CN110314663A - A kind of preparation method of the W/O emulsification base composite porous microballoon of rectorite - Google Patents
A kind of preparation method of the W/O emulsification base composite porous microballoon of rectorite Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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Abstract
The invention discloses a kind of preparation methods of W/O emulsification base composite porous microballoon of rectorite, the following steps are included: it is water phase that rectorite is added in Polymer Solution to prepare uniform mixing suspension, rectorite/macromolecule is carried out microballoon using mono- step emulsion process of W/O as oily phase by the oiliness reagent to contain emulsifier.Rectorite is added in Polymer Solution by the preparation method of the W/O emulsification base composite porous microballoon of rectorite for the first time, the porous microsphere of functionalization required for not having any restrictions, all synthesis macromolecules that can be dispersed or dissolved in aqueous phase solvent or natural polymer that can prepare through the invention high molecular material.The present invention has many advantages, such as, including simple process, cost of material are low, mild condition is widely applicable etc., obtained microballoon even pore distribution is suitable for industrial production, and at home and abroad all still belongs to the first time.
Description
Technical field
The present invention relates to field of material technology, in particular to a kind of preparation of the W/O emulsification base composite porous microballoon of rectorite
Method.
Background technique
Micron order polymer microsphere is a kind of important novel high polymer material, is had a wide range of applications in each field,
In, porous microsphere with unique drug absorption and releasability, high-specific surface area and lower density due to obtaining extensively
Research, hemostasis etc. biomedicine fields have good development prospect.The preparation method of porous microsphere is varied, mainly
Including double emulsion solvent evaporated method, reversed replica method, self-assembly method and phase separation method etc., preparation method is relatively complicated, daily
In production, propose it is simple, quick, environmentally friendly and be easy to produce in batches etc. higher requirement.
Chinese patent " chitosan/silicate nano compound stephanoporate crosslinked microsphere sorbent and preparation method thereof " (publication number
CN101347719A) disclose a kind of preparation method of chitosan/silicate porous microsphere, prepare the chitosan of low molecular weight/
Silicate intercalation solution, mixes with high molecular weight chitosan, then contacts alkaline coagulator and obtains microballoon, then carries out to microballoon pre-
Crosslinking and crosslinking Treatment obtain chitosan/silicate nano compound stephanoporate crosslinked microsphere sorbent, the party after removing precrosslinker
Method need to carry out precrosslink and crosslinking Treatment to microballoon, be directed to the requirement such as concussion, temperature, and operating procedure is complicated, and introducing is pre-payed
Join agent, precrosslinker removing is difficult to be desorbed completely.
Chinese patent " a kind of preparation method of the microsphere adsorbing agent based on rectorite " (publication number CN102302924A) is public
It is full a kind of boric acid that PVP/ sodium alginate/HDTMA property of modified rectorite mixed liquor is instilled into calcium chloride using syringe pellet fabrication device has been opened
With microballoon is formed by curing in solution, which prepares microballoon using syringe pellet fabrication device, raw material rectorite need to carry out HDTMA it is modified at
Reason, operating process is cumbersome, and the used time is longer.
Chinese patent " a kind of degradable multiporous microballoon and Preparation method and use " (publication number CN106540308A) is open
One kind is using native protein and natural polysaccharides aqueous solution as water phase, to be oily phase dissolved with the fat-soluble solvent of emulsifier；Emulsification
It is crosslinked the method for preparing degradable multiporous microballoon, this method is emulsion-crosslinking method, needs introducing crosslinked agent.
Summary of the invention
The present invention for the technical problems in the prior art, it is base composite porous micro- to provide a kind of W/O emulsification rectorite
The preparation method of ball can prepare a kind of tool by simple technique using the architectural characteristic of rectorite and macromolecule itself
There is the porous complex microsphere of surface and internal run-through reticular structure.
The technical scheme to solve the above technical problems is that a kind of W/O emulsification rectorite base/high-molecular porous micro-
The preparation method of ball, comprising the following steps:
1) it prepares rectorite/macromolecule mixing suspension: tired support of the partial size at 5~100 μm being added in Polymer Solution
Stone, mechanical stirring obtains rectorite/macromolecule mixing suspension, the high molecular component to being uniformly mixed under normal temperature conditions
For one or more synthesis macromolecules and/or natural polymer；
2) it prepares oily phase reagent: emulsifier and oiliness reagent being taken to mix, mechanical stirring obtains oil and mutually try to being uniformly mixed
Agent；
3) it emulsifies: rectorite/macromolecule mix suspending made from step 1) being added into oil phase reagent made from step 2)
Liquid, continues stirring until uniformly mixed, obtains W/O water-in-oil emulsion；
4) finished product: W/O water-in-oil emulsion made from step 3) is poured into reversed solution, and magnetic agitation takes solid
Mutually after washing, drying, rectorite base/porous polymer bead is made.
Based on the above technical solution, the present invention can also be improved as follows.
Further, it is described 1) in rectorite and high molecular mixing suspension mass volume ratio concentration be 0.1~15%.
Further, the high molecular component in the step 1) is sodium alginate, cellulose, starch, carboxymethyl starch, crust
One of element, chitosan and its derivative, cellulose acetate, fibroin albumen and collagen or more than one combination.
Further, the emulsifier in the step 2) is w/o type emulsifier Span80 or Span85, the use of the emulsifier
Amount is 0.1g~3g/100mL.
Further, the oiliness reagent in the step 2) is one of vegetable oil, mineral oil or organic solvent.The oil
Property reagent most preferably limonene or D- limonene or both mixture.
Further, the reverse phase solution in the step 4) be with the incompatible solvent of macromolecule dispersion solvent, can will
Macromolecule is recrystallized from dissolved state into solid state.
Further, in the step 4), rectorite is with macromolecule content ratio in rectorite base/porous polymer bead
1:99~4:1.
The present invention also provides a kind of W/O emulsifications to prepare chitosan/rectorite composite porous microspheres method, including following
Step:
1) it prepares chitosan/rectorite mixing suspension: tired support of the partial size at 5~100 μm being added in chitosan solution
Stone, mechanical stirring obtains chitosan/rectorite mixing suspension to being uniformly mixed under normal temperature conditions；
2) it prepares oily phase reagent: emulsifier and oiliness reagent being taken to mix, mechanical stirring obtains oil and mutually try to being uniformly mixed
Agent；
3) it emulsifies: chitosan/rectorite mix suspending made from step 1) being added into oil phase reagent made from step 2)
Liquid, continues stirring until uniformly mixed, obtains W/O water-in-oil emulsion；
4) finished product: W/O water-in-oil emulsion made from step 3) is placed in magnetic agitation in NaOH solution, takes solid phase
After washing, freeze-drying, chitosan/rectorite composite porous microspheres are made.
Further, the deacetylating degree of chitosan is 50~100%, and molecular weight is 5~1,200,000.
Further, the emulsifier in the step 2) is w/o type emulsifier Span80 or Span85.
Further, the oiliness reagent in the step 2) is limonene or D- limonene or both mixture.
Further, in the step 4), rectorite and chitosan content ratio in chitosan/rectorite composite porous microspheres
For 1:99~4:1.
The beneficial effects of the present invention are: the preparation method of the W/O emulsification base composite porous microballoon of rectorite of the invention is for the first time
Rectorite is added in Polymer Solution, rectorite/macromolecule is subjected to microballoon using mono- step emulsion process of W/O, to high score
Sub- material does not have any restrictions, all synthesis macromolecules or natural polymer that can be dispersed or dissolved in aqueous phase solvent
The porous microsphere of functionalization required for can preparing through the invention, the present invention have many advantages, such as, including technique letter
Singly, cost of material is low, mild condition is widely applicable etc., obtained microballoon even pore distribution, is suitable for industrial production.This hair
The bright architectural characteristic for also utilizing chitosan and phyllosilicate itself for the first time, by using mono- step emulsion process of W/O, with chitosan/
Rectorite mixed solution is added the oily phase reagent containing emulsifier and is mixed, then prepares through lye solidification with uniform
The porous complex microsphere of reticular structure, present invention process is simple, raw material is easy to get, and is convenient for industrial production, obtained microballoon hole
It is evenly distributed, it is widely applicable, it is used as hemostatic material, haemostatic effect is very significant.
Detailed description of the invention
Fig. 1 is chitosan of the invention/rectorite composite porous microspheres scanning electron microscope (SEM) photograph；
Fig. 2 is the water absorption rate distribution map of chitosan of the invention/rectorite composite porous microspheres and its raw material；
Fig. 3 is chitosan of the invention/rectorite composite porous microspheres specific area measuring figure；
Fig. 4 is chitosan of the invention/rectorite composite porous microspheres microscope figure；
Fig. 5 is chitosan of the invention, rectorite and chitosan/rectorite composite porous microspheres infrared spectrogram.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
A kind of W/O of the invention emulsifies rectorite base/porous polymer bead preparation method, comprising the following steps:
1) it prepares rectorite/macromolecule mixing suspension: tired support of the partial size at 5~100 μm being added in Polymer Solution
Stone, mechanical stirring obtains rectorite/macromolecule mixing suspension, the high molecular component to being uniformly mixed under normal temperature conditions
For one or more synthesis macromolecules and/or natural polymer；
2) it prepares oily phase reagent: emulsifier and oiliness reagent being taken to mix, mechanical stirring obtains oil and mutually try to being uniformly mixed
Agent；
3) it emulsifies: rectorite/macromolecule mix suspending made from step 1) being added into oil phase reagent made from step 2)
Liquid, continues stirring until uniformly mixed, obtains W/O water-in-oil emulsion；
4) finished product: W/O water-in-oil emulsion made from step 3) is poured into reversed solution, and magnetic agitation takes solid
Mutually after washing, drying, rectorite base/porous polymer bead is made.
Preferably, it is described 1) in rectorite and high molecular mixing suspension mass volume ratio concentration be 0.1~15%.
Preferably, the high molecular component in the step 1) is sodium alginate, cellulose, starch, carboxymethyl starch, crust
One of element, chitosan and its derivative, cellulose acetate, fibroin albumen and collagen or more than one combination.
Preferably, the emulsifier in the step 2) is w/o type emulsifier Span80 or Span85.
Preferably, the preferable amount of the emulsifier is 0.1g~3g/100mL.Inventor's discovery uses the cream of this dosage
Agent, emulsifying effectiveness are best.
Preferably, when the step 2) configures oily phase reagent, using 800rpm middle and slow speed of revolution mechanical stirring below, to keep away
Exempt from that revolving speed is excessively high to cause oily phase morphology that can not be formed.It is preferred that rectorite and macromolecule are added immediately when being stirred in oily phase
Mixing suspension.
Preferably, the oiliness reagent in the step 2) is one of vegetable oil, mineral oil or organic solvent.The oil
Property reagent most preferably limonene or D- limonene or both mixture.Inventor has found to select limonene or D- limonene or both
Mixture, obtained emulsion form is optimal, the aperture one of the internal void of final rectorite base/porous polymer bead obtained
Cause rate is best, and distribution of pores is the most uniform, and quality is best.
Preferably, the step 3) emulsifying step, using revolving speed mechanical stirring 1h or more high in 1000~2500rpm,
By formed it is preferable in the form of lotion.
Reverse phase solution in step 4) of the present invention be with the incompatible solvent of macromolecule dispersion solvent, can will be high
Molecule is recrystallized from dissolved state into solid state.
Preferably, in the step 4), rectorite is with macromolecule content ratio in rectorite base/porous polymer bead
1:99~4:1.
Preferably, in the step 4), magnetic agitation preferably stirs 15~45min, to guarantee that rectorite base/macromolecule is more
Hole microballoon can be precipitated completely, while in turn ensure shorter preparation time, find after inventor's research, when using above-mentioned stirring
Between, rectorite base/porous polymer bead eduction rate can reach 95% or more.
Preferably, it in the step 4), is dried by the way of freeze-drying, high temperature drying is avoided to destroy microballoon
Structure.
A kind of W/O emulsification of the invention prepares chitosan/rectorite composite porous microspheres method, comprising the following steps:
1) it prepares chitosan/rectorite mixing suspension: tired support of the partial size at 5~100 μm being added in chitosan solution
Stone, mechanical stirring obtains chitosan/rectorite mixing suspension to being uniformly mixed under normal temperature conditions；
2) it prepares oily phase reagent: emulsifier and oiliness reagent being taken to mix, mechanical stirring obtains oil and mutually try to being uniformly mixed
Agent；
3) it emulsifies: chitosan/rectorite mix suspending made from step 1) being added into oil phase reagent made from step 2)
Liquid, continues stirring until uniformly mixed, obtains W/O water-in-oil emulsion；
4) finished product: W/O water-in-oil emulsion made from step 3) is placed in magnetic agitation in NaOH solution, takes solid phase
After washing, freeze-drying, chitosan/rectorite composite porous microspheres are made.
Preferably, the deacetylating degree of chitosan is 50~100%, and molecular weight is 5~1,200,000.
Preferably, the emulsifier in the step 2) is w/o type emulsifier Span80 or Span85.
Preferably, the oiliness reagent in the step 2) is limonene or D- limonene or both mixture.
Preferably, in the step 4), rectorite and chitosan content ratio in chitosan/rectorite composite porous microspheres
For 1:99~4:1.
1 rectorite base of embodiment/chitosan porous microsphere
(1) it prepares chitosan solution: weighing the Chitosan powder that 4.0g molecular weight is 620000 in 250mL beaker, add
Enter the dilute acetic acid solution that 100mL concentration is 2.0% (V/V), mechanical stirring, configuration concentration is 4.0% chitosan solution, and standing is gone
Bubble removing；
(2) prepare rectorite/chitosan mixing suspension: weigh 50 μm of rectorites of 4.0g be added above-mentioned preparation shell it is poly-
In sugar juice, mechanical stirring obtains rectorite/chitosan mixing suspension to being uniformly mixed；
(3) it prepares oily phase reagent: in the three-necked flask of 250mL, weighing 0.8g span80,100mL kerosene is added, beats
It opens mechanical agitator and keeps revolving speed 600rpm, be uniformly mixed, obtain oily phase reagent；
(4) rectorite/chitosan mixing suspension made from 50mL step (2) is added into the three-necked flask of step (3),
Revolving speed 1000rpm persistently stirs 1h, forms uniform water-in-oil emulsion；
(5) rectorite/chitosan porous microsphere is made: water-in-oil emulsion made from step (4) is quickly poured into 220mL's
In the NaOH solution of 1.0mol/L, magnetic agitation 20min stops stirring, supernatant liquid is discarded after standing, washs solid phase, wash
Freeze-drying, obtains rectorite base/chitosan porous microsphere after net.
2 rectorite base of embodiment/starch porous microsphere
(1) it prepares starch solution: weighing 4.5g starch powder in 250mL beaker, addition 100mL concentrated water, mechanical stirring,
Configuration concentration is 4.0% starch solution, and standing removes bubble removing；
(2) it prepares rectorite/starch mixing suspension: weighing the starch solution that above-mentioned preparation is added in 5 μm of rectorites of 4.0g
In, mechanical stirring obtains rectorite/starch mixing suspension to being uniformly mixed；
(3) it prepares oily phase reagent: in the three-necked flask of 250mL, weighing 0.4g span80,100mL olive oil is added,
It opens mechanical agitator and keeps revolving speed 700rpm, be uniformly mixed, obtain oily phase reagent；
(4) rectorite/starch mixing suspension made from 80mL step (2) is added into the three-necked flask of step (3), turns
Fast 1200rpm persistently stirs 1h, forms uniform water-in-oil emulsion；
(5) rectorite base/starch porous microsphere is made: water-in-oil emulsion made from step (4) is quickly poured into short chain alcohol
In solution, magnetic agitation 20min stops stirring, supernatant liquid is discarded after standing, washs solid phase, dry after cleaning, and is tired out
Hold in the palm ground mass/starch porous microsphere.
3 rectorite base of embodiment/polyglycol porous microballoon
(1) it prepares polyethylene glycol mixed solution: weighing 4.5g polyethylene glycol in 250mL beaker, it is ultrapure that 100mL is added
Water, configuration quality score are 4.0% polyglycol solution；
(2) it prepares rectorite/polyethylene glycol suspensoid: 4.0g25 μm of tired support being added in 100mL polyglycol solution
Stone, mechanical stirring to solution is uniformly mixed under normal temperature conditions, obtains rectorite/polyethylene glycol mixing suspension；
(3) it prepares oily phase reagent: weighing the Span80 of 1.0g mass in three-necked flask, 100mL kerosene is added, open machine
Tool blender keeps the revolving speed of 500rpm, is uniformly mixed, obtains oily phase reagent；
(4) rectorite made from 40mL step (2)/poly- second is slowly injected into the three-necked flask of step (3) with syringe
Glycol mixing suspension, revolving speed 1000rpm persistently stir 60min, obtain uniform water-in-oil emulsion；
(5) rectorite base/polyglycol porous microballoon is made: 2.0g calcium chloride is added in 100mL saturation boric acid solution,
Calcium chloride/boric acid mixed solution is obtained, water-in-oil emulsion made from 80mL step (4) is poured into 100mL calcium chloride/boric acid and is mixed
In solution, magnetic agitation 30min, after discard supernatant liquid, wash solid phase, it is more that rectorite base/polyethylene glycol is made after dry
Hole microballoon.
4 rectorite base of embodiment/collagen porous microsphere
(1) it prepares collagen solution: weighing the collagen that 2.0g molecular weight is 300000 in 250mL beaker, add
Enter the dilute acetic acid solution that 100mL concentration is 2.0% (V/V), mechanical stirring, configuration concentration is 2.0% collagen solution, is stood
Remove bubble removing；
(2) it prepares rectorite/collagen mixing suspension: weighing the glue that above-mentioned preparation is added in 100 μm of rectorites of 0.5g
In former protein solution, mechanical stirring obtains rectorite/collagen mixing suspension to being uniformly mixed；
(3) it prepares oily phase reagent: in the three-necked flask of 250mL, weighing 0.5g span80,100mLD- lemon is added
Alkene opens blender and keeps certain revolving speed, it is uniformly mixed, obtains oily phase reagent；
(4) rectorite/collagen made from 80mL step (2) is slowly injected into the three-necked flask of step (3) with syringe
Albumen mixing suspension, revolving speed 1000rpm persistently stir 1.5h, form uniform water-in-oil emulsion；
(5) rectorite/collagen microballoon is made: water-in-oil emulsion made from step (4) is quickly poured into 250mL's
In the NaOH solution of 1.0mol/L, magnetic agitation 20min stops stirring, supernatant liquid is discarded after standing, washs solid phase, wash
Freeze-drying, obtains rectorite base/collagen porous microsphere after net.
5 rectorite base of embodiment/sodium alginate porous microsphere
(1) it prepares sodium alginate soln: weighing 2.0g sodium alginate in 250mL beaker, 100mL ultrapure water, machine is added
Tool stirring, configuration concentration are 2.0% sodium alginate soln, and standing removes bubble removing；
(2) it prepares rectorite/sodium alginate mixing suspension: weighing the sea that above-mentioned preparation is added in 75 μm of rectorites of 0.5g
In solution of sodium alginate, mechanical stirring obtains rectorite/sodium alginate mixing suspension to being uniformly mixed；
(3) it prepares oily phase reagent: in the three-necked flask of 250mL, weighing 0.5g span80,100mLD- lemon is added
Alkene opens blender and keeps certain revolving speed,
(4) rectorite/seaweed made from 60mL step (2) is slowly injected into the three-necked flask of step (3) with syringe
Sour sodium mixing suspension, revolving speed 1100rpm persistently stir 1.5h, form uniform water-in-oil emulsion；
(5) rectorite base/sodium alginate porous microsphere is made: water in oil emulsion liquid emulsion made from step (4) is quickly poured into
In the CaCl2 solution that the concentration of 250mL is 3.0%, magnetic agitation 20min stops stirring, discards supernatant liquid after standing, wash
Solid phase is washed, is freeze-dried after cleaning, obtains rectorite base/sodium alginate porous microsphere.
Through being detected to porous microsphere made from Examples 1 to 5, the base composite porous microballoon sphere diameter of rectorite be 1~
1000 μm, internal void is evenly distributed, and pore size consistency is preferable, and adsorption rate is extremely strong.
Mono- one-step emulsification method of W/O of the present invention directly by preparing water-in-oil emulsion, carries out reverse phase solidification preparation
Porous microsphere can save double emulsion process, without crosslinking, be not necessarily to pore-foaming agent, and pollution-free, easy to operate, the production time is short, for the first time will
Rectorite, which is added in Polymer Solution, prepares porous microsphere, gives full play to the effect of rectorite molecular sieve, and to macromolecule material
Expect no any restrictions, raw materials for production are extensive, inside prepared microballoon, surface have perforation and evenly dispersed netted knot
Structure, specific surface area is larger, applied widely, and at home and abroad all still belongs to the first time.In the present invention, rectorite is applied to for the first time
In the preparation of porous microsphere.Phyllosilicate rectorite is as natural minerals, by dioctahedron mica elementary layer and sixteen
Face body montmorillonite elementary layer is alternately accumulated under special natural condition with 1:1 ratio and is formed, and not only the high fever with mica is steady
Qualitative and heat-resisting quantity, hydrophily, dilatancy, colloidality and cationic exchangeability also with montmorillonite.Rectorite and high score
The base composite porous microballoon of the rectorite that son is prepared both had possessed the universal feature of porous microsphere, but also with rectorite and high score
The advantage of sub- self structure has widened the application range of porous microsphere.In field of material technology, directly emulsified using mono- step of W/O
Technology not yet occurs rectorite and the compound method for preparing microballoon of high molecular material.
Embodiment 6
(1) it prepares chitosan solution: measuring 2mL glacial acetic acid in the beaker of 250mL with pipette, it is ultrapure that 100mL is added
Water, it is 92.4% that 5.0g deacetylation, which is added, the Chitosan powder that molecular weight is 212000, and mechanical stirring is completely molten to chitosan
Solution, obtains the chitosan solution that concentration is 5.0%, and standing removes bubble removing；
(2) it prepares chitosan/rectorite solution: weighing the chitosan solution that above-mentioned preparation is added in 50 μm of rectorites of 5.0g
In, mechanical stirring obtains chitosan/rectorite mixed solution to being uniformly mixed；
(3) it emulsifies: in the three-necked flask of 250mL, weighing 1.0g span80, the D- limonene of 100mL is added, open
Mechanical agitator keeps revolving speed 600rpm, and the above-mentioned chitosan of 80mL/rectorite mixed solution is added, and revolving speed 1500rpm is persistently stirred
1.5h is mixed, uniform water-in-oil emulsion is formed；
(4) it prepares chitosan/rectorite porous microsphere: lotion obtained is quickly poured into the 1.0mol/L NaOH of 240mL
In solution, magnetic agitation 20min stops stirring, supernatant liquid is discarded after standing, wash microballoon, is freeze-dried, obtains after cleaning
Chitosan/rectorite composite porous microspheres.
Embodiment 7
(1) it prepares chitosan solution: measuring 2mL glacial acetic acid in the beaker of 250mL with pipette, it is ultrapure that 100mL is added
Water, it is 92.4% that 5.0g deacetylation, which is added, the Chitosan powder that molecular weight is 212000, and mechanical stirring is completely molten to chitosan
Solution, obtains the chitosan solution that concentration is 5.0%, and standing removes bubble removing；
(2) it prepares chitosan/rectorite solution: weighing the chitosan solution that above-mentioned preparation is added in 5 μm of rectorites of 1.0g
In, mechanical stirring obtains chitosan/rectorite mixed solution to being uniformly mixed；
(3) it emulsifies: in the three-necked flask of 250mL, weighing 1.0g span80, the D- limonene of 100mL is added, open
Blender keeps revolving speed 600rpm, is slowly added to the above-mentioned chitosan of 80mL/rectorite mixed solution, revolving speed 1900rpm is persistently stirred
1.5h is mixed, uniform water-in-oil emulsion is formed；
(4) it prepares chitosan/rectorite porous microsphere: lotion obtained is quickly poured into the 1.0mol/L NaOH of 240mL
In solution, magnetic agitation 20min stops stirring, supernatant liquid is discarded after standing, wash microballoon, is freeze-dried, obtains after cleaning
Chitosan/rectorite composite porous microspheres.
Embodiment 8
(1) it preparing chitosan solution: measuring 2mL glacial acetic acid in the beaker of 250mL with pipette, addition 100mL is ultrapure,
It is 90% that 4.0g deacetylation, which is added, and molecular weight is 620000 Chitosan powders, and mechanical stirring to chitosan is completely dissolved, obtains
The chitosan solution that concentration is 4.0%, standing remove bubble removing；
(2) it prepares chitosan/rectorite solution: weighing the chitosan solution that above-mentioned preparation is added in 25 μm of rectorites of 1.0g
In, mechanical stirring obtains chitosan/rectorite mixed solution to being uniformly mixed；
(3) it emulsifies: in the three-necked flask of 250mL, weighing 1.5g span80,100mL limonene is added, open stirring
Device keeps certain revolving speed, is slowly added to 80mL with syringe and obtains chitosan/rectorite mixed solution, revolving speed 1000rpm is held
Continuous stirring 1.5h, forms uniform water-in-oil emulsion；
(4) it prepares chitosan/rectorite porous microsphere: lotion obtained is quickly poured into the 1.0mol/L NaOH of 250mL
In solution, magnetic agitation 20min stops stirring, supernatant liquid is discarded after standing, wash microballoon, is freeze-dried, obtains after cleaning
Chitosan/rectorite composite porous microspheres.
Embodiment 9
(1) it preparing chitosan solution: measuring 2mL glacial acetic acid in the beaker of 250mL with pipette, addition 100mL is ultrapure,
It is 90% that 4.0g deacetylation, which is added, and molecular weight is 620000 Chitosan powders, and mechanical stirring to chitosan is completely dissolved, obtains
The chitosan solution that concentration is 4.0%, standing remove bubble removing；
(2) it prepares chitosan/rectorite solution: weighing the chitosan solution that above-mentioned preparation is added in 100 μm of rectorites of 2.0g
In, mechanical stirring obtains chitosan/rectorite mixed solution to being uniformly mixed；
(3) it emulsifies: in the three-necked flask of 250mL, weighing 1.2g span80, the D- limonene of 100mL is added, open
Blender keeps certain revolving speed, is slowly added to 7mL with syringe and obtains chitosan/rectorite mixed solution, revolving speed 1700rpm
1.5h is persistently stirred, uniform water-in-oil emulsion is formed；
(4) it prepares chitosan/rectorite porous microsphere: lotion obtained is quickly poured into the 1.5mol/L NaOH of 200mL
In solution, magnetic agitation 30min stops stirring, supernatant liquid is discarded after standing, wash microballoon, is freeze-dried, obtains after cleaning
Chitosan/rectorite composite porous microspheres.
Embodiment 10
(1) it preparing chitosan solution: measuring 2mL glacial acetic acid in the beaker of 250mL with pipette, addition 100mL is ultrapure,
It is 90% that 4.5g deacetylation, which is added, and molecular weight is 620000 Chitosan powders, and mechanical stirring to chitosan is completely dissolved, obtains
The chitosan solution that concentration is 4.5%, standing remove bubble removing；
(2) it prepares chitosan/rectorite solution: weighing the chitosan solution that above-mentioned preparation is added in 75 μm of rectorites of 4.5g
In, mechanical stirring obtains chitosan/rectorite mixed solution to being uniformly mixed；
(3) it emulsifies: in the three-necked flask of 250mL, weighing 1.0g span80, the D- limonene of 100mL is added, open
Blender keeps certain revolving speed, is slowly added to 80mL with syringe and obtains chitosan/rectorite mixed solution, revolving speed
1500rpm persistently stirs 1.5h, forms uniform water-in-oil emulsion；
(4) it prepares chitosan/rectorite porous microsphere: lotion obtained is quickly poured into the 1.5mol/L NaOH of 200mL
In solution, magnetic agitation 30min stops stirring, supernatant liquid is discarded after standing, wash microballoon, is freeze-dried, obtains after cleaning
Chitosan/rectorite composite porous microspheres.
Chitosan made from embodiment 6~10/rectorite composite porous microspheres are most suitable for being used as hemostatic material.By embodiment
6~10 obtained porous microspheres carry out clotting time (CT) test, using the external test tube of classical detection Hemostatics effect
Blood coagulation method: take 1mL White Rabbit venous blood (3.8% sodium citrate containing anti-coagulants, blood volume ratio are 1:9) injection 40mg dry
It in sample, is placed in 37 DEG C of water-baths, overturns a test tube every 10s, record blood coagulation time, and blank group is set, cloud
Southern baiyao is control group, 6~10 chitosans of embodiment/rectorite composite porous microspheres group.Blank group and Yunnan Baiyao control group
25 samples of every group of setting, calculate every group of average clotting time.6~10 chitosans of embodiment/rectorite composite porous microspheres
The porous microsphere of each embodiment of group sets 25 samples, and the porous microsphere of each embodiment calculates average clotting time.It surveys
The equal round numbers of test result, the results are shown in Table 1.
1 styptic powder of the table external clotting time (CT)
Blank control blood cannot solidify completely, and the Yunnan Baiyao positive controls clotting time is about 3014s.And embodiment
6~10 porous microsphere is added in blood sample, and blood coagulation time is greatly shortened to 190s, the results showed that, by this
Chitosan/rectorite composite porous microspheres of invention preparation have extremely good haemostatic effect.
The chitosan of Example 8/rectorite composite porous microspheres and other styptic powders do zoopery, verify this hair
Bright chitosan/rectorite composite porous microspheres haemostatic effect, specific experiment the results are shown in Table 2.
The 2 styptic powder zoopery clotting time of table
The chitosan of Example 8/rectorite composite porous microspheres and other styptic powders do clotting assay, right after blood coagulation
Thrombus is accordingly detected, and acquired results are shown in Table 3.
3 thrombelastogram instrument (TEG) of table detects major parameter
According to the result of table 2 and table 3 it is found that chitosan of the invention/rectorite composite porous microspheres and other styptic powders
Compare, no matter be formed by the clotting time or after blood coagulation in the performance of thrombus be intended to improve it is very much, haemostatic effect compared with
Existing hemostatic material will improve very much.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (16)
1. a kind of W/O emulsifies rectorite base/porous polymer bead preparation method, it is characterised in that the following steps are included:
1) it prepares rectorite/macromolecule mixing suspension: rectorite of the partial size at 5~100 μm being added in Polymer Solution,
Mechanical stirring obtains rectorite/macromolecule mixing suspension to being uniformly mixed under normal temperature condition, and the high molecular component is one kind
Or a variety of synthesis macromolecules and/or natural polymer；
2) it prepares oily phase reagent: emulsifier and oiliness reagent being taken to mix, mechanical stirring obtains oily phase reagent to being uniformly mixed；
3) it emulsifies: rectorite/macromolecule mixing suspension made from step 1) being added into oil phase reagent made from step 2), holds
Continuous stirring obtains W/O water-in-oil emulsion to being uniformly mixed；
4) finished product: W/O water-in-oil emulsion made from step 3) is poured into reversed solution, and magnetic agitation takes solid phase to wash
After washing, drying, rectorite base/porous polymer bead is made.
2. the preparation method of the W/O emulsification base composite porous microballoon of rectorite according to claim 1, it is characterised in that: institute
The rectorite and high molecular mixing suspension mass volume ratio concentration stated in 1) are 0.1~15%.
3. the preparation method of the W/O emulsification base composite porous microballoon of rectorite according to claim 2, it is characterised in that: institute
Stating the high molecular component in step 1) is sodium alginate, cellulose, starch, carboxymethyl starch, chitin, chitosan and its derivative
One of object, cellulose acetate, fibroin albumen and collagen or more than one combination.
4. the preparation method of the W/O emulsification base composite porous microballoon of rectorite according to claim 1, it is characterised in that: institute
Stating the emulsifier in step 2) is w/o type emulsifier Span80 or Span85, and the dosage of the emulsifier is 0.1g~3g/
100mL。
5. the preparation method of the W/O emulsification base composite porous microballoon of rectorite according to claim 1, it is characterised in that: institute
Stating the oiliness reagent in step 2) is one of vegetable oil, mineral oil or organic solvent.
6. the preparation method of the W/O emulsification base composite porous microballoon of rectorite according to claim 5, it is characterised in that: institute
Stating oiliness reagent is limonene or D- limonene or both mixture.
7. the preparation method of the W/O emulsification base composite porous microballoon of rectorite according to claim 1, it is characterised in that: institute
State reverse phase solution in step 4) be with the incompatible solvent of macromolecule dispersion solvent, can be by macromolecule from dissolved state weight
Crystallize into solid state.
8. the preparation method of the W/O emulsification base composite porous microballoon of rectorite according to claim 1, it is characterised in that: institute
It states in step 4), rectorite and macromolecule content ratio are 1:99~4:1 in rectorite base/porous polymer bead.
9. a kind of W/O emulsification prepares chitosan/rectorite composite porous microspheres method, it is characterised in that the following steps are included:
1) it prepares chitosan/rectorite mixing suspension: rectorite of the partial size at 5~100 μm being added in chitosan solution,
Mechanical stirring obtains chitosan/rectorite mixing suspension to being uniformly mixed under normal temperature condition；
2) it prepares oily phase reagent: emulsifier and oiliness reagent being taken to mix, mechanical stirring obtains oily phase reagent to being uniformly mixed；
3) it emulsifies: chitosan/rectorite mixing suspension made from step 1) being added into oil phase reagent made from step 2), holds
Continuous stirring obtains W/O water-in-oil emulsion to being uniformly mixed；
4) finished product: W/O water-in-oil emulsion made from step 3) is placed in magnetic agitation in NaOH solution, solid phase is taken to wash
After washing, being lyophilized, chitosan/rectorite composite porous microspheres are made.
10. W/O emulsification according to claim 8 prepares chitosan/rectorite composite porous microspheres method, feature exists
In: the deacetylating degree of chitosan is 50~100%, and molecular weight is 5~1,200,000.
11. W/O emulsification according to claim 8 prepares chitosan/rectorite composite porous microspheres method, feature exists
In: it is described 1) in chitosan and rectorite mixing suspension mass volume ratio concentration be 0.1~15%.
12. W/O emulsification according to claim 8 prepares chitosan/rectorite composite porous microspheres method, feature exists
In: the emulsifier in the step 2) is w/o type emulsifier Span80 or Span85.
13. W/O emulsification according to claim 8 prepares chitosan/rectorite composite porous microspheres method, feature exists
In: the oiliness reagent in the step 2) is limonene or D- limonene or both mixture.
14. W/O emulsification according to claim 8 prepares chitosan/rectorite composite porous microspheres method, feature exists
In: in the step 4), rectorite and chitosan content ratio are 1:99~4:1 in chitosan/rectorite composite porous microspheres.
15. a kind of W/O emulsification according to described in claim 8~14 prepares chitosan/rectorite composite porous microspheres method
The chitosan of preparation/rectorite composite porous microspheres.
16. a kind of chitosan described in claim 15/rectorite composite porous microspheres are in the application in hemostatic material field.
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