CN107027746A - A kind of slow-release pesticide microemulsion and preparation method thereof - Google Patents
A kind of slow-release pesticide microemulsion and preparation method thereof Download PDFInfo
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- CN107027746A CN107027746A CN201710228807.4A CN201710228807A CN107027746A CN 107027746 A CN107027746 A CN 107027746A CN 201710228807 A CN201710228807 A CN 201710228807A CN 107027746 A CN107027746 A CN 107027746A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
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Abstract
The invention discloses a kind of slow-release pesticide microemulsion and preparation method thereof, the microemulsion is made by pesticide original medicine, lignin-base emulsifying agent, assistant for emulsifying agent, antifreeze, polar solvent and deionized water；Described lignin-base emulsifying agent is prepared by the following method; alkali lignin is dissolved in polar solvent, tertiary amine catalyst is added, acylating reagent is then added dropwise under heating and stirring condition and reacts certain time; then product is purified, dried, that is, obtain lignin-base emulsifying agent.The present invention is embedded using the hydrophobic modification alkali lignin of polarity as macromolecule wall material to fat-soluble active compound, and the wall material also has the effect of emulsifying dispersant concurrently due to containing hydrophilic radicals such as a large amount of carboxyls；The introducing of the wall material, can not only substantially reduce the consumption of petroleum base emulsifying agent, but also can slow down the rate of release of active compound, extend the drug effect of microemulsion.
Description
Technical field
The invention belongs to pesticide field, and in particular to a kind of slow-release pesticide microemulsion and preparation method thereof.
Background technology
Microemulsion (abbreviation ME) is active ingredients of the original drug and emulsifying agent, dispersant, antifreeze, stabilizer, hydrotropy
The auxiliary agents such as agent are evenly dispersed in substrate water, form the homogeneous liquid of transparent or semitransparent emulsus.It is characterized in based on water
Medium is wanted, containing a certain amount of polar solvent, its micellar radius is general between 0.1~0.01 μm, belongs to a kind of half aqueous pesticide
Formulation.
Microemulsion mainly has the advantage that：1. flash-point is higher than missible oil, simple production process more environmentally friendly compared to missible oil；2.
The particle diameter of dilution is ultra tiny, far below the water base formulation such as missible oil, suspending agent, aqueous emulsion, the covering of unit volume active ingredient
Area is big, efficiency high, strong to target body permeability, and absorptivity is high, therefore the drug effect of unit dose is high.
But, the shortcoming of microemulsion is also that obviously, major defect is as follows：1. compared to aqueous emulsion, suspending agent etc.
For green formulation, microemulsion is very thin due to particle diameter, to realize so thin particle diameter, it is necessary to compound substantial amounts of surface in formula
Activating agent to realize the solubilising of active compound, therefore in formula surfactant consumption it is big, the addition of exhibiting high surface activating agent makes micro-
The cost of emulsion is improved, and brings pollution to agroecological environment；2. the addition of surfactant is very big in microemulsion, former
The particle of pharmaceutically active ingredient is by surface active agent solubilization, adsorption substantial amounts of anionic and nonionic surfactant, surface charge
With steric hindrance all than larger therefore highly stable, also cause active compound particle to be difficult to adhere in plant leaf surface, cause active ingredient
It is easy to run off and wastes；3. the particle diameter of microemulsion is very thin (0.1~0.01 μm), the unit coverage rate after sprinkling decoction is very high, therefore
Drug effect is come soon, but go it is also fast, drug effect is not lasting, and the killing rate disposably sprayed for resistant insect is inadequate.
Due to there is disadvantage mentioned above, although microemulsion was commercially in fashion one section as a kind of half aqueous pesticide preparation
Between, but the development speed in later stage is decreased obviously, the linear downward trend of registration quantity of the agriculture microemulsion of China in recent years.
The content of the invention
In order to overcome the existing unabiding problem of microemulsion drug effect, and in order to reduce emulsifier, save
Cost, primary and foremost purpose of the invention is to provide a kind of slow-release pesticide microemulsion.
Another object of the present invention is to provide the preparation method of above-mentioned slow-release pesticide microemulsion.
The purpose of the present invention is achieved through the following technical solutions：
A kind of slow-release pesticide microemulsion, is made by the composition of following mass percent：
Described lignin-base emulsifying agent is prepared by the following method, and 100 parts of alkali lignins are dissolved in polar solvent, plus
Enter 60~200 parts of tertiary amine catalysts, 40~220 parts of acylating reagents are then added dropwise under heating and stirring condition and a timing is reacted
Between, then product is purified, dried, that is, obtains lignin-base emulsifying agent；Described number is parts by weight；
Described reaction certain time preferably 0.5~4.0h；
Above-mentioned lignin-base emulsifying agent is the lignin of hydrophobic modification, and it has the hydrophobic groupings such as phenyl ring, alkyl chain,
And the hydrophilic radical such as carboxyl, carbonyl, ester group, emulsifying agent effect can be played fat-soluble pesticide original medicine is dispersed in water
In, thermodynamic stable system is formed, and can effectively reduce the consumption of petroleum base emulsifying agent.
What is more important, hydrophobic modification lignin combines and is avoided that the agricultural chemicals and human body skin on pesticide original medicine surface
The stimulation for directly contacting and producing, and hydrophobic modification lignin can make pesticide original medicine produce slow release effect, the agricultural chemicals after dispenser
It can in a long time be sustained release on plant and in environment, effectively reduce dispenser frequency.
Described pesticide original medicine is fat-soluble pesticide original medicine, preferably Rynaxypyr, Diacloden, imidacloprid, efficient chlorine
One kind in flucythrinate, Permethrin, chlopyrifos, AVM, pyraclostrobin or Tebuconazole.
Described assistant for emulsifying agent be AEO, sapn, tristyrylphenol polyoxyethylene ether, tween,
One or more of polyoxyethylene laurate, Myrj 45 or polyoxyethylene oleate；
The preferred peregal o-10 of described AEO, peregal o-15, peregal o-20, peregal o-25
One or more of or peregal o-30；
One or more of the preferred Tween-20 of described tween, Tween-40, Tween-60, Tween-80 or Tween-85.
Described antifreeze is one or more of ethylene glycol, propane diols, diethylene glycol or DPG.
Described polar solvent is DMAC N,N' dimethyl acetamide, butyrolactone, dimethyl carbonate, butyl acetate, acetic acid Zhong Ding
One or more of ester, 1-METHYLPYRROLIDONE, ethanol, isopropanol, isophorone, ethylene glycol ethyl ether or ethylene glycol phenyl ether.
The preferred trimethylamine of described tertiary amine catalyst, N, N- dipropyl -1- propylamine, triethylamine, N, accelerine or
One kind in Dodecyl Dimethyl Amine.
Described acylating reagent is one or more of chloroacetic chloride, caprylyl chloride, lauroyl chloride or chlorobenzoyl chloride.
The preparation method of the slow-release pesticide microemulsion, comprises the following steps：
By lignin-base emulsifying agent, pesticide original medicine and assistant for emulsifying agent, mixed dissolution is uniform in polar solvent, then dropwise
Add into deionized water and shear-mixed, add antifreeze, it is slow-release pesticide microemulsion to obtain semitransparent colloidal solution；
The antifreeze can polar solvent add deionized water before first be added to the water, also can polar solvent add go from
Added after sub- water in water.
The microemulsion as made from the above method, because the lignin-base emulsifying agent of use has embedding effect, therefore
Obtained microemulsion has sustained release performance, can apply in agricultural field.
The present invention has the following advantages and effect relative to prior art：
1st, the present invention is wrapped using the hydrophobic modification alkali lignin of polarity as macromolecule wall material to fat-soluble active compound
Bury, the wall material also has the effect of emulsifying dispersant concurrently due to containing hydrophilic radicals such as a large amount of carboxyls；The introducing of the wall material,
The consumption of petroleum base emulsifying agent can be not only substantially reduced, but also the rate of release of active compound can be slowed down, extension microemulsion
Drug effect.
2nd, the embedded material that uses of the present invention is reproducible natural lignin's raw material, environmental protection, easy natural degradation,
Catabolite is organic fertilizer；Therefore particle diameter that the slow-release pesticide microemulsion prepared not only inherits traditional microemulsion is thin, medicine
Effect is high, half water base advantage, also overcomes the shortcoming that cost is high, drug effect loss is fast, not environmentally friendly enough of traditional microemulsion, belongs to one
Plant the slow-release pesticide microemulsion of new environmental protection.
Brief description of the drawings
Fig. 1 is the grain size distribution of microemulsion.
Fig. 2 is that the gained microemulsion of embodiment 3 is diluted with water the figures of the SEM after 1000 times.
Fig. 3 is that the gained microemulsion of embodiment 3 is diluted with water the figures of the TEM after 10 times.
Fig. 4 is the elution profiles figure of microemulsion.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
A kind of spacetabs type chlorpyrifos micro emulsion, is made by following steps：
(1) 10g alkali lignins are dissolved in 200g DMFs, adding 13g trimethylamines makes solution alkaline
Change, be then added dropwise after 22g chlorobenzoyl chlorides, completion of dropping and react 3 hours under 65 DEG C and stirring condition；Reacted solution is fallen
Enter in 1.2kg running water, suction filtration takes solid, gained solid puts into 1kg water and adds NaOH to adjust pH value small to 13 washings 2 again
When, suction filtration takes solid, and gained solid puts into 1kg water and adds watery hydrochloric acid again adjusts pH value to 4 washing 2 hours, and suction filtration takes solid
Body, gained solid is put into 50 DEG C of hot water of 1kg and washed 2 hours again, and suction filtration takes solid, and 50 DEG C of conditions are dried, and obtain benzoylation
Modified lignin-base emulsifying agent.
(2) lignin-base emulsifying agent, 2.5g chlopyrifos and the 4g Tween-80s being modified 1.5g benzoylations are dissolved in 14g second
The secondary butyl ester of acid, is added in the 76g deionized waters dissolved with 2g ethylene glycol and shear agitation, you can obtain benzoylation modification wooden
The chlorpyrifos micro emulsion of spacetabs type 2.5% of element emulsification.
Embodiment 2
A kind of spacetabs type Rynaxypyr microemulsion, is made by following steps：
(1) 10g alkali lignins are dissolved in 110g dimethyl sulfoxide (DMSO)s, adding 8g N, N- dipropyl -1- propylamine makes solution
Alkalization, is then added dropwise after 9.5g chloroacetic chlorides, completion of dropping under 55 DEG C and stirring condition and reacts 1.5 hours；Will be reacted
Solution is poured into 0.8kg running water, and suction filtration takes solid, is dried, is obtained the lignin-base emulsifying agent of acetylated modification.
(2) by the lignin-base emulsifying agent of 0.8g acetylated modifications, 2.5g Rynaxypyrs, 1.5g Tween-60s and
0.7g polyoxyethylene laurates are dissolved in 30g DMAs, are added to the 61.5g deionizations dissolved with 3g propane diols
In water and shear agitation, you can obtain the Rynaxypyr microemulsion of spacetabs type 2.5% of acetylated modification lignin emulsification.
Embodiment 3
A kind of slow release high-efficiency lambda-cyhalothrin microemulsion, is made by following steps：
(1) 10g alkali lignins are dissolved in 110g DMFs, adding 6g triethylamines makes solution alkaline
Change, be then added dropwise after 5.7g caprylyl chlorides, completion of dropping and react 2 hours under 50 DEG C and stirring condition；Reacted solution is fallen
Enter in 0.8kg running water, suction filtration takes solid, gained solid puts into 1kg water and adds NaOH again adjusts pH value to pH=12.5
Washing 2 hours, suction filtration takes solid, and gained solid puts into 1kg water and adds watery hydrochloric acid again adjusts pH value to pH=2.5 washings 2
Hour, suction filtration takes solid, and gained solid puts into 80 DEG C of hot water of 1kg and washed 2 hours again, and suction filtration takes solid, dries, obtains pungent
The lignin-base emulsifying agent of acylation modification.
(2) the lignin-base emulsifying agent of the octanylated modifications of 0.5g, 2.5g gamma cyhalothrins are dissolved in 20g N, N- bis-
Methylacetamide, is added in the 74g deionized waters dissolved with 3g ethylene glycol and shear agitation, you can obtain octanylated modification wooden
The gamma cyhalothrin microemulsion of spacetabs type 2.5% of element emulsification.
Embodiment 4
A kind of spacetabs type thiamethoxam micro-emulsion, is made by following steps：
(1) 10g alkali lignins are dissolved in 80g 1-METHYLPYRROLIDONEs, addition 6g DMAs make molten
Liquid alkalization, is then added dropwise after 13g lauroyl chlorides, completion of dropping under 30 DEG C and stirring condition and reacts 4 hours；Will be reacted
Solution is poured into 0.8kg running water, and suction filtration takes solid, and gained solid puts into 1kg water and adds NaOH again adjusts pH value to pH
=12.5 washings 2 hours, suction filtration takes solid, and gained solid puts into 80 DEG C of hot water of 1kg and washed 2 hours again, and suction filtration takes solid,
Dry, obtain the lignin-base emulsifying agent of bay acylation modification.
(2) by the lignin-base emulsifying agent of 3.0g bay acylation modifications, 2.5g Diaclodens, 0.5g peregals o-15 and 1.0g
Tween-40 is dissolved in 15g butyrolactone, is added in the 73g deionized waters dissolved with 5g diethylene glycols and shear agitation, you can obtain the moon
The thiamethoxam micro-emulsion of spacetabs type 2.5% of osmanthus acylation modification lignin emulsification.
Embodiment 5
A kind of spacetabs type ethiprole microemulsion, is made by following steps：
(1) 10g alkali lignins are dissolved in 130g acetone, adding 20g Dodecyl Dimethyl Amines makes solution alkaline
Change, be then added dropwise after 14g caprylyl chlorides, completion of dropping and react 0.5 hour under 75 DEG C and stirring condition；Reacted solution is fallen
Enter in 1kg running water, suction filtration takes solid, gained solid puts into 1kg water and adds NaOH again adjusts pH value to pH=13 washings 2
Hour, suction filtration takes solid, and gained solid puts into 1kg water and adds watery hydrochloric acid again adjusts pH value to pH=4 washings 1 hour, takes out
Leaching solid, gained solid puts into 1kg deionized waters and washed 1 hour again, and suction filtration takes solid, dries, obtains octanylated modification
Lignin-base emulsifying agent.
(2) it is the lignin-base emulsifying agent, 2.5g ethiproles and 2g polyoxyethylene laurates of the octanylated modifications of 1.1g is molten
In 20g butyl acetates, it is added in the 69.4g deionized waters dissolved with 5g ethylene glycol and shear agitation, you can obtain octanylated change
Property lignin emulsification the ethiprole microemulsion of spacetabs type 2.5%.
Embodiment effect explanation
Raw material alkali lignin and the modified octanylated modified alkali lignin hydroxyl of gained and carboxyl-content in embodiment 3 are determined,
As shown in table 1.
The alkali lignin of table 1 and octanylated modified alkali lignin hydroxyl, carboxyl-content
Hydroxyl and carboxyl-content assay method are as follows in table 1：
Using nonaqueous phase potentiometric determination hydroxy radical content, the instrument used is the logical intelligent potentiometric titrimeter of Switzerland ten thousand.
Wherein with P-hydroxybenzoic acid (AR) be internal standard compound, while using TBAH aqueous isopropanol as titrant,
And its actual concentrations carries out back titration using Potassium Hydrogen Phthalate.Its specific operating process is as follows：
(1) preparation of titer：It is 25% TBAH aqueous solution 64g to take mass fraction, adds 1120ml's
Isopropanol in large beaker be placed on after diaphragm seal supersonic wave cleaning machine processing 30min after stand it is standby to treat.
(2) preparation of sample：Accurate weighing 0.03g hydrophobic modification lignin posts label in beaker, then adds
Enter the good 0.05g of accurate weighing p-hydroxybenzoic acid solid as internal standard compound, then adding about 40ml DMF is used to dissolve sample
Product.1 drop concentrated hydrochloric acid is added before finally sealed processing into beaker to be acidified.Then a series of samples is put into ultrasonic wave cleaning
Setup test after 30min is handled in machine.(each sample and following blank, back titration sample titrate 3 times to reduce random error)
(3) preparation of blank sample：Accurate weighing 0.05g P-hydroxybenzoic acid is dissolved in about 40ml DMF, same to add
Sealing, which is put into supersonic wave cleaning machine, after other conditions are consistent by 1 drop concentrated hydrochloric acid handles 30min.
(4) preparation of back titration sample：In precise 0.05g Potassium Hydrogen Phthalate and beaker, super deionized water is used
Dissolved sealing after be put into supersonic wave cleaning machine handle 30min it is standby.
(5) titration curve of each sample is determined, treats that all having gone out 3 postpeaks closes.The wherein calculating of the content of phenolic hydroxyl group
Formula：
Wherein M represents the quality of the sample weighed, and unit is g；V3’、V2' and V1' it is sample drop timing first-order derivative curve
On the 3rd, second and corresponding volume during first peak value；V3、V2And V1Represent first-order derivative curve during blank titration
On the 3rd, second and corresponding volume unit is ml during first peak value；CTBAHRepresent the standard of standard liquid
True concentration, is obtained using back titration；M represents Potassium Hydrogen Phthalate quality；MrRepresent relative point of Potassium Hydrogen Phthalate
Protonatomic mass；V represents first peak value corresponding volume on first-order derivative curve during back titration.
Its hydroxy radical content after hydrophobic modification is carried out by alkali lignin it can be seen from the data of table 1 to greatly reduce, and it is hydrophilic
Hydroxyl is replaced by hydrophobic long alkyl chain, so that modified alkali lignin hydrophobicity is greatly increased.Octanylated modified alkali wood
The contact angle of quality and water is 79.5 °.
The microemulsion prepared to embodiment 3 carries out particle size determination, and is carried out with microemulsion made from conventional emulsifying agent
Compare, as a result as shown in table 2.
Control group one is with 2.5g gamma cyhalothrins, 15g op-10,20g DMAC N,N' dimethyl acetamide and 62.5g
2.5% gamma cyhalothrin microemulsion made from deionized water；
Control group two be with 2.5g gamma cyhalothrins, 10g agricultural emulsifier NO.600s, 20g DMAC N,N' dimethyl acetamides and
2.5% gamma cyhalothrin microemulsion made from 67.5g deionized waters.
The granularmetric analysis of microemulsion and two control groups is made in the embodiment 3 of table 2
Table 2 is that the microemulsion prepared to embodiment 3 carries out particle size determination, and is compared with two microemulsion control groups.
The particle diameter that microemulsion is made in particle diameter test proof embodiment 3 is less than 100nm, and narrow distribution, belongs to microemulsion category, the present invention
The microemulsion particle diameter prepared using lignin is qualified.Two other control group is prepared in laboratory conditions, follow-up
Proof is played to the sustained release performance of lignin-base microemulsion in sustained release experiment, therefore particle diameter test also is carried out to it herein, is demonstrate,proved
It is bright its also in microemulsion category, really with comparativity.
Dynamic light scattering is carried out to the microemulsion of embodiment 3, control group one and control group two by ZetaPALS laser particle analyzers
Dynamic Light Scattering (DLS) granularmetric analysis mapping is as shown in Figure 1.In Fig. 1, G (d) is differential curve, is represented
The signal intensity of the particle of corresponding particle diameter, using peak signal as 100, remaining signal value is proportionally calculated.Belong to grain
The master data of footpath test, effective grain size and polydispersity coefficient PDI are that particle diameter tests most important data.
Fig. 1 more can intuitively illustrate that colloidal spheres mainly have two distributions in the particle diameter distribution of embodiment 3, the colloidal solution
Scope, and it is mainly distributed near 81nm, it is that a small amount of small colloidal spheres are reunited and caused to be distributed in the colloidal spheres near 169nm
, it will be proved in figs. 2 and 3.
Fig. 2 schemes for the SEM SEM of the microemulsion of embodiment 3, shows that the nano particle of microemulsion is big on figure
Small inhomogenous ellipsoidal particle.
Fig. 3 schemes for the transmission electron microscope TEM of the microemulsion of embodiment 3.Due to the factor of sample preparation, nano-particle is in copper mesh
It is upper to reunite, but still it is observed that be spheric granules, and be solid sphere.Particle diameter distribution is slightly wider, but is deposited without large scale spheroid
, illustrate survey its particle diameter when larger peak be aggregate.This phenomenon can also prove second peak in granularmetric analysis result (Fig. 1)
It is to be formed larger aggregate by the small nanoparticle agglomerates at first peak and produced.
Just because of the presence of aggregate, it is turbid solution when concentration is higher to cause obtained microemulsion.But regulation and control
The concentration of active compound and the ratio with hydrophobic modification lignin, can be made brown clear colloidal solution, and effective grain size is down to
About 35nm, but concentration need to be down to about 0.1%.
This patent most importantly studies the sustained release performance of microemulsion, and next embodiment 3 and its control group are delayed
Experiment is released to be illustrated.
Sustained release performance test concrete operations be：
1. 50ml microemulsions are poured into bag filter of the retention more than 1000 molecular weight, sealing, which is placed in filling 500ml, delays
In the cylindrical tank for releasing liquid, tank is placed in 25 DEG C of constant-temperature tables and vibrated, rotating speed is 200r/min.Wherein sustained-release liquid is configured to：
70% absolute ethyl alcohol, 30% deionized water.Control group one is with microemulsion made from 15% emulsifying agent op-10.Control group two is
With microemulsion made from 10% emulsifying agent agriculture breast 600.
2. the method for sampling is each extraction 1ml sustained-release liquids, sustained-release liquid is not supplemented.
3. sample medicine content is measured using high performance liquid chromatography, method of testing is：Use the reverse posts of C18, mobile phase
For 80% acetonitrile and 20% deionized water, flow velocity 1.25ml/min, 30 DEG C of column temperature, Detection wavelength 230nm, retention time is about
10.5min.According to standard curve, by each sample integrate obtained by calculated by peak area its concentration.
4. elution profiles are into release percentage by each sample concentration conversion, and draw curve and obtain.
It is sustained result as shown in Figure 4.
As seen from Figure 4, microemulsion made from embodiment 3 and two control groups are respectively provided with higher release in 10h in the early stage
Medicine speed, when medicine realeasing rate is near 80%, rate of releasing drug substantially slows down, until release is complete when drug release time is about 40h.And
The medicine realeasing rate of embodiment 3 is always below two control groups in whole drug release process, and this says obtained lignin-base microemulsion
The sustained release of agricultural chemicals can be realized.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of slow-release pesticide microemulsion, it is characterised in that be made by the composition of following mass percent：
Described lignin-base emulsifying agent is prepared by the following method, and 100 parts of alkali lignins are dissolved in polar solvent, adds 60
~200 parts of tertiary amine catalysts, 40~220 parts of acylating reagents are then added dropwise under heating and stirring condition and react certain time,
Then product is purified, dried, that is, obtain lignin-base emulsifying agent；Described number is parts by weight.
2. slow-release pesticide microemulsion according to claim 1, it is characterised in that：Described pesticide original medicine is fat-soluble agriculture
Medicine active compound.
3. slow-release pesticide microemulsion according to claim 1, it is characterised in that：Described pesticide original medicine is chlorine worm benzene first
In acid amides, Diacloden, imidacloprid, gamma cyhalothrin, Permethrin, chlopyrifos, AVM, pyraclostrobin or Tebuconazole
One kind.
4. slow-release pesticide microemulsion according to claim 1, it is characterised in that：Described assistant for emulsifying agent is poly alkyl alcohol
Oxygen vinethene, sapn, tristyrylphenol polyoxyethylene ether, tween, polyoxyethylene laurate, Myrj 45
One or more of or polyoxyethylene oleate.
5. slow-release pesticide microemulsion according to claim 1, it is characterised in that：Described antifreeze is ethylene glycol, third
One or more of glycol, diethylene glycol or DPG.
6. slow-release pesticide microemulsion according to claim 1, it is characterised in that：Described polar solvent is N, N- diformazans
It is yl acetamide, butyrolactone, dimethyl carbonate, butyl acetate, sec-butyl acetate, 1-METHYLPYRROLIDONE, ethanol, isopropanol, different
One or more of phorone, ethylene glycol ethyl ether or ethylene glycol phenyl ether.
7. slow-release pesticide microemulsion according to claim 1, it is characterised in that：Described tertiary amine catalyst is front three
One kind in amine, N, N- dipropyl -1- propylamine, triethylamine, N, accelerine or Dodecyl Dimethyl Amine.
8. slow-release pesticide microemulsion according to claim 1, it is characterised in that：Described acylating reagent be chloroacetic chloride,
One or more of caprylyl chloride, lauroyl chloride or chlorobenzoyl chloride.
9. the preparation method of the slow-release pesticide microemulsion described in claim any one of 1-8, it is characterised in that including following step
Suddenly：
By lignin-base emulsifying agent, pesticide original medicine and assistant for emulsifying agent, mixed dissolution is uniform in polar solvent, is then added dropwise
Into deionized water and shear-mixed, antifreeze is added, it is slow-release pesticide microemulsion to obtain semitransparent colloidal solution.
10. slow-release pesticide microemulsion described in claim any one of 1-8 is in the application in agricultural field.
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