CN109938019A - A kind of method that Simple coacervation prepares natural pyrethrin microcapsules - Google Patents
A kind of method that Simple coacervation prepares natural pyrethrin microcapsules Download PDFInfo
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Abstract
The invention discloses a kind of methods that Simple coacervation prepares natural pyrethrin microcapsules, belong to microcapsules technology field.The present invention is using pure natural high molecular material gelatin as wall material, natural pyrethrin is core material, glutamine transaminage is curing agent, the polymer overmold natural pyrethrin core material for being generated gelatin through single aggregation using Simple coacervation, realize the microencapsulation of oily pyrethrins, product highly stableization, effective component sustained releaseization, while solving the problems, such as that pyrethrins is light-exposed labile；Preparation process does not use any organic solvent and toxic component, meets Green Chemistry, and microcapsule product obtained is safe to the human body nontoxic, and performance is stablized, and good disinsection effect can be widely applied to the expeling of various crop pests and public environment mosquito.
Description
Technical field
The present invention relates to a kind of preparation methods of microcapsules, and in particular to it is micro- that a kind of Simple coacervation prepares natural pyrethrin
The method of capsule belongs to microcapsules technology field.
Background technique
Be extracted from the natural pyrethrin of Dalmatian chrysanthemum at present, there is environmental-friendly characteristic, it to people, warm-blooded animal and from
While so environment is nontoxic, there are efficient, wide spectrum, low toxicity, low-residual insecticidal properties.The insecticidal action master of pyrethrins
If leading to death by the nerve for benumbing insect, so comparing with other biological pesticide, have the advantages that knock down fireballing.
However pyrethrins is very easy to decompose to lose effect under the action of high temperature, metal ion, air and ultraviolet light.This
So that pyrethrins is very easy to decompose loss in production, transportational process, while the effect also influenced in its use process is held
Long property, and then lead to the reduction of pyrethrins insecticidal power and the increase of use cost.
Microcapsules technology is wrapped up core material ingredient by using wall material, is relatively isolated core material with external environment, from certain
Influence of the external environment to core material is reduced in degree, it is also possible to reduce the evaporation rate of volatile materials.Early in 20th century
The seventies, microcapsules technology started to process applied to the formulations of pesticide, the advantage based on microcapsule formulations itself, and Pesticidal products are micro-
The encapsulated preventive effect for having many advantages, such as to extend the lasting period, reduce environmental pollution, had.The method of Pesticidal products microencapsulation has
It is a variety of, wherein Simple coacervation is to keep wall material molten after flocculating agent is added after being dispersed therein core material using a kind of macromolecule wall material
Xie Du decline is precipitated from solution, and core material is embedded to form microcapsules, compares other such as in-situ polymerizations and collosol and gel
Microencapsulation Method, Simple coacervation is since technique and equipment requirement are simple, operating condition is mild, easy to control and load with higher
Medicine and release characteristics have been widely used at present in the microencapsulation of Pesticidal products, such as packet grain husk (Bao Ying, Zhang Guocai Dan Ning
Research [J] the Beijing Forestry University journal of poly- method preparation artemisiifolia extract microcapsules agent, 2013,35 (04): 101-105.) with
Gelatin is wall material, and using artemisiifolia extract as core material, using glutaraldehyde as curing agent, it is micro- to be prepared for artemisiifolia extract using Simple coacervation
Capsule powders, can influence to avoid external environment to artemisiifolia extract and decompose and even inactivate.
Solidify however, being often used toxic glutaraldehyde work during preparing pesticide micro capsule using Simple coacervation at present
Agent can generate certain harm to human body and natural environment.In addition, inventor has found in practical study, and not all
Agricultural chemical insecticide is all suitable for being prepared into microcapsules, and natural pyrethrin is a kind of compounding substances, (is removed by six kinds of chemical components
Worm chrysanthemum element I, pyrethrin II, II cinerin II I, II cinerin II II, II jasmolin II I and II jasmolin II II) composition, compared to general
Agricultural chemical insecticide, by the more demanding of its microencapsulation, the difference such as wall material, curing agent and its dosage, which is all likely to result in, naturally to be removed
The microencapsulation failure of worm pyrethroids influences microcapsules carrying drug ratio, performance and insecticidal effect.Therefore how Simple coacervation system is used
Standby environmentally friendly and function admirable natural pyrethrin microcapsules are one and need the problem of studying.
Summary of the invention
For the problems of the prior art, the present invention provides the side that a kind of Simple coacervation prepares natural pyrethrin microcapsules
Method, for the present invention using pure natural high molecular material gelatin as wall material, natural pyrethrin is core material, and glutamine transaminage is solidification
Agent, the polymer overmold natural pyrethrin core material for being generated gelatin through single aggregation using Simple coacervation, is successfully prepared
Pyrethrins microcapsule formulations, realize the microencapsulation of liquid pyrethrins, and the sustained release of effective component can effectively prevent deinsectization
Loss and decomposition of the pyrethroids in production, transportational process, improve its persistence in use, which was preparing
Journey does not use any organic solvent and toxic component, environmentally friendly, and the pyrethrins properties of microcapsules being prepared is stablized, and kills
Worm effect is good.
To realize the above technical purpose, the technical scheme is that
A kind of method that Simple coacervation prepares natural pyrethrin microcapsules, which comprises the steps of:
(a) it dissolves: gelatin particle is dissolved in the water to obtain mass percent concentration to be 0.1~6.0% gelatin solution；
(b) it emulsifies: adding pyrethrins after addition emulsifier for mixing in gelatin solution and stir to form uniformly mixing cream
Liquid；Wherein, the mass fraction of emulsifier is 0.1%~6.0% in mixed emulsion, and the mass ratio of natural pyrethrin and gelatin is
2:1~1:6；
(c) it agglomerates: dehydrated alcohol being added dropwise into mixed emulsion, formation condensation product between wall material is made to be adsorbed on pyrethrins table
Face, insulated and stirred 20min~3h at 25~60 DEG C；
(d) mixed emulsion after cohesion gelation: is cooled to 10 DEG C or less with ice-water bath；
(e) solidify: the pH of the mixed emulsion after cooling be adjusted to 5.0~8.0, be added TG enzyme stir 3 at 0~10 DEG C~
10h obtains microcapsule emulsion；Wherein, TG enzyme and gelatin mass ratio are 1:1~8:1；
(f) it post-processes: being freeze-dried after microcapsule emulsion is centrifugated supernatant, obtain target microcapsules.
Preferably, the mass percent concentration of gelatin solution is 0.5~3.0% in step (a).
Preferably, emulsifier is polysorbas20-80 in step (b), and emulsifier is 0.33% to the mass fraction of mixed emulsion
~3.0%.
Preferably, the mass ratio of natural pyrethrin and gelatin is 2:1~1:4 in step (b).
Preferably, in step c the additive amount of ethyl alcohol account for total system (mixed emulsion after adding ethyl alcohol) 30~
80wt.%.
Preferably, the TG enzyme and gelatin mass ratio being added in step (e) are 3:1~6:1.
Preferably, holding temperature is 30~40 DEG C in step (c), and soaking time is 0.5~2h.
Preferably, pH is adjusted to 6.0~7.0 in step (e).
Preferably, mixed emulsion pH is adjusted by using 10% sodium hydroxide solution in step e.
Using the natural pyrethrin microcapsules as made from claim 1~9 any the method.
Microcapsule formulations of the invention can be used in the sanitary insect pest such as prevention and treatment of mosquito, fly, screen-like mountain peak dung beetle, ant, be also used for
The control of insect on garden crop and lawn in garden is used in the livestocks such as pet and ox, sheep, can eliminate louse, flea etc. and post
It is infested.Meanwhile arranging pyrethrins microcapsules into the daily necessities such as clothes fabric, cosmetics, tool of camping, product can be made to have
There is continual and steady insect prevention characteristic and harm will not be generated to human body.In actually application, microcapsule formulations dosage can be according to specific
The content for being administered natural pyrethrin in object and drug used be adjusted.
From the above, it can be seen that the present invention has following advantages:
The present invention is using using pure natural high molecular material gelatin as wall material, natural pyrethrin is core material, and glutamine turns amine
Enzyme is curing agent, the polymer overmold natural pyrethrin core material for being generated gelatin through single aggregation using Simple coacervation, at
Function is prepared for pyrethrins microcapsule formulations, realizes the microencapsulation of liquid pyrethrins, the sustained release of effective component can be effective
Loss and decomposition of the pyrethrins in production, transportational process are prevented, its persistence in use, the microcapsules are improved
Any organic solvent and toxic component, environmentally friendly, the pyrethrins microcapsules being prepared are not used in preparation process
It can stablize, good disinsection effect.
Detailed description of the invention
Fig. 1 is natural pyrethrin microcapsules scanning electron microscope (SEM) photograph prepared by embodiment 1；
Fig. 2 is scanning electron microscope (SEM) photograph of the natural pyrethrin microcapsules in different storage times of the preparation of embodiment 2；
Fig. 3 is the carrying drug ratio versus time curve of natural pyrethrin microcapsules prepared by embodiment 2；
Fig. 4 is the DTA curve of natural pyrethrin microcapsules prepared by embodiment 3；
Fig. 5 is the DTG curve of natural pyrethrin microcapsules prepared by embodiment 3；
Appended drawing reference:
Specific embodiment
Below by examples of implementation, the characteristics of the present invention is further explained, but claim of the invention is not done any
It limits.
Embodiment 1
A kind of method that Simple coacervation prepares natural pyrethrin microcapsules, includes the following steps:
A. dissolve: the gelatin particle for weighing 0.5g, which is dissolved in 50ml deionized water, obtains gelatin solution；
B. it emulsifies: 0.5g polysorbas20-80,1500r/min high-speed stirred 3min being added in gelatin solution, adds 0.5g
(commercially available) stirring of pyrethrins forms uniform mixed emulsion；
C. it agglomerates: 50mL dehydrated alcohol being added dropwise into mixed emulsion, formation condensation product between wall material is made to be adsorbed on pyrethrins
Surface, insulated and stirred 1h at 40 DEG C；
D. gelation: heating source is closed, the mixed emulsion after cohesion is cooled to 4 DEG C with ice-water bath.
E. solidify: pH being adjusted to 6.0 by 10% sodium hydroxide solution of the mixed emulsion after cooling, 2.5g is added
TG enzyme (commercially available) stirs 6h at 4 DEG C, obtains microcapsule emulsion.
F. it post-processes: being freeze-dried for 24 hours after microcapsule emulsion is centrifugated supernatant, obtain the micro- glue of natural pyrethrin
Capsule.
Natural pyrethrin microcapsules obtained by the present embodiment are characterized using scanning electron microscope, as a result as shown in Figure 1, through
The average grain diameter for measuring natural pyrethrin microcapsules obtained by the present embodiment is 3.5 μm.
The carrying drug ratio for measuring natural pyrethrin microcapsules obtained by the present embodiment using high performance liquid chromatograph device is (i.e. natural
The mass percentage of pyrethrins) it is 34.4%.
Embodiment 2
A kind of method that Simple coacervation prepares natural pyrethrin microcapsules, includes the following steps:
A. it dissolves: weighing 1g gelatin particle and be dissolved in 50ml deionized water and obtain gelatin solution；
B. it emulsifies: 1g polysorbas20-80,1500r/min high-speed stirred 3min being added in gelatin solution, adds 1.25g
(commercially available) stirring of pyrethrins forms uniform mixed emulsion；
C. it agglomerates: 40mL dehydrated alcohol being added dropwise into mixed emulsion, formation condensation product between wall material is made to be adsorbed on pyrethrins
Surface, insulated and stirred 1.5h at 40 DEG C；
D. gelation: heating source is closed, the mixed emulsion after cohesion is cooled to 4 DEG C with ice-water bath.
E. solidify: pH being adjusted to 6.5 by 10% sodium hydroxide solution of the mixed emulsion after cooling, 4g TG is added
Enzyme (commercially available) stirs 5h at 4 DEG C, obtains microcapsule emulsion.
F. it post-processes: being freeze-dried for 24 hours after microcapsule emulsion is centrifugated supernatant, obtain the micro- glue of natural pyrethrin
Capsule.
Natural pyrethrin microcapsules obtained by the present embodiment are characterized using scanning electron microscope, the results showed that, naturally remove
Worm pyrethroids is successfully embedded, and the average grain diameter for being measured natural pyrethrin microcapsules obtained by the present embodiment is 4.7 μm.
The carrying drug ratio for measuring natural pyrethrin microcapsules obtained by the present embodiment using high performance liquid chromatograph device is (i.e. natural
The mass percentage of pyrethrins) it is 32.5%.
Embodiment 3
A kind of method that Simple coacervation prepares natural pyrethrin microcapsules, includes the following steps:
A. it dissolves: weighing 0.5g gelatin particle and be dissolved in 50ml deionized water and obtain gelatin solution；
B. it emulsifies: 0.6g polysorbas20-80,1500r/min high-speed stirred 3min being added in gelatin solution, adds 0.5g
(commercially available) stirring of pyrethrins forms uniform mixed emulsion；
C. it agglomerates: 40mL dehydrated alcohol being added dropwise into mixed emulsion, formation condensation product between wall material is made to be adsorbed on pyrethrins
Surface, insulated and stirred 40min at 40 DEG C；
D. gelation: heating source is closed, the mixed emulsion after cohesion is cooled to 4 DEG C with ice-water bath.
E. solidify: pH being adjusted to 7 by 10% sodium hydroxide solution of the mixed emulsion after cooling, 3g TG enzyme is added
(commercially available) stirs 7h at 4 DEG C, obtains microcapsule emulsion.
F. it post-processes: being freeze-dried for 24 hours after microcapsule emulsion is centrifugated supernatant, obtain the micro- glue of natural pyrethrin
Capsule.
Natural pyrethrin microcapsules obtained by the present embodiment are characterized using scanning electron microscope, the results showed that, naturally remove
Worm pyrethroids is successfully embedded；The average grain diameter for being measured natural pyrethrin microcapsules obtained by the present embodiment is 3.9 μm.
The carrying drug ratio for measuring natural pyrethrin microcapsules obtained by the present embodiment using high performance liquid chromatograph device is (i.e. natural
The mass percentage of pyrethrins) it is 30.8%.
Embodiment 4
A kind of method that Simple coacervation prepares natural pyrethrin microcapsules, includes the following steps:
A. it dissolves: weighing 0.25g gelatin particle and be dissolved in 50ml deionized water and obtain gelatin solution；
B. it emulsifies: 0.17g polysorbas20-80,1500r/min high-speed stirred 3min being added in gelatin solution, adds
(commercially available) stirring of 0.07g pyrethrins forms uniform mixed emulsion；
C. it agglomerates: 30mL dehydrated alcohol being added dropwise into mixed emulsion, formation condensation product between wall material is made to be adsorbed on pyrethrins
Surface, insulated and stirred 3h at 25 DEG C；
D. gelation: heating source is closed, the mixed emulsion after cohesion is cooled to 0 DEG C with ice-water bath.
E. solidify: pH being adjusted to 5 by 10% sodium hydroxide solution of the mixed emulsion after cooling, 0.25g TG is added
Enzyme (commercially available) stirs 10h at 0 DEG C, obtains microcapsule emulsion.
F. it post-processes: being freeze-dried for 24 hours after microcapsule emulsion is centrifugated supernatant, obtain the micro- glue of natural pyrethrin
Capsule.
Natural pyrethrin microcapsules obtained by the present embodiment are characterized using scanning electron microscope, the results showed that, naturally remove
Worm pyrethroids is successfully embedded；The average grain diameter for being measured natural pyrethrin microcapsules obtained by the present embodiment is 4.6 μm.
The carrying drug ratio for measuring natural pyrethrin microcapsules obtained by the present embodiment using high performance liquid chromatograph device is (i.e. natural
The mass percentage of pyrethrins) it is 32.7%.
Embodiment 5
A kind of method that Simple coacervation prepares natural pyrethrin microcapsules, includes the following steps:
A. it dissolves: weighing 1.5g gelatin particle and be dissolved in 50ml deionized water and obtain gelatin solution；
B. it emulsifies: 1.5g polysorbas20-80,1500r/min high-speed stirred 3min being added in gelatin solution, adds 0.9g
(commercially available) stirring of pyrethrins forms uniform mixed emulsion；
C. it agglomerates: 200mL dehydrated alcohol being added dropwise into mixed emulsion, formation condensation product between wall material is made to be adsorbed on pyrethrins
Surface, insulated and stirred 20min at 60 DEG C；
D. gelation: heating source is closed, the mixed emulsion after cohesion is cooled to 10 DEG C with ice-water bath.
E. solidify: pH being adjusted to 8 by 10% sodium hydroxide solution of the mixed emulsion after cooling, 4.5g TG is added
Enzyme (commercially available) stirs 3h at 10 DEG C, obtains microcapsule emulsion.
F. it post-processes: being freeze-dried for 24 hours after microcapsule emulsion is centrifugated supernatant, obtain the micro- glue of natural pyrethrin
Capsule.
Natural pyrethrin microcapsules obtained by the present embodiment are characterized using scanning electron microscope, the results showed that, naturally remove
Worm pyrethroids is successfully embedded, and the average grain diameter for being measured natural pyrethrin microcapsules obtained by the present embodiment is 4.1 μm.
The carrying drug ratio for measuring natural pyrethrin microcapsules obtained by the present embodiment using high performance liquid chromatograph device is (i.e. natural
The mass percentage of pyrethrins) it is 35.2%.
Embodiment 6
A kind of method that Simple coacervation prepares natural pyrethrin microcapsules, includes the following steps:
A. it dissolves: weighing 3g gelatin particle and be dissolved in 50ml deionized water and obtain gelatin solution；
B. it emulsifies: 3g polysorbas20-80,1500r/min high-speed stirred 3min being added in gelatin solution, adds 6g deinsectization
(commercially available) stirring of pyrethroids forms uniform mixed emulsion；
C. it agglomerates: 100mL dehydrated alcohol being added dropwise into mixed emulsion, formation condensation product between wall material is made to be adsorbed on pyrethrins
Surface, insulated and stirred 2h at 30 DEG C；
D. gelation: heating source is closed, the mixed emulsion after cohesion is cooled to 7 DEG C with ice-water bath；
E. solidify: pH being adjusted to 7 by 10% sodium hydroxide solution of the mixed emulsion after cooling, 18g TG enzyme is added
(commercially available) stirs 5h at 7 DEG C, obtains microcapsule emulsion；
F. it post-processes: being freeze-dried for 24 hours after microcapsule emulsion is centrifugated supernatant, obtain the micro- glue of natural pyrethrin
Capsule.
Natural pyrethrin microcapsules obtained by the present embodiment are characterized using scanning electron microscope, the results showed that, naturally remove
Worm pyrethroids is successfully embedded, and the average grain diameter for being measured natural pyrethrin microcapsules obtained by the present embodiment is 2.7 μm.
The carrying drug ratio for measuring natural pyrethrin microcapsules obtained by the present embodiment using high performance liquid chromatograph device is (i.e. natural
The mass percentage of pyrethrins) it is 29.7%.
Embodiment 7
A kind of method that Simple coacervation prepares natural pyrethrin microcapsules, includes the following steps:
A. it dissolves: weighing 0.1g gelatin particle and be dissolved in 50ml deionized water and obtain gelatin solution；
B. it emulsifies: 0.1g polysorbas20-80,1500r/min high-speed stirred 3min being added in gelatin solution, adds 0.2g
(commercially available) stirring of pyrethrins forms uniform mixed emulsion；
C. it agglomerates: 80mL dehydrated alcohol being added dropwise into mixed emulsion, formation condensation product between wall material is made to be adsorbed on pyrethrins
Surface, insulated and stirred 30min at 50 DEG C；
D. gelation: heating source is closed, the mixed emulsion after cohesion is cooled to 4 DEG C with ice-water bath；
E. solidify: pH being adjusted to 7 by 10% sodium hydroxide solution of the mixed emulsion after cooling, 0.8g TG is added
Enzyme (commercially available) stirs 7h at 4 DEG C, obtains microcapsule emulsion.
F. it post-processes: being freeze-dried for 24 hours after microcapsule emulsion is centrifugated supernatant, obtain the micro- glue of natural pyrethrin
Capsule.
Natural pyrethrin microcapsules obtained by the present embodiment are characterized using scanning electron microscope, the results showed that, naturally remove
Worm pyrethroids is successfully embedded, and the average grain diameter for being measured natural pyrethrin microcapsules obtained by the present embodiment is 3.3 μm.
The carrying drug ratio for measuring natural pyrethrin microcapsules obtained by the present embodiment using high performance liquid chromatograph device is (i.e. natural
The mass percentage of pyrethrins) it is 30.4%.
Comparative example 1:
A kind of method that Simple coacervation prepares natural pyrethrin microcapsules, includes the following steps:
A. dissolve: the gelatin particle for weighing 0.5g, which is dissolved in 50ml deionized water, obtains gelatin solution；
B. it emulsifies: 0.5g polysorbas20-80,1500r/min high-speed stirred 3min being added in gelatin solution, adds 1.5g
(commercially available) stirring of pyrethrins forms uniform mixed emulsion；
C. it agglomerates: 50mL dehydrated alcohol being added dropwise into mixed emulsion, formation condensation product between wall material is made to be adsorbed on pyrethrins
Surface, insulated and stirred 1h at 40 DEG C；
D. gelation: heating source is closed, the mixed emulsion after cohesion is cooled to 4 DEG C with ice-water bath.
E. solidify: pH being adjusted to 6.0 by 10% sodium hydroxide solution of the mixed emulsion after cooling, 0.25g is added
TG enzyme (commercially available) stirs 6h at 4 DEG C, obtains microcapsule emulsion.
F. it post-processes: being freeze-dried for 24 hours after microcapsule emulsion is centrifugated supernatant, obtain the micro- glue of natural pyrethrin
Capsule.Natural pyrethrin microcapsules obtained by the present embodiment are characterized using scanning electron microscope, the results showed that, natural pyrethrin
It is successfully embedded, the average grain diameter for being measured natural pyrethrin microcapsules obtained by the present embodiment is 2.4 μm.
The carrying drug ratio for measuring natural pyrethrin microcapsules obtained by the present embodiment using high performance liquid chromatograph device is (i.e. natural
The mass percentage of pyrethrins) it is 9.5%.
Comparative example 2:
A kind of method that Simple coacervation prepares natural pyrethrin microcapsules, includes the following steps:
A. dissolve: the gelatin particle for weighing 0.8g, which is dissolved in 50ml deionized water, obtains gelatin solution；
B. it emulsifies: 4g polysorbas20-80,1500r/min high-speed stirred 3min being added in gelatin solution, adds 5.2g and removes
(commercially available) stirring of worm pyrethroids forms uniform mixed emulsion；
C. it agglomerates: 100mL dehydrated alcohol being added dropwise into mixed emulsion, formation condensation product between wall material is made to be adsorbed on pyrethrins
Surface, insulated and stirred 1h at 40 DEG C；
D. gelation: heating source is closed, the mixed emulsion after cohesion is cooled to 4 DEG C with ice-water bath.
E. solidify: pH being adjusted to 6.0 by 10% sodium hydroxide solution of the mixed emulsion after cooling, 1.6g is added
TG enzyme (commercially available) stirs 6h at 4 DEG C, obtains microcapsule emulsion.
F. it post-processes: being freeze-dried for 24 hours after microcapsule emulsion is centrifugated supernatant, obtain the micro- glue of natural pyrethrin
Capsule.Natural pyrethrin microcapsules obtained by the present embodiment are characterized using scanning electron microscope, the results showed that, natural pyrethrin
It is successfully embedded, the average grain diameter for being measured natural pyrethrin microcapsules obtained by the present embodiment is 2.2 μm.
The carrying drug ratio for measuring natural pyrethrin microcapsules obtained by the present embodiment using high performance liquid chromatograph device is (i.e. natural
The mass percentage of pyrethrins) it is 8.0%.
Comparative example 3:
A kind of method that Simple coacervation prepares natural pyrethrin microcapsules, includes the following steps:
A. dissolve: the gelatin particle for weighing 1.5g, which is dissolved in 50ml deionized water, obtains gelatin solution；
B. it emulsifies: 0.04g polysorbas20-80,1500r/min high-speed stirred 3min being added in gelatin solution, adds
(commercially available) stirring of 1.5g pyrethrins forms uniform mixed emulsion；
C. it agglomerates: 20mL dehydrated alcohol being added dropwise into mixed emulsion, formation condensation product between wall material is made to be adsorbed on pyrethrins
Surface, insulated and stirred 1h at 40 DEG C；
D. gelation: heating source is closed, the mixed emulsion after cohesion is cooled to 4 DEG C with ice-water bath.
E. solidify: pH being adjusted to 7.0 by 10% sodium hydroxide solution of the mixed emulsion after cooling, 1.25g is added
TG enzyme (commercially available) stirs 6h at 4 DEG C, obtains microcapsule emulsion.
F. it post-processes: being freeze-dried for 24 hours after microcapsule emulsion is centrifugated supernatant, obtain the micro- glue of natural pyrethrin
Capsule.Natural pyrethrin microcapsules obtained by the present embodiment are characterized using scanning electron microscope, the results showed that, natural pyrethrin
It is successfully embedded, the average grain diameter for being measured natural pyrethrin microcapsules obtained by the present embodiment is 4.1 μm.
The carrying drug ratio for measuring natural pyrethrin microcapsules obtained by the present embodiment using high performance liquid chromatograph device is (i.e. natural
The mass percentage of pyrethrins) it is 7.6%.
In order to test the performance and insecticidal effect of natural pyrethrin microcapsules prepared by the present invention, inventor is further opened up
A series of experiments is opened, length is limited, and is only exemplified by the test example data for most representing power herein.
Test 1: toxotest of the microcapsules to pest
(1) the natural pyrethrin microcapsules for preparing embodiment 1 and each comparative example are respectively to Culex pipiens pallens (Culex
Pipiens pallens) and aedes albopictus (Aedes albopictus) 4 instar larvaes carry out toxotest, test method be children
Worm infusion process: take the medical fluid (acetone is solvent) of the configured good various concentration of 1mL that the burning for filling 149mL dechlorination tap water is added
In cup, stirred with glass bar.30 larvas chosen in advance in another cup together with 50mL water, all inject in above-mentioned beaker,
Total 200mL；It is handled with 1mL coordinative solvent (acetone) as control group；Recording the death toll of test worm afterwards for 24 hours, experiment is repeated 3 times,
Be averaged as a result, result (control group does not have insect abnormal death occur, illustrates above-mentioned environment as shown in Table 1 and Table 2
It is credible with the experimental data of condition；Due to the abnormal death of no insect, result Tables 1 and 2 is not listed in).
(2) natural pyrethrin microcapsules prepared by embodiment 1 and each comparative example are subjected to poison to aphid and mythimna separata respectively
Property test, using black bean aphid (aphid) and mythimna separata 3 age Initial instar larvae progress laboratory test.Test method is leaching worm leaf dipping method, examination
Testing condition is 25 DEG C, humidity 55%.Experimental procedure is as follows: with the water dispersion natural pyrethrin of the emulsifier containing a ten thousandth
Microcapsules are configured to the mother liquor that natural pyrethrin microcapsules concentration is 1000ppm.Mother liquor is diluted with the water containing emulsifier
Required concentration liquid is obtained, for handling aphid and mythimna separata, if distilled water is as blank control.Experiment is repeated 3 times, and is averaged
As a result.Specific processing method are as follows: for aphid, by ready-made Vicia faba seedling and 30 or so black bean aphids one being attached on seedling
It rises and is impregnated 5 seconds in medical fluid, taking-up is inserted in bean seedlings on the sponge of immersion after natural drying, glass tube on cover, normal to cultivate；It is right
In mythimna separata, ready-made fresh corn leaf section is impregnated 10 seconds in medical fluid, takes out naturally dry, put several pieces leaves in each culture dish
Piece, while 10 3 instar larvaes are accessed, it is enclosed in container.Investigation 24 hours as a result, check life or death borer population, and counted
Analysis, as a result (blank control group does not have insect abnormal death occur, illustrates above-mentioned environment and condition as shown in Table 1 and Table 2
Experimental data is credible；Due to the abnormal death of no insect, result Tables 1 and 2 is not listed in).
Table 1
| LC50(ppm) | Culex pipiens pallens larvae | Aedes Albopictus Larva | Mythimna separata | Aphid |
| Embodiment 1 | 0.133±0.004 | 0.265±0.017 | 20.14 | 1.59 |
| Embodiment 2 | 0.242±0.006 | 0.367±0.020 | 22.38 | 2.66 |
| Embodiment 3 | 0.328±0.008 | 0.459±0.021 | 24.62 | 3.82 |
| Comparative example 1 | 7.579±2.142 | 11.937±3.251 | 125.34 | 32.10 |
| Comparative example 2 | 10.254±2.422 | 15.288±3.482 | 135.51 | 38.52 |
| Comparative example 3 | 12.930±2.583 | 18.632±3.577 | 141.26 | 41.80 |
Table 2
As Tables 1 and 2 it is found that natural pyrethrin microcapsules obtained by Examples 1 to 3 keep 4 kinds of pest halves dead
Concentration be below 50g/mL, and so that 4 kinds of Mortality of insect is also only 54.86ppm up to 90% concentration maximum, and make 4 kinds of evils
The concentration of worm half death and make concentration of 4 kinds of Mortality of insect up to 90% well below comparative example 1, this illustrates institute of the present invention
Natural pyrethrin microcapsules obtained are to 4 kinds of pest toxicity with higher, and insecticidal effect is better than each comparative example；(evaluation
Canonical reference " Bioactivity of selected plant essential oils against the yellow
fever mosquito Aedes aegypti larvae”(Sen-Sung Cheng,et al.Bioresource
Technology, in August, 2003), specifically: LC50 > 100g/mL is inactive；50g/mL < LC50 < 100g/mL is to have work
Property；LC50 < 50g/mL is high activity.)
Test 2: the storage stability performance test of microcapsules under field conditions (factors)
It is light-exposed to be placed in room temperature in culture product for the natural pyrethrin microscapsule powder for taking appropriate embodiment 2 to prepare respectively
See in wind natural environment, take out and be measured after a period of time, the variation of its surface topography is observed by scanning electron microscope (SEM) photograph,
The loss amount of core material is judged by calculating carrying drug ratio, to judge its storage stability.As a result as shown in Fig. 2, wherein A is rigid
The microcapsules scanning electron microscope (SEM) photograph prepared, B are the microcapsules scanning electron microscope (SEM) photograph after storing 2 months.The form of microcapsules is certain
It is kept in time complete.
The carrying drug ratio of the natural pyrethrin microcapsules of different storage times is as shown in Figure 3.From the figure 3, it may be seen that microcapsules exist
It is not decomposed completely yet in natural conditions lower 2 months, illustrates that natural pyrethrin microcapsules provided by the invention have preferable storage
Deposit stability.
Test 3: the thermal stability test of microcapsules
Natural pyrethrin microcapsules prepared by 5~10mg embodiment 3 are taken to utilize Q600SDT in alumina crucible
Pattern synthesis thermal analyzer analyzes the thermal stability of microcapsules, and the temperature range of measurement is 50~600 DEG C, and 10 DEG C of heating rate/
Min, protective gas N2.Test result is as shown in Figure 4 and Figure 5, and wherein Fig. 4 is differential thermal analysis curve (DTA curve): (1) table
Show natural pyrethrin microcapsules, (2) indicate natural pyrethrin raw medicine；Fig. 5 is thermal gravimetric analysis curve (DTG curve): (1) table
Show natural pyrethrin microcapsules, (2) indicate natural pyrethrin raw medicine.DTA and DTG curve is compared it is found that pyrethrum
The thermal decomposition temperature of ester microcapsules starts at 250 DEG C or so, and biggest quality loss rate is respectively less than natural pyrethrin raw medicine, and
Thermal decomposition temperature is moved back, and illustrates that natural pyrethrin microcapsules have preferable thermal stability.
It is understood that being merely to illustrate the present invention above with respect to specific descriptions of the invention and being not limited to this
Technical solution described in inventive embodiments.Those skilled in the art should understand that still can be carried out to the present invention
Modification or equivalent replacement, to reach identical technical effect；As long as meet use needs, all protection scope of the present invention it
It is interior.
Claims (10)
1. a kind of method that Simple coacervation prepares natural pyrethrin microcapsules, which comprises the steps of:
(a) it dissolves: gelatin particle is dissolved in the water to obtain mass percent concentration to be 0.1~6.0% gelatin solution；
(b) it emulsifies: adding pyrethrins after addition emulsifier for mixing in gelatin solution and stir to form uniform mixed emulsion；Its
In, the mass fraction of emulsifier is 0.1%~6.0% in mixed emulsion, the mass ratio of natural pyrethrin and gelatin be 2:1~
1:6；
(c) it agglomerates: dehydrated alcohol being added dropwise into mixed emulsion, make to be formed between wall material condensation product and be adsorbed on pyrethrins surface, 25
Insulated and stirred 20min~3h at~60 DEG C；
(d) mixed emulsion after cohesion gelation: is cooled to 10 DEG C or less with ice-water bath；
(e) solidify: the pH of the mixed emulsion after cooling be adjusted to 5.0~8.0, TG enzyme is added in 0~10 DEG C of 3~10h of stirring,
Obtain microcapsule emulsion；Wherein, TG enzyme and gelatin mass ratio are 1:1~8:1；
(f) it post-processes: being freeze-dried after microcapsule emulsion is centrifugated supernatant, obtain target microcapsules.
2. the preparation method of the gelatin-gum arabic microcapsules of natural pyrethrin as described in claim 1, feature exist
In the mass percent concentration of gelatin solution is 0.5~3.0% in step (a).
3. the preparation method of the gelatin-gum arabic microcapsules of natural pyrethrin as described in claim 1, feature exist
In emulsifier is polysorbas20-80 in step (b), and emulsifier is 0.33%~3.0% to the mass fraction of mixed emulsion.
4. the preparation method of the gelatin-gum arabic microcapsules of natural pyrethrin as described in claim 1, feature exist
In the mass ratio of natural pyrethrin and gelatin is 2:1~1:4 in step (b).
5. the preparation method of the gelatin-gum arabic microcapsules of natural pyrethrin as described in claim 1, feature exist
In the additive amount of ethyl alcohol accounts for 30~80wt.% of total system in step c.
6. the preparation method of the gelatin-gum arabic microcapsules of natural pyrethrin as described in claim 1, feature exist
In the TG enzyme and gelatin mass ratio being added in step (e) are 3:1~6:1.
7. the preparation method of the gelatin-gum arabic microcapsules of natural pyrethrin as described in claim 1, feature exist
In holding temperature is 30~40 DEG C in step (c), and soaking time is 0.5~2h.
8. the preparation method of the gelatin-gum arabic microcapsules of natural pyrethrin as described in claim 1, feature exist
In pH is adjusted to 6.0~7.0 in step (e).
9. the preparation method of the gelatin-gum arabic microcapsules of natural pyrethrin as described in claim 1, feature exist
In mixed emulsion pH is adjusted in step e by using 10% sodium hydroxide solution.
10. using the natural pyrethrin microcapsules as made from claim 1~9 any the method.
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