CN102293203A - Spinosad-polylactic acid microsphere suspending agent and preparation method thereof - Google Patents
Spinosad-polylactic acid microsphere suspending agent and preparation method thereof Download PDFInfo
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- CN102293203A CN102293203A CN2011102684863A CN201110268486A CN102293203A CN 102293203 A CN102293203 A CN 102293203A CN 2011102684863 A CN2011102684863 A CN 2011102684863A CN 201110268486 A CN201110268486 A CN 201110268486A CN 102293203 A CN102293203 A CN 102293203A
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Abstract
The invention discloses a spinosad-polylactic acid microsphere suspending agent and a preparation method thereof. The spinosad-polylactic acid microsphere suspending agent consists of spinosad-polylactic acid microspheres, a wetting dispersant, a thickening agent, an anti-freezing agent, a defoaming agent and water. The preparation has high stability, is high in pesticide utilization efficiency and is environment-friendly; and the preparation product basically does not contain an organic solvent and has remarkable economical and social benefits.
Description
Technical field
The invention belongs to pesticide field, relate to a kind of agricultural chemicals, particularly a kind of pleocidin-polylactic acid microsphere suspending agent and preparation method thereof.
Background technology
Agricultural chemicals is an important agricultural material, be widely used in the overall process of agricultural production, it is the important means of human control agricultural disease, worm, grass, the plague of rats and store in a warehouse disease worm mouse and vector insect, can predict, in the quite a long time, agricultural chemicals still has irreplaceable important function in agricultural production.But use the agricultural chemicals also may be for a long time in large quantities to the mankind or the toxic effect of other biological, some agricultural chemicals is owing to be difficult to be degraded in environment or lack the preparation of science and may environment be polluted, and also may produce poisoning and pest to plant in addition and may develop immunity to drugs etc.For the negative effect that reduces agricultural chemicals as far as possible and bring into play its effect in agricultural production most possibly, develop efficient, low toxicity, the agricultural chemicals of low-residual and the heat subject that preparation just becomes current agricultural chemicals research and development field thereof.Because the cycle of exploitation novel pesticide is long, workload is big, and is expensive high, therefore just more and more is subjected to vast novel pesticide initiative worker's attention for the research of the formulations of pesticide.The characteristics that ubiquity formulation structure is single, the quality of the pharmaceutical preparations is not high in the present Pesticidal products of producing of China are as missible oil, wetting powder, pulvis, these four kinds of agricultural chemicals conventional dosage forms of granule.The dispenser utilization ratio of these traditional formulations of pesticide is extremely low, has caused environmental pollution greatly, threatens the ecological balance and threatens human health.Therefore have the people to propose, following pesticide species should be environment friendly agricultural or environment friendly agricultural novel form.
Microballoon (microspheres) mean medicine dissolution and (or) be dispersed in the macromolecular material, form the small spherical entity of matrix type, its particle size range is 1～250 μ m substantially, be mainly used in field of medicaments at present, that the medicines such as preparation, biotech drug such as polypeptide, protein that are widely used in targeting preparation are made is slow, control-release microsphere preparation etc.The agricultural chemicals packing become micro-capsule or forms pesticidal preparations that small spherical entity makes to compare with some regular dosage form agricultural chemicals and can improve the especially stability of biogenic pesticide of agricultural chemicals; If introduce slow, controlled-release technology, can improve the utilization ratio of agricultural chemicals and save pesticide dosage; Can cover the bad smell of agricultural chemicals, suppress the agricultural chemicals volatilization, reduce or covered the inflammability of medicine, reduce contact toxicity, toxicity on inhalation and, made efficacy stability, people, animal, fish and other animal safeties to the poisoning of crops; Water base chemical preparations such as suspending agent are made in agricultural chemicals microencapsulation or microballoonization again, helped preserving the ecological environment; The organophosphorous pesticide that some facile hydrolysis is difficult to be processed into water and milk or microemulsion can be processed into micro-capsule or microballoon, enlarges its scope of application, and realizes that it mixes with other agricultural chemicals or auxiliary agent and chemical reaction does not take place, and helps the formulation processing of agricultural chemicals; Can make the liquid medicine solidification, convenient storage and transportation etc.
(suspension concentrate SC) is water insoluble solids agricultural chemicals or the dispersion of not miscible liquid pesticidal in water or oil to agricultural chemicals suspension agent.And common agricultural chemicals supensoid agent is meant with water to be the formulations of pesticide of dispersion medium, its advantage is evenly to mix dispersion with any ratio with water, and be not subjected to the influence of water quality and water temperature, be difficult for contaminated environment, can be directly or with the desirable formulation that is used for the crop foliar spray after running water, river or the well water dilution, can on target, reach bigger even area coverage, higher tackness and extensibility are also arranged on the crop blade face, easy to use.And the effect fundamental sum missible oil of suspending agent is close for insecticide, and when being used to prevent and kill off the weeds of crop of the same race for certain weed killer herbicide, the drug effect of suspending agent and lasting period are all good than wetting powder.
Pleocidin has another name called the sugared rhzomorph of thorn, and English name: spinosad is a class macrolides compound of initial stage nineties exploitation, in soil
SaccharopolysporaGenus actinomycetes thorn saccharopolyspora strain (
Saccharopolyspora spinosa) secondary metabolite in the born of the same parents that behind aerobic fermentation, produce.Its main active is pleocidin A component (spinosyn A) and pleocidin D component (spinosyn D), and the mixed proportion of the two is about 85: 15, and its structure as shown in Figure 1.Pleocidin has the safety of biopesticide and the low-hanging fruit of chemical synthetic pesticide simultaneously, and pleocidin has low toxicity, low-residual, to advantages such as insect natural enemies security, natural decomposition are fast, once obtained U.S.'s " presidential green chemical challenge prize ".Broad spectrum pesticide as a kind of natural generation, pleocidin has harmful insect tags fast and ingests toxicity, be to one of the highest compound of lepidoptera pest selectivity in the insecticide of having found at present), also can control diptera and thrips insect etc. effectively.Pleocidin is by stimulating the nervous system of insect, cause contraction of muscle, the depletion of insect non-functional, and follow and tremble and benumb, the exercising result of this uniqueness is that nicotinic acetylcholine receptor (nAch-R) is caused that by sustained activation acetylcholine (Ach) prolongs release reaction, make the depolarising of insect nerve cell, cause central nervous system superactivation widely.Pleocidin also acts on γ-An Jidingsuan (GABA) acceptor simultaneously, changes the function of GABA gate chloride channel, and this might further improve its insecticidal activity.Up to now, do not find that as yet certain series products can act on the nervous system of insect with the identical mode of action, and still do not have the report of relevant pleocidin cross tolerance.
Pleocidin mainly finally becomes natural components such as carbon, hydrogen, oxygen, nitrogen in environment the time by light degradation and microbial degradation etc., and degraded rapidly, the soil light degradation half life period is 9～10 d, and the photodegradative half life period of water, the photodegradative half life period of blade face was 1.6～16 d less than 1 d.At present be mainly used in " urge and killing " (pleocidin 48% suspending agent) on the cotton and be used for " dish happiness " (pleocidin 2.5% suspending agent) on the vegetables at the pleocidin of China's registration, formulation is more single, and the light degradation or be hydrolyzed to the problem of inert matter rapidly can't solve pleocidin and use in the field time of this formulation.
The material that the vital movement of microorganism etc. can be degraded into low molecular compound and environmentally safe fully very soon and have the production process green during Biodegradable material was meant under suitable natural conditions by environment.That PLA (PLA) has is nontoxic, bio-compatible and characteristics such as outer degradable in vivo, buries in soil fragmentation can take place after 3～6 months, can be converted into lactic acid by microorganism through 6～12 months degraded, finally becomes carbonic acid gas and water.This material extensively is applied as biological medical polymer material such as pharmaceutical carrier etc. at present, and its important directions slow at medicine, the controlled release carrier application facet is to realize the effective target controlling and releasing effect of medicine as the drug bearing microsphere material, is the Biodegradable material that can be used for human body of FDA (Food and Drug Adminstration) (FDA) approved.
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Summary of the invention
The object of the present invention is to provide a kind of pleocidin-polylactic acid microsphere suspending agent and preparation method thereof, better stability of preparation, agricultural chemicals utilization ratio height, environmental friendliness, and do not contain organic solvent in the formulation products substantially, light degradation or be hydrolyzed to the problem of inert matter has rapidly improved the stability of suspending agent product effectively when having solved the former medicine of the insurmountable pleocidin of traditional suspending agent and using in the field.
For achieving the above object, the present invention adopts following technical scheme:
Raw material components and each component concentrations of pleocidin of the present invention-polylactic acid microsphere suspending agent are: pleocidin-polylactic acid microsphere 40～900 g/L, wetting dispersing agent 5～60 g/L, thickener 1～80 g/L, antifreezing agent 0.8～50 g/L, defoamer 1～2.5 g/L, surplus is a water.Described pleocidin-polylactic acid microsphere be with PLA for becoming ball material, carrene is a solvent, gelatin is that the mass fraction that contains pleocidin of dispersant preparation is 10%～33%, the mass fraction of PLA is 60%～90% drug bearing microsphere.Described wetting dispersing agent is the mixture of one or both and alkyl phenol formaldehyde resin polyoxyethylene ether sulphate (SOPA) in the formaldehyde condensation products (Dispersant MF) of lignosulfonates, methyl naphthalene sulfonic acid sodium.Described thickener is one or both the mixture in aluminium-magnesium silicate, the xanthans.Described antifreezing agent is one or both mixtures in ethylene glycol, the glycerine.Described defoamer is a silicone defoaming agent.
The preparation method's of this pleocidin-polylactic acid microsphere suspending agent preparation method's concrete steps are as follows:
(1) preparation method of pleocidin-polylactic acid microsphere: in ice-water bath, take by weighing PLA by the raw material proportioning and be dissolved in carrene, add pleocidin, be stirred to dissolving fully, add gelatin solution again, mix, in high speed dispersor with behind the 2000-4000 r/min emulsification pretreatment 0.2-1 min, rotating speed lucifuge with 300-600 r/min under 30-40 ℃ is stirred to no carrene smell, collects solid content and gets pleocidin-polylactic acid microsphere in 30-60 ℃ of dry 0.5-1.5 h; The concentration of described gelatin solution is 10-15 mg/mL.
(2) preparation method of suspending agent: take by weighing pleocidin-polylactic acid microsphere by the raw material proportioning, wetting dispersing agent, thickener, antifreezing agent, defoamer and water stir and promptly get the pleocidin that mass fraction is 2.5-5%-polylactic acid microsphere suspending agent.
Remarkable advantage of the present invention is: better stability of preparation, agricultural chemicals utilization ratio height, environmental friendliness, and do not contain organic solvent in the formulation products substantially, light degradation or be hydrolyzed to the problem of inert matter has rapidly improved the stability of suspending agent product effectively when having solved the former medicine of the insurmountable pleocidin of traditional suspending agent and using in the field.
Description of drawings
The 1st, the chemical structural formula of pleocidin;
Fig. 2 is 350 times of pleocidin-polylactic acid microspheres and 3500 times of scanning electron microscope images;
Fig. 3 is that pleocidin exists the influence of form to natural photodegradation: ◆ represent the former medicine of dry pleocidin; The dry pleocidin microballoon of ▲ expression; ■ represents the pleocidin methanol solution.
Embodiment
Raw material components and each component concentrations of pleocidin of the present invention-polylactic acid microsphere suspending agent are: pleocidin-polylactic acid microsphere 40～900 g/L, wetting dispersing agent 5～60 g/L, thickener 1～80 g/L, antifreezing agent 0.8～50 g/L, defoamer 1～2.5 g/L, surplus is a water.Described pleocidin-polylactic acid microsphere be with PLA for becoming ball material, carrene is a solvent, gelatin is that the mass fraction that contains pleocidin of dispersant preparation is 10%～33%, the mass fraction of PLA is 60%～90% drug bearing microsphere.Described wetting dispersing agent is the mixture of one or both and SOPA in lignosulfonates, the Dispersant MF.Described thickener is one or both the mixture in aluminium-magnesium silicate, the xanthans.Described antifreezing agent is one or both mixtures in ethylene glycol, the glycerine.Described defoamer is a silicone defoaming agent.
The preparation method's of this pleocidin-polylactic acid microsphere suspending agent preparation method's concrete steps are as follows:
(1) preparation method of pleocidin-polylactic acid microsphere: in ice-water bath, take by weighing PLA by the raw material proportioning and be dissolved in carrene, add pleocidin, be stirred to dissolving fully, add gelatin solution again, mix, in high speed dispersor with behind the 2000-4000 r/min emulsification pretreatment 0.2-1 min, rotating speed lucifuge with 300-600 r/min under 30-40 ℃ is stirred to no carrene smell, collects solid content and gets pleocidin-polylactic acid microsphere in 30-60 ℃ of dry 0.5-1.5 h; The concentration of described gelatin solution is 10-15 mg/mL.
(2) preparation method of suspending agent: take by weighing pleocidin-polylactic acid microsphere by the raw material proportioning, wetting dispersing agent, thickener, antifreezing agent, defoamer and water stir and promptly get the pleocidin that mass fraction is 2.5-5%-polylactic acid microsphere suspending agent.
Pleocidin of the present invention-polylactic acid microsphere suspending agent, adopt elder generation with former medicine of pleocidin and Biodegradable material---PLA, prepared pleocidin-polylactic acid microsphere by O/W emulsification-solvent evaporation method (also claiming solvent evaporated method, intra-liquid desiccation method or desolventizing method etc.).With the microballoon of medicine carrying amount about 31% is example, can obtain meso-position radius (
D 50) being that 12.73 μ m, span are 1.4811, envelop rate is 100.2%, sealing productive rate to be 89.4% pleocidin microballoon, repeatability is good.ESEM (SEM) observed result (see figure 2) shows that thus obtained microsphere is the more smooth solid little ball in surface.
The pleocidin that to easily degrade in environment is prepared into microballoon earlier, again it is mixed with suspending agent, light degradation or be hydrolyzed to the problem of inert matter has rapidly improved the stability of suspending agent product effectively when having solved the former medicine of the insurmountable pleocidin of traditional suspending agent and using in the field.Use the microballoon suspending agent that Fig. 3 is seen in the influence of preparation stability.
The wetting dispersing agent of selecting for use is the mixture of speed pool (SOPA) and lignosulfonates; Or the mixture of speed pool (SOPA) and Dispersant MF; Or speed pool (SOPA), lignosulfonates and Dispersant MF three's mixture.Solved effectively that single foaming characteristic that may occur with speed pool (SOPA), lignosulfonates or Dispersant MF etc. is strong, suspensibility is lower, problem such as bleed or layering very easily, improved the stability of suspending agent product effectively.Concrete influence sees Table 1.
1 wetting dispersing agent is to the influence of pleocidin microballoon suspending agent moisture dispersibility energy
Add thickener in the prescription of suspending agent, mainly viscosity by increasing system or the thixotropy of utilizing some thickener increase the stability of system.Different types of thickener is because of its viscosity difference, so the amount in the adding system has certain difference, though it is not stratified sometimes system to be stablized, often can influence the mobile and dispersed of suspending agent usually, thereby makes product be difficult for packing and use.The present invention at comprehensive consideration behind the multiple thickener commonly used on the market, selected one or both the mixture in aluminium-magnesium silicate, the xanthans for use, can obtain good fluidity, leave standstill not stratifiedly, disperse the situation good quality production.
Pleocidin of the present invention-polylactic acid microsphere suspending agent is experimental subjects with the diamond-back moth, and indoor Toxicological testing the results are shown in Table 2.
Two kinds of pleocidin suspension of table 2 compare (48 h) to the virulence of diamond-back moth 2 instar larvaes
Pleocidin of the present invention-polylactic acid microsphere suspending agent the results are shown in Table 3 respectively at normal temperature (25 ℃), heat storage (54 ± 1) ℃ and cold storage (0 ± 1) ℃ two weeks back quality analyses.
Table 3 pleocidin-polylactic acid microsphere suspending agent quality analysis result
Various chemical raw material used in the present invention is the general chemistry product, is buied by market.
In order fully to disclose a kind of pleocidin of the present invention-polylactic acid microsphere suspending agent, be illustrated below in conjunction with embodiment.
0.9 g PLA is dissolved in ice-water bath with 10 mL carrene, add the former medicine of 0.45 g pleocidin, be stirred to dissolving fully.The aqueous gelatin solution of measuring 100 mL, 12.5 mg/mL mixes with above-mentioned solution, in high speed dispersor with behind 2000 r/min emulsification pretreatments, 1 min, rotating speed lucifuge with 300 r/min under 30 ℃ is stirred to no carrene smell, collects solid content and gets pleocidin-polylactic acid microsphere in 30 ℃ of dry 1.5h.
Get a certain amount of preparation and dry pleocidin-polylactic acid microsphere powder (microballoon account for suspending agent total amount 15%), is that 50 mg/mL mix as wetting dispersing agent with sodium lignin sulfonate, Dispersant MF and speed pool (SOPA) according to 1: 1: 2 ratio and total consumption, use consumption be 30 mg/mL aluminium-magnesium silicate as thickener and consumption be the ethylene glycol of 50 mg/mL as antifreezing agent, add a small amount of silicone defoaming agent and suitable quantity of water and stir and promptly get 5% pleocidin-polylactic acid microsphere suspending agent.
Per 667 square metres with 5% pleocidin-polylactic acid microsphere suspending agent 15～50 mL, convert water 20～50 kg even spraying, can prevent and treat insects such as crop in cruciferae diamond-back moth, beet armyworm, oriental tobacco budworm and cotton bollworm, thrips.
0.9 g PLA is dissolved in ice-water bath with 10 mL carrene, add the former medicine of 0.33 g pleocidin, be stirred to dissolving fully.The aqueous gelatin solution of measuring 100 mL, 12.5 mg/mL mixes with above-mentioned solution, in high speed dispersor with behind the 3000 r/min emulsification pretreatment 0.5min, rotating speed lucifuge with 450 r/min under 40 ℃ is stirred to no carrene smell, collects solid content and gets pleocidin-polylactic acid microsphere in 40 ℃ of drying 1 h.
Get a certain amount of preparation and dry pleocidin-polylactic acid microsphere powder (microballoon account for suspending agent total amount 15%), with speed pool (SOPA) and sodium lignin sulfonate according to 1: 1 ratio and always consumption be that 50 mg/mL mix as wetting dispersing agent, use consumption be 1.5 mg/mL xanthans as thickener and consumption be the glycerine of 50 mg/mL as antifreezing agent, add a small amount of silicone defoaming agent and suitable quantity of water and stir and promptly get 4% pleocidin-polylactic acid microsphere suspending agent.
0.9 g PLA is dissolved in ice-water bath with 10 mL carrene, add the former medicine of 0.18 g pleocidin, be stirred to dissolving fully.The aqueous gelatin solution of measuring 100 mL, 12.5 mg/mL mixes with above-mentioned solution, in high speed dispersor with behind the 4000 r/min emulsification pretreatment 0.2min, rotating speed lucifuge with 600 r/min under 35 ℃ is stirred to no carrene smell, collects solid content and gets pleocidin-polylactic acid microsphere in 60 ℃ of drying 0.5 h.
Get a certain amount of preparation and dry pleocidin-polylactic acid microsphere powder (microballoon account for suspending agent total amount 15%), with speed pool (SOPA) and Dispersant MF according to 1: 1 ratio and always consumption be that 50 mg/mL mix as wetting dispersing agent, using consumption is that the xanthans of the aluminium-magnesium silicate of 15 mg/mL and 0.5 mg/mL is the ethylene glycol of 50 mg/mL as mixing thickener and consumption: glycerine (mass ratio is 1:1) is as antifreezing agent, adds a small amount of silicone defoaming agent and suitable quantity of water and stirs and promptly get 2.5% pleocidin-polylactic acid microsphere suspending agent.
The above only is preferred embodiment of the present invention, and all equalizations of being done according to the present patent application claim change and modify, and all should belong to covering scope of the present invention.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102696640A (en) * | 2012-06-15 | 2012-10-03 | 福建农林大学 | Emamectin benzoate polylactic acid microsphere suspension and preparation method thereof |
| CN103027071A (en) * | 2013-01-04 | 2013-04-10 | 福建农林大学 | Spinosad and chlopyrifos compound microsphere suspending agent and preparation method thereof |
| CN103918646A (en) * | 2014-04-22 | 2014-07-16 | 福建农林大学 | Synergystic pleocidin microsphere suspending agent and preparation method thereof |
| CN104629279A (en) * | 2015-02-03 | 2015-05-20 | 安徽民祯生物工程有限公司 | Bacteriocin bacteriostatic fresh-keeping biological composite film |
| CN107670113A (en) * | 2017-09-15 | 2018-02-09 | 大连理工大学 | A kind of preparation method of cell three-dimensional amplification cultivation microcarrier |
| CN108477149A (en) * | 2018-02-06 | 2018-09-04 | 浦江县欧立生物技术有限公司 | A kind of preparation method of the suspension emulsion of plant sterilization |
| CN108552204A (en) * | 2018-04-19 | 2018-09-21 | 河北威远生物化工有限公司 | A kind of dispersible microballoon oil-suspending agent of Acetamiprid and preparation method thereof |
| CN109258650A (en) * | 2018-10-26 | 2019-01-25 | 河北大学 | A kind of sea-buckthorn is around trypetid attractant |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101742989A (en) * | 2007-06-25 | 2010-06-16 | 大塚制药株式会社 | Microspheres having core/shell structure |
| CN101755820A (en) * | 2009-10-22 | 2010-06-30 | 深圳诺普信农化股份有限公司 | Pesticide suspension concentrate containing pleocidin and preparation method thereof |
| CN102027904A (en) * | 2011-01-06 | 2011-04-27 | 北京燕化永乐农药有限公司 | Spinosad microcapsule suspending agent |
-
2011
- 2011-09-13 CN CN2011102684863A patent/CN102293203A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101742989A (en) * | 2007-06-25 | 2010-06-16 | 大塚制药株式会社 | Microspheres having core/shell structure |
| CN101755820A (en) * | 2009-10-22 | 2010-06-30 | 深圳诺普信农化股份有限公司 | Pesticide suspension concentrate containing pleocidin and preparation method thereof |
| CN102027904A (en) * | 2011-01-06 | 2011-04-27 | 北京燕化永乐农药有限公司 | Spinosad microcapsule suspending agent |
Non-Patent Citations (2)
| Title |
|---|
| 黄彬彬等: "多杀菌素微球制备关键工艺研究:Ⅰ", 《农药学学报》 * |
| 黄彬彬等: "多杀菌素微球制备关键工艺研究:Ⅱ", 《农药学学报》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102696640A (en) * | 2012-06-15 | 2012-10-03 | 福建农林大学 | Emamectin benzoate polylactic acid microsphere suspension and preparation method thereof |
| CN103027071A (en) * | 2013-01-04 | 2013-04-10 | 福建农林大学 | Spinosad and chlopyrifos compound microsphere suspending agent and preparation method thereof |
| CN103918646A (en) * | 2014-04-22 | 2014-07-16 | 福建农林大学 | Synergystic pleocidin microsphere suspending agent and preparation method thereof |
| CN103918646B (en) * | 2014-04-22 | 2016-02-24 | 福建农林大学 | A kind of Synergistic type pleocidin microballoon suspending agent and preparation method thereof |
| CN104629279A (en) * | 2015-02-03 | 2015-05-20 | 安徽民祯生物工程有限公司 | Bacteriocin bacteriostatic fresh-keeping biological composite film |
| CN104629279B (en) * | 2015-02-03 | 2016-04-06 | 安徽民祯生物工程有限公司 | A kind of bacteriocin antibacterial and fresh-keeping biocomposite film |
| CN107670113A (en) * | 2017-09-15 | 2018-02-09 | 大连理工大学 | A kind of preparation method of cell three-dimensional amplification cultivation microcarrier |
| CN108477149A (en) * | 2018-02-06 | 2018-09-04 | 浦江县欧立生物技术有限公司 | A kind of preparation method of the suspension emulsion of plant sterilization |
| CN108552204A (en) * | 2018-04-19 | 2018-09-21 | 河北威远生物化工有限公司 | A kind of dispersible microballoon oil-suspending agent of Acetamiprid and preparation method thereof |
| CN109258650A (en) * | 2018-10-26 | 2019-01-25 | 河北大学 | A kind of sea-buckthorn is around trypetid attractant |
| CN109258650B (en) * | 2018-10-26 | 2022-04-15 | 河北大学 | A seabuckthorn fly trapping agent |
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Application publication date: 20111228 |