CN108704588B - Preparation method of microencapsulated acidic aqueous solution - Google Patents
Preparation method of microencapsulated acidic aqueous solution Download PDFInfo
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- CN108704588B CN108704588B CN201810693485.5A CN201810693485A CN108704588B CN 108704588 B CN108704588 B CN 108704588B CN 201810693485 A CN201810693485 A CN 201810693485A CN 108704588 B CN108704588 B CN 108704588B
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- aqueous solution
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- methyl ester
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/16—Interfacial polymerisation
Abstract
The invention discloses a preparation method of a microencapsulated acidic aqueous solution, which comprises the following steps: (1) uniformly mixing an emulsifier and fatty acid methyl ester, and adding an acidic aqueous solution under the stirring condition of 500-5000 r/min for emulsifying and dispersing for 10-30min to prepare an emulsion; (2) uniformly mixing furfuryl alcohol and fatty acid methyl ester, adding the mixture into the emulsion prepared in the step (1) under the stirring condition of 400-800 r/min, and reacting for 30-90min to prepare microcapsule suspension; (3) the microcapsule suspension is subjected to conventional centrifugal separation, washing and drying to obtain a powdery microcapsule product. The microcapsule synthesis process is simple, the product controllability is strong, and the microcapsule is safe and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of a microencapsulated acidic aqueous solution.
Background
The microcapsule technology is a protection technology for encapsulating a core material to form micro particles so as to meet the requirements of slow release, instant release or long-term storage of the micro particles, and is widely applied to the fields of medicines, cosmetics, foods, textiles, agriculture and the like. Particularly, the microcapsule treatment can change the appearance form of the acidic aqueous solution from liquid to solid, thereby bringing convenience to the storage and transportation of the acidic aqueous solution, improving the stability of the acidic aqueous solution after the acidic aqueous solution is coated by the microcapsule, realizing slow release, and being hopeful to be applied to the fields of catalysts, curing agents and the like. For another example, phosphoric acid is an excellent wood flame retardant, and the microcapsule treatment can improve the water resistance and reduce the damage to the strength of wood.
The core material involved in the microcapsule is very wide, and the core material can be mainly classified into oil-soluble and water-soluble types according to the solubility of the core material. The substance embedding the core material to realize microcapsule gelatinization is called wall material, and can be used as the wall material of the microcapsule, such as natural polymer, semisynthetic polymer and synthetic polymer material. The selection of the wall material is determined according to the property of the core material substance, the oil-soluble core material is selected from the water-soluble wall material, and the water-soluble core material is selected from the oil-soluble wall material, namely the solubility of the wall material and the core material is different, and the wall material cannot react with the core material and is not mixed with the core material. In the prior art, the variety of water-soluble wall materials is many and easy to obtain, the variety of oil-soluble wall materials suitable for the water-soluble core material is few, and a toxic organic solvent is usually required to be selected in the synthesis process. Therefore, the development of a microencapsulation technology which is simple in process, safe and environment-friendly and aims at water-soluble substances is of great significance.
Furfuryl alcohol is prepared by hydrogenating furfural, which is mainly derived from the hydrolysis of bagasse, corn cobs, wheat straws and other crop byproducts. The thermosetting resin obtained by polymerizing furfuryl alcohol under the action of an acid catalyst belongs to an environment-friendly material, has good water resistance, heat resistance and acid and alkali resistance, and has important application in the fields of adhesives, rubber, fibers and the like. The microcapsule synthesis technology based on furfuryl alcohol polycondensation is developed, so that the variety of oil-soluble wall materials of the microcapsules is enriched, and the green and environment-friendly development of microcapsule products is promoted.
The fatty acid methyl ester is yellow clear transparent liquid (colorless after rectification), has mild and special smell, stable structure and no corrosivity. It also has relatively strong dissolving capacity, low content of volatile organic compounds, high flash point, no toxicity and biodegradability, and is an environment-friendly solvent. In the microcapsule synthesis technology based on furfuryl alcohol polycondensation reaction, fatty acid methyl ester can be used for replacing a toxic organic solvent to dissolve furfuryl alcohol, and a safe and environment-friendly microcapsule technology is developed.
Disclosure of Invention
In order to overcome the defects, the invention provides a preparation method of a microencapsulated acidic aqueous solution, which adopts furfuryl alcohol as a wall material raw material for microencapsulation of the acidic aqueous solution, takes fatty acid methyl ester as a solvent, and gradually polymerizes the furfuryl alcohol in the fatty acid methyl ester at an oil-water interface under the action of a catalyst to form a wall material to wrap the acidic aqueous solution, thereby preparing the microcapsule. The microcapsule has the advantages of simple synthesis process, strong product controllability, safety and environmental protection.
The invention is realized by adopting the following technical scheme:
a method for the preparation of a microencapsulated acidic aqueous solution comprising the steps of:
(1) uniformly mixing an emulsifier and fatty acid methyl ester, and adding an acidic aqueous solution under the stirring condition of 500-5000 r/min for emulsifying and dispersing for 10-30min to prepare an emulsion;
(2) uniformly mixing furfuryl alcohol and fatty acid methyl ester, adding the mixture into the emulsion prepared in the step (1) under the stirring condition of 400-800 r/min, and reacting for 30-90min to prepare microcapsule suspension;
(3) the microcapsule suspension is subjected to conventional centrifugal separation, washing and drying to obtain a powdery microcapsule product.
Further, in the step (1), the acidic aqueous solution is one or more of phosphoric acid, oxalic acid, sulfuric acid, hydrochloric acid and p-toluenesulfonic acid, and the mass fraction of the acid is 30% -85%.
Further, in the step (1), the emulsifier is sorbitan fatty acid ester, specifically any one or a mixture of span 20, span 40, span 60, span 80 and span 85, the mass fraction of the emulsifier in the fatty acid methyl ester is 0.5-3.5%, and the volume ratio of the fatty acid methyl ester to the acidic aqueous solution is 4:1-8: 1.
Further, in the step (2), the furfuryl alcohol accounts for 0.5-8.0% of the mass fraction of the fatty acid methyl ester in the reaction system.
Further, the temperature of the reaction in the above step (2) is 5 to 70 ℃.
Further, in the step (2), the volume ratio of the emulsion to the fatty acid methyl ester solution of furfuryl alcohol is 1:1 to 4: 1.
Further, in the above step (3), the supernatant obtained by the centrifugal separation may be repeatedly used as a solvent for the steps (1) and (2).
Compared with the prior art, the technical scheme has the following beneficial effects:
1. dispersing an acidic aqueous solution under the action of an emulsifier and mechanical stirring to form core material liquid drops; then under the catalytic action of acid in the liquid drops, furfuryl alcohol in fatty acid methyl ester is polymerized at an oil-water interface to gradually form wall material wrapped acidic liquid drops, and the microcapsule is prepared.
2. The furfuryl alcohol is used as a wall material raw material for microencapsulation of the acidic aqueous solution, and the furfuryl alcohol can generate polymerization reaction under an acidic condition to form wall material wrapped core material liquid drops, so that a catalyst for furfuryl alcohol polymerization reaction is not required to be additionally added, and resource cost is saved.
3. According to the invention, the non-toxic biodegradable fatty acid methyl ester with strong dissolving capacity is used as the organic solvent of furfuryl alcohol in the microencapsulation process, so that the environmental protection safety of the microencapsulation process is improved; the separated fatty acid methyl ester clear liquid can be recycled as a solvent for reuse, which is beneficial to saving production cost.
4. The method has simple process and strong product controllability; the particle size of the microcapsule can be effectively controlled by adjusting the addition amount of the emulsifier, the volume ratio of the fatty acid methyl ester to the acidic aqueous solution during emulsification and the emulsification rotating speed, and the wall thickness and the wall material compactness of the microcapsule can be effectively controlled by adjusting the mass fraction of the furfuryl alcohol, the reaction temperature and the reaction time.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but is not to be construed as being limited thereto. The specific experimental conditions and methods not indicated in the following examples are generally conventional means well known to those skilled in the art.
Example 1:
a method for the preparation of a microencapsulated acidic aqueous solution comprising the steps of:
(1) uniformly mixing 0.2g of span 80 and 14.6g of fatty acid methyl ester, dropwise adding 5.0g of phosphoric acid with the mass fraction of 85% under the stirring condition of 750 r/min, and emulsifying and dispersing for 20min to prepare emulsion;
(2) uniformly mixing 1.0g of furfuryl alcohol and 5.4g of fatty acid methyl ester, slowly adding the mixture into the phosphoric acid emulsion under the stirring condition of 500 r/min, and reacting at the temperature of 25 ℃ for 60min to obtain microcapsule suspension;
(3) the microcapsule suspension is subjected to conventional centrifugal separation, washing and drying to obtain a powdery microcapsule product; the supernatant obtained by centrifugation can be repeatedly used as a solvent in step (1) and step (2).
The obtained phosphoric acid microcapsule is in a regular spherical shape, has good dispersibility and has a particle size of 2-11 μm.
Example 2:
a method for the preparation of a microencapsulated acidic aqueous solution comprising the steps of:
(1) uniformly mixing 0.3g of span 80 and 20.9g of fatty acid methyl ester, dropwise adding 7.1g of sulfuric acid with the mass fraction of 60% under the stirring condition of 750 r/min, and emulsifying and dispersing for 10min to prepare emulsion;
(2) uniformly mixing 1.4g of furfuryl alcohol and 7.7g of fatty acid methyl ester, slowly adding the mixture into sulfuric acid emulsion under the stirring condition of 500 r/min, and reacting at the temperature of 25 ℃ for 30min to obtain microcapsule suspension;
(3) the microcapsule suspension is subjected to conventional centrifugal separation, washing and drying to obtain a powdery microcapsule product; the supernatant obtained by centrifugation can be repeatedly used as a solvent in step (1) and step (2).
The obtained sulfuric acid microcapsule is in a regular spherical shape, has good dispersibility and a particle size of 7-25 mu m.
Example 3:
a method for the preparation of a microencapsulated acidic aqueous solution comprising the steps of:
(1) uniformly mixing 0.1g of span 80, 0.1g of span 20 and 15.0g of fatty acid methyl ester, dropwise adding a mixed solution of 6.0g of sulfuric acid and phosphoric acid under the stirring condition of 2000 r/min, wherein the mass fraction of sulfuric acid and the mass fraction of phosphoric acid in the mixed solution are 30%, and emulsifying and dispersing for 10min to prepare an emulsion;
(2) uniformly mixing 0.5g of furfuryl alcohol and 10.0g of fatty acid methyl ester, slowly adding the mixture into the mixed acid emulsion under the stirring condition of 600 r/min, and reacting for 90min at the temperature of 60 ℃ to obtain microcapsule suspension;
(3) the microcapsule suspension is subjected to conventional centrifugal separation, washing and drying to obtain a powdery microcapsule product; the supernatant obtained by centrifugation can be repeatedly used as a solvent in step (1) and step (2).
The obtained sulfuric acid and phosphoric acid mixture microcapsule is in a regular spherical shape, has good dispersibility and has a particle size of 1-10 mu m.
Example 4:
a method for the preparation of a microencapsulated acidic aqueous solution comprising the steps of:
(1) uniformly mixing 0.075g of span 85 and 15.0g of fatty acid methyl ester, dropwise adding 4.5g of p-toluenesulfonic acid with the mass fraction of 30% under the stirring condition of 500 r/min, and emulsifying and dispersing for 30min to prepare emulsion;
(2) uniformly mixing 1.3g of furfuryl alcohol and 17.5g of fatty acid methyl ester, slowly adding the mixture into p-toluenesulfonic acid emulsion under the stirring condition of 400 r/min, and reacting at the temperature of 45 ℃ for 60min to obtain microcapsule suspension;
(3) the microcapsule suspension is subjected to conventional centrifugal separation, washing and drying to obtain a powdery microcapsule product; the supernatant obtained by centrifugation can be repeatedly used as a solvent in step (1) and step (2).
The obtained p-toluenesulfonic acid microcapsule is in a regular spherical shape, has good dispersibility and a particle size of 10-35 mu m.
Example 5:
a method for the preparation of a microencapsulated acidic aqueous solution comprising the steps of:
(1) uniformly mixing 0.7g of span 40 and 20.0g of fatty acid methyl ester, dropwise adding a mixed solution of 4.6g of sulfuric acid and hydrochloric acid under the stirring condition of 3000 r/min, wherein the mass fraction of sulfuric acid and the mass fraction of hydrochloric acid in the mixed solution are 40% and 20%, and emulsifying and dispersing for 30min to prepare an emulsion;
(2) uniformly mixing 2.1g of furfuryl alcohol and 6.3g of fatty acid methyl ester, slowly adding the mixture into the mixed acid emulsion under the stirring condition of 800 r/min, and reacting at the temperature of 5 ℃ for 90min to obtain microcapsule suspension;
(3) the microcapsule suspension is subjected to conventional centrifugal separation, washing and drying to obtain a powdery microcapsule product; the supernatant obtained by centrifugation can be repeatedly used as a solvent in step (1) and step (2).
The obtained sulfuric acid and hydrochloric acid mixture microcapsule is in a regular spherical shape, has good dispersibility and has a particle size of 1-5 mu m.
Example 6:
a method for the preparation of a microencapsulated acidic aqueous solution comprising the steps of:
(1) uniformly mixing 0.2g of span 60, 0.2g of span 80 and 15.0g of fatty acid methyl ester, dropwise adding a mixed solution of 4.5g of oxalic acid and p-toluenesulfonic acid under the stirring condition of 5000 r/min, wherein the mass fraction of oxalic acid in the mixed solution is 10%, the mass fraction of p-toluenesulfonic acid in the mixed solution is 30%, and emulsifying and dispersing for 30min to prepare an emulsion;
(2) uniformly mixing 0.1g of furfuryl alcohol and 5.0g of fatty acid methyl ester, slowly adding the mixture into the mixed acid emulsion under the stirring condition of 800 r/min, and reacting at the temperature of 70 ℃ for 60min to obtain microcapsule suspension;
(3) the microcapsule suspension is subjected to conventional centrifugal separation, washing and drying to obtain a powdery microcapsule product; the supernatant obtained by centrifugation can be repeatedly used as a solvent in step (1) and step (2).
The obtained microcapsule of the mixture of oxalic acid and p-toluenesulfonic acid is in a regular spherical shape, has good dispersibility and has a particle size of 1-8 mu m.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (6)
1. A method for preparing a microencapsulated acidic aqueous solution, comprising: which comprises the following steps:
(1) uniformly mixing an emulsifier and fatty acid methyl ester, and adding an acidic aqueous solution under the stirring condition of 500-5000 r/min for emulsifying and dispersing for 10-30min to prepare an emulsion;
(2) uniformly mixing furfuryl alcohol and fatty acid methyl ester, adding the mixture into the emulsion prepared in the step (1) under the stirring condition of 400-800 r/min, and reacting for 30-90min to prepare microcapsule suspension;
(3) the microcapsule suspension is subjected to conventional centrifugal separation, washing and drying to obtain a powdery microcapsule product;
the acidic aqueous solution in the step (1) is one or a mixture of more of phosphoric acid, oxalic acid, sulfuric acid, hydrochloric acid and p-toluenesulfonic acid, and the mass fraction of the acid is 30-85%.
2. A method of preparing a microencapsulated acidic aqueous solution as claimed in claim 1, wherein: in the step (1), the emulsifier is sorbitan fatty acid ester, specifically any one or a mixture of span 20, span 40, span 60, span 80 and span 85, the mass fraction of the emulsifier in the fatty acid methyl ester is 0.5-3.5%, and the volume ratio of the fatty acid methyl ester to the acidic aqueous solution is 4:1-8: 1.
3. A method of preparing a microencapsulated acidic aqueous solution as claimed in claim 1, wherein: the furfuryl alcohol in the step (2) accounts for 0.5-8.0% of the mass fraction of the fatty acid methyl ester in the reaction system.
4. A method of preparing a microencapsulated acidic aqueous solution as claimed in claim 1, wherein: the temperature of the reaction in the step (2) is 5-70 ℃.
5. A method of preparing a microencapsulated acidic aqueous solution as claimed in claim 1, wherein: in the step (2), the volume ratio of the emulsion to the fatty acid methyl ester solution of furfuryl alcohol is 1:1-4: 1.
6. A method of preparing a microencapsulated acidic aqueous solution as claimed in claim 1, wherein: in the step (3), the supernatant obtained by centrifugation can be repeatedly used as a solvent in the steps (1) and (2).
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