CN109997847B - Alkyd resin/pesticide nano emulsion and preparation method thereof - Google Patents
Alkyd resin/pesticide nano emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN109997847B CN109997847B CN201910363551.7A CN201910363551A CN109997847B CN 109997847 B CN109997847 B CN 109997847B CN 201910363551 A CN201910363551 A CN 201910363551A CN 109997847 B CN109997847 B CN 109997847B
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- CN
- China
- Prior art keywords
- alkyd resin
- pesticide
- water
- emulsifier
- anhydride
- 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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- 229920000180 alkyd Polymers 0.000 title claims abstract description 278
- 239000000575 pesticide Substances 0.000 title claims abstract description 249
- 239000007908 nanoemulsion Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 239000003814 drug Substances 0.000 claims abstract description 57
- 229940079593 drug Drugs 0.000 claims abstract description 56
- 239000002245 particle Substances 0.000 claims abstract description 37
- 238000005538 encapsulation Methods 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 88
- 239000003995 emulsifying agent Substances 0.000 claims description 49
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 30
- 150000008064 anhydrides Chemical class 0.000 claims description 29
- 239000005660 Abamectin Substances 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000006184 cosolvent Substances 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 21
- ATROHALUCMTWTB-OWBHPGMISA-N phoxim Chemical compound CCOP(=S)(OCC)O\N=C(\C#N)C1=CC=CC=C1 ATROHALUCMTWTB-OWBHPGMISA-N 0.000 claims description 21
- 229950001664 phoxim Drugs 0.000 claims description 21
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 21
- 239000008158 vegetable oil Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 17
- 150000007519 polyprotic acids Polymers 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 125000000524 functional group Chemical group 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- 229950008167 abamectin Drugs 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 13
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- IBSREHMXUMOFBB-JFUDTMANSA-N 5u8924t11h 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(O3)C=C[C@H](C)[C@@H](C(C)C)O4)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.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 IBSREHMXUMOFBB-JFUDTMANSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000012874 anionic emulsifier Substances 0.000 claims description 9
- 239000012875 nonionic emulsifier Substances 0.000 claims description 9
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- ZXQYGBMAQZUVMI-RDDWSQKMSA-N (1S)-cis-(alphaR)-cyhalothrin Chemical compound CC1(C)[C@H](\C=C(/Cl)C(F)(F)F)[C@@H]1C(=O)O[C@@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-RDDWSQKMSA-N 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000005910 lambda-Cyhalothrin Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 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 6
- 239000005944 Chlorpyrifos Substances 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 claims description 6
- QQODLKZGRKWIFG-QSFXBCCZSA-N cyfluthrin Chemical compound CC1(C)[C@@H](C=C(Cl)Cl)[C@H]1C(=O)O[C@@H](C#N)C1=CC=C(F)C(OC=2C=CC=CC=2)=C1 QQODLKZGRKWIFG-QSFXBCCZSA-N 0.000 claims description 6
- 229960001591 cyfluthrin Drugs 0.000 claims description 6
- NYPJDWWKZLNGGM-UHFFFAOYSA-N fenvalerate Chemical compound C=1C=C(Cl)C=CC=1C(C(C)C)C(=O)OC(C#N)C(C=1)=CC=CC=1OC1=CC=CC=C1 NYPJDWWKZLNGGM-UHFFFAOYSA-N 0.000 claims description 6
- 229960002418 ivermectin Drugs 0.000 claims description 6
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkylbenzene sulfonate Chemical class 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 4
- 239000000944 linseed oil Substances 0.000 claims description 4
- 235000021388 linseed oil Nutrition 0.000 claims description 4
- 229920000136 polysorbate Polymers 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000002383 tung oil Substances 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 3
- PGOOBECODWQEAB-UHFFFAOYSA-N (E)-clothianidin Chemical compound [O-][N+](=O)\N=C(/NC)NCC1=CN=C(Cl)S1 PGOOBECODWQEAB-UHFFFAOYSA-N 0.000 claims description 3
- HOKKPVIRMVDYPB-UVTDQMKNSA-N (Z)-thiacloprid Chemical compound C1=NC(Cl)=CC=C1CN1C(=N/C#N)/SCC1 HOKKPVIRMVDYPB-UVTDQMKNSA-N 0.000 claims description 3
- 239000005874 Bifenthrin Substances 0.000 claims description 3
- 239000005886 Chlorantraniliprole Substances 0.000 claims description 3
- 239000005888 Clothianidin Substances 0.000 claims description 3
- 239000005892 Deltamethrin Substances 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005940 Thiacloprid Substances 0.000 claims description 3
- OMFRMAHOUUJSGP-IRHGGOMRSA-N bifenthrin Chemical compound C1=CC=C(C=2C=CC=CC=2)C(C)=C1COC(=O)[C@@H]1[C@H](\C=C(/Cl)C(F)(F)F)C1(C)C OMFRMAHOUUJSGP-IRHGGOMRSA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- JLQUFIHWVLZVTJ-UHFFFAOYSA-N carbosulfan Chemical compound CCCCN(CCCC)SN(C)C(=O)OC1=CC=CC2=C1OC(C)(C)C2 JLQUFIHWVLZVTJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- PSOVNZZNOMJUBI-UHFFFAOYSA-N chlorantraniliprole Chemical compound CNC(=O)C1=CC(Cl)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl PSOVNZZNOMJUBI-UHFFFAOYSA-N 0.000 claims description 3
- 239000003240 coconut oil Substances 0.000 claims description 3
- 235000019864 coconut oil Nutrition 0.000 claims description 3
- 235000012343 cottonseed oil Nutrition 0.000 claims description 3
- 239000002385 cottonseed oil Substances 0.000 claims description 3
- 229960002483 decamethrin Drugs 0.000 claims description 3
- OWZREIFADZCYQD-NSHGMRRFSA-N deltamethrin Chemical compound CC1(C)[C@@H](C=C(Br)Br)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 OWZREIFADZCYQD-NSHGMRRFSA-N 0.000 claims description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- AMFGTOFWMRQMEM-UHFFFAOYSA-N triazophos Chemical compound N1=C(OP(=S)(OCC)OCC)N=CN1C1=CC=CC=C1 AMFGTOFWMRQMEM-UHFFFAOYSA-N 0.000 claims description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims 2
- 229910000831 Steel Inorganic materials 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 238000013270 controlled release Methods 0.000 abstract description 8
- 230000002459 sustained effect Effects 0.000 abstract description 8
- 238000013268 sustained release Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 70
- 238000011068 loading method Methods 0.000 description 48
- 239000000839 emulsion Substances 0.000 description 27
- 238000011065 in-situ storage Methods 0.000 description 20
- 241000607479 Yersinia pestis Species 0.000 description 18
- ZXQYGBMAQZUVMI-UNOMPAQXSA-N cyhalothrin Chemical compound CC1(C)C(\C=C(/Cl)C(F)(F)F)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-UNOMPAQXSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000008901 benefit Effects 0.000 description 13
- 239000000376 reactant Substances 0.000 description 11
- 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 description 10
- 230000007613 environmental effect Effects 0.000 description 10
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- 239000008367 deionised water Substances 0.000 description 9
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- 230000007935 neutral effect Effects 0.000 description 9
- 239000003981 vehicle Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- 238000009826 distribution Methods 0.000 description 7
- 230000000749 insecticidal effect Effects 0.000 description 7
- 230000000361 pesticidal effect Effects 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 6
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- 238000001816 cooling Methods 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 150000007529 inorganic bases Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
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- 239000003905 agrochemical Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
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- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
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- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 2
- 238000000614 phase inversion technique Methods 0.000 description 2
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- A01N25/08—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 solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
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Abstract
The application discloses an alkyd resin/pesticide nanoemulsion and a preparation method thereof. The average hydrated particle size of the drug-loaded particles in the alkyd resin/pesticide nano emulsion is 30-250 nm, the solid content is 10-50%, the drug-loaded rate of the alkyd resin is 0.01-50%, the encapsulation rate is not lower than 90%, the alkyd resin nano emulsion has good dispersibility and stability, good leaf surface adhesiveness, long activity, high bioavailability and sustained and controlled release performance, can be directly sprayed for use, and the carrier is biodegradable, green, environment-friendly, safe and efficient.
Description
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to alkyd resin/pesticide nano emulsion and a preparation method thereof.
Background
As an important agricultural chemical, the pesticide is very important and widely applied in the aspects of preventing and controlling pests, protecting crops, improving crop yield and the like. However, due to the influence of factors such as the application mode of the traditional agriculture and environmental conditions, the effective utilization rate of the pesticide finally reaching the crop target is less than 30%, and the actual dosage of the pest is less than 0.1%. The pesticide formulations commonly used in the market at present are mainly missible oil and wettable powder, and the traditional formulations bring a great deal of resource waste and environmental pollution when being used in a large scale. Therefore, research and development of new efficient and green pesticide formulations are receiving much attention.
The pesticide loading technology is an effective way for overcoming the defects of the traditional pesticide formulation. By means of wrapping and coupling the pesticide and the carrier material, the adhesion of the pesticide on the surface of the blade can be obviously improved, the residence time of the pesticide is prolonged, and the pesticide can be continuously and stably released, so that the effective utilization rate of the pesticide is improved, and the loss and pollution of the pesticide are reduced. However, the particle size of the current pesticide load preparation on the market is usually micron-sized, the large particle size easily causes poor water dispersibility, the application process easily causes the problems of drop sliding, dust drifting and the like, and the adhesion, permeability and bioavailability to the crop target are poor. Meanwhile, the preparation process of the traditional pesticide load preparation is complex, difficult to control and poor in repeatability.
Therefore, the existing pesticides are in need of further improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide an alkyd resin/pesticide nano emulsion and a preparation method thereof. The average hydrated particle size of the drug-loaded particles in the alkyd resin/pesticide nano emulsion is 30-250 nm, the solid content is 10-50%, the drug-loaded rate of the alkyd resin is 0.01-50%, the encapsulation rate is not lower than 90%, the alkyd resin nano emulsion has good dispersibility and stability, good leaf surface adhesiveness, long activity, high bioavailability and sustained and controlled release performance, can be directly sprayed for use, and the carrier is biodegradable, green, environment-friendly, safe and efficient.
In one aspect of the invention, the invention provides an alkyd/pesticide nanoemulsion comprising, in accordance with an embodiment of the invention: water-insoluble pesticides, alkyd resins and water. According to the alkyd resin/pesticide nano emulsion disclosed by the embodiment of the invention, the alkyd resin is used as a carrier of a water-insoluble pesticide, and the alkyd resin is a renewable resource and is low in cost; the alkyd resin is biodegradable and is used as a carrier of a water-insoluble pesticide, so that the alkyd resin is green and environment-friendly; by introducing hydrophilic groups into the main chain of the alkyd resin, the waterborne alkyd resin which can be stably dispersed in water can be prepared without adding an emulsifier, and the waterborne alkyd resin has better environmental benefit; the alkyd resin is used as a carrier material of the water-insoluble pesticide, so that the adhesion of a drug-loaded system to the leaf surfaces of crops can be improved, and the off-target loss of the leaf surfaces of the pesticide can be reduced, thereby improving the effective utilization rate and bioavailability of the pesticide. The medium of the drug-carrying system is water, and the drug-carrying system does not contain organic solvent, and has excellent economic and environmental benefits. The drug-loading system of the alkyd resin/pesticide nano emulsion has a nano-scale particle size, the particle size can be as low as 30nm, the particle size distribution range is narrow, and the stability is good; meanwhile, the nano-scale drug loading system is beneficial to improving the contact area of the pesticide and the surfaces of crops, increasing the adhesiveness and the permeability of the pesticide on the leaf surfaces of the crops, obviously reducing the loss of the pesticide and improving the effective utilization rate and the pesticide effect of the pesticide; furthermore, the contact area of the pesticide and the pest target is increased by the nano-scale drug loading system, so that the insecticidal activity of the pesticide on the pest target can be increased. The alkyd resin/pesticide nano emulsion has good dispersibility, and the emulsion can be stored for more than 12 months. The drug-loading rate of the alkyd resin/pesticide nano emulsion carrier can reach 50%, the encapsulation rate is not less than 90%, the solid content and the drug-loading rate of the emulsion can be adjusted according to actual requirements, and the application range is wide. The alkyd resin/pesticide nano emulsion has the drug sustained and controlled release performance, can maintain longer administration time, and reduces administration times and dosage, thereby improving the bioavailability and reducing the pesticide cost.
In addition, the alkyd resin/pesticide nanoemulsion according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, the mass ratio of the water-insoluble pesticide, the alkyd resin and the water is 0.01-25: 9.99-49.99: 50-90. Thus, the quality of the alkyd resin/pesticide nanoemulsion can be further improved.
In some embodiments of the invention, the alkyd resin is obtained by polymerizing a vegetable oil with a polyol, a dibasic acid or anhydride, or a polybasic acid or anhydride having three or more functional groups. Therefore, the cost of the alkyd resin can be further reduced, and the biodegradability of the alkyd resin can be improved.
In some embodiments of the invention, the mass ratio of the vegetable oil to the polyol, the dibasic acid or anhydride, the polybasic acid or anhydride containing three or more functional groups is 10: 2-9: 0.5-9.5: 1.5 to 3. Therefore, the quality of the alkyd resin can be further improved.
In some embodiments of the present invention, the ratio of the total molar amount of-OH to the total molar amount of-COOH in the vegetable oil, the polyol, the dibasic acid or anhydride, and the polybasic acid or anhydride containing three or more functional groups is 1.1 to 1.4. Therefore, the quality of the alkyd resin can be further improved.
In some embodiments of the invention, the alkyd resin has an acid number of 35 to 70 mgKOH/g. Therefore, the quality of the alkyd resin can be further improved.
In some embodiments of the invention, the vegetable oil is at least one selected from the group consisting of linseed oil, soybean oil, tung oil, castor oil, coconut oil and cottonseed oil. Therefore, the cost of the alkyd resin can be further reduced, and the biodegradability of the alkyd resin can be improved.
In some embodiments of the present invention, the polyol is at least one selected from the group consisting of glycerol, pentaerythritol, trimethylolpropane, trimethylolethane, ethylene glycol, propylene glycol, butylene glycol, and neopentyl glycol. This can further improve the quality of the alkyd resin.
In some embodiments of the invention, the dibasic acid or anhydride is at least one selected from the group consisting of isophthalic acid, phthalic anhydride, terephthalic acid, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride. This can further improve the quality of the alkyd resin.
In some embodiments of the present invention, the polybasic acid or anhydride having three or more functional groups is at least one selected from trimellitic anhydride and pyromellitic anhydride. The alkyd resin contains more than three functional groups of polybasic acid or anhydride, and hydrophilic groups are introduced into the main chain of the alkyd resin, so that the nanocrystallization and high stability of a drug-carrying system can be realized by selecting different combinations of polybasic acid or anhydride.
In some embodiments of the invention, the water-insoluble pesticide is at least one selected from the group consisting of lambda-cyhalothrin, cyfluthrin, bifenthrin, deltamethrin, fenvalerate, thiacloprid, clothianidin, triazophos, carbosulfan, abamectin, acetamido abamectin, ivermectin, chlorpyrifos, phoxim, chlorantraniliprole.
In some embodiments of the invention, the water-insoluble pesticide is at least one selected from the group consisting of lambda-cyhalothrin, cyfluthrin, avermectin, ivermectin, chlorpyrifos, and phoxim.
In a further aspect of the invention, the invention provides a method of preparing the alkyd/pesticide nanoemulsion described above, which, according to an embodiment of the invention, comprises:
(1) mixing and neutralizing the alkyd resin with alkali liquor so as to obtain water-based alkyd resin;
(2) mixing a water-insoluble pesticide with a cosolvent to obtain a pesticide solution;
(3) mixing the water-based alkyd resin, the pesticide solution and the emulsifier solution/water, and carrying out phase inversion and reduced pressure distillation treatment so as to obtain the alkyd resin/pesticide nano emulsion.
According to the method for preparing the alkyd resin/pesticide nano emulsion, the alkyd resin/pesticide nano emulsion is prepared by adopting a high-speed in-situ phase inversion method, and compared with the traditional preparation method of a pesticide carrying system, the preparation method provided by the invention is simple and efficient, has good repeatability and is easy for industrial production. The alkyd resin is used as a carrier of the water-insoluble pesticide, and is a renewable resource, so that the cost is low; the alkyd resin is biodegradable and is used as a carrier of a water-insoluble pesticide, so that the alkyd resin is green and environment-friendly; by introducing hydrophilic groups into the main chain of the alkyd resin, the waterborne alkyd resin which can be stably dispersed in water can be prepared without adding an emulsifier, and the waterborne alkyd resin has better environmental benefit; the alkyd resin is used as a carrier material of the water-insoluble pesticide, so that the adhesion of a drug-loaded system to the leaf surfaces of crops can be improved, and the off-target loss of the leaf surfaces of the pesticide can be reduced, thereby improving the effective utilization rate and bioavailability of the pesticide. The drug-loading system of the alkyd resin/pesticide nano emulsion has a nano-scale particle size, the particle size can be as low as 30nm, the particle size distribution range is narrow, and the stability is good; meanwhile, the nano-scale drug loading system is beneficial to improving the contact area of the pesticide and the surfaces of crops, increasing the adhesiveness and the permeability of the pesticide on the leaf surfaces of the crops, obviously reducing the loss of the pesticide and improving the effective utilization rate and the pesticide effect of the pesticide; furthermore, the contact area of the pesticide and the pest target is increased by the nano-scale drug loading system, so that the insecticidal activity of the pesticide on the pest target can be increased. The alkyd resin/pesticide nano emulsion has good dispersibility, and the emulsion can be stored for more than 12 months. The drug-loading rate of the alkyd resin/pesticide nano emulsion carrier can reach 50%, the encapsulation rate is not less than 90%, the solid content and the drug-loading rate of the emulsion can be adjusted according to actual requirements, and the application range is wide. The alkyd resin/pesticide nano emulsion has the drug sustained and controlled release performance, can maintain longer administration time, and reduces administration times and dosage, thereby improving the bioavailability and reducing the pesticide cost.
In addition, the method for preparing the alkyd resin/pesticide nanoemulsion according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the present invention, in step (1), the alkali solution is at least one selected from an organic base or an inorganic base. Thereby being beneficial to improving the quality of the water-based alkyd resin.
In some embodiments of the invention, in step (1), the organic base is at least one selected from triethylamine and trimethylamine. Thereby, the quality of the water-based alkyd resin can be further improved.
In some embodiments of the present invention, in step (1), the inorganic base is at least one selected from the group consisting of aqueous ammonia and sodium hydroxide. Thereby, the quality of the water-based alkyd resin can be further improved.
In some embodiments of the invention, in step (1), the mass ratio of the alkyd resin to the lye is 10: 0.5 to 1.5. Thereby, the quality of the water-based alkyd resin can be further improved.
In some embodiments of the present invention, in step (2), the cosolvent is at least one selected from the group consisting of ethyl acetate, ethanol, methanol, isopropanol, acetone, butanone, cyclohexane, and n-hexane. Therefore, the quality of the pesticide solution is improved.
In some embodiments of the present invention, in the step (2), the co-solvent has a boiling point of 50 to 100 ℃. This can further improve the quality of the agricultural chemical solution.
In some embodiments of the invention, in step (2), the mass ratio of the water-insoluble pesticide to the co-solvent is 1: 0.5 to 2. This can further improve the quality of the agricultural chemical solution.
In some embodiments of the invention, in step (3), the emulsifier solution comprises an anionic emulsifier and a nonionic emulsifier. This is advantageous for improving the quality of the emulsifier.
In some embodiments of the present invention, in step (3), the anionic emulsifier is at least one selected from alkyl sulfate and alkyl benzene sulfonate. This can further improve the quality of the emulsifier.
In some embodiments of the present invention, in step (3), the nonionic emulsifier is at least one selected from the group consisting of alkylphenol ethoxylates, tweens, and span. This can further improve the quality of the emulsifier.
In some embodiments of the invention, the mass of the emulsifier in the emulsifier solution is 0-3% of the mass of the alkyd resin. This can further improve the quality of the emulsifier.
In some embodiments of the invention, in step (3), the mass ratio of the water-based alkyd resin to the pesticide solution, the emulsifier solution/the water is 9.99-49.99: 0.02-60: 50 to 91.5. Thus, the quality of the alkyd resin/pesticide nanoemulsion can be further improved.
In some embodiments of the present invention, in the step (3), the stirring speed of the phase inversion is 1000 to 2000 r/min. Thus, the quality of the alkyd resin/pesticide nanoemulsion can be further improved.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a method for preparing an alkyd/pesticide nanoemulsion according to one embodiment of the present invention;
FIG. 2 is a transmission electron microscope image of the alkyd resin/lambda-cyhalothrin nanoemulsion prepared in example 1.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, the invention provides an alkyd/pesticide nanoemulsion comprising, in accordance with an embodiment of the invention: water-insoluble pesticides, alkyd resins and water. Further, in the alkyd resin/pesticide nano emulsion, the mass ratio of the water-insoluble pesticide to the alkyd resin to the water may be 0.01-25: 9.99-49.99: 50-90. The inventor finds that the excessive use of the water-insoluble pesticide or the excessive use of the water leads to excessive viscosity of the system and low coating rate, and further leads to instability of the alkyd resin/pesticide nano emulsion system.
According to one embodiment of the invention, the alkyd resin is obtained by polymerizing vegetable oil with a polyol, a dibasic acid or anhydride, a polybasic acid or anhydride containing three or more functional groups. Specifically, vegetable oil and polyhydric alcohol are mixed, the temperature is gradually increased to 150-200 ℃ under the stirring condition, then dibasic acid or anhydride is added into a reaction system, the temperature is continuously increased to 200-240 ℃, esterification reaction is carried out for 1-3 hours under the protection of nitrogen, water is continuously separated in the reaction process until the acid value of a reactant is less than 10 mgKOH/g. And then cooling the reaction system to 140-160 ℃, adding polybasic acid or anhydride containing three or more functional groups into the reaction system, heating to 160-190 ℃, continuously reacting for 0.5-3 hours, continuously measuring the acid value of the reactant in the reaction process, and stopping the reaction when the acid value reaches 35-70 mgKOH/g to obtain the alkyd resin. The inventor finds that by adopting the alkyd resin as a carrier of the water-insoluble pesticide, the alkyd resin is a renewable resource and is low in cost; the alkyd resin is biodegradable and is used as a carrier of a water-insoluble pesticide, so that the alkyd resin is green and environment-friendly; by introducing hydrophilic groups into the main chain of the alkyd resin, the waterborne alkyd resin which can be stably dispersed in water can be prepared without adding an emulsifier, and the waterborne alkyd resin has better environmental benefit; the alkyd resin is used as a carrier material of the water-insoluble pesticide, so that the adhesion of a drug-loaded system to the leaf surfaces of crops can be improved, and the off-target loss of the leaf surfaces of the pesticide can be reduced, thereby improving the effective utilization rate and bioavailability of the pesticide.
According to an embodiment of the present invention, the mass ratio of the vegetable oil to the polyhydric alcohol, the dibasic acid or anhydride, the polybasic acid or anhydride having three or more functional groups may be 10: 2-9: 0.5-9.5: 1.5 to 3, for example, 10: 2/3/4/5/6/7/8/9: 0.5/1.5/2.5/3.5/4.5/5.5/6.5/7.5/8.5/9.5: 1.5/2/2.5/3. The inventor finds that too high vegetable oil consumption can cause the alkyd resin to have insufficient hydrophilicity and cannot be prepared into alkyd resin/pesticide nano emulsion, and too low vegetable oil consumption can cause the alkyd resin to have too strong hydrophilicity and low drug-loading rate. Further, the ratio of the total molar amount of-OH groups in the vegetable oil, the polyol, the dibasic acid or anhydride and the polybasic acid or anhydride having three or more functional groups to the total molar amount of-COOH may be 1.1 to 1.4, for example, 1.1, 1.2, 1.3, 1.4, preferably 1.2. The inventor finds that-OH ratio is too low to cause the alkyd resin to have insufficient hydrophilicity and cannot be prepared into alkyd resin/pesticide nano emulsion, and-OH ratio is too high to cause the alkyd resin to have too strong hydrophilicity and low drug loading. Further, the vegetable oil may be at least one selected from the group consisting of linseed oil, soybean oil, tung oil, castor oil, coconut oil and cottonseed oil. The inventor finds that the vegetable oil is a renewable resource, and the adoption of the vegetable oil as the raw material of the alkyd resin can not only save petroleum resources, but also endow the alkyd resin with biodegradable property. Further, the polyol may be at least one selected from the group consisting of glycerol, pentaerythritol, trimethylolpropane, trimethylolethane, ethylene glycol, propylene glycol, butylene glycol and neopentyl glycol, preferably trimethylolpropane and glycerol. Further, the dibasic acid or the acid anhydride may be at least one selected from isophthalic acid, phthalic anhydride, terephthalic acid, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Further, the polybasic acid or anhydride having three or more functional groups may be at least one selected from trimellitic anhydride and pyromellitic anhydride. The inventor finds that the polybasic acid or anhydride containing three or more functional groups can introduce hydrophilic groups into the main chain of the alkyd resin, so that the nano-drug-loading system and high stability can be realized by selecting and using different combinations of the polybasic acid or anhydride. The nano-scale drug loading system is beneficial to improving the contact area of the pesticide and the surfaces of crops, increasing the adhesiveness and the permeability of the pesticide on the leaf surfaces of the crops, obviously reducing the loss of the pesticide and improving the effective utilization rate and the pesticide effect of the pesticide; the nano-scale drug loading system increases the contact area between the pesticide and the pest target, and can increase the insecticidal activity of the pesticide on the pest target.
According to a further embodiment of the present invention, the acid value of the alkyd resin may be 35 to 70mgKOH/g, for example, 35mgKOH/g, 40mgKOH/g, 45mgKOH/g, 50mgKOH/g, 55mgKOH/g, 60mgKOH/g, 65mgKOH/g, 70 mgKOH/g. The inventor finds that the alkyd resin has insufficient hydrophilicity and cannot be prepared into alkyd resin/pesticide nano emulsion due to too low acid value, and the alkyd resin has too high hydrophilicity and even is completely water-soluble due to too high acid value, so that the alkyd resin/pesticide nano emulsion cannot be prepared by coating pesticide in emulsion particles.
According to still another embodiment of the present invention, the water-insoluble pesticide may be at least one selected from the group consisting of lambda-cyhalothrin, cyfluthrin, bifenthrin, deltamethrin, fenvalerate, thiacloprid, clothianidin, triazophos, carbosulfan, abamectin, acetamido abamectin, ivermectin, chlorpyrifos, phoxim, chlorantraniliprole, preferably lambda-cyhalothrin, cyfluthrin, abamectin, ivermectin, chlorpyrifos, and phoxim.
According to an embodiment of the present invention, the alkyd resin/pesticide nanoemulsion described above has at least one of the following advantages:
in the aspect of carrier materials, one of the main raw materials of the carrier alkyd resin of the drug-carrying system is vegetable oil which is green, safe, low in cost and biodegradable; meanwhile, the medium of the drug-carrying system is water, and the drug-carrying system does not contain organic solvents, so that the economic and environmental benefits are excellent;
in terms of particle size, the alkyd resin/pesticide drug-loaded system has the advantages of nanoscale particle size, minimum particle size of 30nm, narrow particle size distribution and good stability. Meanwhile, the nano-scale drug loading system improves the contact area between the pesticide and the surface of the crops, increases the adhesiveness and the permeability of the pesticide on the leaf surfaces of the crops, and obviously reduces the loss of the pesticide, thereby improving the effective utilization rate and the drug effect of the pesticide. Furthermore, the nano-scale drug loading system can increase the contact area between the pesticide and the pest target, thereby increasing the insecticidal activity on the pest target;
in the aspect of emulsion stability, the alkyd resin/pesticide emulsion has small emulsion particles and good dispersibility, and the emulsion can be stored for more than 12 months;
in the aspect of drug loading, the drug loading rate of the alkyd resin/pesticide nano emulsion can reach 50%, and the encapsulation rate is not less than 90%. The alkyd resin can effectively load non-water-soluble pesticide, can adjust the solid content and the drug loading capacity of the emulsion according to actual requirements, and has a wide application range;
in the aspect of pesticide release, the alkyd resin/pesticide drug-loaded system has the property of sustained and controlled release of the pesticide. The slow release of the pesticide can maintain longer administration time, and reduce administration times and dosage, thereby improving bioavailability and reducing pesticide cost;
in the aspect of adhesion, the alkyd resin is used as a carrier material of the water-insoluble pesticide, so that the adhesion of a drug-carrying system to the leaf surface of crops can be improved, the off-target loss of a medicament from the leaf surface is reduced, and the effective utilization rate and the bioavailability of the pesticide are improved.
According to the alkyd resin/pesticide nano emulsion disclosed by the embodiment of the invention, the alkyd resin is used as a carrier of a water-insoluble pesticide, and the alkyd resin is a renewable resource and is low in cost; the alkyd resin is biodegradable and is used as a carrier of a water-insoluble pesticide, so that the alkyd resin is green and environment-friendly; by introducing hydrophilic groups into the main chain of the alkyd resin, the waterborne alkyd resin which can be stably dispersed in water can be prepared without adding an emulsifier, and the waterborne alkyd resin has better environmental benefit; the alkyd resin is used as a carrier material of the water-insoluble pesticide, so that the adhesion of a drug-loaded system to the leaf surfaces of crops can be improved, and the off-target loss of the leaf surfaces of the pesticide can be reduced, thereby improving the effective utilization rate and bioavailability of the pesticide. The medium of the drug-carrying system is water, and the drug-carrying system does not contain organic solvent, and has excellent economic and environmental benefits. The drug-loading system of the alkyd resin/pesticide nano emulsion has a nano-scale particle size, the particle size can be as low as 30nm, the particle size distribution range is narrow, and the stability is good; meanwhile, the nano-scale drug loading system is beneficial to improving the contact area of the pesticide and the surfaces of crops, increasing the adhesiveness and the permeability of the pesticide on the leaf surfaces of the crops, obviously reducing the loss of the pesticide and improving the effective utilization rate and the pesticide effect of the pesticide; furthermore, the contact area of the pesticide and the pest target is increased by the nano-scale drug loading system, so that the insecticidal activity of the pesticide on the pest target can be increased. The alkyd resin/pesticide nano emulsion has good dispersibility, and the emulsion can be stored for more than 12 months. The drug-loading rate of the alkyd resin/pesticide nano emulsion carrier can reach 50%, the encapsulation rate is not less than 90%, the solid content and the drug-loading rate of the emulsion can be adjusted according to actual requirements, and the application range is wide. The alkyd resin/pesticide nano emulsion has the drug sustained and controlled release performance, can maintain longer administration time, and reduces administration times and dosage, thereby improving the bioavailability and reducing the pesticide cost.
In a further aspect of the invention, the invention provides a method of preparing the alkyd/pesticide nanoemulsion described above, according to an embodiment of the invention, with reference to fig. 1, the method comprising:
s100: mixing alkyd resin with alkali liquor for neutralization
In this step, the alkyd resin is mixed with a lye for neutralization in order to obtain a water-based alkyd resin. The inventor finds that alkali can perform a neutralization reaction with-COOH on the molecular chain of the alkyd resin to form a hydrophilic group, so that the alkyd resin is endowed with hydrophilicity. The alkyd resin is used as a carrier of the water-insoluble pesticide, and is a renewable resource, so that the cost is low; the alkyd resin is biodegradable and is used as a carrier of a water-insoluble pesticide, so that the alkyd resin is green and environment-friendly; by introducing hydrophilic groups into the main chain of the alkyd resin, the waterborne alkyd resin which can be stably dispersed in water can be prepared without adding an emulsifier, and the waterborne alkyd resin has better environmental benefit; the alkyd resin is used as a carrier material of the water-insoluble pesticide, so that the adhesion of a drug-loaded system to the leaf surfaces of crops can be improved, and the off-target loss of the leaf surfaces of the pesticide can be reduced, thereby improving the effective utilization rate and bioavailability of the pesticide.
According to an embodiment of the present invention, the alkali solution may be at least one selected from an organic base and an inorganic base, specifically, the organic base may be at least one selected from triethylamine and trimethylamine, and the inorganic base may be at least one selected from ammonia and sodium hydroxide. Further, the mass ratio of the alkyd resin to the alkali liquor can be 10: 0.5 to 1.5. The inventor finds that too little alkali liquor can lead to insufficient neutralization degree of the alkyd resin, the alkyd resin cannot be reversely converted into emulsion, and too much alkali liquor can lead to increase of ionic strength of a system, and the system can be demulsified.
S200: mixing water-insoluble pesticide with cosolvent
In this step, a water-insoluble pesticide is mixed with a cosolvent to obtain a pesticide solution. By using the cosolvent, the dissolution of the water-insoluble pesticide is favorably realized, the pesticide solution is obtained, and the preparation of the alkyd resin/pesticide nano emulsion by mixing the pesticide solution with the water-based alkyd resin and the emulsifier subsequently becomes possible.
According to an embodiment of the present invention, the cosolvent may be at least one selected from the group consisting of ethyl acetate, ethanol, methanol, isopropanol, acetone, butanone, cyclohexane, and n-hexane, and ethyl acetate and ethanol are preferred. Further, the boiling point of the co-solvent may be 50 to 100 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and 100 ℃. The inventor finds that the cosolvent has a low boiling point, so that the cosolvent is volatilized violently in the neutralization process and is not neutralized completely, and the cosolvent has a high boiling point, so that the cosolvent is not beneficial to be removed from the system by reduced pressure distillation at a later stage. Further, the mass ratio of the water-insoluble pesticide to the cosolvent may be 1: 0.5 to 2. The inventor finds that the viscosity of the alkyd resin cannot be effectively reduced by using too low the amount of the cosolvent, the particle size distribution of the prepared emulsion is poor, and the prepared emulsion can dissolve part of the carrier by using too high the amount of the cosolvent, so that the alkyd resin/pesticide emulsion cannot be prepared by phase inversion.
S300: mixing water-based alkyd resin, pesticide solution, emulsifier solution/water, and performing phase inversion and vacuum distillation
In the step, water-based alkyd resin, pesticide solution and emulsifier solution/water are mixed, and subjected to phase inversion and reduced pressure distillation treatment, so as to obtain alkyd resin/pesticide nano emulsion. Specifically, the water-based alkyd resin, the pesticide solution and the emulsifier solution can be mixed and subjected to phase inversion and reduced pressure distillation treatment to obtain the alkyd resin/pesticide nano emulsion, and the water-based alkyd resin, the pesticide solution and water can be mixed and subjected to phase inversion and reduced pressure distillation treatment to obtain the alkyd resin/pesticide nano emulsion. The inventor finds that during the phase inversion process under high-speed stirring, the alkyd resin as an amphiphilic macromolecule can wrap the water-insoluble pesticide solution droplets into the hydrophobic chain segment, and the hydrophilic group of the water-insoluble pesticide solution droplets is close to the water side, so that the water-insoluble pesticide solution droplets can be used as a carrier to help the drug to be dispersed in water. The carrier can greatly reduce the surface energy of the alkyd resin/pesticide nano emulsion, and enhance the wetting, spreading and adhering capability of the pesticide on the surface of a plant or the surface of pests, thereby improving the pesticide effect. Compared with the traditional preparation method of a pesticide carrying system, the preparation method provided by the invention is simple, efficient, good in repeatability and easy for industrial production. The drug-loading system of the alkyd resin/pesticide nano emulsion has a nano-scale particle size, the particle size can be as low as 30nm, the particle size distribution range is narrow, and the stability is good; meanwhile, the nano-scale drug loading system is beneficial to improving the contact area of the pesticide and the surfaces of crops, increasing the adhesiveness and the permeability of the pesticide on the leaf surfaces of the crops, obviously reducing the loss of the pesticide and improving the effective utilization rate and the pesticide effect of the pesticide; furthermore, the contact area of the pesticide and the pest target is increased by the nano-scale drug loading system, so that the insecticidal activity of the pesticide on the pest target can be increased. The alkyd resin/pesticide nano emulsion has good dispersibility, and the emulsion can be stored for more than 12 months. The drug-loading rate of the alkyd resin/pesticide nano emulsion carrier can reach 50%, the encapsulation rate is not less than 90%, the solid content and the drug-loading rate of the emulsion can be adjusted according to actual requirements, and the application range is wide. The alkyd resin/pesticide nano emulsion has the drug sustained and controlled release performance, can maintain longer administration time, and reduces administration times and dosage, thereby improving the bioavailability and reducing the pesticide cost.
According to one embodiment of the invention, the emulsifier solution comprises an anionic emulsifier and a nonionic emulsifier, which can be formulated. Specifically, the anionic emulsifier may be at least one selected from alkyl sulfate and alkyl benzene sulfonate. The nonionic emulsifier may be at least one selected from the group consisting of alkylphenol ethoxylates, tweens, and span. The inventors have found that the combination of an anionic emulsifier and a nonionic emulsifier produces an emulsion having a smaller and more uniform particle size than an emulsion produced by either emulsifier alone.
According to a further embodiment of the invention, the mass of the emulsifier in the emulsifier solution may be 0-3% of the mass of the alkyd resin, for example 0%, 0.5%, 1%, 1.5%, 2.0%, 2.5%, 3.0%. The inventor finds that the addition of the emulsifier can further reduce the surface energy of the alkyd resin/pesticide nano emulsion and enhance the wetting and spreading capability of the alkyd resin/pesticide nano emulsion on the surface of a plant or the surface of pests.
According to another embodiment of the invention, the mass ratio of the water-based alkyd resin to the pesticide solution and the emulsifier solution can be 9.99-49.99: 0.02-60: 50-91.5, for example, 9.99/15/19.99/25/29.99/35/39.99/45/49.99: 0.02/10/20/30/40/50/60: 50/60/70/80/90/91.5. The inventors have found that too high a quantity of pesticide solution or too low a quantity of emulsifier solution leads to a decrease in the stability of the alkyd/pesticide nanoemulsion.
According to another embodiment of the invention, the stirring speed of the phase inversion can be 1000-2000 r/min. The inventors have found that too high or too low a phase inversion stirring rate leads to undesirable phase inversion effects, resulting in poor stability of the resulting alkyd/pesticide nanoemulsion.
According to the method for preparing the alkyd resin/pesticide nano emulsion, the alkyd resin/pesticide nano emulsion is prepared by adopting a high-speed in-situ phase inversion method, and compared with the traditional preparation method of a pesticide carrying system, the preparation method provided by the invention is simple and efficient, has good repeatability and is easy for industrial production. The alkyd resin is used as a carrier of the water-insoluble pesticide, and is a renewable resource, so that the cost is low; the alkyd resin is biodegradable and is used as a carrier of a water-insoluble pesticide, so that the alkyd resin is green and environment-friendly; by introducing hydrophilic groups into the main chain of the alkyd resin, the waterborne alkyd resin which can be stably dispersed in water can be prepared without adding an emulsifier, and the waterborne alkyd resin has better environmental benefit; the alkyd resin is used as a carrier material of the water-insoluble pesticide, so that the adhesion of a drug-loaded system to the leaf surfaces of crops can be improved, and the off-target loss of the leaf surfaces of the pesticide can be reduced, thereby improving the effective utilization rate and bioavailability of the pesticide. The drug-loading system of the alkyd resin/pesticide nano emulsion has a nano-scale particle size, the particle size can be as low as 30nm, the particle size distribution range is narrow, and the stability is good; meanwhile, the nano-scale drug loading system is beneficial to improving the contact area of the pesticide and the surfaces of crops, increasing the adhesiveness and the permeability of the pesticide on the leaf surfaces of the crops, obviously reducing the loss of the pesticide and improving the effective utilization rate and the pesticide effect of the pesticide; furthermore, the contact area of the pesticide and the pest target is increased by the nano-scale drug loading system, so that the insecticidal activity of the pesticide on the pest target can be increased. The alkyd resin/pesticide nano emulsion has good dispersibility, and the emulsion can be stored for more than 12 months. The drug-loading rate of the alkyd resin/pesticide nano emulsion carrier can reach 50%, the encapsulation rate is not less than 90%, the solid content and the drug-loading rate of the emulsion can be adjusted according to actual requirements, and the application range is wide. The alkyd resin/pesticide nano emulsion has the drug sustained and controlled release performance, can maintain longer administration time, and reduces administration times and dosage, thereby improving the bioavailability and reducing the pesticide cost.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The particle size of the latex particles in the examples below was measured on a Zetasizer 3000HSA laser particle size and potential analyzer, Malvern, UK at 25 ℃.
The drug loading rate and the encapsulation rate of the alkyd resin/pesticide nano emulsion are measured by using a Beijing Puproud analysis general instrument Co.Ltd, namely a T6 ultraviolet-visible spectrophotometer, and the specific measurement method is as follows: mixing a proper amount of alkyd resin/pesticide nano emulsion with a small amount of cobalt naphthenate emulsion, wherein the cobalt content in the cobalt naphthenate is 0.1 percent of the mass of the alkyd resin, and drying at room temperature to form a film. And then weighing a certain mass of the emulsion film, soaking the emulsion film in a certain amount of cyclohexane solvent, and measuring the pesticide content through an ultraviolet-visible spectrophotometer after ultrasonic treatment.
The calculation formula of the drug loading and the encapsulation efficiency is as follows:
the drug loading (%) -/mass of the emulsion film x 100%;
the encapsulation ratio (%) - (mass of the prepared emulsion × actual solid content × actual drug load)/mass of the administered drug × 100%.
Example 1: alkyd resin/efficient cyhalothrin nano emulsion
(a) Preparation of alkyd resin vehicle: the design formula is that the mass fraction of the vegetable oil accounting for the theoretical mass of the resin is 50%, and the ratio of the total molar weight of original-OH to the total molar weight of-COOH in the reactant is 1.2. Adding 527g of linseed oil and 263g of trimethylolpropane into a four-mouth bottle, and heating to 180 ℃ under the stirring condition of 300 r/min; adding 249g of isophthalic acid into a four-mouth bottle, continuously heating to 235 ℃, carrying out esterification reaction for 2 hours under the protection of nitrogen, continuously separating water in the reaction process, and entering the next step when the acid value of a reactant is 8.6 mgKOH/g; cooling to 150 ℃, adding 102g of trimellitic anhydride, heating to 178 ℃, continuing to react for 1 hour, continuously measuring the acid value of the reactant in the reaction process, and stopping the reaction when the acid value reaches 56.4mgKOH/g to obtain the alkyd resin.
(b) High speed in situ phase inversion loaded drug: (1) taking 10.1g of alkyd resin in a three-necked bottle, adding 1.03g of triethylamine at 60 ℃ for mixing to make the system neutral, and obtaining water-based alkyd resin; (2) dissolving 9.2g of efficient cyhalothrin in 8mL of ethyl acetate to obtain a pesticide solution; (3) adding a pesticide solution into water-based alkyd resin at 60 ℃, uniformly mixing, dissolving 0.05g of SDBS and 0.1g of TX-10 in 35mL of deionized water to obtain an emulsifier solution, adding the emulsifier solution into the mixed solution of the pesticide solution and the water-based alkyd resin at 60 ℃, performing high-speed in-situ phase inversion under the stirring condition of 1800r/min to ensure that the system is uniformly emulsified, and performing reduced pressure distillation at 40 ℃ to remove ethyl acetate to obtain the alkyd resin/efficient cyhalothrin nano emulsion, wherein a transmission electron microscope image of the alkyd resin/efficient cyhalothrin nano emulsion is shown in figure 2.
The mass solid content of the obtained alkyd resin/efficient cyhalothrin nano-emulsion is 37.5 wt%, the average hydrated particle size is 54.9nm, the drug loading rate of the carrier to the efficient cyhalothrin is 45.7%, and the encapsulation rate is 91.4%.
Example 2: alkyd resin/efficient cyhalothrin nano emulsion
(a) Preparation of alkyd resin vehicle: the design formula is that the mass fraction of the vegetable oil accounting for the theoretical mass of the resin is 60%, and the ratio of the total molar amount of original-OH to the total molar amount of-COOH in reactants is 1.2. Adding 644g of soybean oil and 140g of glycerol into a four-mouth bottle, and heating to 180 ℃ under the stirring condition of 300 r/min; adding 55.4g of isophthalic acid into a four-mouth bottle, carrying out esterification reaction for 1 hour under the protection of nitrogen, continuously separating water in the reaction process, and entering the next step when the acid value of a reactant is 8.2 mgKOH/g; and (3) cooling to 150 ℃, adding 188g of trimellitic anhydride, heating to 178 ℃, continuing to react for 40 minutes, continuously measuring the acid value of the reactant in the reaction process, and stopping the reaction when the acid value reaches 66.7mgKOH/g to obtain the alkyd resin.
(b) High speed in situ phase inversion loaded drug: (1) taking 10.4g of alkyd resin in a three-necked bottle, adding 1.25g of triethylamine at 60 ℃ for mixing to make the system neutral, and obtaining water-based alkyd resin; (2) dissolving 7.9g of efficient cyhalothrin in 8mL of ethyl acetate to obtain a pesticide solution; (3) adding the pesticide solution into the water-based alkyd resin at 60 ℃ and uniformly mixing; 0.05g of SDS and 0.1g of OP-10 are dissolved in 37mL of deionized water to obtain an emulsifier solution, the emulsifier solution is added into the mixed solution of the pesticide solution and the water-based alkyd resin at 60 ℃, the mixture is subjected to high-speed in-situ phase inversion under the stirring condition of 2000r/min to ensure that the system is emulsified uniformly, and the ethyl acetate is removed by reduced pressure distillation at 40 ℃ to obtain the alkyd resin/efficient cyhalothrin nano emulsion.
The mass solid content of the obtained alkyd resin/efficient cyhalothrin nano-emulsion is 35.6 wt%, the average hydrated particle size is 35.1nm, the drug loading rate of the carrier to the efficient cyhalothrin is 40.7%, and the encapsulation rate is 92.5%.
Example 3: alkyd resin/efficient cyhalothrin nano emulsion
(a) Preparation of alkyd resin vehicle: the design formula is that the mass fraction of the vegetable oil accounting for the theoretical mass of the resin is 50%, and the ratio of the total molar weight of original-OH to the total molar weight of-COOH in the reactant is 1.15. Adding 457.5g of tung oil and 203.7g of trimethylolpropane into a four-mouth bottle, and heating to 180 ℃ under the stirring condition of 300 r/min; adding 166.1g of isophthalic acid into a four-mouth bottle, carrying out esterification reaction for 1.5 hours under the protection of nitrogen, continuously separating water in the reaction process, and entering the next step when the acid value of a reactant is 7.8 mgKOH/g; and (3) cooling to 150 ℃, adding 188g of trimellitic anhydride, heating to 178 ℃, continuing to react for 1.5 hours, continuously measuring the acid value of the reactant in the reaction process, and stopping the reaction when the acid value reaches 46.7mgKOH/g to obtain the alkyd resin.
(b) High speed in situ phase inversion loaded drug: (1) putting 11.2g of alkyd resin into a three-necked bottle, adding 0.95g of triethylamine at 70 ℃ for mixing to make the system neutral, and obtaining water-based alkyd resin; (2) dissolving 5.2g of efficient cyhalothrin in 10mL of ethanol to obtain a pesticide solution; (3) adding the pesticide solution into the water-based alkyd resin at 70 ℃, uniformly mixing, adding 40mL of deionized water into the mixed solution of the pesticide solution and the water-based alkyd resin at 70 ℃, carrying out high-speed in-situ phase inversion under the stirring condition of 1500r/min, uniformly emulsifying the system, and carrying out reduced pressure distillation at 45 ℃ to remove ethanol, thereby obtaining the alkyd resin/efficient cyhalothrin nano emulsion.
The mass solid content of the obtained alkyd resin/efficient cyhalothrin nano-emulsion is 31.1 wt%, the average hydrated particle size is 110.8nm, the drug loading rate of the carrier to the efficient cyhalothrin is 30.7%, and the encapsulation rate is 96.1%.
Example 4: alkyd resin/avermectin nano emulsion
(a) Preparation of alkyd resin vehicle: the same as in example 1.
(b) High speed in situ phase inversion loaded drug: (1) taking 10.9g of alkyd resin in a three-necked bottle, adding 1.11g of triethylamine at 70 ℃ for mixing to make the system neutral, and obtaining water-based alkyd resin; (2) dissolving 1.2g of abamectin in 15mL of ethanol to obtain a pesticide solution; (3) adding a pesticide solution into water-based alkyd resin at 70 ℃, uniformly mixing, dissolving 0.05g of SDBS and 0.11g of TX-10 into 38mL of deionized water to obtain an emulsifier solution, adding the emulsifier solution into the mixed solution of the pesticide solution and the water-based alkyd resin at 70 ℃, carrying out high-speed in-situ phase inversion under the stirring condition of 1400r/min to ensure that the system is uniformly emulsified, and carrying out reduced pressure distillation at 45 ℃ to remove ethanol to obtain the alkyd resin/abamectin nano emulsion.
The mass solid content of the obtained alkyd resin/avermectin nano-emulsion is 27.2 wt%, the average hydrated particle size is 147.2nm, the drug-loading rate of the carrier to avermectin is 10.1%, and the encapsulation rate is 93.5%.
Example 5: alkyd resin/avermectin nano emulsion
(a) Preparation of alkyd resin vehicle: the same as in example 2.
(b) High speed in situ phase inversion loaded drug: (1) taking 10.2g of alkyd resin in a three-necked bottle, adding 1.23g of triethylamine at 50 ℃ for mixing to make the system neutral, and obtaining water-based alkyd resin; (2) dissolving 2.8g of abamectin in 10mL of acetone to obtain a pesticide solution; (3) adding a pesticide solution into water-based alkyd resin at 50 ℃, uniformly mixing, dissolving 0.05g of SDS and 0.1g of OP-10 into 36mL of deionized water to obtain an emulsifier solution, adding the emulsifier solution into the mixed solution of the pesticide solution and the water-based alkyd resin at 50 ℃, carrying out high-speed in-situ phase inversion under the stirring condition of 1200r/min to ensure that the system is uniformly emulsified, and carrying out reduced pressure distillation at 40 ℃ to remove acetone to obtain the alkyd resin/abamectin nano emulsion.
The mass solid content of the obtained alkyd resin/avermectin nanoemulsion is 28.9 wt%, the average hydrated particle size is 181.9nm, the drug loading rate of the carrier to avermectin is 20.2%, and the encapsulation rate is 91.0%.
Example 6: alkyd resin/avermectin nano emulsion
(a) Preparation of alkyd resin vehicle: the same as in example 3.
(b) High speed in situ phase inversion loaded drug: (1) putting 11g of alkyd resin into a three-necked bottle, adding 0.93g of triethylamine at 50 ℃ for mixing to make the system neutral, and obtaining water-based alkyd resin; (2) dissolving 4g of abamectin in 15mL of acetone to obtain a pesticide solution; (3) adding the pesticide solution into the water-based alkyd resin at 50 ℃ and mixing uniformly, adding 39mL of deionized water into the mixed solution of the pesticide solution and the water-based alkyd resin at 50 ℃, carrying out high-speed in-situ phase inversion under the stirring condition of 1000r/min to ensure that the system is emulsified uniformly, and carrying out reduced pressure distillation at 40 ℃ to remove acetone to obtain the alkyd resin/abamectin nano emulsion.
The mass solid content of the obtained alkyd resin/avermectin nano-emulsion is 30.2 wt%, the average hydrated particle size is 217.5nm, the drug-loading rate of the carrier to avermectin is 25.7%, and the encapsulation rate is 95.6%.
Example 7: alkyd resin/phoxim nano emulsion
(a) Preparation of alkyd resin vehicle: the same as in example 1.
(b) High speed in situ phase inversion loaded drug: (1) taking 10.8g of alkyd resin in a three-necked bottle, adding 1.11g of triethylamine at 70 ℃ for mixing to make the system neutral, and obtaining water-based alkyd resin; (2) dissolving 8.1g of phoxim in 10mL of isopropanol to obtain a pesticide solution; (3) adding a pesticide solution into water-based alkyd resin at 70 ℃, uniformly mixing, dissolving 0.05g of SDBS and 0.11g of TX-10 into 38mL of deionized water to obtain an emulsifier solution, adding the emulsifier solution into the mixed solution of the pesticide solution and the water-based alkyd resin at 70 ℃, carrying out high-speed in-situ phase inversion under the stirring condition of 1600r/min to ensure that the system is uniformly emulsified, and carrying out reduced pressure distillation at 45 ℃ to remove isopropanol to obtain the alkyd resin/phoxim nano emulsion.
The mass solid content of the obtained alkyd resin/phoxim nano-emulsion is 35.7 wt%, the average hydrated particle size is 87.7nm, the drug-loading rate of the carrier phoxim is 41.1%, and the encapsulation rate is 90.5%.
Example 8: alkyd resin/phoxim nano emulsion
(a) Preparation of alkyd resin vehicle: the same as in example 2.
(b) High speed in situ phase inversion loaded drug: (1) putting 9.9g of alkyd resin into a three-necked bottle, adding 1.19g of triethylamine at 60 ℃, and mixing to make the system neutral to obtain water-based alkyd resin; (2) dissolving 4.8g of phoxim in 8mL of n-hexane to obtain a pesticide solution; (3) adding a pesticide solution into water-based alkyd resin at 60 ℃, uniformly mixing, dissolving 0.05g of SDS and 0.1g of OP-10 into 35mL of deionized water to obtain an emulsifier solution, adding the emulsifier solution into the mixed solution of the pesticide solution and the water-based alkyd resin at 60 ℃, carrying out high-speed in-situ phase inversion under the stirring condition of 1700r/min to ensure that the system is uniformly emulsified, and carrying out reduced pressure distillation at 50 ℃ to remove n-hexane to obtain the alkyd resin/phoxim nano emulsion.
The mass solid content of the obtained alkyd resin/phoxim nano-emulsion is 32.2 wt%, the average hydrated particle size is 63.9nm, the drug-loading rate of the carrier phoxim is 30.7%, and the encapsulation rate is 95.4%.
Example 9: alkyd resin/phoxim nano emulsion
(a) Preparation of alkyd resin vehicle: the same as in example 3.
(b) High speed in situ phase inversion loaded drug: (1) putting 13.1g of alkyd resin into a three-necked bottle, adding 1.1g of triethylamine at 50 ℃ for mixing to make the system neutral, and obtaining water-based alkyd resin; (2) dissolving 10.3g of phoxim in 8mL of acetone to obtain a pesticide solution; (3) adding the pesticide solution into the water-based alkyd resin at 50 ℃ and mixing uniformly, adding 46mL of deionized water into the mixed solution of the pesticide solution and the water-based alkyd resin at 50 ℃, carrying out high-speed in-situ phase inversion under the stirring condition of 1500r/min to ensure that the system is emulsified uniformly, and carrying out reduced pressure distillation at 40 ℃ to remove acetone to obtain the alkyd resin/phoxim nano emulsion.
The mass solid content of the obtained alkyd resin/phoxim nano-emulsion is 35.5 wt%, the average hydrated particle size is 105.1nm, the drug-loading rate of the carrier phoxim is 43.9%, and the encapsulation rate is 94.0%.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (9)
1. An alkyd/pesticide nanoemulsion comprising: the pesticide comprises a water-insoluble pesticide, alkyd resin, alkali liquor, a cosolvent, an emulsifier and water, wherein the mass ratio of the water-insoluble pesticide to the alkyd resin to the water is (0.01-25): 9.99-49.99: 50 to 90 of the total weight of the steel,
the alkyd resin is obtained by polymerizing vegetable oil and polyalcohol, dibasic acid or anhydride, and polybasic acid or anhydride containing three or more functional groups, wherein the mass ratio of the vegetable oil to the polyalcohol to the dibasic acid or anhydride to the polybasic acid or anhydride containing three or more functional groups is 10: 2-9: 0.5-9.5: 1.5 to 3; the ratio of the total molar amount of-OH to the total molar amount of-COOH in the vegetable oil, the polyol, the dibasic acid or anhydride, and the polybasic acid or anhydride containing three or more functional groups is 1.2 to 1.4,
the average hydrated particle size of the drug-loaded particles in the alkyd resin/pesticide nano emulsion is 30-250 nm, the solid content is 10-50%, the drug-loaded rate of the alkyd resin is 0.01-50%, and the encapsulation rate is not lower than 90%,
the alkyd resin/pesticide nano emulsion is prepared by adopting the following method:
(1) mixing and neutralizing the alkyd resin with alkali liquor so as to obtain water-based alkyd resin;
(2) mixing a water-insoluble pesticide with a cosolvent to obtain a pesticide solution;
(3) mixing the water-based alkyd resin, the pesticide solution and an emulsifier solution/water, and carrying out phase inversion and reduced pressure distillation treatment to obtain alkyd resin/pesticide nano emulsion,
wherein:
the vegetable oil is at least one selected from linseed oil, soybean oil, tung oil, castor oil, coconut oil and cottonseed oil;
the polyhydric alcohol is at least one selected from the group consisting of glycerin, pentaerythritol, trimethylolpropane, trimethylolethane, ethylene glycol, propylene glycol, butylene glycol, and neopentyl glycol;
the dibasic acid or the anhydride is at least one selected from isophthalic acid, phthalic anhydride, terephthalic acid, maleic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride;
the polybasic acid or anhydride containing three or more functional groups is at least one selected from trimellitic anhydride and pyromellitic anhydride;
the emulsifier comprises an anionic emulsifier and a nonionic emulsifier, the anionic emulsifier is at least one selected from alkyl sulfate and alkylbenzene sulfonate, and the nonionic emulsifier is at least one selected from alkylphenol polyoxyethylene ethers, tweens and span;
the mass of the emulsifier in the emulsifier solution is 0-3% of the mass of the alkyd resin;
the mass ratio of the water-based alkyd resin to the pesticide solution to the emulsifier solution to the water is 9.99-49.99: 0.02-60: 50 to 91.5.
2. The alkyd resin/pesticide nanoemulsion of claim 1, wherein the alkyd resin has an acid number of 35-70 mgKOH/g.
3. The alkyd resin/pesticide nanoemulsion of claim 1, wherein the water-insoluble pesticide is at least one selected from the group consisting of lambda-cyhalothrin, cyfluthrin, bifenthrin, deltamethrin, fenvalerate, thiacloprid, clothianidin, triazophos, carbosulfan, abamectin, acetamido abamectin, ivermectin, chlorpyrifos, phoxim, and chlorantraniliprole.
4. The alkyd resin/pesticide nanoemulsion of claim 1, wherein the water-insoluble pesticide is at least one selected from the group consisting of lambda-cyhalothrin, cyfluthrin, abamectin, ivermectin, chlorpyrifos, and phoxim.
5. A method of making the alkyd/pesticide nanoemulsion of any of claims 1-4, comprising:
(1) mixing and neutralizing the alkyd resin with alkali liquor so as to obtain water-based alkyd resin;
(2) mixing a water-insoluble pesticide with a cosolvent to obtain a pesticide solution;
(3) mixing the water-based alkyd resin, the pesticide solution and the emulsifier solution/water, and carrying out phase inversion and reduced pressure distillation treatment so as to obtain the alkyd resin/pesticide nano emulsion.
6. The method according to claim 5, wherein in step (1), at least one of the following conditions is satisfied:
the alkali liquor is at least one of organic alkali or inorganic alkali, the organic alkali is at least one of triethylamine and trimethylamine, and the inorganic alkali is at least one of ammonia water and sodium hydroxide;
the mass ratio of the alkyd resin to the alkali liquor is 10: 0.5 to 1.5.
7. The method according to claim 5 or 6, wherein in step (2), at least one of the following conditions is satisfied:
the cosolvent is at least one selected from ethyl acetate, ethanol, methanol, isopropanol, acetone, butanone, cyclohexane and n-hexane;
the boiling point of the cosolvent is 50-100 ℃;
the mass ratio of the water-insoluble pesticide to the cosolvent is 1: 0.5 to 2.
8. The method according to claim 5, wherein in step (3), at least one of the following conditions is satisfied:
the emulsifier comprises an anionic emulsifier and a nonionic emulsifier, the anionic emulsifier is at least one selected from alkyl sulfate and alkylbenzene sulfonate, and the nonionic emulsifier is at least one selected from alkylphenol polyoxyethylene ethers, tweens and span;
the mass of the emulsifier in the emulsifier solution is 0-3% of the mass of the alkyd resin;
the mass ratio of the water-based alkyd resin to the pesticide solution to the emulsifier solution to the water is 9.99-49.99: 0.02-60: 50 to 91.5.
9. The method according to claim 5, wherein in the step (3), the stirring speed of the phase inversion is 1000 to 2000 r/min.
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