CN101536696A - Method and production process of bifenthrin synergistic aqueous emulsion - Google Patents
Method and production process of bifenthrin synergistic aqueous emulsion Download PDFInfo
- Publication number
- CN101536696A CN101536696A CN200910096911A CN200910096911A CN101536696A CN 101536696 A CN101536696 A CN 101536696A CN 200910096911 A CN200910096911 A CN 200910096911A CN 200910096911 A CN200910096911 A CN 200910096911A CN 101536696 A CN101536696 A CN 101536696A
- Authority
- CN
- China
- Prior art keywords
- aqueous emulsion
- bifenthrin
- synergistic
- biphenthrin
- refining petroleum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a method and a production process of bifenthrin synergistic aqueous emulsion and relates to an insecticide/acaricide. The invention provides an environment-friendly multifunctional insecticide/acaricide product with low toxicity, no irritation and no pesticide harm to crops, so as not to use or reduce the using amount of aromatic organic solvents as far as possible and reduce the environmental pollution caused by the organic solvents. The bifenthrin synergistic aqueous emulsion comprises bifenthrin, octachlorodipropyl ether and refined petroleum aqueous emulsion and is prepared by high-speed shearing. The bifenthrin synergistic aqueous emulsion can not only kill main pests, but also show a certain growth regulation role of improving the coldness resistance ability and the disease resistance ability of plants, and the efficacy is higher than an emulsifiable concentrate product with the same dose. The invention takes water as a solvent, the production has no emissions of three wastes, the formula is scientific, the process is advanced and the price is cheap. The invention is characterized by high efficiency, broad spectrum, stability, multiple functions and so on.
Description
Technical field
The present invention relates to Biphenthrin emulsion in water.The manufacturing process and the method that belong to agricultural chemicals.
Background technology
Biphenthrin is a pyrethroid insecticides, miticide.Have and tag and stomach poison function, have repellent and food refusal effect concurrently, its effect is rapid, and the lasting period is long, and insecticidal spectrum is wide.Can prevent and treat insect and evil mites such as lepidopterous larvae on the crops such as fruit tree, vegetables, tealeaves, cotton, aleyrodid, aphid, leaf miner, leafhopper effectively.The main formulation of Biphenthrin is a missible oil at present, and missible oil uses organic solvents such as toluene, dimethylbenzene, acetone, methyl alcohol to make solvent, and these preparation Environmental compatibilities are poor.In the pesticide application process, can evaporate in the air, environment is had contamination; Association was appealing always that domestic agricultural chemicals enterprise developed the good novel form of some Environmental compatibilities in recent years, progressively eliminated existing emulsifiable concentrate pesticide product.
Country encourages agricultural chemicals enterprise to want the active development novel form, promptly every can be with water baseization formulation, just try one's best without missible oil.Still have considerable Biphenthrin pesticide species to exist problems such as old, the easy poisoning of formulation, the incompatibility modern technologies require and environmental protection requirement.It is transformed be developed as novel form, this is a main path of developing novel form at present.
The research of Biphenthrin emulsion in water and microemulsion is also arranged both at home and abroad.Chinese patent 200510040383.6 Biphenthrin emulsion in water and preparation technology thereof, Southwestern University's Chongqing City's entomology and insect Control Engineering key lab have 5% Biphenthrin microemulsion research, Guangxi formulations of pesticide Engineering Technical Research Centre and Guangxi Tianyuan Biochemical Co., Ltd. to unite 2.5% Biphenthrin microemulsion is developed.Jinan green despot's chemicals Co., Ltd 100 grams per liter Biphenthrin emulsion in water obtain agriculture chemical registration (card number: LS20080617).Shanghai, Shanghai inferior safe means of agricultural production Co., Ltd obtains the agricultural chemicals of producing 800 ton of 15% Biphenthrin emulsion in water per year and checks and approves enterprise.However, Biphenthrin emulsion in water and microemulsion exist also that poor stability, drug effect are low, function singleness, easy problem such as poisoning.
Summary of the invention
At the problems referred to above, the object of the invention is to develop a kind of affine to environment, and can increase the resistance of crop, promotes the multi-functional bifenthrin synergistic aqueous emulsion product of plant growing.
The invention scheme: the component of Biphenthrin, Octachlorodipropyl Ether and refining petroleum aqueous emulsion adds in process of production, adopts the high speed shear mixing emulsifier evenly to disperse to make.Its component in percentage by weight is formulated as follows:
Biphenthrin: 1～10%
Octachlorodipropyl Ether: 0～5%
Organic solvent: 0～10%
Refining petroleum aqueous emulsion: surplus
Described Biphenthrin is the former medicine of Biphenthrin (GB 22619-2008), another name Uranus; The spirit of worm mite; Bi Fenning; 2-methyl biphenyl-3-ylmethyl-(Z)-(1RS)-suitable-3-(2-chloro-3,3,3-three fluoro-1-acrylic)-2; 2-dimethyl cyclopropane carboxylic acid ester.English name bifenthrin; FMC-54800; Biphenthrin; Brigade; Capture; Talstar.Molecular formula C23H22F3ClO2.Molecular weight 422.86.Vapour pressure 2.4 * 10-2Pa (25 ℃).57～64 ℃ of fusing points.Dissolubility water 0.1mg/L, acetone 1.25kg/L, and dissolve in chloroform, carrene, ether, toluene.Density 1.210.Outward appearance and proterties are light brown solid.
Described Octachlorodipropyl Ether is a kind of pesticide synergistic agent.Weak yellow liquid.Another name: two (2,3,3,3-tetrachloro propyl group) ether; 1, two (2,3,3, the 3-tetrachloro) propane of 1 '-oxo; S-421 or S2.English name: bis (2,3,3,3-tetrachloropropyl) ether; 1, and 1 '-oxybis (2,3,3,3-tetrachloro-Propane; Octachlorodipropyl ether; Ether, and bis (2,3,3,3-tetrachloropropyl).Molecular formula: C6H6Cl8O.Molecular weight: 377.7, proportion: 1.64-1.65, boiling point: 154-155 ℃/mmHg, index of refraction: 1.528-1.529
Described organic solvent is one or more the combination in toluene, dimethylbenzene, ethanol, acetone, cyclohexanone or the solvent naphtha.
Described refining petroleum aqueous emulsion claims green peace emulsion as synergistic agent for agricultural chemical again, forms configuration by mineral oil, film forming base-material, numerous emulsifiers, growth regulator, plant nutrient substance, defoamer, stabilizing agent, antifreezing agent and water.Its prescription is: refining petroleum: 15～80%; The film forming base-material: 0～40%, emulsifier: 5～28%, plant nutrient substance 2～25%, defoamer: 0.2～1.2%, stabilizing agent: 0.5～3%, antifreezing agent: 0～2%, deionized water: surplus.And the requirement of accord with Q/NBLA001-2006 product standard.
Production technology of the present invention and method: the component of Biphenthrin, Octachlorodipropyl Ether and refining petroleum aqueous emulsion be not simply add and, but divide oiliness and aqueous components in process of production, stir the back respectively and add.Be dispersed in the preparation with the active ingredient of guaranteeing agricultural chemicals.
The first step, Biphenthrin and organic solvent are mixed to whole dissolvings, add the emulsifier and the auxiliary agent of refining petroleum, Octachlorodipropyl Ether, low HLB value, stir 20-60 minute;
Second step, adopt emulsifier, aqueous components and the deionized water of high HLB value to mix, stirred 20-60 minute;
The 3rd step was mixed in stirring in the emulsifier with above-mentioned two kinds of liquid, added defoamer, stabilizing agent, antifreezing agent, and high speed shear stirred 50-120 minute;
In the 4th step, stir and disperse to make milky homogeneous aqueous emulsion.Check, can, packing, finished product.
Advantage of the present invention and good effect:
1. because this product adopts water to replace organic solvent, and preparation is solvent with water, adopt easily degraded chemicals, reduce organic solvents such as benzene, dimethylbenzene, and three-waste free discharge aborning, environmental pollution reduced.Toxicity reduces, to the person poultry safety.Non-stimulated to eyes and skin.Natural enemy to insects such as braconid wasp, ladybug, predacious spiders is hurt less.
2. because this product is made oil-in-water type, and promptly oil is disperse phase, and water is continuous phase, the active ingredient of agricultural chemicals is at oil phase.Determine the most stable formula for a product by chemical industry formulation screening test, auxiliary agent screening test, the water base property product that has solved the Biphenthrin preparation is easy to generate precipitation and quality problems such as separates out when storing, make the physical and chemical performance of preparation stable.
3. because this product has adopted Octachlorodipropyl Ether: its drug effect is higher than the missible oil product with dosage.
4. because this product takes into full account chemical stability, pH value, viscosity, arene content, carbon chain lengths, indexs such as sulfonated bodies content reduce the light toxic action, and plant safety is not had poisoning.
5. because the mineral oil and the film forming base-material of this product, be sprayed on plant or other solids, can form the molecule rete, can play marvellous physical effect, as the repellent insect, press down the ovum hatching, prevent and treat dehiscent fruit, resist windburn, air pollution preventing, minimizing transpiration, promote photosynthesis, increase output, improve multiple efficacies such as quality.
6. because the numerous emulsifiers that adopts anion, nonionic, amphion three classes to form in the refining petroleum aqueous emulsion component, for can oil product is fully emulsified; Make that the preparation emulsifying ability is extremely strong, existing hydrophily has lipophile again.
In a word, bifenthrin synergistic aqueous emulsion have efficiently, wide spectrum, low cost, characteristics such as multi-functional.
Embodiment
Embodiment 1:2% bifenthrin synergistic aqueous emulsion composition prescription (mass percent): 95% Biphenthrin, 2%, 93% Octachlorodipropyl Ether: 1%, benzene 4%, LAO-70 refining petroleum aqueous emulsion 93%.LAO-70 refining petroleum aqueous emulsion composition wherein: 36# hydraulic oil 68%, polyvinyl alcohol 4.4%, neopelex 2.0%, alkylphenol-polyethenoxy (10) ether 1.2%, octyl phenol polyoxy ethene (4) ether 1.5%, lecithin 1%, aliphatic alcohol polyethenoxy (3) ether 2.1%, polyoxyethylene alkyl ether sulfate sodium 0.5%, ethylenediamine tetra-acetic acid 0.2%, 2,4-potassium hexadiene 0.1%, glycerine 0.3%, 500 order bentonite 1%, deionized water adds to 100%.By technological process, mixing and stirring is made.
Embodiment 2:5% bifenthrin synergistic aqueous emulsion composition prescription (mass percent): 95% Biphenthrin 5%, benzene 9%LAT-40 refining petroleum aqueous emulsion 86%.LAT-40 refining petroleum aqueous emulsion composition wherein: 30# machine oil 40%, high fat film 18%, polyvinyl alcohol 3%, alkyl benzene calcium sulfonate (farming breast 500) 8%, alkylphenol polyoxyethylene 2%, sorbitan monooleate APEO (polysorbate65) 3.5%, aliphatic acid polyethenoxy ether 2%, Octachlorodipropyl Ether 1.8%, compound sodium nitrophenolate 1.2%, phosphoric acid magnalium 0.8%, ethylene glycol 0.4%, glycerine 0.2%, deionized water adds to 100%.By technological process, mixing and stirring is made.
Embodiment 3:6% bifenthrin synergistic aqueous emulsion composition prescription (mass percent): 95% Biphenthrin, 6%, 93% Octachlorodipropyl Ether 2%, acetone 4%, LAW-50 refining petroleum aqueous emulsion 88%.LAW-50 refining petroleum aqueous emulsion composition wherein: 46# white oil 50%, high fat film 30%, alkylphenol-polyethenoxy (10) ether phosphate 8%, algae essence 2%,, coconut oil diethanol amide 0.6%, fatty alcohol-polyoxyethylene ether 2%, polyvinylpyrrolidone 1.6%, isopropyl alcohol 0.3%, deionized water adds to 100%.By technological process, mixing and stirring is made.
The safety evaluatio check:
1. rat acute per os toxicity: occurred flocking together in 30 minutes behind the animal contaminated, poisoning symptom such as movable minimizings, recover normally next day.Viewing duration does not have animal dead.Surviving animals is observed 2 all backs weight increase, and execution is done gross anatomy and do not seen that each internal organs has macroscopic material alterations.According to the GB15670-1995 regulation, no longer carry out the more test of high dose.According to above-mentioned result of the test, bifenthrin synergistic aqueous emulsion to male and female rat oral LD50 all greater than 5000mg/kg.Detailed results sees the following form.
Press GB15670-1995 China existing agricultural chemicals acute oral toxicity grade scale, bifenthrin synergistic aqueous emulsion all belongs to low toxicity to male and female rat acute per os toxicity.
2. percutaneous toxicity: animal contaminated is not seen skin irritatin and whole body poisoning symptom after 4 hours, do not occur animal dead in the observation period.Surviving animals is observed 2 all backs weight increase, and execution is done gross anatomy and do not seen that each internal organs has macroscopic material alterations.Press the GB15670-1995 regulation, no longer carry out more high dose test.According to above-mentioned result of the test, bifenthrin synergistic aqueous emulsion to the male and female rat through skin LD
50All greater than 2000mg/kg.Detailed results sees the following form.
Press GB15670-1995 China existing agricultural chemicals acute dermal toxicity grade scale, bifenthrin synergistic aqueous emulsion all belongs to low toxicity to male and female rat acute percutaneous toxicity.
3. rabbit eye mucosa: drip 1 hour visible animal eye conjunctiva mild hyperaemia behind the medicine, with a small amount of secretion, iris and cornea there is no unusually.Above-mentioned symptom was alleviated in 24 hours.All animals all recovered normal in 48 hours.Detailed results is seen attached list.
Press GB15670-1995 China existing agricultural chemicals eye irritation grade scale, bifenthrin synergistic aqueous emulsion is to rabbit eyes nonirritant.
4. rabbit skin: behind the coating 4,24,48 hours, animal experiment position and contrast position skin there is no erythema and oedema forms.Detailed results is seen attached list.
Press GB15670-1995 China existing agricultural chemicals skin irritation grade scale, bifenthrin synergistic aqueous emulsion is to rabbit skin nonirritant.
Conclusion: check is assert through chemical products safety evaluatio center, Zhejiang Province, bifenthrin synergistic aqueous emulsion rat acute per os toxicity (LD50) is greater than 5g/kg, percutaneous toxicity (LD50) to rabbit skin and eye mucosa nonirritant, belongs to the lower toxicity compound greater than 2g/kg.
The indoor biologically active and the test of pesticide effectiveness:
1. Biphenthrin emulsion in water has good indoor biologically active, the LC in the time of 48 hours to diamond-back moth
50Be 5.47mg/L, contrast medicament beta-cypermethrin is 72.14mg/L to the indoor biologically active of diamond-back moth.Utilize the DPS data processing software, try to achieve green peace and send out and beta-cypermethrin LC
5095% confidence interval of ratio is 0.05～0.11, its confidence interval does not comprise 1, illustrate that Biphenthrin emulsion in water and beta-cypermethrin have significant difference to the indoor biologically active of diamond-back moth, and Biphenthrin emulsion in water is significantly higher than beta-cypermethrin to the biologically active of diamond-back moth.
2. Biphenthrin emulsion in water has good indoor biologically active, the LC in the time of 48 hours to prodenia litura
50Be 2.89mg/L, contrast medicament fluorine bell urea is 13.63mg/L to the indoor biologically active of prodenia litura.Utilize the DPS data processing software, try to achieve green peace and send out and fluorine bell urea LC
5095% confidence interval of ratio is 0.15～0.30, and its confidence interval does not comprise 1, illustrate that Biphenthrin emulsion in water and fluorine bell urea have significant difference to the indoor biologically active of prodenia litura, and the biologically active that green peace is sent out prodenia litura is significantly higher than fluorine bell urea.
Through certain plant protection unit how the cloth experimental tests use, applicability and safety experiment on the crops such as vegetables, cotton oranges and tangerines, tealeaves are shown: synergistic effect is obvious, to crop safety, no poisoning.
4. through certain plant protection master station; applicable cases at the oranges and tangerines blade shows: this product also has the plant growing facilitation; can promote the oranges and tangerines leaf growth, make the blade and blade area increase (3%～14%), mesophyll thickens; dry matter increases; (the blade weightening finish reaches 11%～15%) leaf look dark green, and photosynthetic capacity strengthens, and can also strengthen cold tolerance; reduce fallen leaves, thereby improve the quality and the quality of oranges and tangerines greatly.
Bifenthrin synergistic aqueous emulsion is a kind of non-stimulated to people and animals' low toxicity, and crop is not had poisoning, and is affine to environment, the multifunctional insecticide miticide of pest control treatment and optimization quality.The repellent insect is arranged, press down the effect of ovum hatching, resistance to colds and increase crop anti-adversity.Can prevent and treat worm mites such as lepidopterous larvae on the crops such as fruit tree, vegetables, tealeaves, cotton, aleyrodid, aphid, leaf miner, leafhopper effectively.Compare with domestic and international similar technology, have the technology advanced person, Safety and Environmental Protection is good, and function is many, the characteristics that effect is high.
Claims (7)
1. the method for bifenthrin synergistic aqueous emulsion and production technology, it is characterized in that: the component of Biphenthrin, Octachlorodipropyl Ether and refining petroleum aqueous emulsion adds in process of production, its percentage by weight is a Biphenthrin 1～10%, Octachlorodipropyl Ether 0～5%, organic solvent 0～10%, the refining petroleum aqueous emulsion surplus, and following production technology is made:
The first step, Biphenthrin and organic solvent are mixed to whole dissolvings, add the emulsifier and the auxiliary agent of refining petroleum, Octachlorodipropyl Ether, low HLB value, stir 20-60 minute;
Second step, adopt emulsifier, aqueous components and the deionized water of high HLB value to mix, stirred 20-60 minute;
The 3rd step was mixed in stirring in the emulsifier with above-mentioned two kinds of liquid, added defoamer, stabilizing agent, antifreezing agent, and high speed shear stirred 50-120 minute;
The 4th step stirred and disperses to make milky homogeneous aqueous emulsion, check, can, packing, finished product.
2. the method for bifenthrin synergistic aqueous emulsion as claimed in claim 1 and production technology is characterized in that: organic solvent is one or more the combination in toluene, dimethylbenzene, ethanol, acetone, cyclohexanone or the solvent naphtha.
3. the method for bifenthrin synergistic aqueous emulsion as claimed in claim 1 and production technology, it is characterized in that: the prescription of refining petroleum aqueous emulsion is: refining petroleum: 15～80%; The film forming base-material: 0～40%, emulsifier: 5～28%, plant nutrient substance 2～25%, defoamer: 0.2～1.2%, stabilizing agent: 0.5～3%, antifreezing agent: 0～2%, deionized water: surplus.
4. the method for bifenthrin synergistic aqueous emulsion as claimed in claim 1 and production technology, it is characterized in that: the component of Biphenthrin, Octachlorodipropyl Ether and refining petroleum aqueous emulsion is branch oiliness and aqueous components in process of production, stir the back respectively and add, be dispersed in method in the preparation with the active ingredient of guaranteeing agricultural chemicals.
5. the method for bifenthrin synergistic aqueous emulsion as claimed in claim 1 and production technology, it is characterized in that: 2% bifenthrin synergistic aqueous emulsion composition prescription (mass percent): 95% Biphenthrin 2%, 93% Octachlorodipropyl Ether: 1%, benzene 4%, LAO-70 refining petroleum aqueous emulsion 93%.
6. the method for bifenthrin synergistic aqueous emulsion as claimed in claim 1 and production technology is characterized in that: 5% bifenthrin synergistic aqueous emulsion composition prescription (mass percent): 95% Biphenthrin 5%, benzene 9%LAT-40 refining petroleum aqueous emulsion 86%.
7. the method for bifenthrin synergistic aqueous emulsion as claimed in claim 1 and production technology, it is characterized in that: 6% bifenthrin synergistic aqueous emulsion composition prescription (mass percent): 95% Biphenthrin 6%, 93% Octachlorodipropyl Ether 2%, acetone 4%, LAW-50 refining petroleum aqueous emulsion 88%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100969118A CN101536696B (en) | 2009-03-23 | 2009-03-23 | Method and production process of bifenthrin synergistic aqueous emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100969118A CN101536696B (en) | 2009-03-23 | 2009-03-23 | Method and production process of bifenthrin synergistic aqueous emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101536696A true CN101536696A (en) | 2009-09-23 |
| CN101536696B CN101536696B (en) | 2012-05-23 |
Family
ID=41120268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100969118A Expired - Fee Related CN101536696B (en) | 2009-03-23 | 2009-03-23 | Method and production process of bifenthrin synergistic aqueous emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101536696B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108935449A (en) * | 2018-07-09 | 2018-12-07 | 中国热带农业科学院环境与植物保护研究所 | Nanometer Biphenthrin emulsion in water and preparation method thereof, field fly the purposes of anti-application |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6251415B1 (en) * | 1997-10-27 | 2001-06-26 | Fmc Corporation | Solvent system for pesticide products |
| CN1321422A (en) * | 2000-11-19 | 2001-11-14 | 陶松垒 | Special-purpose non-toxic pesticide for tea and vegetables |
| CN100382700C (en) * | 2005-06-03 | 2008-04-23 | 南京第一农药有限公司 | Aqueous emulsion of bifenthrin, and preparation method |
| CN1742576A (en) * | 2005-08-09 | 2006-03-08 | 陶钧炳 | Green safety pesticide |
| CN101283682B (en) * | 2008-04-11 | 2011-06-29 | 浙江科技学院 | Manufacturing technique and method for refining petroleum aqueous emulsion |
-
2009
- 2009-03-23 CN CN2009100969118A patent/CN101536696B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108935449A (en) * | 2018-07-09 | 2018-12-07 | 中国热带农业科学院环境与植物保护研究所 | Nanometer Biphenthrin emulsion in water and preparation method thereof, field fly the purposes of anti-application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101536696B (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103689017B (en) | A kind of composite plant source pesticide and preparation method thereof | |
| CN102640762A (en) | Hot fogging concentrate containing acetamiprid | |
| CN102349539B (en) | Insecticidal composition containing lythidathion and antibiotic compound | |
| CN101564036A (en) | Abamectin-containing aqueous emulsion | |
| CN100397989C (en) | Disinsection emulsion in water containing avermectin | |
| KR20130114537A (en) | Due to the complex at the plant pest control for natural composition and manufacturing method | |
| WO2017045268A1 (en) | Insecticide with high content of pyrethrin | |
| CN101278683A (en) | Pollution-free plant source pesticide rotenone emulsifiable solution formulation and method of preparing the same | |
| CN104872216A (en) | Plant-source synergist and insect aerosol prepared by same | |
| CN103238613A (en) | Insecticidal composition containing tolfenpyrad | |
| CN102511477B (en) | Pyrethrin hot fogging agent and preparation method and application thereof | |
| CN101554159A (en) | Fenpropathrin microemulsion and preparation method thereof | |
| CN102613212A (en) | Botanical pesticide for vegetable root knot nematodes | |
| CN101536696B (en) | Method and production process of bifenthrin synergistic aqueous emulsion | |
| CN1647644A (en) | Natural pyrethrin cream preparation | |
| CN101194621B (en) | Mixed pesticide preparation of tubatoxin and butyl ether urea | |
| CN101199278A (en) | Agricultural chemical composition containing sparteine | |
| CN101548681A (en) | Multi-function aqueous emulsion containing fipronil | |
| CN101554158A (en) | Emamectin-benzoate and methomyl microemulsion and preparation method thereof | |
| CN101379981B (en) | Disinsection composition containing chlorfenapyr and chlorfluazuron with synergistic action | |
| CN101611708A (en) | A kind of rotenone micro-emulsion | |
| CN100571513C (en) | The compound aid composition that is fit to preparation sesquiterpenoids microemulsion | |
| KR102439956B1 (en) | Manufacturing method of eco-friendly bio-pesticides using soybean oil | |
| CN103651597A (en) | Pesticide containing copperleaf herb and derris elliptica extracts, and preparation method and application thereof | |
| CN101049104B (en) | Composite composition of 0.1 % micellar emulsion of cantharidin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 Termination date: 20150323 |
|
| EXPY | Termination of patent right or utility model |