CN116210691A

CN116210691A - Composition for improving rain wash resistance of protective bactericide and preparation method thereof

Info

Publication number: CN116210691A
Application number: CN202211709107.4A
Authority: CN
Inventors: 范亚磊; 董德臻; 曹雄飞; 陈世国
Original assignee: Jiangsu Sinvo Chemical Technology Co ltd
Current assignee: Jiangsu Sinvo Chemical Technology Co ltd
Priority date: 2022-12-29
Filing date: 2022-12-29
Publication date: 2023-06-06

Abstract

The invention discloses a composition for improving the rain wash resistance of a protective bactericide and a preparation method thereof, wherein the composition comprises one or more of high molecular polycarboxylate, high molecular polyvinyl alcohol, guar gum and chitosan; one or more of organic silicon, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether, fatty amine polyoxyethylene ether, alkyl glycoside, block polyether and alkylbenzene sulfonate; water, vegetable oil, methylated vegetable oil.

Description

Composition for improving rain wash resistance of protective bactericide and preparation method thereof

Technical Field

The invention belongs to the field of pesticide auxiliaries, and in particular relates to a composition for improving the rain wash resistance of a medicament and a preparation method thereof.

Background

The bactericides can be classified into protective bactericides and systemic bactericides according to the mode of action, and the protective bactericides are bactericides for protecting or defending crops from being infected by pathogenic bacteria. The protective bactericide is applied on the surface of crops before the crops are infected by germs, and a layer of breathable, water-permeable and light-permeable compact protective medicine film is formed on the surface of the crops, and can inhibit germination and invasion of the spores of the diseases so as to achieve the effects of sterilization and disease prevention. The protective bactericide mainly comprises copper preparations (copper King, copper hydroxide, cuprous chloride and the like); dithiocarbamates (mancozeb, zineb, thiram, etc.); substituted benzenes (pentachloronitrobenzene, chlorothalonil, sodium disul mate, etc.); diimides (iprodione). The important role of the protective bactericide is self-evident because the prevention of agricultural diseases is usually carried out by spraying pesticides before the onset of the diseases, along with the plant protection guidelines of 'prevention and treatment as assistance'.

Rain wash resistance is the ability of agrochemical deposits to resist rain and other environmental factors, an important attribute of protective bactericides where the pesticide active ingredient needs to be permanently attached to the target blade to achieve a durable efficacy. The bad environments such as rain wash not only can lead the pesticide to drop from the target, so that the pesticide effect is greatly reduced and the pesticide application is influenced, but also the pesticide flows into soil and water source to pollute the environment. Because the protective bactericide is mainly composed of a water suspending agent, wettable powder and water dispersible granules, the protective bactericide product on the market has the problems that the liquid medicine is unevenly distributed on the surface of a target leaf, the effective components of the preparation are not resistant to rain wash, the efficacy duration is short and the like due to the limitation of dosage forms and the difference of formulas. And although the bactericide belongs to the bactericides, the bactericides with different active ingredients and different concentrations have huge differences in rain wash resistance, and even manufacturers and different impurity contents can have huge influence on the rain wash resistance. For example, when the 80% concentration mancozeb WP is itself free of additives, the ratio of post-scouring/pro-scouring plaque area can be nearly 50% while chlorothalonil is far from this level.

The literature reports that the oil-type auxiliary agent, the vegetable oil methyl ester compound and the vegetable oil ethoxy compound can improve the rain-proof performance of a protective bactericide (mancozeb and copper oxychloride) pesticide (chlorantraniliprole) on target blades, but the rain-proof improvement effect on hydroxide (Cu-Hyd) is poor, which indicates that the application range of the vegetable oil-type auxiliary agent as the rain-proof auxiliary agent is limited. Gums such as xanthan gum and guar gum can also improve the anti-rain flushing capability of the liquid medicine of bactericides (carbendazim and triazophos) and pesticides (triazophos) on target leaves, but the anti-rain flushing effect of the liquid medicine is lower than that of a high polymer material, such as xanthan gum, and sodium polyacrylate. The materials such as vinyl acetate-acrylic acid copolymer, chitosan, polyvinyl alcohol (PVA) and the like have good film forming property, water permeability, swelling property and the like, so that the materials also have good rain wash resistance, but the rain resistance increases with the increase of molecular weight and crystallinity. The prior art with chinese patent application number CN201280063191.5 discloses that polyethyleneimine having a weight average molecular weight of at least about 750,000g/mol is a rain wash resistant aid, which is a high molecular viscous liquid, and cannot effectively increase the deposition amount of the liquid medicine. The prior art with publication number CN109452271A discloses a rain wash resistant composition of polysaccharide, polyquaternium, alkyl polyoxyethylene ester, emulsifying agent and solvent, which has good hydrophilicity, good rain wash resistant effect on water-soluble herbicide and limited improvement effect on the rain wash resistant performance of protective bactericide.

Disclosure of Invention

1. Problems to be solved

Aiming at the problem that the prior art lacks a rain-resistant auxiliary agent which can not only effectively improve the rain-resistant performance of the protective bactericide, but also ensure the deposition amount of the liquid medicine of the protective bactericide, the invention provides a composition for improving the rain-resistant performance of the protective bactericide;

meanwhile, the invention provides a corresponding preparation method.

2. Technical proposal

A composition for improving the rainfastness properties of a protective bactericide, which is characterized by comprising the following components in parts by weight:

10-30 parts of auxiliary agent I;

20-40 parts of an auxiliary agent II;

30-70 parts of a solvent;

wherein, the liquid crystal display device comprises a liquid crystal display device,

the auxiliary agent I comprises one or more of high molecular polycarboxylate, high molecular polyvinyl alcohol, guar gum and chitosan;

the auxiliary agent II comprises one or more of organic silicon, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether, fatty amine polyoxyethylene ether, alkyl glycoside, block polyether and alkylbenzene sulfonate;

the solvent comprises one or more of water, vegetable oil, rosin-based vegetable oil, methylated vegetable oil.

Further, the auxiliary agent I comprises high molecular polycarboxylate.

Further, the molecular weight of the high molecular polycarboxylate ranges from 30000 to 100000 and the viscosity ranges from 50 to 200mm ² /s。

Further, the second auxiliary agent comprises organic silicon, and the organic silicon comprises polyether modified trisiloxane (C ₁₂ H ₃₂ O ₄ Si ₃ )。

Further, the auxiliary agent is 10-20 parts, the auxiliary agent II is 20-30 parts, and the solvent is 50-70 parts.

Further, the solvent is one or more of water, vegetable oil, rosin-based vegetable oil and methylated vegetable oil.

A method of preparing a composition for improving the rainfastness properties of a protective bactericide according to any one of the above, comprising the steps of: mixing the first auxiliary agent with the solvent, and adding the second auxiliary agent for mixing.

Further, the ratio of the amount of the organosilicon to the amount of the polymeric polycarboxylate is 1 to 2, preferably 1 to 1.5, and most preferably 1.

Further, the protective bactericide comprises any one or more of copper preparations, dithiocarbamates, substituted benzenes and diimides.

Further, the mixing temperature is not more than 50 ℃.

Advantageous effects

The composition for improving the rain erosion resistance of the protective bactericide can provide excellent rain erosion resistance for the protective bactericide with an active ingredient;

meanwhile, the function of improving the wetting and spreading of the liquid medicine is taken into consideration, the contact area of the liquid medicine and a target is increased, the deposition amount of the pesticide is increased, and the duration of the pesticide is prolonged, so that the pesticide effect of the pesticide is increased.

Drawings

FIG. 1 shows microscopic comparison of drug plaques before and after rain wash resistance;

FIG. 2 is a graph comparing the wash out of scindapsus aureus leaves after drying of the drug.

Detailed Description

The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art;

the essential features and significant effects of the invention can be seen from the following examples, which are described as some, but not all, of which, therefore, are not limiting of the invention, and some of the insubstantial modifications and adaptations of the invention by those skilled in the art are within the scope of the invention.

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

In more detail, the implementation and operation of the technical scheme of the invention are as follows:

1. regarding the auxiliary agent I, one of the preparation modes of the high polymer polycarboxylate is as follows:

emulsifying a living polymerization macromonomer and a hydrophobic monomer, adding a water-soluble initiator for block polymerization, and drying to obtain the high polymer polycarboxylate; wherein, the liquid crystal display device comprises a liquid crystal display device,

the active polymerization macromonomer comprises one or more of SP-DF2238, SP-SC3275 and SP-2836 sold by Jiangsu qingyu chemical engineering Co., ltd;

the hydrophobic monomer comprises one or more of styrene, methyl styrene, acrylic ester, methacrylic ester, diethyl amino ethyl methacrylate, 2-tertiary butyl amino ethyl acrylate and 2-tertiary butyl amino ethyl methacrylate;

the initiator is one or more selected from ammonium persulfate, potassium persulfate, sodium persulfate, 2' -azo diisobutyl amidine dihydrochloride and azo diiso Ding Mi hydrochloride.

Further, the product SP-DF2238 sold by Jiangsu Optimu chemical engineering Co., ltdhttps:// www.sinvochem.com/products-16/70.html) The comb-structured polycarboxylate high molecular dispersing agent is prepared based on a controllable polymerization technology, wherein alkyl and benzene ring or benzene-like ring are lipophilic groups, and carboxyl or polyoxyethylene ether chain is hydrophilic group. More specifically, the mass ratio of hydrophilic monomer acrylic acid to succinic acid polyethylene glycol monomethyl ether to hydrophobic monomer styrene to isooctyl acrylate is 1: the ratio of 0.8 is that the RAFT is prepared by adopting a reversible-addition fragmentation chain transfer active free radical polymerization technology, and adopting trithioesters with symmetrical structures as RAFT reagents and azodiisobutyronitrile as an initiator;

mn=7227 of SP-DF2238, pd=1.467 of SP-DF 2238.

The commercial product SP-3275 of Jiangsu Optimu chemical engineering Co., ltdhttps:// www.sinvochem.com/search/？keyword＝SP-3275) Preparation of B by reversible-addition fragmentation chain transfer living radical polymerization (RAFT)The alkenyl monomer polymer is prepared by esterifying S, S' -bis (2-methyl-2-propanoic acid) trithiocarbonate serving as a chain transfer agent and azodiisobutyronitrile serving as an initiator with N, N-dimethylethanolamine to form a group with N, and further oxidizing to form amine oxide weak cations; wherein, the hydrophilic monomer methacrylic acid and maleic anhydride polyethylene glycol monoester, the hydrophobic monomer styrene, the N-containing monomer N, N-dimethylethanolamine are needed to be used, and the mass ratio of the hydrophilic monomer to the hydrophobic monomer to the N-containing monomer is 2:1:0.2.

mn=10233 for SP-SC3275, pd=1.697 for SP-SC 3275.

The commercial product SP-2836 of Jiangsu Optimu chemical engineering Co., ltdhttps:// www.sinvochem.com/search/？keyword＝SP-2836) The method comprises the steps of carrying out a first treatment on the surface of the RAFT was achieved using reversible-addition fragmentation chain transfer living radical polymerization technique): S-dodecyl-S (methyl acetic acid) trithiocarbonate is used as a chain transfer agent, and azodiisobutyronitrile is used as an initiator; more specifically, the hydrophilic monomer acrylic acid and maleic acid polyethylene glycol monoester are needed, the hydrophobic monomer styrene and 1-octene are needed, and the weight ratio of the hydrophilic monomer to the hydrophobic monomer is 2:1.

further, the active polymerization macromer accounts for 50-70% of the total mass of the active polymerization macromer and the hydrophobic monomer;

the addition amount of the initiator is 0.5-2% of the total mass of the active polymerization macromonomer and the hydrophobic monomer;

the temperature of the block polymerization is 70-90 ℃; and/or

The time of the block polymerization is 3 to 5 hours.

The following examples were prepared by selecting a polymeric polycarboxylate (hereinafter abbreviated as SP-4371) commercially available from Jiangsu Optimu chemical engineering Co., ltd.) according to the following steps:

based on 100 percent of the total mass of the active polymerization macromonomer and the hydrophobic monomer;

50% by mass of the reactive polymeric macromer SP-2836 was dissolved in 80g of deionized water;

mixing 25% of hydrophobic monomer styrene, 25% of isooctyl acrylate and an emulsifier SDS, adding into a four-neck flask for emulsification, stirring at normal temperature, introducing nitrogen for 30min, raising the temperature to 80 ℃, dropwise adding a potassium persulfate aqueous solution (KPS+3g deionized water accounting for 0.7% of the total mass of active polymerization macromonomer and hydrophobic monomer) for initiating polymerization, monitoring monomer residues in the reaction process to be less than 0.1%, carrying out spray drying and dehydration on a block polymer after 4 hours of reaction to form a powder P1 with good fluidity, wherein the molecular weight Mn is 53256, preparing the P1 into a 10% solution, and measuring the viscosity to be 119mm < 2 >/s at 25 ℃ by adopting a petroleum product kinematic viscosity meter.

2. Regarding the auxiliary agent II, the organosilicon selected in the following examples is polyether modified trisiloxane, and more specifically, organosilicon products sold by Jiangsu qingyu chemical engineering Co., ltd are selected: polyether modified trisiloxane SP-4026 (hereinafter abbreviated as: SP-4026,https://www.sinvochem.com/products-12/93.html)。

3. the rain wash resistance evaluation method is specifically as follows:

1uL of liquid medicine is dripped into a 10um liquid transferring gun at the position of about 2cm at the tail end of the glass slide, 3 drops of liquid medicine are dripped into each glass slide, and 3 glass slides are dripped repeatedly;

placing in a 30 ℃ incubator for 2-3 hours, fully drying, placing in a microscope 10 x 40 for observation, and recording the state before simulated rain wash by photographing in a hundred-terimage system;

the glass slide is fixed on a plastic plate and placed obliquely at 60 degrees, the glass slide is placed in a spray tower, the spray tower is used for simulating rain wash, 2L of clear water is sprayed, the glass slide is taken out for airing, the glass slide is placed under a microscope for photographing and observation, and the photographing method is the same as the spraying process;

calculating the proportion of the occupied areas of the front and rear drug spots before spraying through image J software, and calculating according to the following formula (1):

P＝S2/S1*100(1)；

the Coverage percentage of the scouring prodrug spots in the area of the selected frame liquid medicine is% Coverage, namely S1;

and (2) covering the scoured medicine spots by the Coverage percent Coverage of the area of the selected medicine liquid, namely S2.

4. Surface tension measurement method:

the surface tension is measured according to the method of measuring the surface tension of GB/T22237-2008 surfactant, the test is stably controlled at 2822 ℃, the measurement is repeated for 3 times, and the average value is obtained.

5. Method for measuring spreading area:

sucking 20uL by a pipette, dripping the liquid onto a PVE plate, and recording the spreading area of the liquid medicine in 3 min;

6. contact angle measurement method:

2uL of the liquid medicine is dripped into the liquid medicine by a micro liquid feeder, the liquid drop is continuously photographed for 20S by a contact angle tester, the contact angle of the 20S liquid drop is measured, and the average value is obtained by repeating three times.

7. Indoor bioassay of cucumber downy mildew disease was performed with reference to NY/T1156.11.11-2008:

after the medicine, observing the occurrence of diseases and the influence of each treatment on cucumber growth, and 5D and 9D after the medicine survey the disease index of each treatment and calculate the control effect. The grading method comprises the following steps:

level 0: no disease;

stage 1: the area of the disease spots accounts for less than 5% of the area of the whole leaf;

3 stages: the area of the disease spots accounts for 6% -15% of the area of the whole leaf;

5 stages: the area of the disease spots accounts for 16% -25% of the area of the whole leaf;

7 stages: the area of the disease spots accounts for 26% -50% of the area of the whole leaf;

stage 9: the area of the disease spots accounts for more than 50% of the area of the whole leaf.

The disease index and the control effect were calculated according to formulas 1 and 2 in percent (%), with the result retaining two decimal places:

the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Example 1

1. The composition for improving the rain wash resistance of the protective bactericide in this example:

high molecular polycarboxylate SP-4371:10 parts;

organosilicon SP-4026:20 parts;

solvent water: 80 parts;

2. the preparation method of the composition for improving the rain wash resistance of the protective bactericide in the embodiment comprises the following steps:

10 parts of high molecular polycarboxylate SP-4371 are added with 80 parts of water, stirred for 10min at normal temperature by a stirrer of 100r/min, and then added with 10 parts of organosilicon SP-4026 to be stirred for 10min, so that SP-4026 and SP-4371 are fully mixed.

Comparative examples 1 to 1

This comparative example is substantially the same as example 1 except that the polycarboxylate polymer auxiliary agent SP-4371 is replaced with polyethylene, and specifically, jiangsu qingyu chemical polyvinyl alcohol SP-1788 can be selected.

Comparative examples 1 to 2

This comparative example is essentially the same as example 1, except that the polycarboxylate polymeric aid SP-4371 is replaced by chitosan.

Comparative examples 1 to 3

This comparative example is essentially the same as example 1, except that the polycarboxylate polymeric aid SP-4371 is replaced with guar gum.

Performance verification experiment 1

Based on 40% chlorothalonil SC sold in the market, 200X was diluted, 3000X of example 1, comparative examples 1-2 and comparative examples 1-3 were added in tank mix, and rainfastness evaluation was performed.

Table 1.40% rain wash resistance evaluation of chlorothalonil SC tank mix rain wash resistant composition

Referring to fig. 1 and table 1, the coffee ring formed by the commercial basic sample 40% chlorothalonil SC after the drug patch is dried after washing is washed away, and meanwhile, a small part of the drug patch is washed away, which shows that the commercial 40% chlorothalonil SC has weaker rain wash resistance; compared with a basic sample, in the embodiment 1 with 3000X added in barrel mixing, the rain wash resistance effect of the dried medicine spots is improved by 51.86 percent, the coffee ring is basically complete, and the rain wash resistance capability of the chlorothalonil active ingredient is obviously improved; and by adding the comparative examples 1-1, 1-2 and 1-3, the anti-scouring capability of the medicine spots can only be improved by 20-30%, the coffee ring is scoured, and the medicine spots on the inner ring have a certain anti-scouring capability, which shows that the anti-rain scouring effect of the polycarboxylate polymer additive SP-4371 on the chlorothalonil is superior to that of the polyvinyl alcohol, the chitosan and the guar gum, so that the additive combination polycarboxylate polymer additive SP-4371 is preferable.

Example 2

high molecular polycarboxylate SP-4371:30 parts;

organosilicon SP-4026:30 parts;

solvent water: 40 parts of

20 parts of high molecular polycarboxylate SP-4371 are added with 50 parts of water, stirred for 10min at normal temperature by a stirrer of 100r/min, and then added with 30 parts of organosilicon SP-4026 for 10min, so that SP-4026 and SP-4371 are fully mixed.

Comparative example 2-1

This comparative example was substantially identical to the preparation method of example 2, except that no silicone SP-4026 was added and the amount of solvent water was 70 parts.

Comparative examples 2 to 2

The comparative example was substantially the same as the preparation method of example 2, except that polymeric polycarboxylate SP-4371 was not added, and the amount of solvent water was 70 parts.

Comparative examples 2 to 3

This comparative example was substantially identical to the preparation method of example 2, except that silicone SP-4026 was replaced by fatty amine polyoxyethylene ether AC-1800.

Comparative examples 2 to 4

This comparative example is essentially the same as example 2 except that the silicone SP-4026 is replaced by the alkyl glycoside APG-1214.

Comparative examples 2 to 5

This comparative example was substantially identical to the preparation method of example 2, except that the silicone SP-4026 was replaced with fatty alcohol polyoxyethylene ether AEO-9.

Performance verification experiment 2

The surface tension, dynamic surface tension, spreading area and contact angle of the diluted liquid medicine were measured by barrel mixing with commercially available 50% mycodan WP in example 2, comparative example 2-1, comparative example 2-2, comparative example 2-3, comparative example 2-4 and comparative example 2-5 at 3000X.

TABLE 2 interfacial properties of commercially available 50% folpet WP tank mix adjuvant compositions compared to rain wash resistance

The wetting spreading performance and the deposition amount of the pesticide droplets on the target plant leaf surface directly relate to the application efficiency of the pesticide, and the wetting spreading performance and the retention amount relate to the surface tension of the pesticide liquid and the contact angle of the pesticide liquid on the plant leaf surface. The smaller the contact angle of the pesticide fog drop on the target plant leaf surface, the lower the surface tension of the pesticide liquid, the better the wetting and spreading performance on the crop leaf surface, the larger the spreading area, the larger the corresponding control area, and the greater the possibility that the pesticide liquid adheres to the crop leaf surface.

From table 2, it can be obtained:

when the common commercial 50% captan WP is diluted by 600X, the surface tension is high, the contact angle is larger than 90 degrees, the liquid drops are in hemispherical liquid drop shape on the paraffin plate, the liquid drops are not wetted, the spreading area is small, the liquid drops sprayed on a target are poor in wetting and spreading, the deposition amount is low, and the drug effect is limited. Under normal conditions, the effect of the wetting dispersant added in the formula of the wettable powder on the interface performance is very limited, and an auxiliary agent II is added in tank mixing when spraying is needed.

Example 2 ensures that the liquid medicine has lower surface tension and larger spreading area, and under the condition of a small amount of spraying, the liquid medicine attached to the target blade is more, the plant is more easily wetted, and the contact area of the liquid medicine and the disease spots is larger.

Comparative example 2-1 has a good rainwash resistance but its spreading effect on the blade is poor.

The comparative examples 2-2 have larger spreading area, and the captan per unit area is effectively and reasonably reduced, but the rain wash resistance effect is reduced compared with the basic sample.

Comparative examples 2-3, 2-4 and 2-5 the two types of additives added were different from example 2. Comparative examples 2-3, 2-4 and 2-5 have limited improvement effect on the wetting spreading area of the medicinal liquid, can be used on hydrophilic plants, and can be inferior to example 2 in hydrophobic plants. The tank mixing of example 2, comparative examples 2-3, comparative examples 2-4 and comparative examples 2-5 can increase the rain wash resistance effect of 50% of the active ingredient of captan WP, and the four treatments have no significant difference and are all obviously superior to the commercial samples. Therefore, the organosilicon is matched with the rain erosion resistant auxiliary agent SP-4371 to have a more synergistic effect.

Example 3

high molecular polycarboxylate SP-4371:20 parts;

organosilicon SP-4026:20 parts;

solvent water: 60 parts of

20 parts of high molecular polycarboxylate SP-4371 are added with 60 parts of water, stirred for 10min at normal temperature by a stirrer of 100r/min, and then added with the corresponding 20 parts of organosilicon SP-4026, and stirred for 10min, so that the SP-4026 and the SP-4371 are fully mixed.

Comparative example 3-1

This comparative example was substantially identical to the preparation method of example 3, except that 20 parts of silicone SP-4026 was replaced by 10 parts, and water was replaced by 70 parts.

Comparative example 3-2

This comparative example was substantially identical to the preparation method of example 3, except that 20 parts of silicone SP-4026 was replaced by 30 parts, and water was replaced by 50 parts.

Comparative examples 3 to 3

This comparative example was substantially identical to the preparation method of example 3, except that 20 parts of silicone SP-4026 was replaced by 50 parts, and water was replaced by 30 parts.

Performance verification experiment 3

The surface tension, spreading area, contact angle and rain wash ratio of the diluted solution were measured by adding 3000X of example 3, comparative example 3-1, comparative example 3-2 and comparative example 3-3 to a commercially available 47% Chunlei copper WP tank mix, and the specific method was the same as in examples 1 and 2.

TABLE 3 interfacial properties of commercially available 47% Chunlei copper WP tank mix adjuvant composition versus rain wash resistance

The method is characterized in that a commercially available 47% spring thunder and copper WP is taken as a basic sample, a rain-wash-resistant auxiliary agent and auxiliary agent compositions with different organosilicon ratios are mixed in a barrel to measure the surface tension, the contact angle, the spreading area and the rain-wash-resistant proportion, so that the content of the rain-wash-resistant auxiliary agent is unchanged, the content of organosilicon is added, the spreading area is increased under the condition that the content of pesticide active ingredients is unchanged, the content of unit area of pesticide spots is reduced before rain wash, and the formed pesticide film is thinner and is more easily corroded by rainwater, thereby causing the loss of the active ingredients. The table shows that the wetting and spreading effect of the liquor of the commercially available 47% Chunlei copper WP barrel-mixed 3000X example 3 is obviously better than that of a basic sample, and the obvious rain wash resistance of the active ingredients of the medicament is obviously improved; the liquid medicine with the barrel mixing proportion of 3-1 has better rain wash resistance, but has low organic silicon content and poor wetting and spreading effects; the liquid medicine of the tank mixing comparative example 3-2 has obviously larger wetting effect than a basic sample and better rainwash resistance, the content of the wetting agent is not easy to be increased continuously at the moment, and the ratio of the organosilicon to the rainwash resistance auxiliary SP-4371 is recommended to be between 1 and 2 according to the test result because the organosilicon content is too high and the spreading area is too large, so that the rainwash resistance is weakened, and the two auxiliary agents can exert better application effect only when being matched properly.

Example 4

high molecular polycarboxylate SP-4371:20 parts;

fatty amine polyoxyethylene ether AC-1800:40 parts;

solvent water: 40 parts;

the amine ether with the special structure of the fatty amine polyoxyethylene ether has the characteristics of wetting permeation, adhesion, sterilization and the like, and the wetting effect is inferior to that of organic silicon, so that the two-use amount of the auxiliary agent is increased to 40 parts.

20 parts of high polymer polycarboxylate SP-4371 are added with 40 parts of water, stirred for 10min at normal temperature by a stirrer of 100r/min, and then added with 40 parts of fatty amine polyoxyethylene ether AC-1800 to be stirred for 10min, so that the fatty amine polyoxyethylene ether AC-1800 and SP-4371 are fully mixed.

Example 5

high molecular polycarboxylate SP-4371:20 parts;

organosilicon SP-4026:20 parts;

solvent rosin-based vegetable oil ND-45 (Fujiannod Biotechnology Co., ltd.): 60 parts;

20 parts of high polymer polycarboxylate SP-4371, 60 parts of solvent rosin-based vegetable oil ND-45 and stirring for 10min at normal temperature by using a stirrer 100r/min, and then adding the corresponding 20 parts of organosilicon SP-4026 and stirring for 10min, so that the organosilicon SP-4026 and SP-4371 are fully mixed.

Performance verification experiment 4

The effect of the auxiliary agent composition on the rain wash resistance of the protective bactericide on the plant leaves is evaluated, and the specific method is as follows: taking commercial 40% chlorothalonil SC, 50% captan WP and 30% copper SC as basic samples, diluting 100X, adding 3000X in barrel mixing, example 5, dripping 10uL of liquid medicine onto scindapsus aureus leaves by using a pipettor, drying at room temperature, performing photographing record, simulating rain wash by using a spray tower, spraying 2L of clear water, airing, and performing photographing observation.

As shown in fig. 2, the mixed addition of example 5 can make the active ingredients of the liquid medicine of 40% chlorothalonil SC, 50% captan WP and 30% copper master SC dried on scindapsus aureus leaves more resistant to washing by naked eyes, and the area of the medicine spots is larger, and the area of the contacted medicine spots is larger, so that the medicine effect is improved. The rosin-based vegetable oil is derived from plants, is compounded by rosin oil and other plant essential oils, is used as a solvent, and has no harm to crops and high safety.

Example 6

high molecular polycarboxylate SP-4371:20 parts;

organosilicon SP-4026:20 parts;

methylated vegetable oil: 60 parts;

20 parts of high polymer polycarboxylate SP-4371 and 60 parts of methylated vegetable oil are added, stirring is carried out for 10min at normal temperature by using a stirrer of 100r/min, and then the corresponding 20 parts of organosilicon SP-4026 are added, stirring is carried out for 10min, so that the organosilicon SP-4026 and SP-4371 are fully mixed.

The methylated vegetable oil also has a certain rain wash resistance effect, can increase the adhesiveness of the liquid medicine on target plant leaves, and has stronger rain wash resistance capability and higher deposition amount by adding the composition and using the pesticide active ingredient.

Performance verification experiment 5

Biological test and experiment of 40% chlorothalonil SC tank mix synergistic composition on cucumber downy mildew

TABLE 4 control of 40% chlorothalonil SC on cucumber downy mildew

From the bioassay test, it can be found that:

1) 5 days after the pesticide, the disease index of 40% chlorothalonil SC sold in the market is 7.94, the prevention effect is only 37.43%, the prevention effects of the tank mixing and adding synergistic auxiliary composition examples 1-6 are all 60-70%, the pesticide effect can be improved by 65.26-85.89%, the synergistic auxiliary composition is shown to have larger spreading area of a medicinal film of the protective bactericide and stronger capability of resisting adverse environment, and therefore the growth of pathogenic bacteria can be obviously inhibited in the initial stage of crop disease, and the pesticide effect is better expressed.

2) The disease index of the basic sample is obviously increased after the pesticide is applied for 9 days, namely the disease is more serious, the disease index increasing trend of the added examples 1-6 is obviously inhibited, the disease index is obviously lower than that of the basic sample, the pesticide effect can reach more than 70%, the synergistic ratio can reach 53.17-68.78%, and the capability of resisting the adverse environment due to rain wash is stronger, so that the lasting period of the pesticide effect is prolonged, and the pesticide effect is more durable.

It should be noted that although the present invention has been described above in terms of the preferred embodiment, it is not intended to limit the invention. Those skilled in the art will appreciate that various modifications and adaptations can be made without departing from the spirit and scope of the present invention. Accordingly, the scope of the invention is defined by the appended claims.

Claims

1. A composition for improving the rainfastness properties of a protective bactericide, which is characterized by comprising the following components in parts by weight:

10-30 parts of auxiliary agent I;

20-40 parts of an auxiliary agent II;

30-70 parts of a solvent;

the auxiliary agent II comprises one or more of organic silicon, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether, fatty amine polyoxyethylene ether, alkyl glycoside, block polyether and alkylbenzene sulfonate.

2. The composition for improving the rainfastness properties of a protective bactericide according to claim 1, wherein the solvent comprises one or more of water, vegetable oil, rosin-based vegetable oil, methylated vegetable oil.

3. The composition for improving the rainfastness properties of a protective bactericide according to claim 1, wherein the auxiliary agent one comprises a polymeric polycarboxylate.

4. A composition for improving the rainfastness properties of a protective bactericide according to claim 3, wherein the molecular weight of the polymeric polycarboxylate is in the range of 30000 to 100000.

5. The composition for improving the rainfastness properties of a protective bactericide according to any one of claims 1 to 4, wherein the second auxiliary agent comprises a silicone.

6. The composition for improving the rainfastness properties of a protective bactericide according to claim 5, wherein the silicone comprises polyether modified trisiloxane.

7. The composition for improving the rainfastness properties of a protective bactericide according to claim 6,

10-20 parts of auxiliary agent I;

20-30 parts of an auxiliary agent II;

50-70 parts of solvent.

8. The composition for improving the rainfastness properties of a protective bactericide according to claim 6, wherein the ratio of the amount of the organosilicon to the amount of the polymeric polycarboxylate is 1 to 2.

9. The use of a composition for improving the rainfastness properties of a protective bactericide according to any one of claims 1 to 8, wherein the protective bactericide comprises any one or more of copper preparations, dithiocarbamates, substituted benzenes, imides.

10. A method for preparing a composition for improving the rainfastness properties of a protective bactericide according to any one of claims 1 to 9, comprising the steps of: mixing the auxiliary agent I with the solvent, and then adding the auxiliary agent II for mixing;

the mixing temperature does not exceed 50 ℃.