CN105532656B - A kind of environmental-friendly dinotefuran micron-emulsion and preparation method thereof - Google Patents
A kind of environmental-friendly dinotefuran micron-emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN105532656B CN105532656B CN201610061491.XA CN201610061491A CN105532656B CN 105532656 B CN105532656 B CN 105532656B CN 201610061491 A CN201610061491 A CN 201610061491A CN 105532656 B CN105532656 B CN 105532656B
- Authority
- CN
- China
- Prior art keywords
- dinotefuran
- emulsion
- environmental
- potassium
- micron
- 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.)
- Active
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
- A01N25/30—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 characterised by the surfactants
-
- 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
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention provides a kind of environmental-friendly dinotefuran micron-emulsion, in percentage by weight, including：1% 20% dinotefuran, 4% 10% anion surfactants, 2% 12% nonionic surfactants, 5% 12% ketones solvents of the boiling point at 150 DEG C or more, 0.01% 0.04% antifoaming agent, surplus is water；Wherein, it is to come from straight chained alkyl or alkenyl that vegetable oil is hydrolyzed or cracked that the anionic surfactant, which is selected from hydrophobic grouping, one or more of the hydrophilic radical in carboxyl, sulfate or sulfonic anion surfactant；The nonionic surfactant selected from hydrophobic grouping be come from vegetable oil or vegetable oil hydrolysis cracking straight chained alkyl or alkenyl polyethenoxy ether class nonionic surfactant in one or more.The present invention also provides the preparation methods of the environmental-friendly dinotefuran micron-emulsion.
Description
Technical field
The invention belongs to pesticides new formulation field, more particularly to a kind of new environmental-friendly furan using plant source wedding agent
Worm amine microemulsion and preparation method thereof.
Background technology
Pesticide (pesticidal preparations are referred in this specification) is control farm-forestry crop disease, worm, the specialty goods of crop smothering, is existing
The indispensable means of production of generation agricultural.But it is one " double-edged sword " again, on the one hand, by applying pesticides, the whole nation every year may be used
Retrieve about 30,000,000,000 kilograms of grain loss.On the other hand, thus caused food security and problem of environmental pollution also show convex day
Go out., also there are solvent and auxiliary agent reason in preparation in the reason for pollution that pesticide is brought, active ingredient itself.Due to solvent and
The dosage of auxiliary agent is generally large, therefore, the secondary hazards to people, animal and environment brought by improperly solvent and/or auxiliary agent
Sometimes more it is more than active ingredient in itself.
In August, 2010, what national four ministries and commissions joint was put into effect《Pesticide industrial policy》, explicitly point out：" country is helped by science and technology
Hold, technological transformation, economic policy guiding etc. measures, support efficiently, safety, economy, environmental-friendly pesticide new product development, add
Fast high pollution, excessive risk product replacement and eliminate, breed structure is promoted to continue to optimize "；" agricultural dosage form is promoted energetically to water base
The direction efficiently, safe such as change, dustlessization, control release, which is developed ... strictly controls the use of poisonous and harmful solvent and auxiliary agent.”
What Ministry of Industry and Information put into effect《Pesticide industry " 12th Five-Year Plan " development plan》Also emphasize：" stringent control is poisonous and harmful containing toluene, dimethylbenzene etc.
The dosage forms such as water baseization are developed and promoted in the use of solvent and auxiliary agent ".Therefore, the pesticidal preparations of development environment close friend, especially water
Base pesticidal preparations are the requirements in epoch.In the case where synthesizing and screening the active ingredient increasingly difficulty of more high-efficiency low-toxicity,
Existing pesticidal preparations are improved with environmentally protective auxiliary agent and/or solvent, become the mainstream hair of development environment close friend's formulations of pesticide
Open up direction.
Completely or partially the water baseization formulations of pesticide of organic solvent is replaced to include using water：Aqua, microemulsion, aqueous emulsion,
Suspending agent and suspension emulsion.Due to most pesticide activity component be all it is fat-soluble or unstable in water, do not wrap
The aqueous pesticide solution kind for including any organic solvent is seldom.
Microemulsion and aqueous emulsion are all that active ingredient is dissolved in a certain amount of organic solvent to form solution, then with fine droplet
Mode uniformly disperse in water.Drop size in microemulsion is generally several nanometers to tens nanometers, less than visible wavelength
A quarter.The drop size of aqueous emulsion is more than visible wavelength, generally at hundreds of nanometers or more or to micron order.Suspending agent
It is typically then that indissoluble or insoluble active ingredient are ground into particle (general≤5 μm) by mechanical force, then makes it scattered outstanding
It floats in water.And suspension emulsion is then the combining form of suspending agent and aqueous emulsion.Obviously, it is micro- in above-mentioned four kinds of water baseization preparations
Pesticide particle in emulsion is minimum, has apparent advantage.Reason is：
1) drug effect of pesticidal preparations is related with pesticide particulate form and size in preparation.Particle size is smaller, particle number
More, surface area is bigger, bigger with the contact area of target organisms, and the drug effect of performance is bigger.Therefore, the efficiency of microemulsion
Higher than other three kinds of preparations；On the premise of identical drug effect, dosage opposite can be reduced.
2) particle of microemulsion is in nano-scale, actually a kind of nanometer formulation.Therefore, microemulsion belongs to thermodynamics
Stabilising system, preparation is transparent, excellent storage stability.And aqueous emulsion, suspending agent and suspension emulsion are all thermodynamic unstable systems, system
Agent is opaque, the problems such as storage there may be flocculating, being layered.
3) microemulsion preparation method is simple, and high speed shearing emulsification (aqueous emulsion) and Mechanical Crushing (suspending agent) is not required, and closes
Suitable formula system only needs gentle agitation.
Organic solvent and emulsifier performance difference contained by microemulsion is very big, all affects microemulsion to some extent
Environmental-friendly performance.
Dinotefuran (dinotefuran), chemical name are (RS) -1- methyl -2- nitros -3- (3- tetrahydrofuran methyls)
Guanidine is the third generation anabasine insecticide of Mitsui chemical company exploitation, is listed within 2002, chemical structural formula is as indicated with 1.
Dinotefuran has sucking insect excellent preventive effect, not only have tag, stomach toxicity and root systemic activity, but also with interior suction
Property it is strong, dosage is few, quick-acting good, active high, the lasting period is long, insecticidal spectrum is wide the features such as.There is no cross resistance with common insecticides, because
And antagonism pest has special efficacy.It is mainly used for preventing rice, cotton, wheat, vegetables, fruit tree, tea tree, flowers, ornamental plant etc.
Sucking pest in various crop, such as stinkbug, aphid, plant hopper, thrips, leafhopper class Hemipteran pest, diamond-back moth, beetle mesh and total
Wing mesh pest and the difficult beans peach prevented and kill off are dived the Diptera pests such as fly；Also just like the brown paddy plant hopper of rice, white backed planthopper, black tail leaf
Aphid, aleyrodid class, a red-spotted lizard class diamondback moth of cicada, striped rice borer, vegetables and fruit etc..In addition, dinotefuran is to blattaria, termite, housefly etc.
Sanitary insect pest also has efficiently.
It is different from the structure of existing nicotinic insecticide, dinotefuran be with tetrahydrofuran ring instead of chloro-pyridine ring,
Chloro-thiazole ring, and be halogen-free.The solubility of dinotefuran is 4g/100gH2O (20 DEG C), belongs to water microsolubility substance, indissoluble
In non-polar organic solvents such as hexamethylene, dimethylbenzene.Obviously, it is relatively difficult to prepare the dinotefuran aqua of high concentration.
Also occur some technical solutions using dinotefuran as the microemulsion of pesticide original medicine in the prior art.
Such as, publication number CN102415405A (publication date on April 18th, 2012), it is entitled " a kind of dinotefuran micron-emulsion and
The Chinese invention patent application of its preparation method " discloses a kind of dinotefuran micron-emulsion.Hexamethylene (is selected from by dinotefuran, solvent
Ketone, toluene, dimethylbenzene, DMSO or DMF), surfactant (compound, the moon selected from anion and nonionic surfactant
Ion gathers with the compound of nonionic surfactant and solvent, calcium dodecyl benzene sulfonate, styrylphenol formaldehyde resin
Ethylene oxide-oxypropylene block type polyethers, non-ionic nonylphenol polyoxyethylene ether or non-ionic octyl phenol polyoxy second
Alkene ether), cosolvent (be selected from ethyl alcohol, propyl alcohol, isopropanol or the tert-butyl alcohol) and water forms.Wherein, weight percent shared by each component
For dinotefuran 1-40%, solvent 10-30%, surfactant 10-25%, cosolvent 5-15%, surplus is water.The microemulsion is also
It can include stabilizer and bleeding agent.Above-mentioned technical proposal there are the problem of be：1. consumption of organic solvent is big.Solvent and cosolvent
Dosage be up to 14-45%, if the solvent in agriculture breast 2201 counted, the dosage bigger of organic solvent；It is 2. used
The toxicity of solvent is larger, such as toluene, dimethylbenzene, DMSO or DMF；3. the Nonyl pheno that emulsifier not environmentally, uses
The nonyl phenol (NP) that ether (OP-10) degradation generates is a kind of generally acknowledged environmental hormone, it can simulate estrogen, and the property of biology is sent out
It educates and has an impact, and disturb the endocrine of biology, there is toxicity to reproductive system.Even if nonyl phenol and its precursor compound content
Seldom, also great harmfulness, it is disabled in the world.
For another example, Publication No. CN1951193A (publication date on April 18th, 2007), it is entitled that " rotenone and dinotefuran are answered
With microemulsion and preparation method thereof " Chinese invention patent application, disclose a kind of dinotefuran complex microemulsion.Complex microemulsion
By rotenone and dinotefuran, emulsifier (being selected from nonyl phenol, phenethyl phenol, xenol and Ben-zylphenol Polyoxyethyl Ether), bleeding agent
(be selected from sulfosuccinate di-sec-octyl sodium salt, Sodium Octylphosphate and azone), stabilizer (selected from butyl glycidyl ether,
Phenyl glycidyl ether or acrylic glycidol ether), cosolvent (be selected from isoamyl alcohol, acetone, ethyl acetate or phenol) and water
Composition.Weight percent shared by each component is rotenone 0.5-25%, dinotefuran 1.5-45%, emulsifier 3-22%, bleeding agent
2-16%, stabilizer 1-15%, cosolvent 2-20%, surplus are water.Above-mentioned technical proposal there are the problem of be：1. auxiliary dosage
Greatly, the total amount of the auxiliary agents such as emulsifier, bleeding agent, stabilizer and cosolvent can be up to 36%；2. emulsifier not environmentally, equally makes
Use nonylphenol polyoxyethylene ether.
In addition, Publication No. CN104186527A (publication date on December 10th, 2014), it is entitled " one kind contain tetrachloro worm
The Chinese invention patent application of the Pesticidal combination of amide and dinotefuran " discloses a kind of agricultural insecticide combination containing dinotefuran
Object, it is disclosed that a kind of four chlorantraniliprole and the microemulsion (embodiment 5) of dinotefuran, wherein four chlorantraniliproles 10%, furan worm
Amine 5%, emulsifier (agriculture breast 500#) 5%, emulsifier (agriculture breast 1601#) 5%, antifreezing agent (ethylene glycol) 10%, surplus is water.
In the program, auxiliary dosage is big：Total dosage of emulsifier and the dosage of antifreezing agent are all 2 times of dinotefuran respectively.In addition, the system
The content of dinotefuran is low in agent, and only 5%.
At present, domestic dinotefuran registration and the water base agent type of dinotefuran registered all are suspending agents, there are no micro emulsion
Agent.Related suspending agent there are the problem of before addressed.This also reflects from another side, prepare meet agriculture chemical registration requirement,
There can be very big technical difficulty with the dinotefuran micron-emulsion of list marketing.
The content of the invention
It is an object of the present invention to overcome the deficiencies of the prior art and provide a kind of new environmental-friendly dinotefuran micro emulsion
Agent.Dinotefuran micron-emulsion of the present invention has the characteristics that be substantially better than the prior art：1. surfactant (emulsifier) is all
From vegetable fat, easily biological-degradable, environmental-friendly performance protrudes；2. without alkylphenol polyoxyethylene ether, especially disable
The emulsifier components such as nonylphenol polyoxyethylene ether, nonyl phenol poly-oxypropylene ether, no environmental hazard；3. without using highly polar or polarity
Cosolvent, antifreezing agent, no environment hidden danger；4. using low toxicity or the ketones solvent of micro- poison, boiling point is at 150 DEG C or more, and dinotefuran
When content is 20%, the ratio between solvent and active compound are only 0.62：1；5. the microemulsion appearance is the solution of faint yellow clear,
Long-term place is stablized, and physical properties meet state specified standards index.
A further object of the invention is the preparation method for providing the environmental-friendly dinotefuran micron-emulsion.
In order to realize foregoing invention purpose, present invention employs following technical solutions：
A kind of environmental-friendly dinotefuran micron-emulsion, in percentage by weight, including：
1%-20% dinotefuran, 4%-10% anion surfactants, 2%-12% nonionic surfactants, 5%-
Ketones solvent of 12% boiling point at 150 DEG C or more, 0.01%-0.04% antifoaming agent, surplus are water；
Wherein, it is the straight chain alkane for coming from vegetable oil hydrolysis or cracking that the anionic surfactant, which is selected from hydrophobic grouping,
Base or alkenyl, one or more of the hydrophilic radical in carboxyl, sulfate or sulfonic anion surfactant；It is described
It is to come from vegetable oil or the straight chained alkyl or alkenyl of vegetable oil hydrolysis or cracking that nonionic surfactant, which is selected from hydrophobic grouping,
One or more in polyethenoxy ether class nonionic surfactant.
Preferably, environmental-friendly dinotefuran micron-emulsion, in percentage by weight, including：
10%-20% dinotefuran, 4%-8% anion surfactants, 6%-12% nonionic surfactants, 6%-
Ketones solvent of 12% boiling point at 150 DEG C or more, 0.01%-0.04% antifoaming agent, surplus are water.
Preferably, the gross mass of the anion surfactant and nonionic surfactant, boiling point are at 150 DEG C or more
Ketones solvent quality and the mass ratio of dinotefuran be 0.9~0.95: 0.6~0.7: 1 respectively.
It is furthermore preferred that the gross mass of the anion surfactant and nonionic surfactant, boiling point 150 DEG C with
On ketones solvent quality and the mass ratio of dinotefuran be 0.93~0.95: 0.62~0.66: 1 respectively.
Preferably, the hydrophobic grouping of the anionic surfactant and nonionic surfactant is with 7-17
The straight chained alkyl or alkenyl of carbon atom.
It is furthermore preferred that the anion surfactant be selected from enuatrol or potassium, linoleic acid sodium or potassium, linolenic acid sodium or
Potassium, sodium ricinoleate or potassium, myristyl carboxylic acid sodium or potassium, sodium tetradecyl sulfate or potassium, myristyl ether sodium sulfate or potassium,
In sodium laurate or potassium, lauryl sodium sulfate or potassium, sodium lauryl tri(oxyethyl) sulfate or potassium and undecenoic acid sodium or potassium
One or more.
Most preferably, the nonionic surfactant is selected from 12 to tetradecyl alchohol polyoxyethylene ether (AEO), ten six to ten
Eight alcohol polyoxyethylene ether (peregal), cocounut oil acid esters polyoxyethylene ether, oleic acid ester APEO, fatty acid esters of sorbitan
The one or more of polyoxyethylene ether (tween) and castor oil polyoxyethylene ether (EL).
Preferably, the boiling point in 150 DEG C or more of ketones solvent in cyclohexanone, methyl cyclohexanone and methyln-hexyl ketone
It is one or more.
Preferably, the antifoaming agent is selected from tributyl phosphate, 6~8 carbon alcohol or organic silicon defoamer.
Another object of the present invention is the preparation method for providing the environmental-friendly dinotefuran micron-emulsion, including such as
Lower step：
I. various raw materials are prepared according to formula；
II. in addition to the ketones solvent and antifoaming agent of dinotefuran, boiling point at 150 DEG C or more, by water in formula and other raw materials
Stirred tank is added in, stirring makes its dissolving, obtains solution A；
III. ketones solvent of the boiling point at 150 DEG C or more is added in into another container, adds dinotefuran, stir, make its molten
Solution, obtains solution B；
IV. solution B is added in solution A, stirs, become clear solution, add antifoaming agent, gentle agitation,
It is static, it filters to get dinotefuran micron-emulsion.
Environmental-friendly dinotefuran micron-emulsion of the present invention without high speed shearization processing, uses common stirring and mistake
Device is filtered, is carried out under normal temperature condition, production is workable, convenient simple.
Environmental-friendly dinotefuran micron-emulsion of the present invention, be mainly used for prevent rice, cotton, wheat, vegetables, fruit tree,
Sucking pest in the various crops such as tea tree, flowers, ornamental plant, such as stinkbug, aphid, plant hopper, thrips, leafhopper class Semiptera
Pest, diamond-back moth, beetle mesh and total wing mesh insect and the difficult beans peach prevented and kill off are dived the Diptera pests such as fly；It is also brown just like rice
Aphid, aleyrodid class, a red-spotted lizard class diamondback moth of plant hopper, white backed planthopper, rice green leafhopper, striped rice borer, vegetables and fruit etc..In addition, this hair
The bright environmental-friendly dinotefuran micron-emulsion also has the sanitary insect pests such as blattaria, termite, housefly efficiently.
After testing, the environmental-friendly dinotefuran micron-emulsion of various concentration provided by the invention, property indices reach
State specified standards：
It, can be rapid scattered, dilute in water in any proportion 1. microemulsion appearance is in faint yellow clear shape, stable storing
It releases, no precipitation, muddy, lamination.
2. the active ingredient highest content of dinotefuran can reach 20% in microemulsion, with containing for the current common suspending agent in the country
Amount maintains an equal level.
3. microemulsion stability in hard water can be qualified, muddy, precipitation does not occur in the hard water of normal concentration.
4. microemulsion high- and low-temperature resistance performance is qualified, storage and use temperature range are -6 DEG C~90 DEG C.
Dinotefuran micron-emulsion of the present invention has excellent environmental-friendly performance, bin stability and drug effect.It is most prominent
It is characterized in, 1. formulation environment is friendly.The auxiliary agent used is all plant source surfactant, biodegradable, without nonyl phenol
Polyoxyethylene ether substance, without highly polar or polar latent solvent.2. reduce in preparation surfactant and organic molten as far as possible
The dosage of agent.The mass ratio of preferred surfactant (including anion and nonionic), solvent and active compound is respectively 0.93~
0.95: 0.62~0.66: 1, the influence to environment is reduced to greatest extent.3. formulation storage is stablized, it is not demulsified or sinks
It forms sediment and assembles.4. drug effect is notable.Indoor virulence dinotefuran to tea lesser leafhopper is 2 times of imidacloprid；Dinotefuran of the present invention
Microemulsion is notable to the killing effect of tea lesser leafhopper 3 age nymph.The LC of 10% microemulsion50For 1.44mg/L, and it is used as control
20% suspending agent be 2.21mg/L.In the case of identical drug effect, dinotefuran can be reduced using the microemulsion of the present invention
Amount of application.Therefore, dinotefuran micron-emulsion of the invention improves the environmental-friendly performance of preparation from many aspects to greatest extent.
Compared with disclosed dinotefuran micron-emulsion in the prior art, the present invention also has the advantages that prominent：
1) microemulsion disclosed in publication number CN102415405A, CN1951193A and CN104186527A, all employs and contains
The surfactant of aromatic group, the later product of such surfactant degradation, which enters in human or animal's body, is not only difficult to generation
It thanks, there is hormone-like effect, harmfulness is big.And the surfactant that the microemulsion of the present invention uses, hydrophobic grouping are straight chain
Alkyl or alkenyl from the hydrolysis or cracking of vegetable oil, will not generate murder by poisoning to the environment or contact humans and animals sprayed.
2) the although entitled microemulsion of preparation disclosed in Publication No. CN1951193A, but used high-speed shearing machine into
Row mixing, really a kind of aqueous emulsion, belong to thermodynamic unstable system, not shelf-stable.
In addition, dinotefuran micron-emulsion provided by the invention, compared with dinotefuran suspending agent, equipment needed for making is with making work
Skill is simple, great industrialization promotion value.The dinotefuran micron-emulsion, the mixing apparatus that can be used insecticide factory usually used, such as
Stirred tank makes, and need not add the Jet Mill of high price, and entire manufacturing process is simple for process, and flow is short, holds
It is easy to operate, it can be automated after completing filling.Therefore, with the present invention dinotefuran micron-emulsion popularization and application,
Significant economic benefit and social benefit will be generated.
Description of the drawings
Below in conjunction with the accompanying drawings, the present invention is explained.
The environmental-friendly dinotefuran micron-emulsion sample photo of Examples 1 to 3 preparation, three samples are shown in the photo of Fig. 1
The appearance of product is faint yellow as clear as crystal liquid.
Specific embodiment
In the following, by preferred embodiment, the present invention is described in detail.But the present invention is not restricted to following realities
Apply example.
Various raw materials used can all be obtained by commercial channel in embodiment.
Embodiment 1A kind of 10% environmental-friendly dinotefuran micron-emulsion
Raw material proportioning：
It is prepared via a method which：
I. matched according to formulation weight, prepare to prepare the various raw materials of 1000kg microemulsions；
II. lauryl sodium sulfate, tween -30, linolenic acid sodium are added in stirred tank respectively, add in deionization
Water, stirring, makes dissolving, obtains solution A；
III. dinotefuran is added in solvent cyclohexanone, stirring makes dissolving, obtains solution B；
IV. solution B is added in solution A, stirs, add tributyl phosphate antifoaming agent, gentle agitation is static, mistake
The target product being transparent to get appearance is filtered, sample photo is referring to Fig. 1.
Detection project, method and the quality standard of 10% dinotefuran micron-emulsion manufactured in the present embodiment are listed in table 1.
Detection project, detection method and the testing result of 1 10% dinotefuran micron-emulsion of table
Embodiment 2A kind of 15% environmental-friendly dinotefuran micron-emulsion
Raw material proportioning：
Using preparation method and step similar to Example 1,1000kg target products are obtained, sample photo is referring to Fig. 1.
15% environmental-friendly dinotefuran micron-emulsion manufactured in the present embodiment is detected according to project described in table 1, except content
Outside 15%, every result is all same or similar with the result of embodiment 1.
Embodiment 3A kind of 20% environmental-friendly dinotefuran micron-emulsion
Raw material proportioning：
Using preparation method and step similar to Example 1,1000kg target products are obtained, sample photo is referring to Fig. 1.
20% environmental-friendly dinotefuran micron-emulsion manufactured in the present embodiment is detected according to project described in table 1, except content
Outside 20%, every result is all same or similar with the result of embodiment 1.
Test example 1The environmental-friendly 10% dinotefuran micron-emulsion insecticidal test of the present invention
1.1 test name：Dinotefuran micron-emulsion is to the Toxicity Determination of tea lesser leafhopper
1.2 controlling object：Tea lesser leafhopper (Empoasca vitis (Gothe)) gathers and Yingde, Guangdong area tea place,
It is filled and collected with cylindrical glass tube.It gathers tea slightly simultaneously, is used for raising and giving birth to survey.
1.3 test medicine：
1) 10% dinotefuran micron-emulsion prepared by embodiment 1；
2) it is prepared by 20% dinotefuran suspending agent, Hebei Shan Si bio tech ltd.
1.4 medicaments are prepared
Test medicine accurately is weighed, directly plus deionized water is diluted, and is configured to the mother liquor of 10000mg/L.
The concentration range determined according to preliminary experiment, each medicament design 5 concentration gradients (pressing active ingredient), set simultaneously
Determine clear water control.
1.5 test method
With reference to agricultural industry criteria NY/T1154.14-2008, carried out using leaf dipping method.It is specific as follows：
The tea leaf of clean health is chosen, is trimmed to appropriately sized.15s is impregnated in various concentration liquid, taking-up is put
It is put into after being covered with and dried in the culture dish of clean filter paper, then by tea leaf in the test tube of base diameter 2.5cm, high 7.5cm,
It is put into a wet cotton balls moisturizing simultaneously.Then tea lesser leafhopper 3 age nymph similar in 30 individuals of often pipe access, is sealed with gauze
Mouthful, it escapes to prevent test worm.If blank control, often processing is repeated 4 times.After processing, it is 25 ± 1 DEG C that test worm is placed in temperature, humidity
For 70% or so, photoperiod L:D=16:It raises and observes in the insectary of 8h.The feelings of tea lesser leafhopper death are investigated after 48h
Condition.
1.6 data processing
The death rate and corrected mortality are calculated according to formula I and formula II respectively, network analysis is carried out with POLO softwares, asks
Go out independent regression equation, LC50、LC90With 95% confidence limit, the virulence effect of medicament is compared in analysis.
The death rate (%)=death toll/total borer population × 100%I,
Corrected mortality (%)=(the processing death rate-corrected mortality)/(1- compares the death rate) × 100%II.
1.7 result of the test
After dinotefuran micron-emulsion and dinotefuran suspending agent the processing tea lesser leafhopper of various concentration, death condition etc. is original
Data are shown in Table 2.
The death condition (48h) of tea lesser leafhopper after the different dinotefuran preparation processing of table 2
Concentration is converted into numerical value, corrected mortality is converted into niqueMin, carries out linear regression.Dinotefuran difference preparation
To tea lesser leafhopper, LC50、LC903 are shown in Table with numerical value such as 95% confidence limits.
The different furan worm preparations of table 3 are to the indoor virulence (48h) of tea lesser leafhopper
From table 3 it can be seen that after leaf dipping method processing 48h, two kinds of dinotefuran preparations all show tea lesser leafhopper good
Good bioactivity, but the LC of 10% dinotefuran micron-emulsion and 20% dinotefuran suspending agent50Respectively 1.44mg/L and
2.21mg/L, there are significant differences for the two.
1.8 conclusion：
The activity of 10% dinotefuran micron-emulsion is better than 20% dinotefuran suspending agent, and the two has differences conspicuousness.
Test example 2The safety evaluatio of 10% dinotefuran micron-emulsion of the present invention
2.1 test name：10% dinotefuran micron-emulsion is to the safety evaluatio of tea tree
2.2 subjects：Tea tree, kind are No. 1 red English, narcissus, white hair；Tea tree does not apply other any medicaments, does not also have
Have and picked.Test site is on Agricultural University Of South China Zengcheng teaching and scientific research base tea plantation.
2.3 test medicine：10% dinotefuran micron-emulsion prepared by the embodiment of the present invention 1
2.4 dosage are set
Based on active ingredient, tri- experiment setting 120g a.i./ha, 240g a.i./ha, 480g a.i./ha dosage,
It is directly watered and carries out cauline leaf spraying.Control spray equivalent clear water.
2.5 test method
With reference to People's Republic of China (PRC) agricultural industry criteria NY/T 1965.1-2010, cauline leaf spray is carried out in the growth of tea plant phase
Mist processing.Specific method is as follows：
Using sprayer according to above-mentioned setting dosage, handled from the order of control, low dosage to high dose.According to every
The planting density of 3000 plants of tea trees of mu, dosage is calculated after conversion, and liquid even spraying is positive and negative to tea tree stem and blade
Face.Each 10 plants of dosage spray tea tree, often handles 4 repetitions.If blank control.Normal water fertilizer management during experiment.
It is bent since tea tree plant exists, the growth rate measurment of plant passes through the growing height of measurement top tender tip
It carries out.5 points for investigation are chosen in each dosage processing cell before medicine, red rope is fastened and marks, measure top height of shoot.
21 days after medicine, the height of shoot of marker site is measured, the growth rate of plant is calculated with this.
2.6 poisoning are observed
1d, 3d, 7d, 10d, 14d, 21d after medicine observe plant forms and color change, judge whether medicament produces plant
Crude drug is done harm to, and records the type and the extent of injury of poisoning.
2.7 symptom of chemical damage describe
Discoloration：Including chlorisis, chrysanthemum, albefaction, floral leaf, rust staining, browning, greening etc..
Necrosis：Spot, withered spot, leaf margin necrosis, growing point or climbing stem is withered, fallen leaves, fallen flowers, shedding, unfilled gtains etc..
Growth and development delays：Dwarfing, shortened internodes, vane extension are suppressed, uneven emergence, maturity period change, growth and development
It stagnates.
It wilts：Plant dehydration wilts, is blue or green withered.
Deformity：Tiller is abnormal, growth adventitious root, lateral growth, excessive growth, leaf rolling or torsional deformation, stem are hung contracting, flower spike
Deformation.
2.8 poisoning extent descriptions
2.8.1 discoloration
It is very safe that dispenser ensuing crop, which does not have any visible symptom of chemical damage,；
Safety can be reverted to by having the crop leaf less than 10% to have after dispenser in light discolouration or 3d~4d；
Slight poisoning can be reverted to by having 11%~20% crop leaf to have after dispenser in apparent discoloration or 7d~10d；
The crop leaf for having 21%~50% after dispenser substantially change colour or 10d in cannot revert to moderate poisoning；
The blade for having more than 50% after dispenser substantially changes colour, and cannot revert to serious poisoning.
It is 2.8.2 downright bad
It is very safe that dispenser ensuing crop, which does not have any visible symptom of chemical damage,；
There is the crop organ within 10% a small number of spots or necrosis occur, account for crop organ's area below 1% or increase
Less than 1% fallen leaves, fallen flowers, shedding or unfilled gtains are safety；
There is spot or necrosis in the crop organ for having 11%~20%, account for crop organ's area below 3% or increase by 3%
Following fallen leaves, fallen flowers, shedding or unfilled gtains are slight poisoning；
There is spot or necrosis in the crop organ for having 21%~50%, accounts for crop organ's area below 10% or increases
Less than 10% fallen leaves, fallen flowers, shedding or unfilled gtains are moderate poisoning；
There is spot or necrosis in the crop organ for having more than 50%, accounts for crop organ's area more than 10% or increase by 10%
Above fallen leaves, fallen flowers, shedding or unfilled gtains are serious poisoning；
2.8.3 growth retardation
It is very safe that dispenser ensuing crop, which does not have any visible symptom of chemical damage,；
After dispenser in 21d growth rate inhibiting rate 10% with for safety；
Growth rate inhibiting rate 11%~20% is slight poisoning in 21d after dispenser；
Growth rate inhibiting rate 21%~50% is moderate poisoning in 21d after dispenser；
Growth rate inhibiting rate more than 50% is serious poisoning in 21d after dispenser.
2.8.4 it wilts
It is very safe that dispenser ensuing crop, which does not have any visible symptom of chemical damage,；
Crop leaf has the of short duration dehydrations of 1h~2h to wilt at noon within 3d after dispenser, is then return to safety；
Crop leaf has 3h~5h dehydrations at noon within 3d after dispenser, reverts to slight poisoning sooner or later；
Crop leaf had more than 5h dehydrations wilting in one day within 3d~5d after dispenser, reverted to moderate poisoning sooner or later；
Dispenser ensuing crop is wilted, and cannot be recovered after 5d and be withered for serious poisoning.
It is 2.8.5 lopsided
It is very safe that dispenser ensuing crop, which does not have any visible symptom of chemical damage,；
21d after dispenser, have abnormal plant tillering within 5%, growth adventitious root, lateral growth, excessive growth, leaf rolling or
Torsional deformation, hang contracting, flower spike of stem are deformed into safety；
There are the abnormal plant tillering within 6%~25%, growth adventitious root, lateral growth, excessive growth, leaf rolling or distortion
Deformation, hang contracting, flower spike of stem are deformed into slight poisoning；
There are the abnormal plant tillering within 26%~50%, growth adventitious root, lateral growth, excessive growth, leaf rolling or torsion
Song deformation, hang contracting, flower spike of stem are deformed into moderate poisoning；
There are abnormal more than 50% plant tillering, growth adventitious root, lateral growth, excessive growth, leaf rolling or torsional deformation,
Hang contracting, flower spike of stem is deformed into serious poisoning.
The calculating of 2.9 poisoning degree
It is evaluated with growth rate inhibiting rate.21d measures each processing plant height after dispenser, by formula III and formula IV
Growth rate and growth rate inhibiting rate are calculated to evaluate security of the medicament to plant.
Newborn height (mm)/time (d) III of growth rate=plant, growth rate inhibiting rate (%)=(control growth speed
Rate-processing growth rate)/control growth rate × 100IV.Wherein, growth rate inhibiting rate=0 is very safe；
Growth rate inhibiting rate≤10%, for safety；
11%≤growth rate inhibiting rate≤20% is slight poisoning；
21%≤growth rate inhibiting rate≤50% is moderate poisoning；
Growth rate inhibiting rate>50%, it is serious poisoning.
2.10 safety evaluatio result of the test
After 10% dinotefuran micron-emulsion spraying treatment, 3 kinds of form growth changes for examination tea tree breed the results are shown in Table 4.
4 10% dinotefuran micron-emulsion of table observes tea tree symptom of chemical damage
Table 4 the result shows that, not to generating discoloration, bad for examination tea tree plant after the processing of 10% dinotefuran micron-emulsion of various dose
Extremely, growth and development delay, wilt and deformity symptom of chemical damage.Said preparation is further determined to the poisoning degree of tea tree and growth
Rate inhibiting rate, the results are shown in Table 5.
5 10% dinotefuran micron-emulsion of table is to the Security test result of tea tree
As can be seen from Table 5, after spraying treatment, 10% dinotefuran micron-emulsion is in 120g a.i./ha, 240g a.i./ha
The phenomenon that with tea tree is not caused to generate discoloration, necrosis, growth retardation, wilting and deformity under the dosage of 480g a.i./ha.Most
It has been more than 10% to 3 growth rate inhibiting rates for examination tea tree breed after high dose 480g a.i./ha processing, highest
For 15.64%, illustrate that high dose processing has slight poisoning.Meanwhile the dosage of 240g a.i./ha also generates white hair kind
Slight poisoning, inhibiting rate 10.61%.Remaining dosage shows as safety.
2.11 conclusion
Measurement result shows with 10% dinotefuran micron-emulsion with 120g a.i./ha, 240g a.i./ha and 480g
After a.i./ha spraying treatments, No. 1 red to English, 3 narcissus, white hair tea tree breeds do not generate symptom of chemical damage.
Statistics and calculating by poisoning degree, by setting dosage spraying treatment English is No. 1 red, narcissus, 3 tea tree product of white hair
After kind, 4 only the dosage of 80g a.i./ha is No. 1 red to English, the life of narcissus, the dosage of white hair and 240g a.i./ha to white hair
Long rate presents slight poisoning, remaining dosage for examination tea tree to showing as safety.
In short, the present invention provides a kind of environmental-friendly dinotefuran micron-emulsion, the surfactant used is all plant
Source, solvent is also low toxicity；And total dosage of auxiliary agent is small.Environmentally friendly dinotefuran micron-emulsion of the present invention also has
There is the advantages of efficient, to stablize.
Specific description of embodiments of the present invention above is not intended to limit the present invention, and those skilled in the art can be according to this
Invention is variously modified or deforms, and without departing from the spirit of the present invention, should all belong to the models of appended claims of the present invention
It encloses.
Claims (8)
1. a kind of environmental-friendly dinotefuran micron-emulsion, in percentage by weight, including：
10%-20% dinotefuran, 4%-8% anion surfactants, 6%-12% nonionic surfactants, 6%-12%
Ketones solvent of the boiling point at 150 DEG C or more, 0.01%-0.04% antifoaming agent, surplus are water；
The ketones solvent of the gross mass of the anion surfactant and nonionic surfactant, boiling point at 150 DEG C or more
The mass ratio of quality and dinotefuran is 0.9~0.95: 0.6~0.7: 1 respectively；
Wherein, the anionic surfactant be selected from hydrophobic grouping be come from vegetable oil hydrolysis or cracking straight chained alkyl or
Alkenyl, one or more of the hydrophilic radical in carboxyl, sulfate or sulfonic anion surfactant；It is described it is non-from
It is to come from vegetable oil or vegetable oil hydrolysis or the straight chained alkyl of cracking or the polyoxy of alkenyl that sub- surfactant, which is selected from hydrophobic grouping,
One or more in ethylene ether nonionic surfactant.
2. environmental-friendly dinotefuran micron-emulsion according to claim 1, which is characterized in that the anion surfactant
Gross mass, boiling point with nonionic surfactant is in 150 DEG C or more of ketones solvent quality and the mass ratio difference of dinotefuran
It is 0.93~0.95: 0.62~0.66: 1.
3. environmental-friendly dinotefuran micron-emulsion according to claim 1 or 2, which is characterized in that the anionic surface
The hydrophobic grouping of activating agent and nonionic surfactant is straight chained alkyl or alkenyl with 7-17 carbon atom.
4. environmental-friendly dinotefuran micron-emulsion according to claim 3, which is characterized in that the anion surfactant
Selected from enuatrol or potassium, linoleic acid sodium or potassium, linolenic acid sodium or potassium, sodium ricinoleate or potassium, myristyl carboxylic acid sodium or potassium,
Sodium tetradecyl sulfate or potassium, myristyl ether sodium sulfate or potassium, sodium laurate or potassium, lauryl sodium sulfate or
One or more in potassium, sodium lauryl tri(oxyethyl) sulfate or potassium and undecenoic acid sodium or potassium.
5. environmental-friendly dinotefuran micron-emulsion according to claim 3, which is characterized in that the nonionic surfactant
Gather selected from 12 to tetradecyl alchohol polyoxyethylene ether, 16 to polyoxyethylene octadecanol, cocounut oil acid esters polyoxyethylene ether, oleate
The one or more of ethylene oxide ether, fatty acid esters of sorbitan polyoxyethylene ether and castor oil polyoxyethylene ether.
6. environmental-friendly dinotefuran micron-emulsion according to claim 1 or 2, which is characterized in that the boiling point 150 DEG C with
On one or more of the ketones solvent in cyclohexanone, methyl cyclohexanone and methyln-hexyl ketone.
7. environmental-friendly dinotefuran micron-emulsion according to claim 1, which is characterized in that the antifoaming agent is selected from tricresyl phosphate
Butyl ester, 6~8 carbon alcohol or organic silicon defoamer.
8. the preparation method of environmental-friendly dinotefuran micron-emulsion, includes the following steps any one of claim 1 to 7：
I. various raw materials are prepared according to formula；
II. in addition to the ketones solvent and antifoaming agent of dinotefuran, boiling point at 150 DEG C or more, water in formula and other raw materials are added in
Stirred tank, stirring, makes its dissolving, obtains solution A；
III. ketones solvent of the boiling point at 150 DEG C or more is added in into another container, adds dinotefuran, stir, make its dissolving, obtain
To solution B；
IV. solution B being added in solution A, stirs, become clear solution, add antifoaming agent, gentle agitation is static,
Filtering is to get dinotefuran micron-emulsion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610061491.XA CN105532656B (en) | 2016-01-28 | 2016-01-28 | A kind of environmental-friendly dinotefuran micron-emulsion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610061491.XA CN105532656B (en) | 2016-01-28 | 2016-01-28 | A kind of environmental-friendly dinotefuran micron-emulsion and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105532656A CN105532656A (en) | 2016-05-04 |
| CN105532656B true CN105532656B (en) | 2018-05-22 |
Family
ID=55812659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610061491.XA Active CN105532656B (en) | 2016-01-28 | 2016-01-28 | A kind of environmental-friendly dinotefuran micron-emulsion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105532656B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109984141A (en) * | 2017-12-31 | 2019-07-09 | 海南正业中农高科股份有限公司 | A kind of microemulsion containing dinotefuran |
| CN109511671A (en) * | 2018-10-19 | 2019-03-26 | 江西博邦生物药业有限公司 | Pesticide dinotefuran aqua and its preparation method |
| CN111513063B (en) * | 2020-05-14 | 2020-12-29 | 广东省科学院产业技术育成中心 | Insecticide additive and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102057941A (en) * | 2011-01-19 | 2011-05-18 | 青岛东生药业有限公司 | Pesticidal compound composite containing dinotefuran |
| CN102415405A (en) * | 2011-10-31 | 2012-04-18 | 联保作物科技有限公司 | Dinotefuran micron-emulsion and preparation method thereof |
| CN102630696A (en) * | 2012-04-05 | 2012-08-15 | 广西田园生化股份有限公司 | Insecticidal composite containing Cyantraniliprole and anabasine compounds |
| CN103238590A (en) * | 2013-05-22 | 2013-08-14 | 广西田园生化股份有限公司 | Solvent composition for preparing neonicotinoid pesticide liquid preparation |
| CN104488949A (en) * | 2014-12-23 | 2015-04-08 | 安徽众邦生物工程有限公司 | Dinotefuran-containing insecticidal combination |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011252025A (en) * | 2011-09-06 | 2011-12-15 | Mitsui Chemicals Agro Inc | Method for preventing sapping from ear of paddy rice by stink-bugs |
-
2016
- 2016-01-28 CN CN201610061491.XA patent/CN105532656B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102057941A (en) * | 2011-01-19 | 2011-05-18 | 青岛东生药业有限公司 | Pesticidal compound composite containing dinotefuran |
| CN102415405A (en) * | 2011-10-31 | 2012-04-18 | 联保作物科技有限公司 | Dinotefuran micron-emulsion and preparation method thereof |
| CN102630696A (en) * | 2012-04-05 | 2012-08-15 | 广西田园生化股份有限公司 | Insecticidal composite containing Cyantraniliprole and anabasine compounds |
| CN103238590A (en) * | 2013-05-22 | 2013-08-14 | 广西田园生化股份有限公司 | Solvent composition for preparing neonicotinoid pesticide liquid preparation |
| CN104488949A (en) * | 2014-12-23 | 2015-04-08 | 安徽众邦生物工程有限公司 | Dinotefuran-containing insecticidal combination |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105532656A (en) | 2016-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2015120786A1 (en) | Environmentally-friendly emamectin benzoate preparation and preparation method therefor | |
| CN105532656B (en) | A kind of environmental-friendly dinotefuran micron-emulsion and preparation method thereof | |
| CN105638650B (en) | A kind of environmental-friendly dinotefuran micron-emulsion of organic solvent-free and preparation method thereof | |
| CN103858862B (en) | A kind of environmentally friendly emamectin-benzoate water solube powder and preparation method thereof | |
| CN104488949A (en) | Dinotefuran-containing insecticidal combination | |
| CN106106476A (en) | A kind of Pesticidal combination containing trifluoro-benzene pyrimidine Yu amides compound | |
| CN102960361A (en) | Insecticide composition and application thereof | |
| CN103858921B (en) | A kind of environmentally friendly Diacloden aqua and preparation method thereof | |
| CN103907643B (en) | A kind of Multifunctional environment friendly Acetamiprid water preparation and preparation method thereof | |
| CN106538586B (en) | A kind of Synergistic insecticidal compositions containing double third ring worm esters | |
| CN100531572C (en) | Agricultural chemical composition containing natural pyrethrum and admire and its application | |
| CN103858922B (en) | A kind of Multifunctional environment friendly Diacloden aqua and preparation method thereof | |
| CN107156160A (en) | A kind of composition and method for preventing and treating oriental fruit months | |
| CN104115861A (en) | Insect and mite killing composition containing xiaochongthion and cyflumetofen | |
| CN104738046B (en) | Pesticidal combination containing pyridine quinazoline and chlorine fluorine cyanogen insect amide | |
| CN109769842A (en) | A kind of insecticide composition containing trifluoro-benzene pyrimidine, rotenoid | |
| CN106561656B (en) | A kind of Pesticidal combination containing Celastrus angulatus and multiple killing teichomycin | |
| CN108208015A (en) | A kind of agricultural chemicals suspension agent and its preparation method and application | |
| CN104521980A (en) | Pymetrozine-containing insecticidal composition | |
| CN108184833A (en) | Pyrethrins microcapsule formulations with beta-cyclodextrin or derivatives thereof for wall material and its preparation method and application | |
| CN101366387B (en) | Agricultural chemical composition | |
| CN110495463B (en) | Synergistic pesticide composition containing trifluoro-benzene pyrimidine and application thereof | |
| CN103004818A (en) | Insecticide composition containing fipronil and spirotetramat | |
| CN103858863B (en) | A kind of environmentally friendly Diacloden water solube powder and preparation method thereof | |
| CN102246800A (en) | Insecticidal composition containing indoxacarb and dinotefuran |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210114 Address after: Room 2202 and 2205, building A1, 32 Fengzhan Road, Yuhuatai District, Nanjing City, Jiangsu Province, 210012 Patentee after: Nanjing Shansi Ecological Technology Co.,Ltd. Address before: 211300 science and technology innovation building, 3 Gutan Avenue, Gaochun Economic Development Zone, Nanjing, Jiangsu Province Patentee before: NANJING SCIENX BIOTECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right |