CN110394129B - Automatic control preparation method of ultra-uniform hollow microspheres - Google Patents
Automatic control preparation method of ultra-uniform hollow microspheres Download PDFInfo
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- CN110394129B CN110394129B CN201910743447.0A CN201910743447A CN110394129B CN 110394129 B CN110394129 B CN 110394129B CN 201910743447 A CN201910743447 A CN 201910743447A CN 110394129 B CN110394129 B CN 110394129B
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Abstract
The invention discloses a method for preparing automatically controlled ultra-uniform hollow microspheres, which adopts wrapped liquid drops as raw materials, uses liquid with highly matched density as a preparation environment, forms ultra-uniform concentric composite wrapped liquid drops by using an external electric field method, adds a polymer precursor into the outer layer liquid of the wrapped liquid drops, and solidifies the outer layer liquid of the wrapped liquid drops by irradiating ultraviolet rays or heating to form the hollow microspheres. The invention has the advantages of easily obtained raw materials, high automation degree, good concentricity and surface roundness and high yield. The hollow microsphere can be widely used in the field of medicines, can also be used as a solid phase substance and a catalyst carrier for chromatographic analysis, and has a large amount of applications in the fields of biochemical analysis, medical diagnosis and the like.
Description
Technical Field
The invention belongs to the technical field of micro-preparation, and particularly relates to an automatically controlled preparation method of ultra-uniform hollow microspheres.
Background
In recent years, the preparation of hollow microspheres of polymers has received much attention. The material with the hollow structure has the characteristics of low density, high specific surface area, high surface permeability, larger internal space and the like, can be used as an intelligent container to coat or control release guest molecules, and has wide application prospects in the fields of filler, drug slow release, catalysis, microreactors, environmental protection and the like.
At present, the methods for preparing the polymer hollow microspheres mainly comprise three types: micro-emulsion method, self-assembly method and template method. Micro-emulsion method: taking polydialkylsiloxane microemulsion as a template, adding disilicon-functional and trisilicon-functional organosilicon monomers, performing polycondensation around the surface of a template core to form polysiloxane microspheres with a core-shell structure, and removing the template core by solvent swelling dialysis to obtain the hollow microsphere molecular box. Self-assembly method: the amphiphilic block copolymer forms a core-shell type micelle or vesicle in a selective solvent, and the shell layer is solidified through a cross-linking reaction to obtain the polymer hollow microsphere with the cross-linked shell layer; or by using a layer-by-layer assembly technology, different substances with opposite charges are deposited on the colloidal particles layer by layer, and then the core part is removed to obtain the hollow microsphere. Template method: and on a stable template interface, polymerizing the reaction monomer around the template to form a polymer shell layer covering the template, and then removing the template by a calcining method or a solvent swelling method to obtain the polymer hollow microspheres. The methods for preparing the hollow polymer microspheres have the advantages that the core body template needs to be removed, the manual operation is complicated, and after the template is removed, the sphere is deformed due to swelling or collapsing in different degrees.
With the development of industrial automation, power electronics have been vigorously developed, and electric fields are applied to various fields. The electric field is added in the manufacturing process of the hollow microspheres, so that the automatic operation of the whole process can be realized, the complexity of manual operation is avoided, the preparation process of the hollow microspheres is effectively simplified, the risk of error occurrence of manual operation is reduced, the technical indexes of concentricity, surface degree and the like of the hollow microspheres are greatly improved, and the yield of the hollow microspheres is also improved.
Disclosure of Invention
The invention aims to provide an automatically controlled preparation method of ultra-uniform hollow microspheres, which improves the concentricity of the hollow microspheres by using an alternating electric field.
The technical solution for realizing the purpose of the invention is as follows: a preparation method of automatically controlled ultra-uniform hollow microspheres is characterized by comprising the following steps: the method for preparing the ultra-uniform hollow microspheres by using the alternating current electric field to adjust the concentricity of the microspheres comprises the following specific steps:
step 1, preparation of a microsphere generation environment: selecting a rectangular container without a top cover, fixing a lower electrode in the rectangular container and at the bottom of the rectangular container, and adding a suspension into the rectangular container to obtain a liquid environment generated by the microspheres;
and 5, powering off the upper electrode and the lower electrode to obtain the microspheres with liquid inside, and removing the liquid inside the microspheres to obtain the hollow microspheres.
Compared with the prior art, the invention has the remarkable advantages that: (1) the concentricity and the surface roundness of the hollow microsphere prepared by adopting the mode of adding the electric field are higher than those of the hollow microsphere prepared by adopting the prior art.
(2) The automatic operation can be realized, and the manual operation is reduced.
(3) The yield of the hollow microspheres is improved to a great extent, the production efficiency is increased, and the cost of a single microsphere is reduced.
Drawings
FIG. 1 is a sectional view of an apparatus for preparing hollow microspheres with ultra-uniformity according to the present invention.
Detailed Description
The invention is described in further detail below with reference to the attached drawing
The invention provides an automatically controlled method for preparing ultra-uniform hollow microspheres, which is used for obtaining the hollow microspheres with high concentricity and surface roundness by applying an alternating current electric field to a solution.
With reference to fig. 1, the method for automatically controlling the ultra-uniform hollow microspheres specifically comprises the following steps:
step 1, preparation of a microsphere generation environment: selecting a rectangular container 6 without a top cover, fixing a lower electrode 5 in the rectangular container 6 and at the bottom of the rectangular container, and adding the suspension 2 into the rectangular container 6 to obtain a liquid environment generated by the microspheres;
and 5, powering off the upper electrode 1 and the lower electrode 5 to obtain the microspheres with liquid inside, and removing the liquid inside the microspheres to obtain the hollow microspheres.
The liquid densities of the microsphere shell liquid 4 containing the polymer precursor, the suspension liquid 2 and the microsphere internal liquid 3 in the step 2 are the same.
The liquid densities of the microsphere shell liquid 4 containing the polymer precursor, the suspension liquid 2 and the microsphere internal liquid 3 in the step 2 are the same.
The encapsulated droplets in step 2 are suspended in suspension 2.
The dielectric constant of the microsphere shell liquid 4 containing the polymer precursor in the step 2 is larger than that of the suspension 2.
The suspension 2 and the microsphere shell liquid 4 are not soluble with each other, and the microsphere shell liquid 4 and the microsphere internal liquid 3 are not soluble with each other.
In the step 3, the effective value of the alternating voltage is more than or equal to 500V, and the frequency is 2M-20 MHz.
In step 2, a T-shaped microchannel or a concentric nozzle can also be adopted to form a wrapping liquid drop.
The polymer precursor in the microsphere shell liquid 4 is resorcinol-formaldehyde or the like.
Example 1:
with reference to fig. 1, the preparation process of the hollow microsphere comprises:
step 1, preparation of a microsphere generation environment: selecting a rectangular container 6 without a top cover, fixing a lower electrode 5 in the rectangular container 6 and at the bottom of the rectangular container, and adding silicone oil serving as a suspension 2 into the rectangular container 6 to obtain a liquid environment generated by the microspheres;
and 4, curing the shell of the hollow microsphere: heating the whole container to 70-90 ℃ and keeping for 1-3 hours, or irradiating the microspheres for 2-10 minutes by using ultraviolet rays with the wavelength of 365nm to solidify the shell, so as to obtain microspheres with silicone oil inside;
and 5, powering off the upper electrode 1 and the lower electrode 5, taking out the microspheres in the container, soaking the microspheres in isopropanol, repeating the soaking for multiple times to ensure that the isopropanol completely replaces water in the shell and silicon oil in the microspheres, then putting the microspheres in liquid carbon dioxide to replace the isopropanol in the microspheres by the carbon dioxide, and removing the carbon dioxide through supercritical drying to obtain the hollow microspheres.
Example 2:
in the step 1, a polyvinyl alcohol aqueous solution is adopted as a suspension 2;
in the step 2, the microsphere shell liquid 4 is a mixed liquid of five liquids of methyl methacrylate, propane ester, polystyrene, azobisisobutyronitrile and toluene, and the mixing mass ratio of the five liquids is 30: 15: 24: 1: 30, of a nitrogen-containing gas; adopting a surfactant DS-101 aqueous solution as microsphere internal liquid 3;
in the step 3, alternating voltage with the amplitude of more than or equal to 500V and the frequency of 20MHz is adopted;
in the step 4, the container is heated to 80 ℃ and kept for 2-3 hours, so that the shell is solidified, and microspheres containing the internal liquid 3 are obtained;
and 5, taking out the solidified microspheres, washing with water to remove the suspension 2 on the surface, putting the microspheres into toluene to extract a soluble polymer in the microsphere shell, immersing the microspheres into dipentane to replace the toluene in the shell and the liquid 3 in the microspheres with dipentane, immersing the microspheres into a mixed solution of the dipentane and water, freezing with liquid nitrogen, putting into vacuum, and drying to remove the dipentane and the water to obtain the hollow microspheres.
The invention provides a preparation method of ultra-uniform hollow microspheres, which greatly improves the concentricity of the microspheres by using the action of an alternating electric field, and has the advantages of less equipment required in the whole process, simple method and high yield. The prepared microsphere can be applied to a plurality of fields such as chemistry, medicine and the like.
Claims (7)
1. A preparation method of automatically controlled ultra-uniform hollow microspheres is characterized by comprising the following steps: the alternating current electric field is utilized to adjust the concentricity of the microspheres to prepare the ultra-uniform hollow microspheres, and the specific implementation method comprises the following steps:
step 1, preparation of a microsphere generation environment: selecting a rectangular container (6) without a top cover, fixing a lower electrode (5) in the rectangular container (6) and at the bottom of the rectangular container, adding a suspension (2) into the rectangular container (6) to obtain a liquid environment generated by the microspheres, wherein the suspension (2) adopts a polyvinyl alcohol aqueous solution;
step 2, microsphere generation: injecting microsphere shell liquid (4) containing a polymer precursor into the suspension (2) uniformly and at a constant speed by using a liquid-transfering gun; then slowly injecting the liquid (3) in the microspheres into the liquid (4) on the shells of the microspheres to form wrapped liquid drops, namely the microspheres;
specifically, the microsphere shell liquid 4 is a mixed liquid of five liquids of methyl methacrylate, propane ester, polystyrene, azobisisobutyronitrile and toluene, and the mixing mass ratio of the five liquids is 30: 15: 24: 1: 30, of a nitrogen-containing gas; adopting a surfactant DS-101 aqueous solution as microsphere internal liquid (3);
step 3, centering the microspheres: arranging an upper electrode (1) on the top surface of a rectangular container (6) to form a complete preparation environment, and then introducing alternating voltage with amplitude more than or equal to 500V and frequency of 20MHz between the upper electrode (1) and a lower electrode (5) for a period of time;
step 4, curing the microsphere shell: heating the container to 80 ℃ and keeping for 2-3 hours to solidify the shell to obtain microspheres containing the internal liquid (3);
and 5, powering off the upper electrode (1) and the lower electrode (5) to obtain microspheres with liquid inside, taking out the solidified microspheres, washing with water to remove the suspension (2) on the surface, putting the microspheres into toluene, extracting the soluble polymer in the shells of the microspheres, immersing the microspheres into dipentane to replace the toluene in the shells and the liquid (3) inside the microspheres with dipentane, finally immersing the microspheres into a mixed solution of the dipentane and water, freezing with liquid nitrogen, putting the microspheres into vacuum, drying, and removing the dipentane and the water to obtain the hollow microspheres.
2. The method for preparing automatically controlled ultra-uniform hollow microspheres according to claim 1, wherein the liquid densities of the microsphere outer shell liquid (4), the suspension liquid (2) and the microsphere inner liquid (3) containing the polymer precursor in the step 2 are the same.
3. The method for preparing automatically controlled ultra-uniform hollow microspheres according to claim 1, wherein the encapsulated droplets of step 2 are suspended in a suspension (2).
4. The method for preparing automatically controlled ultra-uniform hollow microspheres according to claim 1, wherein the dielectric constant of the microsphere shell liquid (4) containing the polymer precursor in step 2 is larger than the dielectric constant of the suspension (2).
5. The method for preparing self-regulating, ultra-uniform hollow microspheres according to claim 1, wherein the suspension (2) is immiscible with the microsphere shell liquid (4) and the microsphere shell liquid (4) is immiscible with the microsphere interior liquid (3).
6. The method for preparing the automatically controlled ultra-uniform hollow microspheres according to claim 1, wherein the method comprises the following steps: in step 2, a T-shaped microchannel or a concentric nozzle can also be adopted to form a wrapping liquid drop.
7. The method for preparing the automatically controlled ultra-uniform hollow microspheres according to claim 1, wherein the method comprises the following steps: the polymer precursor in the microsphere shell liquid (4) adopts resorcinol-formaldehyde, and the suspension (2) adopts silicone oil.
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| CN109589884A (en) * | 2019-01-24 | 2019-04-09 | 中国工程物理研究院激光聚变研究中心 | A kind of preparation method of the degradable polymer tiny balloon of great surface quality |
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| CN101244374A (en) * | 2008-03-07 | 2008-08-20 | 山东大学 | Method for producing nano-particle by using alternative electric field |
| CN103585936A (en) * | 2012-08-17 | 2014-02-19 | 中国石油化工股份有限公司 | Preparation method for plastic hollow globule, and prepared product and application thereof |
| CN105056852A (en) * | 2015-09-14 | 2015-11-18 | 哈尔滨工业大学 | Method for synthesizing oleic acid/sodium oleate vesica under alternating electric field |
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