CN104624129A - Preparation method of starch nanometer microspheres based on ionic liquid-type surfactant microemulsion system - Google Patents
Preparation method of starch nanometer microspheres based on ionic liquid-type surfactant microemulsion system Download PDFInfo
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- 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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- 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 a preparation method of starch nanometer microspheres based on ionic liquid-type surfactant microemulsion system. The method comprises the following steps: firstly adding dried soluble starch into a sodium hydroxide solution and stirring and heating and stirring to be dissolved completely; cooling the obtained solution to room temperature and then adding cyclohexane, an ionic liquid-type surfactant and an auxiliary surfactant until the solution is clear, so as to prepare a water-in-oil ionic liquid microemulsion; adding epoxy chloropropane into the formed water-in-oil ionic liquid microemulsion to react at 40-60 DEG C for 2-6 hours, cooling the solution after completion of the reaction, adding absolute ethyl alcohol to deposit, centrifuging, removing supernate, washing deposits and drying to obtain the starch nanometer microspheres. The starch nanometer microspheres are small in particle sizes, large in surface areas, high in colloid stability and excellent in adsorption performance. Furthermore, the starch nanometer microspheres are also excellent in degradation performance and biocompatibility, so that the starch nanometer microspheres are applicable in fields of drug carrier materials and cosmetics.
Description
Technical field
The present invention relates to the production method of converted starch, refer to the surfactant structure microemulsion substituting classical microemulsion system with Ionic Liquid as Surface Active Agent especially, and be reaction system with this Emulsions, use microemulsion cross-linking method to prepare starch nano-microsphere.
Background technology
Drug delivery system is the important development direction of pharmaceutical field always, and it mainly comprises medicine and carrier two parts, and except medicine itself, drug carrier material also plays important role.Along with developing rapidly of biotechnology, the macromolecular drugs such as protein, polypeptide and gene continue to bring out, but the water-soluble height of these medicines, and molecular weight is large, and the permeability of medicine is poor, medicine not easily absorb by lipophilicity film, difficulty passes through biological barrier.In addition, these medicine stabilities are poor, and easy in inactivation is very restricted in clinical practice.The extensive use of this kind 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, mainly because its poorly water-soluble, not easily balling-up.And native starch particles degradation speed is too fast, be difficult to be used as pharmaceutical carrier.Starch or derivatives thereof is cross-linked balling-up, and decapacitation meets outside the basic demand of pharmaceutical carrier, also there is good biodegradability properties, good biocompatibility, degradation speed be adjustable, between nontoxic and medicine without the advantage such as influencing each other.If spherex is made nanoscale, because nano-starch grain diameter is very little, there is huge Free Surface, make nano-starch particle have higher stability and excellent adsorptivity, comparatively fast can reach adsorption equilibrium, to have through tissue space and by advantages such as Cell uptake, target, slowly-releasings.
The preparation method of starch nano-microsphere comprises Physical, chemical method and W/O microemulsion method.What physical method was most widely used is ball grinding technique, but spherex particle diameter prepared by ball grinding technique is larger and uneven, and cost is high, and partial starch particle exterior surface breaks, and hydrolysis and enzymolysis speed are accelerated greatly.Chemical method is generally used for preparing magnetic starch microcapsule.When W/O microemulsion method prepares spherex, spherex nucleation, growing up is all complete in small water droplet, and drop size directly limits particle growth, obtains the spherex of size tunable.Compared with the preparation method of other spherex, it is simple that W/O microemulsion method has experimental provision, the features such as processing ease, what is more important, by changing microemulsion composition, regulates the particle diameter of microstructure to spherex of microemulsion, crystalline state, pattern to control.
Comprehensive researcher both at home and abroad adopts traditional W/O microemulsion to prepare the process of synthetic starch microballoon, there is risk of environmental pollution, starch granules particle diameter is large, domain size distribution is wide, the problems such as its medicine carrying, release effect are unsatisfactory, its clinical practice is very limited, and 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.The starch-containing microemulsion of tradition is unstable, and extremely responsive to temperature, the change of temperature often brings the change of microstructure, O/W type is changed into from w/o type, sometimes even occur being separated, this just makes the starch cross-linking reaction under this microemulsion system receive very large impact, finally affects product quality.(2) surfactant.Because traditional handicraft is carried out in the basic conditions, this just requires that the surfactant selected has very strong acid-fast alkali-proof, hydrolytic resistance and heat resistance.Although Span and Tween class surfactant can meet the demands to a certain extent, because their emulsifying effectiveness is limited, composite operation is complicated, and this just makes the Sturctures of Microemulsions size of structure be restricted, and is difficult to obtain the less spherex of particle diameter.Narrow size distribution is the inspection target of spherex as pharmaceutical carrier, and directly affecting its stability and body absorption distribution thereof, is also the key factor improving targeting and controlled capability.Therefore, if the range of choice by expansion microemulsion constituent improves the micro emulsion technology of preparing of spherex, improve environment friendly, obtain the spherex close to nanoscale, narrow particle size distribution, improve the drugloading rate of microballoon, improve its Release Performance, will greatly improve the application of spherex in pharmaceutical carrier field.
Summary of the invention
The present invention is directed to existing W/O microemulsion and prepare synthetic starch microballoon Problems existing, adopt the surfactant that ionic liquid replaces in classical microemulsion system, construct have good stability can microemulsion system and prepare starch nano-microsphere by this system.This method propose the new technology of green syt spherex, for the drug carrier material that starch processability is excellent provides larger development potentiality.
Object 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, comprise the steps:
(1) by soluble starch raw material 50 ~ 70 DEG C of oven dry;
(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%, is stirred to 60 ~ 90 DEG C of heated at constant temperature and dissolves completely;
(3) solution of step (2) gained is down to room temperature, first adds cyclohexane, more slowly add Ionic Liquid as Surface Active Agent C
16the mixture of mimBr and cosurfactant n-butanol is clarified to solution, obtained Water-In-Oil ion liquid microemulsion; The starch solution mass ratio of cyclohexane and step (2) gained is 9:1 ~ 7:3; Ionic Liquid as Surface Active Agent C
16mimBr and cosurfactant n-butanol in mass ratio 3:1 ~ 5:1 mix, C
16the quality summation of mimBr and n-butanol accounts for 20% ~ 40% of oily bag ion liquid microemulsion quality;
(4) in the Water-In-Oil ion liquid microemulsion of step (3) gained, epoxychloropropane is added, stirring reaction 2 ~ 6h at 40 ~ 70 DEG C; Epoxychloropropane consumption is 0.5 ~ 3% of described Water-In-Oil ion liquid microemulsion quality;
(5) solution that step (4) obtains is cooled to room temperature, adds absolute ethyl alcohol and precipitate, then centrifugal, remove supernatant, the sediment absolute ethanol washing obtained, dry, obtain starch nano-microsphere.
In order to realize the present invention better, described oven dry refers to and controls starch biodiversity content lower than 3%.
Step adds Ionic Liquid as Surface Active Agent C described in (3)
16to solution clarification, the mixture of mimBr and cosurfactant n-butanol refers to that in adition process, solution slowly becomes clarification from muddiness, and separate out without starch granules.
Step (5) described absolute ethanol washing does not contain Ionic Liquid as Surface Active Agent C with absolute ethanol washing to sediment
16mimBr, cyclohexane, n-butanol and epoxychloropropane.
Step (5) described centrifugal be with the centrifugal 20min of the rotating speed of 5000r/min.
Step (5) described drying be by washing after sediment vacuum drying 12 ~ 48h at 30 ~ 50 DEG C.
The concentration of described sodium hydroxide solution is 2mol/L.
Compared with prior art, tool has the following advantages and beneficial effect in the present invention:
1, Ionic Liquid as Surface Active Agent C used herein
16mimBr, compared with conventional surfactant, there is stronger acid-fast alkali-proof, hydrolysis and heat resistance, and there is good emulsifying effectiveness, can participate in well forming W/O microemulsion, this microemulsion is clarified, transparent, permanent placement can not layering, has good stability, be conducive to the interaction of crosslinking agent and starch molecule in follow-up cross-linking process, improve reaction efficiency.
2, the present invention adopts ion liquid microemulsion cross-linking method synthetic starch Nano microsphere, and the method process route is simple, reaction condition is gentle, and products obtained therefrom average grain diameter is little, can be applied to field of medicaments preferably.In addition, this invention uses Ionic Liquid as Surface Active Agent C
16mimBr substitutes conventional surfactant, and this surfactant is ionic liquid, and safety is nontoxic, harmless, can not impact environment.
3, starch nano-microsphere has good biocompatibility, biological degradability and absorption release performance, therefore can be applied to field of medicaments as pharmaceutical carrier; Starch nano-microsphere has the size of ultra micro, as the natural cover for defense can passed through during pharmaceutical carrier in human body, by drug targeting to each organ of health; When starch is prepared into nanoparticle by intravenous injection, can be eliminated rapidly by the reticuloendothelial system of human body (liver, spleen), therefore there is the good characteristic of passive target.
4, nanoparticle has the features such as long circulating, stealth and stereoscopic stable in vivo, is conducive to slow releasing function and the target location of medicine, when polypeptide and protein drug-carrying nanometer particle enter the circulatory system by small intestine after oral.
Accompanying drawing explanation
Fig. 1 is the grain size distribution that the laser fineness gage of embodiment 6 starch nano-microsphere detects.
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment 6 starch nano-microsphere.
Specific implementation method
For understanding the present invention better; below in conjunction with embodiment, the present invention is described further; inventor is to by furtheing investigate and testing; there are many successful embodiments; enumerate six specific embodiments below, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
Soluble starch raw material is less than 3% 50 DEG C of oven dry to moistures by the first step;
Step (1) gained soluble starch raw material is made into the starch milk that mass percent concentration is 3% by second step 2mol/L NaOH, is stirred to dissolves completely 90 DEG C of heated at constant temperature;
The solution of step (2) gained is down to room temperature by the 3rd step, first adds cyclohexane, more slowly adds Ionic Liquid as Surface Active Agent C
16the mixture of mimBr and cosurfactant n-butanol is clarified to solution, and separates out without starch granules, prepares Water-In-Oil ion liquid microemulsion; The starch solution mass ratio of cyclohexane and step (2) gained is 7:3, Ionic Liquid as Surface Active Agent C
16mimBr and cosurfactant n-butanol in mass ratio 3:1 mix, and both quality summations account for 20% of oily bag ion liquid microemulsion quality;
4th step adds epoxychloropropane in the Water-In-Oil ion liquid microemulsion of step (3) gained, stirring reaction 4h at 50 DEG C; Epoxychloropropane consumption is 0.5% of step (3) gained Water-In-Oil ion liquid microemulsion quality;
The solution that step (4) obtains is cooled to room temperature by the 5th step, adds absolute ethyl alcohol and precipitates, then centrifugal, and remove supernatant, the sediment absolute ethanol washing obtained, 40 DEG C of dry 36h, namely obtain starch nano-microsphere.Detect through laser fineness gage, product average grain diameter is 68.5nm.
Embodiment 2
Soluble starch raw material is less than 3% 60 DEG C of oven dry to moistures by the first step;
Step (1) gained soluble starch raw material is made into the starch milk that mass percent concentration is 10% by second step 2mol/L NaOH, is stirred to dissolves completely 80 DEG C of heated at constant temperature;
The solution of step (2) gained is down to room temperature by the 3rd step, first adds cyclohexane, more slowly adds Ionic Liquid as Surface Active Agent C
16the mixture of mimBr and cosurfactant n-butanol is clarified to solution, prepares Water-In-Oil ion liquid microemulsion; The starch solution mass ratio of cyclohexane and step (2) gained is 7:3, Ionic Liquid as Surface Active Agent C
16mimBr and cosurfactant n-butanol in mass ratio 4:1 mix, and both quality summations account for 30% of oily bag ion liquid microemulsion quality;
4th step adds epoxychloropropane in the Water-In-Oil ion liquid microemulsion of step (3) gained, stirring reaction 2h at 70 DEG C; Epoxychloropropane consumption is 1% of step (3) gained Water-In-Oil ion liquid microemulsion quality;
The solution that step (4) obtains is cooled to room temperature by the 5th step, adds absolute ethyl alcohol and precipitates, then centrifugal, and remove supernatant, the sediment absolute ethanol washing obtained, 50 DEG C of dry 12h, namely obtain starch nano-microsphere.Detect through laser fineness gage, product average grain diameter is 84.3nm.
Embodiment 3
Soluble starch raw material is less than 3% 70 DEG C of oven dry to moistures by the first step;
Step (1) gained soluble starch raw material is made into the starch milk that mass percent concentration is 8% by second step 2mol/L NaOH, is stirred to dissolves completely 70 DEG C of heated at constant temperature;
The solution of step (2) gained is down to room temperature by the 3rd step, first adds cyclohexane, more slowly adds Ionic Liquid as Surface Active Agent C
16the mixture of mimBr and cosurfactant n-butanol is clarified to solution, prepares Water-In-Oil ion liquid microemulsion; The starch solution mass ratio of cyclohexane and step (2) gained is 7:3, Ionic Liquid as Surface Active Agent C
16mimBr and cosurfactant n-butanol in mass ratio 5:1 mix, and both quality summations account for 40% of oily bag ion liquid microemulsion quality;
4th step adds epoxychloropropane in the Water-In-Oil ion liquid microemulsion of step (3) gained, stirring reaction 3h at 60 DEG C; Epoxychloropropane consumption is 2% of step (3) gained Water-In-Oil ion liquid microemulsion quality;
The solution that step (4) obtains is cooled to room temperature by the 5th step, adds absolute ethyl alcohol and precipitates, then centrifugal, and remove supernatant, the sediment absolute ethanol washing obtained, 30 DEG C of dry 48h, namely obtain starch nano-microsphere.Detect through laser fineness gage, product average grain diameter is 91.4nm.
Embodiment 4
Soluble starch raw material is less than 3% 60 DEG C of oven dry to moistures by the first step;
Step (1) gained soluble starch raw material is made into the starch milk that mass percent concentration is 5% by second step 2mol/L NaOH, is stirred to dissolves completely 60 DEG C of heated at constant temperature;
The solution of step (2) gained is down to room temperature by the 3rd step, first adds cyclohexane, more slowly adds Ionic Liquid as Surface Active Agent C
16the mixture of mimBr and cosurfactant n-butanol is clarified to solution, prepares Water-In-Oil ion liquid microemulsion; The starch solution mass ratio of cyclohexane and step (2) gained is 4:1, Ionic Liquid as Surface Active Agent C
16mimBr and cosurfactant n-butanol in mass ratio 5:1 mix, and both quality summations account for 30% of oily bag ion liquid microemulsion quality;
4th step adds epoxychloropropane in the Water-In-Oil ion liquid microemulsion of step (3) gained, stirring reaction 6h at 40 DEG C; Epoxychloropropane consumption is 3% of step (3) gained Water-In-Oil ion liquid microemulsion quality;
The solution that step (4) obtains is cooled to room temperature by the 5th step, adds absolute ethyl alcohol and precipitates, then centrifugal, and remove supernatant, the sediment absolute ethanol washing obtained, 50 DEG C of dry 24h, namely obtain starch nano-microsphere.Detect through laser fineness gage, product average grain diameter is 132.7nm.
Embodiment 5
Soluble starch raw material is less than 3% 70 DEG C of oven dry to moistures by the first step;
Step (1) gained soluble starch raw material is made into the starch milk that mass percent concentration is 8% by second step 2mol/L NaOH, is stirred to dissolves completely 90 DEG C of heated at constant temperature;
The solution of step (2) gained is down to room temperature by the 3rd step, first adds cyclohexane, more slowly adds Ionic Liquid as Surface Active Agent C
16the mixture of mimBr and cosurfactant n-butanol is clarified to solution, prepares Water-In-Oil ion liquid microemulsion; The starch solution mass ratio of cyclohexane and step (2) gained is 9:1, Ionic Liquid as Surface Active Agent C
16mimBr and cosurfactant n-butanol in mass ratio 4:1 mix, and both quality summations account for 40% of oily bag ion liquid microemulsion quality;
4th step adds epoxychloropropane in the Water-In-Oil ion liquid microemulsion of step (3) gained, stirring reaction 3h at 50 DEG C; Epoxychloropropane consumption is 2% of step (3) gained Water-In-Oil ion liquid microemulsion quality;
The solution that step (4) obtains is cooled to room temperature by the 5th step, adds absolute ethyl alcohol and precipitates, then centrifugal, and remove supernatant, the sediment absolute ethanol washing obtained, 30 DEG C of dry 48h, namely obtain starch nano-microsphere.Detect through laser fineness gage, product average grain diameter is 101.3nm.
Embodiment 6
Soluble starch raw material is less than 3% 60 DEG C of oven dry to moistures by the first step;
Step (1) gained soluble starch raw material is made into the starch milk that mass percent concentration is 5% by second step 2mol/L NaOH, is stirred to dissolves completely 80 DEG C of heated at constant temperature;
The solution of step (2) gained is down to room temperature by the 3rd step, first adds cyclohexane, more slowly adds Ionic Liquid as Surface Active Agent C
16the mixture of mimBr and cosurfactant n-butanol is clarified to solution, prepares Water-In-Oil ion liquid microemulsion; The starch solution mass ratio of cyclohexane and step (2) gained is 4:1, Ionic Liquid as Surface Active Agent C
16mimBr and cosurfactant n-butanol in mass ratio 3:1 mix, and both quality summations account for 30% of oily bag ion liquid microemulsion quality;
4th step adds epoxychloropropane in the Water-In-Oil ion liquid microemulsion of step (3) gained, stirring reaction 4h at 50 DEG C; Epoxychloropropane consumption is 2% of step (3) gained Water-In-Oil ion liquid microemulsion quality;
The solution that step (4) obtains is cooled to room temperature by the 5th step, adds absolute ethyl alcohol and precipitates, then centrifugal, and remove supernatant, the sediment absolute ethanol washing obtained, 50 DEG C of dry 48h, namely obtain starch nano-microsphere.Detect through laser fineness gage, product average grain diameter is 95.3nm.
The grain size distribution of the present embodiment gained starch nano-microsphere as shown in Figure 1.Take 0.1g sample in 100mL distilled water, ultrasonic disperse 10min, use Malvern laser fineness gage to measure the domain size distribution of starch nano-microsphere.Fig. 1 shows, the size distribution Relatively centralized of the present embodiment gained starch nano-microsphere, and average grain diameter is 95.3nm.Therefore, illustrate that the present invention can be used for prepared sizes distribution and comparatively concentrate and the less spherex of particle diameter.
The scanning electron microscope (SEM) photograph of the present embodiment gained starch nano-microsphere as shown in Figure 2.Sample test uses Quanta 200 SEM of FEI Co., and accelerating potential is 20KV.Fig. 2 shows, and the present embodiment gained starch nano-microsphere is spheric granules, and particle is less.Wherein the gathering of small part particle is the existence due to Van der Waals force and electrostatic attraction.Therefore, illustrate that the present invention can prepare the good starch nano-microsphere of granule-morphology.
The scanning electron microscope (SEM) photograph of embodiment 1,2,3,4,5 gained starch nano-microsphere is similar to Fig. 1, Fig. 2 with grain size distribution, does not provide one by one.
Obtained by the present invention, product average grain diameter can reach below 150nm, and reason is Ionic Liquid as Surface Active Agent C
16mimBr has stronger acid-fast alkali-proof, hydrolysis and heat resistance, and has good emulsifying effectiveness, can participate in well forming stable W/O ion liquid microemulsion.In addition, starch nano-microsphere is nucleation in ion liquid microemulsion drop, and constantly increases, the size that size limit starch nano-microsphere of microemulsion droplets, is therefore conducive to the formation of the spherex that Size Distribution is narrower, particle diameter is less.
Because starch nano-microsphere has good biocompatibility, biological degradability and absorption 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 can passed through during pharmaceutical carrier in human body, by drug targeting to each organ of health; When starch is prepared into nanoparticle by intravenous injection, can be eliminated rapidly by the reticuloendothelial system of human body (liver, spleen), therefore there is the good characteristic of passive target; In addition, nanoparticle has the features such as long circulating, stealth and stereoscopic stable in vivo, is conducive to slow releasing function and the target location of medicine, when polypeptide and protein drug-carrying nanometer particle enter the circulatory system by small intestine after oral.In sum, starch nano-microsphere obtained by the present invention can be applied to field of medicaments preferably as drug carrier material.
As mentioned above, the present invention can be realized preferably.
Claims (7)
1., based on the preparation method of Ionic Liquid as Surface Active Agent microemulsion system starch nano-microsphere, it is characterized in that comprising the steps:
(1) by soluble starch raw material 50 ~ 70 DEG C of oven dry;
(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%, is stirred to 60 ~ 90 DEG C of heated at constant temperature and dissolves completely;
(3) solution of step (2) gained is down to room temperature, first adds cyclohexane, more slowly add Ionic Liquid as Surface Active Agent C
16the mixture of mimBr and cosurfactant n-butanol is clarified to solution, obtained Water-In-Oil ion liquid microemulsion; The starch solution mass ratio of cyclohexane and step (2) gained is 9:1 ~ 7:3; Ionic Liquid as Surface Active Agent C
16mimBr and cosurfactant n-butanol in mass ratio 3:1 ~ 5:1 mix, C
16the quality summation of mimBr and n-butanol accounts for 20% ~ 40% of oily bag ion liquid microemulsion quality;
(4) in the Water-In-Oil ion liquid microemulsion of step (3) gained, epoxychloropropane is added, stirring reaction 2 ~ 6h at 40 ~ 70 DEG C; Epoxychloropropane consumption is 0.5 ~ 3% of described Water-In-Oil ion liquid microemulsion quality;
(5) solution that step (4) obtains is cooled to room temperature, adds absolute ethyl alcohol and precipitate, then centrifugal, remove supernatant, the sediment absolute ethanol washing obtained, dry, 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, is characterized in that: described oven dry refers to and controls starch biodiversity content lower than 3%.
3. the preparation method based on Ionic Liquid as Surface Active Agent microemulsion system starch nano-microsphere according to claim 1, is characterized in that: step adds Ionic Liquid as Surface Active Agent C described in (3)
16to solution clarification, the mixture of mimBr and cosurfactant n-butanol refers to that in adition process, solution slowly becomes clarification from muddiness, and separate 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, is characterized in that: step (5) described absolute ethanol washing does not contain Ionic Liquid as Surface Active Agent C with absolute ethanol washing to sediment
16mimBr, cyclohexane, 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, is characterized in that: step (5) is described centrifugal for the centrifugal 20min of the rotating speed of 5000r/min.
6. the preparation method based on Ionic Liquid as Surface Active Agent microemulsion system starch nano-microsphere according to claim 1, is characterized in that: step (5) described drying be by washing after sediment vacuum drying 12 ~ 48h at 30 ~ 50 DEG C.
7. the preparation method based on Ionic Liquid as Surface Active Agent microemulsion system starch nano-microsphere according to claim 1, is characterized in that: the concentration of described sodium hydroxide solution is 2mol/L.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105032224A (en) * | 2015-09-05 | 2015-11-11 | 侯颖 | Microemulsion preparing method |
| 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 |
| CN109266318A (en) * | 2017-07-18 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of water-base drilling fluid thickening extracting and cutting agent resistant to high temperatures and preparation method thereof and drilling fluid |
| CN109422817A (en) * | 2017-08-22 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of micron-level crosslinked spherex and its preparation method and application |
| CN110330014A (en) * | 2019-07-16 | 2019-10-15 | 兰州理工大学 | The preparation method of starch porous carbon microsphere for electrode material for super capacitor |
| CN110387050A (en) * | 2019-08-21 | 2019-10-29 | 徐州生物工程职业技术学院 | The method of starch nano-microsphere is prepared in alkali ionic liquid microemulsion system |
| CN115058239A (en) * | 2022-06-22 | 2022-09-16 | 中国石油大学(华东) | Ionic liquid microemulsion thickened oil modifying viscosity reducer and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110230343A1 (en) * | 2008-10-24 | 2011-09-22 | Basf Se | Method for the Manufacture of Microparticles Comprising an Effect Substance |
| CN102225341A (en) * | 2011-04-26 | 2011-10-26 | 山东大学 | Method for preparing hierarchical structure bismuth oxybromide hollow microsphere photocatalysis material |
| CN103007847A (en) * | 2012-12-20 | 2013-04-03 | 华南理工大学 | Magnetic nanoparticle-based immobilized laccase and ionic liquid composite particle and application thereof |
| CN103100358A (en) * | 2012-12-20 | 2013-05-15 | 华南理工大学 | Magnetic nanometer ion liquid composite particles as well as preparation method and application thereof |
| CN103435706A (en) * | 2013-08-23 | 2013-12-11 | 华南理工大学 | Preparation method of starch nanoparticles |
-
2015
- 2015-01-08 CN CN201510009941.6A patent/CN104624129B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110230343A1 (en) * | 2008-10-24 | 2011-09-22 | Basf Se | Method for the Manufacture of Microparticles Comprising an Effect Substance |
| CN102225341A (en) * | 2011-04-26 | 2011-10-26 | 山东大学 | Method for preparing hierarchical structure bismuth oxybromide hollow microsphere photocatalysis material |
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