CN110476964B

CN110476964B - Nano seed coating agent and preparation method thereof

Info

Publication number: CN110476964B
Application number: CN201910859623.7A
Authority: CN
Inventors: 翟喜海; 宋伟丰; 李宝英; 钱化; 李新民; 潘亚清; 焦占力
Original assignee: PLANT PROTECTION INSTITUTE OF HEILONGJIANG PROV AGRICULTURAL SCIENCES ACADEMY
Current assignee: PLANT PROTECTION INSTITUTE OF HEILONGJIANG PROV AGRICULTURAL SCIENCES ACADEMY
Priority date: 2019-09-11
Filing date: 2019-09-11
Publication date: 2021-06-29
Anticipated expiration: 2039-09-11
Also published as: CN110476964A

Abstract

A nano seed coating agent and a preparation method thereof, belonging to the technical field of novel pesticide preparation processes. The invention provides a nano seed coating agent and a preparation method thereof, aiming at solving the problems that the particle size of the active ingredients of the existing seed dressing agent is large, the seed absorption is not facilitated, and the penetrating power is not strong. The seed coating agent consists of tebuconazole, fludioxonil, polyethylene glycol 2000, xanthan gum, neutral hydroxymethyl cellulose, 200-mesh instant polyvinyl alcohol 1788, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, cetyl alcohol, EDTA, succinic acid, alkaline rose essence, zinc sulfate, manganese sulfate, monopotassium phosphate, white carbon black and talcum powder, and the active ingredients in the material group are subjected to nanocrystallization treatment and then used. The nano seed coating agent prepared by the formula and the method can greatly reduce the particle size of the effective component to reach the nano level, improve the penetrating power of the effective component to the seed coat and effectively kill the diseases of the seed.

Description

Nano seed coating agent and preparation method thereof

Technical Field

The invention particularly relates to a nano seed coating agent and a preparation method thereof, belonging to the technical field of novel pesticide preparation processes.

Background

The seed dressing agent is a substance which can be used for improving the seedling emergence condition of seeds, the growth condition of seedlings, preventing and treating diseases and insect pests, promoting beneficial microorganisms in soil, improving the surrounding environment of the seeds in the soil, lightening and preventing the occurrence of soil diseases, promoting crops to have a strengthening function and finally achieving the purpose of increasing yield.

The seed coating agent is mainly a medicament for seed treatment, generally comprises effective components and an auxiliary agent, and is a pesticide preparation which can be directly coated on the surface of seeds or be diluted to form a protective layer film with certain strength and permeability. The mode that the seeds are wrapped by the medicament is gradually developed from the beginning of medicament soaking and seed dressing. The pesticide composition has specific effects of preventing and treating soil-borne pests, soil-borne diseases and seed-borne diseases, improving the germination rate of seeds, promoting the healthy growth of crops, improving the yield of the crops and improving the quality of the crops, and also has the functions of saving seeds, labor and improving economic and ecological benefits.

However, the seed coating agent in the current market has many defects, such as insufficient content, mixed effective components, poor safety and no guarantee of prevention and treatment effect; the seed coating has the advantages of poor film forming property, unstable film forming, uneven seed coating, easy crushing and falling of a coating layer, easy generation of phytotoxicity, low seed germination rate, weak bud vigor, irregular seedling emergence, serious influence on yield, large particle size of effective ingredients, difficult seed absorption, low penetrating power and the like.

Disclosure of Invention

In order to solve the problems that the particle size of the active ingredients of the existing seed dressing agent is large, the seed dressing agent is not beneficial to seed absorption and the penetrating power is not strong, the invention provides a nano seed dressing agent and a preparation method thereof, and the technical scheme is as follows:

a nanometer seed coating agent comprises a medicament, a film forming agent, a dispersion wetting material and an auxiliary material, wherein the medicament comprises tebuconazole and fludioxonil; the film forming agent consists of polyethylene glycol 2000, xanthan gum, neutral hydroxymethyl cellulose and 200-mesh instant polyvinyl alcohol 1788; the dispersing and wetting material consists of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, cetyl alcohol and EDTA; the auxiliary material consists of succinic acid, alkaline rose essence, zinc sulfate, manganese sulfate, potassium dihydrogen phosphate, white carbon black and talcum powder.

Preferably, the medicament consists of 4.0 to 6.0 percent of tebuconazole and 1.5 to 4.0 percent of fludioxonil; the film forming agent consists of 2.0 to 3.0 percent of polyethylene glycol 2000, 0.5 to 0.8 percent of xanthan gum, 10 to 12.0 percent of neutral hydroxymethyl cellulose and 0.5 to 0.8 percent of 200-mesh instant polyvinyl alcohol 1788; the dispersing and wetting material consists of 12.0 to 14.0 percent of sodium dodecyl benzene sulfonate, 1.0 to 1.5 percent of sodium dodecyl sulfate, 1.0 to 2.0 percent of hexadecanol and 2.0 to 4.0 percent of EDTA; the auxiliary material contains 3.0-4.0% of succinic acid, 2.0-3.0% of alkaline rose essence, 2.0-4.0% of zinc sulfate, 2.0-4.0% of manganese sulfate, 12.0-16.0% of monopotassium phosphate, 12.0-14.0% of white carbon black and the balance of talcum powder, wherein the content of each component is the final weight percentage of each component in the nano seed coating agent.

Preferably, the medicament consists of 5.0 percent by weight of tebuconazole and 3.0 percent by weight of fludioxonil, and the content of each component is the final weight percent of each component in the nano seed coating agent.

Preferably, the film forming agent consists of 2.0 percent by weight of polyethylene glycol 2000, 0.5 percent by weight of xanthan gum, 10 percent by weight of neutral hydroxymethyl cellulose and 0.5 percent by weight of 200-mesh instant polyvinyl alcohol 1788, and the content of each component is the final weight percent of each component in the nano seed coating agent. More preferably, the medicament consists of 5.0 percent by weight of tebuconazole and 3.0 percent by weight of fludioxonil, the film forming agent consists of 2.0 percent by weight of polyethylene glycol 2000, 0.5 percent by weight of xanthan gum, 10 percent by weight of neutral hydroxymethyl cellulose and 0.5 percent by weight of 200-mesh instant polyvinyl alcohol 1788, and the content of each component is the final weight percent of each component in the nano seed coating agent.

The preparation method of the nano seed coating agent comprises the following steps:

(1) mixing tebuconazole, fludioxonil, talcum powder and white carbon black, and grinding until more than 80% of particles have the particle size of 80-100 nm;

(2) mixing other components of the seed coating agent, and then crushing, wherein the particle size of the crushed particles is 20-40 mu m;

(3) and (3) mixing the products treated in the steps (1) and (2) to prepare the nano seed coating agent.

Preferably, a nano grinder is adopted for grinding, the rotation speed of a motor of the nano grinder is 1200-1300r/min, the rotation speed of a grinding tank is 800-1000r/min, and the grinding is carried out for 8-10 hours.

Preferably, the rotation speed of the motor of the nano grinder is 1240r/min, the rotation speed of the grinding tank is 900r/min, and the grinding time is 8 hours.

(1) dissolving tebuconazole and fludioxonil in an organic solvent respectively to prepare a solution;

(2) atomizing the prepared solutions respectively through a nano atomization dryer under the condition that the oscillation frequency is 2.0MHz or 3.6MHz, drying after atomization to obtain tebuconazole and fludioxonil particles with the particle size of 80-100nm, wherein the inlet temperature of the fludioxonil solution is 80-90 ℃, and the outlet temperature is 20-40 ℃; the inlet temperature of the tebuconazole solution is 110-120 ℃, and the outlet temperature is 30-50 ℃;

(3) mixing other components of the seed coating agent, and then crushing, wherein the particle size of the crushed particles is 20-40 mu m;

(4) and (3) mixing the products treated in the steps (2) and (3) to prepare the nano seed coating agent.

Preferably, the organic solvent for dissolving fludioxonil is an ethanol solution, the mass concentration of the prepared fludioxonil solution is 6%, the organic solvent for dissolving tebuconazole is a toluene solution, the mass concentration of the prepared tebuconazole solution is 4%, the inlet temperature of the fludioxonil solution is 85 ℃, and the outlet temperature of the fludioxonil solution is 30 ℃; the tebuconazole solution inlet temperature is 115 ℃, and the outlet temperature is 40 ℃.

Advantageous effects

The nano seed coating agent prepared by the formula and the method can greatly reduce the particle size of the effective component to reach the nano level, improve the penetrating power of the effective component to the seed coat and effectively kill the diseases of the seed.

Drawings

FIG. 1 is a graph of cpn1 nanometer detection;

FIG. 2 is a diagram of a cpn1 nm detection column;

FIG. 3 is a CL1 nanometer detection graph;

FIG. 4 is a CL1 nanometer detection column diagram.

Detailed Description

The technical solution of the present invention will be specifically described below with reference to examples, but the following examples are not intended to limit the present invention. In the following examples, "%" represents "% by weight", and the drug ratios in the following examples are all weight ratios.

1. Screening of film Forming Agents

The film forming agent accounts for 13 percent, the specific components are prepared according to table 1, 12 combinations are designed, the components from ZH01 to ZH12 are completely consistent, the medicament is 10 percent of tebuconazole, 13 percent of sodium dodecyl benzene sulfonate, 1 percent of sodium dodecyl sulfate, 2 percent of hexadecanol, 3 percent of EDTA, 3 percent of succinic acid, 3 percent of alkaline rose essence, 3 percent of zinc sulfate, 3 percent of manganese sulfate, 16 percent of potassium dihydrogen phosphate and 13 percent of white carbon black, the talcum powder is added to 100 percent, and two samples are prepared by each combination.

Firstly, grinding tebuconazole, talcum powder and white carbon black by a nano grinder, wherein the rotating speed of a motor of the nano grinder is 1240r/min, the rotating speed of a grinding tank is 900r/min, and the grinding is carried out for 8 hours; mixing the rest components of the seed coating agent and then crushing the mixture by a jet mill; finally, all the processed components are mixed.

For the above 12 combinations, coating uniformity determinations were performed: according to 4.9 in NY 621-2002; and (3) determining the falling rate of the coating: the assay was performed twice per sample according to 4.10 in NY 621-2002.

TABLE 1 film Forming agent screening

TABLE 2 film Forming agent uniformity test results

Table 3: film-forming agent falling-off rate detection result

The 12 combinations are subjected to seed coating treatment, the uniformity and the falling rate of the film forming agent are tested, the analysis in tables 2 and 3 shows that the combination ZH03 and ZH12 are superior to other combinations, and the repeatability test result shows that ZH 03: the results showed that 2% of polyethylene glycol 2000, 0.5% of xanthan gum, 10% of neutral hydroxymethyl cellulose and 0.5% of 200-mesh polyvinyl alcohol 1788 were excellent.

2. Screening of Agents

The specific compositions and components of the medicament are prepared according to table 4, 12 combinations are designed, wherein the total amount of YX 01-

YX

12, 2% of polyethylene glycol 2000, 0.5% of xanthan gum, 10% of neutral hydroxymethyl cellulose and 0.5% of 200-mesh polyvinyl alcohol 1788, 14% of sodium dodecyl benzene sulfonate, 1.5% of sodium dodecyl sulfate, 1.5% of cetyl alcohol, 4% of EDTA, 4% of succinic acid, 3% of basic rose essence, 2% of zinc sulfate, 2% of manganese sulfate, 14% of potassium dihydrogen phosphate and 14% of white carbon black are added to 100% by talcum powder, and two samples are prepared by each combination.

Firstly, grinding the medicament, the talcum powder and the white carbon black by a nano grinder, wherein the rotating speed of a motor of the nano grinder is 1300r/min, the rotating speed of a grinding tank is 800r/min, and the grinding is carried out for 10 hours; mixing the rest components of the seed coating agent and then crushing the mixture by a jet mill; finally, all the processed components are mixed.

A seed dressing ratio (1: 800) of a corn Liaodan-33 variety, a mixed strain test of Pythi mu mgramicola Subram and Fusarium graminearum Schw are selected, various strains are prepared into strain soil according to a ratio of 1/2 respectively and are potted, corn seeds are sown into flowerpots after surface disinfection by 0.1% mercuric chloride liquid, 10 seeds are sown in each pot, and each treatment group is provided with 4 pots. And when the corn grows to 3-5 leaf stage after seedling emergence, pouring the seedlings into pots to investigate the incidence and disease grade of diseases. DJ: 5% tebuconazole single-dose ultra-fine powder (1: 200), CK: uncoated seed blank.

TABLE 4 active ingredient screening design

TABLE 5 root and stem rot control effect in seedling stage with different agents

From the stem-based control effect results in table 5, excellent YX06 with control effect of more than 70 can be obtained, and the control effect can meet the planting requirement.

Example 1. nanometer seed coating agent and its preparation method.

The nano seed coating agent and the preparation method thereof of the present invention are described in detail below.

The nano seed coating agent of the embodiment comprises a medicament, a film forming agent, a dispersing and wetting material and an auxiliary material, wherein the medicament of the seed coating agent comprises tebuconazole and fludioxonil; the film forming agent consists of polyethylene glycol 2000, xanthan gum, neutral hydroxymethyl cellulose and 200-mesh instant polyvinyl alcohol 1788; the dispersing and wetting material consists of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, cetyl alcohol and EDTA; the auxiliary material consists of succinic acid, alkaline rose essence, zinc sulfate, manganese sulfate, monopotassium phosphate, white carbon black and talcum powder, wherein the auxiliary material consists of the following components in percentage by weight: 6% of tebuconazole, 1.5% of fludioxonil, 3% of polyethylene glycol 2000, 0.5% of xanthan gum, 14% of neutral hydroxymethyl cellulose, 0.5% of 200-mesh instant polyvinyl alcohol 1788, 12% of sodium dodecyl benzene sulfonate, 1% of sodium dodecyl sulfate, 2% of hexadecanol, 2% of EDTA, 4% of succinic acid, 2% of basic rose essence, 4% of zinc sulfate, 2% of manganese sulfate, 16.0% of potassium dihydrogen phosphate, 12% of white carbon black and 17.5% of talcum powder.

(1) grinding tebuconazole, fludioxonil, talcum powder and white carbon black by a nano grinder, wherein the rotating speed of a motor of the nano grinder is 1200r/min, the rotating speed of a grinding tank is 1000r/min, and grinding is carried out for 9 hours;

(2) mixing the rest components of the seed coating agent and then crushing the mixture by a jet mill;

(3) finally, all the processed components are mixed to prepare the nano seed coating agent.

Embodiment 2. nanometer seed coating agent and its preparation method.

The nanometer seed coating agent comprises the following components in percentage by weight: 5.5% of tebuconazole, 2.5% of fludioxonil, 2.5% of polyethylene glycol 2000, 0.6% of xanthan gum, 11% of neutral hydroxymethyl cellulose, 0.7% of 200-mesh instant polyvinyl alcohol 1788, 14% of sodium dodecyl benzene sulfonate, 1.5% of sodium dodecyl sulfate, 1.5% of cetyl alcohol, 4% of EDTA (ethylene diamine tetraacetic acid), 4% of succinic acid, 3% of basic rose essence, 2% of zinc sulfate, 2% of manganese sulfate, 14% of potassium dihydrogen phosphate, 14% of white carbon black and 17.2% of talcum powder.

(1) dissolving tebuconazole in a toluene solution to prepare a toluene solution of tebuconazole with the concentration of 6 percent; dissolving fludioxonil in an ethanol solution to prepare a 4% ethanol solution;

(2) respectively atomizing the prepared solutions by a nano atomization dryer under the conditions that the oscillation frequency is 2.0MHz, the inlet temperature of tebuconazole is 115 ℃, the outlet temperature is 40 ℃, the inlet temperature of fludioxonil is 85 ℃ and the outlet temperature is 30 ℃;

(3) mixing the rest components of the seed coating agent and then crushing the mixture by a jet mill;

(4) finally, all the processed components are mixed to prepare the nano seed coating agent.

Embodiment 3. nanometer seed coating agent and preparation method thereof

The nanometer seed coating agent comprises the following components in percentage by weight: 5% of tebuconazole, 3% of fludioxonil, 2% of polyethylene glycol 2000, 0.5% of xanthan gum, 10% of neutral hydroxymethyl cellulose, 0.5% of 200-mesh instant polyvinyl alcohol 1788, 13% of sodium dodecyl benzene sulfonate, 1% of sodium dodecyl sulfate, 1.5% of hexadecanol, 3% of EDTA, 3.5% of succinic acid, 2.5% of basic rose essence, 3% of zinc sulfate, 3% of manganese sulfate, 14.0% of potassium dihydrogen phosphate, 13% of white carbon black and 21.5% of talcum powder.

(1) grinding tebuconazole, fludioxonil, talcum powder and white carbon black by a nano grinder, wherein the rotating speed of a motor of the nano grinder is 1240r/min, the rotating speed of a grinding tank is 900r/min, and grinding is carried out for 8 hours;

example 4. nanometer seed coating agent and its preparation method.

The nanometer seed coating agent comprises the following components in percentage by weight: 4% of tebuconazole, 4% of fludioxonil, 2% of polyethylene glycol 2000, 0.8% of xanthan gum, 10% of neutral hydroxymethyl cellulose, 0.8% of 200-mesh instant polyvinyl alcohol 1788, 12% of sodium dodecyl benzene sulfonate, 1.5% of sodium dodecyl sulfate, 1% of hexadecanol, 4% of EDTA, 3% of succinic acid, 3% of basic rhodamine, 2% of zinc sulfate, 4% of manganese sulfate, 12% of potassium dihydrogen phosphate, 14% of white carbon black and 21.9% of talcum powder.

(2) respectively atomizing the prepared solutions by a nano atomization dryer under the conditions that the oscillation frequency is 3.6MHz, the inlet temperature of tebuconazole is 115 ℃, the outlet temperature is 40 ℃, the inlet temperature of fludioxonil is 85 ℃ and the outlet temperature is 30 ℃;

The nano seed coating agents prepared in the

embodiments

1, 2, 3 and 4 are taken as examples, and the field use effect of the nano seed coating agent prepared in the invention is examined.

The commercial seed dressing agent and the seed coating agents described in the above examples 1, 2, 3 and 4 were selected for seed dressing field tests, and the commercial seed dressing agent was selected from Xianle, Manshijin, Aikoton, Kulas, and Shikuaixin, and Rick produced by Bayer. The seeds of Shingle Ganjin, Manshijin, Aikoton and Rickexiu are mixed according to the ratio of 1:500, the seedlings are young and the seeds of Kulas are mixed according to the ratio of 1:400, the seeds of examples 1, 2, 3 and 4 are mixed according to the ratio of 1:800 and the ratio of water to 100.

TABLE 6 autumn survey test results (significance of difference)

Serial number

The rate of emergence%

Height cm of plant

Diameter of stem

Ear length cm

Ear diameter mm

Weight of hundred grains g

Yield kg/hm2

1

Time of happiness

81aA

232.3aA

23.4aA

22.3aA

52abA

42.1aA

10620

2

Manshijin

79aA

238.3aA

21.2aA

22.4aA

53abA

42.5aA

10820

3

Akton

81aA

246aA

20.7aA

21.9aA

51bA

41.9aA

9792

4

New seedling

82aA

219.5aA

23.1aA

22.2aA

54aA

42.3aA

10418

5

Kulas

79aA

251.1aA

23.6aA

21.7aA

51.3bA

41.0aA

9743

6

Li Ke Xiu

80aA

243.8aA

23.2aA

21.6aA

52abA

41.3aA

9833

7

Example 1

81aA

263.0aA

21.1aA

21.9aA

52.4abA

41.0aA

9134

8

Example 2

79aA

257.3aA

25.5aA

22.6aA

52.8abA

41.9aA

10352

9

Example 3

82aA

257.1aA

21.8aA

22.4aA

52.6abA

42.1aA

10265

10

Example 4

80aA

254.5aA

21.9aA

22.7aA

52.7abA

42.4aA

10642

11

CK

82aA

251.3aA

21.5aA

22.1aA

51.2bA

41.8aA

9750

It can be seen from table 6 that the formulation combinations of the examples of the present invention are comparable to the imports. The difference is not obvious, but the seed dressing ratio is high, and the seed dressing ratio of the commercial seed dressing agent is 1: 400-500, test combination seed dressing ratio 1:800, the use amount of the pesticide is obviously reduced.

Taking the nano seed coating agents prepared in the examples 2 and 3 as examples, the particle size of the nano seed coating agent prepared by the invention is examined.

The detection of the university of chemical industry in China shows that two samples, namely, a particle obtained after the tebuconazole, the fludioxonil, the talcum powder and the white carbon black in example 3 are ground by a nano grinding machine (renamed as cpn1) and a mixed particle of the tebuconazole and the fludioxonil obtained in example 2 by a nano atomization drying machine (renamed as CL1), basically meet the nano requirement (100nm) in design. The average particle size of cpn1 is 108.4nm, and 46% below 105.7nm, as shown in FIG. 1 and FIG. 2. The CL1 has an average particle size of 97.6nm, wherein 76% is below 105.7nm, as shown in FIGS. 3 and 4.

Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims

1. A nanometer seed coating agent consists of a medicament, a film forming agent, a dispersion wetting material and an auxiliary material, and is characterized in that the medicament of the nanometer seed coating agent consists of tebuconazole and fludioxonil; the film forming agent consists of polyethylene glycol 2000, xanthan gum, neutral hydroxymethyl cellulose and 200-mesh instant polyvinyl alcohol 1788; the dispersing and wetting material consists of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, cetyl alcohol and EDTA; the auxiliary material consists of succinic acid, alkaline rose essence, zinc sulfate, manganese sulfate, monopotassium phosphate, white carbon black and talcum powder; the medicament consists of 5.0 percent of tebuconazole and 3.0 percent of fludioxonil in percentage by weight; the film forming agent consists of 2.0 percent of polyethylene glycol 2000, 0.5 percent of xanthan gum, 10 percent of neutral hydroxymethyl cellulose and 0.5 percent of 200-mesh instant polyvinyl alcohol 1788 in percentage by weight; the dispersing and wetting material consists of 13 weight percent of sodium dodecyl benzene sulfonate, 1 weight percent of sodium dodecyl sulfate, 1.5 weight percent of hexadecanol and 3 weight percent of EDTA; the auxiliary material comprises 3.5 percent of succinic acid, 2.5 percent of alkaline rose essence, 3 percent of zinc sulfate, 3 percent of manganese sulfate, 14.0 percent of potassium dihydrogen phosphate, 13 percent of white carbon black and 21.5 percent of talcum powder.

2. The preparation method of the nanometer seed coating agent of claim 1, which is characterized by comprising the following steps:

3. The preparation method of the nanometer seed coating agent of claim 1, which is characterized by comprising the following steps:

4. The method for preparing the nano seed coating agent as claimed in claim 2, wherein the nano grinding machine is used for grinding, the rotation speed of the motor of the nano grinding machine is 1200-1300r/min, the rotation speed of the grinding tank is 800-1000r/min, and the grinding time is 8-10 hours.

5. The method for preparing nanometer seed coating agent of claim 4, wherein the rotation speed of the motor of the nanometer grinding machine is 1240r/min, the rotation speed of the grinding tank is 900r/min, and the grinding is 8 hours.

6. The preparation method of the nanometer seed coating agent according to claim 3, characterized in that the organic solvent for dissolving fludioxonil is ethanol solution, and the mass concentration of the prepared fludioxonil solution is 6%; the organic solvent for dissolving the tebuconazole is a toluene solution, and the mass concentration of the prepared tebuconazole solution is 4 percent; the inlet temperature of the fludioxonil solution is 85 ℃, and the outlet temperature is 30 ℃; the tebuconazole solution inlet temperature is 115 ℃, and the outlet temperature is 40 ℃.