CN104624129B - Preparation method based on Ionic Liquid as Surface Active Agent microemulsion system starch nano-microsphere - Google Patents
Preparation method based on Ionic Liquid as Surface Active Agent microemulsion system starch nano-microsphere Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
Abstract
The invention discloses the preparation method based on Ionic Liquid as Surface Active Agent microemulsion system starch nano-microsphere.The soluble starch that the method first will be dried adds in sodium hydroxide solution, and heating stirring is to being completely dissolved；The solution obtaining is cooled to room temperature, is subsequently added hexamethylene, Ionic Liquid as Surface Active Agent and cosurfactant and clarifies to solution, prepare Water-In-Oil ion liquid microemulsion.Adding epoxychloropropane, 40～60 DEG C of reaction 2～6h in the Water-In-Oil ion liquid microemulsion being formed, reaction treats that solution cools down after terminating, and adds absolute ethyl alcohol precipitation, centrifugal, removes supernatant, and sediment washs, and is dried, and i.e. obtains starch nano-microsphere.This starch nano-microsphere particle diameter is little, surface area big, has higher colloidal stability and excellent absorption property, in addition with good degradation property and biocompatibility performance, has important using value in terms of drug carrier material, cosmetics.
Description
Technical field
The present invention relates to the production method of converted starch, particularly relate to substitute with Ionic Liquid as Surface Active Agent
The surfactant of classical microemulsion system builds microemulsion, and with this microemulsion system as reaction system, makes
Prepare starch nano-microsphere with microemulsion cross-linking method.
Background technology
Drug delivery system is always the important development direction of pharmaceutical field, and it mainly includes medicine and carrier two
Part, in addition to medicine itself, drug carrier material also plays important role.With bioengineering skill
Developing rapidly of art, the macromolecular drug such as protein, polypeptide and gene continues to bring out, but these medicines are water-soluble
Property high, molecular weight is big, the permeability difference of medicine, and medicine is difficult to be absorbed by lipophilicity film, difficult by biology
Barrier.It in addition, these medicine stability differences, easy in inactivation, is very restricted in clinical practice.This kind of
The extensively application of medicine needs the carrier with good biocompatibility and biodegradable.
Starch, as a kind of natural macromolecular material, in early days not by as pharmaceutical carrier raw material, is mainly
It because its poorly water-soluble, is difficult to balling-up.It and native starch particles degradation speed is too fast, is difficult to be used as medicine and carries
Body.By crosslinked for starch or derivatives thereof balling-up, decapacitation meets outside the basic demand of pharmaceutical carrier, also has
Good biodegradability properties, good biocompatibility, degradation speed are adjustable, between nontoxic and medicine without mutual shadow
The advantages such as sound.If spherex is made nanoscale, owing to nano-starch grain diameter is very little, have huge
Big Free Surface, makes nano-starch particle have higher stability and excellent adsorptivity, can comparatively fast reach absorption
Balance, has through tissue space and by advantages such as cell absorption, targeting, sustained releases.
The preparation method of starch nano-microsphere includes Physical, chemical method and W/O microemulsion method.Physical method
Most widely used for ball grinding technique, but spherex particle diameter prepared by ball grinding technique is bigger and uneven, cost
Height, partial starch particle exterior surface ruptures, and hydrolysis and enzymolysis speed greatly speed up.Chemical method is generally used to system
Standby magnetic starch microcapsule.When W/O microemulsion method prepares spherex, spherex nucleation, growing up is all
Completing in small water droplet, drop size directly limits particle growth, obtains the spherex of size tunable.
Compared with the preparation method of other spherexs, it is simple that W/O microemulsion method has experimental provision, and operation is held
The feature such as easily, what is more important can be by changing microemulsion composition, and it is right that the microstructure of regulation microemulsion is come
The particle diameter of spherex, crystalline state, pattern are controlled.
Comprehensive domestic and international researcher uses the process that tradition W/O microemulsion prepares synthetic starch microballoon, exists
Risk of environmental pollution, starch granules particle diameter is big, and particle diameter distribution width, its medicine carrying, release effect are unsatisfactory
Problem so that it is clinical practice is very limited, one of them main cause is that technology of preparing is not mature enough.
There is a lot of real defect in existing W/O microemulsion reaction methods spherex: (1) microemulsion system.Tradition
Starch-containing microemulsion is unstable, and extremely sensitive to temperature, the change of temperature often brings the change of microstructure,
Being changed into O/W type from w/o type, sometimes even occurring being separated, this allows under this microemulsion system
Starch cross-linking reaction receives very big impact, finally affects product quality.(2) surfactant.Due to tradition
Technique is carried out in the basic conditions, this require the surfactant selected have very strong acid-fast alkali-proof,
Hydrolytic resistance and heat resistance.Want although Span and Tween class surfactant can meet to a certain extent
Ask, but owing to their emulsifying effectiveness is limited, compounding use complex process, this just makes the microemulsion of structure tie
Structure size is restricted, it is difficult to obtain the less spherex of particle diameter.Narrow size distribution is spherex
As an inspection target of pharmaceutical carrier, directly affect its stability and body absorption distribution thereof, be also to carry
High targeting and the key factor of controlled capability.Therefore, if can be by extending the selection model of microemulsion constituent
Enclose the micro emulsion technology of preparing improving spherex, improve environment friendly, it is thus achieved that divide close to nanoscale, particle diameter
The narrow spherex of cloth, improves the drugloading rate of microballoon, improves its Release Performance, will be greatly improved starch micro-
Ball is in the application in pharmaceutical carrier field.
Content of the invention
The present invention is directed to existing W/O microemulsion and prepare the problem that synthetic starch microballoon exists, use ionic liquid
Body replaces the surfactant in classical microemulsion system, constructs the Emulsions with good stability energy
Starch nano-microsphere is simultaneously prepared by this system by system.This method propose the new technology of green syt spherex,
Provide bigger development potentiality for the excellent drug carrier material of starch processability.
The purpose of the present invention is achieved through the following technical solutions:
Based on the preparation method of Ionic Liquid as Surface Active Agent microemulsion system starch nano-microsphere, including as
Lower step:
(1) by soluble starch raw material 50～70 DEG C of drying；
(2) with sodium hydroxide solution, step (1) gained soluble starch raw material is made into mass percent dense
Degree is the starch milk of 3～10%, in the stirring of 60～90 DEG C of heated at constant temperature to being completely dissolved；
(3) solution of step (2) gained is down to room temperature, is initially charged hexamethylene, is slow added into ion
Liquid-type surfactant C16The mixture of mimBr and cosurfactant n-butanol is clarified to solution, system
Obtain Water-In-Oil ion liquid microemulsion；The starch solution mass ratio of hexamethylene and step (2) gained be 9:1～
7:3；Ionic Liquid as Surface Active Agent C16MimBr and cosurfactant n-butanol 3:1～5:1 in mass ratio
Mixing, C16The quality summation of mimBr and n-butanol accounts for Water-In-Oil ion liquid microemulsion quality
20%～40%；
(4) in the Water-In-Oil ion liquid microemulsion of step (3) gained, epoxychloropropane is added, 40～
Reaction 2～6h is stirred at 70 DEG C；Epoxychloropropane consumption is described Water-In-Oil ion liquid microemulsion quality
0.5～3%；
(5) solution obtained by step (4) is cooled to room temperature, adds absolute ethyl alcohol to precipitate, so
Rear centrifugal, remove supernatant, the sediment absolute ethanol washing obtaining, be dried, obtain starch nano-microsphere.
In order to the present invention is better achieved, described drying refers to that control starch biodiversity content is less than 3%.
Step (3) described addition Ionic Liquid as Surface Active Agent C16MimBr and the positive fourth of cosurfactant
The mixture of alcohol to solution clarification refers to that in adition process, solution is slowly become clarification from muddiness, and without starch
Size separation goes out.
The described absolute ethanol washing of step (5) is not contain ion liquid type with absolute ethanol washing to sediment
Surfactant C16MimBr, hexamethylene, n-butanol and epoxychloropropane.
Described the centrifuging of step (5) centrifuges 20min for the rotating speed with 5000r/min.
The described drying of step (5) is that the sediment after washing is vacuum dried at 30～50 DEG C 12～48h.
The concentration of described sodium hydroxide solution is 2mol/L.
The present invention compared with prior art, has the advantage that and beneficial effect:
1st, Ionic Liquid as Surface Active Agent C used herein16MimBr, with conventional surfactant phase
Ratio, has stronger acid-fast alkali-proof, hydrolysis and heat resistance, and has good emulsifying effectiveness, can be fine
Ground participates in forming W/O microemulsion, and this microemulsion is clarified, transparent, and permanent placement will not be layered, and has good
Good stability, in beneficially follow-up cross-linking process, crosslinking agent and the interaction of starch molecule, improve reaction
Efficiency.
2nd, the present invention uses ion liquid microemulsion cross-linking method synthetic starch Nano microsphere, the method technique
Route is simple, reaction condition is gentle, and products obtained therefrom average grain diameter is little, can preferably be applied to field of medicaments.
Additionally, this invention uses Ionic Liquid as Surface Active Agent C16MimBr substitutes conventional surfactant, should
Surfactant is ionic liquid, and safety is nontoxic, harmless, will not impact environment.
3rd, starch nano-microsphere has good biocompatibility, biological degradability and adsorbs release performance,
Therefore field of medicaments can be applied to as pharmaceutical carrier；Starch nano-microsphere has the size of ultra micro, as
The natural cover for defense in human body can be passed through, by each organ of drug targeting to health during pharmaceutical carrier；Work as shallow lake
When powder is prepared as nanoparticle by intravenous injection, can be eliminated rapidly by the reticuloendothelial system (liver, spleen) of human body,
Therefore there is the good characteristic of passive target.
4th, nanoparticle has the features, the beneficially sustained release of medicine such as long circulating, stealth and stereoscopic stable in vivo
Effect and targeting positioning, can enter cyclic system by small intestine after polypeptide and protein drug-carrying nanometer particle are administered orally
System.
Brief description
Fig. 1 is the grain size distribution of the laser fineness gage detection of embodiment 6 starch nano-microsphere.
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment 6 starch nano-microsphere.
Specific implementation method
For being more fully understood that the present invention, below in conjunction with embodiment, the present invention is described further, inventor
To by further investigation and test, there are many successful embodiments, six concrete enforcements have been set forth below
Example, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
Soluble starch raw material is dried to moisture less than 3% by the first step at 50 DEG C；
Step (1) gained soluble starch raw material is made into quality hundred by second step 2mol/L NaOH
Proportion by subtraction concentration is the starch milk of 3%, in the stirring of 90 DEG C of heated at constant temperature to being completely dissolved；
The solution of step (2) gained is down to room temperature by the 3rd step, is initially charged hexamethylene, be slow added into from
Sub-liquid-type surfactant C16The mixture of mimBr and cosurfactant n-butanol is clarified to solution,
And separate out without starch granules, prepare Water-In-Oil ion liquid microemulsion；Hexamethylene and step (2) gained
Starch solution mass ratio is 7:3, Ionic Liquid as Surface Active Agent C16MimBr and the positive fourth of cosurfactant
Alcohol 3:1 in mass ratio mixes, and both quality summations account for the 20% of Water-In-Oil ion liquid microemulsion quality；
4th step adds epoxychloropropane in the Water-In-Oil ion liquid microemulsion of step (3) gained, and 50
Stirring reaction 4h at DEG C；Epoxychloropropane consumption is step (3) gained Water-In-Oil ion liquid microemulsion matter
The 0.5% of amount；
Solution obtained by step (4) is cooled to room temperature by the 5th step, adds absolute ethyl alcohol to precipitate,
It is then centrifuged for, remove supernatant, the sediment absolute ethanol washing obtaining, 40 DEG C of dry 36h, i.e. obtain
Obtain starch nano-microsphere.Through laser fineness gage detection, product average grain diameter is 68.5nm.
Embodiment 2
Soluble starch raw material is dried to moisture less than 3% by the first step at 60 DEG C；
Step (1) gained soluble starch raw material is made into quality hundred by second step 2mol/L NaOH
Proportion by subtraction concentration is the starch milk of 10%, in the stirring of 80 DEG C of heated at constant temperature to being completely dissolved；
The solution of step (2) gained is down to room temperature by the 3rd step, is initially charged hexamethylene, be slow added into from
Sub-liquid-type surfactant C16The mixture of mimBr and cosurfactant n-butanol is clarified to solution,
Prepare Water-In-Oil ion liquid microemulsion；Hexamethylene is 7:3 with the starch solution mass ratio of step (2) gained,
Ionic Liquid as Surface Active Agent C16MimBr mixes with cosurfactant n-butanol 4:1 in mass ratio,
Both quality summations account for the 30% of Water-In-Oil ion liquid microemulsion quality；
4th step adds epoxychloropropane in the Water-In-Oil ion liquid microemulsion of step (3) gained, and 70
Stirring reaction 2h at DEG C；Epoxychloropropane consumption is step (3) gained Water-In-Oil ion liquid microemulsion matter
The 1% of amount；
Solution obtained by step (4) is cooled to room temperature by the 5th step, adds absolute ethyl alcohol to precipitate,
It is then centrifuged for, remove supernatant, the sediment absolute ethanol washing obtaining, 50 DEG C of dry 12h, i.e. obtain
Obtain starch nano-microsphere.Through laser fineness gage detection, product average grain diameter is 84.3nm.
Embodiment 3
Soluble starch raw material is dried to moisture less than 3% by the first step at 70 DEG C；
Step (1) gained soluble starch raw material is made into quality hundred by second step 2mol/L NaOH
Proportion by subtraction concentration is the starch milk of 8%, in the stirring of 70 DEG C of heated at constant temperature to being completely dissolved；
The solution of step (2) gained is down to room temperature by the 3rd step, is initially charged hexamethylene, be slow added into from
Sub-liquid-type surfactant C16The mixture of mimBr and cosurfactant n-butanol is clarified to solution,
Prepare Water-In-Oil ion liquid microemulsion；Hexamethylene is 7:3 with the starch solution mass ratio of step (2) gained,
Ionic Liquid as Surface Active Agent C16MimBr mixes with cosurfactant n-butanol 5:1 in mass ratio,
Both quality summations account for the 40% of Water-In-Oil ion liquid microemulsion quality；
4th step adds epoxychloropropane in the Water-In-Oil ion liquid microemulsion of step (3) gained, and 60
Stirring reaction 3h at DEG C；Epoxychloropropane consumption is step (3) gained Water-In-Oil ion liquid microemulsion matter
The 2% of amount；
Solution obtained by step (4) is cooled to room temperature by the 5th step, adds absolute ethyl alcohol to precipitate,
It is then centrifuged for, remove supernatant, the sediment absolute ethanol washing obtaining, 30 DEG C of dry 48h, i.e. obtain
Obtain starch nano-microsphere.Through laser fineness gage detection, product average grain diameter is 91.4nm.
Embodiment 4
Soluble starch raw material is dried to moisture less than 3% by the first step at 60 DEG C；
Step (1) gained soluble starch raw material is made into quality hundred by second step 2mol/L NaOH
Proportion by subtraction concentration is the starch milk of 5%, in the stirring of 60 DEG C of heated at constant temperature to being completely dissolved；
The solution of step (2) gained is down to room temperature by the 3rd step, is initially charged hexamethylene, be slow added into from
Sub-liquid-type surfactant C16The mixture of mimBr and cosurfactant n-butanol is clarified to solution,
Prepare Water-In-Oil ion liquid microemulsion；Hexamethylene is 4:1 with the starch solution mass ratio of step (2) gained,
Ionic Liquid as Surface Active Agent C16MimBr mixes with cosurfactant n-butanol 5:1 in mass ratio, and two
The quality summation of person accounts for the 30% of Water-In-Oil ion liquid microemulsion quality；
4th step adds epoxychloropropane in the Water-In-Oil ion liquid microemulsion of step (3) gained, and 40
Stirring reaction 6h at DEG C；Epoxychloropropane consumption is step (3) gained Water-In-Oil ion liquid microemulsion matter
The 3% of amount；
Solution obtained by step (4) is cooled to room temperature by the 5th step, adds absolute ethyl alcohol to precipitate,
It is then centrifuged for, remove supernatant, the sediment absolute ethanol washing obtaining, 50 DEG C of dry 24h, i.e. obtain
Obtain starch nano-microsphere.Through laser fineness gage detection, product average grain diameter is 132.7nm.
Embodiment 5
Soluble starch raw material is dried to moisture less than 3% by the first step at 70 DEG C；
Step (1) gained soluble starch raw material is made into quality hundred by second step 2mol/L NaOH
Proportion by subtraction concentration is the starch milk of 8%, in the stirring of 90 DEG C of heated at constant temperature to being completely dissolved；
The solution of step (2) gained is down to room temperature by the 3rd step, is initially charged hexamethylene, be slow added into from
Sub-liquid-type surfactant C16The mixture of mimBr and cosurfactant n-butanol is clarified to solution,
Prepare Water-In-Oil ion liquid microemulsion；Hexamethylene is 9:1 with the starch solution mass ratio of step (2) gained,
Ionic Liquid as Surface Active Agent C16MimBr mixes with cosurfactant n-butanol 4:1 in mass ratio,
Both quality summations account for the 40% of Water-In-Oil ion liquid microemulsion quality；
4th step adds epoxychloropropane in the Water-In-Oil ion liquid microemulsion of step (3) gained, and 50
Stirring reaction 3h at DEG C；Epoxychloropropane consumption is step (3) gained Water-In-Oil ion liquid microemulsion matter
The 2% of amount；
Solution obtained by step (4) is cooled to room temperature by the 5th step, adds absolute ethyl alcohol to precipitate,
It is then centrifuged for, remove supernatant, the sediment absolute ethanol washing obtaining, 30 DEG C of dry 48h, i.e. obtain
Obtain starch nano-microsphere.Through laser fineness gage detection, product average grain diameter is 101.3nm.
Embodiment 6
Soluble starch raw material is dried to moisture less than 3% by the first step at 60 DEG C；
Step (1) gained soluble starch raw material is made into quality hundred by second step 2mol/L NaOH
Proportion by subtraction concentration is the starch milk of 5%, in the stirring of 80 DEG C of heated at constant temperature to being completely dissolved；
The solution of step (2) gained is down to room temperature by the 3rd step, is initially charged hexamethylene, is slow added into ion
Liquid-type surfactant C16The mixture of mimBr and cosurfactant n-butanol is clarified to solution, system
Standby Water-In-Oil ion liquid microemulsion；Hexamethylene is 4:1 with the starch solution mass ratio of step (2) gained,
Ionic Liquid as Surface Active Agent C16MimBr mixes with cosurfactant n-butanol 3:1 in mass ratio, and two
The quality summation of person accounts for the 30% of Water-In-Oil ion liquid microemulsion quality；
4th step adds epoxychloropropane in the Water-In-Oil ion liquid microemulsion of step (3) gained, and 50
Stirring reaction 4h at DEG C；Epoxychloropropane consumption is step (3) gained Water-In-Oil ion liquid microemulsion matter
The 2% of amount；
Solution obtained by step (4) is cooled to room temperature by the 5th step, adds absolute ethyl alcohol to precipitate,
It is then centrifuged for, remove supernatant, the sediment absolute ethanol washing obtaining, 50 DEG C of dry 48h, i.e. obtain
Obtain starch nano-microsphere.Through laser fineness gage detection, product average grain diameter is 95.3nm.
The grain size distribution of the present embodiment gained starch nano-microsphere is as shown in Figure 1.Weigh 0.1g sample in
In 100mL distilled water, ultrasonic disperse 10min, use Malvern laser fineness gage to measure starch nano
The particle diameter distribution of microballoon.Fig. 1 shows, the size distribution Relatively centralized of the present embodiment gained starch nano-microsphere,
Average grain diameter is 95.3nm.Therefore, illustrate that the present invention can be used for prepared sizes distribution and more concentrate and particle diameter
Less spherex.
The scanning electron microscope (SEM) photograph of the present embodiment gained starch nano-microsphere is as shown in Figure 2.Sample test uses FEI
Quanta 200 SEM of company, accelerating potential is 20KV.Fig. 2 shows, the present embodiment
Gained starch nano-microsphere is spheric granules, and particle is less.The wherein gathering of small part particle is due to model
De Huali and the existence of electrostatic attraction.Therefore, illustrate that the present invention can prepare the preferable starch of granule-morphology
Nano microsphere.
Embodiment the 1st, the 2nd, the 3rd, the 4th, the scanning electron microscope (SEM) photograph of 5 gained starch nano-microspheres and grain size distribution and figure
1st, Fig. 2 is similar, does not provides one by one.
Obtained by the present invention, product average grain diameter can reach below 150nm, and reason is ion liquid type table
Face activating agent C16MimBr has stronger acid-fast alkali-proof, hydrolysis and heat resistance, and has well emulsification
Effect, can participate in forming stable W/O ion liquid microemulsion well.Additionally, starch nano is micro-
Ball nucleation in ion liquid microemulsion drop, and constantly increasing, microemulsion droplets size limit starch
The size of Nano microsphere, is thus advantageous to the formation of the spherex that Size Distribution is narrower, particle diameter is less.
Owing to starch nano-microsphere has good biocompatibility, biological degradability and adsorbs release performance,
Therefore field of medicaments can be applied to as pharmaceutical carrier；Starch nano-microsphere has the size of ultra micro, as
The natural cover for defense in human body can be passed through, by each organ of drug targeting to health during pharmaceutical carrier；Work as shallow lake
When powder is prepared as nanoparticle by intravenous injection, can be eliminated rapidly by the reticuloendothelial system (liver, spleen) of human body,
Therefore there is the good characteristic of passive target；Additionally, nanoparticle has long circulating in vivo, stealthy and solid is steady
The feature, the beneficially slow releasing function of medicine and targeting positioning such as fixed, when polypeptide and protein drug-carrying nanometer particle quilt
The circulatory system can be entered by small intestine after Kou Fu.In sum, starch nano-microsphere obtained by the present invention can be made
It is preferably applied to field of medicaments for drug carrier material.
As described above, the present invention can preferably be realized.
Claims (7)
1. the preparation method based on Ionic Liquid as Surface Active Agent microemulsion system starch nano-microsphere, it is characterised in that comprise the steps:
(1) by soluble starch raw material 50～70 DEG C of drying；
(2) with sodium hydroxide solution, step (1) gained soluble starch raw material is made into the starch milk that mass percent concentration is 3～10%, in the stirring of 60～90 DEG C of heated at constant temperature to being completely dissolved；
(3) solution of step (2) gained is down to room temperature, is initially charged hexamethylene, be slow added into Ionic Liquid as Surface Active Agent C16The mixture of mimBr and cosurfactant n-butanol is clarified to solution, prepares Water-In-Oil ion liquid microemulsion；Hexamethylene is 9:1～7:3 with the starch solution mass ratio of step (2) gained；Ionic Liquid as Surface Active Agent C16MimBr mixes with cosurfactant n-butanol 3:1～5:1 in mass ratio, C16The quality summation of mimBr and n-butanol accounts for the 20%～40% of Water-In-Oil ion liquid microemulsion quality；
(4) in the Water-In-Oil ion liquid microemulsion of step (3) gained, add epoxychloropropane, at 40～70 DEG C, stir reaction 2～6h；Epoxychloropropane consumption is the 0.5～3% of described Water-In-Oil ion liquid microemulsion quality；
(5) solution obtained by step (4) is cooled to room temperature, adds absolute ethyl alcohol to precipitate, be then centrifuged for, remove supernatant, the sediment absolute ethanol washing obtaining, be dried, obtain starch nano-microsphere.
2. the preparation method based on Ionic Liquid as Surface Active Agent microemulsion system starch nano-microsphere according to claim 1, it is characterised in that: described drying refers to that control starch biodiversity content is less than 3%.
3. the preparation method based on Ionic Liquid as Surface Active Agent microemulsion system starch nano-microsphere according to claim 1, it is characterised in that: step (3) described addition Ionic Liquid as Surface Active Agent C16The mixture of mimBr and cosurfactant n-butanol to solution clarification refers to that in adition process, solution is slowly become clarification from muddiness, and separates out without starch granules.
4. the preparation method based on Ionic Liquid as Surface Active Agent microemulsion system starch nano-microsphere according to claim 1, it is characterised in that: the described absolute ethanol washing of step (5) is not contain Ionic Liquid as Surface Active Agent C with absolute ethanol washing to sediment16MimBr, hexamethylene, n-butanol and epoxychloropropane.
5. the preparation method based on Ionic Liquid as Surface Active Agent microemulsion system starch nano-microsphere according to claim 1, it is characterised in that: described the centrifuging of step (5) centrifuges 20min for the rotating speed with 5000r/min.
6. the preparation method based on Ionic Liquid as Surface Active Agent microemulsion system starch nano-microsphere according to claim 1, it is characterised in that: the described drying of step (5) is that the sediment after washing is vacuum dried at 30～50 DEG C 12～48h.
7. the preparation method based on Ionic Liquid as Surface Active Agent microemulsion system starch nano-microsphere according to claim 1, it is characterised in that: the concentration of described sodium hydroxide solution is 2mol/L.
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| CN105032224A (en) * | 2015-09-05 | 2015-11-11 | 侯颖 | Microemulsion preparing method |
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| CN109422817B (en) * | 2017-08-22 | 2020-11-06 | 中国石油化工股份有限公司 | Micron-sized crosslinked starch microspheres and preparation method and application thereof |
| CN109046791A (en) * | 2018-08-08 | 2018-12-21 | 山东科技大学 | A kind of ion liquid type micro emulsion collecting agent and its preparation method and application |
| CN110330014B (en) * | 2019-07-16 | 2022-07-08 | 兰州理工大学 | Preparation method of starch porous carbon microspheres for supercapacitor electrode material |
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