CN1209022C - Avilamycin water-suspension nano capsule preparation and method for preparing same - Google Patents

Abstract

The present invention discloses an abamectin water-suspending nanocapsule prepared by an emulsion polymerization method. The capsule skin is prepared from a monomer copolymer of styrene, isocyanate, acrylic acid and methacrylic acid, and a capsule core comprises biological source pesticide and veterinary medicine ivermectin as effective components, wherein the content of the ivermectin is from 0.2 to 2%(w/w), the content of the capsule skin is from 5 to 30%(w/w), the content of additives is from 10 to 35%(w/w), and the content of water is proper. The nanocapsule is a monodisperse spherical particle with the average particle diameter of smaller than 100 nanometers. Compared with traditional preparations, the nanocapsule of the present invention has the obvious characteristics of hydrophilic properties of solvents, high dispersivity of effective nanocomponents, high stability of products, and encapsulation for prolonging the drug effect of the nanocapsule. The present invention has the characteristics of super-high efficiency, long-term effect, low toxicity, high safety, economical benefit, environment protection, etc., and can be widely used for preventing and controlling parazoon and various pests on fruit trees, vegetables, flowers, cotton, tobacco, etc.

Description

Outstanding nano-capsule of abamectin water and preparation method thereof

Technical field

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

Background technology

Avermectin is a kind of biogenic pesticide, the veterinary drug through explained hereafter such as microbial fermentation, purifications, be applied in the agricultural production, can prevent and treat intractable insect, the evil mite of plants such as fruit tree, vegetables, flowers, cotton, tobacco, as 80 various pests such as Americal rice leaf miner, diamond-back moth, two spotted spider mite, cabbage caterpillar, root-knot nematode, cotton bollworm, pear suckers; In livestock breeding, be used to kill multiple parasites such as gastrointestinal nematode in the animal body and external warble, red torsalo maggot, sheep nose fly maggot, psoroptes communis, it is one of best, with fastest developing speed, most widely used biogenic pesticide of present control efficiency in the world, its wide spectrum, super-high-efficient, consumption are few, low-residual, characteristics such as be difficult for developing immunity to drugs, and have determined it will play an important role aspect control diseases and pests of agronomic crop.The main formulation of disclosed Avermectin 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, not only wasted resource but also serious environment pollution.

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

3, active ingredient poor permeability remains in effective 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 Avermectin 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 abamectin 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 Avermectin novel form.

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 draw polymer particle with different internal structure, 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 abamectin water of the present invention particularly is expressed as follows by weight percentage:

Avermectin: 0.2%～5%

Mix monomer: 5%～30%

Emulsifier: 7%～20%

Additive: 3%～15%

Initator: 0.05%～1%

Deionized water: surplus

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

Additive is dispersant and protecting colloid.

Initator is azo class or oxidation-reduction 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 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 for use, 4 '-methyl diphenylene diisocyanate, poly methylene poly phenyl poly isocyanate, hexamethylene vulcabond etc.

Use wherein two or more monomer to carry out polymerisation, form the capsule skin of capsule.The capsule-core of capsule is the former medicine of Avermectin.

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 polymethyl-benzene olefin(e) acid salt 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.

Also can contain auxiliary agent in the outstanding Nano capsule of abamectin water of the present invention, auxiliary agent is one or more in preservative, defoamer and the antifreezing agent, and its content is expressed as with percentage by weight and accounts for 5%～8% of total composition.

The preservative that is fit to is commonly used in the polymer emulsion, as penta sodium pentachlorophenate, adjacent chloro-m-cresol, daconil M.

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 continuous phase 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, 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 also be changed within the specific limits.In system, the amount of disperse phase be generally by weight 15%～50%, the concentration of each material following (by weight) in the disperse phase:

Mix monomer 5%～30%

Pesticidal active substance Avermectin 0.2%～5%

Additive is generally 10%～35%, is preferably 12%～25%

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

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

(2) Avermectin is mixed with monomer, additive;

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

(4) emulsion is heated to 50～90C, 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 usage amount of the present invention can change in certain scope, depends on the object that is applied, and the content of Avermectin in Nano capsule.

The present invention compares with conventional art, and obtained technological progress is:

1, its 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 is less than 100 nanometers, only is the one thousandth of microcapsules or littler, 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 cost 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 abamectin 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; The 0.5g Avermectin is dissolved in 7g styrene, 8g butyl acrylate, the acrylic acid mix monomer of 0.2g; 6g polyoxyethylene nonylphenol ether (NP-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 Avermectin, 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 Avermectin 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; The 1g Avermectin is dissolved in the mix monomer of 4g ethyl acrylate, 7g butyl acrylate; 5g polyoxyethylene nonylphenol ether (NP-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 Avermectin, 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, was incubated 2 hours, cooling; Add auxiliary agent, discharging.The content of Avermectin is 0.9% in the product.

Claims (6)

1, the outstanding nano-capsule of abamectin water, it is characterized in that: composition is expressed as by weight:

Avermectin: 0.2-5%

Mix monomer: 5-30%

Emulsifier: 7-20%

Additive: 3-15%

Initator: 0.05-1%

Deionized water: surplus

Wherein, mix monomer is two or more in vinyl monomer, acrylic monomer, metha crylic monomer and the isocyanate-monomer;

Additive is dispersant, protecting colloid;

Initator is the initator of azo class thermal initiator or oxidation-reduction system;

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

2, by the outstanding nano-capsule of the described abamectin water of claim 1, contain auxiliary agent in it is characterized in that forming, auxiliary agent is one or more in preservative, defoamer and the 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 abamectin water of claim 1, it is characterized in that: mix monomer is selected 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.

4, by the outstanding nano-capsule of the described abamectin water of claim 1, it is characterized in that: emulsifier is nonionic emulsifier 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.

5, by the outstanding nano-capsule of the described abamectin water of claim 2, it is characterized in that: preservative is selected penta sodium pentachlorophenate, adjacent chloro-m-cresol or daconil M 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, wherein one or more for use.

6, a kind of method for preparing the outstanding nano-capsule of abamectin water as claimed in claim 1 is characterized in that comprising the steps:

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

(2) Avermectin is mixed 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.