CN1491541A - Pesticide water suspending nano capsule prepn and its preparing method - Google Patents

Abstract

The present invention discloses water suspended nano pesticide capsule preparation prepared via emulsion polymerization process. It has capsule shell of styrene, isocyanate, acrylate and methacrylate copolymer, and core comprising ididacloprid, high effect cypermethrin or diflubenzuron as effective component; contains pesticide 0.2-5 wt%, capsule shell 5-30 wt%, additive 10-35 wt% and water in proper proportion. The nano capsule is disersive spherical particle of size smaller than 100 nm. Compared with traditional pesticide preparation forms, the present invention has the features of water based solvent, nano level dispersive effective component, high stability, etc. and may be used in killing various pests of fruit tree, vegetable, flower, cotton, tobacco, etc.

Description

Outstanding nano-capsule of agricultural chemicals water and preparation method thereof

Technical field

The present invention relates to the outstanding nano-capsule of a kind of agricultural chemicals water, belong to the preparation technology of agricultural chemicals, veterinary drug.

Background technology

Agricultural chemicals is the product of Avermectin through obtaining behind the chemical improvement, is a kind of semisynthetic antibiotics insecticides agricultural chemicals.To the drug effect of lepidoptera pest significantly improve than Avermectin and toxicity lower, be a kind of novel biopesticide.The agent of agricultural chemicals benzoate pesticide has super-high-efficient, nontoxic, nuisanceless, dual insect lethality rate height, the less characteristics such as such environmental effects that are subjected to.Compare with other series of products of Ah's Avermectin, the Lepidoptera harmful shackles worm activity thorny at agricultural community improved 1-3 the order of magnitude, can use on economic crops such as vegetables, tobacco, tealeaves.About per hectare land for growing field crops dosage 2-gram, insect had good control efficiency.The few low-residual of its wide spectrum, super-high-efficient, consumption, characteristics such as be difficult for developing immunity to drugs have determined it will play an important role aspect control diseases and pests of agronomic crop.The main formulation of disclosed agricultural chemicals is a missible oil in the prior art, and it is as a conventional dosage forms of agricultural chemicals, control efficiency still can, but have following problem:

1, contain a large amount of organic solvents, as toluene, dimethylbenzene etc., the organic solvent emission that causes annual kiloton meter is to occurring in nature, and the waste resource is serious environment pollution again.

Need be diluted with water to emulsion when 2, using, effective ingredient belongs to micron order and disperses, and effective ingredient bad dispersibility, effective rate of utilization are low, cause pesticide dosage big, cause this rising of farming and agricultural chemicals residual in a large number, seriously influence the quality of agricultural product.

3, effective ingredient poor permeability remains in active ingredient a large amount of decomposition wastes because of environmental factors such as light, air cause on blade face.

4, the field planting of biogenic pesticide in soil is relatively poor, and the special ecotope of soil often suppresses the drug effect of biogenic pesticide, makes the large tracts of land popularization of biopesticide be subjected to certain limitation.

Compare with missible oil, the microemulsion of agricultural chemicals has solved the problem of water baseization and high dispersive preferably, but is not long-acting dosage form, can not sustained release, the more important thing is that cost is higher, and effect is unsatisfactory.

Summary of the invention

The object of the present invention is to provide a kind of agricultural chemicals water to hang nano-capsule, it has high dispersive, super-high-efficient, advantage such as long-acting, water base, with low cost, is the better biogenic pesticide of a kind of effect, veterinary drug pesticides new formulation.

The objective of the invention is to realize based on following design.Form principle according to polymer particle, in the emulsion polymerization process, suitably regulate monomer ratio, dose auxiliary agent, control reaction condition, can obtain having the polymer particle of different internal structures, difformity, different-grain diameter.Therefore, as long as choose monomer and proportioning thereof, additive, the control reaction condition can obtain the Nano capsule particle.

The composition of the outstanding Nano capsule of agricultural chemicals water of the present invention particularly is expressed as follows by weight percentage:

Agricultural chemicals: 0.2～5%

Mix monomer: 5～30%

Additive: 15～35%

Initator: 0.05～1%

The deionized water surplus

Wherein, polymerization single polymerization monomer is vinyl monomer, acrylic monomer, metha crylic monomer and isocyanate-monomer.

Additive is emulsifier, dispersant and protecting colloid.

Initator is persulfate, azo class or redox system initator.

The capsule number average bead diameter is less than 100 nanometers.

Vinyl monomer, acrylic monomer, metha crylic monomer and isocyanate-monomer, can select for use styrene, vinylacetate, acrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate, butyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, N hydroxymethyl acrylamide, toluene di-isocyanate(TDI), 4,4 '-methyl diphenylene diisocyanate, poly methylene poly phenyl poly isocyanate, hexamethylene vulcabond etc.

Use wherein two or more monomers to carry out polymerisation, form the capsule skin of capsule.

The capsule-core of capsule is a pesticide original medicine.

The emulsifier that is fit to is nonionic emulsifier and anion emulsifier; Nonionic emulsifier can be selected tween, this dish, polyoxyethylene nonylphenol ether, OPEO etc. for use; Anion emulsifier can be selected lauryl sodium sulfate, neopelex, calcium dodecyl benzene sulfonate etc. for use.For controlling the capsule number average bead diameter less than 100 nanometers, the emulsifier consumption is not less than 7%, and preferably consumption is 7%-20%.

The dispersant that is fit to is the copolymer of poly-methyl acrylate and polyacrylate, low molecular weight phenylethylene-maleate.

The protecting colloid that is fit to is many materials commonly used, can be preferably: materials such as polyvinyl alcohol, Sodium Polyacrylate, methylcellulose, carboxymethyl cellulose, pectate, gelatin, gum Arabic, PEO.

Can also contain auxiliary agent in the outstanding nano-capsule of agricultural chemicals water of the present invention, auxiliary agent is one or more in preservative, defoamer and the antifreezing agent, and its content is expressed as the 5-8% that accounts for total composition with percentage by weight.

The preservative that is fit to is commonly used in the polymer emulsion, as benzene two eyeballs between penta sodium pentachlorophenate, adjacent chloro-m-cresol, tetrachloro.

The defoamer that is fit to is the product that can conveniently use, as silane derivative dimethyl silicone polymer class, tributyl phosphate, poly propane diols etc.

The antifreezing agent that is fit to has ethylene glycol, glycerine, propane diols, 2-Butoxyethyl acetate, urea, sucrose etc.

The average grain diameter of the particle of disperse phase is 50 nanometers, is not more than 100 nanometers.

The water of nano-capsule of the present invention is that preservative, defoamer and antifreezing agent are formed by water and additive such as emulsifier, dispersant, protecting colloid and auxiliary agent substantially, and preferred ingredients is top those materials of mentioning.Water can also comprise a spot of dispersed phase component in addition.

Nano-capsule of the present invention is formed and can be changed within the specific limits.In system, the amount of disperse phase is generally 15-50% by weight, the concentration of each material following (by weight) in the disperse phase:

Mix monomer 5-30%;

Pesticidal active substance agricultural chemicals 0.2-5%;

Additive is generally 10-35%, is preferably 12-25%.

The preparation method of the outstanding nano-capsule of agricultural chemicals water of the present invention comprises the steps:

(1) initator is dissolved in the deionized water, and is stand-by;

(2) agricultural chemicals mixes with monomer, additive;

(3) mixture with gained is scattered in the water under high-speed stirred, forms emulsion;

(4) emulsion is heated to 50-90 ℃, adds initiator solution, reacted 1-16 hour, be incubated 0.5-3 hour;

(5) add auxiliary agent, cooling discharge.

Prepare emulsion, can select the device of the strong shearing force of many suitable generations for use.

The inventive method is normally carried out under normal pressure.

Nano-capsule of the present invention needs dilute with water when reality is used, use with conventional method, for example passes through spray application.

Nano capsule of the present invention and usage amount can change in certain scope, depend on to be applied object, and the content of methylamino rhzomorph in Nano capsule.

The present invention compares with technology in the past, and obtained technological progress is:

1, particle diameter is very little, and surface tension is low, so it has fabulous permeability, wetability, levelability and rheological characteristic, can directly infiltrate in the fine capillary channel of plant; Its particle number average bead diameter only is the one thousandth of microcapsules or littler less than 100 nanometers, can make the agricultural chemicals high degree of dispersion.

2, the electric double layer of the stable dependence cyst wall self of nano-capsule particle is that a kind of chemical bond is made a concerted effort, and compares with the dispersion mechanism of microemulsion, and stability improves.

3, solvent is a water, pollutes for a short time, has reduced cost.

4, the function that has sustained release has prolonged lasting period of same dose agricultural chemicals, has improved the availability of agricultural chemicals, has reduced dosage, thereby has reduced the pollution to environment of agricultural basis and agricultural chemicals.

5, suppress medicine decomposition and loss that environmental factor (as: light, heat, rainwater, soil, microorganism and other chemical substance) causes, improved the stability of medicament itself, helped ecotope.

6, reduce acute toxicity, phytotoxicity and fish toxicity.

The outstanding nano-capsule of agricultural chemicals water has solved the problem of water baseization, high degree of dispersionization, stabilisation and the spansuleization of preparation comprehensively, and its drug effect is higher than other formulation, cost is lower than other common formulations, therefore has important generalization and application value.

Embodiment

The present invention illustrates by the following example.

Embodiment one:

The 0.1g ammonium persulfate is dissolved in the 20g water (was divided into two parts) by 4: 1, stand-by; 0.5g pesticide activity thing is dissolved in 7g styrene, 8g butyl acrylate, the acrylic acid mix monomer of 0.2g; 6gOP-40,1g lauryl sodium sulfate are dissolved in the polyvinyl alcohol water solution of 50g 2%, put into a container that has a stirring, under agitation, add the mix monomer that is dissolved with the pesticide activity thing, be dispersed into emulsion, put into reaction vessel.Heating maintains the temperature at 70 ± 2 ℃, adds first part of initator, reacts 6 hours, is incubated 1 hour, makes seed emulsion; Drip 1.5g styrene, 1.5g butyl acrylate, 2g toluene di-isocyanate(TDI) mix monomer and second part of initator, dripped 1 hour, be incubated 2 hours, cooling; Add auxiliary agent, discharging.The content of agricultural chemicals active matter is 0.5% in the product.

Embodiment two:

The 0.1g potassium peroxydisulfate is dissolved in the 10g water (was divided into two parts by 4: 1), the 1g acrylamide is dissolved in the 10g water, and is stand-by; 1g pesticide activity thing is dissolved in the mix monomer of 4g ethyl acrylate 7g butyl acrylate; 5gOP-40,4g lauryl sodium sulfate, 4g sodium polymethacrylate are dissolved in 60g water, put into a container that has a stirring, under agitation, add the mix monomer that is dissolved with the pesticide activity thing, be dispersed into emulsion, put into reaction vessel.Heating maintains the temperature at 70 ± 2 ℃, adds first part of initator and acrylamide aqueous solution, reacts 6 hours, is incubated 1 hour, makes seed emulsion; Drip 1g ethyl acrylate, 1g butyl acrylate, 2g 4,4 '-methyl diphenylene diisocyanate mix monomer, dripped 1 hour, be incubated 2 hours, cooling; Add auxiliary agent, discharging.The content of agricultural chemicals active matter is 0.9% in the product.

Claims (6)

1, the outstanding nano-capsule of agricultural chemicals water is characterized in that, forms by weight:

Agricultural chemicals: 0.2-5%

Mix monomer: 5-30%

Additive: 10-30%

Initator: 0.05-1%

The sub-water of degranulation: surplus

Wherein, mix monomer is vinyl monomer, acrylic monomer, metha crylic monomer and isocyanate-monomer.

Additive is emulsifier, dispersant, protecting colloid.

Initator is the initator of persulfuric acid salt, azo class or redox system.

The capsule number average bead diameter is less than 100 nanometers.

2, by the outstanding nano-capsule of the described agricultural chemicals water of claim 1, contain auxiliary agent in it is characterized in that forming, auxiliary agent is one or more of preservative, defoamer and antifreezing agent, its content is expressed as 5～8% of total composition with percentage by weight.

3, by the outstanding nano-capsule of the described agricultural chemicals water of claim 1, it is characterized in that: mix monomer is selected two or more the material in the following material for use, they are: styrene, acrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate, butyl methacrylate, N hydroxymethyl acrylamide, toluene di-isocyanate(TDI), 4,4 '-methyl diphenylene diisocyanate, many methylenes level polyphenyl polyisocyanate, hexamethylene vulcabond etc.

4, by the outstanding nano-capsule of the described agricultural chemicals water of claim 1, it is characterized in that: emulsifier is nonionic or anion emulsifier, and nonionic emulsifier is selected tween, this dish, polyoxyethylene nonylphenol ether, OPEO for use; Anion emulsifier is selected lauryl sodium sulfate, neopelex, calcium dodecyl benzene sulfonate for use; Dispersant is the copolymer of poly-methyl acrylate, low molecular weight phenylethylene-maleate; Protecting colloid is polyvinyl alcohol, Sodium Polyacrylate, methylcellulose, carboxymethyl cellulose, pectate, gelatin, gum Arabic, PEO etc.

5, by the outstanding nano-capsule of the described agricultural chemicals water of claim 2, it is characterized in that: preservative is selected benzene two eyeballs between penta sodium pentachlorophenate, adjacent chloro-m-cresol or tetrachloro for use; Defoamer is selected dimethyl silicone polymer class, tributyl phosphate, poly propane diols for use; Antifreezing agent is selected ethylene glycol, glycerine, propane diols, 2-Butoxyethyl acetate, urea, sucrose for use.Wherein one or more.

6, the preparation method of the outstanding Nano capsule of a kind of agricultural chemicals water is characterized in that comprising the steps:

(1) initator is dissolved in the deionized water, stand-by;

(2) agricultural chemicals mixes with monomer, additive;

(3) mixture with gained is scattered in the water under high-speed stirred, forms emulsion;

(4) emulsion is heated to 50～90 ℃, adds initiator solution, reacted 1～16 hour, be incubated 0.5～3 hour;

(5) add auxiliary agent, cooling discharge.