CN105010362B - One kind application lignin-base wall material prepares avermectin microcapsule powder and its method - Google Patents
One kind application lignin-base wall material prepares avermectin microcapsule powder and its method Download PDFInfo
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Abstract
The present invention discloses a kind of application lignin-base wall material and prepares avermectin microcapsule powder and its method.The method is configured to the aqueous solution by the amido sodium lignin sulfonate wall material and emulsifying agent of purification are soluble in water, obtains water phase；The former medicine of AVM is dissolved in organic solvent, organic phase is obtained；Organic phase is even added in water phase in rotating condition, then is sheared；Then the pH value of dispersion liquid is adjusted, complex coacervation is carried out；Cooling, adds crosslinking agent to carry out cross-linking reaction, and centrifugation, filtration drying obtains microcapsule powder；The preparation process is simple of avermectin microcapsule powder of the present invention, wall material degradable green, and be prevented from active compound photodissociation, the microcapsules of preparation have drugloading rate higher and contain rate, and slow release effect significantly, can realize the regulation and control to discharging in the range of certain pH.
Description
Technical field
The present invention relates to a kind of avermectin microcapsule powder, more particularly to a kind of application lignin-base wall material prepares AVM hereinafter
Rhzomorph microcapsule powder and its method.
Background technology
China is pesticide producing and consumption big country, and China's pesticidal preparations yield in 2013 and plant demand are respectively at 1,600,000 tons
With 1,000,000 tons or so.According to statistics, China's unit cultivated area Pesticide use amount is 2.5 times of world average level, a large amount of agricultural chemicals
Use kept yield, but severe contamination also is caused to environment.Traditional agricultural chemicals based on pulvis, wettable powder and missible oil
Preparation there are problems that agricultural chemicals utilization rate it is low, easily to environment and mammal, therefore modern preparation gradually to
Efficiently, low toxicity, low-residual, economy, the direction conveniently, safely with environmental harmony are developed.
In recent years, pesticide micro capsule formulation is environment-friendly and low-toxicity because it has, is sustained, the advantage such as efficient stable is gradually subject to people
Pay attention to.Microcapsules technology refers to that core is wrapped in wall material, forms the technology of size particulate between 1~100 μm.Its wall material
Mostly macromolecular material, is easy to get because of natural polymer wide material sources, raw material, non-toxic degradable, simple processing, with low cost etc. excellent
Point, the study hotspot as farm chemical carrier material, wherein, with natural polymers such as Arabic gum, gelatin, sodium alginate, shitosans
The research of sub- material is most widely used.
And lignin is same as a kind of natural reproducible macromolecular compound, as microcapsule wall material research very
It is few.Mariarosaria[Mariarosaria Tortora,Francesca Cavalieri,et al.Ultrasound
Driven Assembly of Lignin into Microcapsules for Storage and Delivery of
Hydrophobic Molecules.Biomacromolecules,2014,15:1634-1643.] etc. cumarin is dissolved in chloroform
Afterwards with mixed with olive oil, then mixed liquor is added in the lignin aqueous solution, after ultrasonic emulsification, centrifugation obtains homogeneous spherical micro-
Capsule product.Microcapsules are carried out with release experiment simultaneously, find in aqueous microcapsules can stable for extended periods of time, it is not bright
Aobvious release.
[all refined LBL self-assemblies are prepared and carry medicine shitosan/sodium lignin sulfonate microcapsules and its drug release behavior north Zhou Bin
Capital:Beijing University of Chemical Technology, 2008.] shitosan/sodium lignin sulfonate microcapsules are prepared using LBL self-assembly mode.First by Ah
Dimension rhzomorph is scattered in sodium dodecyl benzene sulfonate aqueous solution, obtains the AVM with powered adsorption layer, then successively will
AVM is immersed in the aqueous solution of shitosan and sodium lignin sulfonate and carries out LBL self-assembly and obtain microcapsules.To microcapsules
Release Performance is studied, and is found with the increase of the self assembly number of plies, and its drug release rate is substantially reduced.In addition, with system salt
The increase of concentration, microcapsules wall thickness increase, its rate of release is significantly reduced.Prepared using the method for shitosan LBL self-assembly
Microcapsules are a kind of conventional methods, although the microcapsules of preparation have certain slow release effect, but due to chitosan molecule amount too
Greatly, therefore in preparation process it is difficult to operate, the particle diameter of microcapsules is difficult to equal control, contains rate also than relatively low；And use
To substantial amounts of shitosan, high cost, cumbersome, actual application value is little.
Fu Weijin [preparation of the Lignin phenolic base drug bearing microspheres such as Fu Weijin, Zhang Shuting and sustained release performance macromolecule materials
Material scientific and engineering, 2012,28 (10):117-120.] etc. first by lignin and AVM, formaldehyde, phenol and cetyl
Trimethylammonium bromide hybrid reaction, obtains Lignin phenolic performed polymer, then performed polymer is added in peanut oil and continues to react,
Separating drying can obtain lignin phenol's aldehyde radical microcapsules.Sustained release behavior to microcapsules carries out research discovery, when lignin addition
For 50% when, its slow release effect is optimal.The method is by lignin and AVM, formaldehyde, phenol and cetyl trimethyl bromine
Change ammonium a pot of porridge hybrid reaction, preparation process severe reaction conditions, easily the macrolide structure to AVM damage,
Make the reduction of active compound effective content；And the Microcapsules Size for preparing is larger, it is impossible to meet the requirement of microcapsules drug effect.
Chinese invention patent application CN102349509A discloses a kind of preparation side of lignin urea-formaldehyde pesticide microcapsule
Method, is first mixed to get performed polymer, then performed polymer is added into the AVM hereinafter containing Arlacel-85 and chlorobenzene by urea, formaldehyde and lignin
Emulsion is obtained in rhzomorph solution, finally emulsion is added in oxalic acid aqueous solution, microcapsules are obtained after filtration drying.The micro- glue of gained
Capsule particle diameter drugloading rate and contains rate respectively between 15~35% and 60~80% at 20 μm or so, and slow-release time is left in 120h
It is right.Then performed polymer and AVM, solvent, the emulsification of emulsifying agent a pot of porridge are acidified condensation reaction, whole technique mistake by the method
Journey is quite analogous to the preparation method of urea-formaldehyde resin microcapsule, does not have anything to innovate in method, simply in the micro- glue of Lauxite
Increase lignin raw material on the basis of capsule；The method needs a large amount of wall materials, and it is very low to contain rate, and particle is big, belongs to a kind of
Very poorly efficient embedding method, can not industrially realize substantially.
The rare report of research that microcapsules are prepared as main wall material with lignin at present, and generally existing active compound contains rate
The problems such as resolution ratio of the low, active compound in embedding process is big compared with high, Microcapsules Size, preparation technology is complicated, it is relevant to be rung using pH
The lignin derivative of answering property as wall material prepare microcapsules report there is not yet.
The content of the invention
It is an object of the invention to the amido sodium lignin sulfonate with a kind of application with pH responses as wall material prepare Ah
Dimension rhzomorph microcapsule powder and its method, product environment-protecting asepsis are cheap, resistance to sunshine photodissociation.
The present invention is molten by the former medicine of AVM and lignin-base wall material difference with a kind of amido sodium lignin sulfonate as wall material
In solvent and then using complex coacervation encystation, crosslinking agent is finally added to carry out being crosslinked instead to lignin-base wall material in aqueous
Should, a kind of avermectin microcapsule suspension is obtained, by being dried to obtain microcapsule powder.The major wall that wherein microcapsules are used
Material is amido sodium lignin sulfonate, and core is AVM, by adjusting the pH of the amido sodium lignin sulfonate wall material aqueous solution, is made
Amido lignin sulfonic acid sodium molecule is copolymerized collection with avermectin nanometer particle, prepares amido sodium lignin sulfonate/Avermectin
Plain complex microsphere, so that the embedding to AVM is realized, then again by the way of chemical crosslinking to amido lignin sulfonic acid
Sodium wall material carries out cross-linking reaction, the complex microsphere being chemically crosslinked, and it is that can obtain AVM that drying removes moisture
Microcapsule powder.
The present invention is with the pH response type amido sodium lignin sulfonates containing amido and sulfonic group zwitterion functional group simultaneously
It is wall material, the distribution of charges of its molecule is changed by adjusting the pH of amido lignin sulfonic acid sodium water solution, so as to realizes to it
Molecular configuration and aggregation extent are regulated and controled to prepare lignin-base microcapsules, reach the effect of embedding agricultural chemicals.
The purpose of the present invention is to be achieved through the following technical solutions：
A kind of method that application lignin-base wall material prepares avermectin microcapsule powder, comprises the following steps：
1) in terms of mass fraction, the amido sodium lignin sulfonate wall material and 5~20 parts of emulsifying agents that 100 parts are purified are dissolved in
The aqueous solution is configured in 200~500 parts of water, water phase is obtained；
2) the former medicine of AVM is dissolved in organic solvent, obtains organic phase；
3) organic phase is even added in water phase in rotating condition, then is sheared 10~20 minutes；Then regulation dispersion
The pH value of liquid carries out complex coacervation 30~60 minutes to 6~8 at 20~40 DEG C；0~20 DEG C is cooled to, 1~10 part is added
Crosslinking agent carries out cross-linking reaction 1~2 hour, and avermectin microcapsule suspension is obtained；
4) by obtained avermectin microcapsule suspension centrifugation, water and solvent are removed, it is then that residual solid is cold
It is lyophilized dry, obtain avermectin microcapsule powder；
The amido sodium lignin sulfonate wall material is prepared via a method which：It is configured to sodium lignin sulfonate is soluble in water
Lignin sulfonic acid sodium water solution, adjusts the pH value of solution to 10.0~13.0, and 0.5~1.0h is activated at 50~70 DEG C；Add amine
Change modifying agent, aldehydes reagent is then added dropwise, after completion of dropping, 2~4h is reacted at 70~90 DEG C, obtain amido sodium lignin sulfonate
Solution；The amido lignin sulfonic acid sodium solution that will be obtained is stripped with alcohol reagent, and the residual solid thing after extracting uses stone again
Oily ether washing, debris carries out freeze-drying again, you can the powdery amido sodium lignin sulfonate wall material for being purified；It is described
Amination reagent is diethylamine, propane diamine, triethylamine, diethylenetriamine or triethylene tetramine；The aldehydes reagent is formaldehyde, second
Aldehyde, propionic aldehyde, glyoxal or glutaraldehyde；The alcohol reagent is the one kind or many in methyl alcohol, ethanol, propyl alcohol, isopropanol and butanol
Kind.
The emulsifying agent is lauryl sodium sulfate, neopelex, cetomacrogol 1000, cetyl front three
One or more in base ammonium bromide and Tween-80；
The organic solvent is one or more in dimethyl sulfoxide (DMSO), pyrrolidones, dichloromethane, methyl alcohol, ethanol；
The crosslinking agent is the one kind in sodium tripolyphosphate, formaldehyde, glyoxal, glutaraldehyde, epoxychloropropane.
For the object of the invention is better achieved, it is preferable that in terms of mass fraction, the organic phase be by 20~200 parts Ah
Dimension rhzomorph active compound is obtained in being dissolved in 200~500 parts of organic solvents.
Preferably, the rotating speed of the rotating condition is 500-1500rpm；It is described that organic phase is even added in water phase
Time is 20-40 minutes.
Preferably, in terms of mass fraction, the lignin sulfonic acid sodium water solution is to be dissolved in 100 parts of sodium lignin sulfonates
It is configured in 150~400 parts of water.
Preferably, in terms of mass fraction, the addition of the amination modifying agent is 20~200 parts.
Preferably, in terms of mass fraction, the addition of the aldehydes reagent is 20~200 parts.
Preferably, in terms of mass fraction, the dropwise addition is 20~200 parts of aldehydes reagents of addition in 0.5~1.0h.
Preferably, in terms of mass fraction, the amido lignin sulfonic acid sodium solution that will be obtained is taken out with alcohol reagent
Carry is to react 100 parts the amido lignin sulfonic acid sodium solution for obtaining to be stripped with 100~300 parts of alcohol reagents.
Avermectin microcapsule powder prepared by a kind of lignin-base wall material is prepared by above-mentioned method.
The purity of the former medicine of AVM is 92%；Amido sodium lignin sulfonate wall material of the present invention is changed by polyamine
Property sodium lignin sulfonate and obtain, purity>95%；It is preferred that using NaOH, KOH or H2SO4, HCl regulation solution pH value or dispersion
The pH value of liquid.
The present invention in addition to amido sodium lignin sulfonate and the former medicine of AVM, by pure content meter.
Compared with similar products, wall material raw material wide material sources are several cheap；Wall material raw material is natural polymer, can be natural
It is degraded to fertilizer；Contain a large amount of polyhydric phenols structures in wall material molecule, free radical that can be significantly in absorbing material is prevented from active compound
By ultraviolet light photodissociation；The drugloading rate of the microcapsule powder of preparation and contain that rate is all higher, slow release effect is notable；Due to wall used
Material has pH responses, therefore the microcapsule powder for preparing can realize the regulation and control to discharging in the range of certain pH.
The present invention has the following advantages that and effect compared with prior art：
1st, reaction of the present invention is carried out under atmospheric low-temperature, simple to operate, is easily controlled, product environment-protecting asepsis；
2nd, avermectin microcapsule preparation method of the present invention, uses material environment friendly degradable, and reagent is to dynamic plant
The equal nonhazardous effect of thing, and it is cheap, there is certain advantage compared with existing microcapsule product；
3rd, the present invention prepares avermectin microcapsule by main wall material of lignin, due to containing in lignin wall material molecule
A large amount of hindered phenol structures, therefore can effectively solve defect of the former medicine of AVM intolerant to sunshine photodissociation；
4th, microcapsules prepared by the present invention have drugloading rate higher and contain rate, and slow release effect is obvious；
5th, microcapsules prepared by the present invention have pH responses, can realize that agricultural chemicals embedding and sustained release can in certain pH scope
Control, it is applied widely.
Brief description of the drawings
Fig. 1 is cumulative release curve of the microcapsules prepared by embodiment 1 in the dissolution medium of different pH.
Fig. 2 is that microcapsules prepared by embodiment 1 are contrasted with the rate of release of commodity microcapsules.
Fig. 3 is the microscope figure of microcapsules prepared by embodiment 1,96 × 72 μm.
Specific embodiment
The present invention is further illustrated with reference to the accompanying drawings and examples, but embodiment does not constitute and the present invention is wanted
Ask the restriction of the scope of protection.
Embodiment 1
100g sodium lignin sulfonates are dissolved in 400g water, pH to 12 is adjusted, 0.5h is activated in 50 DEG C of water-baths, added
50g diethylenetriamines, are slowly added dropwise 50g formaldehyde, the completion of dropping in 0.5h, are warming up to 70 DEG C, continue to react 4h, obtain amido
Lignin sulfonic acid sodium solution.The amido lignin sulfonic acid sodium solution that will be obtained is stripped with ethanol, the residual solid after extracting
Thing is again with carrying out freeze-drying after petroleum ether, you can the powdery amido sodium lignin sulfonate for being purified.
Amido sodium lignin sulfonate wall material, 8g lauryl sodium sulfate and the 5g cetomacrogol 1000s that 100g is purified are together
It is dissolved in 200g water and is configured to the aqueous solution, obtains water phase；100g AVMs are dissolved in 500g dichloromethane, obtain organic
Phase.Organic phase was even added in water phase in 30 minutes under 1000rpm rotating speeds, then is sheared 15 minutes；Then with 10%
Hydrochloric acid solution adjusts the pH to 8 of dispersion liquid, and complex coacervation is carried out at 20 DEG C, is kept for 60 minutes.5 DEG C are cooled to, 2g is added
Glutaraldehyde carries out cross-linking reaction, and insulation reaction 1 hour is obtained avermectin microcapsule suspension.Obtained AVM is micro-
Capsule suspension liquid centrifugation, removes water and solvent, and residual solid then is freeze-dried to obtain into avermectin microcapsule
Powder.
Embodiment 2
100g sodium lignin sulfonates are dissolved in 150g water, pH to 10 is adjusted, 1.0h is activated in 60 DEG C of water-baths, added
20g triethylamines, are slowly added dropwise 20g acetaldehyde, the completion of dropping in 1h, are warming up to 80 DEG C, continue to react 2h, obtain amido lignin
Sodium sulfonate solution.The amido lignin sulfonic acid sodium solution that will be obtained is stripped with ethanol, and the residual solid thing after extracting is used again
Freeze-drying is carried out after petroleum ether, you can the powdery amido sodium lignin sulfonate for being purified.
The amido sodium lignin sulfonate wall material and 5g Tween-80s that 100g is purified are dissolved in 350g water and are configured to the aqueous solution,
Obtain water phase；20g AVMs are dissolved in 200g dimethyl sulfoxide (DMSO)s, organic phase is obtained.Organic phase is existed under 800rpm rotating speeds
It is even added in 30 minutes in water phase, then is sheared 10 minutes；Then dispersion liquid is adjusted with the HCl solution that mass concentration is 10%
PH to 6.5, carry out complex coacervation at 40 DEG C, kept for 30 minutes.0 DEG C is cooled to, the formalin of 10g 37wt% is added
Solution carries out cross-linking reaction, and insulation reaction 2 hours is obtained avermectin microcapsule suspension.By the micro- glue of obtained AVM
Capsule suspension centrifugation, removes water and solvent, and residual solid then is freeze-dried to obtain into avermectin microcapsule powder.
Embodiment 3
100g sodium lignin sulfonates are dissolved in 200g water, pH to 11 is adjusted, 1.0h is activated in 70 DEG C of water-baths, added
200g diethylamine, is slowly added dropwise 200g propionic aldehyde, the completion of dropping in 1h, is warming up to 90 DEG C, continues to react 3h, obtains amido wooden
Plain sodium sulfonate solution.The amido lignin sulfonic acid sodium solution that will be obtained is stripped with ethanol, and the residual solid thing after extracting is again
With carrying out freeze-drying after petroleum ether, you can the powdery amido sodium lignin sulfonate for being purified.
The amido sodium lignin sulfonate wall material and 12g neopelexes that 100g is purified are prepared in being dissolved in 400g water
Into the aqueous solution, water phase is obtained；80g AVMs are dissolved in 100g pyrrolidones and 200g alcohol mixed solvents, obtain organic
Phase.Organic phase was even added in water phase in 30 minutes under 1000rpm rotating speeds, then is sheared 20 minutes；Then quality is used
Concentration is the pH to 7 of 10% HCl solution regulation dispersion liquid, and complex coacervation is carried out at 30 DEG C, is kept for 50 minutes.It is cooled to
10 DEG C, 10g sodium tripolyphosphates are added to carry out cross-linking reaction, insulation reaction 1 hour is obtained avermectin microcapsule suspension.Will
Obtained avermectin microcapsule suspension centrifugation, removes water and solvent, is then freeze-dried to obtain residual solid
To avermectin microcapsule powder.
Embodiment 4
100g sodium lignin sulfonates are dissolved in 300g water, pH to 13 is adjusted, 0.5h is activated in 50 DEG C of water-baths, added
100g triethylene tetramines, are slowly added dropwise 100g glutaraldehydes, the completion of dropping in 0.5h, are warming up to 70 DEG C, continue to react 2h, obtain
Amido lignin sulfonic acid sodium solution.The amido lignin sulfonic acid sodium solution that will be obtained is stripped with ethanol, the remnants after extracting
Solids is again with carrying out freeze-drying after petroleum ether, you can the powdery amido sodium lignin sulfonate for being purified.
The amido sodium lignin sulfonate wall material and 20g lauryl sodium sulfate that 100g is purified are dissolved in 500g water and being configured to
The aqueous solution, obtains water phase；200g AVMs are dissolved in 200g methyl alcohol and 300g alcohol mixed solvents, organic phase is obtained.
Organic phase was even added in water phase in 30 minutes under 1200rpm rotating speeds, then is sheared 10 minutes；Then it is with mass concentration
10% HCl solution adjusts the pH to 8 of dispersion liquid, and complex coacervation is carried out at 20 DEG C, is kept for 60 minutes.10 DEG C are cooled to,
Adding 5g glyoxals carries out cross-linking reaction, and insulation reaction 1.5 hours is obtained avermectin microcapsule suspension.By obtained Ah
Dimension rhzomorph microcapsule suspensions centrifugation, removes water and solvent, and residual solid then is freeze-dried to obtain into Avermectin
Plain microcapsule powder.
Embodiment 5
100g sodium lignin sulfonates are dissolved in 300g water, pH to 12 is adjusted, 0.5h is activated in 60 DEG C of water-baths, added
150g propane diamine, is slowly added dropwise 150g glyoxals, the completion of dropping in 1h, is warming up to 80 DEG C, continues to react 4h, obtains amido wood
Quality sodium sulfonate solution.The amido lignin sulfonic acid sodium solution that will be obtained is stripped with ethanol, the residual solid thing after extracting
Again with carrying out freeze-drying after petroleum ether, you can the powdery amido sodium lignin sulfonate for being purified.
Amido sodium lignin sulfonate wall material, 1g cetyl trimethylammonium bromides and the 6g Tween-80s one that 100g is purified
Rise to be dissolved in 300g water and be configured to the aqueous solution, obtain water phase；80g AVMs are dissolved in 300g ethanol, organic phase is obtained.
Organic phase was even added in water phase in 30 minutes under 1500rpm rotating speeds, then is sheared 15 minutes；Then it is with mass concentration
10% HCl solution adjusts the pH to 6 of dispersion liquid, and complex coacervation is carried out at 35 DEG C, is kept for 30 minutes.20 DEG C are cooled to,
Adding 1g epoxychloropropane carries out cross-linking reaction, and insulation reaction 2 hours is obtained avermectin microcapsule suspension.Will be obtained
Avermectin microcapsule suspension centrifugation, removes water and solvent, and residual solid then is freeze-dried to obtain into AVM hereinafter
Rhzomorph microcapsule powder.
Embodiment effect explanation
The drugloading rate of microcapsules and rate is contained in each embodiment of table 1
In table 1 drugloading rate and contain rate mensuration mode it is as follows：
(1) precise certain mass microcapsules sample (being accurate to 0.0001g), is added to about 50mL 50%DMF water-soluble
In liquid, 10min then is crushed with cell crushing instrument, then the suspension that will be obtained is transferred in 500mL volumetric flasks, it is fixed with ethanol
Hold, then stand 24h.
(2) a certain amount of volumetric flask clear liquid at the middle and upper levels is taken, after being filtered with 0.45 μm of water phase filtering head, using efficient liquid
Phase chromatography determines the active compound content in filtrate.The drugloading rate of microcapsules is calculated according to below equation and rate is contained：
Drugloading rate=(active compound quality in microcapsules)/(microcapsules gross mass) × 100%
Contain rate=(microcapsules gross mass) × (drugloading rate)/(microcapsules Central Plains medicine theoretical value) × 100%.
Drugloading rate and to contain rate be to weigh the important indicator of microcapsules quality, drugloading rate is closely related with wall material consumption, wall
The small then drugloading rate of timber-used amount is high, and drugloading rate is high, can reduce wall material consumption and reduce the production cost of microcapsules.And contain rate
It is then the utilization rate of medicine, in general, core drug price is generally far above wall material, and raising contains rate equivalent to raising medicine
Utilization rate, reduce medicine loss.Therefore, on the premise of microcapsules quality is ensured, the drugloading rate and bag of microcapsules are improved
Load rate can effectively reduce the production cost of microcapsules.
As seen from Table 1, with existing avermectin microcapsule commodity (1.2% micro-capsule suspension, by polyurethane wall material system
It is standby to form) compare, the microcapsules prepared in each embodiment are respectively provided with drugloading rate higher and contain rate, thus with it is certain into
This advantage.Also, because lignin wall material has good anti-oxidant and anti-light solution ability, therefore Avermectin prepared by the present invention
Plain microscapsule powder has the performance of good uvioresistant photodissociation, as shown in table 2.
The active compound retention rate of the active compound of table 2, commodity microcapsules and embodiment 1 under ultra violet lamp
It is from table 2, the former medicine of AVM powder of identical AVM active constituent content, AVM commodity are micro-
Capsule and the microcapsules of embodiment 1 test the retention rate of AVM active ingredient after UVA ultra violet lamps 24h.As a result table
Bright, after ultra violet lamp, the active ingredient in the former medicine of AVM powder is down to 13.41%, AVM commodity microcapsules
In active ingredient be down to 67.93%, the active ingredient in the microcapsules of embodiment 1 is down to 89.44%.This shows that AVM is former
The anti-light solution poor performance of medicine, active ingredients of the original drug fails substantially after ultraviolet light 24h, and commodity microcapsules then have certain
Anti-light solution performance, and the microcapsules of embodiment 1 then have good anti-light solution performance.Think, contain in AVM molecule
Conjugated double bond, is susceptible to Raolical polymerizable and fails under ultraviolet light；Commodity microcapsules are because wall material is to ultraviolet
The shielding of light and the resolution ratio of active compound is reduced to the protective effect of active compound；The present invention with lignin as main wall material, due to
Contain a large amount of polyhydric phenols structures in lignin molecule, these polyhydric phenols structures can be effectively in trapping material because by ultraviolet lighting
The free radical of generation, so as to play a part of protection materials, therefore lignin-base wall material microcapsules of the invention can be solved effectively
Defect of the former medicine of AVM intolerant to sunlight；
Fig. 1 is accumulation of the avermectin microcapsule of the preparation of embodiment 1 in 50% ethanol water under condition of different pH
Release profiles.It is seen that with the rising of pH, the rate of release of AVM slows down in microcapsules, in pH=8.0
Rate of release is most slow.Because, with the reduction of pH, the increase of amido ion degree of ionization, electric charge on strand in microcapsules
Density increases, and microcapsules switch to loose expansion by contraction state, thus freeing that speed increases.Be can be explained by Fig. 1, prepared by the present invention
Avermectin microcapsule there is certain pH responses, rate of release that can be to AVM by way of adjusting pH is carried out
Regulation and control.
Fig. 2 is avermectin microcapsule and existing avermectin microcapsule commodity (1.2% microcapsules prepared by embodiment 1
Suspending agent, is prepared from by polyurethane wall material) cumulative release curve in 50% ethanol water of pH=6.0.Contrast can
Find out, 20h before release, compared with commodity, rate of releasing drug relatively delays the microcapsules of embodiment 1；After 20h, commodity burst size is basically reached
Balance, cumulative release amount is 89%, and AVM-ASL microcapsules then sustained release, 60h or so reach balance, and burst size is 98%
Left and right.Be can be explained by Fig. 2, avermectin microcapsule and existing goods prepared by the present invention is contrasted to have and quite or be preferably sustained
Effect.
Wherein release experiment is comprised the following steps that：
Certain mass microcapsules (contained AVM quality is equal in microcapsules sample) accurately are weighed, 100mL is added to
In conical flask, with 50% ethanol water constant volume of pH=6~8 and seal.Constant temperature oscillator is put into, is turned at 25 DEG C and 200rpm
Release experiment is carried out under the conditions of speed, 1mL supernatants is taken at regular intervals and is surveyed its AVM content, and supplement 1mL50% second
Alcohol solution keeps constant volume.Draw cumulative release curve.
Fig. 3 is microcapsules microscope figure prepared by embodiment 1.It is seen that the microcapsule size for preparing is homogeneous, grain
Footpath<5 μm, and be uniformly dispersed.
Above implementation result shows that avermectin microcapsule prepared by the present invention is contrasted with existing goods microcapsules, is had
Suitable or more preferable slow release effect, while have drugloading rate higher and contain rate, and wall material raw material wide material sources, price is low
It is honest and clean with cost advantage.Because lignin-base wall material contains a large amount of polyhydric phenols structures, with significant anti-light solution, compared to business
Product microcapsules can more effectively solve defect of the AVM intolerant to sunlight.Lignin-base wall material is environment-friendly changing
Property natural macromolecular material, it is nontoxic, in nature can natural degradation be fertilizer.In sum, what prepared by the present invention is micro-
Capsule has more prominent feature performance benefit compared to current commodity microcapsules, with very big prospects for commercial application.
Claims (4)
1. a kind of method that application lignin-base wall material prepares avermectin microcapsule powder, it is characterised in that comprise the following steps：
1) in terms of mass fraction, the amido sodium lignin sulfonate wall material and 5~20 parts of emulsifying agents of 100 parts of purifications are dissolved in 200~
The aqueous solution is configured in 500 parts of water, water phase is obtained；
2) the former medicine of AVM is dissolved in organic solvent, obtains organic phase；
3) organic phase is even added in water phase in rotating condition, then is sheared 10~20 minutes；Then dispersion liquid is adjusted
PH value carries out complex coacervation 30~60 minutes to 6~8 at 20~40 DEG C；0~20 DEG C is cooled to, 1~10 part of crosslinking is added
Agent carries out cross-linking reaction 1~2 hour, and avermectin microcapsule suspension is obtained；
4) by obtained avermectin microcapsule suspension centrifugation, water and solvent are removed, it is then that residual solid freezing is dry
It is dry, obtain avermectin microcapsule powder；
The amido sodium lignin sulfonate wall material is prepared via a method which：By sodium lignin sulfonate it is soluble in water be configured to it is wooden
Plain sulfonic acid sodium water solution, adjusts the pH value of solution to 10.0~13.0, and 0.5~1.0h is activated at 50~70 DEG C；Amination is added to change
Property agent, then be added dropwise aldehydes reagent, after completion of dropping, 70~90 DEG C react 2~4h, obtain amido sodium lignin sulfonate molten
Liquid；The amido lignin sulfonic acid sodium solution that will be obtained is stripped with alcohol reagent, and the residual solid thing after extracting uses oil again
Ether is washed, and debris carries out freeze-drying again, you can the powdery amido sodium lignin sulfonate wall material for being purified；The amine
Change reagent is diethylamine, propane diamine, triethylamine, diethylenetriamine or triethylene tetramine；The aldehydes reagent be formaldehyde, acetaldehyde,
Propionic aldehyde, glyoxal or glutaraldehyde；The alcohol reagent is one or more in methyl alcohol, ethanol, propyl alcohol, isopropanol and butanol；
The emulsifying agent is lauryl sodium sulfate, neopelex, cetomacrogol 1000, cetyl trimethyl bromine
Change one or more in ammonium and Tween-80；
The organic solvent is one or more in dimethyl sulfoxide (DMSO), pyrrolidones, dichloromethane, methyl alcohol, ethanol；
The crosslinking agent is the one kind in sodium tripolyphosphate, formaldehyde, glyoxal, glutaraldehyde, epoxychloropropane；
In terms of mass fraction, the organic phase is that 20~200 parts of the former medicine of AVM are dissolved in 200~500 parts of organic solvents
Obtain；The lignin sulfonic acid sodium water solution is that 100 parts of sodium lignin sulfonates are dissolved in 150~400 parts of water to be configured to；It is described
The addition of amination modifying agent is 20~200 parts；The addition of the aldehydes reagent is 20~200 parts；
The rotating speed of the rotating condition is 500-1500rpm；Time organic phase being even added in water phase is 20-40
Minute.
2. the method that application lignin-base wall material according to claim 1 prepares avermectin microcapsule powder, its feature exists
In in terms of mass fraction, the dropwise addition is 20~200 parts of aldehydes reagents of addition in 0.5~1.0h.
3. the method that application lignin-base wall material according to claim 1 prepares avermectin microcapsule powder, its feature exists
In in terms of mass fraction, it is anti-by 100 parts that the amido lignin sulfonic acid sodium solution alcohol reagent that will be obtained is stripped
The amido lignin sulfonic acid sodium solution that should be obtained is stripped with 100~300 parts of alcohol reagents.
4. the avermectin microcapsule powder that prepared by a kind of lignin-base wall material, it is characterised in that：It is by claim any one of 1-3
Described method is prepared.
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| CN105475310A (en) * | 2015-12-18 | 2016-04-13 | 华南理工大学 | 80% fipronil water dispersible granules and preparing method thereof |
| US20190037837A1 (en) * | 2016-02-05 | 2019-02-07 | Max-Planck-Gesellschaft Zur Förderung Der Wissenschaften Ev | Lignin biomaterial as agricultural drug carrier |
| CN106035356A (en) * | 2016-06-06 | 2016-10-26 | 南通伟德动力电池研究所（普通合伙） | Preparation method for trunk injecting microcapsule pesticide for controlling Bursaphelenchus xylophilus |
| CN106900703A (en) * | 2017-01-13 | 2017-06-30 | 华南理工大学 | A kind of lignin-base polyureas pesticide micro capsule and preparation method thereof |
| CN106818735A (en) * | 2017-01-13 | 2017-06-13 | 华南理工大学 | A kind of avermectin microcapsule suspending agent and preparation method with anti-photolytic efficiency |
| CN107333758B (en) * | 2017-06-02 | 2021-03-30 | 中国农业科学院植物保护研究所 | Method for preparing abamectin B2 embedded granules by complex coacervation method and obtained product |
| CN111556710A (en) | 2017-12-25 | 2020-08-18 | 陶氏环球技术有限责任公司 | Microencapsulation of insecticides |
| CN109362723B (en) * | 2018-11-30 | 2021-02-19 | 华南理工大学 | Pesticide-loaded lignin microcapsule based on emulsion interface crosslinking and preparation method thereof |
| CN109316461B (en) * | 2018-11-30 | 2021-01-19 | 华南理工大学 | Lignin wall material microcapsule based on Pickering emulsion interface crosslinking, preparation method and application in drug carrier |
| CN110946133B (en) * | 2020-02-17 | 2022-03-25 | 广西田园生化股份有限公司 | Nano photolysis-resistant controlled-release pesticide with lignin as coating matrix and preparation method thereof |
| CN111909646B (en) * | 2020-08-07 | 2021-12-17 | 湖南福湘木业有限责任公司 | Mould-proof modification method for soybean-based adhesive |
| CN113667541B (en) * | 2021-10-25 | 2022-01-07 | 潍坊加易加生物科技有限公司 | Preparation method of essential oil microcapsule |
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