CN102939964A - Controlled-loading hydrophobic pesticide sustained-release microcapsule and preparation method thereof - Google Patents
Controlled-loading hydrophobic pesticide sustained-release microcapsule and preparation method thereof Download PDFInfo
- Publication number
- CN102939964A CN102939964A CN2012105285751A CN201210528575A CN102939964A CN 102939964 A CN102939964 A CN 102939964A CN 2012105285751 A CN2012105285751 A CN 2012105285751A CN 201210528575 A CN201210528575 A CN 201210528575A CN 102939964 A CN102939964 A CN 102939964A
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- CN
- China
- Prior art keywords
- hydrophobic
- preparation
- acrylate
- release
- hydroxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 72
- 238000011068 loading method Methods 0.000 title claims abstract description 51
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 49
- 239000000575 pesticide Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000013268 sustained release Methods 0.000 title abstract description 8
- 239000012730 sustained-release form Substances 0.000 title abstract description 8
- 239000000839 emulsion Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000002775 capsule Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 239000003905 agrochemical Substances 0.000 claims description 35
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 16
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- -1 thiazolinyl carboxylic acid Chemical class 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- 239000005946 Cypermethrin Substances 0.000 claims description 5
- 239000005906 Imidacloprid Substances 0.000 claims description 5
- KAATUXNTWXVJKI-UHFFFAOYSA-N cypermethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 KAATUXNTWXVJKI-UHFFFAOYSA-N 0.000 claims description 5
- 229960005424 cypermethrin Drugs 0.000 claims description 5
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 claims description 5
- 229940056881 imidacloprid Drugs 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 4
- 239000004009 herbicide Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002728 pyrethroid Substances 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- XUNYDVLIZWUPAW-UHFFFAOYSA-N (4-chlorophenyl) n-(4-methylphenyl)sulfonylcarbamate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(=O)OC1=CC=C(Cl)C=C1 XUNYDVLIZWUPAW-UHFFFAOYSA-N 0.000 claims description 3
- AZSNMRSAGSSBNP-UHFFFAOYSA-N 22,23-dihydroavermectin B1a Natural products C1CC(C)C(C(C)CC)OC21OC(CC=C(C)C(OC1OC(C)C(OC3OC(C)C(O)C(OC)C3)C(OC)C1)C(C)C=CC=C1C3(C(C(=O)O4)C=C(C)C(O)C3OC1)O)CC4C2 AZSNMRSAGSSBNP-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- SPBDXSGPUHCETR-JFUDTMANSA-N 8883yp2r6d Chemical compound O1[C@@H](C)[C@H](O)[C@@H](OC)C[C@@H]1O[C@@H]1[C@@H](OC)C[C@H](O[C@@H]2C(=C/C[C@@H]3C[C@@H](C[C@@]4(O[C@@H]([C@@H](C)CC4)C(C)C)O3)OC(=O)[C@@H]3C=C(C)[C@@H](O)[C@H]4OC\C([C@@]34O)=C/C=C/[C@@H]2C)/C)O[C@H]1C.C1C[C@H](C)[C@@H]([C@@H](C)CC)O[C@@]21O[C@H](C\C=C(C)\[C@@H](O[C@@H]1O[C@@H](C)[C@H](O[C@@H]3O[C@@H](C)[C@H](O)[C@@H](OC)C3)[C@@H](OC)C1)[C@@H](C)\C=C\C=C/1[C@]3([C@H](C(=O)O4)C=C(C)[C@@H](O)[C@H]3OC\1)O)C[C@H]4C2 SPBDXSGPUHCETR-JFUDTMANSA-N 0.000 claims description 3
- 239000005660 Abamectin Substances 0.000 claims description 3
- 239000005893 Diflubenzuron Substances 0.000 claims description 3
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 3
- RRZXIRBKKLTSOM-XPNPUAGNSA-N avermectin B1a Chemical compound C1=C[C@H](C)[C@@H]([C@@H](C)CC)O[C@]11O[C@H](C\C=C(C)\[C@@H](O[C@@H]2O[C@@H](C)[C@H](O[C@@H]3O[C@@H](C)[C@H](O)[C@@H](OC)C3)[C@@H](OC)C2)[C@@H](C)\C=C\C=C/2[C@]3([C@H](C(=O)O4)C=C(C)[C@@H](O)[C@H]3OC\2)O)C[C@H]4C1 RRZXIRBKKLTSOM-XPNPUAGNSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 229940019503 diflubenzuron Drugs 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 3
- 229960002418 ivermectin Drugs 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 2
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 claims description 2
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- JCCIFDCPHCKATH-UHFFFAOYSA-N 2-methylbutan-2-yl acetate Chemical compound CCC(C)(C)OC(C)=O JCCIFDCPHCKATH-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- GHUXAYLZEGLXDA-UHFFFAOYSA-N 8-azido-5-ethyl-6-phenylphenanthridin-5-ium-3-amine;bromide Chemical compound [Br-].C12=CC(N=[N+]=[N-])=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 GHUXAYLZEGLXDA-UHFFFAOYSA-N 0.000 claims description 2
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- 230000008542 thermal sensitivity Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
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Abstract
The invention discloses a controlled-loading hydrophobic pesticide slow-release microcapsule, a preparation method and application thereof. The microcapsule comprises a core material and a wall material, wherein the wall material is formed by crosslinking hydroxyl acrylate macromolecules with carboxyl under divalent metal ions, and a hydrophobic pesticide core material is encapsulated in the microcapsule. The preparation method comprises dissolving hydrophobic pesticide and hydroxy acrylate to form polymer solution, adding water, stirring at high speed to form emulsion, adding divalent metal ion solution to obtain granular aggregate, filtering, and drying. The particle size of the capsule can be flexibly regulated and controlled within 0.5-50 mu m, and the mass of the core material accounts for 5-70% of the total weight of the sustained-release capsule. According to the sustained-release capsule, parameters such as wall material composition, solvent variety, core material-wall material ratio and the like are adjusted, so that one or more hydrophobic pesticides can be efficiently loaded, and the obtained drug-loaded microcapsule has the advantages of controllable drug loading rate and sustained-release performance and is suitable for preparation of most hydrophobic pesticide sustained-release microcapsules.
Description
Technical field
The invention belongs to formulations of pesticide manufacture field, particularly hydrophobic pesticide slow-release microcapsules of a kind of controlled loading and preparation method thereof are applicable to efficient, the controlled loading of more than one hydrophobic agricultural chemicals.
Background technology
The disease pest and weed of agricultural chemicals control crops is the essential condition of modern big agriculture, commercial agriculture, and China has been second largest pesticide producing big country in the world now.At present, the main formulation of hydrophobicity agricultural chemicals is missible oil, contains a large amount of organic solvents, and the waste resource is contaminated environment also, bad dispersibility, and effective rate of utilization is low, causes the residual in a large number of agricultural chemicals.Conventional pesticide formulation availability only has 20%～30%, and has the problems such as the active ingredient rate of release is fast, the drug effect efficiency time is short, ecological pollution is serious.Therefore, reduction toxicity, raising drug effect are the trend of Agrochemicals.For former medicine exploitation, realizing reducing toxicity, improve drug effect by formulation development is efficiently approach of a kind of comparatively economy.Pesticide slow-releasing agent is according to pest pests occurrence rule, harm characteristics and environmental condition, by the pesticide processing means, makes on demand metering of agricultural chemicals, specific time, continual and steady release to reach most economical, safe, effectively to control pest.The pesticide slow-release technology can solve the problem that pesticide activity preparation rate of release is fast, effective acting time is short effectively, reduce or avoid the harmful effect of agricultural chemicals, to prolong the service life of agricultural chemicals, wherein microcapsules technology namely is most important technology in the control release technic.
Pesticide micro capsule refers to utilize natural or synthetic macromolecule cyst material, and agricultural chemicals solid, liquid is overmolding to the microcapsules of semi permeability or sealing cyst membrane, and the molecular diffusion that is relied on the wall material by the load agricultural chemicals realizes slowly-releasing.The required wall material of microcapsules not should with agricultural chemicals generation chemical reaction, need simultaneously to consider the factor such as permeability, stability, hygroscopicity of product.The pesticide micro capsule preparation method has a lot, and wherein interfacial polymerization is the common method of hydrophobicity pesticide micro capsule.Its technique is that agricultural chemicals is dissolved in organic solvent, it is dispersed in water the formation drop again.By forming the coating film of resin in the polymerization at oil phase drop and aqueous phase interface place, and then obtain drug-loading microcapsule.To wherein during preparation, the oil-soluble raw material is dissolved in the middle of the hanging drop of agricultural chemical compound, water-soluble material is dissolved in aqueous phase, between hanging drop and water, carry out at the interface polymerisation, comprise polyurethane, carbamide resin, polyamide, mylar, polysulfonates resin, polysulfonamide resin, amino resin and melamine formaldehyde resin for the preparation of the material of cyst wall.By the particle diameter of adjusting drop and the amount of resin that forms coating film, can control the thickness of coating film, the particle diameter of preparation microcapsules is usually at 1～500 μ m.Have now and utilize preparing pesticide microcapsules by interfacial polymerization method technique to have complex process, manufacturing technique requirent is strict, and microcapsule structure control difficulty is not suitable for large-scale industrial production.
Different medicaments, using method, controlling object need different-grain diameter, coat the microcapsule granule of intensity, rate of release, therefore control the importance that capsule medicine carrying amount, wall thickness and granularity are the preparation capsules.Existing pesticide micro capsule preparation mostly is suspending agent, and storage stability and the suspensibility of suspending agent are low, is easy to the layering caking, and such preparation contains a large amount of moisture, and active constituent content is low, is restricted in the storage liquid of cold district.Preparation method's complicated operation of existing pesticide micro capsule preparation, technique is wayward.Chinese patent CN1771804, CN101036457, CN101084747 disclose the preparation method of the microemulsion that contains pesticide activity component.Microemulsion has solved the problem of water baseization and polymolecularity preferably, but can not effectively control release, is not long-acting dosage form.Chinese patent CN1491541, CN1491551, the method that CN1491558 discloses a series of use emulsion polymerisations prepares the method for pesticide water suspending nano capsule prepn, its capsule skin is styrene, isocyanates, acrylic acid series and metha crylic monomer copolymer, and capsule-core is pesticide active ingredient Imidacloprid, High effect cypermethrin, diflubenzuron, ivermectin, Affirm (Merck Co.) etc.But in the polymerization monomer in polymerization process unavoidably can be wrapped agricultural chemicals and be combined the reduction that causes drug effect.The natural polymers such as Chinese patent CN 101461358 usefulness sodium lignin sulfonates, shitosan, gum Arabic, gelatin are regulated the pH value of microemulsion as polymeric material, make macromolecule behind the drop Interfacial coagulation, add crosslinking agent and fixedly obtain microcapsules.In the polymer agglomeration process, suitably regulate the proportioning of microemulsion, high molecular addition, control reaction condition, obtain having different-grain diameter, the microcapsule particle of different structure.Limited by cyst wall macromolecular material kind, the hydrophobic pesticide variety of this method load is limited and the medicine carrying amount is limited.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, primary and foremost purpose of the present invention is to provide the preparation method of the hydrophobic pesticide slow-release microcapsules of a kind of controlled loading; Contain carboxyl and hydroxyl on the wall material hydroxy acrylate strand, possesses certain hydrophily, soluble oils forms O/w emulsion mutually, add that cross-linking agent solution obtains take hydroxy acrylate as the wall material, hydrophobic agricultural chemicals is the granular carried medicine sustained-release capsule of core, wherein hydrophobic agricultural chemicals accounts for 5～70% of spansule gross weight.
The hydrophobic pesticide slow-release microcapsules of controlled loading that provide said method to prepare are provided.
A further object of the present invention is to provide the application of the hydrophobic pesticide slow-release microcapsules of above-mentioned controlled loading.
Purpose of the present invention realizes by following technical proposals:
The preparation method of the hydrophobic pesticide slow-release microcapsules of a kind of controlled loading comprises following operating procedure:
(1) hydrophobic agricultural chemicals being become mass fraction with organic solvent dissolution is 20～80% solution, then be that 30～80% hydroxy acrylic acid ester solution mixes with mass fraction, stir at normal temperatures and form the homogeneous phase Polymer Solution, wherein the mass ratio of hydrophobic agricultural chemicals and hydroxy acrylate is 0.05～2;
(2) under high speed shear dispersion or ultrasonic dispersion condition, in step (1) gained homogeneous phase Polymer Solution, add entry formation O/w emulsion;
(3) add cross-linking agent solution in step (2) gained O/w emulsion, tiny white precipitate appears in system, obtains the hydrophobic pesticide slow-release capsule of controlled loading after filtration, the drying.
The described hydroxy acrylic acid ester solution of step (1) prepares in accordance with the following methods: with (methyl) alkyl acrylate of mass percent 10～80%, (methyl) acrylic acid hydroxy alkyl ester of mass percent 10～30%, the thiazolinyl carboxylic acid of mass percent 1～10%, other vinyl monomers of the oil-soluble initiator of mass percent 0.2～5% and mass percent 0～30% mix, in 4 hours, splash in the reactor that organic solvent is housed with constant speed, 60～150 ℃ of lower isothermal reactions, insulation is 1～3 hour after the reaction, obtains mass fraction and be 30～80% hydroxy acrylic acid ester solution.
Described (methyl) alkyl acrylate is more than one in methyl methacrylate, EMA, butyl methacrylate, isobornyl methacrylate, hexyl methacrylate, n octyl methacrylate, EHMA, methyl acrylate, ethyl acrylate, butyl acrylate, isobornyl acrylate, Hexyl 2-propenoate, acrylic acid n-octyl and the Isooctyl acrylate monomer;
Described (methyl) acrylic acid hydroxy alkyl ester is more than one in hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid hydroxy butyl ester, hydroxyethyl methacrylate and the hydroxy propyl methacrylate;
Described thiazolinyl carboxylic acid is more than one in acrylic acid, methacrylic acid and the itaconic acid;
Described other vinyl monomers are more than one in styrene, AMS and (methyl) acrylamide.
Described oil-soluble initiator is radical initiator, comprise azo-initiator and/or peroxide initator, wherein azo-initiator is one or both in azodiisobutyronitrile and the AMBN, and the peroxide initator is more than one in benzoyl peroxide, peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate, di-t-butyl peroxide, peroxidating two tertiary pentyls, TBHP and the t-amyl peroxy hydrogen;
Described organic solvent is more than one in toluene, dimethylbenzene, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, propylene-glycol ethyl ether acetate and the diethylene glycol ether acetate.
The described hydrophobic agricultural chemicals of step (1) is more than one in diflubenzuron, chlopyrifos, Affirm (Merck Co.), Avermectin, Imidacloprid, ivermectin, High effect cypermethrin and the pyrethroid; Described organic solvent is more than one in methyl alcohol, ethanol, isopropyl alcohol, acetone, toluene, dimethylbenzene, ethyl acetate, the butyl acetate; The addition of the described water of step (2) is 0.5～5 times of homogeneous phase Polymer Solution volume, and it is to shear with 500～7000 rev/mins that described high speed shear is disperseed, and described ultrasonic dispersion is to carry out ultrasonic dispersion under 20～100KHz.
The concentration of the described cross-linking agent solution of step (3) is 0.05～0.5M, and its addition is 1～20% of O/w emulsion volume fraction; Described crosslinking agent is bivalent metal ion, is preferably calcium chloride or barium chloride.
A kind of hydrophobic pesticide slow-release microcapsules of controlled loading that prepare according to said method.The particle diameter of described microcapsules is 0.5～50 μ m.
The hydrophobic pesticide slow-release microcapsules of above-mentioned controlled loading are applied to agriculture and forestry field, livestock breeding or building material field as the slow release formulation of insecticide or weed killer herbicide.
Slow-release microcapsule of the present invention comprises core and wall material, be by with the hydroxy acrylate macromolecule of carboxyl at the crosslinked lower wall material that forms of bivalent metal ion, inside is surrounded by the microcapsules of hydrophobicity agricultural chemicals core.Its concrete preparation method at first is dissolved in hydrophobic agricultural chemicals and hydroxy acrylate to form Polymer Solution in the organic solvent, then add entry, high-speed stirred formation emulsion, add at last bivalent metal ion solution and obtain granular condensation product, obtain the carried medicine sustained-release capsule after filtration, the drying.The gained Microcapsules Size can be regulated and control flexibly at 0.5～50 mu m range, and the core quality is in 5～70% range regulation of spansule gross mass.The slow-release microcapsule that the present invention relates to, by regulating wall material (hydroxy acrylate) composition, solvent species and the parameters such as core and wall material proportioning, can realize more than one hydrophobic agricultural chemicals is efficiently loaded, the drug-loading microcapsule that obtains has medicine carrying amount and the controlled advantage of sustained release performance, is applicable to the preparation of most hydrophobicity pesticide slow-release microcapsules.
Principle of the present invention is to utilize to have the large molecule of wall material of emulsification function to hydrophobic pesticidal emulsifiable, dispersion, the ratio of hydrophilic monomer and hydrophobic monomer during by the change polymerization, the large molecule of wall material be can conveniently adjust to the emulsifying effectiveness of hydrophobic agricultural chemicals, particle diameter, the controlled emulsion particle of medicine carrying amount obtained; The a large amount of carboxylic acid ions of emulsion particle surface distributed and hydroxyl, wherein carboxylate radical can with bivalent metal ion crosslinking agent such as Ca
2+Complexing provide crosslinked, fixing to the medicine carrying emulsion particle, and hydroxyl provides auxiliary emulsification for emulsion particle, relies on simultaneously itself and the affinity interaction of water, adjusts the channel sized of crosslinked drug bearing microsphere, and convenient realization is to the regulation and control of pesticide slow-release speed.
The present invention has following advantage and beneficial effect with respect to prior art:
(1) high to the agricultural chemicals clad ratio, the medicine carrying amount is controlled.By changing the molecular structure of hydroxy acrylate, the capable of regulating hydroxy acrylate is realized the regulation and control of pesticide micro capsule medicine carrying amount to the emulsifying effectiveness of hydrophobic agricultural chemicals.
(2) hydroxyl that distributes on the wall material component macromolecular chain can give drug-loading microcapsule certain hydrophilicity, is beneficial to the swelling of wall material under wet environment, thereby realizes the regulation and control to pesticide slow-release speed.
(3) the present invention adopts in the preparation process take hydroxy acrylate as dispersant, realizes the emulsification to hydrophobic agricultural chemicals, does not use little molecular surface active agent in the preparation process, and the Microcapsules Size of preparation is controlled.
(4) the inventive method is carried out at normal temperatures and pressures, and mild condition operates simplyr, is convenient to suitability for industrialized production, simultaneously applicable to some thermal sensitivity pesticide micro capsules, uses face width.
Description of drawings
Fig. 1 is the infrared spectrogram of the drug-loading microcapsule of the embodiment of the invention 6 gained; Wherein, a is former medicine chlopyrifos, and b is wall material hydroxy acrylate, and c is drug-loading microcapsule.The contrast as can be known, the successful load of hydroxy acrylic acid microcapsules chlopyrifos, have hydrogen bond action between the two.
Fig. 2 is the electron scanning micrograph figure of the drug-loading microcapsule of the embodiment of the invention 6 gained.
Fig. 3 is the thermogravimetric analysis figure of the drug-loading microcapsule of the embodiment of the invention 6 gained; Wherein, a is the thermogravimetric curve of the former medicine of chlopyrifos, and b is the thermogravimetric curve of wall material hydroxy acrylate, and c is the thermogravimetric curve of drug-loading microcapsule.
Fig. 4 is the differential scanning calorimetric curve figure of the drug-loading microcapsule of the embodiment of the invention 6 gained; Wherein a is the differential scanning calorimetric curve of the former medicine of chlopyrifos, and b is the differential scanning calorimetric curve of drug-loading microcapsule.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited to this.
Embodiment 1
In the 500ml four-hole bottle of thermometer, agitating device and condenser is housed, add 180ml ethyl acetate and intensification, after temperature rises to 75 ℃ in bottle, begin to drip the mixed solution of acrylic ester monomer and initator, it consists of methyl methacrylate 70g, methyl acrylate 10g, butyl methacrylate 10g, hydroxy-ethyl acrylate 8g, acrylic acid 2g and azodiisobutyronitrile 0.6g, drips off in 3 hours.After monomer dropping is complete, add the 0.1g azodiisobutyronitrile, continue insulation cooling after 2 hours, obtain mass fraction and be 35% hydroxy acrylic acid ester solution.
Embodiment 2
In the 500ml four-hole bottle of thermometer, agitating device and condenser is housed, add 100ml butyl acetate and intensification, after temperature rises to 90 ℃ in bottle, begin to drip the mixed solution of acrylic ester monomer and initator, it consists of methyl methacrylate 60g, styrene 20g, methyl acrylate 5g, butyl acrylate 5g, hydroxyethyl methacrylate 10g, methacrylic acid 4g and benzoyl peroxide 0.6g, drips off in 3 hours.After monomer dropping is complete, add the 0.09g benzoyl peroxide, continue insulation cooling after 2 hours, obtain mass fraction and be 50% hydroxy acrylic acid ester solution.
Embodiment 3
In the 500ml four-hole bottle of thermometer, agitating device and condenser is housed, add 100ml 1-Methoxy-2-propyl acetate and intensification, after temperature rises to 100 ℃ in bottle, begin to drip the mixed solution of acrylic ester monomer and initator, it consists of methyl methacrylate 70g, styrene 15g, butyl methacrylate 5g, hydroxyethyl methacrylate 10g, acrylic acid 4g and benzoyl peroxide 0.8g, drips off in 3 hours.After monomer dropping is complete, add the 0.1g benzoyl peroxide, continue insulation cooling after 2 hours, obtain mass fraction and be 50% hydroxy acrylic acid ester solution.
Embodiment 4
In the 500ml four-hole bottle of thermometer, agitating device and condenser is housed, add 55ml 1-Methoxy-2-propyl acetate and intensification, after temperature rises to 130 ℃ in bottle, begin to drip the mixed solution of acrylic ester monomer and initator, it consists of methyl methacrylate 55g, isobornyl methacrylate 10g, styrene 10g, Isooctyl acrylate monomer 10g, hydroxy-ethyl acrylate 10g, methacrylic acid 6g and peroxidating two tertiary pentyl 0.7g, drips off in 3-3.5 hour.After monomer dropping is complete, add 0.1g peroxidating two tertiary pentyls, continue insulation cooling after 2 hours, obtain mass fraction and be 65% hydroxy acrylic acid ester solution.
(1) cypermethrin technical material being dissolved into mass fraction with ethyl acetate is 20% solution, then mix with embodiment 1 gained hydroxy acrylic acid ester solution, stir at normal temperatures and form the homogeneous phase Polymer Solution, wherein the mass ratio of hydrophobic agricultural chemicals and hydroxy acrylate is 0.05:1;
(2) under 2000 rev/mins of high speed shear dispersion conditions, add entry in step (1) the gained homogeneous phase Polymer Solution and form milky O/w emulsion; The addition of water is 0.5 times of homogeneous phase Polymer Solution volume;
(3) ultrasonic auxiliary lower, in step (2) gained O/w emulsion, add the 0.1M calcium chloride solution, the addition of calcium chloride solution is 15% of O/w emulsion volume fraction, tiny white precipitate appears in system, obtain loading the drug-loading microcapsule of cypermethrin after filtration, the drying, institute's carrying medicament amount is about 4%.
Embodiment 6
(1) the former medicinal alcohol of chlopyrifos being dissolved into mass fraction is 60% solution, then mixes with embodiment 1 gained hydroxy acrylic acid ester solution, stirs at normal temperatures and forms the homogeneous phase Polymer Solution, and wherein the mass ratio of hydrophobic agricultural chemicals and hydroxy acrylate is 1:1;
(2) under the ultrasonic dispersion condition of 40KHz, add entry in step (1) the gained homogeneous phase Polymer Solution and form milky O/w emulsion; The addition of water is 2 times of homogeneous phase Polymer Solution volume;
(3) in step (2) gained O/w emulsion, add the 0.1M calcium chloride solution, the addition of calcium chloride solution is 20% of O/w emulsion volume fraction, white precipitate appears in system, obtains loading the drug-loading microcapsule of chlopyrifos after filtration, the drying, and institute's carrying medicament amount is about 45%.
The infrared spectrogram of gained drug-loading microcapsule as shown in Figure 1, the contrast as can be known, the successful load of hydroxy acrylic acid microcapsules chlopyrifos, have hydrogen bond action between the two.
The electron scanning micrograph figure of gained drug-loading microcapsule as shown in Figure 2, visible drug-loading microcapsule is particle diameter 0.5～10 μ m irregular particle, these irregular particles are assembled by less spherical microcapsule and are formed.
The thermogravimetric analysis figure of gained drug-loading microcapsule contrasts the chlopyrifos warm tolerance that loads on as can be known in the hydroxy acrylate carrier cross-linked network and obviously promotes as shown in Figure 3.
The differential scanning calorimetric curve figure of gained drug-loading microcapsule as shown in Figure 4, to distribute be to exist with crystalline state and two kinds of forms of amorphous state to the microcapsules Chlorpyrifos as seen from the figure.
Embodiment 7
(1) the former medicinal carrene of Imidacloprid being dissolved into mass fraction is 80% solution, then mix with embodiment 1 gained hydroxy acrylic acid ester solution, stir at normal temperatures and form the homogeneous phase Polymer Solution, wherein the mass ratio of hydrophobic agricultural chemicals and hydroxy acrylate is 1:5;
(2) in the 40KHz ultrasonic cleaning machine under the hand operated mixing condition, add entry in step (1) the gained homogeneous phase Polymer Solution and form milky O/w emulsion; The addition of water is 3 times of homogeneous phase Polymer Solution volume;
(3) ultrasonic auxiliary lower, in step (2) gained O/w emulsion, add the 0.05M calcium chloride solution, the addition of calcium chloride solution is 20% of O/w emulsion volume fraction, tiny white precipitate appears in system, obtain loading the drug-loading microcapsule of Imidacloprid after filtration, the drying, institute's carrying medicament amount is about 15%.
Embodiment 8
(1) the former medicinal butyl acetate of Avermectin being dissolved into mass fraction is 40% solution, then mix with embodiment 2 gained hydroxy acrylic acid ester solutions, stir at normal temperatures and form the homogeneous phase Polymer Solution, wherein the mass ratio of hydrophobic agricultural chemicals and hydroxy acrylate is 1:5;
(2) under the ultrasonic dispersion condition of 100KHz, add entry in step (1) the gained homogeneous phase Polymer Solution and form milky O/w emulsion; The addition of water is 5 times of homogeneous phase Polymer Solution volume;
(3) ultrasonic auxiliary lower, in step (2) gained O/w emulsion, add the 0.3M calcium chloride solution, the addition of calcium chloride solution is 5% of O/w emulsion volume fraction, tiny white precipitate appears in system, obtain loading the drug-loading microcapsule of chlopyrifos after filtration, the drying, institute's carrying medicament amount is about 15%.
Embodiment 9
(1) the former medicinal alcohol of pyrethroid being dissolved into mass fraction is 30% solution, then mix with embodiment 3 gained hydroxy acrylic acid ester solutions, stir at normal temperatures and form the homogeneous phase Polymer Solution, wherein the mass ratio of hydrophobic agricultural chemicals and hydroxy acrylate is 1:3;
(2) under 7000 rev/mins of lower high speed shear dispersion conditions, add entry in step (1) the gained homogeneous phase Polymer Solution and form milky O/w emulsion; The addition of water is 4 times of homogeneous phase Polymer Solution volume;
(3) ultrasonic auxiliary lower, in step (2) gained O/w emulsion, add the 0.2M calcium chloride solution, the addition of calcium chloride solution is 12% of O/w emulsion volume fraction, tiny white precipitate appears in system, obtain loading the drug-loading microcapsule of pyrethroid after filtration, the drying, institute's carrying medicament amount is about 20%.
(1) the former medicinal isopropyl alcohol of Affirm (Merck Co.) being dissolved into mass fraction is 70% solution, then mix with embodiment 4 gained hydroxy acrylic acid ester solutions, stir at normal temperatures and form the homogeneous phase Polymer Solution, wherein the mass ratio of hydrophobic agricultural chemicals and hydroxy acrylate is 1:4;
(2) under 5000 rev/mins of lower high speed shear dispersion conditions, add entry in step (1) the gained homogeneous phase Polymer Solution and form milky O/w emulsion; The addition of water is 0.5 times of homogeneous phase Polymer Solution volume;
(3) ultrasonic auxiliary lower, in step (2) gained O/w emulsion, add the 0.05M calcium chloride solution, the addition of calcium chloride solution is 20% of O/w emulsion volume fraction, tiny white precipitate appears in system, obtain particle diameter after filtration, the drying for loading the drug-loading microcapsule of Affirm (Merck Co.), particle diameter is that institute's carrying medicament amount is about 17%.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of the hydrophobic pesticide slow-release microcapsules of controlled loading is characterized in that comprising following operating procedure:
(1) hydrophobic agricultural chemicals being become mass fraction with organic solvent dissolution is 20～80% solution, then be that 30～80% hydroxy acrylic acid ester solution mixes with mass fraction, stir at normal temperatures and form the homogeneous phase Polymer Solution, wherein the mass ratio of hydrophobic agricultural chemicals and hydroxy acrylate is 0.05～2;
(2) under high speed shear dispersion or ultrasonic dispersion condition, in step (1) gained homogeneous phase Polymer Solution, add entry formation O/w emulsion;
(3) add cross-linking agent solution in step (2) gained O/w emulsion, tiny white precipitate appears in system, obtains the hydrophobic pesticide slow-release capsule of controlled loading after filtration, the drying.
2. the preparation method of the hydrophobic pesticide slow-release microcapsules of a kind of controlled loading according to claim 1, it is characterized in that: the described hydroxy acrylic acid ester solution of step (1) prepares in accordance with the following methods: with (methyl) alkyl acrylate of mass percent 10～80%, (methyl) acrylic acid hydroxy alkyl ester of mass percent 10～30%, the thiazolinyl carboxylic acid of mass percent 1～10%, other vinyl monomers of the oil-soluble initiator of mass percent 0.2～5% and mass percent 0～30% mix, in 4 hours, splash in the reactor that organic solvent is housed with constant speed, 60～150 ℃ of lower isothermal reactions, insulation is 1～3 hour after the reaction, obtains mass fraction and be 30～80% hydroxy acrylic acid ester solution.
3. the preparation method of the hydrophobic pesticide slow-release microcapsules of a kind of controlled loading according to claim 2, it is characterized in that: described (methyl) alkyl acrylate is more than one in methyl methacrylate, EMA, butyl methacrylate, isobornyl methacrylate, hexyl methacrylate, n octyl methacrylate, EHMA, methyl acrylate, ethyl acrylate, butyl acrylate, isobornyl acrylate, Hexyl 2-propenoate, acrylic acid n-octyl and the Isooctyl acrylate monomer;
Described (methyl) acrylic acid hydroxy alkyl ester is more than one in hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid hydroxy butyl ester, hydroxyethyl methacrylate and the hydroxy propyl methacrylate;
Described thiazolinyl carboxylic acid is more than one in acrylic acid, methacrylic acid and the itaconic acid;
Described other vinyl monomers are more than one in styrene, AMS and (methyl) acrylamide.
4. the preparation method of the hydrophobic pesticide slow-release microcapsules of a kind of controlled loading according to claim 2, it is characterized in that: described oil-soluble initiator is radical initiator, comprise azo-initiator and/or peroxide initator, wherein azo-initiator is one or both in azodiisobutyronitrile and the AMBN, and the peroxide initator is benzoyl peroxide, peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate, di-t-butyl peroxide, peroxidating two tertiary pentyls, in TBHP and the t-amyl peroxy hydrogen more than one;
Described organic solvent is more than one in toluene, dimethylbenzene, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, propylene-glycol ethyl ether acetate and the diethylene glycol ether acetate.
5. the preparation method of the hydrophobic pesticide slow-release microcapsules of a kind of controlled loading according to claim 1, it is characterized in that: the described hydrophobic agricultural chemicals of step (1) is more than one in diflubenzuron, chlopyrifos, Affirm (Merck Co.), Avermectin, Imidacloprid, ivermectin, High effect cypermethrin and the pyrethroid; Described organic solvent is more than one in methyl alcohol, ethanol, isopropyl alcohol, acetone, toluene, dimethylbenzene, ethyl acetate, the butyl acetate; The addition of the described water of step (2) is 0.5～5 times of homogeneous phase Polymer Solution volume, and it is to shear with 500～7000 rev/mins that described high speed shear is disperseed, and described ultrasonic dispersion is to carry out ultrasonic dispersion under 20～100KHz.
6. the preparation method of the hydrophobic pesticide slow-release microcapsules of a kind of controlled loading according to claim 1, it is characterized in that: the concentration of the described cross-linking agent solution of step (3) is 0.05～0.5M, and its addition is 1～20% of O/w emulsion volume fraction; Described crosslinking agent is bivalent metal ion.
7. the preparation method of the hydrophobic pesticide slow-release microcapsules of a kind of controlled loading according to claim 6, it is characterized in that: described crosslinking agent is calcium chloride or barium chloride.
8. hydrophobic pesticide slow-release microcapsules of controlled loading of preparing of each described method according to claim 1～7.
9. hydrophobic pesticide slow-release microcapsules of controlled loading according to claim 8, it is characterized in that: the particle diameter of described capsule is 0.5～50 μ m.
10. the hydrophobic pesticide slow-release microcapsules of controlled loading according to claim 8 are applied to agriculture and forestry field, livestock breeding or building material field as the slow release formulation of insecticide or weed killer herbicide.
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