CN108684699A - A kind of food-grade mosquito eradication children's preparation and its preparation method and application - Google Patents
A kind of food-grade mosquito eradication children's preparation and its preparation method and application Download PDFInfo
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- CN108684699A CN108684699A CN201810739257.7A CN201810739257A CN108684699A CN 108684699 A CN108684699 A CN 108684699A CN 201810739257 A CN201810739257 A CN 201810739257A CN 108684699 A CN108684699 A CN 108684699A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/46—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=C=S groups
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
- A01N25/12—Powders or granules
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Abstract
The invention discloses a kind of food-grade mosquito eradication children's preparations and its preparation method and application.Active ingredient in mosquito eradication children's preparation is propenyl mustard oil, present invention applicant has found and proves for the first time in laboratory, the propenyl mustard oil that content is 5~50ppm is to the lethality of mosquito children up to 90~100%, and its safety, drug effect and use cost are better than Swebate.Preferably, mosquito eradication children preparation of the present invention is made of each raw material of following weight percent:Propenyl mustard oil 1~40%, emulsifier 2~40%, carrier 20~97%.In addition, the invention also provides a kind of method preparing food-grade propenyl mustard oil mosquito eradication children's preparation, including high-pressure homogeneous technique.It is demonstrated experimentally that mosquito eradication children preparation diluent of the present invention is sprayed on water surface to a concentration of 5~50ppm of propenyl mustard oil with water, mosquito larvae can be quickly killed.The it is proposed of the present invention has very important significance to reducing mosquito children population quantity and preserving the ecological environment.
Description
Technical field
It is the present invention relates to a kind of mosquito larvae control preparation and its preparation method and application, more particularly to a kind of to use food additives
Mosquito eradication children's preparation and its preparation method and application prepared by isothiocyanic acid propylene, the invention belongs to biomedicine technical fields.
Background technology
It is well known that mosquito is the important evil for propagating the multiple infectious diseases such as dengue fever, malaria, yellow fever, filariasis, encephalitis
Worm, according to incompletely statistics, the death toll as caused by spreading the disease mosquito is about 75~1,000,000 every year in the whole world.Wherein, malaria is
One kind of mosquito matchmaker's infectious disease, great healthy hidden danger is caused to subtropical and tropical zones.Another important mosquito matchmaker is infected
Disease is dengue fever virus, is propagated by Aedes aegypti, annual to infect 100,000,000 people or so, mainly in Latin America and Asia.Mosquito matchmaker passes
It broadcasts disease and is in recent years in the U.S. and rise situation.Since human infection being reported from New York in 1999 for the first time, West Nile Virus
It is to the south step by step and westwards move, there is detection to record in all states of continental United States at present.Eastern equine encephalitis virus
(EEE) be another kind by mosquito-borne arboviruse, also result in the illness of the U.S. and Sino-U.S. and South America human body.EEE feels
Dye is characterized as twitching and go into a coma, and leads to the death of approximately half of patient.Except, it is a large amount of using chemical mosquitocide, lead to mosquito
Drug resistance in sharp increase, therefore, the whole world be badly in need of safer, more environmentally friendly, more effective, non-resistant medicament protect the mankind from
The infringement of carried by mosquitoes disease.
The Chinese medicine of China has thousands of years of history so far, and important contribution is made that for the mankind, wherein including many institute's weeks
The qinghaosu known has played important function, as a result, the inventor of qinghaosu for treatment malaria infection disease caused by bite by mosquitos
Slaughter cry of a deer win Nobel world prize.If we can invent a kind of new, Swebate without drug resistance, alternative food
Grade mosquito eradication children's preparation, then, we are desirable to reduce the population quantity of adult mosquito from the root cause, this to control mosquito matchmaker infectious disease and
It preserves the ecological environment and has very important significance.
Currently, the mosquitocide of existing a few types, majority are lower toxicity chemicals both at home and abroad, still, low toxicity is simultaneously not equal to
It is nontoxic, including Swebate and pyrethroids class mosquitocide, if use for a long time, easily causes human body or environment danger at a specified future date or unknown
Evil, including the problem of drug resistance, therefore cause the highest attention of the developed countries such as European Union.
Swebate (young agent of going out), 4,4'Bis- (O, O- dimethyl thio phosphinylidyne oxygroup) diphenyl sulfides, nickname temefos are changed
Formula C16H20O6P2S3, molecular weight 466.4689, CAS 3383-96-8.White crystalline solid, insecticidal action wide spectrum.Acute warp
Mouth toxicity:Rat LD501000mg/kg;Mouse LD50223mg/kg。
Swebate is that a kind of most common mosquito eradication children preparation is applied in the current whole world, potential or remote due to having to environment and water body
Swebate is included in limitation or disabling list by the risk of phase, therefore, the country such as European Union.
Chrysanthemum ester insecticide equally because there are potential risks, is equally included in by states such as European Union and is prevented or restricted from using mesh
Record.Wherein, Canadian pest management office (PMRA) suggested forbidding pyrethroid insectide Permethrin in November, 2017
Certain purposes.2015, gamma cyhalothrin was because the reasons such as toxicity height are appointed as candidate by substitute materials by European Union.
2017, PMRA propositions were forbidden pyrethroid insecticides gamma cyhalothrin being used for all food and forage crop,
And stop at Indoor Residential Ecological use.2013, after examining insecticide, the insecticidal/acaricidal agent of Biphenthrin was non-agricultural for European Union
Purposes is eliminated.
In addition, application No. is 201510394924.9, a kind of entitled " preparation and its preparation for mosquito larvae control
And application " Chinese patent application in, it is used go out young mosquito active matter be tert-butyl phenol compound, it is toxic to aquatile or
There is harmful effect.Application No. is 87104588, in the Chinese patent application of entitled " slow-releasing agent for killing larvel mosquito ", activity used
Object is mostly toxic chemical insecticide.Application No. is 201310733631.X, a kind of entitled " Soviet Union killing larvae
In the Chinese patent application of cloud gold bacillus preparation and preparation method thereof ", used carrier is not degradable glass microballoon, and Bt pairs
Mosquito larvae effect is limited.Application No. is 201310419640.1, entitled " matrine plant source insecticidal emulsifiable concentrate " (mosquito eradication is young
Agent) Chinese patent application, preparation process is complicated, and application cost is high, not sufficiently effective.
In conclusion chemical mosquitocide can fast and effeciently control harmful insect, while environment can also be generated a variety of
Various side effect.As chemicals is increasingly improved in the whole world to the dangerous cognition that public health and environment are brought, naturalization
Close the substitute that object is increasingly becoming harmful chemicals.Wherein, Environmental Protection Agency USA has taken up legislative means by certain days
The raw-food material of right compound or high safety divides " Environmental security compound (insecticide) " into, to protect these Environmental securities
The use for closing object is not limited by government regulation.(note:Usually said " Environmental security compound " refers to the shadow to ecological environment
Ring compound that is limited or not causing damages.)
According to the deficiency of safety and the feature of environmental protection existing for domestic and international existing mosquito eradication children agent, especially Swebate and pyrethroids class
Insecticide is included in limitation or disabling list by states such as European Union, and therefore, research, which can substitute harmful mosquitocide such as Swebate, to seem
It is very urgent, meanwhile, there is particularly important meaning to reducing mosquito matchmaker infectious disease and preserving the ecological environment.
Propenyl mustard oil (abbreviation AITC), English name Allyl isothiocyanate, chemical formula C4H5NS, molecule
Amount 99.15, -80 DEG C of fusing point, 151~153 DEG C of boiling point, density 1.013,46 DEG C of flash-point, CAS 57-06-7.Isothiocyanic acid propylene
Ester is also known as mustard oil or athomin, is the flavouring that people generally like, and is included in food additives catalogue by more than 100 a countries
In, Chinese Industrial Standards (CIS) is GB 29980-2013"National food safety standard food additives allyl isothiocyanate".In addition, beautiful
State FDA has specific limitation guidance, FEMA (mg/kg) to the application of propenyl mustard oil:Soft drink 0.02~0.50;Cold drink
0.50;Candy 0.50;Bakery product 5.2.Appropriateness is limited (FDA-172.515,2000).
Propenyl mustard oil is in addition to for flavouring, the application in terms of agricultural insecticidal, food fresh keeping, medical treatment, medicine
Research is also very active, for example the number of patent application for vegetables in greenhouse booth disinfection is a kind of 201610431130.X " canopy rooms
Sterilization method " is used for for the Patent No. 200810112497.0 " a kind of Athomin capsule and its application " of soil disinfection
The number of patent application of soil disinfection be 201510757165.8 " it is a kind of using silica as the athomin microcapsule controlled-release agent of carrier and
Preparation method ", Patent No. 201310238688.2 " a kind of mustard oil nanometer emulsion and its preparation side for food preservative
Method ", etc..
Although the application study of propenyl mustard oil is extensive with purposes, so far there are no, and propenyl mustard oil is used
In the report of mosquito eradication children.
Present invention applicant has found and proves for the first time, and content is the propenyl mustard oil of 5~50ppm, the cause to mosquito children
For dead rate up to 40~100%, safety, drug effect, use cost are superior to Swebate.Meanwhile proposition of the invention is to reducing
The protection of mosquito children population quantity and ecological environment has very important significance.
Invention content
The purpose of the present invention is to provide a kind of food-grade allyl isothiocyanate mosquito eradication children's preparation and preparation method thereof and
Using for solving safety deficiency and resistance problems existing for chemical mosquito eradication children preparation.
In order to achieve the above object, present invention employs following technological means:
Present invention firstly provides purposes of the propenyl mustard oil in preparing mosquito eradication children's preparation.
Wherein, it is preferred that the propenyl mustard oil is food-grade propenyl mustard oil, meets China
GB299801-2013"Food security standard food additives allyl isothiocyanate"Standard requirement, effective content >=98.0%.
Wherein, it is preferred that the effective concentration of the mosquito eradication children of the propenyl mustard oil is 5~50ppm.
Further, the invention also provides a kind of food-grade mosquito eradication children's preparations, using propenyl mustard oil as mosquito eradication
The active ingredient of larva.
Wherein, it is preferred that in mosquito eradication children's preparation, also contain emulsifier and carrier.
Wherein, it is preferred that in mosquito eradication children's preparation, the carrier is micropore starch or SILICA FUME, it is preferred that described
SILICA FUME grain size be 400~800 mesh.The problem of in view of application cost, used carrier preferred microporous starch of the present invention;It examines
The problem of considering stability or lasting effect, the present invention then preferred SILICA FUME of 400 mesh.
Wherein, it is preferred that the mosquito eradication children preparation is made of each raw material of following weight percent:
Propenyl mustard oil 1~40%
Emulsifier 2~40%
Carrier 20~97%
Wherein, it is preferred that the emulsifier is AS02-30 sodium lauroyl sarcosines, Monododecylphosphate potassium, alkane
Base phenol polyethenoxy ether (OP-10), Phosphate of Polyoxyethylene Isooctyl Ether, nonylphenol polyoxyethylene ether, Nonyl pheno
It is ether phosphate, polyoxyethylene ether, lauryl sodium sulfate, calcium dodecyl benzene sulfonate, Tea Saponin, sodium lignin sulfonate, wooden
Plain sulfoacid calcium, neopelex, alcohol ether carboxylate AEC-9, plant type polyoxyethylene ether, Tween 80, glycol ester, third
One or more of mixing of diol ester and polyethylene glycol, it is preferred that the emulsifier is AS02-30 Hamposyl Ls
Sodium, alkyl phenol polyoxyethylene ether (OP-10), Tea Saponin, polyethylene glycol, NSF-10E polyoxyethylene ether, more preferably AS02-30
Sodium lauroyl sarcosine.
Wherein, it is preferred that the plant type polyoxyethylene ether includes NSF-10E polyoxyethylene ether, NSF-7 polyoxyethylene
Ether, NSF-9 polyoxyethylene ether, NSF-10 polyoxyethylene ether and NSF-20 polyoxyethylene ether.
Described in inventive formulation or the carrier that uses, it can be micropore starch, can also be SILICA FUME.Wherein, micropore
Starch also known as porous-starch are a kind of natural macromolecular materials, safe and non-toxic, have cellular structures, 1~2 μ of aperture
The volume of m, hole account for 50% of particle volume or so, can adsorb and embedding medicinal, improve the stability of drug, and make with sustained release
With.
The SILICA FUME, also known as superfine silica gel powder are a kind of inorganic chemical products of white powder, nontoxic, tasteless, no
Combustion, not quick-fried, non-volatile, corrosion-free, large pore volume, surface-active are strong, and chemical property is stablized, and have the work of absorption and embedding medicinal
With by the production of Guangzhou Xin Xi chemical metallurgies Co., Ltd.
It is worth noting that by adjusting mosquito eradication children proposed by the present invention formula, proportioning, different content can be not only produced
Propenyl mustard oil mosquito eradication children's lotion, include the isothiocyanic acid propylene of 1%, 5%, 20%, 40% weight percent content
Ester, moreover, it is also possible to produce different carriers, the pulvis of different content propenyl mustard oil and anhydrous product emulsion.
It should be noted that if being fitted in 5% propenyl mustard oil product below by inventive formulation production content
Together in preparing pulvis;If producing content in the product of 5% or more propenyl mustard oil by inventive formulation, it is suitable for preparing
Emulsion type products.
In the present invention, prepared by mosquito eradication children's preparation, and the content and dosage form of propenyl mustard oil can be as needed,
It is adjusted in the formula range that the present invention provides, the product that content is different, dosage form is different, including 1~5% different sulphur cyanogen can be made
The anhydrous lotion of the pulvis of acid propylene ester and 5~40% propenyl mustard oils.Because of the use concentration of propenyl mustard oil
Unusual low (5~50ppm), and can arbitrarily be diluted with water, the propenyl mustard oil of 1% content, it can be used as mother completely
Expect commodity production and sale.Before use, only propenyl mustard oil need to be diluted to 5~50ppm with water, storage, using,
It transports extremely convenient.In short, without departing from the use concentration (5~50ppm) of propenyl mustard oil proposed by the present invention, appoint
What adjustment of content or change of dosage form does not interfere with the mosquito-killing effect and final purpose of the present invention.
Citing:Prepare propenyl mustard oil mosquito eradication children's lotion that weight percent content is 20%.Weigh the different sulphur of 20kg
Cyanic acid acrylic ester, 20kg emulsifiers, 60kg micropore starch (carrier) form sediment the propenyl mustard oil weighed, emulsifier, micropore
Powder mixes, and is pumped into high pressure homogenizer by liquid pump, selects suitable operating pressure and feed pressure, homogeneous, can will be different
Thiocyanic acid acrylic ester is pressed into micropore starch hole, and the anhydrous lotion of propenyl mustard oil that 100kg contents are 20% is made, should
Product content is high, and good water solubility can arbitrarily dilute, and extension rate is big, can be used as raw material sale.Before use, 20% is contained with water
The anhydrous lotion of propenyl mustard oil of amount is diluted to 5~50ppm concentration, is sprayed on water surface, you can quickly kill mosquito larvae.
Example again:Prepare the anhydrous lotion of propenyl mustard oil mosquito eradication children that weight percent content is 40%.Using 40kg
Propenyl mustard oil, 40kg emulsifiers, 20kg SILICA FUMEs, the propenyl mustard oil weighed, emulsifier, SILICA FUME are mixed
It closes, is pumped into high pressure homogenizer by liquid pump, selects suitable operating pressure and feed pressure, homogeneous can be by different sulphur cyanogen
Acid propylene ester is pressed into SILICA FUME hole, and the lotion that 100kg propenyl mustard oil contents are 40%, products made thereby content is made
Height, extension rate is big, using simple, good water solubility, can be used as raw material sale.Before use, with water by the different sulphur cyanogen of 40% content
Acid propylene ester lotion is diluted to 5~50ppm concentration, is sprayed on water surface, you can quickly kill mosquito larvae.
By the preparation of the anhydrous lotion of above-mentioned two high-content propenyl mustard oil mosquito eradication children, it is not difficult to find out, one dense
Degree is 20%, and one a concentration of 40%, carrier and content is altered or varied, and has no effect on the using effect of the present invention.
By adjusting the composition of raw materials of the invention provided, proportioning, powder product can also be produced.
Citing:Prepare propenyl mustard oil mosquito eradication children's pulvis that SILICA FUME load weight degree is 5%.
Weigh 5kg propenyl mustard oils, 5kg methyl glycol fatty acid esters emulsifier (commercial goods), 90kg micropore starch
(production of Liaoning bio tech ltd Li Da), it is spare.
Preparation method:(1) first propenyl mustard oil and methyl glycol fatty acid ester emulsifier are mixed;(2) micropore is formed sediment
Powder is put into common grinder, booting;(3) in the state of stirring, by propenyl mustard oil and methyl glycol fatty acid ester
Liquid mixture is slowly added into the pulverizer equipped with micropore starch, makes propenyl mustard oil and methyl glycol fatty acid ester
It uniformly contacts, adsorb with micropore starch, after having filled liquid mixture, pulverizer works on 20~40min, makes material more
Uniformly, it then shuts down, discharges, vacuum packaging, you can the isothiocyanic acid propylene of micropore starch load 5% of the present invention is made
Ester mosquito eradication children's pulvis.
Example again:Prepare propenyl mustard oil mosquito eradication children's pulvis that SILICA FUME load weight degree is 1%.
It is micro- to weigh 1kg propenyl mustard oil mosquito eradication childrens agent, 2kg Tea Saponins emulsifier (commercial goods) and 400 mesh of 97kg
Silica flour carrier (is produced) by Guangzhou Xin Xi chemical metallurgies Co., Ltd, spare.
Preparation method:(1) first propenyl mustard oil and Tea Saponin emulsifier are mixed;(2) 400 mesh SILICA FUMEs are put into
In common grinder, booting;(3) in the state of stirring, by the liquid mixture of propenyl mustard oil and Tea Saponin, slowly
It is added in the pulverizer equipped with SILICA FUME, so that propenyl mustard oil and Tea Saponin are uniformly contacted, are adsorbed with micropore starch, add
After having noted liquid mixture, pulverizer continues 20~40min of mixing, keeps material more uniform, then shuts down, discharging, vacuum packet
Dress, you can mosquito eradication children's pulvis of the propenyl mustard oil of micropore starch load 1% of the present invention is made.The pulvis it is steady
Qualitative and lasting effect is better than micropore starch, and shortcoming is that production cost is slightly higher.
Further, the invention also provides a kind of method preparing mosquito eradication children's preparation, include the following steps:
When mosquito eradication children's preparation is lotion:
(1) each raw material is weighed respectively according to following weight percent, it is spare;
Propenyl mustard oil 1~40%
Emulsifier 2~40%
Carrier 20~97%
(2) propenyl mustard oil weighed, emulsifier, carrier are mixed, are pumped into high pressure homogenizer by liquid pump,
Select suitable operating pressure and feed pressure, homogeneous, you can mosquito eradication children's lotion containing propenyl mustard oil is made;
Wherein, the operating pressure of preferred high pressure homogenizer be 60~200MPa, preferred operating pressure be 80~
120MPa, feed pressure are 0.1~2MPa, and preferably 0.8MPa, homogenizing time is 10~50min;
When mosquito eradication children's preparation is pulvis:
(1) each raw material is weighed respectively according to following weight percent, it is spare;
Propenyl mustard oil 1~40%
Emulsifier 2~40%
Carrier 20~97%
(2) propenyl mustard oil and emulsifier are mixed;
(3) carrier is put into common grinder, is switched on;
(4) it in the state of stirring, by the liquid mixture of propenyl mustard oil and emulsifier, is slowly added into and is equipped with
In the pulverizer of carrier, so that propenyl mustard oil and emulsifier are uniformly contacted, are adsorbed with carrier, filled liquid mixture
Afterwards, pulverizer works on 20~40min, then shuts down, and discharges, vacuum packaging, you can propenyl mustard oil mosquito eradication is made
Young pulvis.
The preparation process and feature of the present invention is to act on by the internal pressure of high pressure homogenizer, by propenyl mustard oil
In the hole for forcing indentation micropore starch or SILICA FUME, play the role of embedding, stabilization, storage and sustained release.Through high pressure homogenizer
Propenyl mustard oil mosquito eradication children's lotion obtained, appearance transparent, homogeneous, without suspend and precipitation, it is not aqueous, in water easily it is voluntarily molten
Solution, and can slow release propenyl mustard oil, mosquito eradication children effect is fast.
Further, the purposes the invention also provides the mosquito eradication children preparation in administering mosquito children, wherein preferably
, the mosquito children includes Aedes (Aedes), Culex (Culex), Aedes aegypti (Aedes aegypti), Anopheles
(Anopheles), anopheles annulipes annulipes (Anophelesannulipes), Armigeres (Armigeres), Chinese mugwort uranotaenia
(Ayurakitia), Bironella (Bironella), Bao uranotaenia (Borichinda), Qia Shi uranotaenias (Chagasia), Ke mosquitos
Belong to (Coquillettidia), Culex quinquefasciatus (Culex quinquefasciatus), ring grain culex (Culex
Annulirostris), Culiseta (Culiseta), take uranotaenia (Ficalbia), Haemagogus (Haemagogus), neck mosquito
Belong to (Heizmannia), suddenly uranotaenia (Hodgesia), golden uranotaenia (Kimia), Malaya (Malaya), Mansonia
(Mansonia), small uranotaenia (Mimomyia), Orthopodomyia (Orthopodomyia), Psorophora, evil spirit uranotaenia (Sabethes),
Native uranotaenia (Topomyia), Toxorhynchites (Toxorhynchites), Trichoprosopon (Trichoprosopon), pestle uranotaenia
(Tripteroides) and outstanding uranotaenia (Udaya) mosquito is young.
Mosquito eradication children's preparation that the propenyl mustard oil content that the present invention is prepared is 1~40% is high concentration masterbatch,
Not directly use.Before use, need to dilute within the scope of a concentration of 5~50ppm of propenyl mustard oil, then dispense again in there is mosquito
The place of children, it is preferred to use water, talcum powder and/or maize cob meal are diluted.
Laboratory experiment the result shows that, propenyl mustard oil it is directly proportional to the rate of mosquito eradication children using concentration.
Wherein, content is the propenyl mustard oil of 0.005% (50ppm), 12h is acted on, to the lethality of mosquito children
Up to 99~100%;Content is the propenyl mustard oil of 0.0025% (25ppm), acts on 12h, reachable to the lethality of mosquito children
99~100%;Content is the propenyl mustard oil of 0.0005% (5ppm), acts on 12h, to the lethality of mosquito children up to 90~
100%.Content is the propenyl mustard oil of 0.00025% (2.5ppm), acts on 12h, to the lethality of mosquito children up to 40~
70%, still, reproducibility is bad, and therefore, the present invention limits the minimum of propenyl mustard oil and uses effective concentration as 5ppm.
The method of evaluating drug effect of propenyl mustard oil mosquito eradication children's preparation of the present invention is:
(1) Experimental Method in Laboratory
Method is supported in the liquid leaching recommended using the World Health Organization (WHO) or the life of China national south pesticides discovery center is surveyed
Dip method in SOP.
(2) field condition is tested
According to China GB/T 31711-2015"Hygienic insecticide field efficacy measures and evaluation mosquitocidal children's agent"Standard.
(3) standard of mosquito eradication children raw material (propenyl mustard oil)
Using Chinese GB 29980-2013"National food safety standard food additives allyl isothiocyanate"Standard.
(4) auxiliary material standard
Auxiliary material used includes emulsifier and carrier, is all made of the corresponding product technical standard of enterprise's offer.
Compared to the prior art, the beneficial effects of the invention are as follows:
(1) present invention applicant has found and proves for the first time, and use of the food-grade propenyl mustard oil in 5~50ppm is dense
Under degree, there is effect of reliably killing, and the safety with food-grade and the use cost less than Swebate to mosquito larvae.
(2) propenyl mustard oil source be easy, can be extracted from plant, can also chemical synthesis, in can meeting
The standard requirement of country of state GB 29980-2013.
(3) proposition of the invention carries to reduce mosquito children population quantity and solving the resistance problems that chemical mosquitocide generates
New technological approaches is supplied.
Specific implementation mode
With reference to specific embodiment come the characteristics of further illustrating the present invention, meanwhile, with retouching for embodiment and method
State, it will help to the present invention carry out in more detail, more clearly understand.But these examples are merely exemplary, it is not right
The scope of the present invention constitutes any restrictions.It will be understood by those skilled in the art that in spirit and model without departing from the present invention
Under enclosing, can the details and form of technical solution of the present invention be modified or be replaced, but these modifications and replacement each fall within this
In the protection domain of invention.
The preparation of the propenyl mustard oil mosquito eradication children lotion (masterbatch) of embodiment 1 40% (w/w) content
(1) weighing the propenyl mustard oil that 40kg contents are 98%, (Pingxiang County Tian Bang seasoned foods Co., Ltd gives birth to
Production), it is spare;40kg OP-10 alkyl phenol polyoxyethylene ether emulsifier (Jiangsu Hai'an Petrochemical Plant's production) is weighed, it is spare;
20kg micropore starch carrier (production of Liaoning bio tech ltd Li Da) is weighed, it is spare.
(2) propenyl mustard oil weighed up, OP-10 alkyl phenol polyoxyethylene ether and micropore starch stainless steel is put into stir
It mixes in machine and is pre-mixed, then mixture is pumped into the high pressure of promise pool fluid science and technology (Shanghai) Co., Ltd. production with liquid pump
In homogenizer, operating pressure is set as 80MPa, feed pressure 0.15MPa, booting homogeneous 20min, you can obtained content is
Propenyl mustard oil mosquito eradication children's lotion of 40% (w/w).
The preparation of the propenyl mustard oil mosquito eradication children lotion (masterbatch) of embodiment 2 20% (w/w) content
(1) weighing the propenyl mustard oil that 20kg contents are 98%, (Pingxiang County Tian Bang seasoned foods Co., Ltd gives birth to
Production), it is spare;20kg OP-10 alkyl phenol polyoxyethylene ether emulsifier (Jiangsu Hai'an Petrochemical Plant's production) is weighed, it is spare;
400 mesh SILICA FUMEs of 60kg (production of Guangzhou Xin Xi chemical metallurgies Co., Ltd) are weighed, it is spare.
(2) propenyl mustard oil weighed up, OP-10 alkyl phenol polyoxyethylene ether and SILICA FUME are put into stainless steel stirring
It is pre-mixed in machine, then high pressure that mixture is pumped into the production of promise pool fluid science and technology (Shanghai) Co., Ltd. with liquid pump is equal
In matter machine, operating pressure is set as 80MPa, feed pressure 0.15MPa, be switched on homogeneous 20min, you can it is 20% that content, which is made,
(w/w) propenyl mustard oil mosquito eradication children's lotion.For products obtained therefrom because containing SILICA FUME, stability is good compared with micropore starch, can use
Water arbitrarily dilutes, non-hazardous to environment and people and animals.
The preparation of the propenyl mustard oil mosquito eradication children pulvis (masterbatch) of embodiment 3 5% (w/w)
(1) propenyl mustard oil, 5kg methyl glycol fatty acid esters emulsifier (the commercially available quotient that 5kg contents are 98% are weighed
Product), 90kg micropore starch, it is spare.
(2) first propenyl mustard oil and methyl glycol fatty acid ester emulsifier are mixed;
(3) micropore starch is put into common grinder, is switched on;
(4) in the state of stirring, the liquid mixture of propenyl mustard oil and methyl glycol fatty acid ester slowly adds
Enter into the pulverizer equipped with micropore starch, propenyl mustard oil and methyl glycol fatty acid ester is made uniformly to be connect with micropore starch
It touches, absorption, after having filled liquid mixture, pulverizer continues 20~40min of mixing, keeps material more uniform, then shuts down, goes out
Material, vacuum packaging, you can propenyl mustard oil mosquito eradication children's powder that micropore starch of the present invention loads 5% (w/w) is made
Agent, the preparation method is simple, and use and storage are convenient.
The preparation of the propenyl mustard oil mosquito eradication children pulvis (masterbatch) of embodiment 4 1% (w/w)
(1) it is micro- that propenyl mustard oil, 2kg Tea Saponins (delicatessen food), 97kg800 mesh that 1kg contents are 98% are weighed
Silica flour carrier, it is spare.
(2) first propenyl mustard oil and Tea Saponin emulsifier are mixed;
(3) 800 mesh SILICA FUMEs are put into common grinder, are switched on;
(4) it in the state of stirring, by the liquid mixture of propenyl mustard oil and Tea Saponin, is slowly added into and is equipped with
In the pulverizer of SILICA FUME, propenyl mustard oil and Tea Saponin is made uniformly to contact, adsorb with SILICA FUME, has filled liquid mixing
After object, pulverizer is made to work on 20~40min, shut down, discharged, vacuum packaging, you can prepare SILICA FUME and load 1% (w/
W) propenyl mustard oil mosquito eradication children's pulvis.
The preparation of the propenyl mustard oil mosquito eradication children lotion (masterbatch) of embodiment 5 20% (w/w)
(1) propenyl mustard oil that 20kg contents are 98% is weighed;Weigh 30kg Tween 80s emulsifier (delicatessen food);
50kg micropore starch carriers are weighed, it is spare.
(2) propenyl mustard oil weighed, Tween 80 emulsifier, micropore starch are put into stainless steel storage vat and are premixed
Close, with liquid pump be pumped into promise pool fluid science and technology (Shanghai) Co., Ltd. production high pressure homogenizer in, set operating pressure as
90MPa, feed pressure 0.2MPa, booting homogeneous 25min, you can the propenyl mustard oil that content is 20% (w/w) is made
Mosquito eradication children's lotion.Products made thereby appearance transparent, homogeneous, good water solubility, stabilization, use and storage are convenient.
The preparation of the propenyl mustard oil mosquito eradication children lotion (masterbatch) of embodiment 6 25% (w/w)
(1) propenyl mustard oil that 25kg contents are 98% is weighed;Weigh 30kg Tea Saponins emulsifier (delicatessen food);
45kg micropore starch is weighed, it is spare.
(2) propenyl mustard oil weighed, Tea Saponin, micropore starch are put into stainless steel storage vat and are pre-mixed, led to
It crosses liquid pump to be pumped into premix in the high pressure homogenizer of promise pool fluid science and technology (Shanghai) Co., Ltd. production, sets operating pressure
For 120MPa, feed pressure 0.4MPa, booting homogeneous 25min, you can the isothiocyanic acid propylene that content is 25% (w/w) is made
Ester lotion.Products made thereby clear appearance, soluble in no suspension and precipitation, water, use and storage are convenient.
The lotion average grain diameter that 25% content propenyl mustard oil is measured through laser particle analyzer is 199nm.
The preparation of the propenyl mustard oil mosquito eradication children lotion (masterbatch) of embodiment 7 30% (w/w)
(1) propenyl mustard oil that 30kg contents are 98% is weighed;Weigh 40kg amino acid surfactants AS02-
30 sodium lauroyl sarcosines (commercial goods);30kg micropore starch carriers are weighed, it is spare.
(2) propenyl mustard oil weighed, AS02-30 sodium lauroyl sarcosines, micropore starch are put into stainless steel storage
Premix, the high pressure homogenizer of promise pool fluid science and technology (Shanghai) Co., Ltd. production is pumped into liquid pump by premixing in charging basket
It is interior, operating pressure is set as 120MPa, feed pressure 0.2MPa, be switched on homogeneous 35min, you can it is 30% (w/ that content, which is made,
W) propenyl mustard oil mosquito eradication children's lotion.Products made thereby good water solubility after being added in water, is also easy to produce foam, has and prolongs
The effect of slow drug effect.
The measurement of 8 propenyl mustard oil mosquito eradication children's drug effect of embodiment
Mosquito eradication children's preparation and the preparation method and application thereof, inventor are prepared according to propenyl mustard oil proposed by the present invention
Give 7 different embodiments, be described in detail propenyl mustard oil proposed by the present invention prepare mosquito eradication children preparation and its
Preparation method and application.Wherein, in the range of inventive formulation, proportioning and high-pressure homogeneous technique and disintegrating process, trial-production
Propenyl mustard oil mosquito eradication children's preparation of different content, different carriers, different emulsifiers, meanwhile, the present invention highlights different sulphur
A concentration of 5~50ppm of optimal use of cyanic acid acrylic ester raw material mosquito eradication children.In view of in different embodiments it is raw materials used it is identical, make
With concentration is identical, application target is identical, therefore, it is very necessary using unified evaluation of pesticide effectiveness method, below with embodiment 1
With 2 made 40% and 20% content propenyl mustard oil lotion for, illustrate effect evaluation method and the survey of mosquito eradication children
Determine result.
The assay method of one, drug effects
1. the measurement of indoor harmacological effect
1.1 method
The liquid leaching recommended using the World Health Organization (WHO) is supported the center life of method or country southern pesticides discovery and surveyed in SOP
Dip method.
1.2 for examination mosquito children
It is provided by Shanxi Ba Dun environmental protection technologies research institute, including aedes albopictus and culex.Tested mosquito children is in temperature
26 ± 1 DEG C, relative humidity 70% ± 10%, photoperiod L/D:Cultivated under conditions of 12h/12h, select 2~3 ages it is energetic,
The consistent mosquito larvae of body size.
1.3 test procedure
(1) the propenyl mustard oil lotion 2g or Example 2 that 1 made content of embodiment is 40% (w/w) are weighed
Made content is the propenyl mustard oil lotion 4.7g of 20% (w/w), and instillation is placed with the beaker that 14mL removes chlorion tap water
In, mixing obtains the propenyl mustard oil solution that content is 5% (w/w).
(2) the propenyl mustard oil lotion that 2g contents are 5% (w/w) is weighed, instillation is placed with 18mL and removes chlorion originally
In the beaker of water, mix to get the propenyl mustard oil solution to content for 0.5% (w/w).
(3) take 4 50mL beakers, number 1,2,3,4 that 25mL is respectively added into beaker and removes chlorion tap water, and each
Introduce 30 vigor stalwartnesses, 3 age aedes albopictus of the same size or Ability of Culex Pipiens Larvae.
(4) the propenyl mustard oil solution of 25 μ L, 12.5 μ L 5% (w/w) are drawn respectively with micropipette rifle, respectively
1, No. 2 beaker is added, draws the propenyl mustard oil solution of 25 μ L, 12.5 μ L 0.5% (w/w) respectively with micropipette rifle,
Be separately added into 3, No. 4 beakers, in this way, in 1-4 beakers the final concentration of propenyl mustard oil be respectively 0.005% (50ppm),
0.0025% (25ppm), 0.0005% (5ppm), 0.00025% (2.5ppm), each beaker of weak vibrations make liquid uniformly divide
Cloth is in water.
Each concentration processing sets 3 groups of repetitions, including propenyl mustard oil test group, blank control and 1% Swebate
Granula compares.
1.4 test result
When propenyl mustard oil final concentration of 0.005% (w/w, 50ppm) in beaker of water, 12h after dosing, mosquito children's is dead
Rate is died up to 99~100%.
When propenyl mustard oil final concentration of 0.0025% (w/w, 25ppm) in beaker of water, 12h after dosing, mosquito children's
The death rate is up to 99~100%.
When propenyl mustard oil final concentration of 0.0005% (w/w, 5ppm) in beaker of water, 12h after dosing, mosquito children's is dead
Rate is died up to 90~100%.
As propenyl mustard oil final concentration of 0.00025% (w/w, 2.5ppm) in beaker of water, 12h after dosing, mosquito children
The death rate up to 40~70%.But the experiment reproducibility is bad.
1% Swebate particles of 1g are added in comparison medicament in the beaker of 25mL dechlorination ionized waters, and it is strong to be put into 30 vigor
The death rate of strong, 3 age children mosquito of the same size, 12h after dosing, aedes albopictus and culex is up to 99~100%.
It is white to be directly placed into 30 vigor stalwartnesses, 3 age of the same size in the beaker of 25mL dechlorination ionized waters for blank control
Line yellow-fever mosquito and culex, not dosing, observation 1~for 24 hours, the death rate of mosquito children is 0.
2. the measurement of field efficacy
2.1 test method
Using national GB/T 31711-2015"Hygienic insecticide field efficacy measures and evaluation mosquitocidal children's agent"Standard.
Mosquito is used in 2.2 experiments
The field culture pond provided from Shanxi Ba Dun environmental protection technologies research institute, the area 1m in each pond2, the depth of water
20cm has enough 2~3 age yellow-fever mosquitos and culex in pond.
2.3 dosage
By 1.0g/m2Medication gauge.
2.4 test result
Every square metre of propenyl mustard oil lotion 1g with 0.005% concentration (w/w, 50ppm) is sprayed in the water surface, medicine
12h afterwards, the death rate of mosquito children is up to 90%, for 24 hours afterwards up to 100%.
For comparison medicament using 1% Swebate particle (Germany's peace times is produced), every square metre of medication 1g is artificial to dispense, and is sunken to water
Bottom, the death rate of mosquito children is 80% after 12h, for 24 hours afterwards up to 99%.
Blank control, no dosing, rear mosquito children's death rate is 0 for 24 hours.
Two, brief summary
1, indoor harmacological effect
(1) the propenyl mustard oil lotion of a concentration of 5ppm, 25ppm, 50ppm acts on 12h, to the lethality of mosquito children
Reach 80~100%;
(2) the propenyl mustard oil lotion of a concentration of 2.5ppm acts on 12h, should to the lethality 40~70% of mosquito children
It is bad to test reproducibility, needs further to be studied.
2, field efficacy
The propenyl mustard oil of (1) 0.005% concentration (50ppm) has the mosquitos children such as culex, yellow-fever mosquito reliable, quick
Effect is killed, moreover, the variation of carrier and emulsifier does not influence the drug effect of propenyl mustard oil.
The propenyl mustard oil lotion of (2) 0.005% concentration (50ppm) is compared with 1% Swebate granule, mosquito eradication children
Effect no significant difference.
According to above-mentioned identical method, the present invention determines the room of embodiment 3-7 and other embodiments that do not enumerate
Interior and field efficacy, a large amount of experimental study and experiment prove, if ensure the use concentration of propenyl mustard oil 5~
Within the scope of 50ppm, suitably adjustment is formulated and matches in range of the present invention, especially adjusts or replace different emulsification
Agent or carrier do not interfere with the killing mosquito larvae efficacy and final purpose of the present invention.
The embodiment of the present invention describes whole technologies specificallyly and full and accurately, therefore, contributes to those skilled in the art or non-
Professional understands the present invention.No matter the present invention can not take off for those skilled in the art or non-those skilled in the art
It from the present invention, finds, under the premise of, easily prepares propenyl mustard oil mosquito eradication children's preparation of the similar present invention,
And several deformations or innovative product can also be made, include the product of the different dosage forms such as solid, powder, microcapsules, suspending agent,
These deformations or improvement all belong to the scope of protection of the present invention.
Claims (10)
1. purposes of the propenyl mustard oil in preparing mosquito eradication children's preparation.
2. purposes as described in claim 1, which is characterized in that effective working concentration of the propenyl mustard oil is 5
~50ppm.
3. a kind of food-grade mosquito eradication children's preparation, which is characterized in that contain active ingredient of the propenyl mustard oil as mosquito eradication children.
4. mosquito eradication children preparation as claimed in claim 3, which is characterized in that the mosquito eradication children preparation is by following weight percent
Each raw material composition:
Propenyl mustard oil 1~40%
Emulsifier 2~40%
Carrier 20~97%.
5. mosquito eradication children preparation as claimed in claim 4, which is characterized in that the emulsifier is AS02-30 lauroyl flesh ammonia
Sour sodium, Monododecylphosphate potassium, alkyl phenol polyoxyethylene ether (OP-10), Phosphate of Polyoxyethylene Isooctyl Ether, nonyl phenol
Polyoxyethylene ether, thermally coupled distillation columns, polyoxyethylene ether, lauryl sodium sulfate, calcium dodecyl benzene sulfonate,
Tea Saponin, sodium lignin sulfonate, calcium lignosulfonate, neopelex, alcohol ether carboxylate AEC-9, plant type polyoxy
One or more of mixing of vinethene, Tween 80, glycol ester, propylene glycol ester and polyethylene glycol, it is preferred that the breast
Agent is AS02-30 sodium lauroyl sarcosines, alkyl phenol polyoxyethylene ether (OP-10), Tea Saponin, polyethylene glycol or NSF-10E
Polyoxyethylene ether, more preferably AS02-30 sodium lauroyl sarcosines;The carrier is micropore starch or SILICA FUME, it is preferred that institute
The grain size for the SILICA FUME stated is 400~800 mesh.
6. mosquito eradication children preparation as claimed in claim 5, which is characterized in that the plant type polyoxyethylene ether includes NSF-
10E polyoxyethylene ether, NSF-7 polyoxyethylene ether, NSF-9 polyoxyethylene ether, NSF-10 polyoxyethylene ether and NSF-20 polyoxies
Vinethene.
7. mosquito eradication children preparation as claimed in claim 4, which is characterized in that mosquito eradication children's preparation is pulvis or lotion.
8. a kind of method preparing claim 3-7 any one of them mosquito eradication children's preparations, which is characterized in that including following step
Suddenly:
When mosquito eradication children's preparation is lotion:
(1) each raw material is weighed respectively according to following weight percent, it is spare;
Propenyl mustard oil 1~40%
Emulsifier 2~40%
Carrier 20~97%
(2) propenyl mustard oil weighed, emulsifier, carrier are mixed, is pumped into high pressure homogenizer by liquid pump, selected
Suitable operating pressure and feed pressure, homogeneous, you can mosquito eradication children's lotion containing propenyl mustard oil is made;
Wherein, the operating pressure of preferred high pressure homogenizer is 60~200MPa, and preferred operating pressure is 80~120MPa,
Feed pressure is 0.1~2MPa, and preferably 0.8MPa, homogenizing time is 10~50min;
When mosquito eradication children's preparation is pulvis:
(1) each raw material is weighed respectively according to following weight percent, it is spare;
Propenyl mustard oil 1~40%
Emulsifier 2~40%
Carrier 20~97%
(2) propenyl mustard oil and emulsifier are mixed;
(3) carrier is put into common grinder, is switched on;
(4) in the state of stirring, the liquid mixture of propenyl mustard oil and emulsifier is slowly added into equipped with carrier
Pulverizer in, so that propenyl mustard oil and emulsifier are uniformly contacted, are adsorbed with carrier, after having filled liquid mixture, powder
Broken machine works on 20~40min, then shuts down, and discharges, vacuum packaging, you can propenyl mustard oil mosquito eradication children's powder is made
Agent.
9. purposes of the claim 3-7 any one of them mosquito eradication children preparation in administering mosquito children, wherein it is preferred, it is described
Mosquito children includes Aedes (Aedes), Culex (Culex), Aedes aegypti (Aedes aegypti), Anopheles
(Anopheles), anopheles annulipes annulipes (Anophelesannulipes), Armigeres (Armigeres), Chinese mugwort uranotaenia
(Ayurakitia), Bironella (Bironella), Bao uranotaenia (Borichinda), Qia Shi uranotaenias (Chagasia), Ke mosquitos
Belong to (Coquillettidia), Culex quinquefasciatus (Culex quinquefasciatus), ring grain culex (Culex
Annulirostris), Culiseta (Culiseta), take uranotaenia (Ficalbia), Haemagogus (Haemagogus), neck mosquito
Belong to (Heizmannia), suddenly uranotaenia (Hodgesia), golden uranotaenia (Kimia), Malaya (Malaya), Mansonia
(Mansonia), small uranotaenia (Mimomyia), Orthopodomyia (Orthopodomyia), Psorophora, evil spirit uranotaenia (Sabethes),
Native uranotaenia (Topomyia), Toxorhynchites (Toxorhynchites), Trichoprosopon (Trichoprosopon), pestle uranotaenia
(Tripteroides) and outstanding uranotaenia (Udaya) mosquito is young.
10. purposes as claimed in claim 9, which is characterized in that by the mosquito eradication children preparation diluent to isothiocyanic acid propylene
The working concentration of ester uses for 5~50ppm.
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| CN201810739257.7A CN108684699A (en) | 2018-07-06 | 2018-07-06 | A kind of food-grade mosquito eradication children's preparation and its preparation method and application |
| PCT/CN2019/000127 WO2020007018A1 (en) | 2018-07-06 | 2019-06-17 | Food-grade mosquito larvicide, preparation method therefor and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020007018A1 (en) * | 2018-07-06 | 2020-01-09 | 王渊 | Food-grade mosquito larvicide, preparation method therefor and application thereof |
| CN114467929A (en) * | 2022-02-24 | 2022-05-13 | 山西巴盾环境保护技术研究所 | Recyclable mosquito eradication young material capable of being suspended on water surface for long time and preparation method and application thereof |
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| JP2012180297A (en) * | 2011-02-28 | 2012-09-20 | Kohendo:Kk | Wriggler exterminating composition |
| CN103719166A (en) * | 2013-12-12 | 2014-04-16 | 江苏集贤绿色化学科技研究院有限公司 | Composite fumigation insecticide and preparation method thereof |
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| CN100448924C (en) * | 2005-06-17 | 2009-01-07 | 华南农业大学 | Preparation for fly-repellent plastic-bottle cap and use in seasoning package product thereof |
| CN101186772B (en) * | 2007-12-04 | 2011-04-27 | 华南农业大学 | Helminthic emulsion paint and preparation method thereof |
| US8697752B2 (en) * | 2010-04-09 | 2014-04-15 | Pacific Tech Industries, Inc. | Grease-like gel for repelling insects and preventing undesirable behavior in hoofed animals |
| CN103379827B (en) * | 2010-12-20 | 2015-11-25 | Mpt芥末产品和技术公司 | For mixture and the preparation method of the juncea plants material of Control pests |
| CN108684699A (en) * | 2018-07-06 | 2018-10-23 | 王渊 | A kind of food-grade mosquito eradication children's preparation and its preparation method and application |
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| JP2012180297A (en) * | 2011-02-28 | 2012-09-20 | Kohendo:Kk | Wriggler exterminating composition |
| CN103719166A (en) * | 2013-12-12 | 2014-04-16 | 江苏集贤绿色化学科技研究院有限公司 | Composite fumigation insecticide and preparation method thereof |
| CN107027826A (en) * | 2017-04-25 | 2017-08-11 | 黄山力神日用品有限公司 | A kind of plant source culicifuge |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020007018A1 (en) * | 2018-07-06 | 2020-01-09 | 王渊 | Food-grade mosquito larvicide, preparation method therefor and application thereof |
| CN114467929A (en) * | 2022-02-24 | 2022-05-13 | 山西巴盾环境保护技术研究所 | Recyclable mosquito eradication young material capable of being suspended on water surface for long time and preparation method and application thereof |
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