WO2020232779A1 - Prothioconazole dry suspending agent, preparation method therefor and application thereof - Google Patents

Abstract

A prothioconazole dry suspending agent, comprising the following components according to percentage by weight: 50%-80% prothioconazole, 10%-25% of a dispersant, 0.5%-6% of a wetting agent, 5%-10% of a disintegrant, 1%-5% of a binder, 0.5%-1% of a defoamer, and the remainder is a filler. The dispersant is a mixture of sodium polycarboxylate and octylphenol polyether-9. The grinding efficiency is increased by means of improving the dispersant. The particle size of the suspending agent is 1 μm or below, and the prepared dry suspending agent disintegrates quickly, has a high suspension rate, excellent stability, highly effective content, and a remarkable control effect. The use dosage is reduced, medication costs are lowered, and moreover, the prothioconazole dry suspending agent is environmentally friendly and free of dust pollution during production or use. The agent has the characteristics of high efficacy, strong permeability and the like, the use dosage may be reduced, the cost to farmers and environmental pollution are lowered, and the agent is resistant to rain erosion. The problem in which prothioconazole has difficulty permeating plants is solved, and the control effect on crop diseases is improved.

Description

Prothioconazole dry suspension, its preparation method and application

This application claims the priority of a Chinese patent application filed with the Chinese Patent Office on May 22, 2019, the application number is 2019104294384, and the invention title is "Prothioconazole Dry Suspension Concentrate, Its Preparation Method and Application", and the entire content of it is passed The reference is incorporated in this application.

Technical field

The invention relates to the technical field of pharmaceutical preparations, in particular to a prothioconazole dry suspension, its preparation method and application.

Background technique

Prothioconazole, a new broad-spectrum triazole thione fungicide, is an inhibitor of sterol demethylation (ergosterol biosynthesis). It has a good systemic effect, excellent protection, treatment and eradication activity. And it lasts for a long time. A large number of field efficacy test results show that prothioconazole has good safety to crops, has good disease prevention and treatment effects, and has a significant increase in production.

At present, most of the frequently used prothioconazole preparation products are mainly suspensions, emulsifiable concentrates, and seed coatings. These dosage forms can indeed play a better role under certain conditions. However, with the increasing attention of human beings to environmental protection and the high demands of the market on products, these dosage forms have shown corresponding limitations. For example, the suspension concentrate is easy to bottom and layer during storage; the emulsifiable concentrate uses a large amount of organic solvents, which is not friendly to the environment.

Summary of the invention

In view of this, the technical problem to be solved by the present invention is to provide a prothioconazole dry suspension, its preparation method and application. The prepared prothioconazole dry suspension has high suspension rate, rapid disintegration, long shelf life, and preparation Convenience.

In order to solve the above technical problems, the present invention provides a dry suspension of prothioconazole, which is calculated as a percentage by weight and includes:

The remaining amount of packing;

The dispersant is a mixture of sodium polycarboxylate and octylphenol polyether-9.

In the present invention, the content of prothioconazole is preferably 50% to 80%, more preferably 60% to 75%. In some specific embodiments of the present invention, the content of prothioconazole is 60% , 65%, 70% or 75%.

Preferably in the present invention, the dispersant is a mixture of sodium polycarboxylate and octylphenol polyether-9.

Further preferably, the mass ratio of the sodium polycarboxylate and octylphenol polyether-9 is 4:6.

In the present invention, the content of the dispersant is preferably 10%-25%, more preferably 10%-15%. In some specific embodiments of the present invention, the content of the dispersant is 13%.

The present invention uses a mixture of polycarboxylate sodium salt and octylphenol polyether-9 as the dispersant of prothioconazole dry suspending agent, so that 99% of the particle size of the suspending agent after secondary grinding is below 1 μm, and the prepared dry The suspending agent disintegrates very quickly and the suspension rate is very high. Moreover, due to its very fine particle size, it has strong adhesion on the surface of the leaf and is resistant to rain washing. Therefore, the duration of the suspension is comparable to that of the suspending agent. The water dispersant has a long duration.

The polycarboxylate sodium salt and octylphenol polyether-9 are mixed according to the mass ratio of 4:6. As a dispersant, it has better dispersibility than 3:7 and 5:5 or other ratios. The disintegration speed is relatively fast, and it can disintegrate in the shortest time after entering the water, and quickly obtain a cloud-like dispersion suspension, which can maximize the disintegration speed and suspension rate and obtain the best effect.

Preferably in the present invention, the wetting agent is sodium lignin sulfonate, sodium laurate, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium naphthalene sulfonate, powder BX, alkane Sodium naphthalene sulfonate, sodium alkylnaphthalene sulfonate formaldehyde condensate, alkylphenol polyoxyethylene ether.

More preferably, the wetting agent is naphthalenesulfonic acid sodium salt.

In the present invention, the content of the wetting agent is preferably 0.5% to 6%, more preferably 2% to 4%. In some specific embodiments of the present invention, the content of the wetting agent is 3%.

Preferably, the disintegrant is one or more of sulfate, carbonate, phosphate, urea, sodium chloride, polyvinylpyrrolidone, magnesium aluminum silicate, sodium methylcellulose and ammonium sulfate. Kind.

More preferably, the disintegrant is sulfate.

In the present invention, the content of the disintegrant is preferably 5% to 10%, more preferably 5% to 8%. In some specific embodiments of the present invention, the content of the disintegrant is 5%.

Preferably in the present invention, the binder is one or more of xanthan gum, gelatin, gum arabic, carboxymethyl cellulose, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone and starch.

Further preferably, the binder is xanthan gum.

In the present invention, the content of the binder is preferably 1% to 5%, more preferably 1% to 3%. In some specific embodiments of the present invention, the content of the binder is 1%.

Preferably, the defoamer is higher alcohol, tributyl phosphate, polyethylene glycol fatty acid ester, polyoxypropylene glycerol ether, fatty acid-based defoamer, silicone oil-based defoamer, polyoxypropylene propylene glycol Ethers, stearates, organosiloxanes, higher alcohol fatty acid ester complexes, organosilicones, phenylethyl oleate, C8～C10 fatty alcohols, C10～C20 saturated aliphatic carboxylic acids and C10～ One or more of C20 saturated aliphatic carboxylic acid esters.

Further preferably, the defoamer is organosiloxane.

In the present invention, the content of the defoaming agent is preferably 0.5% to 1%, more preferably 0.5% to 0.8%. In some specific embodiments of the present invention, the content of the defoaming agent is 0.5%.

Preferably, the filler is one or more of sodium citrate, light calcium carbonate, diatomaceous earth, kaolin, bentonite, attapulgite, activated clay, white carbon black and fumed white carbon black.

Further preferably, the filler is sodium citrate.

In the present invention, the filler makes up 100% of the total amount of the prothioconazole dry suspension.

The contents mentioned in the present invention are all mass contents.

Preferably, the particle size of each component of the prothioconazole dry suspending agent is less than 1 μm.

The present invention also provides a preparation method of the prothioconazole dry suspension, which includes the following steps:

Mix prothioconazole, dispersant, wetting agent, disintegrant, binder, defoamer, and filler with water to form a suspended material of 40% to 70%, and then grind until the particle size of the material is below 1μm , And then spray drying and sieving to obtain prothioconazole dry suspension.

Firstly, the components in the formula are prepared into a suspended material of 40% to 70% with water according to the percentage, and then the material is ground until the particle size of the material is below 1 μm.

Then the ground material is pressure sprayed, dried and granulated in a pressure spray dryer.

Preferably in the present invention, the spray pressure is 3 to 5 MPa. The inlet temperature of the material is preferably 130-140°C, and the outlet temperature is preferably 60°C.

After screening, prothioconazole dry suspension can be prepared.

The particle size of the prothioconazole dry suspension is preferably 20-200 mesh.

Upon inspection, the prothioconazole dry suspension prepared by the invention has a suspension rate of more than 99% and a wetting time of less than 30s.

The prepared prothioconazole dry suspending agent has stable performance and avoids the use of organic solvents. There is no dust pollution during field application and factory production. It is more environmentally friendly and safer for the applicator, which is in line with the development of current pesticide formulations direction.

The present invention also provides the application of the prothioconazole dry suspending agent or the prothioconazole dry suspending agent prepared by the above preparation method in preventing and controlling cereal crop diseases.

The cereal crops include, but are not limited to, wheat, barley, rape, peanut, rice, beans and other crops.

The diseases include but are not limited to wheat and barley head blight, powdery mildew, sheath blight, fusarium wilt, leaf spot, rust, sclerotinia, net spot, moir and the like. As well as the soil-borne diseases of Youlai and peanuts, such as sclerotinia, and major foliar diseases such as gray mold, black spot, brown spot, black shank, sclerotinia and rust.

The test results show that the prothioconazole dry suspension prepared by the present invention is better than prothioconazole wettable powder.

Compared with the prior art, the present invention provides a dry suspension of prothioconazole, in terms of weight percentage, comprising: prothioconazole 50% to 80%; dispersant 10% to 25%; wetting agent 0.5 %～6%; disintegrant 5%～10%; binder 1%～5%; defoamer 0.5%～1%; balance filler; the dispersant is sodium polycarboxylate and octyl A mixture of phenolic polyether-9. The invention improves the grinding efficiency by improving the dispersant, and controls the particle size of the suspending agent below 1 μm. The prepared dry suspending agent disintegrates very quickly, has a very high suspension rate, and has excellent stability, high effective content, and preventive The effect is remarkable, the dosage can be reduced, the cost of medication can be reduced, it is environmentally friendly, and there is no dust pollution during production or use.

The test results show that the prothioconazole dry suspension provided by the present invention has a suspension rate of more than 99% after 14 days of heat storage, a disintegration time of less than 30s, and more than 95% of particles have been sieved without particles. It has the characteristics of high efficacy and strong penetration, which can reduce the dosage, reduce the use cost and environmental pollution of farmers, and is resistant to rain erosion. The invention solves the problem that prothioconazole is difficult to penetrate in plants, thereby greatly improving the control effect on crop diseases.

Detailed ways

In order to further illustrate the present invention, the prothioconazole dry suspension provided by the present invention, its preparation method and application will be described in detail below in conjunction with examples.

In the present invention, the thermal storage stability test method is as follows: put the sample in an ampoule and store it at 54°C for 14 days, then test the specified items, and the content decomposition rate is ≤5%, and the suspension rate is ≥80%. , The disintegration time does not exceed 60 seconds, and the fineness ≥90% is qualified.

Example 1 60% prothioconazole dry suspension

Effective content of 98% prothioconazole 614g, polycarboxylate sodium salt and octylphenol polyether-9 (4:6) mixture 130g, naphthalenesulfonic acid sodium salt 30g, sulfate 50g, xanthan gum 10g, silicone 5g of oxane, 161g of sodium citrate, then add 2kg of water, stir evenly, first wet grinding for 1h, after grinding 99% of the particle size is less than 1μm, then pump the suspension into a pressure spray dryer for drying and granulation, spray The pressure is controlled at 3 to 5MPa, the inlet temperature is controlled at 130-140°C, the outlet temperature is controlled at 60°C, and the 60% prothioconazole dry suspension is prepared after granulation and screening.

After inspection, the active ingredient content is 60.17%, the suspension rate is 99.5%, the moisture content is 0.2%, the pH value is 5.6, the disintegration time is 24s, the fineness (passing 45μm) ≥99%, basically no dust, the content after heat storage It is 60.05%, pH value is 5.5, suspension rate is 97.1%, disintegration time is 27s, fineness (passing 45μm) is ≥99%, basically no dust, and thermal storage stability is qualified.

Comparative example 1 60% prothioconazole dry suspension

The effective content of 98% prothioconazole is 614g, calcium lignosulfonate 130g, sodium naphthalenesulfonate 30g, sulfate 50g, xanthan gum 10g, organosiloxane 5g, sodium citrate 161g, then add 2kg water and stir Uniform, first wet grinding for 1 hour, the particle size is unqualified, only 50% of the particle size is less than 1μm. Then the suspension is pumped into a pressure spray dryer for drying and granulation. The spray pressure is controlled at 3～5MPa, the inlet temperature is controlled at 130～140℃, the outlet temperature is controlled at 60℃, and 60% acrylic is obtained after granulation and screening. Thioconazole dry suspension.

After inspection, the active ingredient content is 60.08%, the suspension rate is 90.1%, the moisture content is 0.3%, the pH value is 5.5, the disintegration time is 54s, the fineness (passing 45μm) ≥91%, basically no dust, the content after thermal storage It is 59.96%, the pH value is 5.5, the suspension rate is 78.1%, the disintegration time is 70s, the fineness (passing 45μm) is ≥85%, basically no dust, and the thermal storage stability is unqualified.

Example 2 65% prothioconazole dry suspension

Effective content of 98% prothioconazole 665g, polycarboxylate sodium salt and octylphenol polyether-9 (4:6) mixture 130g, naphthalenesulfonic acid sodium salt 30g, sulfate 50g, xanthan gum 10g, silicone 5g of oxane, 110g of sodium citrate, add 2kg of water, stir evenly, first wet grinding for 1h, after grinding 99% of the particle size is less than 1μm, then pump the suspension into a pressure spray dryer for drying and granulation, spray The pressure is controlled at 3～5MPa, the inlet temperature is controlled at 130～140℃, the outlet temperature is controlled at 60℃, and the 65% prothioconazole dry suspension is prepared after granulation and screening.

After inspection, the active ingredient content is 65.08%, the suspension rate is 99.1%, the moisture content is 0.3%, the pH value is 5.5, the disintegration time is 26s, the fineness (passing 45μm) ≥96%, basically no dust, the content after thermal storage It is 65.05%, the pH value is 5.5, the suspension rate is 98.2%, the disintegration time is 27s, the fineness (passing 45μm) is ≥99%, there is basically no dust, and the thermal storage stability is qualified.

Comparative example 2 65% prothioconazole dry suspension

Effective content 98% prothioconazole 665g, alkylphenol polyoxyethylene ether formaldehyde condensate 130g, naphthalenesulfonic acid sodium salt 30g, sulfate 50g, xanthan gum 10g, organosiloxane 5g, sodium citrate 110g, and then Add 2kg of water, stir evenly, first wet grinding for 1 hour, the particle size is unqualified, and only 50% of the particle size is less than 1μm after grinding. Then pump the suspension into a pressure spray dryer for drying and granulation. The spray pressure is controlled at 3～5MPa, the inlet temperature is controlled at 130～140℃, and the outlet temperature is controlled at 60℃. After granulation and sieving, 65% acrylic is obtained. Thioconazole dry suspension.

After inspection, the active ingredient content is 65.05%, the suspension rate is 91.8%, the moisture content is 0.2%, the pH value is 5.1, the disintegration time is 55s, the fineness (passing 45μm) ≥90%, basically no dust, the content after thermal storage It is 64.05%, the pH value is 5.2, the suspension rate is 79.1%, the disintegration time is 76s, the fineness (passing 45μm) is ≥80%, there is basically no dust, and the thermal storage stability is unqualified.

Example 3 70% prothioconazole dry suspension

Effective content 98% prothioconazole 715g, polycarboxylate sodium salt and octylphenol polyether-9 (4:6) mixture 130g, naphthalenesulfonic acid sodium salt 30g, sulfate 50g, xanthan gum 10g, silicone 5g of oxane, 60g of sodium citrate, and 2kg of water, stir evenly, first wet grinding for 1h, 99% particle size <1μm, then pump the suspension into a pressure spray dryer for drying and granulation, spray pressure control At 3 to 5 MPa, the inlet temperature is controlled at 130-140°C, the outlet temperature is controlled at 60°C, and the 70% prothioconazole dry suspension is prepared after granulation and screening.

After inspection, the active ingredient content is 70.05%, the suspension rate is 99.5%, the moisture content is 0.2%, the pH value is 5.6, the disintegration time is 27s, the fineness (passing 45μm) ≥99%, basically no dust, and the content after thermal storage It is 69.85%, the pH value is 5.5, the suspension rate is 98.1%, the disintegration time is 30s, the fineness (passing 45μm) is ≥99%, basically no dust, and the thermal storage stability is qualified.

Comparative example 3 70% prothioconazole dry suspension

Effective content 98% prothioconazole 715g, alkylphenol polyoxyethylene ether formaldehyde condensate 130g, naphthalenesulfonic acid sodium salt 30g, sulfate 50g, xanthan gum 10g, organosiloxane 5g, sodium citrate 60g, and then Add 2kg of water, stir evenly, first wet grinding for 1h, the particle size is unqualified, only 50% of the particle size is less than 1μm. Then the suspension is pumped into a pressure spray dryer for drying and granulation, the spray pressure is controlled at 3～5MPa, the inlet temperature is controlled at 130～140℃, the outlet temperature is controlled at 60℃, and 70% acrylic is obtained after granulation and screening. Thioconazole dry suspension.

After inspection, the active ingredient content is 70.02%, the suspension rate is 89.2%, the moisture content is 0.25%, the pH value is 5.7, the disintegration time is 76s, the fineness (passing 45μm) ≥86%, basically no dust, the content after thermal storage It is 67.05%, the pH value is 5.5, the suspension rate is 77.1%, the disintegration time is 80s, the fineness (passing 45μm) is ≥79%, there is basically no dust, and the thermal storage stability is unqualified.

Example 4 75% prothioconazole dry suspension

Effective content of 98% prothioconazole 766g, polycarboxylate sodium salt and octylphenol polyether-9 (4:6) mixture 130g, naphthalenesulfonic acid sodium salt 30g, sulfate 50g, xanthan gum 10g, silicone 5g of oxane, 9g of sodium citrate, add 2kg of water, stir evenly, first wet grinding for 1h, 99% particle size <1μm, then pump the suspension into a pressure spray dryer for drying and granulation, spray pressure control At 3 to 5MPa, the inlet temperature is controlled at 130-140°C, the outlet temperature is controlled at 60°C, and 75% prothioconazole dry suspension is prepared after granulation and screening.

After inspection, the active ingredient content is 74.96%, the suspension rate is 99.7%, the moisture content is 0.1%, the pH value is 5.8, the disintegration time is 25s, the fineness (passing 45μm) ≥99%, basically no dust, the content after heat storage It is 74.05%, pH value is 5.5, suspension rate is 97.9%, disintegration time is 30s, fineness (passing 45μm) ≥97%, basically no dust, and thermal storage stability is qualified.

Comparative example 4 75% prothioconazole dry suspension

Effective content of 98% prothioconazole 766g, sodium lignosulfonate 130g, sodium naphthalenesulfonate 30g, sulfate 50g, xanthan gum 10g, organosiloxane 5g, sodium citrate 9g, then add 2kg water, stir Uniform, first wet grinding for 1 hour, the particle size is unqualified, only 50% of the particle size is less than 1μm, then the suspension is pumped into a pressure spray dryer for drying and granulation, the spray pressure is controlled at 3～5MPa, and the temperature is controlled at 130-140°C, the outlet temperature is controlled at 60°C, and 75% prothioconazole dry suspension is prepared after granulation and screening.

After inspection, the active ingredient content is 75.06%, the suspension rate is 86.8%, the moisture content is 0.2%, the pH value is 5.2, the disintegration time is 88s, the fineness (passing 45μm) ≥87%, basically no dust, the content after heat storage It is 73.05%, pH value is 5.5, suspension rate is 76.1%, disintegration time is 101s, fineness (passing 45μm) is ≥74%, basically no dust, and thermal storage stability is unqualified.

It can be seen from the above examples that the prothioconazole dry suspending agent uses a mixture of polycarboxylate sodium salt and octylphenol polyether-9 (4:6) as the dispersant, which can effectively increase the grinding efficiency and the suspension particles The diameter can reach 99% of the particle size <1μm after grinding for 1h. Suspension rate, disintegration time, thermal storage stability and other indicators are more excellent.

Example 5 Application Example

The preparation products produced in the above-mentioned embodiments are used to prevent and control wheat head blight.

The dosage of this test agent is set to three treatment concentrations according to the different active ingredients. The control agents are commercially available pesticides and clean water blank controls, specifically: 75% prothioconazole wettable powder, 480 g/L prothioconazole suspension Control agent and water blank.

Test method: The test was carried out in a field with a serious incidence of wheat head blight, and each plot of the test was 30 m ² , repeated 4 times.

The investigation method and drug efficacy evaluation were conducted according to NY/T 1464.15-2017.

The experimental results are shown in Table 1.

Table 1 Summary of field test results of the present invention

The above field efficacy test shows that the prothioconazole dry suspension prepared by the present invention has a good control effect on wheat head blight, and the control effect is significantly better than the control agent 75% prothioconazole wettable powder and the control agent 480 g/L prothioconazole suspension is equivalent.

The description of the above embodiments is only used to help understand the method and core idea of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims (10)

1. A dry suspension of prothioconazole, which is characterized in that, in terms of weight percentage, it comprises:

   

   The dispersant is a mixture of sodium polycarboxylate and octylphenol polyether-9.
2. The prothioconazole dry suspension of claim 1, wherein the mass ratio of the sodium polycarboxylate and octylphenol polyether-9 is 4:6.
3. The dry suspension of prothioconazole according to claim 1, wherein the particle size of each component of the dry suspension of prothioconazole is less than 1 μm.
4. The prothioconazole dry suspension of claim 1, wherein the wetting agent is sodium lignosulfonate, sodium laurate, sodium lauryl sulfate, dodecylbenzene sulfonic acid Sodium, sodium naphthalene sulfonate, open powder BX, sodium alkyl naphthalene sulfonate, sodium alkyl naphthalene sulfonate formaldehyde condensate, alkylphenol polyoxyethylene ether.
5. The prothioconazole dry suspension of claim 1, wherein the disintegrant is sulfate, carbonate, phosphate, urea, sodium chloride, polyvinylpyrrolidone, magnesium aluminum silicate, One or more of sodium methyl cellulose and ammonium sulfate.
6. The prothioconazole dry suspension of claim 1, wherein the binder is xanthan gum, gelatin, acacia, carboxymethyl cellulose, polyvinyl alcohol, polyethylene glycol, poly One or more of vinylpyrrolidone and starch.
7. The prothioconazole dry suspension of claim 1, wherein the antifoaming agent is higher alcohol, tributyl phosphate, polyethylene glycol fatty acid ester, polyoxypropylene glycerol ether, fatty acid based Antifoaming agent, silicone oil-based antifoaming agent, polyoxypropylene propylene glycol ether, stearate, organosiloxane, higher alcohol fatty acid ester complex, organosilicone, phenylglycol oleate, C8～C10 One or more of fatty alcohol, C10～C20 saturated aliphatic carboxylic acid and C10～C20 saturated aliphatic carboxylic acid ester; the filler is sodium citrate, light calcium carbonate, diatomaceous earth, kaolin, bentonite, One or more of attapulgite, activated clay, white carbon black and fumed white carbon black.
8. The prothioconazole dry suspension of claim 1, wherein the suspension rate of the prothioconazole dry suspension is greater than 99%, and the wetting time is less than 30s.
9. The preparation method of prothioconazole dry suspension according to any one of claims 1 to 8, characterized in that it comprises the following steps:

   Mix prothioconazole, dispersant, wetting agent, disintegrant, binder, defoamer, and filler with water to form a suspended material of 40% to 70%, and then grind until the particle size of the material is below 1μm , Then spray drying and screening to obtain prothioconazole dry suspension.
10. Use of the prothioconazole dry suspension of any one of claims 1 to 8 or the prothioconazole dry suspension prepared by the preparation method of claim 9 in preventing and controlling cereal crop diseases.