A pesticide water dispersible granule containing modified polyvinyl pyrrolidone

Abstract

The invention relates to a pesticide water-dispersible granule containing modified polyvinyl pyrrolidone. The modified polyvinyl pyrrolidone has unique dispersibility, adhesion, solubility and film-forming properties by utilizing its hydrophilicity. The prepared pesticide water-dispersible granule has stable physical and chemical properties and is not easy to decompose and deteriorate, thus solving the difficulty of producing corresponding preparations of some low-melting-point and easy-to-coke original drugs.

Description

Technical Field

[0001] The invention belongs to the technical field of pesticides, and particularly relates to a pesticide water-dispersible granule containing modified polyvinyl pyrrolidone and a preparation method thereof. Background Art

[0002] The preparation of water-dispersible granules of low-melting-point pesticides is a difficult problem in the current formulation processing. Due to the low melting point of the original drug, the prepared water-dispersible granules are unstable in thermal storage and are prone to agglomeration, resulting in the failure of the formulation to disintegrate, unqualified wet screening, and low suspension rate, which seriously affects its use.

[0003] Polyvinyl pyrrolidone (PVP), referred to as PVP, is a non-ionic polymer compound. It is the most distinctive, most studied and most extensive fine chemical among N-vinylamide polymers. It has developed into three major categories: non-ionic, cationic and anionic, three specifications: industrial grade, pharmaceutical grade and food grade, and a series of homopolymers, copolymers and cross-linked polymers with relative molecular weights ranging from thousands to more than one million, and has been widely used for its excellent and unique properties. As a synthetic water-soluble polymer compound, PVP has the general properties of water-soluble polymer compounds, such as colloid protection, film-forming, adhesion, hygroscopicity, solubilization or coagulation, but its most distinctive and therefore valued properties are its excellent solubility and physiological compatibility. Among synthetic polymers, PVP is rare, which is soluble in water and most organic solvents, has low toxicity and good physiological compatibility. Especially in the fields of medicine, food and cosmetics, which are closely related to people's health, with the reduction of the price of its raw material butyrolactone, it will surely show a good prospect for its development. However, it is rarely used in the field of pesticides, mainly because the dispersibility and wettability of polyvinyl pyrrolidone are not obvious, which limits its application in pesticides. Therefore, it is of great significance to develop a pesticide water-dispersible granule containing modified polyvinyl pyrrolidone to expand its scope of application and improve the performance of pesticide formulations. Summary of the invention

[0004] The purpose of the present invention is to provide a pesticide water dispersible granule containing modified polyvinyl pyrrolidone on the basis of the prior art. The polyvinyl pyrrolidone is first sulfonated with chlorosulfonic acid to form a salt, and the modified polyvinyl pyrrolidone is used as an important component of the pesticide water dispersant. The hydrophilicity of the modified polyvinyl pyrrolidone is utilized to make the modified polyvinyl pyrrolidone have unique dispersibility, adhesion, solubility and film-forming properties, thereby providing a stable water dispersible granule for the original drug with low melting point and easy to coke in the pesticide preparation.

[0005] Another object of the present invention is to provide a method for preparing the above-mentioned pesticide water-dispersible granules containing modified polyvinyl pyrrolidone.

[0006] Another object of the present invention is to provide a method for preparing the modified polyvinyl pyrrolidone.

[0007] The technical solution of the present invention is as follows:

[0008] A pesticide water dispersible granule containing modified polyvinyl pyrrolidone, which comprises the following components in parts by weight: 25-80 parts of active components, 3-5 parts of modified polyvinyl pyrrolidone, 8-10 parts of dispersants, 3-5 parts of disintegrants, and 5-59 parts of fillers. Among them, the active component is butyronitrile, propanil or cyprodinil; the dispersant is one or more of polycarboxylate, lignin sulfonate or sodium dodecylbenzene sulfonate; the disintegrant is ammonium sulfate, sodium carboxymethyl starch or sodium butyl naphthalene sulfonate; and the filler is bentonite or glauber powder.

[0009] The modified polyvinyl pyrrolidone is prepared according to the following method: chlorosulfonic acid is added dropwise to polyvinyl pyrrolidone at 120-160° C. After the reaction is completed, the obtained reaction solution is slowly added to a sodium hydroxide aqueous solution, and the pH value thereof is controlled to 7-9, and then the obtained mixed solution is spray-dried to obtain the modified polyvinyl pyrrolidone.

[0010] In a preferred embodiment, in the process of preparing modified polyvinyl pyrrolidone, the reaction temperature is 120-160°C, which can be but not limited to 120°C, 130°C, 135°C, 140°C, 145°C, 150°C or 160°C. In order to obtain better results, the reaction temperature is 140°C.

[0011] Furthermore, after the addition of chlorosulfonic acid is completed, the reaction is continued by keeping warm for 2 to 3 hours, preferably 2 hours.

[0012] In a preferred embodiment, the mass ratio of polyvinyl pyrrolidone to chlorosulfonic acid is 1:0.1-0.5, which may be but not limited to 1:0.1, 1:0.11, 1:0.12, 1:0.13, 1:0.15, 1:0.2, 1:0.3 or 1:0.5. In order to obtain better effects, the mass ratio of polyvinyl pyrrolidone to chlorosulfonic acid is 1:0.12.

[0013] Furthermore, the polyvinyl pyrrolidone mentioned in the present invention is polyvinyl pyrrolidone K-30.

[0014] In a preferred embodiment, the pesticide water-dispersible granules containing modified polyvinyl pyrrolidone provided by the present invention comprise the following components in parts by weight: 25 parts of butyrochlore, 3 parts of modified polyvinyl pyrrolidone, 2 parts of polycarboxylate, 3 parts of lignin sulfonate, 3 parts of sodium dodecylbenzene sulfonate, 5 parts of ammonium sulfate, and 59 parts of bentonite.

[0015] In a preferred embodiment, the pesticide water-dispersible granules containing modified polyvinyl pyrrolidone provided by the present invention comprise the following components in parts by weight: 80 parts of propanil, 3 parts of modified polyvinyl pyrrolidone, 8 parts of lignin sulfonate, 3 parts of sodium butyl naphthalene sulfonate, and 5 parts of sodium sulfate.

[0016] In a preferred embodiment, the pesticide water-dispersible granules containing modified polyvinyl pyrrolidone provided by the present invention comprise the following components in parts by weight: 75 parts of cyprodinil, 5 parts of modified polyvinyl pyrrolidone, 8 parts of polycarboxylate, 2 parts of sodium dodecylbenzene sulfonate, 2 parts of sodium carboxymethyl starch, 3 parts of ammonium sulfate, and 5 parts of bentonite.

[0017] The present invention also provides a method for preparing the above pesticide water dispersible granules, characterized in that it comprises the following steps:

[0018] (1) The active component, modified polyvinyl pyrrolidone, dispersant, disintegrant and filler are uniformly mixed, and during the mixing process, air flow milling is performed to prepare fine powder of 800-1000 mesh;

[0019] (3) collecting the fine powder obtained in step (1) and mixing again to collect powder with a particle size of 30-70 μm;

[0020] (3) The powder collected in step (2) is kneaded with water, granulated, dried and sieved to obtain 20-40 mesh columnar uniform granules.

[0021] The present invention also provides a method for preparing the modified polyvinyl pyrrolidone, which comprises the following steps: adding chlorosulfonic acid dropwise to polyvinyl pyrrolidone at 120-160° C. to carry out a sulfonation reaction; after the reaction is completed, slowly adding the obtained reaction solution into a sodium hydroxide aqueous solution, and controlling the pH value thereof to 7-9; and then spray-drying the obtained mixed solution to obtain the modified polyvinyl pyrrolidone.

[0022] In a preferred embodiment, in the process of preparing modified polyvinyl pyrrolidone, the reaction temperature is 120-160°C, which can be but not limited to 120°C, 130°C, 135°C, 140°C, 145°C, 150°C or 160°C. In order to obtain better results, the reaction temperature is 140°C.

[0023] Furthermore, after the addition of chlorosulfonic acid is completed, the reaction is continued by keeping warm for 2 to 3 hours, preferably 2 hours.

[0024] In a preferred embodiment, the mass ratio of polyvinyl pyrrolidone to chlorosulfonic acid is 1:0.1-0.5, which may be but not limited to 1:0.1, 1:0.11, 1:0.12, 1:0.13, 1:0.15, 1:0.2, 1:0.3 or 1:0.5. In order to obtain better effects, the mass ratio of polyvinyl pyrrolidone to chlorosulfonic acid is 1:0.12.

[0025] Furthermore, the polyvinyl pyrrolidone mentioned in the present invention is polyvinyl pyrrolidone K-30.

[0026] Adopt the technical scheme of the present invention, the advantages are as follows:

[0027] The pesticide water-dispersible granules containing modified polyvinyl pyrrolidone provided by the present invention utilize the hydrophilicity of the modified polyvinyl pyrrolidone to make the modified polyvinyl pyrrolidone have unique dispersibility, adhesion, solubility and film-forming properties. The prepared pesticide water-dispersible granules have stable physical and chemical properties and are not easy to decompose and deteriorate, thus solving the difficulty of producing corresponding preparations of some low-melting-point and easy-to-coke original drugs. DETAILED DESCRIPTION

[0028] The pesticide water dispersible granules containing modified polyvinyl pyrrolidone of the present invention are further described by the following examples, but these examples do not constitute any limitation to the present invention.

[0029] Preparation of modified polyvinyl pyrrolidone:

[0030] 200g of polyvinyl pyrrolidone K-30 was put into a 500ml reaction bottle and heated to 140°C. After it was completely dissolved, 24g of chlorosulfonic acid was added dropwise for 0.5 hour. After the addition was completed, the mixture was kept warm for 2 hours. After the insulation was completed, the reaction solution was slowly added to 165g of 10% sodium hydroxide aqueous solution, and the pH value was controlled to 7-9. The resulting mixed solution was then spray-dried to obtain 228g of modified polyvinyl pyrrolidone.

[0031] The modified polyvinyl pyrrolidone used in the following examples was prepared by the above method.

[0032] Embodiment 1: 25% butyclobutanil water dispersible granules, which comprises the following components in parts by weight:

[0033]

[0034] The preparation method is as follows:

[0035] After the active component, modified polyvinyl pyrrolidone, dispersant, disintegrant and filler are crushed, they are premixed in a double cone mixer for 20 minutes according to the formula ratio, and then the mixture is placed in a double screw mixer (I), and the mixture is crushed by a jet mill to obtain a fine powder with a particle size of 800-1000 meshes while mixing, and the fine powder is collected by a cyclone separator and a bag dust collector, and mixed again in a double screw mixer (II) to obtain a uniform powder with a particle size of 30-70μm. Accurately weigh a certain amount of powder in a trough mixer, spray water, knead for 5 minutes, and then add the obtained mixture to an extrusion granulator for granulation, drying, sieving, and obtaining 20-40 mesh columnar uniform particles, metering, and packaging.

[0036] Comparative Example 1: 25% butyclobutanil water dispersible granules, which include the following components in parts by weight:

[0037]

[0038] The preparation method is as follows:

[0039] After the active component, polyvinyl pyrrolidone (K-30), dispersant, disintegrant and filler are crushed, they are premixed in a double cone mixer for 20 minutes according to the formula ratio, and then the mixture is placed in a double helix mixer (I), and the mixture is crushed by a jet mill to obtain a fine powder with a particle size of 800-1000 meshes while mixing, and the fine powder is collected by a cyclone separator and a bag dust collector, and mixed again in a double helix mixer (II) to obtain a uniform powder with a particle size of 30-70μm. Accurately weigh a certain amount of powder in a trough mixer, spray water, knead for 5 minutes, and then add the obtained mixture to an extrusion granulator for granulation, drying, sieving, and obtaining 20-40 mesh columnar uniform particles, which are measured and packaged.

[0040] The samples in Example 1 and Comparative Example 1 were subjected to stability tests, and the results are shown in Table 1.

[0041] Table 1 Stability test data

[0042]

[0043] As can be seen from Table 1, the performance of the 25% butyclobutanil water dispersible granules after storage is more stable when modified polyvinyl pyrrolidone is added in Example 1 compared with the unmodified polyvinyl pyrrolidone (K-30) in Comparative Example 1.

[0044] Embodiment 2: 80% propanil water dispersible granules, which comprises the following components in parts by weight:

[0045]

[0046] The preparation method is as follows:

[0047] After the active component, modified polyvinyl pyrrolidone, dispersant, disintegrant and filler are crushed, they are premixed in a double cone mixer for 20 minutes according to the formula ratio, and then the mixture is placed in a double screw mixer (I), and the mixture is crushed by a jet mill to obtain a fine powder with a particle size of 800-1000 meshes while mixing, and the fine powder is collected by a cyclone separator and a bag dust collector, and mixed again in a double screw mixer (II) to obtain a uniform powder with a particle size of 30-70μm. Accurately weigh a certain amount of powder in a trough mixer, spray water, knead for 5 minutes, and then add the obtained mixture to an extrusion granulator for granulation, drying, sieving, and obtaining 20-40 mesh columnar uniform particles, metering, and packaging.

[0048] Comparative Example 2: 80% propanil water dispersible granules, which include the following components in parts by weight:

[0049]

[0050] The preparation method is as follows:

[0051] After the active component, polyvinyl pyrrolidone (K-30), dispersant, disintegrant and filler are crushed, they are premixed in a double cone mixer for 20 minutes according to the formula ratio, and then the mixture is placed in a double helix mixer (I), and the mixture is crushed by a jet mill to obtain a fine powder with a particle size of 800-1000 meshes while mixing, and the fine powder is collected by a cyclone separator and a bag dust collector, and mixed again in a double helix mixer (II) to obtain a uniform powder with a particle size of 30-70μm. Accurately weigh a certain amount of powder in a trough mixer, spray water, knead for 5 minutes, and then add the obtained mixture to an extrusion granulator for granulation, drying, sieving, and obtaining 20-40 mesh columnar uniform particles, which are measured and packaged.

[0052] The samples in Example 2 and Comparative Example 2 were subjected to stability tests, and the results are shown in Table 2.

[0053] Table 2 Stability test data

[0054]

[0055] As can be seen from Table 2, the performance of 80% propanil water dispersible granules after storage is more stable when modified polyvinyl pyrrolidone is added in Example 2 compared with the unmodified polyvinyl pyrrolidone (K-30) in Comparative Example 2.

[0056] Embodiment 3: 75% cyprodinil water dispersible granules, which comprises the following components in parts by weight:

[0057]

[0058] After the active component, modified polyvinyl pyrrolidone, dispersant, disintegrant and filler are crushed, they are premixed in a double cone mixer for 20 minutes according to the formula ratio, and then the mixture is placed in a double screw mixer (I), and the mixture is crushed by a jet mill to obtain a fine powder with a particle size of 800-1000 meshes while mixing, and the fine powder is collected by a cyclone separator and a bag dust collector, and mixed again in a double screw mixer (II) to obtain a uniform powder with a particle size of 30-70μm. Accurately weigh a certain amount of powder in a trough mixer, spray water, knead for 5 minutes, and then add the obtained mixture to an extrusion granulator for granulation, drying, sieving, and obtaining 20-40 mesh columnar uniform particles, metering, and packaging.

[0059] Comparative Example 3: 75% cyprodinil water dispersible granules, comprising the following components in parts by weight:

[0060]

[0061] After the active component, polyvinyl pyrrolidone (K-30), dispersant, disintegrant and filler are crushed, they are premixed in a double cone mixer for 20 minutes according to the formula ratio, and then the mixture is placed in a double helix mixer (I), and the mixture is crushed by a jet mill to obtain a fine powder with a particle size of 800-1000 meshes while mixing, and the fine powder is collected by a cyclone separator and a bag dust collector, and mixed again in a double helix mixer (II) to obtain a uniform powder with a particle size of 30-70μm. Accurately weigh a certain amount of powder in a trough mixer, spray water, knead for 5 minutes, and then add the obtained mixture to an extrusion granulator for granulation, drying, sieving, and obtaining 20-40 mesh columnar uniform particles, which are measured and packaged.

[0062] The samples in Example 3 and Comparative Example 3 were subjected to stability tests, and the results are shown in Table 2.

[0063] Table 3 Stability test data

[0064]

[0065] As can be seen from Table 3, the performance of the 75% cyprodinil water dispersible granules after storage is more stable when modified polyvinyl pyrrolidone is added in Example 3 compared with the unmodified polyvinyl pyrrolidone (K-30) in Comparative Example 3.

[0066] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, a person skilled in the art should understand that it is still possible to modify the technical solutions described in the aforementioned embodiments, or to perform equivalent replacements on some of the technical features therein. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A pesticide water dispersible granule containing modified polyvinyl pyrrolidone, characterized in that: The invention comprises the following components in parts by weight: 25 parts of butyrochlore, 3 parts of modified polyvinyl pyrrolidone, 2 parts of polycarboxylate, 3 parts of lignin sulfonate, 3 parts of sodium dodecylbenzene sulfonate, 5 parts of ammonium sulfate and 59 parts of bentonite; the modified polyvinyl pyrrolidone is prepared according to the following method: under the condition of 120-160 DEG C, chlorosulfonic acid is added dropwise to polyvinyl pyrrolidone to carry out sulfonation reaction, after the reaction is completed, the obtained reaction solution is slowly added to a sodium hydroxide aqueous solution, and the pH value thereof is controlled to 7-9, and then the obtained mixed solution is spray-dried to obtain the modified polyvinyl pyrrolidone.

2. The pesticide water dispersible granules according to claim 1, characterized in that: In the process of preparing modified polyvinyl pyrrolidone, the reaction temperature is 140° C.; the mass ratio of the polyvinyl pyrrolidone to chlorosulfonic acid is 1:0.1-0.

5.

3. The pesticide water dispersible granules according to claim 1, characterized in that: In the process of preparing modified polyvinyl pyrrolidone, the polyvinyl pyrrolidone is polyvinyl pyrrolidone K-30; the mass ratio of the polyvinyl pyrrolidone to chlorosulfonic acid is 1:0.

12.

4. A pesticide water dispersible granule containing modified polyvinyl pyrrolidone, characterized in that: The invention comprises the following components in parts by weight: 80 parts of propanil, 3 parts of modified polyvinyl pyrrolidone, 8 parts of lignin sulfonate, 3 parts of sodium butyl naphthalene sulfonate and 5 parts of sodium sulfate. The modified polyvinyl pyrrolidone is prepared according to the following method: under the condition of 120-160 DEG C, chlorosulfonic acid is added dropwise to polyvinyl pyrrolidone to carry out sulfonation reaction, after the reaction is completed, the obtained reaction solution is slowly added to a sodium hydroxide aqueous solution, and the pH value thereof is controlled to 7-9, and then the obtained mixed solution is spray-dried to obtain the modified polyvinyl pyrrolidone.

5. The pesticide water dispersible granules according to claim 4, characterized in that: In the process of preparing modified polyvinyl pyrrolidone, the reaction temperature is 140° C.; the mass ratio of the polyvinyl pyrrolidone to chlorosulfonic acid is 1:0.1-0.

5.

6. The pesticide water dispersible granules according to claim 4, characterized in that: In the process of preparing modified polyvinyl pyrrolidone, the polyvinyl pyrrolidone is polyvinyl pyrrolidone K-30; the mass ratio of the polyvinyl pyrrolidone to chlorosulfonic acid is 1:0.

12.

7. A pesticide water dispersible granule containing modified polyvinyl pyrrolidone, characterized in that: The invention comprises the following components in parts by weight: 75 parts of cyprodinil, 5 parts of modified polyvinyl pyrrolidone, 8 parts of polycarboxylate, 2 parts of sodium dodecylbenzene sulfonate, 2 parts of sodium carboxymethyl starch, 3 parts of ammonium sulfate and 5 parts of bentonite; the modified polyvinyl pyrrolidone is prepared according to the following method: under the condition of 120-160 DEG C, chlorosulfonic acid is added dropwise to polyvinyl pyrrolidone to carry out sulfonation reaction, after the reaction is completed, the obtained reaction solution is slowly added to a sodium hydroxide aqueous solution, and the pH value thereof is controlled to 7-9, and then the obtained mixed solution is spray-dried to obtain the modified polyvinyl pyrrolidone.

8. The pesticide water dispersible granules according to claim 7, characterized in that: In the process of preparing modified polyvinyl pyrrolidone, the reaction temperature is 140° C.; the mass ratio of the polyvinyl pyrrolidone to chlorosulfonic acid is 1:0.1-0.

5.

9. The pesticide water dispersible granules according to claim 7, characterized in that: In the process of preparing modified polyvinyl pyrrolidone, the polyvinyl pyrrolidone is polyvinyl pyrrolidone K-30; the mass ratio of the polyvinyl pyrrolidone to chlorosulfonic acid is 1:0.12.

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