CN108124899A - A kind of athomin micro-capsule suspension and preparation method thereof - Google Patents

A kind of athomin micro-capsule suspension and preparation method thereof Download PDF

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CN108124899A
CN108124899A CN201810099421.2A CN201810099421A CN108124899A CN 108124899 A CN108124899 A CN 108124899A CN 201810099421 A CN201810099421 A CN 201810099421A CN 108124899 A CN108124899 A CN 108124899A
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athomin
parts
micro
capsule
thickener
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段永恒
樊渊
丁建云
崔建臣
张建华
姚丹丹
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/46—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=C=S groups
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/16—Interfacial polymerisation

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

A kind of athomin micro-capsule suspension the invention belongs to novel agrochemical formulations field and preparation method thereof.The micro-capsule suspension is using athomin as capsule-core, and oiliness monomeric diisocyanate class compound and aqueous monomers multiamino compound are cyst wall by the polyureas that interface polymerization reaction obtains, and the mass ratio of capsule-core and cyst wall is (1 40):(1‑10).The preparation method of athomin micro-capsule suspension of the present invention makes cyst wall ambient temperature curing, reduce energy consumption, effectively slow down the volatilization of athomin, extend the drug effect phase of athomin, and pass through and add in the stability that appropriate stabilizer improves athomin, the injury to dispenser personnel is alleviated, prepared Microcapsules Size is 0.5 40 μm.

Description

A kind of athomin micro-capsule suspension and preparation method thereof
Technical field
The invention belongs to novel agrochemical formulations fields, and in particular to a kind of athomin micro-capsule suspension and its preparation side Method.
Background technology
Athomin belongs to a kind of botanical biological pesticide, is used at present mainly as antibacterials, fungicide, insecticide, For colourless or light amber oil liquid, volatile, irritant smell, chemical name is allyl group isosulfocyanate, chemistry Formula is C4H5NS.Structural formula such as following formula 1.
Athomin has the anti-corrosion and bacteriostasis property of wide spectrum, all has very strong inhibiting effect to bacterium, mould and yeast, Specifically, the substance is to various plants disease fungus such as sickle-like bacteria, Rhizoctonia solani Kuhn, mould, the dahlia Verticillium dahliaes of root-rot silk capsule Have certain inhibiting effect, the main pathogen to postharvest fruit and vegetable, including grape embrace mould, distiller's yeast bacterium, candida albicans, Mucor and Mould plays the role of inhibiting conidiospore rudiment and mycelia growth；Capsule nematode is embraced to soybean, beet embraces capsule nematode, southern root The nematodes such as tie lines worm, M hapla, Cobb root all have certain insecticidal activity；In addition athomin to lesser grain borer, A variety of storage pests such as booklice, red flour beetle also have very strong smoked kill effect.Although athomin have wide spectrum bactericidal activity with Insecticidal activity, but itself there is strong volatility and tearing property, directly applying crude oil has dispenser personnel certain wound Evil property, and easily cause the volatilization loss of pesticide, it is impossible to its maximum drug action is played, the lasting period is short.
Pesticide micro capsule be it is a kind of utilize natural or synthetic macromolecule filming material, by physics, chemical method formed core- Shell structure small container by pesticide cladding wherein, forms a kind of Novel rural of the microencapsulation with one layer of semipermeability cyst membrane Pharmaceutically dosage form.Capsule is processed to be formed after, them is also needed it steadily to be mixed using certain concentration, is suspended in water as continuous phase In, therefore also known as micro-capsule suspension.It includes cyst wall and capsule-core two parts, and capsule-core is pesticide active ingredient and partial solvent And auxiliary agent, cyst wall are the high molecular materials of film forming.Compared with conventional pesticide dosage form, microcapsule formulations, which have, to be extended the lasting period, improves Pesticide efficacy keeps pharmaceutical activity and stability, pesticide is reduced or avoided loss is decomposed caused by external environment, is subtracted The effects that light toxicity and poisoning and reduction environmental pollution.
The preparation method of pesticide micro capsule has Simple coacervation, complex coacervation, spray drying process, hypobaric drying method, original position to gather Legal, interfacial polymerization etc., wherein, interfacial polymerization have it is easy to operate, production cost is low, normal-temperature reaction is fast, the reaction time The advantages such as short, at present using relatively broad.Interfacial polymerization is to emulsify or be blended in the continuous phase dissolved with wall material by core material In, then microcapsules are formed by monomer polymerization reactions on the surface of core material material.
Existing pesticide micro capsule is mostly suspending agent, but the suspensibility of suspending agent is low, and agglomeration easily occurs, and influences drug Normal use, and reaction process medium temperature spend height can be so that some thermally labile pesticides decompose under high temperature heating conditions.
By literature search, athomin is mainly registered as the use of before seedling processing soil treatment agent in Environmental Protection Agency USA, and dosage form is Content reaches 96% finish；Mitsui Co., Ltd. in 2004 has applied for a patent:Solid containing soil fumigant Substance (CN1878465A) coats athomin using gelatin；The patent of Tianjin Business College application in 2006 (CN200610013059.X) inclusion is carried out using hydroxypropyl-β-cyclodextrin and athomin, obtains a kind of solid of good water solubility Molecular microcapsule powder；The patent (200810112497.0) of Lushiji Bio-Engineering Co Ltd, Wuhan's application in 2008 A kind of Athomin capsule and its application are disclosed, athomin is coated with using aqueous colloidal and glycerine, so as to prepare microcapsules.
At present, athomin is less as the dosage form of Pesticide use, mainly there is aqueous emulsion and finish, microcapsule formulations report phase To less.The preparation of athomin microcapsules is mainly coated with using beta-cyclodextrin, and beta-cyclodextrin is mainly used for food additive and suppression Microbial inoculum is higher for pesticides application cost.
Invention content
The purpose of the present invention is to propose to a kind of athomin micro-capsule suspensions and preparation method thereof.Specific technical solution is such as Under：
A kind of athomin micro-capsule suspension, using athomin as capsule-core, with oiliness monomeric diisocyanate class compound and water Property the polyureas that is obtained by interface polymerization reaction of monomer multiamino compound be cyst wall, the mass ratio of capsule-core and cyst wall is (1- 40):(1-10)。
The capsule-core further includes stabilizer, emulsifier and thickener.
The isocyanate ester compound is polyphenyl polyisocyanate or alkylene diisocyanate；
The multiamino compound is one or more of diethylenetriamine, ethylenediamine, tetraethyl triethylammonium tetrakis；
The stabilizer is rapeseed oil, epoxychloropropane, acetone, acetic acid, glyceryl triacetate, tributyl phosphate, hexichol One or more of ketone, DBPC 2,6 ditertiary butyl p cresol, disodium ethylene diamine tetraacetate, zinc chloride；
The emulsifier is nonionic emulsifier and/or anionic emulsifier；
The thickener is xanthans, Arabic gum, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid One or more of sodium, guar gum, polyvinyl alcohol.
The emulsifier is nonionic emulsifier and anionic emulsifier, and mass ratio is (1:0.1)-(1:100).
The nonionic emulsifier for phenethyl phenol polyethenoxy ether, phenethyl phenol formaldehyde resin polyoxyethylene ether, Phenethyl phenol polyoxyethylene poly-oxygen propylene aether, castor oil polyoxyethylene ether or alkyl phenol polyoxyethylene ether；The anionic Emulsifier is lauryl sodium sulfate, neopelex or calcium dodecyl benzene sulfonate.
Preferably, the emulsifier is castor oil polyoxyethylene ether and the mixture of dodecyl benzene sulfonic acid.
The preparation method of above-mentioned athomin micro-capsule suspension, includes the following steps：
(1) athomin, isocyanate ester compound, stabilizer and emulsifier are uniformly mixed according to a certain ratio, obtain oil Mix liquid；
(2) thickener is dissolved in deionized water, obtains aqueous phase solution；
(3) the oil phase mixed liquor of step (1) is mixed with the aqueous phase solution of step (2), high speed shearing emulsification obtains O/W The fine suspension of system；
(4) fine suspension obtained by mixing slowly step (3), is slowly added dropwise multiamino compound aqueous solution, normal-temperature reaction obtains To athomin micro-capsule suspension.
The step (1) is in terms of parts by weight, matches and mixes by number：Athomin is 1.0-40.0 parts, isocyanates Class compound is 0.1-5.0 parts, and stabilizer is 0.1-6.0 parts, and emulsifier is 0.1-5.0 parts；The step (2) is with parts by weight Number meter, thickener are 0.05-5.0 parts, and the mass percentage of thickener is 0.5%-5.0% in aqueous phase solution；The step (4) it is in terms of parts by weight, multiamino compound aqueous solution is 0.1-5.0 parts, polyamino in multiamino compound aqueous solution The mass percentage for closing object is 0.1%-1%.
Preferably, the step (1) is in terms of parts by weight, matches and mixes by number：Athomin is 20.0 parts, isocyanic acid Ester type compound is 4.0 parts, and stabilizer is 4.0 parts, and emulsifier is 2.5 parts；The step (2) is the thickening in terms of parts by weight Agent is 1.0 parts, and the mass percentage of thickener is 1.0% in aqueous phase solution；The step (4) be in terms of parts by weight, it is more Amino-compound aqueous solution is 2.0 parts, and the mass percentage of multiamino compound is 1% in multiamino compound aqueous solution.
Preferably, in terms of parts by weight, the athomin is 1.0-40.0 parts, isocyanate ester compound 1.0-5.0 Part, stabilizer is 0.5-5.0 parts, and emulsifier is 1.0-4.0 parts, and thickener is 0.1-5.0 parts, and multiamino compound aqueous solution is 1.0-3.0 part；In the multiamino compound aqueous solution mass percentage of multiamino compound be 0.2%-1%, water phase The mass percentage of thickener is 0.5%-5.0% in solution.
In terms of parts by weight, the athomin is 20.0 parts, and isocyanate ester compound is 4.0 parts, stabilizer 4.0 Part, emulsifier is 2.5 parts, and thickener is 1.0 parts, and multiamino compound aqueous solution is 2.0 parts；The multiamino compound is water-soluble The mass percentage of multiamino compound is 1% in liquid, and the mass percentage of thickener is 1.0% in aqueous phase solution.
The condition of the high speed shearing emulsification is：Temperature is 0 DEG C -30 DEG C, rotating speed 1000rpm-6000rpm, and the time is 0.2min-5.0min.Preferably, rotating speed 2000rpm-4000rpm.It is highly preferred that the condition of the high speed shearing emulsification is： Temperature is 20 DEG C, rotating speed 3000rpm, time 0.5min.
The multiamino compound aqueous solution 5-30min is added dropwise, normal-temperature reaction 1-5h.Preferably, the polyamino Compound water solution 10min is added dropwise, normal-temperature reaction 3h.
Beneficial effects of the present invention are；
(1) athomin micro-capsule suspension of the present invention is with oiliness monomeric diisocyanate class compound and aqueous monomers polyamino Compound is cyst wall by the polyureas that interface polymerization reaction obtains, anti-compared to isocyanate ester compound and polymerizeing for organic amine Should, the medium of polymerisation of the present invention is water, at low cost；Reaction rate is more than the polymerisation with organic amine, and the reaction time is short. Compared to isocyanate ester compound and the interface polymerization reaction of water, the reaction rate of polymerisation of the present invention is big, and cyst wall is has Machine sky shape structure, stability are good；Reaction can be completed in the short time at normal temperatures, and production cost is low, be suitble to promote and apply.
(2) cyst wall solidification temperature is no more than 30 DEG C in the preparation method of athomin micro-capsule suspension of the present invention, effectively hinders The volatilization of athomin under the high temperature conditions is stopped；Stabilizer (such as epoxychloropropane) can reduce athomin under the high temperature conditions It decomposes, keeps the activity of athomin, so as to keep the effective concentration of athomin, improve the stability of product；Active ingredient is peppery Root element is coated and slow release by polyureas high molecular material, effectively prevents the photodissociation and hydrolysis of active ingredient, extends holding effect Phase reduces application times and amount of application, can mitigate its injury to dispenser personnel, improve the safety of medication.
(3) the athomin micro-capsule suspension prepared is spherical in shape using optical microphotograph sem observation, and surface is smooth, average grain diameter It is 1.0-40.0 μm, it is good in cold storage (0 ± 1 DEG C) 7 days, heat storage (54 ± 2 DEG C) 14 days stability, it is not easy layering caking.
Specific embodiment
Following embodiment facilitates a better understanding of the present invention.
Embodiment 1：Athomin micro-capsule suspension
1. preparation method
1) prepared by oil phase：By 0.15g emulsifiers (0.10g castor oil polyoxyethylene ether+0.05g calcium dodecyl benzene sulfonates) It adds in the athomin of 2.00g, is uniformly mixed, adds 0.10g stabilizers epoxychloropropane and the oil phase monomer first of 0.20g Benzene -2,4- diisocyanate is uniformly mixed, and obtains oil phase mixed liquor.
2) prepared by water phase：The thickener hydroxyethyl cellulose of 1.00g is dissolved into the deionized water of 99.00g, is obtained 1.00% hydroxyethyl cellulose solution.
3) it mixes：By the thickener hydroxyethyl cellulose solution in the oil phase mixed liquor 2.45g and step 2) in step 1) 16.55g is mixed, and is stirred evenly, the 3000rpm high speed shearing emulsifications 0.5min at 20 DEG C obtains the fine suspension of O/W systems.
4) it polymerize：Fine suspension obtained by step 3) is mixed slowly, 1% ethylenediamine solution of 1.00g is slowly added dropwise, 5min is added dropwise, and mixes slowly, then normal-temperature reaction 3h obtains athomin micro-capsule suspension.
2. study on the stability
Optical microphotograph Microscopic observation obtains the 10% athomin micro-capsule suspension that average grain diameter is 3.0-10.0 μm, warp Under conditions of 14 days, resolution ratio is respectively 0.22%, 3.04% for cold storage (0 ± 1 DEG C) 7 days, heat storage (54 ± 2 DEG C).
Embodiment 2：Athomin micro-capsule suspension
1. preparation method
1) prepared by oil phase：By 0.15g emulsifiers (0.10g castor oil polyoxyethylene ether+0.05g calcium dodecyl benzene sulfonates) It adds in the athomin of 2.00g, is uniformly mixed, adds 0.20g stabilizers epoxychloropropane and the oil phase monomer first of 0.20g Benzene -2,4- diisocyanate is uniformly mixed, and obtains oil phase mixed liquor.
2) prepared by water phase：The thickener hydroxyethyl cellulose of 1.00g is dissolved into the deionized water of 99.00g, is obtained 1.00% hydroxyethyl cellulose solution.
3) it mixes：By the thickener hydroxyethyl cellulose solution in the oil phase mixed liquor 2.45g and step 2) in step 1) 16.55g is mixed, and is stirred evenly, the 3000rpm high speed shearing emulsifications 0.5min at 20 DEG C obtains the fine suspension of O/W systems.
4) it polymerize：Fine suspension obtained by step 3) is mixed slowly, 0.5% ethylenediamine solution of 1.00g is slowly added dropwise, 5min is added dropwise, and mixes slowly, then normal-temperature reaction 3h obtains athomin micro-capsule suspension.
2. study on the stability
Optical microphotograph Microscopic observation obtains the 10% athomin micro-capsule suspension that average grain diameter is 3.0-10.0 μm, warp Under conditions of 14 days, resolution ratio is respectively 0.10%, 2.58% for cold storage (0 ± 1 DEG C) 7 days, heat storage (54 ± 2 DEG C).
Embodiment 3：Athomin micro-capsule suspension
1. preparation method
1) prepared by oil phase：By 0.15g emulsifiers (0.10g castor oil polyoxyethylene ether+0.05g calcium dodecyl benzene sulfonates) It adds in the athomin of 2.00g, is uniformly mixed, adds 0.10g stabilizers epoxychloropropane and the oil phase monomer first of 0.20g Benzene -2,4- diisocyanate is uniformly mixed, and obtains oil phase mixed liquor.
2) prepared by water phase：The thickener xanthans of 0.50g is dissolved into the deionized water of 99.50g, obtains 0.50% Xanthan gum solution.
3) it mixes：By the thickener xanthan gum solution 16.55g in the oil phase mixed liquor 2.45g and step 2) in step 1) Mixing, stirs evenly, the 3000rpm high speed shearing emulsifications 0.5min at 20 DEG C obtains the fine suspension of O/W systems.
4) it polymerize：Fine suspension obtained by step 3) is mixed slowly, 1% ethylenediamine solution of 1.00g is slowly added dropwise, 5min is added dropwise, and mixes slowly, then normal-temperature reaction 3h obtains athomin micro-capsule suspension.
2. study on the stability
Optical microphotograph Microscopic observation obtains the 10% athomin micro-capsule suspension that average grain diameter is 4.0-12.0 μm, warp Under conditions of 14 days, resolution ratio is respectively 0.34%, 3.15% for cold storage (0 ± 1 DEG C) 7 days, heat storage (54 ± 2 DEG C).
Embodiment 4：Athomin micro-capsule suspension
1. preparation method
1) prepared by oil phase：By 0.25g emulsifiers (0.20g castor oil polyoxyethylene ether+0.05g calcium dodecyl benzene sulfonates) It adds in the athomin of 4.00g, is uniformly mixed, adds 0.10g stabilizers epoxychloropropane and the oil phase monomer first of 0.40g Benzene -2,4- diisocyanate is uniformly mixed, and obtains oil phase mixed liquor.
2) prepared by water phase：The thickener hydroxyethyl cellulose of 1.00g is dissolved into the deionized water of 99.00g, is obtained 1.00% hydroxyethyl cellulose solution；
3) it mixes：By the thickener hydroxyethyl cellulose solution in the oil phase mixed liquor 4.75g and step 2) in step 1) 13.25g is mixed, and is stirred evenly, the 3000rpm high speed shearing emulsifications 0.5min at 20 DEG C obtains the fine suspension of O/W systems.
4) it polymerize：Fine suspension obtained by step 3) is mixed slowly, 1% ethylenediamine solution of 2.00g is slowly added dropwise, 5min is added dropwise, and mixes slowly, then normal-temperature reaction 3h obtains athomin micro-capsule suspension.
2. study on the stability
Optical microphotograph Microscopic observation obtains the 20% athomin micro-capsule suspension that average grain diameter is 4.0-12.0 μm, warp Under conditions of 14 days, resolution ratio is respectively 0.15%, 2.56% for cold storage (0 ± 1 DEG C) 7 days, heat storage (54 ± 2 DEG C).
Embodiment 5：Athomin micro-capsule suspension
1. preparation method
1) prepared by oil phase：By 0.25g emulsifiers (0.20g castor oil polyoxyethylene ether+0.05g calcium dodecyl benzene sulfonates) It adds in the athomin of 4.00g, is uniformly mixed, adds 0.10g stabilizers epoxychloropropane and the oil phase monomer first of 0.40g Benzene -2,4- diisocyanate is uniformly mixed, and obtains oil phase mixed liquor.
2) prepared by water phase：The thickener hydroxyethyl cellulose of 1.00g is dissolved into the deionized water of 99.00g, is obtained 1.00% hydroxyethyl cellulose solution.
3) it mixes：By the thickener hydroxyethyl cellulose solution in the oil phase mixed liquor 4.75g and step 2) in step 1) 14.25g is mixed, and is stirred evenly, the 3000rpm high speed shearing emulsifications 0.5min at 20 DEG C obtains the fine suspension of O/W systems.
4) it polymerize：Microemulsion obtained by step 3) is mixed slowly, 1% ethylenediamine solution of 1.00g, 5min is slowly added dropwise It is added dropwise, mixes slowly, then normal-temperature reaction 3h obtains athomin micro-capsule suspension.
2nd, study on the stability
Optical microphotograph Microscopic observation obtains the 20% athomin micro-capsule suspension that average grain diameter is 3.0-10.0 μm, warp Under conditions of 14 days, resolution ratio is respectively 0.25%, 3.16% for cold storage (0 ± 1 DEG C) 7 days, heat storage (54 ± 2 DEG C).
Embodiment 6：Athomin micro-capsule suspension
1. preparation method
1) prepared by oil phase：By 0.25g emulsifiers (0.20g castor oil polyoxyethylene ether+0.05g calcium dodecyl benzene sulfonates) It adds in the athomin of 4.00g, is uniformly mixed, adds 0.20g stabilizers epoxychloropropane and the oil phase monomer first of 0.40g Benzene -2,4- diisocyanate is uniformly mixed, and obtains oil phase mixed liquor.
2) prepared by water phase：The thickener hydroxyethyl cellulose of 1.00g is dissolved into the deionized water of 99.00g, is obtained 1.00% hydroxyethyl cellulose solution.
3) it mixes：By the thickener hydroxyethyl cellulose solution in the oil phase mixed liquor 4.85g and step 2) in step 1) 14.15g is mixed, and is stirred evenly, the 3000rpm high speed shearing emulsifications 0.5min at 20 DEG C obtains the fine suspension of O/W systems.
4) it polymerize：Microemulsion obtained by step 3) is mixed slowly, 1% ethylenediamine solution of 1.00g, 5min is slowly added dropwise It is added dropwise, mixes slowly, then normal-temperature reaction 3h obtains athomin micro-capsule suspension.
2. study on the stability
Optical microphotograph Microscopic observation obtains the 20% athomin micro-capsule suspension that average grain diameter is 5.0-15.0 μm, warp Under conditions of 14 days, resolution ratio is respectively 0.11%, 2.78% for cold storage (0 ± 1 DEG C) 7 days, heat storage (54 ± 2 DEG C).
Embodiment 7：Athomin micro-capsule suspension
1. preparation method
1) prepared by oil phase：By 0.25g emulsifiers (0.20g castor oil polyoxyethylene ether+0.05g calcium dodecyl benzene sulfonates) It adds in the athomin of 4.00g, is uniformly mixed, adds 0.10g stabilizers epoxychloropropane and the oil phase monomer first of 0.40g Benzene -2,4- diisocyanate is uniformly mixed, and obtains oil phase mixed liquor.
2) prepared by water phase：The thickener xanthans of 0.50g is dissolved into the deionized water of 99.50g, obtains 0.50% Xanthan gum solution.
3) it mixes：By the thickener xanthan gum solution 14.25g in the oil phase mixed liquor 4.75g and step 2) in step 1) Mixing, stirs evenly, the 3000rpm high speed shearing emulsifications 0.5min at 20 DEG C obtains the fine suspension of O/W systems.
4) it polymerize：Fine suspension obtained by step 3) is mixed slowly, 1% ethylenediamine solution of 1.00g is slowly added dropwise, 5min is added dropwise, and mixes slowly, then normal-temperature reaction 3h obtains athomin micro-capsule suspension.
2. study on the stability
Optical microphotograph Microscopic observation obtains the 20% athomin micro-capsule suspension that average grain diameter is 3.0-10.0 μm, warp Under conditions of 14 days, resolution ratio is respectively 0.29%, 3.24% for cold storage (0 ± 1 DEG C) 7 days, heat storage (54 ± 2 DEG C).
Embodiment 8：Athomin micro-capsule suspension
1. preparation method
1) prepared by oil phase：By 0.25g emulsifiers (0.20g castor oil polyoxyethylene ether+0.05g calcium dodecyl benzene sulfonates) It adds in the athomin of 4.00g, is uniformly mixed, adds 0.20g stabilizers epoxychloropropane and the oil phase monomer first of 0.40g Benzene -2,4- diisocyanate is uniformly mixed, and obtains oil phase mixed liquor.
2) prepared by water phase：The thickener hydroxyethyl cellulose of 1.00g is dissolved into the deionized water of 99.00g, is obtained 1.00% hydroxyethyl cellulose solution.
3) it mixes：By the thickener hydroxyethyl cellulose solution in the oil phase mixed liquor 4.85g and step 2) in step 1) 13.15g is mixed, and is stirred evenly, the 3000rpm high speed shearing emulsifications 0.5min at 20 DEG C obtains the fine suspension of O/W systems.
4) it polymerize：Fine suspension obtained by step 3) is mixed slowly, 1% ethylenediamine solution of 2.00g is slowly added dropwise, 10min is added dropwise, and mixes slowly, then normal-temperature reaction 3h obtains athomin micro-capsule suspension.
2. study on the stability
Optical microphotograph Microscopic observation obtains the 20% athomin micro-capsule suspension that average grain diameter is 4.0-15.0 μm, warp Under conditions of 14 days, resolution ratio is respectively 0.22%, 3.04% for cold storage (0 ± 1 DEG C) 7 days, heat storage (54 ± 2 DEG C).
Embodiment 9：Athomin micro-capsule suspension
1. preparation method
1) prepared by oil phase：0.15g emulsifiers castor oil polyoxyethylene ether is added in the athomin of 2.00g, is uniformly mixed, 0.10g stabilizers epoxychloropropane and the oil phase monomer Toluene-2,4-diisocyanate of 0.20g are added, 4- diisocyanate is uniformly mixed, obtains Oil phase mixed liquor.
2) prepared by water phase：The thickener hydroxyethyl cellulose of 1.00g is dissolved into the deionized water of 99.00g, is obtained 1.00% hydroxyethyl cellulose solution.
3) it mixes：By the thickener hydroxyethyl cellulose solution in the oil phase mixed liquor 2.45g and step 2) in step 1) 16.45g is mixed, and is stirred evenly, the 3000rpm high speed shearing emulsifications 0.5min at 20 DEG C obtains the fine suspension of O/W systems.
4) it polymerize：Fine suspension obtained by step 3) is mixed slowly, 1% ethylenediamine solution of 1.00g is slowly added dropwise, 10min is added dropwise, and mixes slowly, then normal-temperature reaction 3h obtains athomin micro-capsule suspension.
Embodiment 10：Athomin micro-capsule suspension
1. preparation method
1) prepared by oil phase：0.15g emulsifiers calcium dodecyl benzene sulfonate is added in the athomin of 2.00g, is uniformly mixed, 0.10g stabilizers epoxychloropropane and the oil phase monomer Toluene-2,4-diisocyanate of 0.20g are added, 4- diisocyanate is uniformly mixed, obtains Oil phase mixed liquor.
2) prepared by water phase：The thickener hydroxyethyl cellulose of 1.00g is dissolved into the deionized water of 99.00g, is obtained 1.00% hydroxyethyl cellulose solution.
3) it mixes：By the thickener hydroxyethyl cellulose solution in the oil phase mixed liquor 2.45g and step 2) in step 1) 16.45g is mixed, and is stirred evenly, the 3000rpm high speed shearing emulsifications 0.5min at 20 DEG C obtains the fine suspension of O/W systems.
4) it polymerize：Fine suspension obtained by step 3) is mixed slowly, 1% ethylenediamine solution of 1.00g is slowly added dropwise, 10min is added dropwise, and mixes slowly, then normal-temperature reaction 3h obtains athomin micro-capsule suspension.
By the athomin micro-capsule suspension that above-described embodiment is prepared compared with existing main dosage form aqueous emulsion not only Stability is improved, has delayed the volatilization of drug, so as to extend the lasting period, improves and walking quickly and keeping away for storage entomophthora is made with killing With alleviating the injury to dispenser personnel, improve the safety of medication.In addition, athomin microcapsules have bin stability The characteristics of high, sustained release, low toxicity.

Claims (10)

1. a kind of athomin micro-capsule suspension, which is characterized in that the athomin micro-capsule suspension using athomin as capsule-core, Using oiliness monomeric diisocyanate class compound and aqueous monomers multiamino compound by the polyureas that interface polymerization reaction obtains as The mass ratio of cyst wall, capsule-core and cyst wall is (1-40):(1-10).
2. athomin micro-capsule suspension according to claim 1, which is characterized in that the capsule-core further include stabilizer, Emulsifier and thickener.
3. athomin micro-capsule suspension according to claim 2, which is characterized in that the isocyanate ester compound is Polyphenyl polyisocyanate or alkylene diisocyanate；
The multiamino compound is one or more of diethylenetriamine, ethylenediamine, tetraethyl triethylammonium tetrakis；
The stabilizer for rapeseed oil, epoxychloropropane, acetone, acetic acid, glyceryl triacetate, tributyl phosphate, benzophenone, One or more of DBPC 2,6 ditertiary butyl p cresol, disodium ethylene diamine tetraacetate, zinc chloride；
The emulsifier is nonionic emulsifier and/or anionic emulsifier；
The thickener is xanthans, Arabic gum, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, Sodium Polyacrylate, melon One or more of your glue, polyvinyl alcohol.
4. athomin micro-capsule suspension according to claim 3, which is characterized in that the emulsifier is non-ionic breast Agent and anionic emulsifier, mass ratio are (1:0.1)-(1:100).
5. athomin micro-capsule suspension according to claim 3, which is characterized in that the nonionic emulsifier is benzene Ethyl phenol polyethenoxy ether, phenethyl phenol formaldehyde resin polyoxyethylene ether, phenethyl phenol polyoxyethylene poly-oxygen propylene aether, castor Sesame oil polyoxyethylene ether or alkyl phenol polyoxyethylene ether；The anionic emulsifier is lauryl sodium sulfate, dodecyl Benzene sulfonic acid sodium salt or calcium dodecyl benzene sulfonate.
6. the preparation method of any one of the claim 1-5 athomin micro-capsule suspensions, which is characterized in that including walking as follows Suddenly：
(1) athomin, isocyanate ester compound, stabilizer and emulsifier are uniformly mixed according to a certain ratio, obtain oil phase and mix Close liquid；
(2) thickener is dissolved in deionized water, obtains aqueous phase solution；
(3) the oil phase mixed liquor of step (1) is mixed with the aqueous phase solution of step (2), high speed shearing emulsification obtains O/W systems Fine suspension；
(4) fine suspension obtained by mixing slowly step (3), is slowly added dropwise multiamino compound aqueous solution, normal-temperature reaction obtains peppery Root element micro-capsule suspension.
7. preparation method according to claim 6, which is characterized in that the step (1) is in terms of parts by weight, by number Proportioning mixing：Athomin is 1.0-40.0 parts, and isocyanate ester compound is 0.1-5.0 parts, and stabilizer is 0.1-6.0 parts, breast Agent is 0.1-5.0 parts；The step (2) is in terms of parts by weight, and thickener is 0.05-5.0 parts, thickener in aqueous phase solution Mass percentage be 0.5%-5.0%；The step (4) is in terms of parts by weight, and multiamino compound aqueous solution is 0.1-5.0 parts, the mass percentage of multiamino compound is 0.1%-1% in multiamino compound aqueous solution.
8. preparation method according to claim 6, which is characterized in that the step (1) is in terms of parts by weight, by number Proportioning mixing：Athomin is 20.0 parts, and isocyanate ester compound is 4.0 parts, and stabilizer is 4.0 parts, and emulsifier is 2.5 parts； The step (2) is in terms of parts by weight, and thickener is 1.0 parts, and the mass percentage of thickener is in aqueous phase solution 1.0%；The step (4) is in terms of parts by weight, and multiamino compound aqueous solution is 2.0 parts, multiamino compound aqueous solution The mass percentage of middle multiamino compound is 1%.
9. preparation method according to claim 6, which is characterized in that the condition of the high speed shearing emulsification is：Temperature is 0 DEG C -30 DEG C, rotating speed 1000rpm-6000rpm, time 0.2min-5.0min.
10. preparation method according to claim 6, which is characterized in that the multiamino compound aqueous solution 5-30min drops Add complete, normal-temperature reaction 1-5h.
CN201810099421.2A 2018-01-31 2018-01-31 A kind of athomin micro-capsule suspension and preparation method thereof Pending CN108124899A (en)

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CN111053087A (en) * 2019-12-30 2020-04-24 江苏腾龙生物药业有限公司 Horseradish pesticide and preparation method thereof
CN111632564A (en) * 2020-06-11 2020-09-08 上海应用技术大学 Polyurethane peppermint oil microcapsule and preparation method thereof
WO2020194910A1 (en) * 2019-03-28 2020-10-01 富士フイルム株式会社 Microcapsules, microcapsule composition, softener, and detergent
CN113956111A (en) * 2021-09-24 2022-01-21 广东清远金正大农业研究院有限公司 Nematode-preventing growth-promoting liquid pesticide fertilizer and preparation method and application thereof

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CN105660690A (en) * 2016-01-06 2016-06-15 中农立华生物科技股份有限公司 Fosthiazate microcapsule suspending agent and preparation method thereof
CN106818734A (en) * 2017-01-09 2017-06-13 深圳诺普信农化股份有限公司 Microcapsule formulation and its preparation, micro-capsule suspension

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CN105248444A (en) * 2015-11-09 2016-01-20 中国农业大学 Horseradish micro-capsule slow releasing agent taking silicon dioxide as carrier and preparation method thereof
CN105660690A (en) * 2016-01-06 2016-06-15 中农立华生物科技股份有限公司 Fosthiazate microcapsule suspending agent and preparation method thereof
CN106818734A (en) * 2017-01-09 2017-06-13 深圳诺普信农化股份有限公司 Microcapsule formulation and its preparation, micro-capsule suspension

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020194910A1 (en) * 2019-03-28 2020-10-01 富士フイルム株式会社 Microcapsules, microcapsule composition, softener, and detergent
CN111053087A (en) * 2019-12-30 2020-04-24 江苏腾龙生物药业有限公司 Horseradish pesticide and preparation method thereof
CN111632564A (en) * 2020-06-11 2020-09-08 上海应用技术大学 Polyurethane peppermint oil microcapsule and preparation method thereof
CN113956111A (en) * 2021-09-24 2022-01-21 广东清远金正大农业研究院有限公司 Nematode-preventing growth-promoting liquid pesticide fertilizer and preparation method and application thereof

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Application publication date: 20180608