hydroxypropyl trimethyl ammonium chloride chitosan solution with the concentration of 0.3%, and the anionic solution component is sodium hexadecyl sulfonate with the concentration of 0.1%. The spraying mode is spraying in sequence, wherein the pesticide solution containing the anion solution component is sprayed firstly, and then the pesticide solution containing the cation solution component is sprayed.
Example 2
The pesticide auxiliary agent comprises a cationic solution component and an anionic solution component, wherein the pH value of the pesticide auxiliary agent is 5, the cationic solution component is a 0.1% hydroxypropyl trimethyl ammonium chloride chitosan solution, and the anionic solution component is 0.3% sodium hexadecyl sulfonate. The spraying mode is 45 degrees included angle simultaneous spraying.
Example 3
The pesticide adjuvant comprises a cation solution component and an anion solution component, wherein the pH value of the pesticide adjuvant is 5, the cation solution component is a polyethyleneimine solution with the concentration of 0.1%, and the anion solution component is sodium dodecyl diphenyl ether disulfonate with the concentration of 0.1%. The spraying mode is 45 degrees included angle simultaneous spraying.
Example 4
The pesticide adjuvant comprises a cationic solution component and an anionic solution component, wherein the pH value of the pesticide adjuvant is 5, the cationic solution component comprises hydroxypropyl trimethyl ammonium chloride chitosan with the concentration of 0.15% and didodecyldimethyl-polyamine-biquaternary ammonium salt with the concentration of 0.15%, and the anionic solution component comprises sodium dodecyl diphenyl ether disulfonate with the concentration of 0.3%. The spraying mode is 45 degrees included angle simultaneous spraying.
The pesticide adjuvant in examples 1 to 4 was sprayed on the surfaces of tobacco and loquat leaves with 1000 times azoxystrobin aqueous solution as a blank control, and the adhesion effect was measured. The results are shown in table 1 below:
TABLE 1 measurement of adhesion Effect
Figure BDA0003033598360000051
As can be seen from Table 1, the combination of the polycation and the anionic surfactant of the invention shows excellent performance of enhancing the adhesion of the pesticide, and can greatly improve the adhesion performance of the pesticide. FIG. 2 is a microscope picture of the invention after spraying, from which it can be seen that after two-phase spray droplets meet, macroscopic precipitation occurs, and under the microscope, the azoxystrobin emulsion particles are in an aggregated state. FIG. 8 is a schematic structural diagram of the present invention and the existing polyionic crosslinker, and it can be seen that the structures of the present invention and the existing polyionic crosslinker are significantly different.
The formulation screening process of the present invention is described below:
1. determining the influence of pH value and spraying mode on adhesion effect
Respectively preparing single-component aqueous solutions of 4 cations (PEI, HACC, CS and SS 2) and 6 anions (SHP, PAA, SSOS, MADs, LAS and SAS) with the mass volume percentage of 1.0 percent and the pH value of natural pH and pH = 5.0. And meanwhile, the gardenia blue pigment is additionally dissolved in the cation solution to reach the final concentration of 5 percent by mass. The natural pH of the aqueous solutions of PEI, SHP, PAA, SSOS, LAS and SAS are, in order: 9.6, 6.5, 2.8, 5.7, 8.0, 7.5. The 4 kinds of cation solutions are separately sprayed, and the adhesion effect of the two kinds of pH value solutions under the condition of single-phase spraying is measured. And orthogonal combination spraying was performed on the cationic solution group and the anionic solution group of pH =5.0, the adhesion effect was measured, and the combination was preliminarily screened.
Table 2.pH Natural and pH = 5.0% relative adhesion ratio in PEI spray group 1.0%
Figure BDA0003033598360000061
The relative adhesion rates of PEI and 6 anions such as LAS with simultaneous spraying at sequential (ST spray) and BS angle (BS spray) at pH =5.0 and natural pH of the aqueous solution are shown in table 2. As can be seen from Table 2, the relative adhesion rate of 10 treatment groups including PEI spray alone increased after pH adjustment to 5.0, and the decrease of the other 3 treatment groups occurred, with the number of the increased groups being 3 times that of the decreased groups. Comparing the data of each group to find that the relative adhesion rate of the LAS-PEI combination is lower than that of other groups on the whole; the SAS-PEI combination has the maximum difference of the relative adhesion rate of BS spraying to ST spraying of 0.41 at the pH value of 5.0; the average of the relative adhesion rates of 4 MADS-PEI groups was 1.0, which was the highest for all treatment groups. And considering the possible difference of products of different manufacturers and the possible difference of different product batches of the same manufacturer, the pH value of the solution is selected and adjusted in subsequent tests. The screening of combinations of cations and anions such as CS, SS2, HACC, etc. was performed at pH =5.0, and the results are shown in fig. 3. As can be seen from FIG. 3, at pH5.0, a higher relative adhesion rate can be obtained by single spraying 1% of CS and SS2, and the two-phase spray combination is higher than that of the single-spraying control; the 3 groups with the highest relative attachment rates among the HACC groups appeared in the combination of LAS, SAS, MADs and HACC, respectively. Because the 1.0% concentration (equivalent to 100 times dilution) has no possibility of being applied in the practical pesticide application, part of the formula is selected subsequently, and the adhesion effect test is further carried out after the dilution times are increased.
3. Optimizing the concentration of the auxiliary agent and the concentration ratio of the A phase to the B phase
Respectively preparing 4 cations with pH =5.0 and mass volume percentage of 0.1% and 0.3%, respectively: single component aqueous solutions of PEI, HACC, CS, SS2 and 4 anions: single component aqueous solutions of MADs, LAS, SAS, PAA. Relative adhesion rates of the ST and BS spray modes were measured by an adhesion effect evaluation method, and adhesion promotion performance of the low-concentration auxiliary agent (mass volume percentage: 0.1%) was evaluated. And according to phase B: phase a concentration ratios are 1,1,3.
The effect of improving the adhesion rate of the aqueous solution agent by using 3 low-concentration auxiliaries with concentration ratios is tested, and the results show that the single-phase spraying relative adhesion rates of the cationic PEI, the CS, the SS2 and the HACC which account for 0.1 percent by mass volume are respectively as follows: 0.82 plus or minus 0.04, 1.05 plus or minus 0.05, 0.67 plus or minus 0.03 and 0.96 plus or minus 0.04. Compared with 1% concentration, the average value is respectively increased and decreased: -10.87%, -3.67%, -50.69%, +29.73%. FIG. 4 shows the relative adhesion at a mass volume percent concentration of both phases AB of 0.1%. As can be seen from FIG. 4, the highest relative adhesion rate of 1.41 occurs under BS spray conditions for the MADS-PEI combination; the SAS-PEI combinations achieve relative adhesion rates of greater than 1.1 and approach values no matter whether the combinations are sprayed with ST or BS; CS then achieved two high relative attachment rates of 1.22 and 1.18 under BS spray combined with MADs and LAS; the highest relative adhesion rate of the combination of SS2 and PAA is 1.08; HACC in combination with SAS gave relative adhesion rates of 1.31 and 1.21 under ST and BS sprays, respectively; HACC combined with MADs achieved two highly consistent relative attachment rates of 1.06 and 1.07 under ST and BS sprays, respectively.
The further concentration ratio optimization results are shown in fig. 5. As can be seen from FIG. 5, the PEI-MADs combination showed the highest relative attachment at ST spray concentration ratio of 3; the relative adhesion rate is highest when the concentration ratio of BS to BS is 1; the PEI-SAS combination showed the highest relative adhesion in both spray modes compared to 1 concentration. In the CS group, when the concentration ratio of MADs to CS is 1; the relative adhesion rate of the LAS-CS combination is higher at a concentration ratio of 1. The SS2 combined with PAA gave the highest relative adhesion rate of the same spray set in both ST and BS modes, respectively, at concentration ratios 1 and 1. HACC achieves higher relative attachment rates at LAS and SAS concentrations of 1 and 1.
3. Effect of adjuvant solution pH on relative adhesion Rate
Further suitable pH screens were performed on the preferred adjuvant concentrations in the 4 cation groups in combination with spray, with pH gradients of 4.0, 5.0, 6.0. Since CS is poorly soluble at pH =6.0, this group had only two pH treated groups of 4.0 and 5.0. The preferred combinations for transfer to the pH-optimized screen are shown in Table 3.
TABLE 3 combination of initial concentration and spray mode with shift to pH optimization
Figure BDA0003033598360000071
Figure BDA0003033598360000081
The results of pH condition optimization of the concentration ratio preferred formulations are shown in fig. 6. As can be seen from FIG. 6, the preferred pH of the PEI group is ST-0.3% PEI-pH4.0, BS-0.1% PEI-pH5.0, ST-0.1% PEI-pH5.0, BS-0.1% SAS-0.1% PEI-pH6.0, the relative adhesion of which is increased by 35.05%, 45.36%, 18.56%, 24.74%, respectively, compared to the 0.3% PEI maximum of 0.97 sprayed alone. The highest relative adhesion of the CS group was BS-0.1%. The maximum relative adhesion of SS2 group was 1.14, which was increased by 70.15% as compared with the spray of SS2 alone (relative adhesion of 0.67) at the same concentration, as a result of treatment with BS-0.1% for PAA-0.1% and SS2-pH4.0%. The highest relative adhesion of the HACC group was 1.31, which was generated by ST-0.1% SAS-0.1% of the HACC-pH5.0 treatment group, was 36.46% higher than 0.1% of the HACC alone spray control; BS-0.3% SAS-0.1% HACC-pH5.0 treated group obtained a 2 nd high relative adhesion of 1.28, which was improved by 33.33% as compared with the single spray control group. The pH value of the solution affects the electrical property of the auxiliary agent, and the electrostatic copolymerization speed and degree of the positive and negative electrical compounds under different pH values are different, so that the exposed quantity and proportion of hydrophobic functional groups are different, and the adhesion effect of the pesticide is affected finally.
4. Pesticide adhesion test for preferred adjuvant formulations
After the optimization, 8 auxiliary agent formulas are preferably selected for carrying out the test of the spraying adhesion effect on the surface of the azoxystrobin blade. The test auxiliary agents are respectively: 1) CK1: 1000 azoxystrobin aqueous solution control; 2) Taz1: SN-pH6-0.3% SS2; 3) Taz2: SN-pH5-0.3% HACC; 4) Taz3: SN-pH5-0.3% CS; 5) Taz4: BS-pH5-0.1% MADs-0.1% PEI; 6) Taz5: BS-pH5-0.1% MADs-0.1% CS; 7) Taz6: BS-pH4-0.1% PAA-0.1% SS2; 8) Taz7: ST-pH6-0.1% SAS-0.3% HACC; 9) Taz8: BS-pH5-0.3% SAS-0.1% HACC. The preferable auxiliary agent is applied to 1 000-fold azoxystrobin aqueous solution to carry out adhesion performance test, wherein in the two-phase spraying auxiliary agent combination, the phase A is pesticide-free aqueous solution containing an A anion auxiliary agent, and the phase B is 1 000-fold azoxystrobin aqueous solution containing a B cation auxiliary agent. The test method is the same as the relative adhesion rate measurement in 1.2.1, and the test sample pieces are respectively a PTFE membrane, fresh tobacco and loquat leaves. The azoxystrobin content is measured by an HPLC method, and the mobile phase is acetonitrile: 0.1% aqueous phosphoric acid =50:50, the column temperature is 35 ℃, the flow rate is 1mL/min, the detection wavelength is 245nm, and the chromatographic column is sunfire C18, 25034.6mm and 5um.
The results of the evaluation of the use of the preferred auxiliary are shown in FIG. 7. As can be seen from FIG. 7, the relative adhesion rates of azoxystrobin on the polytetrafluoroethylene membrane (PTFE membrane), the tobacco leaf and the loquat leaf were all improved to different degrees after the test auxiliary was added. In most experimental groups, the relative adhesion rate of azoxystrobin on the PTFE membrane is higher than that of tobacco leaves and loquat leaves, which is related to formulation screening by taking the PTFE membrane as an object in the early stage. The difference in surface structure between the PTFE membrane and the vane results in a difference in the value between the vane set and the PTFE set. In addition, the relative adhesion rate measured on the loquat leaves is generally lower than that of the tobacco leaves, and may be related to more villi on the surfaces of the loquat leaves and stronger water drop rebounding capacity. Comprehensive comparison shows that 3 groups with the highest relative attachment rate on the tobacco leaves sequentially comprise: taz7 (0.95), taz4 (0.86), taz8 (0.78), increased by 3.27, 2.96 and 2.68 times, respectively, over azoxystrobin control CK1 (0.29); the 3 groups with the highest relative adhesion rate on the loquat leaves are also Taz7, taz4 and Taz8, which are respectively increased to 2.17 times, 1.82 times and 1.58 times of the control group.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (5)

1. The pesticide adjuvant based on anion/cation in-situ precipitation is characterized by consisting of a cation solution component containing hydroxypropyl trimethyl ammonium chloride chitosan with the concentration of 0.3% and an anion solution component containing sodium hexadecyl sulfonate with the concentration of 0.1%, wherein the pH value of the pesticide adjuvant is 6, and the pesticide adjuvant is applied by respectively spraying an aqueous solution containing 1000 times of azoxystrobin of the cation solution component and a pesticide-free aqueous solution containing the anion solution component in a sequential spraying manner.
2. The pesticide adjuvant based on anion/cation in-situ precipitation is characterized by consisting of a cation solution component containing hydroxypropyl trimethyl ammonium chloride chitosan with the concentration of 0.1% and an anion solution component containing sodium hexadecyl sulfonate with the concentration of 0.3%, wherein the pH value of the pesticide adjuvant is 5, and the pesticide adjuvant is applied by respectively spraying an aqueous solution containing 1000 times of azoxystrobin of the cation solution component and a pesticide-free aqueous solution containing the anion solution component in a 45-degree included angle staggered simultaneous spraying manner.
3. The pesticide adjuvant based on anion/cation in-situ precipitation is characterized by consisting of a cation solution component containing polyethyleneimine with the concentration of 0.1% and an anion solution component containing sodium dodecyl diphenyl ether disulfonate with the concentration of 0.1%, wherein the pH value of the pesticide adjuvant is 5, and the pesticide adjuvant application method comprises the step of spraying 1000 times of azoxystrobin aqueous solution containing the cation solution component and pesticide-free aqueous solution containing the anion solution component in a 45-degree included angle staggered simultaneous spraying manner.
4. The pesticide adjuvant based on anion/cation in-situ precipitation is characterized by consisting of a cation solution component containing chitosan with the concentration of 0.1% and an anion solution component containing sodium dodecyl diphenyl ether disulfonate with the concentration of 0.1%, wherein the pH value of the pesticide adjuvant is 5, and the pesticide adjuvant is applied by respectively spraying 1000 times of azoxystrobin aqueous solution containing the cation solution component and pesticide-free aqueous solution containing the anion solution component in a mode of spraying at the same time in a staggered mode at an included angle of 45 degrees.
5. The pesticide adjuvant based on anion/cation in-situ precipitation is characterized by consisting of a cationic solution component containing 0.1% of didodecyldimethyl-polyamine-biquaternary ammonium salt and an anionic solution component containing 0.1% of polyacrylic acid, wherein the pH value of the pesticide adjuvant is 4, and the pesticide adjuvant is applied by respectively spraying an aqueous solution containing 1000 times of azoxystrobin of the cationic solution component and a pesticide-free aqueous solution containing the anionic solution component in a staggered and simultaneous spraying manner at an included angle of 45 degrees.
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