CN101341871A - Macromolecule emulsifying agent special for pesticide, preparation and application thereof - Google Patents
Macromolecule emulsifying agent special for pesticide, preparation and application thereof Download PDFInfo
- Publication number
- CN101341871A CN101341871A CNA200810030281XA CN200810030281A CN101341871A CN 101341871 A CN101341871 A CN 101341871A CN A200810030281X A CNA200810030281X A CN A200810030281XA CN 200810030281 A CN200810030281 A CN 200810030281A CN 101341871 A CN101341871 A CN 101341871A
- Authority
- CN
- China
- Prior art keywords
- stearic acid
- preparation
- emulsifying agent
- pesticide
- agent special
- 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 provides polymer emulsifier special for agricultural chemical, and a preparation method and the application thereof. The polymer emulsifier is A-B-A type, the hydrophilic chain is polyethylene glycol and the molecular weight is 400 to 10000; the hydrophobic chain is stearic acid poly-stearate, and the polymerization degree m=2 to 7, wherein, stearic acid is taken as end capping group. The preparation method of the invention comprises the following steps: 1. the stearic acid reacts with thionyl chloride, to obtain stearic acid acyl chloride; 2. the stearic acid acyl chloride reacts with 12 hydroxide radical stearic acid, to obtain stearic acid hydroxide radical stearate; 3. steps 1 and 2 are repeated for a plurality of times, to obtain stearic acid poly-stearate; 4. the stearic acid poly-stearate reacts with the polyethylene glycol, to obtain polycarboxylic acid multipolymer. The polymer emulsifier of the invention can be used to improve the storage stability of aqua agricultural chemical preparation, is characterized by high particle absorption capability, sale and high temperature resistant, etc., and is in particular suitable to be agricultural chemical emulsifier; and the aqua agricultural chemical preparation prepared by the polymer emulsifier is characterized by long-termed storage stability.
Description
Technical field
The invention belongs to the agricultural chemicals technical field, be specifically related to a kind of macromolecule emulsifying agent special for pesticide and preparation method thereof and application.
Background technology
Current, China's pesticide processing formulation is based on missible oil and pulvis, and wherein missible oil accounts for more than 50%.Contain volatile organic solvents such as a large amount of toluene, dimethylbenzene and methyl alcohol in the missible oil, for example, contain dimethylbenzene in 4.5% r to reach more than 80%, and 1.8% abamectin emulsifiable concentrate contains nearly 90% dimethylbenzene.These volatile organic solvents not only cause serious harm to human body in production, packing and use, particularly in use, what have is dispersed in the atmosphere, what have remains in the soil, river, river, lake, sea are poured in penetrating in the underground water or by rainwater of also having, and existent environment of people is formed severe contamination.The dust that produces in the processing of pulvis and wetting powder is used also exists and is detrimental to health and problem of environment pollution caused equally.
Aqueous emulsion (O/W emulsion) is as a kind of important green aqueous formulation, do not contain or only contain a small amount of organic solvent, organic solvent in the water replacement missible oil is as medium, little to eyes, skin irritation, environmental pollution is few, can significantly improve the safety to production, storing and user, and is matrix with the water of cheapness, cost of material is lower, is internationally recognized environmentally safe pesticides new formulation.
Aqueous emulsion is the thermodynamic instability state, must form emulsion by the external force effect, emulsifier is exactly wherein indispensable auxiliary agent, it plays emulsification, disperse, prevent to flocculate and keep the important function of emulsion-stabilizing, make pesticide active ingredient spread and sticking on crops and disease, worm, weeds easily, and be easy to infiltrate in their body, give full play to the effect of agricultural chemicals.A kind of good emulsifier can not only be given new function of medicament and characteristic, and can also reach and improve itself and the compatibility of environment, enlarges range of application, and the minimizing dosage reduces cost, and then promotes developing rapidly of some pesticides new formulations and high-quality pesticidal preparations.At present, the emulsifier that uses in the formulations of pesticide mainly is traditional missible oil emulsifier, it is this because relative molecular weight is lower, can not cover particle surface fully, also easily shift from the surface, cause their adhesions between flocculation, gathering and the particle of lay up period particle (oil droplet) to increase, can not reach effect steady in a long-term.
Summary of the invention
The purpose of this invention is to provide a kind of macromolecule emulsifying agent special for pesticide, can not effectively realize the defective that the aqueous emulsion long-term storage is stable to overcome conventional emulsifier.
The present invention also provides the preparation method and the application of above-mentioned macromolecule emulsifying agent special for pesticide.
Macromolecule emulsifier provided by the present invention has following feature:
Described macromolecule emulsifier is the A-B-A type, and its hydrophilic chain is a polyethylene glycol, and described polyethylene glycol structures formula is-(O-CH
2-CH
2-O) n-, molecular weight is 400～10000; Hydrophobic chain is the poly-hydroxy stearic acid ester CH of stearic acid
3(CH
2)
16-(CO-O-CH (R
2)-R
1) m-COOH, degree of polymerization m=2～7, wherein, R
2Be CH
3(CH
2)
5-, R
1For-(CH
2)
10-, stearic acid is as end-capping group.
The preparation method of macromolecule emulsifier of the present invention comprises the steps:
Under 60～100 ℃ of temperature with stearic acid and thionyl chloride reaction, obtain the stearic acid acyl chlorides;
2. stearic acid acyl chlorides that under 60～100 ℃ of temperature step 1 is obtained and 12-hydroxy stearic acid reaction obtains the stearic acid hydroxy stearic acid ester;
3. the stearic acid hydroxy stearic acid ester that step 2 is obtained repeats 1 and 2 step, through repeatedly repeating, obtains the poly-hydroxy stearic acid ester of stearic acid;
4. the poly-hydroxy stearic acid ester of the stearic acid that under 60～100 ℃ of temperature step 3 is obtained reacts with polyethylene glycol, obtains the polycarboxylic acids copolymerization product.
Current techique is all adopted in reaction in the above steps.
Preferred raw material proportioning is: the mol ratio of stearic acid and dichloro industry sulfone is 1: 1～2 in the step 1, the mol ratio of acyl chlorides and 12-hydroxy stearic acid is 1: 1～1.5 in the step 2, and the mol ratio of poly-hydroxy stearic acid ester of stearic acid and polyethylene glycol is 1: 1～1.5 in the step 4.
The hydrogen chloride gas that produces in the step 1 and 2 adopts the alkali lye retracting device to recycle.
Number of repetition is 1～6 in the step 2, and the degree of polymerization of the poly-hydroxy stearic acid of stearic acid is 2～7.
The molecular weight of polyethylene glycol is 400～10000 in the step 4.
Gained macromolecule emulsifier HLB value is 4.
Macromolecule emulsifier of the present invention can be used as emulsifier and is applied in the agricultural chemicals preparation, to improve water aqua type pesticidal preparations storage stability.Especially at mass percent 10% cypermethrin.
Macromolecule emulsifier of the present invention is applicable to that great majority can be prepared into the agricultural chemicals of aqueous emulsion, for example: (mass percent is 20% to phenothrin, below identical), ether chrysanthemum ester (5%), permethrin (20%, 10.4%), fenpropathrin (20%), cycloprothrin (20%), cypermethrin (20%), cis chlorine cyanogen (hectogram of efficiently going out α-chlorine cyanogen) (10%), efficient chlorine cyanogen (β-chlorine cyanogen) (10%, 5%), Zeta chlorine cyanogen (18%), decis (5%, 1.5%), bromine mite fat (mite is for controlling) (10%), alkynes mite spy (25%), flumorph (10%), efficient metalaxyl, cyflufenamid (15%, 5%), napropamide (10%), fluazifop (10%), efficient fluazifop (10%) fenoxaprop (6.9%, 6.9%), Quizalotop-ethyl (10%), alachlor (25%) or the like, and can effectively improve the storage ability of pesticide emulsion in water.
Macromolecule emulsifier of the present invention has the particle high adsorption capacity, and salt tolerant, characteristic such as high temperature resistant especially have the ability of very strong granule for absorbing (oil droplet), is difficult for coming off from the surface and shifting, can guarantee that the long-term storage of aqueous emulsion is stablized.Be especially suitable for use as farm chemical emulgent, preparation water aqua type preparation has the long term storage stable properties by the pesticidal preparations of its preparation.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.These embodiment only are used to the present invention is described and are not used in and limit the scope of the invention.After the content of having read the present invention's instruction, those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the protection domain of the present invention equally.
Embodiment 1
(1) preparation of stearic acid hydroxy stearic acid ester
In the reactor that agitator, distillation cascade and alkali lye recovery pond are housed, add the 284g stearic acid, heat temperature raising to 60 ℃ melts it.Drip the 178.5g thionyl chloride under this temperature, after dropwising, be warming up to 80 ℃, isothermal reaction 2h.Hydrogen chloride, the sulfur dioxide gas of excessive thionyl chloride and generation removed in decompression distillation, obtains rufous liquid.Under 80 ℃, add the 356.8g12-hydroxy stearic acid, isothermal reaction 2h, the hydrogen chloride gas of generation is removed in decompression distillation, obtains yellow solid.Infrared and nuclear-magnetism is determined as the stearic acid hydroxy stearic acid ester, acid number 107.72mgKOH/g.
(2) preparation of stearic acid trimerization hydroxy stearic acid ester
In the reactor that agitator, distillation cascade and alkali lye recovery pond are housed, add 611g stearic acid hydroxy stearic acid ester, heat temperature raising to 60 ℃ melts it, drips the 209.4g thionyl chloride under this temperature, is warming up to 80 ℃ after dropwising, isothermal reaction 2h.Hydrogen chloride, the sulfur dioxide gas of excessive thionyl chloride and generation removed in decompression distillation, obtains rufous liquid.Under 80 ℃, add the 419.5g12-hydroxy stearic acid, isothermal reaction 2h, the hydrogen chloride gas of generation is removed in decompression distillation, obtains yellow liquid.Acid number 75.33mgKOH/g.Repeat aforesaid operations 1 time, obtain stearic acid trimerization hydroxy stearic acid ester, acid number 60.81mgKOH/g.
(3) preparation of macromolecule emulsifier
In the reactor that agitator, distillation cascade and alkali lye recovery pond are housed, add 1436g stearic acid trimerization hydroxy stearic acid ester, heat temperature raising to 60 ℃ melts it, drips the 209.4g thionyl chloride under this temperature, is warming up to 80 ℃ after dropwising, isothermal reaction 2h.Hydrogen chloride, the sulfur dioxide gas of excessive thionyl chloride and generation removed in decompression distillation, obtains rufous liquid.Under 80 ℃, add 622.8g polyethylene glycol 800, isothermal reaction 2h, the hydrogen chloride gas of generation is removed in decompression distillation, obtains the rufous solid.
Embodiment 2
(1) preparation of stearic acid hydroxy stearic acid ester
In the reactor that agitator, distillation cascade and alkali lye recovery pond are housed, add the 56.8g stearic acid, heat temperature raising to 60 ℃ melts it.Dropwise 35 .7g thionyl chloride under this temperature, after dropwising, 60 ℃ of isothermal reaction 2h.Hydrogen chloride, the sulfur dioxide gas of excessive thionyl chloride and generation removed in decompression distillation, obtains rufous liquid.Under 60 ℃, add the 71.4g12 hydroxy stearic acid, isothermal reaction 2h, the hydrogen chloride gas of generation is removed in decompression distillation, obtains yellow solid.Infrared and nuclear-magnetism is determined as the stearic acid hydroxy stearic acid ester, acid number 105.33mgKOH/g.
(2) preparation of poly-stearic acid four poly-hydroxy stearic acid esters
In the reactor that agitator, distillation cascade and alkali lye recovery pond are housed, add 122.2g stearic acid hydroxy stearic acid ester, heat temperature raising to 60 ℃ melts it, drips the 41.9g thionyl chloride under this temperature, after dropwising, 60 ℃ of isothermal reaction 2h.Hydrogen chloride, the sulfur dioxide gas of excessive thionyl chloride and generation removed in decompression distillation, obtains rufous liquid.Under 60 ℃, add the 83.9g12-hydroxy stearic acid, isothermal reaction 2h, the hydrogen chloride gas of generation is removed in decompression distillation, obtains yellow liquid.Acid number 73.78mgKOH/g.Repeat aforesaid operations 2 times, obtain stearic acid four poly-hydroxy stearic acid esters, acid number 51.43mgKOH/g.
(3) preparation of macromolecule emulsifier
In the reactor that agitator, distillation cascade and alkali lye recovery pond are housed, add 380g stearic acid four poly-hydroxy stearic acid esters, heat temperature raising to 60 ℃ melts it, drips the 45.6g thionyl chloride under this temperature, after dropwising, 60 ℃ of isothermal reaction 2h.Hydrogen chloride, the sulfur dioxide gas of excessive thionyl chloride and generation removed in decompression distillation, obtains rufous liquid.Under 60 ℃, add the 261.3g Macrogol 2000, isothermal reaction 2h, the hydrogen chloride gas of generation is removed in decompression distillation, obtains the rufous solid.
Embodiment 3
(1) preparation of stearic acid hydroxy stearic acid ester
In the reactor that agitator, distillation cascade and alkali lye recovery pond are housed, add the 31.6g stearic acid, heat temperature raising to 60 ℃ melts it.Drip the 19.8g thionyl chloride under this temperature, after dropwising, be warming up to 100 ℃, isothermal reaction 2h.Hydrogen chloride, the sulfur dioxide gas of excessive thionyl chloride and generation removed in decompression distillation, obtains rufous liquid.Under 100 ℃, add the 39.6g12-hydroxy stearic acid, isothermal reaction 2h, the hydrogen chloride gas of generation is removed in decompression distillation, obtains yellow solid.Infrared and nuclear-magnetism is determined as the stearic acid hydroxy stearic acid ester, acid number 109.96mgKOH/g.
(2) preparation of stearic acid six poly-hydroxy stearic acid esters
In the reactor that agitator, distillation cascade and alkali lye recovery pond are housed, add 67.9g stearic acid hydroxy stearic acid ester, heat temperature raising to 60 ℃ melts it, drips the 23.3g thionyl chloride under this temperature, is warming up to 100 ℃ after dropwising, isothermal reaction 2h.Hydrogen chloride, the sulfur dioxide gas of excessive thionyl chloride and generation removed in decompression distillation, obtains rufous liquid.Under 100 ℃, add the 46.6g12-hydroxy stearic acid, isothermal reaction 2h, the hydrogen chloride gas of generation is removed in decompression distillation, obtains yellow liquid.Acid number 84.77mgKOH/g.Repeat aforesaid operations 4 times, obtain stearic acid six poly-hydroxy stearic acid esters, acid number 64.06mgKOH/g.
(3) preparation of macromolecule emulsifier
In the reactor that agitator, distillation cascade and alkali lye recovery pond are housed, add 300.9g stearic acid six poly-hydroxy stearic acid esters, heat temperature raising to 60 ℃ melts it, drips the 45.0g thionyl chloride under this temperature, is warming up to 100 ℃ after dropwising, isothermal reaction 2h.Hydrogen chloride, the sulfur dioxide gas of excessive thionyl chloride and generation removed in decompression distillation, obtains rufous liquid.Under 100 ℃, add 343.6g cetomacrogol 1000 0, isothermal reaction 2h, the hydrogen chloride gas of generation is removed in decompression distillation, obtains the rufous solid.
Can the test macromolecule emulsifier improve into the shelf stability of pesticide emulsion in water.
Test result one
Take by weighing the 5g cypermethrin, add 3.25g NP-10, the 0.25gNP-10 phosphate, 0.5gSP-80 (emulsifier) is heated to 60 ℃, under high-speed stirred on the dispersion machine, adds water 41g, is prepared into aqueous emulsion.
Other gets the 5g cypermethrin, adds 3.25g NP-10,0.25gNP-10 phosphate, the macromolecule emulsifier 0.5g that embodiment 1 prepares (addition be pesticide quality 10%).Get the adding conventional emulsifier for preparing and the aqueous emulsion of macromolecule emulsifier, measure water dispersible, the heat cold storage stability of storage and normal temperature shelf-stability.Assay method carries out according to GB HG/T 2467.2-2003, and measurement result sees Table 1.
The stability test of table 1 aqueous emulsion of cypermethrin
By table 1 as seen, the storage of aqueous emulsion of cypermethrin heat and the cold storage qualified stability that add macromolecule emulsifier of the present invention, and than the water and milk that is prepared into by conventional emulsifier more outstanding water dispersible and normal temperature shelf-stability are arranged, wherein the normal temperature shelf-stability was 2 years.
Test result two
Method of testing is described with test result one, just changes the agricultural chemicals cypermethrin into alachlor, and addition is 6% of a pesticide quality, and measurement result is as shown in table 2.
The stability test of table 2 alachlor aqueous emulsion
As can be seen from Table 2, aqueous emulsion heat of the present invention storage and cold storage qualified stability.Water dispersible and normal temperature shelf-stability are suitable substantially with (one).Test result shows that macromolecule emulsifier of the present invention can obviously improve the storage ability of pesticide emulsion in water.
Claims (9)
1. macromolecule emulsifying agent special for pesticide, it is characterized in that: be the A-B-A type, its hydrophilic chain is a polyethylene glycol, described polyethylene glycol structures formula is-(O-CH2-CH2-O) n-, molecular weight is 400～10000; Hydrophobic chain is the poly-hydroxy stearic acid ester CH of stearic acid
3(CH
2)
16-(CO-O-CH (R
2)-R
1) m-COOH, degree of polymerization m=2～7, wherein, R
2Be CH
3(CH
2)
5-, R
1For-(CH
2)
10-, stearic acid is as end-capping group.
2. the preparation method of the described macromolecule emulsifying agent special for pesticide of claim 1 comprises the steps:
(1) with stearic acid and thionyl chloride reaction, obtains the stearic acid acyl chlorides;
(2) stearic acid acyl chlorides that step (1) is obtained and 12-hydroxy stearic acid reaction obtains the stearic acid hydroxy stearic acid ester;
(3) the stearic acid hydroxy stearic acid ester that step (2) is obtained repeats 1 and 2 step, through repeatedly repeating, obtains the poly-hydroxy stearic acid ester of stearic acid;
(4) poly-hydroxy stearic acid ester of the stearic acid that step (3) is obtained and polyethylene glycol reaction obtain the polycarboxylic acids copolymerization product.
3. the preparation method of macromolecule emulsifying agent special for pesticide according to claim 2, it is characterized in that: the reaction temperature in step (1) and (2) is 60～100 ℃.
4. the preparation method of macromolecule emulsifying agent special for pesticide according to claim 2, it is characterized in that: the reaction temperature in the step (4) is 60～100 ℃.
5. the preparation method of macromolecule emulsifying agent special for pesticide according to claim 2 is characterized in that: the hydrogen chloride gas that produces in step (1) and (2), adopt the alkali lye retracting device to recycle.
6. the preparation method of macromolecule emulsifying agent special for pesticide according to claim 2 is characterized in that: number of repetition is 1～6 in the step (3), and the degree of polymerization of the poly-hydroxy stearic acid of stearic acid is 2～7.
7. the preparation method of macromolecule emulsifying agent special for pesticide according to claim 2 is characterized in that: the molecular weight of polyethylene glycol is 400～10000 in the step (4).
8. the application of the described macromolecule emulsifying agent special for pesticide of claim 1 aspect raising water aqua type pesticidal preparations storage stability.
9. the application of macromolecule emulsifying agent special for pesticide according to claim 8 aspect raising water aqua type pesticidal preparations storage stability, it is characterized in that: described water aqua type pesticidal preparations is the cypermethrin of mass percent 10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810030281XA CN101341871B (en) | 2008-08-20 | 2008-08-20 | Macromolecule emulsifying agent special for pesticide, preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810030281XA CN101341871B (en) | 2008-08-20 | 2008-08-20 | Macromolecule emulsifying agent special for pesticide, preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101341871A true CN101341871A (en) | 2009-01-14 |
| CN101341871B CN101341871B (en) | 2011-03-09 |
Family
ID=40244077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810030281XA Expired - Fee Related CN101341871B (en) | 2008-08-20 | 2008-08-20 | Macromolecule emulsifying agent special for pesticide, preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101341871B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250271A (en) * | 2011-05-23 | 2011-11-23 | 沧州大洋化工有限责任公司 | Preparation method for emulsifier |
| CN103980476A (en) * | 2014-05-29 | 2014-08-13 | 湖南尔康制药股份有限公司 | Synthesis method of polyethyleneglycol-12-hydroxystearate |
| CN113929838A (en) * | 2021-11-18 | 2022-01-14 | 西南石油大学 | Preparation of high-salt-resistant self-elasticizing type hydrophobically associating polymer and application of polymer in fracturing fluid |
-
2008
- 2008-08-20 CN CN200810030281XA patent/CN101341871B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250271A (en) * | 2011-05-23 | 2011-11-23 | 沧州大洋化工有限责任公司 | Preparation method for emulsifier |
| CN102250271B (en) * | 2011-05-23 | 2013-02-13 | 河北德大化工有限公司 | Preparation method for emulsifier |
| CN103980476A (en) * | 2014-05-29 | 2014-08-13 | 湖南尔康制药股份有限公司 | Synthesis method of polyethyleneglycol-12-hydroxystearate |
| CN103980476B (en) * | 2014-05-29 | 2015-10-28 | 湖南尔康制药股份有限公司 | A kind of synthetic method of HS15 |
| CN113929838A (en) * | 2021-11-18 | 2022-01-14 | 西南石油大学 | Preparation of high-salt-resistant self-elasticizing type hydrophobically associating polymer and application of polymer in fracturing fluid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101341871B (en) | 2011-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107836461B (en) | Environment-friendly pesticide emulsifiable concentrate | |
| CA2609476C (en) | Method of producing suspended agricultural chemical composition | |
| EP2183968B1 (en) | Pesticide composition potentiated in efficacy and method for potentiating the efficacy of pesticidal active ingredients | |
| TW200822862A (en) | Stabilized and suspended pest control composition | |
| CN101341871B (en) | Macromolecule emulsifying agent special for pesticide, preparation and application thereof | |
| CN102123590A (en) | A method for modulating the release rate of microencapsulated actives | |
| BR112016011573B1 (en) | AGRICULTURAL CONCENTRATE, METHODS FOR PREPARING A CONCENTRATE AND FOR TREATING VEGETATION TO CONTROL PESTING, AGRICULTURAL FORMULATION, STRUCTURING, AND USE OF A POLYESTER | |
| KR100357844B1 (en) | Low volatile clomazone preparation | |
| CN110250197A (en) | A kind of Pesticidal combination and its application of dinotefuran and Biphenthrin | |
| CN103299994B (en) | Solid microemulsion and preparation method thereof | |
| CN109645021A (en) | A kind of aqueous suspoemulsion and its preparation and application containing gamma cyhalothrin | |
| CN102499236A (en) | Solid microemulsion comprising pyrethroid pesticide and preparation method of solid microemulsion | |
| CN107114368A (en) | A kind of dimethomorph dispersible oil-suspending agent and preparation method and application | |
| CN107593758B (en) | The missible oil and its preparation method and application of gamma cyhalothrin and chlorpyrifos mixture | |
| CN103651552B (en) | Ultra-low-volume liquor containing chlorfenapyr | |
| WO2006006596A1 (en) | Clathrate compound, method of controlling concentration of aqueous solution of agricultural-chemical active ingredient, and agricultural-chemical preparation | |
| CN111165474A (en) | Pesticide dissolution promoter, application thereof and high-content preparation | |
| CN1237337A (en) | Avermectin and ivermectin micro emulsion | |
| CN109953021A (en) | Pyrethroids microcapsules, preparation method and insect prevention preparation | |
| CN103299992A (en) | Azadirachtin microemulsion and preparation method thereof | |
| CN106561666A (en) | Insecticidal composition containing flupyradifurone and cyclaniliprole | |
| CN107593693B (en) | Different monooctyl ester missible oil of fluroxypyr of high-efficiency environment friendly and its preparation method and application | |
| JP3739804B2 (en) | Agrochemical composition | |
| US8173576B2 (en) | Method of producing suspended agricultural chemical composition | |
| CN108967422A (en) | Emamectin-benzoate nano-emulsion and preparation method thereof |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110309 Termination date: 20170820 |