CN105885069A - Method for preparing starch nano-microsphere in basic ionic liquid micro-emulsion system - Google Patents
Method for preparing starch nano-microsphere in basic ionic liquid micro-emulsion system Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a method for preparing starch nano-microspheres in a basic ionic liquid micro-emulsion system. The method comprises the following steps of synthetizing ionic liquid [C3OHmim] Ac through a two-step method; adding dried starch raw materials into the [C3OHmim] Ac until completely dissolving the starch; then adding cyclohexane, a surface active agent and cosurfactant; preparing an ionic liquid-in-oil micro-emulsion; adding cross-linking agent epoxy chloropropane; after reacting, obtaining the starch nano-microspheres through cooling, drying and other processing. According to the method for preparing the starch nano-microspheres in the basic ionic liquid micro-emulsion system provided by the invention, the particle sizes and the shapes of the nano-microspheres can be well controlled, the nano-microspheres are ensured to have favorable dispersion stability and adsorbability, meanwhile, the starch nano-microspheres are smaller in particle sizes and concentrated in distribution, have favorable biocompatibility and degradability, in addition, cannot produce antigenicity in vivo, and can be used as carriers of small molecular substances such as medicines and essences and flavors so as to be widely applied to the fields of medicines and food.
Description
Technical field
The present invention relates to the production method of modified starch, particularly relate to a kind of alkali ionic liquid Emulsions
The method preparing starch nano-microsphere in system, specifically refers to synthesize a kind of novel alkaline ionic liquid, in order to molten
Solve starch, and replace the polarity phase in classical microemulsion, build ion liquid microemulsion, and at this microemulsion
Synthetic starch Nano microsphere in system.
Background technology
Starch is that one is passed through α-Isosorbide-5-Nitrae glycosidic bond and α-1 by D-Glucose unit, and 6 glycosidic bonds are formed by connecting
Natural polymer, there is the features such as degradability, nontoxic and recyclability.Form sediment as one
Powder derivant, spherex because of its preferable biocompatibility, nontoxic, storage stability, degradation speed can
Control property and medicine is had the advantages such as certain targeting and be extensively used as pharmaceutical carrier and adsorbent should
It is used in the fields such as medicament slow release, targeted therapy and nasal-cavity administration, becomes the focus of people's research.Work as shallow lake
After the size of powder microsphere reaches micron level and Nano grade, its bulk effect and skin effect then occur very
Big change.The specific surface area of microsphere increases, and stability of solution significantly improves, and absorbability and surface group are dense
Degree all becomes big, can carry the drug molecule of different structure and performance.The microsphere obtained after crosslinked can be significantly
Improve Drug loading capacity, can keep the long period mainly due to its skeleton, thus effectively extend drug release
Time.
Prepare the method for spherex at present and mainly have following three kinds of methods: (1) Physical.Prepare starch micro-
The Main physical method of ball is ball grinding technique, abrading-ball extruded starch granule in water or alcohol solvent, thus
Destroy starch molecular structure and obtain the uneven little granule of size.This microsphere surface is coarse, and size inequality is also
And structure is insecure is easily broken.(2) chemical coprecipitation.The method is continuously to be added by non-solvent
Enter to dissolve in the weak solution of starch, be stirred continuously and make spherex separate out, be mostly used for magnetic starch microcapsule
Preparation.(3) reverse microemulsion process.The most most widely used method preparing spherex is reverse microemulsion
Liquid method.Owing to the formation of microsphere completes in microemulsion drop reactor, droplet size limits microsphere
Growing up of grain, therefore the size by controlling microemulsion can obtain the spherex of specific dimensions.
The spherex that the most both at home and abroad prepared by the W/O microemulsion system of research often occurs that particle diameter is distributed not
Uniformly, particle size is relatively big, the phenomenon that its medicine carrying drug release process is unsatisfactory, has had a strong impact on microsphere doctor
Application on medicine biological industry.Traditional W/O microemulsion method is prepared spherex and be there is a lot of defect: (1)
Microemulsion system.Classical microemulsion drips particle diameter very greatly, and the size of the spherex prepared would generally reach micron
Rank；Secondly classical microemulsion system is the most sensitive to temperature, and the change of temperature can cause Sturctures of Microemulsions
Change, even can cause separated.(2) polarity selects mutually.The polarity of tradition W/O microemulsion mostly is molten mutually
Solving the alkali liquor of starch, starch material mostly also is soluble starch, so greatly limit the utilization of raw material, with
Time environment is also resulted in certain pollution, the spherex cross-linking preparation under this system shows bigger grain
Footpath, assembles pockets of phenomenon.Therefore, in order to overcome tradition W/O microemulsion to prepare lacking of spherex existence
Outside Xianing, ion liquid microemulsion is also used to prepare spherex.Although at existing ion liquid microemulsion
System can be prepared and be evenly distributed, the starch nano-microsphere that particle size is less, but due to expensive
Ionic liquid make starch nano-microsphere production industrially have certain limitation, strongly limit shallow lake
The application of powder microsphere, and starch nano-microsphere agglomeration prepared by existing method is serious, poor dispersion.
Summary of the invention
The present invention is directed to problem present in current starch nano-microsphere building-up process, it is provided that a kind of alkali ion
The method preparing starch nano-microsphere in liquid micro liquid system, the starch nano-microsphere particle diameter of preparation is little, point
Dissipate good.
The present invention synthesizes a kind of novel ion liquid in order to dissolve starch, and replaces the polarity in classical microemulsion
Build ion liquid microemulsion mutually and carry out synthetic starch Nano microsphere.This method provide a kind of novel alkaline from
The synthetic method of sub-liquid, in order to dissolve starch and to replace the polarity in classical microemulsion to build optical lens mutually
Ion liquid microemulsion system bright, that have good stability.Can prepare under this system that particle diameter is little, good dispersion
Starch nano-microsphere, provide a new technology for synthetic starch Nano microsphere, be medicine, food simultaneously
The development of carrier material provides a more preferable development prospect.
The purpose of the present invention is achieved through the following technical solutions:
The method preparing starch nano-microsphere in alkali ionic liquid microemulsion system, comprises the following steps:
(1) be 1:(1.1～1.5 by mol ratio) N-Methylimidazole. and trimethylene chlorohydrin add in container,
Under nitrogen protective condition, obtain thick product 1 60～80 DEG C of reacting by heating；Thick product 1 passes through washing,
Stand, separatory, be dried, obtain intermediate product [C3OHmim]Cl；
(2) with methanol as solvent, be 1:(1.2～1.5 by mol ratio) [C3OHmim] Cl and potassium acetate
Being dissolved in methanol, at ambient temperature after reaction 24～36h, sucking filtration removes solid content, and rotary evaporation obtains
To thick product 2；Thick product 2 is washed by ether, is dried, obtains object ion liquid [C3OHmim]Ac；
(3) starch material is dried under the conditions of 50～70 DEG C；
(4) with ionic liquid [C3OHmim] starch of step (3) gained is made into mass content and is by Ac
2～the starch milk of 5%, under the protection of nitrogen, under the conditions of 80～100 DEG C, stir 2～5h；
(5) step (4) gained solution is down to room temperature, adds hexamethylene, be slow added into surface activity
Agent TX-100 and cosurfactant n-butyl alcohol, prepare oil bag ion liquid microemulsion；
(6) in the oily bag ion liquid microemulsion of step (5) gained, addition accounts for microemulsion quality 0.5～3%
Epoxychloropropane, under the conditions of 40～60 DEG C react 3～5h；
(7) step (6) gained solution is cooled down, add dehydrated alcohol and precipitate, centrifugal, remove molten
Liquid, gained precipitate absolute ethanol washing, it is dried, obtains starch nano-microsphere.
In order to the present invention is better achieved, it is preferable that the described thick product 1 of step (1) through washing be by
Thick product 1 and ethyl acetate washing are (1～1.5) according to mass ratio: carry out in 1 addition separatory funnel；Wash
Wash, stand, separatory repeats 2-4 time.
Preferably, described being dried of step (1) refers to that the sample after washing being separated is dried at 50～80 DEG C
24～36h.
Preferably, the described thick product of step (2) 2 by ether washing be mass ratio be (0.8～1.2): 1
Ether and thick product 2 add conical flask is stirred washing, be filtered to remove solid content, rotary evaporation removes
Remove ether；So repeat 2-4 time；Described being dried of step (2) is to be dried 24～36h under the conditions of 45～65 DEG C.
Preferably, step (3) described starch material is ocentyl succinic corn starch, octenyl succinic
Acid potato starch, ocentyl succinic tapioca, ocentyl succinic wheaten starch or octenyl succinic
Acid waxy corn starch.
Preferably, the substitution value of described starch material is 0.01～0.03.
Preferably, step (3) described drying refers to control starch biodiversity content less than 3%.
Preferably, step (5) described oil bag ion liquid microemulsion is that hexamethylene forms sediment with step (4) gained
Powder solution quality is than being (5～9): 1；Surfactant TX-100 and cosurfactant n-butyl alcohol are by quality
Percentage ratio (1～3): 1 mixture, the thick product of surfactant accounts for the quality summation of cosurfactant
The 30～50% of whole microemulsion quality；
Preferably, step (7) described absolute ethanol washing is with the ion in dehydrated alcohol eccysis precipitate
Liquid, hexamethylene, TX-100, n-butyl alcohol and epoxychloropropane.
Preferably, the described starch nano-microsphere being dried after referring to washing of step (7) is placed in 40～60 DEG C
Under be dried 24～36h.
The present invention compared with prior art, has the advantage that and beneficial effect:
1, the present invention is dripped as reaction system with ion liquid microemulsion, synthetic starch under the effect of cross-linking agent
Nano microsphere, its process route is simple, mild condition, the starch nano-microsphere good dispersion of preparation, averagely
Particle diameter is about 100nm.Van der Waals force between spherex prepared by conventional art and electrostatic interaction
Power makes mutually to flock together between microsphere, presents the tufted structure of densification.The inventive method is with nanoscale
Other microemulsion drop is separate reactors, the starch nano-microsphere independence balling-up of synthesis, and the octene used
Base succinic acid starch gelatinizing or dissolve time ionizable go out anion, intermolecular repulsion can weaken even offsets shallow lake
Electrostatic interaction between powder microsphere so that it is have good dispersibility, bigger specific surface area, can conduct
The carrier of the small-molecule substance such as medicine, essence and flavoring agent is applied to medicine, field of food, plays good slow release
Effect.
2, as a kind of novel ion liquid, [C3OHmim] Ac at high temperature can effectively dissolve starch, and
And the particle diameter participating in the ion liquid microemulsion of structure reaches Nano grade, optical clear can be formed, stablize
The ion liquid microemulsion system that property is excellent, the synthesis for follow-up spherex creates reaction advantageously
Condition.
3, ionic liquid [C used in the present invention3OHmim] Ac (l-(3-hydroxyl) propyl group-3 Methylimidazole. vinegar
Hydrochlorate) it is the novel alkaline ionic liquid being synthesized by two-step process, the synthesis for ionic liquid provides one
New technology.
Accompanying drawing explanation
Fig. 1 is embodiment 2 ionic liquid [C3OHmim] Ac (l (3 hydroxyl) propyl group 3 Methylimidazole. acetate)
Infrared spectrogram.
Fig. 2 is embodiment 2 ionic liquid [C3OHmim] Ac (l (3 hydroxyl) propyl group 3 Methylimidazole. acetate)
's1H nuclear magnetic resonance spectrogram.
Fig. 3 is the grain size distribution of the laser fineness gage detection of embodiment 2 starch nano-microsphere.
Fig. 4 is the scanning electron microscope (SEM) photograph of embodiment 2 starch nano-microsphere.
Detailed description of the invention
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, existing many successfully embodiments, six specific embodiments are set forth below,
But the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
N-Methylimidazole. and the trimethylene chlorohydrin that mol ratio is 1:1.1 is added in container, at nitrogen by the first step
Under the conditions of gas shielded, load onto condensation reflux unit, obtain thick product 1 60 DEG C of reacting by heating.By mass ratio
Add in separatory funnel for the ethyl acetate of 1:1 and thick product 1 and wash, stand, take off layer sample also
Mix for 1:1 in mass ratio with ethyl acetate carry out washing, stand, separatory, by sample after being so repeated 2 times
Product, at 60 DEG C of dry 36h, obtain intermediate product [C3OHmim]Cl；
Mol ratio, with methanol as solvent, is [the C of 1:1.2 by second step3OHmim] Cl and potassium acetate dissolve
In methanol, at ambient temperature after reaction 24h, sucking filtration removes solid content, and then rotary evaporation obtains slightly
Product 2.Ether that mass ratio is 0.8:1 and thick product 2 are added conical flask is stirred washing, mistake
Filtering solid content, rotary evaporation removes ether.After the thick product of ether repeated washing 4 times of equal in quality
It is dried 36h under the conditions of sample is placed in 45 DEG C, obtains object ion liquid [C3OHmim]Ac；
The octenylsuccinate potato starch that substitution value is 0.01 is dried under the conditions of 50 DEG C by the 3rd step
To water content less than 3%；
4th step ionic liquid [C3OHmim] starch of step (3) gained is made into mass fraction and is by Ac
The starch milk of 3%, under the protection of nitrogen, stirs 4h under the conditions of 90 DEG C；
Step (4) gained solution is down to room temperature by the 5th step, adds hexamethylene, is slow added into surface and lives
Property agent TX-100 and cosurfactant n-butyl alcohol, prepare oil bag ion liquid microemulsion；Hexamethylene and
Four step gained starch solution mass ratioes are 9:1；Surfactant TX-100 and cosurfactant n-butyl alcohol
3:1 mixture by mass percentage, both quality summations account for the 30% of whole microemulsion quality；
6th step adds in the oily bag ion liquid microemulsion of step (5) gained and accounts for microemulsion quality 1%
Epoxychloropropane, under the conditions of 40 DEG C react 5h.
Step (6) gained solution is cooled down by the 7th step, adds dehydrated alcohol and precipitates, centrifugal, removes
Solution, gained precipitate absolute ethanol washing, at 50 DEG C of dry 36h, obtain starch nano-microsphere.Through swashing
Light particles distribution instrument detects, and product mean diameter is 94.3nm.
Embodiment 2
N-Methylimidazole. and the trimethylene chlorohydrin that mol ratio is 1:1.2 is added in container, at nitrogen by the first step
Under the conditions of gas shielded, load onto condensation reflux unit, obtain thick product 1 70 DEG C of reacting by heating.By mass ratio
Add in separatory funnel for the ethyl acetate of 1.2:1 and crude product 1 and wash, stand, take off a layer sample
And mix for 1.2:1 in mass ratio with ethyl acetate carry out washing, stand, separatory, after being so repeated 3 times
Sample is obtained intermediate product [C at 50 DEG C of dry 36h3OHmim]Cl；
Mol ratio, with methanol as solvent, is [the C of 1:1.3 by second step3OHmim] Cl and potassium acetate dissolve
In methanol, at ambient temperature after reaction 30h, sucking filtration removes solid content, and then rotary evaporation obtains slightly
Product 2.Ether that mass ratio is 1:1 and thick product 2 are added conical flask is stirred washing, filter
Removing solid content, rotary evaporation removes ether.With will after the thick product of ether repeated washing 3 times of equal in quality
Sample is dried 30h under the conditions of being placed in 50 DEG C, obtains object ion liquid [C3OHmim]Ac；
Substitution value is that 0.02 ocentyl succinic corn starch is dried to containing under the conditions of 60 DEG C by the 3rd step
The water yield is less than 3%；
4th step ionic liquid [C3OHmim] starch of step (3) gained is made into mass fraction by Ac
It is the starch milk of 2%, under the protection of nitrogen, under the conditions of 80 DEG C, stirs 5h；
Step (4) gained solution is down to room temperature by the 5th step, adds hexamethylene, is slow added into surface and lives
Property agent TX-100 and cosurfactant n-butyl alcohol, prepare oil bag ion liquid microemulsion；Hexamethylene and
Four step gained starch solution mass ratioes are 7:1；Surfactant TX-100 and cosurfactant n-butyl alcohol
1:1 mixture by mass percentage, both quality summations account for the 45% of whole microemulsion quality；
6th step adds in the oily bag ion liquid microemulsion of step (5) gained and accounts for microemulsion quality 2%
Epoxychloropropane, under the conditions of 50 DEG C react 4h.
Step (6) gained solution is cooled down by the 7th step, adds dehydrated alcohol and precipitates, centrifugal, removes
Solution, gained precipitate absolute ethanol washing, at 40 DEG C of dry 36h, obtain starch nano-microsphere.Through swashing
Light particles distribution instrument detects, and product mean diameter is 105nm.
The present embodiment gained ionic liquid [C3OHmim] Ac (l (3 hydroxyl) propyl group 3 Methylimidazole. acetate)
Infrared spectrogram as shown in Figure 1.Use liquid-film method fourier infrared analyser (Nicolet 510,
Thermo Electron) the upper infrared spectrum measuring ionic liquid.As it is shown in figure 1,3412cm‐1For O H
Stretching vibration, 3144cm‐1For imidazole ring unsaturation C H stretching vibration, 2953cm‐1Saturated for alkyl chain
C H stretching vibration, 1570cm‐1For imidazole ring skeletal vibration, 1405cm‐1For carboxylate radical stretching vibration, 1167
And 1157cm‐1Vibrate for imidazole ring C H in-plane deformation.
The present embodiment gained ionic liquid [C3OHmim] Ac (l-(3-hydroxyl) propyl group-3 Methylimidazole. acetate)
's1H nuclear magnetic resonance spectrogram is as shown in Figure 2.Use nuclear magnetic resonance analyser (DMX300, Bruke)
Upper mensuration ionic liquid1H nuclear magnetic resonance spectrogram.[C3OHmim] Ac1H NMR:(600
MHz, DMSO) δ=9.83 (s, 1H), 7.81 (d, 1H), 7.71 (d, 1H), 4.26 (t, 2H), 3.86 (s, 3H),
3.37(s,1H),2.50(m,2H),1.88(m,2H),1.59(s,3H)。
Infared spectrum and nuclear magnetic spectrum prove ionic liquid [C3OHmim] Ac the most successfully synthesizes, and there is no other miscellaneous
Mass peak occurs.
The grain size distribution of the present embodiment gained starch nano-microsphere is as shown in Figure 3.Take 0.1g starch nano micro-
Ball adds in the distilled water of 500mL, and ultrasonic a period of time makes starch nano-microsphere be completely dispersed, and then uses
Zetasizer dynamic light scattering measures size and the distribution of sizes of starch nano-microsphere.Fig. 3 shows,
The mean diameter of the present embodiment gained starch nano-microsphere is 105nm.Therefore, the present invention can be used for preparing
The starch nano-microsphere that particle diameter is less.
The scanning electron microscope (SEM) photograph of the present embodiment gained starch nano-microsphere is as shown in Figure 4.Spherex is dispersed in
Ultrasonic 30min in dehydrated alcohol, takes a small amount of dripping on microscope slide, dries, be fixed on sample stage, then
Metal spraying is placed under Quanta 200 type scanning electron microscope (FEI, Oregon, USA) observing granule-morphology.Fig. 4
Showing, spherex is then the spherical or almost spherical shape in rule, and its grain size reaches Nano grade,
And spherex good dispersion, occurs without clustering phenomena.
Van der Waals force and electrostatic force between spherex prepared by conventional art make between microsphere
Mutually flock together, present the tufted structure of densification.Compared with spherex prepared by conventional art, this
Invent with the microemulsion drop of Nano grade as separate reactors, the starch nano-microsphere independence balling-up of synthesis, and
And the octenyl succinic acid starch used can ionize out anion, intermolecular repulsion energy when gelatinizing or dissolving
Weaken and even offset the electrostatic interaction between starch nano-microsphere so that it is there is good dispersibility, bigger
The feature such as specific surface area and not reunion, can apply as the carrier of the small-molecule substance such as medicine, essence and flavoring agent
To medicine, field of food, play good slow releasing function.
[C be can be observed by polarizing microscope3OHmim] Ac can effectively destroy the structure of starch thus reach
Dissolve the effect of starch；Ionic liquid [C3OHmim] Ac participate in build ion liquid microemulsion particle diameter reach
Nano grade, can form clear, stable homogeneous phase.
Embodiment 3
N-Methylimidazole. and the trimethylene chlorohydrin that mol ratio is 1:1.5 is added in container, at nitrogen by the first step
Under the conditions of gas shielded, load onto condensation reflux unit, obtain thick product 1 80 DEG C of reacting by heating.By mass ratio
Add in separatory funnel for the ethyl acetate of 1.5:1 and thick product 1 and wash, stand, take off a layer sample
And mix for 1.5:1 in mass ratio with ethyl acetate carry out washing, stand, separatory, after being so repeated 4 times
80 DEG C of dry 24h of sample are obtained intermediate product [C3OHmim]Cl；
Mol ratio, with methanol as solvent, is [the C of 1:1.4 by second step3OHmim] Cl and potassium acetate dissolve
In methanol, at ambient temperature after reaction 36h, sucking filtration removes solid content, and then rotary evaporation obtains
Thick product 2.Ether that mass ratio is 1.2:1 and thick product 2 are added conical flask are stirred washing,
Being filtered to remove solid content, rotary evaporation removes ether.With the thick product of ether repeated washing 3 of equal in quality
It is dried 24h under the conditions of sample being placed in 60 DEG C after secondary, obtains object ion liquid [C3OHmim]Ac；
3rd step the ocentyl succinic tapioca that substitution value is 0.03 is dried under the conditions of 70 DEG C to
Water content is less than 3%；
4th step ionic liquid [C3OHmim] starch of step (3) gained is made into mass fraction by Ac
It is the starch milk of 4%, under the protection of nitrogen, under the conditions of 90 DEG C, stirs 5h；
Step (4) gained solution is down to room temperature by the 5th step, adds hexamethylene, is slow added into surface and lives
Property agent TX-100 and cosurfactant n-butyl alcohol, prepare oil bag ion liquid microemulsion；Hexamethylene and
Four step gained starch solution mass ratioes are 5:1；Surfactant TX-100 and cosurfactant n-butyl alcohol
2:1 mixture by mass percentage, both quality summations account for the 50% of whole microemulsion quality；
6th step adds in the oily bag ion liquid microemulsion of step (5) gained and accounts for microemulsion quality 3%
Epoxychloropropane, under the conditions of 60 DEG C react 3h.
Step (6) gained solution is cooled down by the 7th step, adds dehydrated alcohol and precipitates, centrifugal, removes
Solution, gained precipitate absolute ethanol washing, at 60 DEG C of dry 24h, obtain starch nano-microsphere.Through swashing
Light particles distribution instrument detects, and product mean diameter is 113.4nm.
Embodiment 4
N-Methylimidazole. and the trimethylene chlorohydrin that mol ratio is 1:1.3 is added in container, at nitrogen by the first step
Under the conditions of gas shielded, load onto condensation reflux unit, obtain thick product 1 70 DEG C of reacting by heating.By mass ratio
Add in separatory funnel for the ethyl acetate of 1.2:1 and thick product 1 and wash, stand, take off a layer sample
And mix for 1.2:1 in mass ratio with ethyl acetate carry out washing, stand, separatory, after being so repeated 3 times
65 DEG C of dry 28h of sample are obtained intermediate product [C3OHmim]Cl；
Mol ratio, with methanol as solvent, is [the C of 1:1.5 by second step3OHmim] Cl and potassium acetate dissolve
In methanol, at ambient temperature after reaction 30h, sucking filtration removes solid content, and then rotary evaporation obtains slightly
Product 2.Ether that mass ratio is 0.8:1 and thick product 2 are added conical flask is stirred washing, mistake
Filtering solid content, rotary evaporation removes ether.After the thick product of ether repeated washing 2 times of equal in quality
It is dried 24h under the conditions of sample is placed in 65 DEG C, obtains object ion liquid [C3OHmim]Ac；
3rd step the ocentyl succinic wheaten starch that substitution value is 0.01 is dried under the conditions of 70 DEG C to
Water content is less than 3%；
4th step ionic liquid [C3OHmim] starch of step (3) gained is made into mass fraction by Ac
It is the starch milk of 5%, under the protection of nitrogen, under the conditions of 100 DEG C, stirs 2h；
Step (4) gained solution is down to room temperature by the 5th step, adds hexamethylene, is slow added into surface and lives
Property agent TX-100 and cosurfactant n-butyl alcohol, prepare oil bag ion liquid microemulsion；Hexamethylene and
Four step gained starch solution mass ratioes are 7:1；Surfactant TX-100 and cosurfactant n-butyl alcohol
1:1 mixture by mass percentage, both quality summations account for the 40% of whole microemulsion quality；
6th step adds in the oily bag ion liquid microemulsion of step (5) gained and accounts for microemulsion quality 0.5%
Epoxychloropropane, under the conditions of 50 DEG C react 4h.
Step (6) gained solution is cooled down by the 7th step, adds dehydrated alcohol and precipitates, centrifugal, removes
Solution, gained precipitate absolute ethanol washing, at 50 DEG C of dry 30h, obtain starch nano-microsphere.Through swashing
Light particles distribution instrument detects, and product mean diameter is 97.8nm.
Embodiment 5
N-Methylimidazole. and the trimethylene chlorohydrin that mol ratio is 1:1.1 is added in container, at nitrogen by the first step
Under the conditions of gas shielded, load onto condensation reflux unit, obtain thick product 1 75 DEG C of reacting by heating.By mass ratio
Add in separatory funnel for the ethyl acetate of 1.3:1 and thick product 1 and wash, stand, take off a layer sample
And mix for 1.3:1 in mass ratio with ethyl acetate carry out washing, stand, separatory, after being so repeated 3 times
70 DEG C of dry 24h of sample are obtained intermediate product [C3OHmim]Cl；
Mol ratio, with methanol as solvent, is [the C of 1:1.2 by second step3OHmim] Cl and potassium acetate dissolve
In methanol, at ambient temperature after reaction 28h, sucking filtration removes solid content, and then rotary evaporation obtains
Thick product 2.Ether that mass ratio is 1:1 and thick product 2 are added conical flask is stirred washing, mistake
Filtering solid content, rotary evaporation removes ether.After the thick product of ether repeated washing 4 times of equal in quality
It is dried 28h under the conditions of sample is placed in 45 DEG C, obtains object ion liquid [C3OHmim]Ac；
The ocentyl succinic waxy corn starch that substitution value is 0.02 is dried under the conditions of 55 DEG C by the 3rd step
Do to water content less than 3%；
4th step ionic liquid [C3OHmim] starch of step (3) gained is made into mass fraction by Ac
It is the starch milk of 2%, under the protection of nitrogen, under the conditions of 80 DEG C, stirs 3h；
Step (4) gained solution is down to room temperature by the 5th step, adds hexamethylene, is slow added into surface and lives
Property agent TX-100 and cosurfactant n-butyl alcohol, prepare oil bag ion liquid microemulsion；Hexamethylene and
Four step gained starch solution mass ratioes are 8:1；Surfactant TX-100 and cosurfactant n-butyl alcohol
2:1 mixture by mass percentage, both quality summations account for the 45% of whole microemulsion quality；
6th step adds in the oily bag ion liquid microemulsion of step (5) gained and accounts for microemulsion quality 2%
Epoxychloropropane, under the conditions of 45 DEG C react 5h.
Step (6) gained solution is cooled down by the 7th step, adds dehydrated alcohol and precipitates, centrifugal, removes
Solution, gained precipitate absolute ethanol washing, it is dried, obtains starch nano-microsphere.Through Laser particle-size distribution
Instrument detects, and product mean diameter is 110.7nm.
Embodiment 6
N-Methylimidazole. and the trimethylene chlorohydrin that mol ratio is 1:1.4 is added in container, at nitrogen by the first step
Under the conditions of gas shielded, load onto condensation reflux unit, obtain thick product 1 65 DEG C of reacting by heating.By mass ratio
Add in separatory funnel for the ethyl acetate of 1:1 and thick product 1 and wash, stand, take off layer sample also
Mix for 1:1 in mass ratio with ethyl acetate carry out washing, stand, separatory, by sample after being so repeated 2 times
60 DEG C of dry 30h of product obtain intermediate product [C3OHmim]Cl；
Mol ratio, with methanol as solvent, is [the C of 1:1.4 by second step3OHmim] Cl and potassium acetate dissolve
In methanol, at ambient temperature after reaction 28h, sucking filtration removes solid content, and then rotary evaporation obtains slightly
Product 2.Ether that mass ratio is 0.9:1 and thick product 2 are added conical flask is stirred washing, mistake
Filtering solid content, rotary evaporation removes ether.After the thick product of ether repeated washing 3 times of equal in quality
It is dried 30h under the conditions of sample is placed in 50 DEG C, obtains object ion liquid [C3OHmim]Ac；
3rd step the ocentyl succinic corn starch that substitution value is 0.03 is dried under the conditions of 60 DEG C to
Water content is less than 3%；
4th step ionic liquid [C3OHmim] starch of step (3) gained is made into mass fraction by Ac
It is the starch milk of 3%, under the protection of nitrogen, under the conditions of 85 DEG C, stirs 4h；
Step (4) gained solution is down to room temperature by the 5th step, adds hexamethylene, is slow added into surface and lives
Property agent TX-100 and cosurfactant n-butyl alcohol, prepare oil bag ion liquid microemulsion；Hexamethylene and
Four step gained starch solution mass ratioes are 6:1；Surfactant TX-100 and cosurfactant n-butyl alcohol
1:1 mixture by mass percentage, both quality summations account for the 40% of whole microemulsion quality；
6th step adds in the oily bag ion liquid microemulsion of step (5) gained and accounts for microemulsion quality 1%
Epoxychloropropane, under the conditions of 60 DEG C react 3h.
Step (6) gained solution is cooled down by the 7th step, adds dehydrated alcohol and precipitates, centrifugal, removes
Solution, gained precipitate absolute ethanol washing, it is dried, obtains starch nano-microsphere.Through Laser particle-size distribution
Instrument detects, and product mean diameter is 118.6nm.
Embodiment 1,3,4,5,6 gained ionic liquid [C3OHmim] Ac infrared spectrogram and1H NMR
Nmr spectrum is similar to Fig. 1, Fig. 2, the scanning electron microscope (SEM) photograph of starch nano-microsphere and grain size distribution with
Fig. 3, Fig. 4 are similar, provide the most one by one.
As it has been described above, the present invention can preferably be realized.
Claims (10)
1. the method preparing starch nano-microsphere in alkali ionic liquid microemulsion system, it is characterised in that bag
Include following steps:
(1) be 1:(1.1～1.5 by mol ratio) N-Methylimidazole. and trimethylene chlorohydrin add in container,
Under nitrogen protective condition, obtain thick product 1 60～80 DEG C of reacting by heating；Thick product 1 passes through washing,
Stand, separatory, be dried, obtain intermediate product [C3OHmim]Cl；
(2) with methanol as solvent, be 1:(1.2～1.5 by mol ratio) [C3OHmim] Cl and potassium acetate
Being dissolved in methanol, at ambient temperature after reaction 24～36h, sucking filtration removes solid content, and rotary evaporation obtains
To thick product 2；Thick product 2 is washed by ether, is dried, obtains object ion liquid [C3OHmim]Ac；
(3) starch material is dried under the conditions of 50～70 DEG C；
(4) with ionic liquid [C3OHmim] starch of step (3) gained is made into mass content and is by Ac
2～the starch milk of 5%, under the protection of nitrogen, under the conditions of 80～100 DEG C, stir 2～5h；
(5) step (4) gained solution is down to room temperature, adds hexamethylene, be slow added into surface activity
Agent TX-100 and cosurfactant n-butyl alcohol, prepare oil bag ion liquid microemulsion；
(6) in the oily bag ion liquid microemulsion of step (5) gained, addition accounts for microemulsion quality 0.5～3%
Epoxychloropropane, under the conditions of 40～60 DEG C react 3～5h；
(7) step (6) gained solution is cooled down, add dehydrated alcohol and precipitate, centrifugal, remove molten
Liquid, gained precipitate absolute ethanol washing, it is dried, obtains starch nano-microsphere.
Alkali ionic liquid microemulsion system the most according to claim 1 prepares starch nano-microsphere
Method, it is characterised in that: the described thick product 1 of step (1) is by thick product 1 and acetic acid through washing
Ethyl ester washing is (1～1.5) according to mass ratio: carry out in 1 addition separatory funnel；Washing, standing, separatory
Repeat 2-4 time.
Alkali ionic liquid microemulsion system the most according to claim 1 prepares starch nano-microsphere
Method, it is characterised in that: step (1) described be dried refer to will washing separate after sample 50～80
24～36h it are dried at DEG C.
Alkali ionic liquid microemulsion system the most according to claim 1 prepares starch nano-microsphere
Method, it is characterised in that: the described thick product of step (2) 2 is that mass ratio is by ether washing
(0.8～1.2): the ether of 1 and thick product 2 add conical flask is stirred washing, be filtered to remove solid content,
Rotary evaporation removes ether；So repeat 2-4 time；Described being dried of step (2) is 45～65 DEG C of conditions
Under be dried 24～36h.
Alkali ionic liquid microemulsion system the most according to claim 1 prepares starch nano-microsphere
Method, it is characterised in that: step (3) described starch material is ocentyl succinic corn starch, pungent
Alkenyl succinic acid potato starch, ocentyl succinic tapioca, ocentyl succinic wheaten starch or pungent
Alkenyl succinic acid waxy corn starch.
Alkali ionic liquid microemulsion system the most according to claim 5 prepares starch nano-microsphere
Method, it is characterised in that: the substitution value of described starch material is 0.01～0.03.
Alkali ionic liquid microemulsion system the most according to claim 1 prepares starch nano-microsphere
Method, it is characterised in that: step (3) described drying refers to control starch biodiversity content less than 3%.
Alkali ionic liquid microemulsion system the most according to claim 1 prepares starch nano-microsphere
Method, it is characterised in that: step (5) described oil bag ion liquid microemulsion is hexamethylene and step (4)
Gained starch solution mass ratio is (5～9): 1；Surfactant TX-100 and cosurfactant n-butyl alcohol
By mass percentage (1～3): 1 mixture, surfactant accounts for the quality summation of cosurfactant
The 30～50% of whole microemulsion quality.
Alkali ionic liquid microemulsion system the most according to claim 1 prepares starch nano-microsphere
Method, it is characterised in that: step (7) described absolute ethanol washing is with dehydrated alcohol eccysis precipitate
In ionic liquid, hexamethylene, TX-100, n-butyl alcohol and epoxychloropropane.
Alkali ionic liquid microemulsion system the most according to claim 1 prepares starch nano-microsphere
Method, it is characterised in that: step (7) described be dried refer to will washing after starch nano-microsphere be placed in
24～36h it are dried at 40～60 DEG C.
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| CN102675209A (en) * | 2012-04-30 | 2012-09-19 | 青岛科技大学 | Hydroxyl-containing bivalent imidazole type ionic liquid, preparation method thereof, and application thereof |
| CN103435706A (en) * | 2013-08-23 | 2013-12-11 | 华南理工大学 | Preparation method of starch nanoparticles |
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| CN102675209A (en) * | 2012-04-30 | 2012-09-19 | 青岛科技大学 | Hydroxyl-containing bivalent imidazole type ionic liquid, preparation method thereof, and application thereof |
| CN103435706A (en) * | 2013-08-23 | 2013-12-11 | 华南理工大学 | Preparation method of starch nanoparticles |
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| ZHIMIN XUE ET AL.: ""Thermal stabilities and decomposition mechanism of amino- and hydroxyl-functionalized ionic liquids"", 《THERMOCHIMICA ACTA》 * |
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