CN104521955A - Pesticide microcapsule and preparation method thereof - Google Patents
Pesticide microcapsule and preparation method thereof Download PDFInfo
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- CN104521955A CN104521955A CN201410762586.5A CN201410762586A CN104521955A CN 104521955 A CN104521955 A CN 104521955A CN 201410762586 A CN201410762586 A CN 201410762586A CN 104521955 A CN104521955 A CN 104521955A
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- microcapsules
- silicon source
- natural polymer
- hydrolyzed
- silica
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 94
- 239000000575 pesticide Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 36
- 239000000839 emulsion Substances 0.000 claims abstract description 25
- 229920005615 natural polymer Polymers 0.000 claims abstract description 23
- 230000000694 effects Effects 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 44
- 239000010703 silicon Substances 0.000 claims description 44
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000008346 aqueous phase Substances 0.000 claims description 27
- 239000012074 organic phase Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- 239000003905 agrochemical Substances 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000013019 agitation Methods 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- 238000005406 washing Methods 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- VNTPGSZQKARKHG-UHFFFAOYSA-N trimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound C[Si](C)(C)CCCOCC1CO1 VNTPGSZQKARKHG-UHFFFAOYSA-N 0.000 claims description 11
- 101710200191 Feather keratin Proteins 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- -1 siloxanes Chemical class 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 7
- WCXDHFDTOYPNIE-RIYZIHGNSA-N (E)-acetamiprid Chemical compound N#C/N=C(\C)N(C)CC1=CC=C(Cl)N=C1 WCXDHFDTOYPNIE-RIYZIHGNSA-N 0.000 claims description 6
- 239000005660 Abamectin Substances 0.000 claims description 6
- 239000005875 Acetamiprid Substances 0.000 claims description 6
- 239000005906 Imidacloprid Substances 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 claims description 6
- 229940056881 imidacloprid Drugs 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- QDZOEBFLNHCSSF-PFFBOGFISA-N (2S)-2-[[(2R)-2-[[(2S)-1-[(2S)-6-amino-2-[[(2S)-1-[(2R)-2-amino-5-carbamimidamidopentanoyl]pyrrolidine-2-carbonyl]amino]hexanoyl]pyrrolidine-2-carbonyl]amino]-3-(1H-indol-3-yl)propanoyl]amino]-N-[(2R)-1-[[(2S)-1-[[(2R)-1-[[(2S)-1-[[(2S)-1-amino-4-methyl-1-oxopentan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]amino]-1-oxo-3-phenylpropan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]pentanediamide Chemical compound C([C@@H](C(=O)N[C@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC(C)C)C(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](N)CCCNC(N)=N)C1=CC=CC=C1 QDZOEBFLNHCSSF-PFFBOGFISA-N 0.000 claims description 2
- 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 2
- 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 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005946 Cypermethrin Substances 0.000 claims description 2
- 239000005893 Diflubenzuron Substances 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- 102100024304 Protachykinin-1 Human genes 0.000 claims description 2
- 101800003906 Substance P Proteins 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229960005424 cypermethrin Drugs 0.000 claims description 2
- 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 2
- QQQYTWIFVNKMRW-UHFFFAOYSA-N diflubenzuron Chemical compound FC1=CC=CC(F)=C1C(=O)NC(=O)NC1=CC=C(Cl)C=C1 QQQYTWIFVNKMRW-UHFFFAOYSA-N 0.000 claims description 2
- 229940019503 diflubenzuron Drugs 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229960002418 ivermectin Drugs 0.000 claims description 2
- 239000002728 pyrethroid Substances 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 2
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims 2
- 239000002775 capsule Substances 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 3
- 230000001276 controlling effect Effects 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 229910021529 ammonia Inorganic materials 0.000 description 15
- 150000002118 epoxides Chemical class 0.000 description 9
- 230000002045 lasting effect Effects 0.000 description 4
- 229920001661 Chitosan Polymers 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000013270 controlled release Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000005944 Chlorpyrifos Substances 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000000361 pesticidal effect Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to a pesticide microcapsule and a preparation method thereof, the pesticide/silicon dioxide microcapsule is prepared by an emulsion in-situ coating method, then the surface of the pesticide/silicon dioxide microcapsule is functionalized, and the pesticide/silicon dioxide/natural polymer double-layer wall material pesticide microcapsule is prepared by crosslinking a functional group and a natural polymer. The pesticide microcapsule prepared by the invention has high drug loading capacity and obvious slow release effect, the used wall material is harmless to the environment, and the release of pesticide can be controlled by regulating and controlling the wall material.
Description
Technical field
The present invention relates to a kind of microcapsules and preparation method thereof, particularly a kind of agricultural chemicals double-coating microcapsules and preparation method thereof.
Background technology
The extermination of disease and insect pest is an important step in agricultural production, and applying pesticides is the main path of the agriculture field extermination of disease and insect pest, but traditional agricultural chemicals availability is low, and persticide residue is large, causes waste and environmental pollution.For effectively utilizing agricultural chemicals and reducing environmental pollution, sustained-release pesticides receives publicity, wherein microcapsule formulations, and cladded type slow release agent research is more.The natural polymer such as sodium alginate, shitosan is that carrier has the deficiencies such as intensity is low, drugloading rate is low, easy violent release.The acid monomer generated after the synthesis such as Lauxite, melamine resin macromolecule exists residual component difficult degradation, degraded or oligomer make soil pH value reduction cause the problems such as soil acidification.
In order to overcome the deficiency of above-mentioned microcapsule formulations, people propose to use sol-gel emulsion polymerization by drug encapsulation in silica shell.As Chinese patent ZL200610114438.8 discloses the microencapsulated water soluble drug of silica, Chinese patent application publication number CN103153050A discloses the metallized pesticide micro capsule of a kind of silica shell makes agricultural chemicals be able to controlled release, Chinese patent application publication number CN102515176A discloses a kind of Diplopore silica particles and uses thereof, United States Patent (USP) 8,889,044 discloses sol-gel process for being encapsulated in unmodified silica shell by agricultural chemicals.
Although these silica microcapsules provide slowly-releasing to a certain degree, because be all that individual layer is coated, slow release effect is limited, and the lasting period is short, and people wish that developed agricultural chemicals has certain lasting period, and clad again can not to environment.
Summary of the invention
The object of this invention is to provide a kind ofly have that drugloading rate is high, slow release effect is obvious, the lasting period is long, the pesticide micro capsule of wall material environmental sound and preparation method thereof.
Object of the present invention can be realized by following measure: the agricultural chemicals/silica microcapsules first by utilizing sol-gel process in-stiu coating to prepare with nucleocapsid structure, then coupling agent treatment is used, its surface band is made to have function base, recycling function base and natural polymer are cross-linked, prepare agricultural chemicals/silica/natural polymer double-coating pesticide micro capsule, hydrophobic pesticidal can be embedded in hollow interior, improve agricultural chemicals load capacity, and by regulating wall equipment structure and composition control farm chemical release, reach release/controlled release object.
Invention main points:
Pesticide slow-release microcapsules of the present invention, for having the core-shell particles of double shells, its kernel is pesticide activity component, and inner layer wall material is silica, and outer wall material is the natural polymer such as shitosan, feather keratin, and drugloading rate one quality counts 10 ~ 50%.
Preparation method of the present invention, specifically comprises the following steps:
A) be hydrolyzed in advance by siloxanes eka-silicon source material, obtain being hydrolyzed silicon source A, hydrolysising condition pH value is 8 ~ 12;
B) surfactant is soluble in water, form aqueous phase B, surfactant concentration is 1g/100mL ~ 5g/100 mL;
C) be dissolved in organic solvent by agricultural chemicals, form organic phase C, pesticide concentration is 50-1200mg/ mL;
D) under high velocity agitation, organic phase C is added aqueous phase B, the volume ratio of organic phase C and aqueous phase B is 1:50 ~ 1:10, continues stirring until Star City stable oil-in-water (O/W) type emulsion D;
E) in emulsion, add the silicon source A be hydrolyzed in advance, Keep agitation, aging, ageing time is 12 ~ 48 hours, silicon source material is fully hydrolyzed and polycondensation, forms coated with silica microcapsules E;
F) adding silane coupler to not being separated in microcapsules E system, stirring, reaction, temperature is 50 ~ 80 DEG C, and the reaction time is 1 ~ 6h.Centrifugal, dry, obtain function of surface microcapsules F;
G) natural polymer is water-soluble, form natural polymer solution, the concentration of natural polymer is 0.2 ~ 1.0w/v, function of surface microcapsules F is joined in Polymer Solution, the consumption of natural polymer is 3 ~ 20% of microcapsules F, adds thermal response, and reaction temperature is 30 ~ 80 DEG C, reaction time is that 6 ~ 24h. is centrifugal, and washing also drying obtains agricultural chemicals/silica/natural polymer core-shell particles microcapsules.
Described agricultural chemicals is more than one in diflubenzuron, Acetamiprid, chlopyrifos, Affirm (Merck Co.), Avermectin, Imidacloprid, ivermectin, High effect cypermethrin and pyrethroid.
Described natural polymer is the one of shitosan or feather keratin.
In step a, siloxanes eka-silicon source material is methyl silicate or ethyl orthosilicate.
In step a, siloxanes eka-silicon source Substance P hydrolysis catalyzer is ammoniacal liquor.
Surfactant in step b is softex kw or hexadecyltrimethylammonium chloride.
Organic solvent in step c is the one in ethyl acetate, butyl acetate, toluene, n-hexane, normal heptane, chloroform.
Silane coupler in step f is γ-glycidyl-oxypropyl trimethyl silane, isocyanatopropyl triethoxysilane.
Beneficial effect of the present invention:
Pesticide micro capsule of the present invention, adopt using to the nontoxic silica of soil and degradable and can as the natural polymer of Fertilizer application for double wall material, drugloading rate be high, has obvious pesticide slow-release/controlled-release effect, effectively can extend the lasting period of agricultural chemicals.Slow-release microcapsule of the present invention can provide desirable injurious insect control under lower frequency and/or rate of application.In addition, preparation method of the present invention is fairly simple, easy to implement.
Embodiment:
Embodiment 1
Be be hydrolyzed 1.5h in advance in the ammonia spirit of 9 at pH value by 4g silicon source material ethyl orthosilicate, obtain being hydrolyzed silicon source A; 2g softex kw is dissolved in 100mL deionized water, obtains aqueous phase B; 1g chlopyrifos is dissolved in 4mL ethyl acetate, obtains organic phase C; Under agitation, organic phase C is joined in aqueous phase B, continue stirring until and form stable O/w emulsion D; Drip in emulsion D and be hydrolyzed silicon source A, the aging 24h of stirring at room temperature in advance, obtain coated with silica pesticide micro capsule E; In system E, add 1mL γ-glycidyl-oxypropyl trimethyl silane, at 60 DEG C, react 4h, obtain epoxide modified coated with silica pesticide micro capsule F; 0.3% feather keratin solution 100mL is configured with ammonia spirit (PH10), add 3 g pesticide micro capsule F again, 6h is reacted at 60 DEG C, by solution centrifugal, respectively with deionized water, ethanol washing, drying obtains the coated pesticide micro capsule of double wall material, and load capacity is that 21.5%(load capacity refers to that pesticide quality accounts for the mass ratio of whole microcapsules).
Embodiment 2
Be be hydrolyzed 1.5h in advance in the ammonia spirit of 9 at pH value by 4g silicon source material ethyl orthosilicate, obtain being hydrolyzed silicon source A; 2g softex kw is dissolved in 100mL deionized water, obtains aqueous phase B; 2g chlopyrifos is dissolved in 4mL ethyl acetate, obtains organic phase C; Under agitation, organic phase C is joined in aqueous phase B, continue stirring until and form stable O/w emulsion D; Drip in emulsion D and be hydrolyzed silicon source A, the aging 24h of stirring at room temperature in advance, obtain coated with silica pesticide micro capsule E; In system E, add 1mL γ-glycidyl-oxypropyl trimethyl silane, at 60 DEG C, react 4h, obtain epoxide modified coated with silica pesticide micro capsule F; 0.3% feather keratin solution 100mL is configured with ammonia spirit (PH10), add 3 g pesticide micro capsule F, 6h is reacted at 60 DEG C, by solution centrifugal, respectively with deionized water, ethanol washing, drying obtains the coated chlorpyrifos microcapsule of double wall material, and load capacity is that 26.7%(load capacity refers to that pesticide quality accounts for the mass ratio of whole microcapsules).
Embodiment 3
Be be hydrolyzed 1.5h in advance in the ammonia spirit of 9 at pH value by 4g silicon source material ethyl orthosilicate, obtain being hydrolyzed silicon source A; 2g softex kw is dissolved in 100mL deionized water, obtains aqueous phase B; 1.5g chlopyrifos is dissolved in 4mL ethyl acetate, obtains organic phase C; Under agitation, organic phase C is joined in aqueous phase B, continue stirring until and form stable O/w emulsion D; Drip in emulsion D and be hydrolyzed silicon source A, the aging 24h of stirring at room temperature in advance, obtain coated with silica pesticide micro capsule E; In system E, add 1mL γ-glycidyl-oxypropyl trimethyl silane, at 60 DEG C, react 4h, obtain epoxide modified coated with silica pesticide micro capsule F; 0.3% feather keratin solution 100mL is configured with ammonia spirit (PH10), add 3 g pesticide micro capsule F again, 6h is reacted at 60 DEG C, by solution centrifugal, respectively with deionized water, ethanol washing, drying, obtains the coated chlorpyrifos microcapsule of double wall material, and load capacity is that 23.8%(load capacity refers to that pesticide quality accounts for the mass ratio of whole microcapsules).
Embodiment 4
Be be hydrolyzed 1.5h in advance in the ammonia spirit of 10 at pH value by 4g silicon source material ethyl orthosilicate, obtain being hydrolyzed silicon source A; 2g softex kw is dissolved in 100mL deionized water, obtains aqueous phase B; 1g Avermectin is dissolved in 4mL toluene, obtains organic phase C; Under agitation, organic phase C is joined in aqueous phase B, continue stirring until and form stable O/w emulsion D; Drip in emulsion D and be hydrolyzed silicon source A, the aging 24h of stirring at room temperature in advance, obtain coated with silica pesticide micro capsule E; In system E, add 1mL γ-glycidyl-oxypropyl trimethyl silane, at 60 DEG C, react 4h, obtain epoxide modified coated with silica pesticide micro capsule F; 0.3% feather keratin solution 100mL is configured with ammonia spirit (PH10), add 3 g pesticide micro capsule F, 6h is reacted at 60 DEG C, by solution centrifugal, respectively with deionized water, ethanol washing, drying obtains the coated avermectin microcapsule of double wall material, and load capacity is that 17.3%(load capacity refers to that pesticide quality accounts for the mass ratio of whole microcapsules).
Embodiment 5
Be be hydrolyzed 1.5h in advance in the ammonia spirit of 10 at pH value by 4g silicon source material ethyl orthosilicate, obtain being hydrolyzed silicon source A; 2g softex kw is dissolved in 100mL deionized water, obtains aqueous phase B; 2g Avermectin is dissolved in 4mL toluene, obtains organic phase C; Under agitation, organic phase C is joined in aqueous phase B, continue stirring until and form stable O/w emulsion D; Drip in emulsion D and be hydrolyzed silicon source A, the aging 24h of stirring at room temperature in advance, obtain coated with silica pesticide micro capsule E; In system E, add 1mL γ-glycidyl-oxypropyl trimethyl silane, 60 DEG C, reaction 4h, obtains epoxide modified coated with silica pesticide micro capsule F; 0.2% chitosan solution 100mL is configured with acetum (PH5), add 3 g pesticide micro capsule F again, 6h is reacted at 60 DEG C, by solution centrifugal, respectively with deionized water, ethanol washing, drying, obtains the coated avermectin microcapsule of double wall material, and load capacity is that 19.8%(load capacity refers to that pesticide quality accounts for the mass ratio of whole microcapsules).
Embodiment 6
Be be hydrolyzed 1.5h in advance in the ammonia spirit of 9 at pH value by 4g silicon source material ethyl orthosilicate, obtain being hydrolyzed silicon source A; 2g softex kw is dissolved in 100mL deionized water, obtains aqueous phase B; 1g Imidacloprid is dissolved in 4mL chloroform, obtains organic phase C; Under agitation, organic phase C is joined in aqueous phase B, continue stirring until and form stable O/w emulsion D; Drip in emulsion D and be hydrolyzed silicon source A, the aging 24h of stirring at room temperature in advance, obtain coated with silica pesticide micro capsule E; In system E, add 1mL γ-glycidyl-oxypropyl trimethyl silane, at 60 DEG C, react 4h, obtain epoxide modified coated with silica pesticide micro capsule F; 0.3% feather keratin solution 100mL is configured with ammonia spirit (PH10), add 2.5g pesticide micro capsule F, 6h is reacted at 60 DEG C, by solution centrifugal, respectively with deionized water, ethanol washing, drying obtains the coated Imidacloprid microcapsules of double wall material, and load capacity is that 16.8%(load capacity refers to that pesticide quality accounts for the mass ratio of whole microcapsules).
Embodiment 7
Be be hydrolyzed 1.5h in advance in the ammonia spirit of 9 at pH value by 4g silicon source material ethyl orthosilicate, obtain being hydrolyzed silicon source A; 2g softex kw is dissolved in 100mL deionized water, obtains aqueous phase B; 2g Imidacloprid is dissolved in 4mL chloroform, obtains organic phase C; Under agitation, organic phase C is joined in aqueous phase B, continue stirring until and form stable O/w emulsion D; Drip in emulsion D and be hydrolyzed silicon source A, the aging 24h of stirring at room temperature in advance, obtain coated with silica pesticide micro capsule E; In system E, add 1mL γ-glycidyl-oxypropyl trimethyl silane, at 60 DEG C, react 4h, obtain epoxide modified coated with silica pesticide micro capsule F; 0.2% chitosan solution 100mL is configured with acetum (PH5), add 3g pesticide micro capsule F again, 6h is reacted at 60 DEG C, by solution centrifugal, respectively with deionized water, ethanol washing, drying obtains the coated Imidacloprid microcapsules of double wall material, and load capacity is that 20.3%(load capacity refers to that pesticide quality accounts for the mass ratio of whole microcapsules).
Embodiment 8
Be be hydrolyzed 1.5h in advance in the ammonia spirit of 9 at pH value by 4g silicon source material ethyl orthosilicate, obtain being hydrolyzed silicon source A; 2g hexadecyltrimethylammonium chloride is dissolved in 100mL deionized water, obtains aqueous phase B; 1g Acetamiprid is dissolved in 4mL chloroform, obtains organic phase C; Under agitation, organic phase C is joined in aqueous phase B, continue stirring until and form stable O/w emulsion D; Drip in emulsion D and be hydrolyzed silicon source A, the aging 24h of stirring at room temperature in advance, obtain coated with silica pesticide micro capsule E; In system E, add 1mL γ-glycidyl-oxypropyl trimethyl silane, at 40 DEG C, react 12h, obtain epoxide modified coated with silica pesticide micro capsule F; 0.2% chitosan solution 100mL is configured with acetum (PH5), add 3g pesticide micro capsule F again, 8h is reacted at 50 DEG C, by solution centrifugal, respectively with deionized water, ethanol washing, drying obtains the coated acetamiprid microcapsule of double wall material, and load capacity is that 16.3%(load capacity refers to that pesticide quality accounts for the mass ratio of whole microcapsules).
Embodiment 9
Be be hydrolyzed 1.5h in advance in the ammonia spirit of 9 at pH value by 4g silicon source material ethyl orthosilicate, obtain being hydrolyzed silicon source A; 2g hexadecyltrimethylammonium chloride is dissolved in 100mL deionized water, obtains aqueous phase B; 2g Acetamiprid is dissolved in 5mL chloroform, obtains organic phase C; Under agitation, organic phase C is joined in aqueous phase B, continue stirring until and form stable O/w emulsion D; Drip in emulsion D and be hydrolyzed silicon source A, the aging 24h of stirring at room temperature in advance, obtain coated with silica pesticide micro capsule E; In system E, add 1mL γ-glycidyl-oxypropyl trimethyl silane, at 40 DEG C, react 12h, obtain epoxide modified coated with silica pesticide micro capsule F; 0.3% feather keratin solution 100mL is configured with ammonia spirit (PH8), add 3g pesticide micro capsule F again, 8h is reacted at 50 DEG C, by solution centrifugal, respectively with deionized water, ethanol washing, drying obtains the coated acetamiprid microcapsule of double wall material, and load capacity is that 21.4%(load capacity refers to that pesticide quality accounts for the mass ratio of whole microcapsules).
Claims (9)
1. microcapsules, it comprises core, and this core comprises the active component being encapsulated in capsule material, it is characterized in that, described capsule material is silica and the natural polymer double wall material of loose structure, and drugloading rate is 10-50% in mass; Specifically comprise the following steps:
A) siloxanes eka-silicon source material is hydrolyzed in advance, obtains being hydrolyzed silicon source A;
B) surfactant is soluble in water, form aqueous phase B;
C) agricultural chemicals is dissolved in organic solvent, forms organic phase C;
D) under high velocity agitation, organic phase C is added aqueous phase B, the volume ratio of organic phase C and aqueous phase B is 1:50 ~ 1:10, continues stirring until and forms stable oil-in-water (O/W) type emulsion D;
E) in emulsion, the silicon source A be hydrolyzed is in advance added, Keep agitation, aging, silicon source material is fully hydrolyzed and polycondensation, forms coated with silica microcapsules E;
F) adding silane coupler to not being separated in microcapsules E system, stirring, reaction, centrifugal, drying obtains function of surface microcapsules F;
G) natural polymer is water-soluble, form natural polymer solution, join in Polymer Solution, add thermal response by function of surface microcapsules F, centrifugal, washing also drying obtains natural polymer/silica/agricultural chemicals core-shell particles microcapsules.
2. microcapsules as claimed in claim 1, it is characterized in that, described active component is agricultural chemicals.
3. microcapsules as claimed in claim 1, it is characterized in that, described natural polymer wall material is the one of shitosan or feather keratin.
4. as claimed in claim 2 microcapsules, is characterized in that, described agricultural chemicals is more than one in diflubenzuron, Acetamiprid, chlopyrifos, Affirm (Merck Co.), Avermectin, Imidacloprid, ivermectin, High effect cypermethrin and pyrethroid.
5. microcapsules as claimed in claim 1, it is characterized in that, its preparation method comprises the following steps:
A) siloxanes eka-silicon source material is hydrolyzed in advance, obtains being hydrolyzed silicon source A;
B) surfactant is soluble in water, form aqueous phase B;
C) agricultural chemicals is dissolved in organic solvent, forms organic phase C;
D) under high velocity agitation, organic phase C is added aqueous phase B, the volume ratio of organic phase C and aqueous phase B is 1:50 ~ 1:10, continues stirring until Star City stable oil-in-water (O/W) type emulsion D;
E) in emulsion, the silicon source A be hydrolyzed is in advance added, Keep agitation, aging, silicon source material is fully hydrolyzed and polycondensation, forms coated with silica microcapsules E;
F) adding silane coupler to not being separated in microcapsules E system, stirring, reaction, centrifugal, drying obtains function of surface microcapsules F;
G) natural polymer is water-soluble, form natural polymer solution, join in Polymer Solution by function of surface microcapsules F, heating, reaction, centrifugal, washing also drying obtains natural polymer/silica/agricultural chemicals core-shell particles microcapsules;
In step a, siloxanes eka-silicon source material is methyl silicate or ethyl orthosilicate;
In step a, siloxanes eka-silicon source Substance P hydrolysis catalyzer is ammoniacal liquor;
Surfactant in step b is softex kw or hexadecyltrimethylammonium chloride;
Organic solvent in step c is the one in ethyl acetate, butyl acetate, toluene, n-hexane, normal heptane, chloroform;
Silane coupler in step f is γ-glycidyl-oxypropyl trimethyl silane, isocyanatopropyl triethoxysilane;
Microcapsules as claimed in claim 5, is characterized in that, the pH value of solution A hydrolysis is 8 ~ 12;
Microcapsules as claimed in claim 5, is characterized in that, the concentration of solution B surfactant is 0.5g/100mL ~ 5g/100 mL;
Microcapsules as claimed in claim 5, is characterized in that, solution C Pesticides concentration is 50-1200mg/mL.
Microcapsules as claimed in claim 5, is characterized in that, in step e, ageing time is 16 ~ 48h, and temperature is room temperature.
6. microcapsules as claimed in claim 5, it is characterized in that, in step f, silane coupler consumption is 5 ~ 20% of siloxanes eka-silicon source material.
7. microcapsules as claimed in claim 5, it is characterized in that, in step f, reaction temperature is 50 ~ 80 DEG C, and the reaction time is 1 ~ 6h.
8. microcapsules as claimed in claim 5, it is characterized in that, in step g, the concentration of natural polymer is 0.2 ~ 1.0w/v, and the consumption of natural polymer is 3 ~ 20% of microcapsules F.
9. microcapsules as claimed in claim 5, it is characterized in that, in step g, reaction temperature is 30 ~ 80 DEG C, and the reaction time is 6 ~ 24h.
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