CN103416402B - A kind of propamidine water dispersible granules and preparation method thereof - Google Patents

Abstract

The invention discloses a propaneamidine water-dispersible granule and a preparation method thereof. The prepared propaneamidine water-dispersible granule is composed of the following raw materials in mass percentage: propaneamidine: 85%-90%, dispersant: 2.5%-5% %, wetting agent: 2.5% to 5%, disintegrant 2.5% to 5%, the sum of the mass percentages of raw materials is 100%. Its preparation method is to mix the raw material propaneamidine, wetting agent, dispersant and disintegrant in the formula quantity evenly, and then pulverize it through a jet mill to make superfine wettable powder, then add a certain amount of water, and pass through extrusion Granulate with a granulator, dry with an airflow dryer, and sieve to obtain water-dispersible granules. It can effectively reduce packaging and transportation costs, increase the storage stability and shelf life of the medicament, improve the safety and environmental protection of propaneamidine preparations from production to use, and has a high control effect on plant Botrytis cinerea.

Description

A kind of propaneamidine water dispersible granule and preparation method thereof

technical field

The invention belongs to the field of pesticide preparations, and relates to a propaneamidine water-dispersible granule and a preparation method thereof.

technical background

In the chemical structure of saponins, due to the different degrees of lipophilicity of aglycones and the strong hydrophilicity of sugar chains, saponins become a kind of natural surfactant, and the aqueous solution can produce persistent soap-like foam after shaking. This is why it is called saponin. At the same time, saponin also exhibits direct agricultural activities such as: bactericidal, insecticidal and synergistic effects on other pesticides.

As a wetting agent for pesticides, tea saponin has the advantages of fast wetting speed and good dispersibility. When added to pesticides, it can significantly improve the physical and chemical properties of the pesticide liquid, increase the effective deposition amount of the pesticide on the target body, help the full play of the pesticide effect, improve the use effect, and reduce the toxicity of the pesticide accordingly. The pollution of chemical pesticides to the environment is reduced, and the cost of pesticides is reduced. Tea saponin mixed with dimehypo, malathion, methomyl, kaufenthrin, nisolan, vechyfone, nicotine, dimethoate, rotenone, BT, tolk, glyphosate, etc. It has obvious synergistic effects on the control of aphids, diamondback moth, citrus panonychia, and crabgrass (weeds). As a spreading agent for pesticide spraying, tea saponin can improve the adhesion and extension of pesticides on the surface of crops and target organisms, thereby improving the poisonous effect of pesticides. Tea saponin is used as a dispersant, suspending agent, and emulsifier in the processing of pesticides to improve the wetting and dispersing ability of the original drug, reduce the surface tension of the pesticide, and enhance its wettability. The contact angle of the drops on the target body surface can increase the effective deposition amount of the drug on the target body, making it easier to wet and spread on the target body, thereby improving the efficacy of the drug. At the same time, using tea saponin, a natural surfactant, to produce pesticides can reduce the toxicity of pesticides and reduce environmental pollution.

Due to the expansion of vegetable planting area in protected areas year by year, botrytis cinerea has risen from a secondary disease to a major disease. The damage is particularly severe on crops such as cucumbers, tomatoes, eggplants and strawberries. According to estimates, the annual loss reaches 20%-30%, and the loss in popular years can reach 40%-60%, which is so severe that it will be completely lost. The control of Botrytis cinerea has been dominated by chemical control, and Botrytis cinerea has produced varying degrees of resistance to most fungicides, especially the most serious resistance to benzimidazoles and diformamide fungicides. The control effect of these agents on gray mold is greatly reduced. Due to the high price of Xeroxal and Sukling, which have good application effects in production practice, they are not widely used in actual prevention and control. The main advantage of propaneamidine water dispersible granule is its price compared with Shijiale and Sukling. Because of its low control cost, it has strong market competitiveness. At the same time, propaneamidine is a fungicide variety independently developed by my country, with independent intellectual property rights, different from other imitation fungicide varieties, and has the potential to enter the international market.

In conclusion, propaneamidine water-dispersible granules, as an efficient, safe, economical, and convenient fungicide variety, conform to the development direction of pesticides and have broad application prospects. Propanamidine is a new type of fungicide developed by the Pesticide Research Service Center of Northwest A&F University. It has the characteristics of high efficiency, low toxicity, low residue, and environmental friendliness. But the dosage form developed at present has only 2% propaneamidine aqueous solution.

Contents of the invention

Aiming at the defects of propaneamidine aqueous solution transportation cost, packaging cost, easy to be taken by mistake, etc., the object of the present invention is to provide a high-content propaneamidine water-dispersible granule with better stability, longer shelf life and better safety .

In order to achieve the above tasks, the present invention can be achieved through the following technical solutions:

A propaneamidine water-dispersible granule, characterized in that the prepared propaneamidine water-dispersible granule is composed of the following raw materials in mass percentage: propaneamidine: 85%-90%, dispersant: 2.5%-5%, moist Agent: 2.5% to 5%, disintegrant 2.5% to 5%, the sum of the mass percentages of raw materials is 100%.

The purity of the propaneamidine is 80%-90%.

The mass ratio of the dispersant, wetting agent and disintegrant is 1:1:1.

The percentage consumption of described dispersant, wetting agent and disintegrant is 3.5%.

The wetting agent is tea saponin or sodium dodecylsulfonate, the dispersant is tea saponin or sodium lignosulfonate, and the disintegrating agent is ammonium sulfate.

The preparation method of the above-mentioned propaneamidine water-dispersible granule is characterized in that, after mixing the raw material propaneamidine, wetting agent, dispersant and disintegrating agent of the formulation amount uniformly, it is pulverized by a jet mill to make an ultrafine wettable powder, Then add a certain amount of water, carry out granulation through an extrusion granulator, dry with an air dryer, and sieve to obtain a water-dispersible granule.

The present invention uses the natural surface active substance-tea saponin and the synergistic effect of tea saponin, as the main auxiliary agent of the water-dispersible granule to obtain a new dosage form that is environmentally friendly, safe, and drug-effective, and expands the use of tea saponin in application in production.

The propaneamidine water-dispersible granule prepared by the present invention brings the following technical effects:

1) Changed the liquid dosage form of low-content propaneamidine aqueous solution, making it more difficult for impulsive eaters and those who take it by mistake, which is of great help to prevent people who will only take it as a drink by mistake.

2) During storage and transportation of low-content propaneamidine aqueous solution, 98% of the weight is water, which increases transportation costs and packaging costs. The invention is a high-content propaneamidine water-dispersible granule, which can effectively reduce packaging and transportation costs, and is convenient to use, thereby enabling farmers to obtain greater benefits.

3) Creatively replace the artificially synthesized surfactant with the natural surface active substance-tea saponin, and successfully use it as the main auxiliary agent of propaneamidine water-dispersible granules, which reduces the pollution of industrial chemicals to the environment and improves the safety of the drug sex.

4) The synergistic effect of tea saponin is used to further improve the efficacy.

5) For the further expansion and application of tea saponin, a by-product of agricultural production, it has a promoting effect on improving its economic benefits, increasing agricultural added value, and increasing farmers' income.

6) The prepared propaneamidine water-dispersible granules have significantly improved stability compared with water formulations, and overcome the problems of flocculation, precipitation, and easy deterioration that often exist in water formulations; their shelf life can be greatly extended compared with water formulations.

7) The formula and preparation method of the propaneamidine water-dispersible granule can reduce the solvent residual rate of the propaneamidine during use, and improve the safety problem during use.

8) Water-soluble disintegrants (also known as fillers) are used, no mineral fillers are used, and there is no adsorption of propaneamidine by mineral fillers, which makes the drug effect of the preparation more stable. The combination of wetting agent, dispersant and disintegrating agent can make propamidine form a uniform solution or suspension in water, so that the dry propaneamidine solid preparation shows a stable bactericidal effect, and can strengthen the bactericidal effect of propamidine Effect. Compared with the known corresponding water agents, it has a more significant preventive effect.

The using method of the propaneamidine water-dispersible granule of the present invention is not particularly limited, and the suggested using method is as follows:

To control Botrytis cinerea on tomato, cucumber, strawberry and other crops, the dosage is 6-12 (ai) g/mu. Specifically, 6-8 (a.i.) g/mu of strawberries, 8-10 (a.i.) g/mu of cucumbers, and 10-12 (a.i.) g/mu of tomatoes. It is better to use it in the early stage of Botrytis cinerea. When preventing gray mold of tomato and strawberry, use 60kg of water per mu, and control gray mold of cucumber with 45kg of water per mu. Sprayer for regular foliar spray. It is better to use it in the early stage of Botrytis cinerea.

Detailed ways

The technical idea of the present invention is that, compared with water preparations, water dispersible granules have many advantages, which are summarized as follows:

1) Easy to measure

2) Solvent-free and dust-free, safe for operators and the environment.

3) Sufficient hardness and strength, convenient and low cost during packaging, storage and transportation.

4) The apparent specificity is large, the packaging container is small, the volume can be measured, and the user is convenient to use.

5) It can be made into high-concentration active ingredients, and the general content can be more than 50%, up to 90%.

6) Good storage stability, even if commercial storage conditions and user storage conditions are poor, it can maintain a longer shelf life.

Therefore, using the active characteristics of the natural surface active substance-tea saponin, it is used as an auxiliary agent for the new fungicide propaneamidine, and the formulation of its water-dispersible granule is studied, which will promote the application of propaneamidine environmentally friendly new dosage forms and serve as saponin The comprehensive utilization provides basis and basis.

This example provides a formula for propaneamidine water-dispersible granules, and the prepared propaneamidine water-dispersible granules are composed of the following raw materials in mass percentage: propaneamidine: 85% to 90%, dispersant: 2.5% to 5% %, wetting agent: 2.5% to 5%, disintegrant 2.5% to 5%, the sum of the mass percentages of raw materials is 100%.

In this embodiment, the purity of propaneamidine is 80%-90%. In order to achieve the desired biological effect, the mass ratio of wetting agent/dispersing agent/disintegrating agent is preferably 1:1:1, and the content of wetting agent, dispersing agent and disintegrating agent in the formula is preferably 3.5%.

The wetting agent is tea saponin or sodium dodecylsulfonate, the dispersant is tea saponin or sodium lignosulfonate, and the disintegrating agent is ammonium sulfate.

The preparation method of the above-mentioned propaneamidine water-dispersible granule is to mix evenly the raw material propaneamidine, wetting agent, dispersant and disintegrant in the formulation amount, and then pulverize it through a jet mill to make ultrafine wettable powder, and then add a certain amount of The water is granulated by an extrusion granulator, dried with an airflow dryer, and sieved to obtain a water-dispersible granule.

The following are examples given by the inventors.

Preparation Example 1～Example 5:

The following table 1 shows the specific formulations of Examples 1-5.

Table 1: Propanamidine water dispersible granule formula:

Production Process:

Mix propaneamidine raw powder with a purity of 85% to 90%, wetting agent, dispersant, and disintegrating agent evenly, and then pulverize it through a jet mill to make ultrafine wettable powder, then add a certain amount of water, squeeze The granulator is used for granulation, dried by air flow, and sieved to obtain water-dispersible granules.

Certainly, the propaneamidine water-dispersible granule of this embodiment can also be prepared according to the conventional water-dispersible granule and its preparation method.

Embodiment 6: prevention effect experiment

Field efficacy test:

Test medicament: propaneamidine water-dispersible granules prepared in Examples 1-5;

Control agent 1: 2% propaneamidine aqueous solution;

Control drug 2: 50% Proxaline wettable powder, product of Sumitomo Chemical Co., Ltd., Japan.

Control drug 3: 40% Xerkol SC, produced by Eigerfort, Germany.

Control drug 4: 50% carbendazim wettable powder, produced by Jiangsu Jiangyin No. 2 Pesticide Factory.

Control agent 5: 40% sclerotia net wettable powder, Shandong Shouguang Shuangxing Pesticide Factory.

Test crops: tomato; cucumber; strawberry

experimental method:

Strawberry 6-8(ai)g/mu, cucumber 8-10(ai)g/mu, tomato 10-12(ai)g/mu. Each test agent was prepared according to the dosage and water consumption per mu, and clear water was used as the blank control. Each treatment was repeated 4 times, and each plot was repeated, and the area of the plot was 15-30m ² . The plots were arranged randomly in the field.

When preventing and controlling gray mold of tomato and strawberry, use 60kg of water per mu, and 45kg of water per mu for the control of gray mold of cucumber. The medicine was applied once every 7 days, and the medicine was applied 4 times in total.

1) Crop Safety Survey

On the third day after each spraying, the crops were observed for phytotoxicity.

2) Drug efficacy investigation and statistical methods

Investigation and Statistical Methods of Control Effects of Cucumber and Tomato Botrytis

The investigation of the control effect of gray mold on cucumber and tomato mainly takes fruit as the investigation object. Each plot is sampled at 5 points, and 2 to 3 plants are investigated at each point, and 3 to 5 fruits are investigated at each plant, and recorded according to the presence or absence of diseased spots and their size. Use (1), (2), (3) and (or) (4) to calculate the disease index, disease index growth rate and control effect, and use DMRT method to analyze the differences in disease index, disease index growth rate and control effect among treatments significant.

If there is no disease before application (that is, the disease base is 0), the relative control effect is calculated according to the following formula:

Grading standard for tomato diseased fruit:

Grade 0: no disease spots on the fruit;

Grade 1: The diameter of the lesion is less than 1cm;

Grade 3: lesion diameter 1-2cm;

Grade 5: The diameter of the lesion is 2-3cm;

Grade 7: The diameter of the lesion is 3-4cm;

Grade 9: The diameter of the lesion is greater than 5cm.

Cucumber diseased fruit grading standard:

Grade 0: no lesions;

Grade 1: Residual petal disease;

Grade 3: The residual petal disease spreads to the navel of the fruit;

Grade 5: Lesions account for 1/5 of the length of the melon strips;

Grade 7: Lesions account for 1/5 to 2/5 of the length of the melon strips;

Grade 9: Lesions account for more than 2/5 of the length of the melon strips.

Investigate the disease base of Botrytis cinerea before spraying, and investigate and record the disease after spraying.

Investigation and statistical method of control effect of strawberry gray mold:

Sampling at five points on the diagonal, 5 plants at each point, 25 plants per plot, fixed-point observation of the incidence, and grading and recording the occurrence of gray mold according to the following grading standards. Use (1), (2), (3) and (or) (4) to calculate the disease index, disease index growth rate and control effect, and use the DMRT method to analyze the differences in disease index or disease index growth rate and control effect among treatments significant.

Grading standards for strawberry diseased fruit:

Grade 0: no disease on the fruit;

Level 1: Lesions account for less than 5% of the entire fruit area;

Grade 3: Lesions account for 6% to 15% of the entire fruit area;

Grade 5: Lesions account for 16% to 25% of the entire fruit area;

Grade 7: Lesions account for 26% to 50% of the entire fruit area;

Grade 9: Lesions occupy more than 50% of the entire fruit area.

The propaneamidine water-dispersible granule preventive effect experiment that embodiment 1,2,5 prepares is as shown in table 2:

Table 2: Test results of three formulations for controlling Botrytis cinerea

Note: In table 1, data in the same column with the same letter after the same letter means there is no significant difference at the 0.05 level.

The field efficacy test results of table 2 show that, under the concentration of test agent, the control effect of the water-dispersible granule embodiment 1 and embodiment 2 containing tea saponin is equivalent, but all are better than the embodiment 3 not containing saponin . It shows that tea saponin does play a certain synergistic effect.

The propaneamidine water-dispersible granules prepared in Example 2 were tested in a spring-stubble greenhouse tomato field in Nanzhuang Township, Yangcun Township, Yangling Demonstration Area, Shaanxi Province. Botrytis cinerea occurred heavily in this tomato field over the years. The soil fertility is medium, pH6.9; clear the diseased fruit before spraying. The control effect on Botrytis cinerea is shown in Table 3.

Table 3: Efficacy test results of water dispersible granules for controlling Botrytis cinerea 1

Note: In the table, the data in the same column are marked with the same letter, indicating that there is no significant difference at the 0.05 level;

The results of the drug efficacy test in Table 3 show that under the dosage of 6-12 (ai) g/mu, the control effect of propaneamidine water-dispersible granules on tomato gray mold is more than 70%, which is significantly higher than that of the control agent saccharin The control effect of 30(ai)g/mu dosage. The investigation of phytotoxicity showed that the dosage form had no effect on tomato fruit, leaves and flowers under the test dose.

The applicant also conducted an experiment on the propaneamidine water-dispersible granule prepared in Example 2 in a greenhouse tomato field in Xifeng Town, Sanyuan County, Shaanxi Province. Botrytis cinerea occurred heavily in this tomato field over the years. Soil fertility is moderate; remove diseased fruit before application. The control effect on Botrytis cinerea is shown in Table 4.

Table 4: Test results of water dispersible granules for controlling Botrytis cinerea 2

Note: 1. Data in the same column with the same letter after the same column means no significant difference at the 0.05 level;

As can be seen from the test results in Table 4, 7 days after the second spraying, the control effects of propaneamidine 12(ai)g/mu and 6(ai)g/mu were 79.57% and 71.05% respectively, and 7d after the 4th spraying The control effects were 81.41% and 74.73%, and the difference was not significant compared with the control effect of 30(ai) g/mu of saccharin. It can be seen that the control effect of propaneamidine 12(ai)g/mu and 6(ai)g/mu is equivalent to the control effect of 30(ai)g/mu, a commonly used agent for the control of tomato gray mold, and 3g(ai)/mu is less effective. The investigation of phytotoxicity showed that propaneamidine water dispersible granules had no effect on tomato fruit, leaves and flowers under the test dose.

Field experiment of cucumber gray mold disease:

The applicant conducted experiments on the propaneamidine water-dispersible granules prepared in Example 2 in a cucumber field in a greenhouse in Dawangzhuang Village, Qu'an Township, Sanyuan County, Shaanxi Province. Botrytis cinerea occurred heavily in this cucumber field over the years. Soil fertility is moderate; remove diseased fruit before application. The control effect on cucumber gray mold disease is shown in Table 5.

Table 5: Results of efficacy test on control of cucumber gray mold

Note: In table 1, data in the same column with the same letter after the same letter means there is no significant difference at the 0.05 level.

As can be seen from the results in Table 5, when propaneamidine was used at a dose of 9 (ai) g/mu and 4.5 (ai) g/mu, the control effects of 7 days after the second spraying reached 79.40% and 76.55% respectively. The control effect of (ai)/mu dosage is 75.99%; 7 days after the 4th spraying, the control effect of propaneamidine 9(ai)/g mu and 4.5(ai)g/mu usage dosage is respectively 77.84% and 74.88%, and the control effect of 22.5g(ai)/mu of Shijiale is 73.42%. The control effects of the two agents are equivalent. The test found that propaneamidine water dispersible granules had obvious stimulating effect on the growth of cucumber.

See Table 6 for the test results of controlling strawberry gray mold.

Table 6: Control effect of water dispersible granules on strawberry gray mold

Note: 1 embodiment 2 is water dispersible granule 2, and medicament 2 is 40% sclerotia;

2. Data in the same column with the same letter in the same column means there is no significant difference at the 0.05 level;

As can be known from the test result of table 5, propaneamidine water dispersible granule 212 (ai) g/mu application dosage process, the control effect of the 3rd, 7, 14 days is all higher than 40% sclerotia net wp48 (ai) g/ The control effect of the application dose per mu; the control effect of the propaneamidine water dispersible granule 6(ai)g/mu application dose is equivalent to that of 40% Sclerotinia wp48(ai)g/mu application dose. It was observed in the test that the propaneamidine water-dispersible granules had no adverse effects on the whole growth and development process of strawberries, and the strawberries grew and developed well. The dosage of propaneamidine water dispersible granule is lower than that of 40% sclerotia net wp, and the control effect is better than 40% sclerotia net wp.

Embodiment 7: investigation of preparation stability quality

Table 7: Thermal Storage Stability

water dispersible granules Propanamidine content before thermal storage (%) Propanamidine content after thermal storage (%) Decomposition rate (%) Example 1 75.80 74.31 1.97 Example 2 75.40 73.91 1.98 Example 5 76.01 74.50 1.99 2% propaneamidine aqueous solution 2.06 1.97 4.37

The stability of the preparation in Table 7 is 54°C, and the AI (active ingredient content) is determined: put 20g of the sample into a clean ampoule (avoid the sample from touching the neck of the bottle), place the ampoule in ice-salt solution for refrigeration, and use a high-temperature flame to Quickly seal, seal at least 3 bottles, and weigh them separately. Put the sealed ampoule in a metal container, and place the metal container in a thermostat at 54°C±2°C for 14 days. After taking out, wipe the outside of the ampoules clean and weigh them respectively. Take the sample that has not changed in quality and measure the specified items within 24 hours, and calculate the relative decomposition rate.

As can be seen from the results in Table 7, the average decomposition rate of the three propaneamidine water-dispersible granules is all less than 2%, while the thermal storage average decomposition rate of 2% propaneamidine aqueous solution is 4.37%, so the stability of the water-dispersible granules is obviously better in water agent.

Embodiment 8: Take the original powder of propaneamidine according to mass percentage: 89.5%, tea saponin: 7%, ammonium sulfate is filled up to 100%; After mixing evenly, pulverize by jet mill, make superfine wettable powder, then A certain amount of water is added, granulated by an extrusion granulator, dried with an airflow, and sieved to obtain a water-dispersible granule.

Embodiment 9: Take the original powder of propaneamidine according to mass percentage: 89.5%, tea saponin: 3.5%, sodium lignosulfonate: 3.5%, and ammonium sulfate is filled up to 100%; After mixing evenly, pulverize by jet mill, Make superfine wettable powder, then add a certain amount of water, granulate through an extrusion granulator, dry with airflow, and sieve to obtain water-dispersible granules.

Example 10: Take propaneamidine raw powder by mass percentage: 89.5%, sodium dodecylsulfonate: 3.5%, sodium lignosulfonate: 3.5%, ammonium sulfate to 100%; after mixing evenly, pass through the airflow Pulverize with a pulverizer to make ultrafine wettable powder, then add a certain amount of water, granulate through an extrusion granulator, dry with airflow, and sieve to obtain water-dispersible granules.

Claims (2)

1. a propamidine water dispersible granules, it is characterized in that, this obtained propamidine water dispersible granules is made up of by mass percentage following raw material: propamidine: 85% ~ 90%, dispersant: 2.5% ~ 5%, wetting agent: 2.5% ~ 5%, disintegrant 2.5% ~ 5%, the mass percent sum of raw material is 100%;

Described wetting agent selects Tea Saponin or dodecyl sodium sulfate, and described dispersant selects Tea Saponin or sodium lignin sulfonate, and ammonium sulfate selected by described disintegrant, and the mass ratio of dispersant, wetting agent and disintegrant is 1:1:1;

The purity of described propamidine is 80% ~ 90%;

The percentage consumption of described dispersant, wetting agent and disintegrant is 3.5%;

This obtained propamidine water dispersible granules is made up of by mass percentage following raw material: propamidine: 89.5%, Tea Saponin: 7%, ammonium sulfate 3.5%;

Or this obtained propamidine water dispersible granules is made up of by mass percentage following raw material: propamidine: 89.5%, Tea Saponin: 3.5%, sodium lignin sulfonate: 3.5%, ammonium sulfate 3.5%.

2. propamidine water dispersible granules as claimed in claim 1; it is characterized in that; the preparation method of described propamidine water dispersible granules is; after the raw material propamidine of formula ratio, wetting agent, dispersant, disintegrant are mixed, pulverized by airslide disintegrating mill, make ultra-fine wettable powder; then a certain amount of water is added; carry out granulation by extruded type comminutor, dry with pneumatic conveyer dryer, namely screening obtains water dispersible granules.