CN109350606B - Preparation method of polyelectrolyte hollow capsule and hollow capsule obtained by preparation method - Google Patents
Preparation method of polyelectrolyte hollow capsule and hollow capsule obtained by preparation method Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/4816—Wall or shell material
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/4891—Coated capsules; Multilayered drug free capsule shells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
Abstract
The invention discloses a preparation method of a polyelectrolyte hollow capsule and the hollow capsule obtained by the preparation method, wherein, a low molecular weight polyelectrolyte solution is dripped into a high molecular weight polyelectrolyte solution, and the hollow capsule can be formed under the oscillation treatment; the preparation method is simple, low in cost and suitable for large-scale production, and meanwhile, the prepared hollow capsule has controllable layer number, can be used for medical biomaterials and drug carriers, and has good adsorption performance.
Description
Technical Field
The invention relates to the field of capsules, in particular to a preparation method of a hollow capsule, and particularly relates to a preparation method of a polyelectrolyte hollow capsule and the hollow capsule.
Background
Hollow capsules have been widely used in the industrial fields of food, medicine, cosmetics, bioengineering, tissue engineering and the like, and with the continuous improvement of requirements on product structure and performance indexes, different problems or technical bottlenecks have been met more or less by emulsion method and template method preparation process technologies commonly adopted in the prior art.
For example, in the template method in the prior art, the particles are used as templates, the polymer ultrathin film is assembled on the template particles by using a layer-by-layer self-assembly technology, and after the templates are removed, microcapsules with controllable structures and properties, which are easily endowed with various unique functions and meet the use requirements of end products are obtained.
However, the material of the template is generally CaCO3Gold, silicon or other inorganic materials, the template manufacturing process is complex, the cost is high, and the flexible production cannot be carried out due to the limitation of factors such as the shape and the size of the template.
The emulsion method has the problems and disadvantages that firstly, because a large amount of surfactant or other chemical stabilizer is added in the preparation process, the capsule product inevitably has certain congenital defects of more or less residual toxic chemical components. Secondly, the production cost is relatively high and the treatment process is complex. In addition, side reactions during the synthesis process have a significant influence on the capsule properties.
Disclosure of Invention
In order to overcome the problems, the inventor of the present invention has conducted intensive research and provides a simple and environment-friendly method for preparing a polyelectrolyte hollow capsule, which is a one-step method, has a low preparation cost and is suitable for large-scale production; meanwhile, the prepared polyelectrolyte hollow capsule has controllable layer number, can be used for medical biomaterials and drug carriers, and has good research, development and utilization prospects. The invention aims to provide a preparation method of a polyelectrolyte hollow capsule, which is embodied in the following aspects:
(1) a method for preparing a polyelectrolyte hollow capsule, wherein the method comprises the following steps:
step 1, adding a low-molecular-weight polyelectrolyte into water to obtain a solution A;
step 2, adding high molecular weight polyelectrolyte into water to obtain solution B;
step 3, dropwise adding the solution A obtained in the step 1 into the solution B, and then carrying out oscillation treatment to obtain the polyelectrolyte hollow capsule; wherein the content of the first and second substances,
the low molecular weight polyelectrolyte is selected from polyacrylic acid or poly (dimethylaminoethyl methacrylate);
the high molecular weight polyelectrolyte is selected from sodium alginate or chitosan.
(2) The production method according to the above (1), wherein the low-molecular-weight polyelectrolyte and the high-molecular-weight polyelectrolyte have opposite charges.
(3) The production method according to the above (1) or (2), wherein, in the step 1,
the molecular weight of the low molecular weight polyelectrolyte is 2000-10000 Da, preferably 2000-4000 Da.
(4) The production method according to one of the above (1) to (3), wherein, in step 2,
the molecular weight of the high molecular weight polyelectrolyte is 100000-800000 Da, preferably 300000-700000 Da, and more preferably 400000-600000 Da.
(5) The production method according to one of the above (1) to (4), wherein in the step 1, the concentration of the low-molecular-weight polyelectrolyte in the solution A is 5 to 60% by mass, preferably 10 to 40% by mass, more preferably 10 to 30% by mass, for example 10 to 20% by mass; and/or
In the step 2, the mass percentage concentration of the high molecular weight polyelectrolyte in the solution B is 0.5-5%, preferably 1-3%.
(6) The production method according to one of the above (1) to (5), wherein, in step 3,
adding the solution A into the solution B according to the volume ratio of 1 (10-500), preferably 1 (10-200), more preferably 1: 50; and/or
The oscillation or stirring is carried out for 1-24 hours, preferably for 2-8 hours, and more preferably for 4-6 hours.
(7) The production method according to one of the above (1) to (6), wherein, in the step 1, NaCl is optionally added, preferably, 0.1 to 5M NaCl is optionally added, more preferably,
when the low molecular weight polyelectrolyte is selected from polyacrylic acid and the high molecular weight polyelectrolyte is selected from chitosan, 3-5M NaCl is preferably added;
when the low molecular weight polyelectrolyte is selected from dimethylaminoethyl methacrylate and the high molecular weight polyelectrolyte is selected from sodium alginate, 0.5-1.5M NaCl, such as 1M NaCl, is preferably added.
(8) The production process according to one of the above (1) to (7), wherein, in the step 1, the pH of the solution A is optionally adjusted to 2 to 6, preferably, the pH of the solution A is optionally adjusted to 2 to 5.
The second purpose of the present invention is to provide a polyelectrolyte hollow capsule obtained by the above preparation method.
Drawings
FIG. 1 shows one of the electron micrographs of the polyacrylic acid/chitosan capsules produced in example 1 (mainly showing the overall cross section of the capsule);
FIG. 2 shows a second electron micrograph of a polyacrylic acid/chitosan capsule prepared in example 1 (mainly showing the layer structure of the capsule);
FIG. 3 is an electron micrograph of a sodium alginate/dimethylaminoethyl methacrylate capsule prepared in example 3 (mainly showing the whole cross section of the capsule);
FIG. 4 is a second electron micrograph of the sodium alginate/dimethylaminoethyl methacrylate capsule prepared in example 3 (mainly showing the layer-by-layer structure of the capsule);
FIG. 5 is an electron micrograph of a polyacrylic acid/chitosan capsule prepared in comparative example 2 (mainly showing an overall cross section of the capsule).
Detailed Description
The present invention will be described in further detail below with reference to examples and experimental examples. The features and advantages of the present invention will become more apparent from the description. The invention provides a preparation method of a polyelectrolyte hollow capsule, which comprises the following steps:
step 1, adding a low-molecular-weight polyelectrolyte into water to obtain a solution A;
step 2, adding high molecular weight polyelectrolyte into water to obtain solution B;
and 3, dropwise adding the solution A obtained in the step 1 into the solution B, and then carrying out oscillation treatment to obtain the polyelectrolyte hollow capsule.
Wherein, the electrostatic interaction between the low molecular weight polyelectrolyte and the high molecular weight polyelectrolyte (with opposite positive and negative charges respectively) is utilized to complex the low molecular weight polyelectrolyte and the high molecular weight polyelectrolyte to form a polyelectrolyte complex membrane; then, under the driving action of osmotic pressure, the low molecular weight polyelectrolyte can spontaneously penetrate through the complexing membrane to continuously diffuse towards the direction of the high molecular weight polyelectrolyte, and then is complexed with the high molecular weight polyelectrolyte again to form a new complexing membrane. The solution is spontaneously and continuously repeated with the complexing-diffusing-re-complexing process, and the capsules with different capsule wall layer numbers can be obtained by controlling. According to a preferred embodiment of the invention, the low molecular weight polyelectrolyte and the high molecular weight polyelectrolyte are oppositely charged.
Thus, an electrostatic interaction can be formed between the two.
In a further preferred embodiment, the molecular weight of the low molecular weight polyelectrolyte is lower than the molecular weight of the high molecular weight polyelectrolyte.
According to a preferred embodiment of the invention, the low molecular weight polyelectrolyte is selected from polyacrylic acid or polydimethylaminoethyl methacrylate.
In a further preferred embodiment, the high molecular weight polyelectrolyte is selected from chitosan or sodium alginate.
The hollow capsule obtained in the invention has good adsorption performance and is suitable for sewage treatment of chemical components such as oil-containing agents, organic solvents or organic dyes. The reason is that: (1) even though the polyelectrolyte has positive and negative charges, the polyelectrolyte has functional groups with charges which are not involved in the reaction on the molecular chain and become potential binding sites which can react with organic dyes, so that the binding sites can perform electrostatic interaction with the ionic dyes with positive or negative charges to realize adsorption. (2) The prepared capsule adsorbs oil (pump oil, silicone oil, etc.) and organic solvent (chloroform, toluene, etc.) because pores existing in the capsule itself act as capillaries, and thus adsorption of oil or organic solvent is achieved by capillary action.
According to a preferred embodiment of the present invention, in step 1, the low molecular weight polyelectrolyte has a molecular weight of 2000 to 10000 Da.
In a further preferred embodiment, in step 1, the low molecular weight polyelectrolyte has a molecular weight of 2000 to 4000 Da.
When the number average molecular weight of the low molecular weight polyelectrolyte is less than 2000Da, the low molecular weight polyelectrolyte and the high molecular weight polyelectrolyte have complexation reaction, and the low molecular weight polyelectrolyte and the high molecular weight polyelectrolyte have few binding sites and insufficient entanglement, so that the low molecular weight polyelectrolyte cannot support a film, especially a film with a certain curvature, and finally composite precipitated particles are formed. Meanwhile, if the number average molecular weight of the low molecular weight polyelectrolyte is more than 10000Da, the low molecular weight polyelectrolyte and the high molecular weight polyelectrolyte have electrostatic complexation to form a complexing layer with a compact structure, the low molecular weight polyelectrolyte cannot penetrate through the complexing layer, the diffusion process is prevented, and finally a hollow structure cannot be formed.
According to a preferred embodiment of the present invention, in step 2, the molecular weight of the high molecular weight polyelectrolyte is 100000 to 800000 Da.
In a further preferred embodiment, in step 2, the high molecular weight polyelectrolyte has a molecular weight of 300000 to 700000 Da.
In a further preferred embodiment, in step 2, the high molecular weight polyelectrolyte has a molecular weight of 400000 to 600000 Da.
If the molecular weight of the high molecular weight polyelectrolyte exceeds the above range, the polyelectrolyte film formed by the complexation reaction of the high molecular weight polyelectrolyte and the low molecular weight polyelectrolyte is too compact, which may result in that the low molecular weight polyelectrolyte molecules cannot pass through the polyelectrolyte film, thereby hindering the further diffusion of the low molecular weight polyelectrolyte, and not performing the complexation-diffusion-re-complexation process, and finally, only one layer of film with a compact structure can be obtained.
According to a preferred embodiment of the present invention, in step 1, the concentration of the low molecular weight polyelectrolyte in the solution a is 5 to 60% by mass. In a further preferred embodiment, in step 1, the concentration of the low molecular weight polyelectrolyte in the solution A is 10 to 40% by mass.
In a further preferred embodiment, in step 1, the concentration of the low molecular weight polyelectrolyte in the solution A is 10 to 30% by mass, for example 10 to 20% by mass.
The inventor finds that the concentration of the low-molecular-weight polyelectrolyte in the solution A has an important influence on the number of layers of the obtained hollow capsules through a large number of experiments, specifically, the concentration of the low-molecular-weight polyelectrolyte in the solution A is increased, so that the number of layers of the hollow capsules can be changed from single layer to multiple layers, and the number of the layers of the obtained hollow capsules is increased along with the increase of the concentration, so that the hollow capsules with controllable number of the layers can be obtained by using the method.
According to a preferred embodiment of the present invention, in step 2, the mass percentage concentration of the high molecular weight polyelectrolyte in the solution B is 0.5-5%. In a further preferred embodiment, in the step 2, the mass percentage concentration of the high molecular weight polyelectrolyte in the solution B is 1-3%.
Wherein, the low molecular weight polyelectrolyte is controlled under a higher concentration (5-60%), and the high molecular weight polyelectrolyte is controlled under a relatively low concentration (0.5-5%), so that osmotic pressure is formed by the ion concentration difference between the low molecular weight polyelectrolyte and the high molecular weight polyelectrolyte, the low molecular weight polyelectrolyte diffuses to the high molecular weight polyelectrolyte under the osmotic pressure, and then the low molecular weight polyelectrolyte and the high molecular weight polyelectrolyte are combined by utilizing electrostatic action to form a membrane.
According to a preferred embodiment of the invention, in the step 3, the solution A is added into the solution B according to the volume ratio of 1 (10-500).
In a further preferred embodiment, in the step 3, the solution A is added into the solution B according to the volume ratio of 1 (10-200).
In a further preferred embodiment, in step 3, the solution A is added to the solution B in a volume ratio of 1 (10-100), for example 1: 50.
According to a preferred embodiment of the present invention, in step 3, the oscillation treatment is performed for 1 to 24 hours.
In a further preferred embodiment, in step 3, the shaking treatment is performed for 2 to 8 hours.
In a further preferred embodiment, in step 3, the shaking treatment is performed for 4 to 6 hours.
Among them, the purpose of shaking is to promote the molecular diffusion better, prevent the capsule from adhering to the wall.
According to a preferred embodiment of the invention, in step 1, NaCl is optionally added.
In a further preferred embodiment, in step 1, 0.1 to 5M NaCl is optionally added.
In a further preferred embodiment, in step 1, 3 to 5M NaCl is preferably added when the low molecular weight polyelectrolyte is selected from polyacrylic acid and the high molecular weight polyelectrolyte is selected from chitosan, and 0.5 to 1.5M NaCl, for example 1M NaCl, is preferably added when the low molecular weight polyelectrolyte is selected from polydimethylaminoethyl methacrylate and the high molecular weight polyelectrolyte is selected from sodium alginate.
The sodium chloride is used as a micromolecular electrolyte, can shield the charges of the low-molecular-weight polyelectrolyte and the high-molecular-weight polyelectrolyte, and weakens the electrostatic action between the low-molecular-weight polyelectrolyte and the high-molecular-weight polyelectrolyte, so that the capsule wall structure of the capsule is looser, namely the capsule wall structure with larger pore diameter is obtained, and the hollow capsule with looser structure is more beneficial to the application of oil absorption. In addition, after the sodium chloride is added, part of polyelectrolyte is temporarily shielded from charges, and some binding sites capable of reacting with the organic dye are stored/reserved, so that the obtained hollow capsule has more excellent adsorption performance on the organic dye.
According to a preferred embodiment of the present invention, in step 2, the pH of solution B is optionally adjusted to 2-6.
Wherein, because the low molecular weight polyelectrolyte and the high molecular weight polyelectrolyte both have certain acidity coefficients pKa, the charge density can be changed by adjusting the pH of the reaction system, thereby influencing the electrostatic complexation degree between the low molecular weight polyelectrolyte and the high molecular weight polyelectrolyte. Specifically, the farther away from the acidity coefficient pKa, the greater the charge density, the stronger the binding force between the low molecular weight polyelectrolyte and the high molecular weight polyelectrolyte, and the tighter the structure of the resulting complex film; on the contrary, the closer to the acidity coefficient pKa, the smaller the charge density, the weaker the binding force between the low molecular weight polyelectrolyte and the high molecular weight polyelectrolyte, and the looser the structure of the resulting complex film.
In a further preferred embodiment, in step 2, the pH of solution B is optionally adjusted to 2-5.
Therefore, in an acidic pH environment, the hollow capsule with a loose capsule wall can be obtained, so that the capsule is endowed with more excellent adsorption performance.
In a further preferred embodiment, acetic acid is used for adjusting the pH value, for example, the volume ratio of acetic acid to water is 1 (30-80), preferably 1 (40-60).
In a second aspect of the present invention, there is provided a hollow capsule obtained by the method according to the first aspect of the present invention.
The invention has the advantages that:
(1) the preparation method is simple, the capsule can be prepared at normal temperature and normal pressure, the preparation process is carried out at normal temperature and normal pressure, the process parameters are easy to control, and the production efficiency is high;
(2) the preparation method can be used for preparing the capsule with a single-layer structure or a plurality of layers of capsule wall structures, and more importantly, the pore size gradient, the number of layers and the components of the capsule wall of the capsule can be randomly adjusted and controlled according to the needs.
(3) Each layer of the capsule obtained by the preparation method is a closed sphere, so that the prepared capsule product is particularly suitable for being used as a medicine carrier;
(4) the capsule prepared by the preparation method has good adsorption performance and is suitable for sewage treatment of chemical components such as oil-containing agents, organic solvents or organic dyes.
Examples
The invention is further described below by means of specific examples. However, these examples are only illustrative and do not limit the scope of the present invention.
Example 1
According to the mass ratio of 15: 1, respectively weighing polyacrylic acid with molecular weight of 2000Da and chitosan with molecular weight of 75 ten thousand Da for later use;
adding the taken polyacrylic acid into 29.25% sodium chloride (5M NaCl) solution for dissolving to prepare solution A with the mass percentage concentration of 15%;
adding deionized water and acetic acid (50:1) into the chitosan to prepare a solution B with the mass percentage concentration of 1%;
and (3) dropwise soaking the solution A into the solution B according to the volume ratio of 1:50 under shaking, and continuously shaking for 1h to obtain the hollow capsule.
The electron microscope examination of the obtained hollow capsule shows that the result is shown in fig. 1-2, and the polyacrylic acid/chitosan capsule is a hollow multi-layer structure, the diameter of the capsule is about 2mm, and the number of layers is 4.
Example 2
According to the mass ratio of 20:1, respectively weighing polyacrylic acid with molecular weight of 2000Da and chitosan with molecular weight of 75 ten thousand Da for later use;
adding the taken polyacrylic acid into 29.25% sodium chloride (5M NaCl) solution for dissolving to prepare solution A with the mass percentage concentration of 20%;
adding deionized water and acetic acid (50:1) into the chitosan to prepare a solution B with the mass percentage concentration of 1%;
and (3) dropwise soaking the solution A into the solution B according to the volume ratio of 1:50 under shaking, and continuously shaking for 1h to obtain the hollow capsule.
And (3) carrying out electron microscope detection on the obtained hollow capsule, wherein the prepared polyacrylic acid/chitosan capsule is of a hollow multilayer structure, the diameter of the capsule is about 3mm, and the number of layers is 6.
Example 3
Weighing dimethylaminoethyl methacrylate with the molecular weight of 4000Da and sodium alginate with the molecular weight of 30 ten thousand Da respectively according to the mass ratio of 20:1 for later use; adding the obtained dimethylaminoethyl methacrylate into a 5.85% sodium chloride (1M NaCl) solution for dissolving to prepare a solution A with the mass percentage concentration of 20%;
adding the sodium alginate into deionized water, dissolving, and preparing into a solution B with the mass percentage concentration of 1%;
and (3) dropwise soaking the solution A into the solution B in a volume ratio of 1:50 under shaking, and continuously shaking for 4 hours to obtain the hollow capsule.
The electron microscope examination of the obtained hollow capsule shows that the results are shown in fig. 3-4, and it can be seen that the prepared sodium alginate/poly (dimethylaminoethyl methacrylate) capsule is a hollow multilayer structure, the diameter is about 4mm, and the number of layers is 3.
Example 4
Weighing dimethylaminoethyl methacrylate with the molecular weight of 4000Da and sodium alginate with the molecular weight of 30 ten thousand Da respectively according to the mass ratio of 20:1 for later use; adding the obtained dimethylaminoethyl methacrylate into a 5.85% sodium chloride (1M NaCl) solution for dissolving to prepare a solution A with the mass percentage concentration of 20%;
adding the sodium alginate into deionized water, dissolving, and preparing into a solution B with the mass percentage concentration of 2%;
and (3) dropwise soaking the solution A into the solution B in a volume ratio of 1:50 under shaking, and continuously shaking for 4 hours to obtain the hollow capsule.
And (3) detecting the obtained hollow capsule by an electron microscope (the magnification is 40 times), wherein the prepared sodium alginate/dimethylamino ethyl polymethacrylate capsule has a hollow multilayer structure, the diameter of the capsule is about 3mm, and the number of layers is 2.
Example 5
According to the mass ratio of 15: 1, respectively weighing polyacrylic acid with the molecular weight of 1 ten thousand Da and chitosan with the molecular weight of 80 ten thousand Da for later use;
adding the taken polyacrylic acid into 29.25% sodium chloride (5M NaCl) solution for dissolving to prepare solution A with the mass percentage concentration of 10%;
adding deionized water and acetic acid (50:1) into the chitosan to prepare a solution B with the mass percentage concentration of 3%;
and (3) dropwise soaking the solution A into the solution B in a volume ratio of 1:40 under shaking, and continuously shaking for 6 hours to obtain hollow capsules.
Example 6
According to the mass ratio of 15: 1, respectively weighing polyacrylic acid with molecular weight of 6000Da and chitosan with molecular weight of 70 ten thousand Da for later use;
adding the taken polyacrylic acid into 29.25% sodium chloride (5M NaCl) solution for dissolving to prepare solution A with the mass percentage concentration of 30%;
adding deionized water and acetic acid (40:1) into the chitosan to prepare a solution B with the mass percentage concentration of 5%;
and (3) dropwise soaking the solution A into the solution B according to the volume ratio of 1:60 under shaking, and continuously shaking for 8 hours to obtain the hollow capsule.
Example 7
According to the mass ratio of 15: 1, respectively weighing polyacrylic acid with the molecular weight of 5000Da and chitosan with the molecular weight of 60 ten thousand Da for later use;
adding the taken polyacrylic acid into 29.25% sodium chloride (5M NaCl) solution for dissolving to prepare solution A with the mass percentage concentration of 40%;
adding deionized water and acetic acid (60:1) into the chitosan to prepare a solution B with the mass percentage concentration of 4%;
and (3) dropwise soaking the solution A into the solution B according to the volume ratio of 1:100 under shaking, and continuously shaking for 2 hours to obtain the hollow capsule.
Example 8
The procedure of example 1 was repeated except that: the molar concentration of sodium chloride was 3M, and hollow capsules were also obtained.
Comparative example
Comparative example 1
The procedure of example 1 was repeated except that: the mass percentage concentration of chitosan in solution B was very low, only 0.1%.
As a result, it was found that when the concentration of chitosan (high molecular weight polyelectrolyte) is very low, a precipitate is formed. Due to insufficient entanglement between chitosan chains and between sodium alginate and polyacrylic acid, insufficient binding sites of chitosan and polyacrylic acid only form precipitates, which are insufficient for supporting the membrane, especially for forming a membrane with a certain curvature.
Comparative example 2
The procedure of example 1 was repeated except that: the molar concentration of sodium chloride was 2M. The obtained capsule was examined by electron microscopy, and as shown in FIG. 5, it was found that the obtained capsule had a solid structure.
Comparative example 3
The procedure of example 2 was repeated except that: the solution A is directly added into the solution B and stirred and mixed, but not dropwise added.
It was found that the hollow capsule could not be formed at all, but was in a state like "slimy" as a whole.
The invention has been described in detail with reference to the preferred embodiments and illustrative examples. It should be noted, however, that these specific embodiments are only illustrative of the present invention and do not limit the scope of the present invention in any way. Various modifications, equivalent substitutions and alterations can be made to the technical content and embodiments of the present invention without departing from the spirit and scope of the present invention, and these are within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (8)
1. A method for preparing a polyelectrolyte hollow capsule, which is characterized by comprising the following steps:
step 1, adding a low-molecular-weight polyelectrolyte into water to obtain a solution A;
step 2, adding high molecular weight polyelectrolyte into water to obtain solution B;
step 3, dropwise adding the solution A obtained in the step 1 into the solution B, and then carrying out oscillation treatment to obtain the polyelectrolyte hollow capsule; wherein the content of the first and second substances,
the low molecular weight polyelectrolyte is selected from polyacrylic acid or poly (dimethylaminoethyl methacrylate);
the high molecular weight polyelectrolyte is selected from sodium alginate or chitosan;
the low molecular weight polyelectrolyte and the high molecular weight polyelectrolyte have opposite charges;
in the step 1, the mass percent concentration of the low molecular weight polyelectrolyte in the solution A is 10-60%, and in the step 2, the mass percent concentration of the high molecular weight polyelectrolyte in the solution B is 0.5-3%;
adding the solution A into the solution B according to the volume ratio of 1 (10-500);
the molecular weight of the low molecular weight polyelectrolyte is 2000-10000 Da;
the molecular weight of the high molecular weight polyelectrolyte is 100000-800000 Da.
2. The production method according to claim 1,
in the step 1, in the solution A, the mass percent concentration of the low-molecular-weight polyelectrolyte is 10-40%; and/or
In the step 2, the mass percentage concentration of the high molecular weight polyelectrolyte in the solution B is 1-3%.
3. The production method according to claim 1, wherein, in step 3,
adding the solution A into the solution B according to the volume ratio of 1 (10-200); and/or
The shaking is carried out for 1-24 h.
4. The production method according to claim 3, wherein, in step 3,
adding the solution A into the solution B according to the volume ratio of 1: 50; and/or
The shaking is carried out for 2-8 h.
5. The method according to any one of claims 1 to 4, wherein 0.1 to 5M NaC1 is added in step 1.
6. The production method according to claim 5,
when the low molecular weight polyelectrolyte is selected from polyacrylic acid and the high molecular weight polyelectrolyte is selected from chitosan, 3-5M NaCl is added;
when the low molecular weight polyelectrolyte is selected from dimethylaminoethyl methacrylate and the high molecular weight polyelectrolyte is selected from alginic acid, 0.5-1.5M NaC1 is added.
7. The method according to claim 6, wherein the pH of the solution A is adjusted to 2 to 6 in the step 1.
8. A polyelectrolyte hollow capsule obtained by the production method according to any one of claims 1 to 7.
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| WO2000001373A1 (en) * | 1998-07-06 | 2000-01-13 | Ecole Polytechnique Federale De Lausanne | Materials and methods relating to encapsulation |
| WO2003067952A2 (en) * | 2002-02-12 | 2003-08-21 | Ranbaxy Laboratories Limited | Glucosamine-polyacrylate inter-polymer complex and applications thereof |
| CN102058562A (en) * | 2011-01-26 | 2011-05-18 | 上海应用技术学院 | Method for preparing gamma-polyglutamic acid/chitosan nano capsules |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2000001373A1 (en) * | 1998-07-06 | 2000-01-13 | Ecole Polytechnique Federale De Lausanne | Materials and methods relating to encapsulation |
| WO2003067952A2 (en) * | 2002-02-12 | 2003-08-21 | Ranbaxy Laboratories Limited | Glucosamine-polyacrylate inter-polymer complex and applications thereof |
| CN102058562A (en) * | 2011-01-26 | 2011-05-18 | 上海应用技术学院 | Method for preparing gamma-polyglutamic acid/chitosan nano capsules |
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| 添加物对聚电解质成膜特性的影响及相关机理探讨;陈国等;《物理化学学报》;20070915;第23卷(第9期);全文 * |
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