CN108184826A - A kind of discoloration mosquito repellent hydrogel and preparation method thereof - Google Patents
A kind of discoloration mosquito repellent hydrogel and preparation method thereof Download PDFInfo
- Publication number
- CN108184826A CN108184826A CN201711464372.XA CN201711464372A CN108184826A CN 108184826 A CN108184826 A CN 108184826A CN 201711464372 A CN201711464372 A CN 201711464372A CN 108184826 A CN108184826 A CN 108184826A
- Authority
- CN
- China
- Prior art keywords
- oil
- discoloration
- mosquito repellent
- hydrogel
- water
- 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.)
- Granted
Links
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
- A01N25/18—Vapour or smoke emitting compositions with delayed or sustained release
-
- 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
-
- 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
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
-
- 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
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
- A01N65/06—Coniferophyta [gymnosperms], e.g. cypress
-
- 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
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
- A01N65/08—Magnoliopsida [dicotyledons]
-
- 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
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
- A01N65/08—Magnoliopsida [dicotyledons]
- A01N65/28—Myrtaceae [Myrtle family], e.g. teatree or clove
-
- 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
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
- A01N65/08—Magnoliopsida [dicotyledons]
- A01N65/34—Rosaceae [Rose family], e.g. strawberry, hawthorn, plum, cherry, peach, apricot or almond
-
- 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
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
- A01N65/08—Magnoliopsida [dicotyledons]
- A01N65/36—Rutaceae [Rue family], e.g. lime, orange, lemon, corktree or pricklyash
-
- 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
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
- A01N65/40—Liliopsida [monocotyledons]
- A01N65/44—Poaceae or Gramineae [Grass family], e.g. bamboo, lemon grass or citronella grass
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Natural Medicines & Medicinal Plants (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Mycology (AREA)
- Microbiology (AREA)
- Biotechnology (AREA)
- Pest Control & Pesticides (AREA)
- Botany (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of discoloration mosquito repellent hydrogels, and by percentage to the quality, the hydrogel is polymerize to obtain by following components：Water-soluble polymeric monomer 17 32%, crosslinking agent 0.6 1.8%, culicifuge 0.1 1.5%, oil-soluble coloring agent 0.04 0.2%, solubilizer 0.8 1.6%, initiator 0.04 0.12%, surplus is water.The hydrogel is crosslinked by chemical constituent, with higher mechanical strength, hydrogel structure caused by the variation of the use environments such as rainwater and solarization can be resisted changes, avoid the problem of anophelifuge loss causes hydrogel repelling effect to weaken, and there is oil-soluble coloring agent in hydrogel, the indicating effect to carrying medicine surplus is realized using the physical characteristic of oil-soluble coloring agent, avoids repelling effect decrease or the situation of the wasting of resources caused by not knowing load medicine surplus.The preparation method of the hydrogel is also disclosed, preparation process is simple, and mild condition is suitable for industrialized mass production.
Description
Technical field
The invention belongs to daily chemical product production technical fields, are related to a kind of mosquito repellent product and preparation method, specifically relate to
And a kind of discoloration mosquito repellent hydrogel and preparation method thereof.
Background technology
Mosquito is a kind of sanitary insect pest most commonly seen in people's daily life, not only influences the working and learning of people
Daily lifes are waited, the primary vehicle of even more a variety of communicable diseases, according to textual criticism, the whole world is caused every year due to bite by mosquitos
Dead number is about 800,000 people.Mosquito survival ability is extremely strong, and extensive evil life is in such as water channel, pond, outdoor gutter, flowerpot etc.
There is the place of ponding, with being significantly increased for people's outdoor activities time, how to solve to avoid bite by mosquitos in outdoor activities
Become one of hot issue of scientific research personnel's research, and research and develop a series of product of mosquito dispersings, at present, market
Upper common mosquito repellent product mainly has insect aerosol, mosquito-repellent incense, mosquito-driving liquid etc., wherein, insect aerosol energy moment kill mosquito,
But it does not have the lasting mosquito-proof ability of outdoor mosquito repellent；Occasion mosquitocidal repelling effect is poor outdoors for mosquito-repellent incense, and exists certain
Fire safety evaluating hidden danger；Mosquito-driving liquid need to smear use, and repelling effect is easily influenced by body sweats.Therefore, a kind of nothing is developed
Need to spray, be easy to carry about with one use and can the slow-release mosquito repellant product of long-acting mosquito-driving solve bite by mosquitos in people's outdoor activities
Problem is imperative.
For this purpose, Chinese patent literature CN103068410A discloses a kind of aqueous gel compositions of drug volatilization body,
Disclosed gel combination by anionic oil dispersion polymer composition, volatile medicine, water, solvent, colorant, antifoggant,
The compositions such as antioxidant, gelling agent, thickener and natural deodorant, said components are particularly adopted by being physical crosslinking plastic
Gel, this hydrogel right and wrong are formed with physical force such as winding of electrostatic interaction, ion phase interaction, hydrogen bond action, chain etc.
Permanent, by heating, solarization, the structure of hydrogel can change, the rigid water-setting than chemical plastic of colloid of formation
Glue is far short of what is expected, and when in use, which is easily influenced by solarization, drying, rainwater, causes base material damaged, if in colloid
Volatile medicine be pest repellant or insecticide, damaged base material easilys lead to the loss of effective anthelmintic ingredient, weakens expelling parasite
Effect.
Chinese patent literature CN101133072B discloses a kind of controlled release hydrogel for bioactive materials,
In the hydrogel preparation process, it can be imitated into the reaction system using guanosine hydrazide derivatives as substrate added with flavoring
Fruit, flavor effect, effect of drugs, pest repellant or attractant effect component, to obtain the controlled release water for possessing corresponding effect
Gel products.But the product can not provide the function of remaining usage time instruction, greatly reduce product in use just
Sharp degree.Chinese patent literature CN103004757A discloses a kind of porous temperature-sensitive hydrogel slow release formulation and preparation method thereof.This is specially
Profit adds in crosslinking agent, initiator into reaction system, carries medicine and sustained release promotion using n-isopropyl acrylamide as monomer
Agent obtains the hydrogel with slow release effect by polymerisation.Likewise, hydrogel prepared by this method also can not carry
The function for residue usage time of waking up.
Chinese patent literature CN101288408B discloses a kind of clothing insect-proof agent, by oil-containing pyrethrins liquid
An indicating gage for being impregnated with liquid is added in medicine storehouse, the difference using indicating gage luminosity when whetheing there is liquid is to indicate liquid
No to use up, this Pesticidal technology can only indicate the surplus of fluid product, can not indicate solid insect prevention product Chinese medicine liquid
Remaining situation, and in actual use, there are inconveniences for liquid insect-proof agent.
Above-mentioned technology contents generally existing mosquito repellent hydrogel can not accurately understand anophelifuge in product after opening use
Remaining situation, consumer can not be reminded to be replaced when pharmaceutical quantities are too low causes to be stung by mosquito to avoid medicament deficiency
It stings or dose deficiency is mistaken as in the case of medicament abundance and is abandoned, not only cause the wasting of resources, a large amount of anophelifuge
Agent also can cause harmful effect to environment to a certain extent.
Invention content
For this purpose, the present invention is exactly to solve above-mentioned technical problem, so as to propose a kind of high physical strength, stable structure and tool
There is discoloration mosquito repellent hydrogel of the remaining usage time of instruction and preparation method thereof.
In order to solve the above technical problems, the technical scheme is that：
The present invention provides a kind of discoloration mosquito repellent hydrogel, and by percentage to the quality, the hydrogel is polymerize by following components
It obtains：Water-soluble polymeric monomer 17-32%, crosslinking agent 0.6-1.8%, culicifuge 0.1-1.5%, oil-soluble coloring agent 0.04-
0.2%, solubilizer 0.8-1.6%, initiator 0.04-0.12%, surplus are water.
Preferably, the water-soluble polymeric monomer includes component A and component B, wherein, the component A is N- vinyl
Pyrrolidones, the component B is hydroxyethyl methacrylate, in methyl methacrylate, ethyl methacrylate, acrylamide
At least one.
Preferably, the mass ratio of the component A and component B is 1:4-15.
Preferably, the solubilizer is sorbitan fatty acid ester or polyoxyethylene fatty acid ester；The crosslinking agent
For ethylene glycol dimethacrylate.
Preferably, the oil-soluble coloring agent is Isosorbide-5-Nitrae-two (fourth amino) -9,10- amerantrones；The initiator is even
One kind in nitrogen bis-isobutyronitrile, peroxidating two acyl, persulfate.
Preferably, the culicifuge is at least one of pyrethroid or plants essential oil.
Preferably, the pyrethroid is selected from D-empenthrin, metofluthrin, transfluthrin and dextrorotation
At least one of prallethrin；The plants essential oil is selected from lemon, oil of Cymbopogon winterianus, Lavender, clove oil, outstanding
Add sharp essential oil, Peppermint essential oil, deodar essential oil, Rosemary Oil, lemon grass essential oil, pelargonium roseum essential oil, Melaleuca oil,
At least one of thyme essential oil, Catnip essential oil, artemisia annua essential oil, eucalyptus citriodora essential oil.
The present invention also provides a kind of methods for preparing the discoloration mosquito repellent hydrogel, include the following steps：
S1, proportionally by water-soluble polymeric monomer, crosslinking agent, culicifuge, oil-soluble coloring agent, initiator, solubilizer
It is uniformly mixed with water, leads to nitrogen treatment after being placed in brown container；
S2, the obtained mixed solutions of step S1 are placed in molding die, discoloration mosquito repellent hydrogel is made in temperature reaction.
Preferably, in the step S1, it is 6-15min to lead to the nitrogen time.
Preferably, in the step S2, the temperature reaction is specially：The sustained response in 50-80 DEG C of water-bath
12h。
The above technical solution of the present invention has the following advantages over the prior art：
(1) discoloration mosquito repellent hydrogel of the present invention, by percentage to the quality, the hydrogel is polymerize by following components
It obtains：Water-soluble polymeric monomer 17-32%, crosslinking agent 0.6-1.8%, culicifuge 0.1-1.5%, oil-soluble coloring agent 0.04-
0.2%, solubilizer 0.8-1.6%, initiator 0.04-0.12%, surplus are water.The hydrogel by chemical constituent be crosslinked and
Into with higher mechanical strength, hydrogel structure caused by can resisting the variation of the use environments such as rainwater and solarization changes, keeps away
Exempt from the problem of anophelifuge loss causes hydrogel repelling effect to weaken, and there is oil-soluble coloring agent in hydrogel, profit
The indicating effect to carrying medicine surplus is realized with the physical characteristic of oil-soluble coloring agent, medicine volatilization is carried when having in the hydrogel that changes colour
Afterwards, meltage of the oil-soluble coloring agent in hydrogel gradually decreases, until all be precipitated, make hydrogel occur color by deeply to
Shallow variation, this variation can be arrived by direct visual perception, it may be appreciated that the remaining situation of mosquito component in mosquito repellent hydrogel avoids
Because do not know carry medicine surplus caused by repelling effect weaken or the situation of the wasting of resources.
(2) preparation method of discoloration mosquito repellent hydrogel of the present invention, includes the following steps：S1, proportionally by water
Soluble polymeric monomer, crosslinking agent, culicifuge, oil-soluble coloring agent, initiator, solubilizer and water are uniformly mixed, and are placed in brown appearance
Lead to nitrogen treatment after device；S2, the obtained mixed solutions of step S1 are placed in molding die, discoloration mosquito-repellent water is made in temperature reaction
Gel.The preparation method step is simple, and mild condition is suitable for industrialized mass production.
Specific embodiment
In order to make the content of the present invention more clearly understood, below according to specific embodiments of the present invention to this hair
It is bright to be described in further detail.
Embodiment 1
The present embodiment provides a kind of discoloration mosquito repellent hydrogels, polymerize to obtain by following components by percentage to the quality：First
Base hydroxy-ethyl acrylate 16%, n-vinyl pyrrolidone 4%, ethylene glycol dimethacrylate 0.6%, D-empenthrin
0.8%, Isosorbide-5-Nitrae-two (fourth amino) -9,10- amerantrones 0.1%, polyoxyethylene fatty acid ester 1.2%, azodiisobutyronitrile
0.08%, surplus is deionized water.
This implementation also provides a kind of method for preparing the discoloration mosquito repellent hydrogel, includes the following steps：
S1, hydroxyethyl methacrylate, n-vinyl pyrrolidone, second slowly are added according to aforementioned proportion in brown bottle
Diol dimethacrylate, polyoxyethylene fatty acid ester, azodiisobutyronitrile and deionized water, stirring 5-10min to initiation
Agent is fully dissolved, and uniformly mixed D-empenthrin and Isosorbide-5-Nitrae-two (fourth amino) -9,10- anthracenes two are added under conditions of stirring
Ketone persistently stirs 5-10min, obtains blue-tinted transparent solution, and dry nitrogen 10min is passed through into solution.
S2, the obtained mixed solutions of step S1 are placed in the circular glass vessel of diameter 6cm, high 3cm, the water at 60 DEG C
Bath reaction 12h, is made discoloration mosquito repellent hydrogel.
Embodiment 2
The present embodiment provides a kind of discoloration mosquito repellent hydrogels, polymerize to obtain by following components by percentage to the quality：First
Base hydroxy-ethyl acrylate 15%, ethyl methacrylate 15%, n-vinyl pyrrolidone 2%, ethyleneglycol dimethacrylate
Ester 1.8%, metofluthrin 1.36%, Isosorbide-5-Nitrae-two (fourth amino) -9,10- amerantrones 0.12%, sorbitan fatty acid
Ester (sapn -120) 1.6%, azodiisobutyronitrile 0.12%, surplus is deionized water.
This implementation also provides a kind of method for preparing the discoloration mosquito repellent hydrogel, includes the following steps：
S1, hydroxyethyl methacrylate, ethyl methacrylate, N- second slowly are added according to aforementioned proportion in brown bottle
Vinyl pyrrolidone, ethylene glycol dimethacrylate, sapn -120, azodiisobutyronitrile and deionized water stir 5-10min
It is fully dissolved to initiator, uniformly mixed metofluthrin and Isosorbide-5-Nitrae-two (fourth amino) -9 is added under conditions of stirring,
10- amerantrones, persistently stir 5-10min, obtain blue-tinted transparent solution, and dry nitrogen 15min is passed through into solution.
S2, the obtained mixed solutions of step S1 are placed in the circular glass vessel of diameter 6cm, high 3cm, the water at 80 DEG C
Bath reaction 12h, is made discoloration mosquito repellent hydrogel.
Embodiment 3
The present embodiment provides a kind of discoloration mosquito repellent hydrogels, polymerize to obtain by following components by percentage to the quality：Third
Acrylamide 28%, n-vinyl pyrrolidone 5%, ethylene glycol dimethacrylate 0.6%, transfluthrin 0.4%, Isosorbide-5-Nitrae-
Two (fourth amino) -9,10- amerantrones 0.06%, sorbitan fatty acid ester (sapn -120) 0.8%, peroxidating two acyl
0.04%, surplus is deionized water.
This implementation also provides a kind of method for preparing the discoloration mosquito repellent hydrogel, includes the following steps：
S1, acrylamide, n-vinyl pyrrolidone, glycol dinitrate slowly are added according to aforementioned proportion in brown bottle
Base acrylate, sapn -120, peroxidating two acyl and deionized water, stirring 5-10min is fully dissolved to initiator, in stirring
Under the conditions of add in uniformly mixed transfluthrin and Isosorbide-5-Nitrae-two (fourth amino) -9,10- amerantrones, persistently stir 5-10min, obtain
To blue-tinted transparent solution, dry nitrogen 6min is passed through into solution.
S2, the obtained mixed solutions of step S1 are placed in the circular glass vessel of diameter 6cm, high 3cm, the water at 50 DEG C
Bath reaction 12h, is made discoloration mosquito repellent hydrogel.
Embodiment 4
The present embodiment provides a kind of discoloration mosquito repellent hydrogels, polymerize to obtain by following components by percentage to the quality：First
Base hydroxy-ethyl acrylate 14.2%, n-vinyl pyrrolidone 2.8%, ethylene glycol dimethacrylate 1.42%, methoxy benzyl
Flumethrin 0.1%, Isosorbide-5-Nitrae-two (fourth amino) -9,10- amerantrones 0.04%, sapn -120 1.4%, persulfate 0.04% are remaining
It measures as deionized water.
This implementation also provides a kind of method for preparing the discoloration mosquito repellent hydrogel, includes the following steps：
S1, hydroxyethyl methacrylate, n-vinyl pyrrolidone, second slowly are added according to aforementioned proportion in brown bottle
Diol dimethacrylate, sapn -120, persulfate and deionized water, stirring 5-10min are fully dissolved to initiator,
Uniformly mixed metofluthrin and Isosorbide-5-Nitrae-two (fourth amino) -9,10- amerantrones are added under conditions of stirring, persistently stirs 5-
10min, obtains blue-tinted transparent solution, and dry nitrogen 9min is passed through into solution.
S2, the obtained mixed solutions of step S1 are placed in the circular glass vessel of diameter 6cm, high 3cm, the water at 70 DEG C
Bath reaction 12h, is made discoloration mosquito repellent hydrogel.
Embodiment 5
The present embodiment provides a kind of discoloration mosquito repellent hydrogels, polymerize to obtain by following components by percentage to the quality：First
Base hydroxy-ethyl acrylate 10%, methyl methacrylate 5%, ethyl methacrylate 5%, n-vinyl pyrrolidone 5%, second
Diol dimethacrylate 1.6%, transfluthrin 0.5%, lemon 1%, Isosorbide-5-Nitrae-two (fourth amino) -9,10- anthracenes two
Ketone 0.2%, sapn -120 1.4%, azodiisobutyronitrile 0.12%, surplus are deionized water.
This implementation also provides a kind of method for preparing the discoloration mosquito repellent hydrogel, includes the following steps：
S1, hydroxyethyl methacrylate, methyl methacrylate 5% slowly are added according to aforementioned proportion in brown bottle,
Ethyl methacrylate, n-vinyl pyrrolidone, ethylene glycol dimethacrylate, sapn -120, azodiisobutyronitrile and
Deionized water, stirring 5-10min fully dissolved to initiator, added under conditions of stirring uniformly mixed transfluthrin,
Lemon and Isosorbide-5-Nitrae-two (fourth amino) -9,10- amerantrones, persistently stir 5-10min, obtain blue-tinted transparent solution, to solution
In be passed through dry nitrogen 8min.
S2, the obtained mixed solutions of step S1 are placed in the circular glass vessel of diameter 6cm, high 3cm, the water at 55 DEG C
Bath reaction 12h, is made discoloration mosquito repellent hydrogel.
Embodiment 6
The present embodiment provides a kind of discoloration mosquito repellent hydrogels, polymerize to obtain by following components by percentage to the quality：First
Base hydroxy-ethyl acrylate 10%, ethyl methacrylate 10%, n-vinyl pyrrolidone 5%, ethyleneglycol dimethacrylate
Ester 1.6%, pelargonium roseum essential oil 1.3%, deodar essential oil 0.2%, Isosorbide-5-Nitrae-two (fourth amino) -9,10- amerantrones 0.2%, department
Disk -120 1.4%, azodiisobutyronitrile 0.12%, surplus are deionized water.
This implementation also provides a kind of method for preparing the discoloration mosquito repellent hydrogel, includes the following steps：
S1, hydroxyethyl methacrylate, n-vinyl pyrrolidone, second slowly are added according to aforementioned proportion in brown bottle
Diol dimethacrylate, sapn -120, azodiisobutyronitrile and deionized water, stirring 5-10min are fully molten to initiator
Solution, adds in uniformly mixed pelargonium roseum essential oil, deodar essential oil and Isosorbide-5-Nitrae-two (fourth amino) -9,10- under conditions of stirring
Amerantrone persistently stirs 5-10min, obtains blue-tinted transparent solution, and dry nitrogen 10min is passed through into solution.
S2, the obtained mixed solutions of step S1 are placed in the circular glass vessel of diameter 6cm, high 3cm, the water at 65 DEG C
Bath reaction 12h, is made discoloration mosquito repellent hydrogel.
Embodiment 7
The present embodiment provides a kind of discoloration mosquito repellent hydrogels, polymerize to obtain by following components by percentage to the quality：First
Base hydroxy-ethyl acrylate 29%, n-vinyl pyrrolidone 2%, ethylene glycol dimethacrylate 1.8%, prallethrin
0.3%, lemon grass essential oil 1.06%, Isosorbide-5-Nitrae-two (fourth amino) -9,10- amerantrones 0.12%, sapn -120 1.3%, azo
Bis-isobutyronitrile 0.08%, surplus are deionized water.
This implementation also provides a kind of method for preparing the discoloration mosquito repellent hydrogel, includes the following steps：
S1, hydroxyethyl methacrylate, n-vinyl pyrrolidone, second slowly are added according to aforementioned proportion in brown bottle
Diol dimethacrylate, sapn -120, azodiisobutyronitrile and deionized water, stirring 5-10min are fully molten to initiator
Solution, adds in uniformly mixed prallethrin, lemon grass essential oil and Isosorbide-5-Nitrae-two (fourth amino) -9 under conditions of stirring,
10- amerantrones, persistently stir 5-10min, obtain blue-tinted transparent solution, and dry nitrogen 12min is passed through into solution.
S2, the obtained mixed solutions of step S1 are placed in the circular glass vessel of diameter 6cm, high 3cm, the water at 70 DEG C
Bath reaction 12h, is made discoloration mosquito repellent hydrogel.
Embodiment 8
The present embodiment provides a kind of discoloration mosquito repellent hydrogels, polymerize to obtain by following components by percentage to the quality：First
Base methyl acrylate 26%, n-vinyl pyrrolidone 3%, ethylene glycol dimethacrylate 1.4%, eucalyptus citriodora essential oil
1.5%, Isosorbide-5-Nitrae-two (fourth amino) -9,10- amerantrones 0.1%, sapn -1201.2%, azodiisobutyronitrile 0.1%, surplus is
Deionized water.
This implementation also provides a kind of method for preparing the discoloration mosquito repellent hydrogel, includes the following steps：
S1, methyl methacrylate, n-vinyl pyrrolidone, second two slowly are added according to aforementioned proportion in brown bottle
Alcohol dimethylacrylate, sapn -120, azodiisobutyronitrile and deionized water, stirring 5-10min are fully dissolved to initiator,
Uniformly mixed eucalyptus citriodora essential oil and Isosorbide-5-Nitrae-two (fourth amino) -9,10- amerantrones are added under conditions of stirring, persistently stirs 5-
10min, obtains blue-tinted transparent solution, and dry nitrogen 13min is passed through into solution.
S2, the obtained mixed solutions of step S1 are placed in the circular glass vessel of diameter 6cm, high 3cm, the water at 60 DEG C
Bath reaction 12h, is made discoloration mosquito repellent hydrogel.
Comparative example 1
This comparative example provides a kind of discoloration mosquito repellent hydrogel, by percentage to the quality, is polymerize by following components and is made：First
Base hydroxy-ethyl acrylate 12%, n-vinyl pyrrolidone 4%, ethylene glycol dimethacrylate 1.0%, metofluthrin
0.5%, Isosorbide-5-Nitrae-two (fourth amino) -9,10- amerantrones 0.10%, sapn -120 0.6%, azodiisobutyronitrile 0.10%, go from
Sub- water 81.7%.
It is prepared using any methods of embodiment 1-8, the complete mosquito repellent hydrogel of shape can not be obtained.
Comparative example 2
This comparative example provides a kind of discoloration mosquito repellent hydrogel, by percentage to the quality, is polymerize by following components and is made：First
Base hydroxy-ethyl acrylate 30%, n-vinyl pyrrolidone 10%, ethylene glycol dimethacrylate 3.0%, methoxy benzyl fluorine chrysanthemum
Ester 1.5%, Isosorbide-5-Nitrae-two (fourth amino) -9,10- amerantrones 0.20%, sapn -120 1.0%, azodiisobutyronitrile 0.12% are gone
Ionized water 54.18%.
It is prepared using any methods of embodiment 1-8, obtains discoloration mosquito repellent hydrogel.
Comparative example 3
This comparative example provides a kind of discoloration mosquito repellent hydrogel, by percentage to the quality, is polymerize by following components and is made：First
Base hydroxy-ethyl acrylate 20%, n-vinyl pyrrolidone 5%, ethylene glycol dimethacrylate 1.0%, metofluthrin
4.0%, Isosorbide-5-Nitrae-two (fourth amino) -9,10- amerantrones 0.10%, sapn -120 0.6%, azodiisobutyronitrile 0.10%, go from
Sub- water 69.2%.
It is prepared using any the methods of embodiment 1-8, obtains discoloration mosquito repellent hydrogel.
Comparative example 4
This comparative example provides a kind of discoloration mosquito repellent hydrogel, by percentage to the quality, is polymerize by following components and is made：First
Base hydroxy-ethyl acrylate 20%, n-vinyl pyrrolidone 5%, ethylene glycol dimethacrylate 1.0%, metofluthrin
1.5%, Isosorbide-5-Nitrae-two (fourth amino) -9,10- amerantrones 0.01%, sapn -120 0.6%, azodiisobutyronitrile 0.02%, go from
Sub- water 71.87%.
It is prepared using any the methods of embodiment 1-8, obtains discoloration mosquito repellent hydrogel.
Test case
1st, the discoloration mosquito repellent hydrogel being prepared by embodiment 1-8, comparative example 1-4 the methods is suspended on temperature 28
± 1 DEG C, relative humidity 60 ± 10%, air charge rate 50m3The interior of/h, at the 1st, 3,5,7,9,11 day to the mosquito repellent water-setting that changes colour
The color of glue sample carries out naked eye, and the results are shown in Table 1：
Table 1
| 1st day | 3rd day | 5th day | 7th day | 9th day | 11st day | |
| Embodiment 1 | It is dark blue | It is dark blue | It is light blue | It is light blue | In vain | In vain |
| Embodiment 2 | It is dark blue | It is dark blue | It is light blue | It is light blue | It is light blue | In vain |
| Embodiment 3 | It is dark blue | It is light blue | It is light blue | In vain | In vain | In vain |
| Embodiment 4 | It is light blue | It is light blue | In vain | In vain | In vain | In vain |
| Embodiment 5 | It is dark blue | It is dark blue | It is dark blue | It is light blue | It is light blue | In vain |
| Embodiment 6 | It is dark blue | It is dark blue | It is dark blue | It is light blue | It is light blue | In vain |
| Embodiment 7 | It is dark blue | It is dark blue | It is light blue | It is light blue | It is light blue | In vain |
| Embodiment 8 | It is dark blue | It is dark blue | It is light blue | It is light blue | It is light blue | In vain |
| Comparative example 2 | It is dark blue | It is dark blue | It is dark blue | It is dark blue | It is dark blue | It is dark blue |
| Comparative example 3 | It is dark blue | It is dark blue | It is dark blue | It is dark blue | It is dark blue | It is dark blue |
| Comparative example 4 | It is light blue | In vain | In vain | In vain | In vain | In vain |
The test result of table 1 shows discoloration mosquito repellent hydrogel described in embodiment 1-2,5-8 at the 1st, 3,5,7,9,11 day
The variation from dark blue, light blue to white occurs under the conditions of usage time is increased, color change is apparent, expelling parasite in embodiment 3,4
The content of agent and oil-soluble coloring agent is relatively low, therefore priming color is shallower, consistent with repelling effect to be light blue.
Comparative example 1 only has 16% due to the content of water-soluble polymeric monomer, it is impossible to obtain shape and completely change colour mosquito-repellent water
Gel causes 1 distribution of color of comparative example uneven, can not carry out color observation.Higher water-soluble of content is employed in comparative example 2
Property polymerized monomer, the discoloration mosquito-repellent water gel hardness of preparation is higher, in 11 days, color change unobvious.Described in comparative example 3
The mosquito component content of discoloration mosquito repellent hydrogel reaches 4%, color change unobvious.Comparative example 4 is due to oil-soluble coloring agent
Additive amount is too low, and the color of hydrogel is shallower, is light blue.
2nd, by the discoloration mosquito repellent gel being prepared by embodiment 1-8, comparative example 1-4 the methods be suspended on temperature 28 ±
1 DEG C, the interior of relative humidity 60 ± 10% promote mosquito component to discharge using cross-ventilation, test each discoloration mosquito repellent gel
Repelling effect.Specific test method is as follows：
With reference to GB/T 13917.5-2009 test methods, in the transparent glass square chest of 70cm × 70cm × 70cm, release
After test worm activity is normal, glass square chest center 40cm from the ground is suspended on by small goalkeeper's sample for 50 Culex quinquefasciatus, is closed
Entire square box device, and timing immediately check the test worm number gone down per 5min, terminate test after 60min, according to record result
Calculate the KT50 times.Data are recorded according to following standard：KT50 times≤10min is with obvious effects；During 10min ＜ KT50
Between≤30min for effect it is general；KT50 times ＞ 30min is to no effect.
Test result is as shown in table 2：
Table 2
Result is as it can be seen that the color of the discoloration mosquito repellent hydrogel described in embodiment 1-8 can be one by one with repelling effect as shown in Table 2
Corresponding, the hydrogel repelling effect in cyan stage is apparent, and the hydrogel repelling effect in the light blue stage is general, in white
The hydrogel of color range section without repelling effect, wherein embodiment 4 due to the additive amount of oil-soluble coloring agent and culicifuge it is relatively low, initially
Color is light blue, and correspondingly, repelling effect is general, and color becomes after white without repelling effect, can be according to the face of hydrogel
Color judges its repelling effect.
For comparative example 2, when color is navy blue, corresponding repelling effect is general, and color and repelling effect can not correspond to.
In 11 days of observation, apparent color change does not occur for comparative example 3, therefore can not judge.Comparative example 4, when color is shallow
When blue, corresponding repelling effect is apparent.
The above results show that the discoloration mosquito repellent hydrogel described in embodiment 1-8 can carry out repelling effect according to color
Accurately judge, the color of comparative example 1-4 can not be directed to, accurate judgement is carried out to repelling effect.
Obviously, the above embodiments are merely examples for clarifying the description, and is not intended to limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
1. a kind of discoloration mosquito repellent hydrogel, which is characterized in that by percentage to the quality, the hydrogel is polymerize by following components
It arrives：Water-soluble polymeric monomer 17-32%, crosslinking agent 0.6-1.8%, culicifuge 0.1-1.5%, oil-soluble coloring agent 0.04-
0.2%, solubilizer 0.8-1.6%, initiator 0.04-0.12%, surplus are water.
2. discoloration mosquito repellent hydrogel according to claim 1, which is characterized in that the water-soluble polymeric monomer includes component
A and component B, wherein, the component A is n-vinyl pyrrolidone, and the component B is hydroxyethyl methacrylate, methyl-prop
At least one of e pioic acid methyl ester, ethyl methacrylate, acrylamide.
3. discoloration mosquito repellent hydrogel according to claim 2, which is characterized in that the quality of the component A and component B
Than being 1:4-15.
4. discoloration mosquito repellent hydrogel according to claim 3, which is characterized in that the solubilizer is sorbitan fatty
Acid esters or polyoxyethylene fatty acid ester；The crosslinking agent is ethylene glycol dimethacrylate.
5. changed colour mosquito repellent hydrogel according to claim 1-4 any one of them, which is characterized in that the oil-soluble coloring agent is
1,4- bis- (fourth amino) -9,10- amerantrones；The initiator is one in azodiisobutyronitrile, peroxidating two acyl, persulfate
Kind.
6. discoloration mosquito repellent hydrogel according to claim 5, which is characterized in that the culicifuge is pyrethroid or plant
At least one of object essential oil.
7. discoloration mosquito repellent hydrogel according to claim 6, which is characterized in that the pyrethroid is selected from dextrorotation alkynes penta
At least one of chrysanthemum ester, metofluthrin, transfluthrin and prallethrin；The plants essential oil is selected from lemon extract
Oil, oil of Cymbopogon winterianus, Lavender, clove oil, eucalyptus quintessence oil, Peppermint essential oil, deodar essential oil, Rosemary Oil, lemon
Oil of Cymbopogon winterianus, pelargonium roseum essential oil, Melaleuca oil, thyme essential oil, Catnip essential oil, artemisia annua essential oil, eucalyptus citriodora essential oil
At least one of.
A kind of 8. method for preparing the mosquito repellent hydrogel that changes colour as described in claim any one of 1-7, which is characterized in that including as follows
Step：
S1, proportionally by water-soluble polymeric monomer, crosslinking agent, culicifuge, oil-soluble coloring agent, initiator, solubilizer and water
It is uniformly mixed, leads to nitrogen treatment after being placed in brown container；
S2, the obtained mixed solutions of step S1 are placed in molding die, discoloration mosquito repellent hydrogel is made in temperature reaction.
9. the preparation method of discoloration mosquito repellent hydrogel according to claim 8, which is characterized in that in the step S1, lead to
The nitrogen time is 6-15min.
10. the preparation method of discoloration mosquito repellent hydrogel according to claim 9, which is characterized in that in the step S2, institute
Stating temperature reaction is specially：The sustained response 12h in 50-80 DEG C of water-bath.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711464372.XA CN108184826B (en) | 2017-12-28 | 2017-12-28 | Color-changing mosquito-repelling hydrogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711464372.XA CN108184826B (en) | 2017-12-28 | 2017-12-28 | Color-changing mosquito-repelling hydrogel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108184826A true CN108184826A (en) | 2018-06-22 |
| CN108184826B CN108184826B (en) | 2021-01-08 |
Family
ID=62585275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711464372.XA Active CN108184826B (en) | 2017-12-28 | 2017-12-28 | Color-changing mosquito-repelling hydrogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108184826B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111773140A (en) * | 2020-07-21 | 2020-10-16 | 广州润峰婴儿用品有限公司 | Plant essential oil composition and application thereof |
| CN111944263A (en) * | 2020-08-12 | 2020-11-17 | 帝欧家居股份有限公司 | Insect-proof polymethyl methacrylate and preparation method thereof |
| CN112107567A (en) * | 2020-02-16 | 2020-12-22 | 江苏科兴诺生物技术有限公司 | Multi-purpose spraying film-forming disinfectant and preparation method thereof |
| CN112189970A (en) * | 2020-11-11 | 2021-01-08 | 北京零立科技有限公司 | Hair straightener |
| CN112280389A (en) * | 2020-11-05 | 2021-01-29 | 三棵树(上海)新材料研究有限公司 | Mosquito-repellent interior wall coating added with Chinese herbal medicine extract and preparation method thereof |
| CN112972352A (en) * | 2021-02-25 | 2021-06-18 | 烟台中科恩吉科创新产业园管理有限公司 | Preparation method of color-changeable essential oil hair care module |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10158628A (en) * | 1996-11-28 | 1998-06-16 | Rengo Co Ltd | Functional material with effect with visibly recognizable end point |
| CN1210921A (en) * | 1997-08-29 | 1999-03-17 | 联合株式会社 | Functional material containing volatile agent |
| CN102504117A (en) * | 2011-09-27 | 2012-06-20 | 浙江大学 | Aquagel with high water absorbing capacity and preparation method thereof |
| CN103004757A (en) * | 2012-12-25 | 2013-04-03 | 山东大学 | Porous temperature-sensitive hydrogel slow release formulation and preparation method thereof |
| CN103068410A (en) * | 2010-08-05 | 2013-04-24 | 高砂香料工业株式会社 | Aqueous gel composition of drug volatilization body |
| CN103262839A (en) * | 2013-05-31 | 2013-08-28 | 广州立白企业集团有限公司 | Mosquito repelling gel composition with natural plant essential oil |
-
2017
- 2017-12-28 CN CN201711464372.XA patent/CN108184826B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10158628A (en) * | 1996-11-28 | 1998-06-16 | Rengo Co Ltd | Functional material with effect with visibly recognizable end point |
| CN1210921A (en) * | 1997-08-29 | 1999-03-17 | 联合株式会社 | Functional material containing volatile agent |
| CN103068410A (en) * | 2010-08-05 | 2013-04-24 | 高砂香料工业株式会社 | Aqueous gel composition of drug volatilization body |
| CN102504117A (en) * | 2011-09-27 | 2012-06-20 | 浙江大学 | Aquagel with high water absorbing capacity and preparation method thereof |
| CN103004757A (en) * | 2012-12-25 | 2013-04-03 | 山东大学 | Porous temperature-sensitive hydrogel slow release formulation and preparation method thereof |
| CN103262839A (en) * | 2013-05-31 | 2013-08-28 | 广州立白企业集团有限公司 | Mosquito repelling gel composition with natural plant essential oil |
Non-Patent Citations (1)
| Title |
|---|
| 孙敏等: "《智能材料技术》", 31 January 2014, 国防工业出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112107567A (en) * | 2020-02-16 | 2020-12-22 | 江苏科兴诺生物技术有限公司 | Multi-purpose spraying film-forming disinfectant and preparation method thereof |
| CN111773140A (en) * | 2020-07-21 | 2020-10-16 | 广州润峰婴儿用品有限公司 | Plant essential oil composition and application thereof |
| CN111773140B (en) * | 2020-07-21 | 2022-06-21 | 润本生物技术股份有限公司 | Plant essential oil composition and application thereof |
| CN111944263A (en) * | 2020-08-12 | 2020-11-17 | 帝欧家居股份有限公司 | Insect-proof polymethyl methacrylate and preparation method thereof |
| CN112280389A (en) * | 2020-11-05 | 2021-01-29 | 三棵树(上海)新材料研究有限公司 | Mosquito-repellent interior wall coating added with Chinese herbal medicine extract and preparation method thereof |
| CN112280389B (en) * | 2020-11-05 | 2022-04-05 | 三棵树(上海)新材料研究有限公司 | Mosquito-repellent interior wall coating added with Chinese herbal medicine extract and preparation method thereof |
| CN112189970A (en) * | 2020-11-11 | 2021-01-08 | 北京零立科技有限公司 | Hair straightener |
| CN112972352A (en) * | 2021-02-25 | 2021-06-18 | 烟台中科恩吉科创新产业园管理有限公司 | Preparation method of color-changeable essential oil hair care module |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108184826B (en) | 2021-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108184826A (en) | A kind of discoloration mosquito repellent hydrogel and preparation method thereof | |
| CN106172400B (en) | A kind of film-forming type fruits and vegetables or crop bagging composite material and its preparation and application by spraying | |
| CN101558767A (en) | Composition for driving and killing mosquitoes and preparation method thereof | |
| Czarnobai De Jorge et al. | Novel nanoscale pheromone dispenser for more accurate evaluation of Grapholita molesta (Lepidoptera: Tortricidae) attract‐and‐kill strategies in the laboratory | |
| CN103385262A (en) | Compound essential oil for expelling mosquito | |
| US5290556A (en) | Plastic bait composition for attracting and killing crop pests | |
| CN102308797A (en) | Liquid fly-killing incense | |
| CN104872216A (en) | Plant-source synergist and insect aerosol prepared by same | |
| CA1250229A (en) | Pest control | |
| CN104886171A (en) | Polyurethane mosquito-repellent tablet and preparation method thereof | |
| CN107646841A (en) | A kind of sex pheromone for being used to prevent and treat silver ingot noctuid | |
| CN114794097B (en) | Explosion bead containing insect pheromone or trapping agent and preparation method and application thereof | |
| CN110623002A (en) | Preparation method of sweet wormwood wax oil insect repellent | |
| CN102388913B (en) | Chip for trapping and killing citrus fruit fly, and preparation method thereof | |
| CN1201659C (en) | Electric heating mosquito-repellent incense and preparation thereof | |
| CN107637614A (en) | A kind of mosquito repellent composition and mosquito repellent crystal champignon | |
| CN105104422A (en) | Micro-capsule suspending agent containing fosthiazate and pyraclostrobin | |
| CN112471146A (en) | Environment-friendly pesticide hand polishing agent and preparation method thereof | |
| CN104782680A (en) | Environment-friendly poly(butylene succinate) mosquito-repellent tablet and preparation method thereof | |
| CN105188367A (en) | Microencapsulated volatile insect repellent and/or insecticide agent and methods of making and using the same | |
| JP4647979B2 (en) | Food pest repellent using natural products | |
| CN103155955A (en) | Insect repellant | |
| KR102605232B1 (en) | Harmful bird repellent of pellet type and manufacturing method thereof | |
| US20100304968A1 (en) | process of manufacture for deer repellant, pest and rodent control, weed-killer, fungicide and insecticide, and combinations thereof in powder and liquid spray formulations | |
| TW201929664A (en) | Gel-type insect pest repellent for human body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |