CN105080445B - A kind of is that template prepares method of the ferric tannate ionomer as the microcapsules of wall material using interfacial reaction using microemulsion - Google Patents

A kind of is that template prepares method of the ferric tannate ionomer as the microcapsules of wall material using interfacial reaction using microemulsion Download PDF

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CN105080445B
CN105080445B CN201510582586.1A CN201510582586A CN105080445B CN 105080445 B CN105080445 B CN 105080445B CN 201510582586 A CN201510582586 A CN 201510582586A CN 105080445 B CN105080445 B CN 105080445B
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acid
microcapsules
oleic acid
microemulsion
wall material
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CN105080445A (en
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韩晓军
王剑飞
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

A kind of is that template prepares method of the ferric tannate ionomer as the microcapsules of wall material using interfacial reaction using microemulsion, the invention belongs to medical carrier, biomedical engineering and film engineering field, it is in order to solve the complex process that existing method prepares ferric tannate ionomer microcapsules, the problem of universality is poor.Preparation method:First, tannic acid solid is dissolved in deionized water, ultrasonically treated to obtain tannin aqueous acid;2nd, anhydrous ferric trichloride solid is placed in oleic acid-alcohol mixture, prepares oleic acid-ethanol-chlorination iron liquid miscella phase;3rd, tannin aqueous acid and oleic acid-ethanol-chlorination iron liquid miscella are mixed, and are carried out ultrasonically treated after vortex processing, are obtained this microcapsules.The present invention is combined using interfacial polymerization with template, using oleic acid as oil phase, simplifies the formation process of microcapsules, and obtained capsule universality is strong, can both encapsulate water soluble drug, can also encapsulate oil-soluble medicine.

Description

One kind prepares tannic acid-Polymerization of Ferric Ions by template of microemulsion using interfacial reaction Thing is the method for the microcapsules of wall material
Technical field
The invention belongs to medical carrier, biomedical engineering and film engineering field, and in particular to one kind is with microemulsion droplets For template, the method that microcapsules are prepared using interfacial reaction.
Background technology
Microcapsules refer to a kind of miniature vessel or packing material with polymeric shell wall, micro- with semi permeability or sealing Small particles, wherein wrapped material is referred to as core, the material of parcel core is referred to as wall material.Tannic acid-Polymerization of Ferric Ions thing category In a kind of supermolecule-metal ion polymer, the coordination ability of iron ion and phenolic hydroxyl group increases and strengthened with pH, with significant PH response characteristics, are a kind of ideal materials as pH controlled release capsule wall materials.Preparing the main method of microcapsules at present has cohesion Method, phase separation method, interfacial polymerization and soft template method etc..But the above method is not able to simply applied to applied widely Tannic acid-iron ion microcapsules prepare, therefore, invent that a kind of yield is high, flow is simple, the preparation of universality by force is with tannin Acid-Polymerization of Ferric Ions thing will have important meaning to the popularization of such microcapsules for the method for the pH controlled release capsules of wall material with application Justice.
The content of the invention
The complex process of tannic acid-Polymerization of Ferric Ions thing microcapsules is prepared the invention aims to solve existing method, The problem of universality is poor, and one kind is provided and prepares tannic acid-Polymerization of Ferric Ions thing using interfacial reaction by template of microemulsion For the method for the microcapsules of wall material.
The present invention is that template prepares microcapsules of the tannic acid-Polymerization of Ferric Ions thing as wall material using interfacial reaction using microemulsion Method follow these steps realize:
First, tannic acid solid is placed in deionized water, it is ultrasonically treated it is uniform after obtain tannin aqueous acid;
2nd, anhydrous ferric trichloride solid is weighed, is 10 by the mol ratio of oleic acid and anhydrous ferric trichloride:1~100:1 by nothing Aqueous ferric chloride solid is placed in oleic acid, is 10 according still further to oleic acid and absolute ethyl alcohol volume ratio:1 adds at absolute ethyl alcohol, ultrasound Oleic acid-ethanol-chlorination iron liquid miscella phase is obtained after reason is uniform;
3rd, oleic acid-ethanol that the tannin aqueous acid and step 2 obtained step one is obtained-chlorination iron liquid miscella Mix, ultrasonically treated formation microemulsion, tannic acid and trivalent are carried out again after carrying out vortex processing, standing by vortex mixed instrument In oil-water interfaces complex reaction occurs for iron ion, obtains the microcapsules using tannic acid-Polymerization of Ferric Ions thing as wall material.
The present invention relates to one kind using microemulsion droplets as template, the method that microcapsules are prepared using interfacial reaction.With tannin The aqueous solution of acid is as aqueous phase, and oleic acid-ethanol-chlorination iron liquid miscella is as oil phase, by the ratio for adjusting oil and water Through vortex mixed instrument and ultrasonically treated prepare oil-in-water or water-in-oil microemulsion again.The tannin in the forming process of microemulsion Acid and ferric ion occur complex reaction in oil-water interfaces and formed in supermolecule-metal ion thin polymer film, cladding emulsion Dispersed phase formation do not carry the soft template microcapsules of medicine.The loading of medicine can be dissolved in aqueous phase or oil phase by previously by medicine It is middle to realize, can also be after removing template be removed by soaking realization.
The present invention is that template prepares microcapsules of the tannic acid-Polymerization of Ferric Ions thing as wall material using interfacial reaction using microemulsion Method include advantages below:
1st, combined, be prepared into using microemulsion soft template with oil-water interfaces polymerisation with template using interfacial polymerization Tannic acid-Polymerization of Ferric Ions thing microcapsules are arrived.
2nd, the main component that can dissolve the oleic acid of iron chloride as oil phase is employed, the formation work of microcapsules is simplified Skill.It is also nutriment needed by human and oleic acid is not only nontoxic so that the more environmental protection of capsule formation process.
3rd, the capsule universality that the technique is prepared is strong, can both encapsulate water soluble drug, can also encapsulate oil-soluble Medicine.
Brief description of the drawings
Fig. 1 is the electron microscope (microscope figure) for the oil-soluble medicine microcapsules that embodiment one is prepared;
Fig. 2 is the electron microscope (microscope figure) for the oil-soluble medicine microcapsules that embodiment two is prepared.
Embodiment
Embodiment one:Present embodiment prepares tannic acid-iron ion by template of microemulsion using interfacial reaction Polymer follows these steps to realize for the method for the microcapsules of wall material:
First, tannic acid solid is placed in deionized water, it is ultrasonically treated it is uniform after obtain tannin aqueous acid;
2nd, anhydrous ferric trichloride solid is weighed, is 10 by the mol ratio of oleic acid and anhydrous ferric trichloride:1~100:1 by nothing Aqueous ferric chloride solid is placed in oleic acid, is 10 according still further to oleic acid and absolute ethyl alcohol volume ratio:1 adds at absolute ethyl alcohol, ultrasound Oleic acid-ethanol-chlorination iron liquid miscella phase is obtained after reason is uniform;
3rd, oleic acid-ethanol that the tannin aqueous acid and step 2 obtained step one is obtained-chlorination iron liquid miscella Mix, ultrasonically treated formation microemulsion, tannic acid and trivalent are carried out again after carrying out vortex processing, standing by vortex mixed instrument In oil-water interfaces complex reaction occurs for iron ion, obtains the microcapsules using tannic acid-Polymerization of Ferric Ions thing as wall material.
Preparation method described in present embodiment had both combined interfacial polymerization and template prepares the advantage of microcapsules, again With simple to operate, reaction condition is gentle, reaction speed is fast, the features such as generation capsule size is uniform, enrich tannic acid-iron from The preparation method of sub- polymer microcapsule.
Embodiment two:Present embodiment and the tannin sour water described in step one unlike embodiment one The concentration of solution is 0.1~10mg/mL.Other steps and parameter are identical with embodiment one.
Embodiment three:Present embodiment and the tannin sour water described in step one unlike embodiment two The concentration of solution is 0.5~5mg/mL.Other steps and parameter are identical with embodiment two.
Embodiment four:Present embodiment and the tannin sour water described in step one unlike embodiment two The concentration of solution is 0.5~2mg/mL.Other steps and parameter are identical with embodiment two.
Embodiment five:Step 2 presses oleic acid unlike one of present embodiment and embodiment one to four Mol ratio with anhydrous ferric trichloride is 10:1~20:1 is placed in anhydrous ferric trichloride solid in oleic acid, according still further to oleic acid and nothing Water-ethanol volume ratio is 10:1 adds absolute ethyl alcohol.Other steps and parameter are identical with one of embodiment one to four.
Embodiment six:Described in step 2 unlike one of present embodiment and embodiment one to five It is ultrasonically treated to be carried out at a temperature of 40 DEG C.Other steps and parameter are identical with one of embodiment one to five.
Embodiment seven:Step 3 presses tannin unlike one of present embodiment and embodiment one to six The volume ratio of aqueous acid and oleic acid-iron chloride liquid complexes is (80~110):1 by tannin aqueous acid and oleic acid-second Alcohol-chlorination iron liquid miscella is mixed.Other steps and parameter are identical with one of embodiment one to six.
Present embodiment obtains oil-in-water microemulsion.
Embodiment eight:Step 3 presses tannin unlike one of present embodiment and embodiment one to seven The volume ratio of aqueous acid and oleic acid-ethanol-chlorination iron liquid miscella phase is 1:(80~110) by tannin aqueous acid with oil Acid-iron chloride liquid complexes mixing.Other steps and parameter are identical with one of embodiment one to seven.
Present embodiment obtains water-in-oil microemulsion.
Embodiment nine:Described in step 3 unlike one of present embodiment and embodiment one to eight It is ultrasonically treated to be carried out at a temperature of 25 DEG C.Other steps and parameter are identical with one of embodiment one to eight.
Embodiment one:The present embodiment prepares tannic acid-Polymerization of Ferric Ions thing by template of microemulsion using interfacial reaction The method of the microcapsules of wall material follows these steps to realize:
First, tannic acid solid is placed in deionized water, obtained after being handled 5 minutes with 50W power ultrasonic at 25 DEG C Concentration is 1mg/mL tannin aqueous acid;
2nd, anhydrous ferric trichloride solid is weighed, is 10 by the mol ratio of oleic acid and anhydrous ferric trichloride:1 by anhydrous trichlorine Change iron solid to be placed in oleic acid, be 10 according still further to oleic acid and absolute ethyl alcohol volume ratio:1 add absolute ethyl alcohol, at 40 DEG C with 350W power ultrasonic obtains oleic acid-ethanol-chlorination iron liquid miscella phase after handling 30 minutes;
3rd, it is 1 according to the volume ratio of tannin aqueous acid and oleic acid-ethanol-chlorination iron liquid miscella phase:100 will be single Peaceful aqueous acid is mixed with oleic acid-ethanol-chlorination iron liquid miscella, is vortexed by vortex mixed instrument and is handled 30s, is stood With 50W power ultrasonic 5min formation water-in-oil microemulsions at 25 DEG C after 1min, tannic acid and ferric ion are in profit circle The oil phase formation that face occurs in complex reaction, cladding emulsion is micro- using tannic acid-Polymerization of Ferric Ions thing as the oil-soluble medicine of wall material Capsule.
The loading of water soluble drug:Water soluble drug is dissolved in cushioning liquid, then will be obtained by the present embodiment Water-in-oil microemulsion is mixed with the aqueous solution of medicine, capsule is separated in lower floor's aqueous phase by centrifugal treating, the timing of immersion one Between after centrifuge out capsule, be stored in cushioning liquid.
Embodiment two:The present embodiment prepares tannic acid-Polymerization of Ferric Ions thing by template of microemulsion using interfacial reaction The method of the microcapsules of wall material follows these steps to realize:
First, tannic acid solid is placed in deionized water, obtained after being handled 5 minutes using 350W power ultrasonic concentration as 1mg/mL tannin aqueous acid;
2nd, anhydrous ferric trichloride solid is weighed, is 10 by the mol ratio of oleic acid and anhydrous ferric trichloride:1 by anhydrous trichlorine Change iron solid to be placed in oleic acid, be 10 according still further to oleic acid and absolute ethyl alcohol volume ratio:1 adds at absolute ethyl alcohol, 40 DEG C with 350W Power ultrasonic handle 30 minutes after obtain oleic acid-ethanol-chlorination iron liquid miscella phase;
3rd, it is 100 according to the volume ratio of tannin aqueous acid and oleic acid-ethanol-chlorination iron liquid miscella phase:1 will be single Peaceful aqueous acid is mixed with oleic acid-ethanol-chlorination iron liquid miscella, is vortexed by vortex mixed instrument and is handled 30s, is stood In oil-water interfaces complex reaction, cladding occur for ultrasound 5min formation oil-in-water microemulsion after 1min, tannic acid and ferric ion Oil-soluble medicine microcapsules of the oil phase formation using tannic acid-Polymerization of Ferric Ions thing as wall material in emulsion.
The loading of oil-soluble medicine:Oil-soluble medicine is dissolved in ethanol, then the oil-in-water microemulsion that the present embodiment is formed It is immersed in the ethanol solution of medicine 10 minutes, centrifugation isolates capsule in 3 minutes, is stored in pH=8.5 tris-HCl bufferings In solution.

Claims (8)

1. a kind of is that template prepares tannic acid-Polymerization of Ferric Ions thing as the side of the microcapsules of wall material using interfacial reaction using microemulsion Method, it is characterised in that be to realize according to the following steps:
First, tannic acid solid is placed in deionized water, it is ultrasonically treated it is uniform after obtain tannin aqueous acid;
2nd, anhydrous ferric trichloride solid is weighed, is 10 by the mol ratio of oleic acid and anhydrous ferric trichloride:1~100:1 by anhydrous three Iron chloride solid is placed in oleic acid, is 10 according still further to oleic acid and absolute ethyl alcohol volume ratio:1 adds absolute ethyl alcohol, ultrasonically treated equal Oleic acid-ethanol-chlorination iron liquid miscella phase is obtained after even;
3rd, oleic acid-ethanol that the tannin aqueous acid for obtaining step one is obtained with step 2-chlorination iron liquid miscella is mutually mixed Close, vortex processing carried out by vortex mixed instrument, carry out ultrasonically treated formation microemulsion after standing again, tannic acid and ferric iron from In oil-water interfaces complex reaction occurs for son, obtains the microcapsules using tannic acid-Polymerization of Ferric Ions thing as wall material;
The concentration of tannin aqueous acid wherein described in step one is 0.1~10mg/mL.
2. one kind according to claim 1 prepares tannic acid-Polymerization of Ferric Ions by template of microemulsion using interfacial reaction Thing is the method for the microcapsules of wall material, it is characterised in that the concentration of the tannin aqueous acid described in step one is 0.5~5mg/mL.
3. one kind according to claim 2 prepares tannic acid-Polymerization of Ferric Ions by template of microemulsion using interfacial reaction Thing is the method for the microcapsules of wall material, it is characterised in that the concentration of the tannin aqueous acid described in step one is 0.5~2mg/mL.
4. one kind according to claim 1 prepares tannic acid-Polymerization of Ferric Ions by template of microemulsion using interfacial reaction Thing is the method for the microcapsules of wall material, it is characterised in that step 2 is 10 by the mol ratio of oleic acid and anhydrous ferric trichloride:1~ 20:1 is placed in anhydrous ferric trichloride solid in oleic acid, is 10 according still further to oleic acid and absolute ethyl alcohol volume ratio:1 adds anhydrous second Alcohol.
5. one kind according to claim 1 prepares tannic acid-Polymerization of Ferric Ions by template of microemulsion using interfacial reaction Thing for the microcapsules of wall material method, it is characterised in that ultrasonically treated described in step 2 is carried out at a temperature of 40 DEG C.
6. one kind according to claim 1 prepares tannic acid-Polymerization of Ferric Ions by template of microemulsion using interfacial reaction Thing is the method for the microcapsules of wall material, it is characterised in that step 3 is mixed by tannin aqueous acid with oleic acid-ethanol-chlorination iron liquid The volume ratio for closing oil phase is (80~110):1 mixes tannin aqueous acid with oleic acid-ethanol-chlorination iron liquid miscella.
7. one kind according to claim 1 prepares tannic acid-Polymerization of Ferric Ions by template of microemulsion using interfacial reaction Thing is the method for the microcapsules of wall material, it is characterised in that step 3 is mixed by tannin aqueous acid with oleic acid-ethanol-chlorination iron liquid The volume ratio for closing oil phase is 1:(80~110) mix tannin aqueous acid with oleic acid-ethanol-chlorination iron liquid miscella.
8. one kind according to claim 1 prepares tannic acid-Polymerization of Ferric Ions by template of microemulsion using interfacial reaction Thing for the microcapsules of wall material method, it is characterised in that ultrasonically treated described in step 3 is carried out at a temperature of 25 DEG C.
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