WO2009086741A1 - Water soluble granule of spinosad and its preparation - Google Patents

Abstract

The invention provides a water soluble granule of spinosad. It is made from (by wt%) spinosad 0.5-40%, emulsifier 1-30%, dispersing agent 1-10%, wetting agent 1-5%, binder 2-4%, stabilizer 1-3% and the rest is filling material. The invention comprises no or small toxic and inflammable aromatic hydrocarbon solvent, therefore the risk of burning and exploding during manufacture, storage and transportation can be reduced. Its advantages include no poison and pollution, no unpleasant odor, low eye irritation, higher safety for producers, transporters and users.

Description

 Spinosad water soluble granule and preparation method thereof

 The present invention relates to a novel dosage form of the insecticide, and more particularly to a water-soluble granule containing spinosyn and a preparation method thereof. Background technique

 With the increasing awareness of environmental protection and the importance attached by governments to the ecological environment, high-efficiency, low-toxic, low-residue, non-polluting environmentally-friendly bio-pesticide and chemical pesticides are needed for crop pest control and pollution-free production. Demand is growing.

 Spinosad, also known as spinosad, is a macrocyclic lactone-free and highly effective biocide extracted from the fermentation broth of Saccharopolyspora spinosa. The spinosyn acts in a novel manner and can continuously activate the target insect acetylcholine nicotinic receptor, but its binding site is different from nicotine and imidacloprid. Spinosad can also affect GABA receptors, but the mechanism of action is unclear. It is not known whether there is cross-resistance with other types of pesticides. These compounds can cause rapid death of target herbivorous insects such as caterpillars, leaf miner, thrips, and leaf-feeding beetles.

 There are many types of insecticides for plant protection. The most widely used dosage forms in various countries are emulsifiable concentrates, suspending agents, wettable powders, powders, granules, liquids, poison baits, mother liquors, and mother powders. As we all know, emulsifiable concentrate contains a large amount of organic solvents, which are easy to volatilize and ignite, poisonous to humans and plants, pollute the environment, and inconvenient to transport. Wet powders have a large amount of dust in production and use, pollute the environment and affect the health of operators. At present, the development trend of pesticide formulations is mainly to promote the development of environmentally friendly new dosage forms, such as: 1. Liquid preparations tend to be water-based. Water emulsion (EW), microemulsion (ME), aqueous suspension (SC), water-soluble liquid (SL), etc. are representative new forms of water-based preparations. The common feature is that water replaces a large amount of organic solvents and reduces solvents. Waste and pollution, reduce the toxicity of the preparation, improve safety, is a new dosage form to replace emulsifiable concentrate. 2. The solid preparation is granulated. The powder preparation is granulated to avoid dust pollution, and packaging is also the direction of dosage form research. Water dispersible granules (WDG) are representative granules. The dosage form has a granular appearance and is rapidly disintegrated and dispersed in water when used, thereby forming a highly suspended dispersion system for use in spray application. The preparation content and suspension rate are much higher than wettable powder, good fluidity, no dust pollution, convenient packaging, storage and transportation. It is a new dosage form integrating the advantages of wettable powder, suspoemulsion and granules. However, these dosage forms do not combine the advantages of both, but also manifest. Summary of the invention

The object of the present invention is to overcome the disadvantages of the prior art described above and to provide a substitute for a large amount of organic solvent with water. It reduces solvent waste and pollution, reduces the toxicity of the preparation, improves safety, and has a granular appearance. The spinosad-containing water-soluble granules (WSG) which are rapidly disintegrated and dispersed in water during use and a preparation method thereof.

 In order to solve the above technical problem, the present invention is achieved by the following technical solutions:

 A spinosyn water-soluble granule, mainly made of the following weight percentages:

 Spinosad: 0. 5~40%;

 Emulsifier: 1~30%;

 Dispersing agent: 1~10%;

 Wetting agent: 1~5 %;

Binder: 2~4% _;

 Stabilizer: 1~3 %;

 The balance is a filler.

 The spinosyn water-soluble granule of the present invention, wherein the emulsifier is selected from the group consisting of castor oil ethylene oxide adduct, alkylphenol ethoxylate, benzyl phenol polyoxyethylene ether and the like, phenethyl phenol One or a mixture of polyoxyethylene ether or fatty alcohol polyoxyethylene ether and the like.

The alkylphenol ethoxylate may be nonylphenol ethoxylate, octylphenol ethoxylate, etc.; the benzyl phenol ethoxylate and the like may be benzyl phenol ethoxylate, a benzyl alkyl phenol polyoxyethylene ether or the like; the fatty alcohol polyoxyethylene ether and the like may be a product containing lauryl alcohol as a main component C _n H _2n+1 0 (E0) _m H, wherein n=12~ 16, m = 15~30.

 The spinosyn water-soluble granule of the present invention, wherein the dispersing agent is selected from the group consisting of alkylnaphthalenesulfonate, bisnaphthalenesulfonate formaldehyde condensate or sodium lignosulfonate.

 The alkylnaphthalenesulfonate may be a pull-off powder BX, a pull-up powder AC or the like; and the bisnaphthalenesulfonate formaldehyde condensate may be a dispersant N, a dispersant NN0 or the like.

 The spinosyn water-soluble granule of the present invention, wherein the wetting agent is selected from the group consisting of alkylbenzenesulfonate, fatty acid amide N-methylsulfonate, alkylaryl polyoxyethylene ether sulfate or Two mixtures.

 The spinosyn water-soluble granule of the present invention, wherein the binder is one or a mixture of two selected from the group consisting of β-cyclodextrin, polyvinyl alcohol, and methyl cellulose.

 The spinosyn water-soluble granule of the present invention, wherein the stabilizer is selected from the group consisting of borax and sodium benzoate.

 The spinosyn water-soluble granule of the present invention, wherein the filler is selected from one or a mixture of hydrogencarbonate, anhydrous citric acid, maltose, and anhydrous sodium sulfate.

The preparation method of the spinosyn water-soluble granules of the present invention is as follows: the materials are homogenized, kneaded and extruded granulated according to the ratio, dried under vacuum at 65 to 75 ° C for 1 to 2 hours, sieved, sieved The product is packaged after testing; the product that cannot pass the sieve Repeat the above steps for the product that cannot pass through the sieve.

 The specific preparation method comprises the following steps:

1 homogenization: mixing the spinosyn drug with binder and wetting agent in 50~60 ° C water, stirring and homogenizing under 420~450 kg / cm ² high pressure;

 2 spraying the above-mentioned liquid mixture after homogenization to form a composite parent drug;

3 kneading: After the emulsifier is thermally dissolved, it is mixed with the dispersing agent, the stabilizer, the filler and the composite parent drug at a temperature of 45 to 50 ° C, and then stirred and kneaded under a pressure of 4 to 6 kg / cm ^{2 to} obtain Group agent

4 extrusion granulation: the group is extruded under the pressure of 6~12 kg / cm ² into columnar particles;

 5 The columnar particles were vacuum dried at 70 ° C for 1 hour, and then sieved and shaped.

 The water-soluble granules of the invention meet the requirements of the current development trend of pesticides by replacing the organic solvents such as xylene, methanol and toluene with the aqueous solvent, the solid granulation or tableting of the drug form, the high content of the pesticide and the functionalization. The adhesive is embedded in the original drug and the stability and anti-oxidation effect of the stabilizer, so that the anti-radiation and illumination ability of the original drug is improved, and the shelf life of the drug is prolonged; the bicarbonate and citric acid in the filler can effervescent The role of the agent to promote the dissolution of the granules. The water-soluble granule of the invention can be quickly dissolved in water, has high dispersing rate, has no floating and sinking phenomenon, has a large amount of organic solvent replaced by water, reduces solvent waste and pollution, reduces preparation toxicity, improves safety, and has appearance as granules. It has the characteristics of rapid disintegration and dispersion in water, convenient transportation and storage, and long shelf life. The preparation method is simple, easy to operate and control.

 Compared with the existing mainstream insecticide dosage forms, the invention contains no or only a small amount of toxic and flammable aromatic hydrocarbon solvents, thereby avoiding flammable and explosive phenomena during production, storage and transportation. This dosage form has no unpleasant toxic odor, is less irritating to the eyes, reduces environmental pollution, and greatly improves the safety of production, storage, transportation and users. Therefore, after industrialization, not only the economic benefits are obvious, but also the development of high-tech green pesticide technology is promoted. It has obvious social benefits for promoting environmental protection and is the research direction of sustainable development. detailed description

 The present invention will be further described below in conjunction with the embodiments:

Example 1

Preparation process of spinosad water-soluble granules:

1 Preparation: Prepare the raw materials according to the following formula:

 Spinosad: 0.5%;

 Castor oil ethylene oxide adduct: 5%;

Sodium dodecylbenzene sulfonate: 4%; --cyclodextrin: 1.5%;

 Dispersant NN0: 4%;

 Sodium benzoate: 1%;

 Sodium bicarbonate: 44%;

 Anhydrous citric acid: 40%;

2 Mixing the spinosyn drug with β-cyclodextrin and sodium dodecylbenzenesulfonate in water at 55 ° C, stirring and homogenizing under a high pressure of 420 kg / cm ² , and conducting the homogenized liquid mixture Spray drying to form a composite parent drug;

3 After the castor oil ethylene oxide adduct is thermally dissolved, it is mixed with dispersing agent NN0, sodium benzoate, sodium hydrogencarbonate, anhydrous citric acid and compound parent drug at 45 ° C, and then at 6 kg / cm. ² stirring under pressure, kneading evenly, to obtain a bolus;

4 squeezing the granules into columnar granules under a pressure of 8 kg/cm ² ;

 5 The columnar particles are vacuum dried at 70 ° C for 1 hour, and then sieved. The sieved product is packaged after testing; the product that cannot pass through the sieve is repeated after the above process is tested and qualified.

 The above preparations were used for 400g of cotton bollworm per acre, 250g per acre for the cruciferous vegetable pest Plutella xylostella, and 390g per acre for the control of the squash, and the control effect was good. The control effect is shown in Table 1:

 Table 1

Example 2

 The preparation process is the same as in Example 1. The raw material formula used is:

 Spinosad: 10%;

 Nonylphenol ethoxylate: 11%;

 Benzyl phenol ethoxylate: 1%;

 Sodium lignosulfonate: 3%;

 Fatty acid amide N-methylsulfonate: 4%;

 Methyl cellulose: 2%;

 Sodium benzoate: 1%;

Maltose: 30%; Anhydrous citric acid: 38%.

 This preparation used 21g per mu for cotton bollworm, 1 lg per acre for the cruciferous vegetable pest Plutella xylostella, 20g per acre for the prevention and control test, and the control effect is good. The control effect is shown in Table 2:

 Table 2

Example 3

 The preparation process is the same as in Example 1. The raw material formula used is:

 Spinosad: 25%;

 Phenylethyl phenol polyoxyethylene ether: 9%;

 Fatty alcohol polyoxyethylene ether: 2%;

 Pull open powder BX: 1%;

 Pull open powder AC: 2%;

 Sodium dodecylnaphthalene sulfonate: 4%;

 --cyclodextrin: 2%;

 Borax: 1%;

 Anhydrous sodium sulfate: 28%;

 Anhydrous citric acid: 26%.

 For this preparation, 8.5g per mu should be used for cotton bollworm, 4.6g per acre for the cruciferous vegetable pest Plutella xylostella, and 8g per acre for the control of the squash, and the control effect is good. The control effect is shown in Table 3:

 table 3

Example 4 The preparation process was the same as in Example 1, and the formulation used was:

 Spinosad: 40%;

 Phenylethyl phenol polyoxyethylene ether: 9%;

 Fatty alcohol polyoxyethylene ether: 2%;

 Dispersant N: 3%;

 Alkyl aryl polyoxyethylene ether sulfate: 4%;

 Polyvinyl alcohol: 2%;

 Borax: 1%;

 Anhydrous sodium sulfate: 20%;

 Anhydrous citric acid: 19%.

 This preparation used 5g per mu for cotton bollworm, 3g per acre for the cruciferous vegetable pest Plutella xylostella, and 4.8g per acre for the prevention and control test, and the control effect is good. The control effect is shown in Table 4:

 Table 4

Industrial applicability

 Compared with the existing mainstream insecticide dosage forms, the invention contains no or only a small amount of toxic and flammable aromatic hydrocarbon solvents, thereby avoiding flammable and explosive phenomena during production, storage and transportation. This dosage form has no unpleasant toxic odor, is less irritating to the eyes, reduces environmental pollution, and greatly improves the safety of production, storage, transportation and users. Therefore, after industrialization, not only the economic benefits are obvious, but also the development of high-tech green pesticide technology is promoted. It has obvious social benefits for promoting environmental protection and is the research direction of sustainable development. Notes on the application documents: Unless otherwise stated, the percentages referred to in this application are percentages by weight.

Claims

Rights request

The spinosyn: 0. 5~40%;

 Emulsifier: 1~30%;

 Dispersing agent: 1~10%;

 Wetting agent: 1~5 %;

Binder: 2~4% _;

 Stabilizer: 1~3 %;

 The balance is a filler.

 The spinosyn water-soluble granule according to claim 1, wherein the emulsifier is selected from the group consisting of castor oil ethylene oxide adduct, alkylphenol ethoxylate, and benzyl phenol polyoxygen. One or a mixture of vinyl ether and the like, phenethyl phenol ethoxylate or fatty alcohol ethoxylate and the like.

The spinosyn water-soluble granule according to claim 2, wherein the alkylphenol ethoxylate is nonylphenol ethoxylate, octylphenol ethoxylate; the benzyl group Phenolic polyoxyethylene ether and the like are benzylphenol polyoxyethylene ether, benzyl alkyl phenol polyoxyethylene ether; the fatty alcohol polyoxyethylene ether and the like are products containing lauryl alcohol as a main component C _n H _2n+1 0 (E0) _m H, where n=12~16, m=15~30.

 The spinosyn water-soluble granule according to claim 1, wherein the dispersing agent is selected from the group consisting of alkylnaphthalenesulfonate, bisnaphthalenesulfonate formaldehyde condensate or sodium lignosulfonate.

 The spinosyn water-soluble granule according to claim 4, wherein the alkylnaphthalenesulfonate is a pull-open powder BX and a pull-open powder AC; and the bisnaphthalenesulfonate formaldehyde condensate is Dispersant ^ Dispersant NN0.

 The spinosyn water-soluble granule according to any one of claims 1 to 5, wherein the wetting agent is selected from the group consisting of alkyl benzene sulfonate, fatty amide N-methyl sulfonate, and alkane One or two mixtures of aryl ethoxylates.

 The spinosyn water-soluble granule according to claim 6, wherein the binder is one or a mixture of two selected from the group consisting of β-cyclodextrin, polyvinyl alcohol, and methyl cellulose.

 The spinosyn water-soluble granule according to claim 7, wherein the stabilizer is selected from the group consisting of borax and sodium benzoate.

 The spinosyn water-soluble granule according to claim 8, wherein the filler is selected from the group consisting of hydrogencarbonate, anhydrous citric acid, maltose, anhydrous sodium sulfate, or a mixture of two.

A method for preparing a spinosyn water-soluble granule, characterized in that: Quality, kneading and extrusion granulation, vacuum drying at 65~75 °C for 1~2 hours, screening, the sieved product is packaged after testing; the product that can not pass the sieve repeats the above steps.

 The method for preparing a spinosyn water-soluble granule according to claim 10, comprising the steps of:

1 homogenization: mixing the spinosyn drug with binder and wetting agent in 50~60 ° C water, stirring and homogenizing under 420~450 kg / cm ² high pressure;

 2 spraying the above-mentioned liquid mixture after homogenization to form a composite parent drug;

3 kneading: After the emulsifier is thermally dissolved, it is mixed with the dispersing agent, the stabilizer, the filler and the composite parent drug at a temperature of 45 to 50 ° C, and then stirred and kneaded under a pressure of 4 to 6 kg / cm ^{2 to} obtain Group agent

4 extrusion granulation: the group is extruded under the pressure of 6~12 kg / cm ² into columnar particles;

 5 The columnar particles were vacuum dried at 70 ° C for 1 hour, and then sieved and shaped.