CN1919445A - Method for preparing microcapsule by using doping porous calcium carbonate mould plates - Google Patents
Method for preparing microcapsule by using doping porous calcium carbonate mould plates Download PDFInfo
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- CN1919445A CN1919445A CN 200610052940 CN200610052940A CN1919445A CN 1919445 A CN1919445 A CN 1919445A CN 200610052940 CN200610052940 CN 200610052940 CN 200610052940 A CN200610052940 A CN 200610052940A CN 1919445 A CN1919445 A CN 1919445A
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- polyelectrolyte
- calcium carbonate
- caco
- porous calcium
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Abstract
The invention discloses a preparing method of micro-capsule through doping porous calcium carbonate mode, which comprises the following steps: reacting inorganic salt with calcium and inorganic salt with carbonate to prepare porous calcium carbonate colloid particle doped by negative charge electrolyte, adsorbing polyelectrolyte with positive charge on the colloid particle surface, decomposing diluted acid or complexing ethylenediamine tetra acetic acid to remove calcium carbonate particle, forming hollow micro-capsule through ionic bond action of positive and negative charge polyelectrolyte.
Description
Technical field
The present invention relates to a kind of method for preparing microcapsules, especially utilize doping porous calcium carbonate mould plates to prepare the method for microcapsules.
Background technology
Microcapsules are by film forming matter the space in the capsule and the capsule external space to be kept apart to form the material of particular geometric configuration.The shape of microcapsules also can be oval, square or rectangular, polygonal and various irregularly shaped based on spherical structure.Tradition microcapsules size usually at micron to the millimeter level, wall thickness in sub-micron to the hundreds of micron.Microcapsules all have crucial application in food, medicine, cosmetics, bioengineering and organizational project.
The preparation method of microcapsules has a lot.According to the principle that cyst wall forms, the traditional preparation process technology of microcapsules cardinal principle can be divided three classes: the physical method of the chemical method of utilization reaction generation cyst wall, the physico-chemical process that utilizes the formation cyst wall that is separated and utilization machinery or other physical action formation cyst wall.Cyst wall is made up of natural or synthetic macromolecular material usually, also inorganic compound.
In recent years, developed the preparation method of many new microcapsules again, as template assembling, matrix polymerization, surface grafting polymerization, dispersin polymerization etc.Wherein, has structure based on the microcapsules of the layer one deck self-assembling technique preparation of weak interaction and performance is controlled, easily give characteristics such as various unique functions.These weak interactions comprise electrostatic force, hydrogen bond, hydrophobic force etc.Wherein, by the microcapsules that electrostatic interaction forms, its preparation process can be carried out in water, can avoid the pollution to environment.The size of gained microcapsules is controlled in advance by template, and its wall thickness can be controlled in the nanoscale.The permeability of microcapsules and the release performance of embedding substance can be controlled by environmental condition such as temperature, ionic species and ionic strength, pH value, SOLUTION PROPERTIES, light, electricity, sound etc.Therefore discharge in medicine control, fields such as the embedding of enzyme and catalytic reaction, organizational project have shown crucial application prospect.But, many, the consuming time length of this preparation method's step, waste raw material, and preparation process easily causes the gathering and the final aggregation that forms microcapsules of particulate.These drawbacks limit its promotion and application.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing doping porous calcium carbonate mould plates to prepare microcapsules simply and rapidly.
The method of utilizing doping porous calcium carbonate mould plates to prepare microcapsules of the present invention may further comprise the steps:
1) be to add electronegative polyelectrolyte in the calcic inorganic salt solution of 0.001-0.33M in concentration, stir or ultrasonic concussion under add the aqueous solution with the carbonate inorganic salts of the amount of calcic inorganic salts same substance; The ratio of electronegative polyelectrolyte and calcium ion is 0.1～20g/mol, stir reaction down 1 minute～4 hours, or left standstill after ultrasonic 2～20 seconds 1 minute～4 hours, centrifugal filtration obtains diameter and is the CaCO that the anionic polyelectrolyte of 500 nanometers～20 micron mixes
3Colloidal particles;
2) in the NaCl of 0.1～3M solution, with concentration the polyelectrolyte of positively charged of 0.2～10mg/mL and the CaCO of step 1)
3Colloidal particles are mixed after 10 minutes, and the water cyclic washing is removed the not polyelectrolyte of the positively charged of absorption, obtains the CaCO that skin is coated with the polyelectrolyte of positively charged
3Colloidal particles;
3) add diluted acid and decompose or ethylenediamine tetra-acetic acid (EDTA) complexing, remove CaCO
3Colloidal particles form hollow microcapsule.
Among the present invention, said calcic inorganic salts can be calcium nitrate or calcium chloride, and the said carbonate inorganic salts that contain can be sodium carbonate, potash or ammonium hydrogencarbonate.
Among the present invention, said electronegative polyelectrolyte can be kayexalate, polyacrylic acid, polymethylacrylic acid, chondroitin sulfate, heparin sulfate, hyaluronic acid, dextran sulfate, DNA or sodium carboxymethylcellulose.
Among the present invention, the polyelectrolyte of said positively charged can be polyene propyl ammonium hydrochloride, polydiene propyl-dimethyl quaternary ammonium salt, shitosan, collagen, polylysine, cationization glucan, cationization polyacrylate or polymine.The said diluted acid of step 3) of the present invention is hydrochloric acid or nitric acid.
The principle of the inventive method is: in the presence of electronegative polyelectrolyte, by calcic inorganic salts and the reaction that contains the carbonate inorganic salts, obtain to include the porous calcium carbonate particulate of electronegative polyelectrolyte, this CaCO
3Colloidal particles have the characteristics of rough surface, inner porous.By electrostatic interaction and physisorption, adsorb the polyelectrolyte that one deck has positive charge at this microparticle surfaces, because the surface of particulate is very coarse, the amount of the positively charged polyelectrolyte of absorption is therefore very big.Then by decomposing with diluted acid or ethylenediamine tetra-acetic acid (EDTA) complexing removal calcium carbonate microparticle.In this process, the inner electronegative polyelectrolyte of calcium carbonate discharges and combines with the positively charged polyelectrolyte of microparticle surfaces absorption immediately and forms elementary cyst wall; Along with the continuous release and the absorption of the electronegative polyelectrolyte of inside, elementary cyst wall constantly thickens and finally obtains hollow microcapsule.
Preparation method of the present invention is simple and efficient, material source is extensive, and a step can obtain the polyelectrolyte hollow microcapsule, can keep the plurality of advantages of static assembling microcapsules simultaneously, has excellent industrial application foreground.
Description of drawings
Fig. 1 is a) for containing the CaCO of PSS
3The stereoscan photograph of particulate is b) for containing the CaCO of PSS
3Stereoscan photograph after amplify the part of particulate;
Fig. 2 is the stereoscan photograph of dry back microcapsules;
Fig. 3 is the transmission electron microscope photo of dry back microcapsules;
Fig. 4 is the laser confocal microscope picture of microcapsules;
Fig. 5 is the CaCO that contains PSS
3The stereoscan photograph of particulate;
Fig. 6 is the stereoscan photograph of dry back microcapsules;
Fig. 7 is the laser confocal microscope picture of microcapsules.
The specific embodiment
Further specify the present invention below in conjunction with example, but these examples are not used for limiting the present invention.
Example 1
1) be that the calcium nitrate solution of 0.05M mixes (PSS/[Ca with 100mg kayexalate (PSS) with 100mL concentration
2+]=2g/mol) after 10 minutes, adds the sodium carbonate liquor that 100mL concentration is 0.05M, ultrasonic concussion 10 seconds fast.After leaving standstill 1 hour, the calcium carbonate that contains PSS that generates (is expressed as CaCO
3(PSS)) precipitate centrifugal collection, wash with water 3 times.The CaCO of preparation
3(PSS) mean particle dia is about 5 microns, and stereoscan photograph is seen Fig. 1 a, b.
2) get an amount of above-mentioned CaCO
3(PSS) particulate places the centrifuge tube of 2mL, washes with water 3 times.In the NaCl of 1M solution, add PAH hydrochloride (PAH) solution of 1mL, the vibration centrifuge tube.After 10 minutes, wash with water 3 times, remove unnecessary PAH, thereby at CaCO
3(PSS) surface has been adsorbed one deck PAH and (has been expressed as CaCO
3(PSS)-PAH).
3) adding concentration to this core-shell particle solution is ethylenediamine tetra-acetic acid (EDTA) solution of 0.02M, reacts 15 minutes, removes CaCO
3Particulate.With EDTA solution repeated washing for several times.Centrifugal removal supernatant washes with water 3 times, obtains being suspended in the poly-dielectric hollow microcapsule in the water.Dried microcapsules stereoscan photograph is seen Fig. 2, and transmission electron microscope photo is seen Fig. 3.The laser confocal microscope photo of the microcapsules of the rhodamine mark that disperses in the water is seen Fig. 4.
Example 2
1) method with example 1 step 1) prepares CaCO
3But time of repose is 2 minutes (PSS).The CaCO of preparation
3(PSS) mean particle dia is about 500 nanometers.
Step 2) and 3) with the step 2 of example 1) and 3).
Example 3
1) method with example 1 step 1) prepares CaCO
3But time of repose is 4 hours (PSS).The CaCO of preparation
3(PSS) mean particle dia is about 20 microns.
Step 2) and 3) with the step 2 of example 1) and 3).
Example 4
1) be that the calcium nitrate solution of 0.05M mixes (PSS/[Ca with 100mg kayexalate (PSS) with 100mL concentration
2+]=2g/mol), after 10 minutes, under agitation adding 100mL concentration fast is sodium carbonate liquor and lasting stirring of 0.05M.Calcium carbonate (the CaCO that contains PSS that will generate after 30 minutes
3(PSS)) precipitate centrifugal collection, wash with water 3 times.
Step 2) and 3) with the step 2 of example 1) and 3)
Example 5
1) method with example 1 prepares the CaCO that contains PSS
3Particulate, but used calcic inorganic salts are calcium chloride, and the used carbonate inorganic salts that contain are ammonium hydrogencarbonates, leave standstill to collect the calcium carbonate (CaCO that contains PSS after 30 minutes
3(PSS)).The CaCO of preparation
3(PSS) stereoscan photograph of particulate is seen Fig. 5.
Step 2) and 3) with the step 2 of example 1) and 3).
Example 6
1) method with example 1 step 1) prepares the CaCO that contains PSS
3Particulate, but the addition of PSS is 500mg (PSS/[Ca
2+]=10g/mol) collected the calcium carbonate (CaCO that contains PSS after 1 hour
3(PSS)).
Step 2) and 3) with the step 2 of example 1) and 3).
Dried microcapsules stereoscan photograph is seen Fig. 6.
Example 7
1) prepares the CaCO of electronegative polyelectrolyte with the method for example 1 step 1)
3Particulate, but the electronegative polyelectrolyte that adds is a sodium carboxymethylcellulose, collects the calcium carbonate that contains sodium carboxymethylcellulose after 30 minutes.
Step 2) and 3) with the step 2 of example 1) and 3).
The PAH that with electronegative polyelectrolyte is sodium carboxymethylcellulose, rhodamine mark sees Fig. 7 for the microcapsules laser confocal microscope picture that the positively charged polyelectrolyte obtains.
Example 8
1) prepares the CaCO of electronegative polyelectrolyte with the method for example 1 step 1)
3Particulate, but the electronegative polyelectrolyte that adds is a dextran sulfate, collects the calcium carbonate that contains dextran sulfate after 30 minutes.
Step 2) and 3) with the step 2 of example 1) and 3).
Example 9
1) method with example 1 step 1) prepares the CaCO that contains PSS
3Particulate;
2) method usefulness example 1 step 2) is at CaCO
3(PSS) surface absorption one deck positively charged polyelectrolyte, but the positively charged polyelectrolyte that adds is polymine (PEI).Adsorb after 10 minutes, wash with water 3 times, remove unnecessary PEI;
Step 3) is with the step 3) of example 1.
Example 10
1) method with example 1 step 1) prepares the CaCO that contains PSS
3Particulate;
2) method usefulness example 1 step 2) is at CaCO
3(PSS) surface absorption one deck positively charged polyelectrolyte, but the positively charged polyelectrolyte that adds is a polylysine.Adsorb after 10 minutes, wash with water 3 times, remove unnecessary polylysine;
Step 3) is with the step 3) of example 1.
Example 11
Step 1) and 2) with the step 1) and 2 of example 1).
3) method with example 1 step 3) prepares microcapsules, but used stoning agent is HCl.After the PAH assembling finished and adds water washing, adding pH value was 3～4 the HCl aqueous solution, reacts 15 minutes, removes CaCO
3Particulate.With HCl aqueous solution repeated washing for several times, centrifugal removal supernatant.Wash with water 3 times, obtain being suspended in the poly-dielectric hollow microcapsule in the water.
Claims (6)
1. method of utilizing doping porous calcium carbonate mould plates to prepare microcapsules, this method may further comprise the steps:
1) be to add electronegative polyelectrolyte in the calcic inorganic salt solution of 0.001-0.33M in concentration, stir or ultrasonic concussion under add the aqueous solution with the carbonate inorganic salts of the amount of calcic inorganic salts same substance; The ratio of electronegative polyelectrolyte and calcium ion is 0.1～20g/mol, stir reaction down 1 minute～4 hours, or left standstill after ultrasonic 2～20 seconds 1 minute～4 hours, centrifugal filtration obtains diameter and is the CaCO that the anionic polyelectrolyte of 500 nanometers～20 micron mixes
3Colloidal particles;
2) in the NaCl of 0.1～3M solution, with concentration the polyelectrolyte of positively charged of 0.2～10mg/mL and the CaCO of step 1)
3Colloidal particles are mixed after 10 minutes, and the water cyclic washing is removed the not polyelectrolyte of the positively charged of absorption, obtains the CaCO that skin is coated with the polyelectrolyte of positively charged
3Colloidal particles;
3) add diluted acid and decompose or EDTA complex, remove CaCO
3Colloidal particles form hollow microcapsule.
2. the method for utilizing doping porous calcium carbonate mould plates to prepare microcapsules according to claim 1 is characterized in that said calcic inorganic salts are calcium nitrate or calcium chloride.
3. the method for utilizing doping porous calcium carbonate mould plates to prepare microcapsules according to claim 1 is characterized in that the said carbonate inorganic salts that contain are sodium carbonate, potash or ammonium hydrogencarbonate.
4. the method for utilizing doping porous calcium carbonate mould plates to prepare microcapsules according to claim 1 is characterized in that said electronegative polyelectrolyte is kayexalate, polyacrylic acid, polymethylacrylic acid, chondroitin sulfate, heparin sulfate, hyaluronic acid, dextran sulfate, DNA or sodium carboxymethylcellulose.
5. the method for utilizing doping porous calcium carbonate mould plates to prepare microcapsules according to claim 1, the polyelectrolyte that it is characterized in that said positively charged are polyene propyl ammonium hydrochloride, polydiene propyl-dimethyl quaternary ammonium salt, shitosan, collagen, polylysine, cationization glucan, cationization polyacrylate or polymine.
6. the method for utilizing doping porous calcium carbonate mould plates to prepare microcapsules according to claim 1 is characterized in that the said diluted acid of step 3) is hydrochloric acid or nitric acid.
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