CN110583708A - Mosquito-repelling microcapsule and preparation method thereof - Google Patents

Mosquito-repelling microcapsule and preparation method thereof Download PDF

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CN110583708A
CN110583708A CN201910836835.3A CN201910836835A CN110583708A CN 110583708 A CN110583708 A CN 110583708A CN 201910836835 A CN201910836835 A CN 201910836835A CN 110583708 A CN110583708 A CN 110583708A
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essential oil
wall material
mixed
mixing
mass concentration
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CN110583708B (en
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姚明路
胡冰
高隽
胡军
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Tianjin Chengxi Guangyuan Power Engineering Co Ltd
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Tianjin Chengxi Guangyuan Power Engineering Co Ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/26Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28Microcapsules or nanocapsules
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N27/00Biocides, pest repellants or attractants, or plant growth regulators containing hydrocarbons
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N31/00Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/04Oxygen or sulfur attached to an aliphatic side-chain of a carbocyclic ring system
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N49/00Biocides, pest repellants or attractants, or plant growth regulators, containing compounds containing the group, wherein m+n>=1, both X together may also mean —Y— or a direct carbon-to-carbon bond, and the carbon atoms marked with an asterisk are not part of any ring system other than that which may be formed by the atoms X, the carbon atoms in square brackets being part of any acyclic or cyclic structure, or the group, wherein A means a carbon atom or Y, n>=0, and not more than one of these carbon atoms being a member of the same ring system, e.g. juvenile insect hormones or mimics thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N65/00Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N65/00Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08Magnoliopsida [dicotyledons]
    • A01N65/22Lamiaceae or Labiatae [Mint family], e.g. thyme, rosemary, skullcap, selfheal, lavender, perilla, pennyroyal, peppermint or spearmint
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N65/00Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/40Liliopsida [monocotyledons]
    • A01N65/44Poaceae or Gramineae [Grass family], e.g. bamboo, lemon grass or citronella grass
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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Abstract

The invention discloses a mosquito-repellent microcapsule, which is prepared by mixing a mixed essential oil microcapsule emulsion and a delphene microcapsule emulsion according to the mass ratio of 1 (0.5-1); the mixed essential oil microcapsule emulsion is formed by mixing a wall material A, a wall material B and a core material A; the wall material A is gelatin emulsifier solution; the wall material B is Arabic gum emulsifier solution; the core material A comprises mixed plant essential oil and butylated hydroxyanisole, wherein the mixed plant essential oil is formed by mixing Span-80, Tween-20, lavender essential oil and citronella essential oil; the deet microcapsule emulsion is formed by mixing a wall material C and a core material B, wherein the wall material C is a arabic gum emulsifier solution; the core material B is formed by mixing gelatin aqueous solution, Tween-20 and deet according to the mass ratio of 0.5 (0.1-0.5) to 1. The mosquito repellent agent can enhance the mosquito repellent effect after microencapsulating the diethyltoluamide and the mosquito repellent plant essential oil, and has long repellent time and less transdermal absorption.

Description

Mosquito-repelling microcapsule and preparation method thereof
Technical Field
The invention relates to the technical field of daily chemical articles, in particular to a mosquito-repellent microcapsule and a preparation method thereof.
Background
The microcapsule technology is a technology of encapsulating a target material (core material) into a spherical microcapsule having a particle diameter of 1 to 5000 μm by a physical or chemical method using a film-forming material (wall material). The main purpose is to prolong the storage time of the core material, prevent the core material from being oxidized by air, cover the bad smell of the core material, improve the use effect and the like. The existing mosquito-repellent microcapsules only contain one mosquito-repellent component, such as mosquito-repellent amine microcapsules taking hydrophilic polyethylene as a wall material and mosquito-repellent amine as a core material, and mosquito-repellent ester microcapsules taking polyurethane, polyester, polyurea, polyamide or urea resin as a wall material and mosquito-repellent amine as a core material. It has limited mosquito repelling effect because it contains only one kind of mosquito repelling component. Moreover, most wall materials are synthetic polymer materials, so that the cost is high, and the wall materials do not have reproducibility and biodegradability, thereby being not in accordance with the sustainable development principle.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a mosquito-repellent microcapsule and a preparation method thereof.
A mosquito-repellent microcapsule is prepared by mixing an essential oil microcapsule emulsion and a delphene microcapsule emulsion according to a mass ratio of 1 (0.5-1);
the mixed essential oil microcapsule emulsion is formed by mixing a wall material A, a wall material B and a core material A according to the mass ratio of (1-2) to (2-4); the wall material A is a gelatin emulsifier solution with the mass concentration of 1%; the wall material B is Arabic gum emulsifier solution with the mass concentration of 1%; the core material A comprises mixed plant essential oil and fat antioxidant butylated hydroxyanisole, wherein the mixed plant essential oil is formed by mixing surfactant Span-80, surfactant Tween-20, lavender essential oil and citronella essential oil according to the mass ratio of (0.5-1) to (1-2) to (2-2.5), and the butylated hydroxyanisole accounts for 0.5% of the mass of the mixed plant essential oil;
the deet microcapsule emulsion is formed by mixing wall material C and core material B according to the mass ratio of 0.5 (1.5-2), wherein the wall material C is a gum arabic emulsifier solution with the mass concentration of 3%; the core material B is formed by mixing gelatin aqueous solution, Tween-20 and deet according to the mass ratio of 0.5 (0.1-0.5) to 1, and the mass concentration of the gelatin aqueous solution is 3%.
The invention compounds the mixed essential oil microcapsule emulsion and the delphene amine microcapsule emulsion to prepare the compound mosquito repellent, which contains citronellal, citronellol, terpineol, limonene, delphene and other substances, and the combined action of the various substances has good mosquito repellent effect. Compared with the simple mixed liquid of the mosquito repellent amine and the natural plant essential oil extract, the mosquito repellent microcapsule provided by the invention has micropores on the surface, and the good slow release property of the mosquito repellent microcapsule is convenient for various mosquito repellent substances to be slowly released outwards, so that the heat stability is high; the microcapsule is prepared by compounding the gelatin and the Arabic gum, has the advantages of no toxicity, easy biodegradation and environmental friendliness, and is particularly suitable for wrapping nonpolar volatile oily liquid.
Preferably, the mosquito-repellent microcapsule is formed by mixing an essential oil microcapsule emulsion and a delphene microcapsule emulsion according to the mass ratio of 1: 0.5;
the mixed essential oil microcapsule emulsion is formed by mixing a wall material A, a wall material B and a core material A according to the mass ratio of 1:1: 2; the wall material A is a gelatin emulsifier solution with the mass concentration of 1%; the wall material B is Arabic gum emulsifier solution with the mass concentration of 1%; the core material A comprises mixed plant essential oil and butylated hydroxyanisole, wherein the mixed plant essential oil is formed by mixing Span-80, Tween-20, lavender essential oil and citronella essential oil according to the mass ratio of 1:2:2.5:2.5, and the butylated hydroxyanisole accounts for 0.5% of the mass of the mixed plant essential oil;
the deet microcapsule emulsion is formed by mixing a wall material C and a core material B according to the mass ratio of 0.5:1.5, wherein the wall material C is a arabic gum emulsifier solution with the mass concentration of 3%; the core material B is formed by mixing gelatin aqueous solution, Tween-20 and deet according to the mass ratio of 0.5:0.1:1, and the mass concentration of the gelatin aqueous solution is 3%.
The invention also provides a preparation method of the mosquito-repellent microcapsule, which comprises the following operation steps:
step 1: preparation of Mixed essential oil microcapsule emulsion
Preparation of wall material A: dissolving gelatin in distilled water to prepare gelatin emulsifier solution with mass concentration of 1%;
preparing a wall material B: dissolving Arabic gum in distilled water to prepare an Arabic gum emulsifier solution with the mass concentration of 1%;
preparation of core material A: mixing Span-80, Tween-20, lavender essential oil, citronella essential oil and butylated hydroxyanisole in proportion, stirring until the mixture is dissolved and uniformly mixed;
preparing mixed essential oil microcapsule emulsion: mixing the wall material A, the wall material B and the core material A in proportion, filtering, homogenizing and curing to obtain a mixed essential oil microcapsule emulsion;
step 2: preparation of deet microcapsule emulsion
Preparation of wall material C: adding distilled water into arabic gum to prepare a arabic gum emulsifier solution with the mass concentration of 3%;
preparation of core material B: adding water into gelatin to prepare gelatin water solution with mass concentration of 3%, adding Tween-20 and diethyltoluamide in proportion, and stirring to form uniform emulsion;
preparing a delphene microcapsule emulsion: mixing the wall material C and the core material B in proportion, filtering, homogenizing and curing to obtain the deet microcapsule emulsion;
and step 3: preparing mosquito-repellent microcapsule
And mixing the mixed essential oil microcapsule emulsion and the delphene microcapsule emulsion in a ratio and stirring uniformly.
Preferably, the method comprises the following operation steps:
step 1: preparation of Mixed essential oil microcapsule emulsion
Preparation of wall material A: putting gelatin in a constant temperature jacket reaction kettle, adding distilled water with the volume 5 times that of the gelatin, heating to 80 ℃, stirring at the speed of 100r/min until the gelatin is dissolved and uniformly mixed, cooling to 45 ℃, and adding cold distilled water to prepare gelatin emulsifier solution with the mass concentration of 1%;
preparing a wall material B: placing Arabic gum into a constant temperature jacket reaction kettle, adding distilled water with the volume 10 times that of Arabic gum, heating to 90 ℃, stirring at the speed of 100r/min until the Arabic gum is dissolved and uniformly mixed, cooling to 45 ℃, and adding cold distilled water to prepare Arabic gum emulsifier solution with the mass concentration of 1%;
preparation of core material A: mixing Span-80, Tween-20, lavender essential oil and citronella essential oil in proportion, adding 0.5% of dihydroxyanisole in mass of the mixture, then placing in a constant-temperature jacket reaction kettle, heating to 80 ℃, stirring at a speed of 100r/min until the mixture is dissolved and uniformly mixed, cooling to 45 ℃, and continuously stirring at a speed of 40r/min in the cooling process;
preparing mixed essential oil microcapsule emulsion: mixing the wall material A, the wall material B and the core material A in proportion, filtering by a filter, introducing into a high-pressure homogenizer preheated to 50 ℃, setting the flow rate to be 15L/h, homogenizing at the first stage of homogenizing pressure of 17MPa and the second stage of homogenizing pressure of 4 MPa; homogenizing, introducing into a constant-temperature jacket reaction kettle preheated to 40 ℃, stirring at the speed of 400r/min, adding a glacial acetic acid aqueous solution with the mass concentration of 10% while adjusting the pH of the material to 4, keeping the temperature for 20min, introducing cooling water until the material is cooled to 25 ℃, adding a sodium hydroxide aqueous solution with the mass concentration of 10% to adjust the pH to 10, adding a glutaraldehyde solution with the mass concentration of 25% and the volume of the mixed material of 0.5-2% after 20min for curing and finishing, stirring at the speed of 400r/min at the temperature of 25 ℃ and keeping the temperature for 30min, and quickly heating the constant-temperature jacket reaction kettle to 40 ℃ to obtain a mixed essential oil microcapsule emulsion;
step 2: preparation of deet microcapsule emulsion
Preparation of wall material C: putting Arabic gum into a constant-temperature jacket reaction kettle, adding distilled water with the volume 10 times that of the Arabic gum, heating to 90 ℃, stirring at the speed of 100r/min until the Arabic gum is dissolved and uniformly mixed, cooling to 45 ℃, and adding cold distilled water to prepare an Arabic gum emulsifier solution with the mass concentration of 3%;
preparation of core material B: putting gelatin in a constant-temperature jacket reaction kettle, adding distilled water with the volume 10 times that of the gelatin, heating to 80 ℃, stirring at the speed of 100r/min until the gelatin is dissolved and mixed uniformly, adding cold distilled water to prepare gelatin aqueous solution with the mass concentration of 3%, cooling to 50 ℃, adding Tween-20 and diethyltoluamide, stirring at the speed of 200r/min until a uniform emulsion is formed, cooling to 45 ℃, and continuously stirring at the speed of 80 r/min;
preparing a delphene microcapsule emulsion: mixing the wall material C and the core material B in proportion, filtering by a filter, introducing into a high-pressure homogenizer preheated to 50 ℃, and homogenizing at a flow rate of 10L/h and a homogenizing pressure of 17MPa in the first section and 4MPa in the second section; homogenizing, introducing into a constant-temperature jacket reaction kettle preheated to 40 ℃, stirring at the speed of 400r/min, adding a glacial acetic acid aqueous solution with the mass concentration of 10% while adjusting the pH of the material to 4, keeping the temperature for 20min, introducing cooling water until the material is cooled to 25 ℃, adding a sodium hydroxide aqueous solution with the mass concentration of 10% to adjust the pH to 10, adding a glutaraldehyde solution with the mass concentration of 25% and the volume of the mixed material of 0.5-2% after 20min for curing and finishing, stirring at the speed of 400r/min at 25 ℃ and keeping the temperature for 30min, and quickly heating the constant-temperature jacket reaction kettle to 40 ℃ to obtain a mosquito amine microcapsule emulsion;
and step 3: preparing mosquito-repellent microcapsule
And mixing the mixed essential oil microcapsule emulsion and the delphene microcapsule emulsion in proportion, and stirring uniformly at the speed of 400 r/min.
When the mixed essential oil microcapsule emulsion and the deet microcapsule emulsion are prepared, the release rate of the deet essential oil and the deet can be controlled by controlling the dosage of the cross-linking curing agent glutaraldehyde, the larger the dosage of the glutaraldehyde, the fewer the pore structures on the wall film, the slower the slow release rate, and vice versa. The invention utilizes the microcapsule technology to microencapsulate the diethyltoluamide and the anopheline essential oil, can not only fully exert the mosquito repelling effect of various mosquito repelling substances, but also play roles in prolonging the repelling time and reducing transdermal absorption by utilizing the characteristic of microcapsule controlled release, and is an effective method for improving the mosquito repelling activity and durability of the anopheline.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A mosquito-repellent microcapsule is prepared by mixing an essential oil microcapsule emulsion and a delphene microcapsule emulsion according to a mass ratio of 1: 1;
the mixed essential oil microcapsule emulsion is formed by mixing a wall material A, a wall material B and a core material A according to the mass ratio of 1.5:1: 4; the wall material A is a gelatin emulsifier solution with the mass concentration of 1%; the wall material B is Arabic gum emulsifier solution with the mass concentration of 1%; the core material A comprises mixed plant essential oil and butylated hydroxyanisole, wherein the mixed plant essential oil is formed by mixing Span-80, Tween-20, lavender essential oil and citronella essential oil according to the mass ratio of 0.8:1:2.5:2.2, and the butylated hydroxyanisole accounts for 0.5% of the mass of the mixed plant essential oil;
the deet microcapsule emulsion is formed by mixing a wall material C and a core material B according to the mass ratio of 0.5:1.5, wherein the wall material C is a arabic gum emulsifier solution with the mass concentration of 3%; the core material B is formed by mixing gelatin aqueous solution, Tween-20 and deet according to the mass ratio of 0.5:0.5:1, and the mass concentration of the gelatin aqueous solution is 3%.
The preparation method of the mosquito-repellent microcapsule comprises the following steps:
step 1: preparation of Mixed essential oil microcapsule emulsion
Preparation of wall material A: putting gelatin in a constant temperature jacket reaction kettle, adding distilled water with the volume 5 times that of the gelatin, heating to 80 ℃, stirring at the speed of 100r/min until the gelatin is dissolved and uniformly mixed, cooling to 45 ℃, and adding cold distilled water to prepare gelatin emulsifier solution with the mass concentration of 1%;
preparing a wall material B: placing Arabic gum into a constant temperature jacket reaction kettle, adding distilled water with the volume 10 times that of Arabic gum, heating to 90 ℃, stirring at the speed of 100r/min until the Arabic gum is dissolved and uniformly mixed, cooling to 45 ℃, and adding cold distilled water to prepare Arabic gum emulsifier solution with the mass concentration of 1%;
preparation of core material A: mixing Span-80, Tween-20, lavender essential oil and citronella essential oil in proportion, adding 0.5% of dihydroxyanisole in mass of the mixture, then placing in a constant-temperature jacket reaction kettle, heating to 80 ℃, stirring at a speed of 100r/min until the mixture is dissolved and uniformly mixed, cooling to 45 ℃, and continuously stirring at a speed of 40r/min in the cooling process;
preparing mixed essential oil microcapsule emulsion: mixing the wall material A, the wall material B and the core material A in proportion, filtering by a filter, introducing into a high-pressure homogenizer preheated to 50 ℃, setting the flow rate to be 15L/h, homogenizing at the first stage of homogenizing pressure of 17MPa and the second stage of homogenizing pressure of 4 MPa; homogenizing, introducing into a constant-temperature jacket reaction kettle preheated to 40 ℃, stirring at the speed of 400r/min, adding a glacial acetic acid aqueous solution with the mass concentration of 10% while adjusting the pH of the material to 4, keeping the temperature for 20min, introducing cooling water until the material is cooled to 25 ℃, adding a sodium hydroxide aqueous solution with the mass concentration of 10% to adjust the pH to 10, adding a glutaraldehyde solution with the mass concentration of 25% and the volume of the mixed material of 0.5-2% after 20min for curing and finishing, stirring at the speed of 400r/min at the temperature of 25 ℃ and keeping the temperature for 30min, and quickly heating the constant-temperature jacket reaction kettle to 40 ℃ to obtain a mixed essential oil microcapsule emulsion;
step 2: preparation of deet microcapsule emulsion
Preparation of wall material C: putting Arabic gum into a constant-temperature jacket reaction kettle, adding distilled water with the volume 10 times that of the Arabic gum, heating to 90 ℃, stirring at the speed of 100r/min until the Arabic gum is dissolved and uniformly mixed, cooling to 45 ℃, and adding cold distilled water to prepare an Arabic gum emulsifier solution with the mass concentration of 3%;
preparation of core material B: putting gelatin in a constant-temperature jacket reaction kettle, adding distilled water with the volume 10 times that of the gelatin, heating to 80 ℃, stirring at the speed of 100r/min until the gelatin is dissolved and mixed uniformly, adding cold distilled water to prepare gelatin aqueous solution with the mass concentration of 3%, cooling to 50 ℃, adding Tween-20 and diethyltoluamide, stirring at the speed of 200r/min until a uniform emulsion is formed, cooling to 45 ℃, and continuously stirring at the speed of 80 r/min;
preparing a delphene microcapsule emulsion: mixing the wall material C and the core material B in proportion, filtering by a filter, introducing into a high-pressure homogenizer preheated to 50 ℃, and homogenizing at a flow rate of 10L/h and a homogenizing pressure of 17MPa in the first section and 4MPa in the second section; homogenizing, introducing into a constant-temperature jacket reaction kettle preheated to 40 ℃, stirring at the speed of 400r/min, adding a glacial acetic acid aqueous solution with the mass concentration of 10% while adjusting the pH of the material to 4, keeping the temperature for 20min, introducing cooling water until the material is cooled to 25 ℃, adding a sodium hydroxide aqueous solution with the mass concentration of 10% to adjust the pH to 10, adding a glutaraldehyde solution with the mass concentration of 25% and the volume of the mixed material of 0.5-2% after 20min for curing and finishing, stirring at the speed of 400r/min at 25 ℃ and keeping the temperature for 30min, and quickly heating the constant-temperature jacket reaction kettle to 40 ℃ to obtain a mosquito amine microcapsule emulsion;
and step 3: preparing mosquito-repellent microcapsule
And mixing the mixed essential oil microcapsule emulsion and the delphene microcapsule emulsion in proportion, and stirring uniformly at the speed of 400 r/min.
Example 2
A mosquito-repellent microcapsule is prepared by the same preparation method as in example 1, and is prepared by mixing an essential oil microcapsule emulsion and a delphene microcapsule emulsion according to the mass ratio of 1: 0.8;
the mixed essential oil microcapsule emulsion is formed by mixing a wall material A, a wall material B and a core material A according to the mass ratio of 1:2: 3; the wall material A is a gelatin emulsifier solution with the mass concentration of 1%; the wall material B is Arabic gum emulsifier solution with the mass concentration of 1%; the core material A comprises mixed plant essential oil and butylated hydroxyanisole, wherein the mixed plant essential oil is formed by mixing Span-80, Tween-20, lavender essential oil and citronella essential oil according to the mass ratio of 0.5:2:2.2:2, and the butylated hydroxyanisole accounts for 0.5% of the mass of the mixed plant essential oil;
the deet microcapsule emulsion is formed by mixing a wall material C and a core material B according to the mass ratio of 0.5:2, wherein the wall material C is a gum arabic emulsifier solution with the mass concentration of 3%; the core material B is formed by mixing gelatin aqueous solution, Tween-20 and deet according to the mass ratio of 0.5:0.8:1, and the mass concentration of the gelatin aqueous solution is 3%.
Example 3
A mosquito-repellent microcapsule is prepared by the same preparation method as in example 1, and is prepared by mixing an essential oil microcapsule emulsion and a delphene microcapsule emulsion according to the mass ratio of 1: 0.5;
the mixed essential oil microcapsule emulsion is formed by mixing a wall material A, a wall material B and a core material A according to the mass ratio of 2:1.5: 2; the wall material A is a gelatin emulsifier solution with the mass concentration of 1%; the wall material B is Arabic gum emulsifier solution with the mass concentration of 1%; the core material A comprises mixed plant essential oil and butylated hydroxyanisole, wherein the mixed plant essential oil is formed by mixing Span-80, Tween-20, lavender essential oil and citronella essential oil according to the mass ratio of 1:1.5:2:2.5, and the butylated hydroxyanisole accounts for 0.5% of the mass of the mixed plant essential oil;
the deet microcapsule emulsion is formed by mixing a wall material C and a core material B according to the mass ratio of 0.5:1.8, wherein the wall material C is a arabic gum emulsifier solution with the mass concentration of 3%; the core material B is formed by mixing gelatin aqueous solution, Tween-20 and deet according to the mass ratio of 0.5:0.1:1, and the mass concentration of the gelatin aqueous solution is 3%.
Example 4
A mosquito-repellent microcapsule is prepared by the same preparation method as in example 1, and is prepared by mixing an essential oil microcapsule emulsion and a delphene microcapsule emulsion according to the mass ratio of 1: 0.5;
the mixed essential oil microcapsule emulsion is formed by mixing a wall material A, a wall material B and a core material A according to the mass ratio of 1:1: 2; the wall material A is a gelatin emulsifier solution with the mass concentration of 1%; the wall material B is Arabic gum emulsifier solution with the mass concentration of 1%; the core material A comprises mixed plant essential oil and butylated hydroxyanisole, wherein the mixed plant essential oil is formed by mixing Span-80, Tween-20, lavender essential oil and citronella essential oil according to the mass ratio of 1:2:2.5:2.5, and the butylated hydroxyanisole accounts for 0.5% of the mass of the mixed plant essential oil;
the deet microcapsule emulsion is formed by mixing a wall material C and a core material B according to the mass ratio of 0.5:1.5, wherein the wall material C is a arabic gum emulsifier solution with the mass concentration of 3%; the core material B is formed by mixing gelatin aqueous solution, Tween-20 and deet according to the mass ratio of 0.5:0.1:1, and the mass concentration of the gelatin aqueous solution is 3%.
Testing the mosquito repelling effect:
in view of the fact that no test standard of mosquito repellent liquid exists in China at present, the test is carried out by referring to GB 13917.3-1992, pesticide indoor efficacy test method for pesticide registration hygiene, small aerosol and aerosol tablet test method, GB 13917.1-1992, pesticide indoor efficacy test method for rural registration hygiene, propellant indoor efficacy test method and GB/T17322.10-1998, pesticide indoor efficacy evaluation for pesticide registration hygiene, repellent. The mosquitoes used in the tests were all female Anopheles sinensis (Anopheles sinensis) caught in the field, and were raised temporarily in dark room cages at 25 ℃ and a relative humidity RH of 70 since the catching. 100 female anopheles sinensis are placed into an organic glass box with the specification of 60cm multiplied by 60cm, the upper surface of the organic glass box is provided with an opening and is covered by a nylon gauze, and the nylon gauze is provided with an opening for taking and placing the mosquitoes and seven hand stretching openings. The testers (all women of 20-40 ages and all B blood types) wear disposable latex gloves with openings of 6cm x 6cm on the backs of the gloves. 1 tester (the record of the test group that this tester belongs to is blank test) do not do any processing and directly stretch into organic glass case with the hand from stretching out the hand mouth, other 6 testers have painted the equivalent respectively at the opening part of gloves after wearing gloves: mosquito repellent essential oil (mixture of water solution of lavender essential oil and citronella essential oil, concentration of each essential oil is the same as that in example 1), mosquito repellent amine water solution (concentration is the same as that in mosquito repellent amine microcapsule emulsion in example 1) and mosquito repellent microcapsule prepared in example 1-4 are mixed. Each tester places their hands in the perspex chamber for 10min, counts the number of mosquitoes falling and repeats the averaging 5 times, each time at least 1h apart. And (4) comparing with a blank test, and calculating the mosquito repelling rate (the mosquito repelling rate is (blank test mosquito number-specific mosquito number)/blank test mosquito number).
Mosquito repellent Number of mosquitoes falling Percent of mosquito repelling (%)
Blank test 49 -
Mixed mosquito-repellent essential oil 15 69.39
Mosquito repellent amine aqueous solution 14 71.43
Example 1 3 93.88
Example 2 2 95.92
Example 3 2 95.92
Example 4 1 97.96
Obviously, after the deet and the deet plant essential oil are microencapsulated, the mosquito repelling effect of various deets can be fully exerted, and the mosquito repelling rate is at least more than 95%. And after 5h, the mosquito repellent rate can still be kept over 80 percent by testing again.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (4)

1. A mosquito-repellent microcapsule is characterized in that: the mosquito-repellent microcapsule is formed by mixing a mixed essential oil microcapsule emulsion and a delphene microcapsule emulsion according to the mass ratio of 1 (0.5-1);
the mixed essential oil microcapsule emulsion is formed by mixing a wall material A, a wall material B and a core material A according to the mass ratio of (1-2) to (2-4); the wall material A is a gelatin emulsifier solution with the mass concentration of 1%; the wall material B is a Arabic gum emulsifier solution with the mass concentration of 1%; the core material A comprises mixed plant essential oil and butylated hydroxyanisole, wherein the mixed plant essential oil is formed by mixing Span-80, Tween-20, lavender essential oil and citronella essential oil according to the mass ratio of (0.5-1) to (1-2) to (2-2.5), and the butylated hydroxyanisole accounts for 0.5% of the mass of the mixed plant essential oil;
the DEET microcapsule emulsion is formed by mixing a wall material C and a core material B according to the mass ratio of 0.5 (1.5-2), wherein the wall material C is a arabic gum emulsifier solution with the mass concentration of 3%; the core material B is formed by mixing gelatin aqueous solution, Tween-20 and deet according to the mass ratio of 0.5 (0.1-0.5) to 1, and the mass concentration of the gelatin aqueous solution is 3%.
2. A mosquito repellent microcapsule according to claim 1, wherein: the mosquito-repellent microcapsule is formed by mixing a mixed essential oil microcapsule emulsion and a delphene microcapsule emulsion according to the mass ratio of 1: 0.5;
the mixed essential oil microcapsule emulsion is formed by mixing a wall material A, a wall material B and a core material A according to the mass ratio of 1:1: 2; the wall material A is a gelatin emulsifier solution with the mass concentration of 1%; the wall material B is a Arabic gum emulsifier solution with the mass concentration of 1%; the core material A comprises mixed plant essential oil and butylated hydroxyanisole, wherein the mixed plant essential oil is formed by mixing Span-80, Tween-20, lavender essential oil and citronella essential oil according to the mass ratio of 1:2:2.5:2.5, and the butylated hydroxyanisole accounts for 0.5% of the mixed plant essential oil;
the deet microcapsule emulsion is formed by mixing a wall material C and a core material B according to the mass ratio of 0.5:1.5, wherein the wall material C is a gum arabic emulsifier solution with the mass concentration of 3%; the core material B is formed by mixing gelatin aqueous solution, Tween-20 and deet according to the mass ratio of 0.5:0.1:1, and the mass concentration of the gelatin aqueous solution is 3%.
3. A method for preparing a mosquito repellent microcapsule as claimed in claim 1 or 2, characterized in that: the method comprises the following operation steps:
step 1: preparation of Mixed essential oil microcapsule emulsion
Preparation of wall material A: dissolving gelatin in distilled water to prepare gelatin emulsifier solution with mass concentration of 1%;
preparing a wall material B: dissolving Arabic gum in distilled water to prepare an Arabic gum emulsifier solution with the mass concentration of 1%;
preparation of core material A: mixing Span-80, Tween-20, lavender essential oil, citronella essential oil and butylated hydroxyanisole in proportion, stirring until the mixture is dissolved and uniformly mixed;
preparing mixed essential oil microcapsule emulsion: mixing the wall material A, the wall material B and the core material A in proportion, filtering, homogenizing and curing to obtain a mixed essential oil microcapsule emulsion;
step 2: preparation of deet microcapsule emulsion
Preparation of wall material C: adding distilled water into arabic gum to prepare a arabic gum emulsifier solution with the mass concentration of 3%;
preparation of core material B: adding water into gelatin to prepare gelatin water solution with mass concentration of 3%, adding Tween-20 and diethyltoluamide in proportion, and stirring to form uniform emulsion;
preparing a delphene microcapsule emulsion: mixing the wall material C and the core material B in proportion, filtering, homogenizing and curing to obtain the deet microcapsule emulsion;
and step 3: preparing mosquito-repellent microcapsule
And mixing the mixed essential oil microcapsule emulsion and the diethyltoluamide microcapsule emulsion in proportion and stirring uniformly.
4. A method for preparing mosquito repellent microcapsules according to claim 3, wherein the method comprises the following steps: the method comprises the following operation steps:
step 1: preparation of Mixed essential oil microcapsule emulsion
Preparation of wall material A: putting gelatin in a constant-temperature jacket reaction kettle, adding distilled water with the volume 5 times that of the gelatin, heating to 80 ℃, stirring at the speed of 100r/min until the gelatin is dissolved and uniformly mixed, cooling to 45 ℃, and adding cold distilled water to prepare a gelatin emulsifier solution with the mass concentration of 1%;
preparing a wall material B: putting Arabic gum into a constant-temperature jacket reaction kettle, adding distilled water with the volume 10 times that of the Arabic gum, heating to 90 ℃, stirring at the speed of 100r/min until the Arabic gum is dissolved and uniformly mixed, cooling to 45 ℃, and adding cold distilled water to prepare an Arabic gum emulsifier solution with the mass concentration of 1%;
preparation of core material A: mixing Span-80, Tween-20, lavender essential oil and citronella essential oil in proportion, adding 0.5% of dihydroxyanisole in mass of the mixture, then placing in a constant-temperature jacket reaction kettle, heating to 80 ℃, stirring at a speed of 100r/min until the mixture is dissolved and uniformly mixed, cooling to 45 ℃, and continuously stirring at a speed of 40r/min in the cooling process;
preparing mixed essential oil microcapsule emulsion: mixing the wall material A, the wall material B and the core material A in proportion, filtering by a filter, introducing into a high-pressure homogenizer preheated to 50 ℃, setting the flow rate to be 15L/h, homogenizing at the first stage of homogenizing pressure of 17MPa and the second stage of homogenizing pressure of 4 MPa; homogenizing, introducing into a constant-temperature jacket reaction kettle preheated to 40 ℃, stirring at the speed of 400r/min, adding a glacial acetic acid aqueous solution with the mass concentration of 10% while adjusting the pH of the material to 4, keeping the temperature for 20min, introducing cooling water until the material is cooled to 25 ℃, adding a sodium hydroxide aqueous solution with the mass concentration of 10% to adjust the pH to 10, adding a glutaraldehyde solution with the mass concentration of 25% and the volume of the mixed material of 0.5-2% after 20min for curing and finishing, stirring at the speed of 400r/min at the temperature of 25 ℃ and keeping the temperature for 30min, and quickly heating the constant-temperature jacket reaction kettle to 40 ℃ to obtain a mixed essential oil microcapsule emulsion;
step 2: preparation of deet microcapsule emulsion
Preparation of wall material C: putting Arabic gum into a constant-temperature jacket reaction kettle, adding distilled water with the volume 10 times that of the Arabic gum, heating to 90 ℃, stirring at the speed of 100r/min until the Arabic gum is dissolved and uniformly mixed, cooling to 45 ℃, and adding cold distilled water to prepare an Arabic gum emulsifier solution with the mass concentration of 3%;
preparation of core material B: putting gelatin in a constant-temperature jacket reaction kettle, adding distilled water with the volume 10 times that of the gelatin, heating to 80 ℃, stirring at the speed of 100r/min until the gelatin is dissolved and mixed uniformly, adding cold distilled water to prepare gelatin aqueous solution with the mass concentration of 3%, cooling to 50 ℃, adding Tween-20 and diethyltoluamide, stirring at the speed of 200r/min until a uniform emulsion is formed, cooling to 45 ℃, and continuously stirring at the speed of 80 r/min;
preparing a delphene microcapsule emulsion: mixing the wall material C and the core material B in proportion, filtering by a filter, introducing into a high-pressure homogenizer preheated to 50 ℃, and homogenizing at a flow rate of 10L/h and a homogenizing pressure of 17MPa in the first section and 4MPa in the second section; homogenizing, introducing into a constant-temperature jacket reaction kettle preheated to 40 ℃, stirring at the speed of 400r/min, adding a glacial acetic acid aqueous solution with the mass concentration of 10% while adjusting the pH of the material to 4, keeping the temperature for 20min, introducing cooling water until the material is cooled to 25 ℃, adding a sodium hydroxide aqueous solution with the mass concentration of 10% to adjust the pH to 10, adding a glutaraldehyde solution with the mass concentration of 25% and the volume of the mixed material of 0.5-2% after 20min for curing and finishing, stirring at the speed of 400r/min at 25 ℃ and keeping the temperature for 30min, and quickly heating the constant-temperature jacket reaction kettle to 40 ℃ to obtain a mosquito amine microcapsule emulsion;
and step 3: preparing mosquito-repellent microcapsule
And mixing the mixed essential oil microcapsule emulsion and the delphene microcapsule emulsion in proportion, and stirring uniformly at the speed of 400 r/min.
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