CN110479192B - Method for preparing microcapsule based on pH response type switch solvent by emulsion method - Google Patents

Method for preparing microcapsule based on pH response type switch solvent by emulsion method Download PDF

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CN110479192B
CN110479192B CN201910810476.4A CN201910810476A CN110479192B CN 110479192 B CN110479192 B CN 110479192B CN 201910810476 A CN201910810476 A CN 201910810476A CN 110479192 B CN110479192 B CN 110479192B
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emulsion
phase solution
dimethylcyclohexylamine
ethyl cellulose
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CN110479192A (en
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吴洋
孙灵
潘康康
郑晓明
卢俊
安恩鹏
陈萌
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Southwest Petroleum University
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/12—Processes in which the treating agent is incorporated in microcapsules

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  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
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Abstract

The invention discloses a method for preparing microcapsules by an emulsion method based on a pH response type switch solvent, belonging to the technical field of microcapsule preparation and comprising the following steps: sequentially dissolving glyceryl tribenzoate, ethyl cellulose and span-80 in an N, N-dimethyl cyclohexylamine solution to obtain an oil phase solution; dissolving tween-80 in deionized water to obtain an aqueous phase solution; mixing the oil phase solution and the water phase solution, and stirring to obtain emulsion; adjusting the pH value of the emulsion to 6-7 to demulsify the emulsion to generate a precipitate, and performing suction filtration on the emulsion to obtain the precipitate, and drying the precipitate to obtain the glyceryl tribenzoate/ethyl cellulose microcapsule; and adjusting the pH value of the filtrate to 12-14, and then carrying out centrifugal separation to obtain an upper layer liquid of N, N-dimethylcyclohexylamine. The method changes the hydrophilic/hydrophobic performance of the solvent by adjusting the pH value of the emulsion to realize emulsion breaking and emulsification of the emulsion, and the solvent is recycled, so that the pollution to the environment is reduced, and the method conforms to the concept of green chemistry.

Description

Method for preparing microcapsule based on pH response type switch solvent by emulsion method
Technical Field
The invention relates to the technical field of microcapsule preparation in the field of fine chemical engineering, in particular to a method for preparing microcapsules by an emulsion method based on a pH response type switch solvent.
Background
The glyceryl tribenzoate is a plasticizer which can be applied to leather coating, but in the leather production and processing process, the plasticizer can act with protein and nitrocellulose fiber coating agents in leather, so that the leather becomes brittle and hard, and by microencapsulating the glyceryl tribenzoate, the glyceryl tribenzoate can be slowly released in the leather production and use process, so that the action of the glyceryl tribenzoate with the protein and nitrocellulose coating agents is avoided, and the original toughness of the leather is maintained.
The emulsion method for preparing the microcapsule is a common method, has simple process steps and wider application, but the traditional emulsion method for preparing the microcapsule also has a plurality of problems, and various oils or organic solvents, such as white oil, diesel oil, trichloromethane, toluene and the like, are required to be used when the emulsion is prepared; freeze drying or heat spray drying is often used in the drying process. For example, chinese published patent CN107455370A provides a method for preparing microcapsules by aqueous emulsion electrospinning, and chinese published patent CN103691376A provides a method for preparing microcapsules by layer-by-layer assembly technology using oil-in-water microemulsion as a template, which all use the traditional emulsion method to prepare microcapsules.
At present, the methods all use a freeze drying method or a heating spray drying method to remove the solvent, and in the preparation process, the freeze drying method consumes longer time, the spray drying method needs to consume a large amount of heat, and the thermal efficiency is lower; meanwhile, a large amount of toxic and harmful organic solvents such as formaldehyde, chloroform, toluene and the like are required to be used in the two methods, and in the drying process, the solvents are directly volatilized and cannot be recycled, so that the environment is polluted, the cost is increased, and the method does not conform to the concept of green chemistry.
Disclosure of Invention
In view of the above technical problems, an object of the present invention is to provide a method for preparing microcapsules based on an emulsion method of a pH-responsive switching solvent. The solvent can be recycled, so that the pollution to the environment is reduced, and the green chemical concept is met.
The invention adopts the following technical scheme:
the solvent selected in the invention is N, N-dimethyl cyclohexylamine which is taken as an oil phase of the emulsion, the emulsifier is a composite emulsifier, specifically span-80 and tween-80, the microcapsule core material is glycerol tribenzoate, and the wall material is ethyl cellulose; the N, N-dimethylcyclohexylamine is selected as a pH response type switch solvent, a pH response type emulsion can be prepared based on the switch solvent, the hydrophilic/hydrophobic performance of the switch solvent is changed by adjusting the pH value of an emulsion system, the emulsion breaking and emulsification of the emulsion are realized, the precipitate after the emulsion breaking is treated to obtain the glycerol tribenzoate/ethyl cellulose microcapsule, and the N, N-dimethylcyclohexylamine can be separated out for continuous cycle use by treating the solution after the emulsion breaking.
The invention provides a method for preparing microcapsules by an emulsion method based on a pH response type switch solvent, which specifically comprises the following steps:
(1) sequentially dissolving glyceryl tribenzoate, ethyl cellulose and span-80 in N, N-dimethylcyclohexylamine, and stirring during the dissolving process to obtain an oil phase solution;
(2) dissolving tween-80 in ionized water, and stirring during the dissolving process to obtain an aqueous phase solution;
(3) mixing the oil phase solution prepared in the step (1) with the water phase solution prepared in the step (2), and stirring until the oil phase solution and the water phase solution are completely emulsified to obtain an emulsion;
(4) and (3) adding a pH value regulator A into the emulsion prepared in the step (3) to regulate the pH value to 6-7, completely demulsifying the emulsion to generate precipitates, standing the emulsion, performing suction filtration to obtain filtrate and precipitates, and drying the precipitates to obtain the glyceryl tribenzoate/ethyl cellulose microcapsules.
(5) And (3) adding a pH value regulator B into the filtrate obtained in the step (4) to regulate the pH value of the filtrate to 12-14, and then carrying out centrifugal separation, wherein the upper layer liquid of the filtrate is mainly N, N-dimethylcyclohexylamine, and the lower layer liquid is mainly water, separating the upper layer N, N-dimethylcyclohexylamine, and recycling the upper layer N, N-dimethylcyclohexylamine to the step (1).
Preferably, the pH regulator a in the step (4) is one of sulfuric acid and hydrochloric acid, and the pH regulator B in the step (5) is one of sodium hydroxide and potassium hydroxide.
Preferably, the mass ratio of the glycerol tribenzoate to the N, N-dimethylcyclohexylamine in the step (1) is 1: 4-20, the mass ratio of the ethyl cellulose to the glycerol tribenzoate is 1-5: 1, and the mass ratio of the span-80 to the N, N-dimethylcyclohexylamine in the step (1) is 1: 4-20; the mass ratio of the Tween-80 to the deionized water in the step (2) is 1: 5-10; the mass ratio of the oil phase solution to the water phase solution in the step (3) is 3: 2-7.
Has the advantages that:
(1) according to the invention, the pH value of the emulsion is adjusted to change the hydrophilic/hydrophobic properties of the solvent, so that emulsion breaking and emulsification of the emulsion are realized, the N, N-dimethylcyclohexylamine can be recovered and recycled, the single recovery rate can reach more than 80%, the environmental pollution is reduced, and the green chemical concept is met.
(2) The drying step in the invention only needs to dry the precipitate generated by emulsion breaking, thus greatly reducing the amount of solvent to be dried and evaporated, and having short drying time and low heat consumption.
(3) The embedding rate of the glycerol tribenzoate/ethyl cellulose microcapsule prepared by the invention is not less than 80%, and the effective content of the glycerol tribenzoate in the microcapsule is not less than 30%.
Drawings
FIG. 1 is a graph showing the relationship between the concentration of glycerol tribenzoate and the absorbance.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Preparation of glycerin tribenzoate/ethyl cellulose microcapsule
Example 1:
adding 3g of glycerol tribenzoate into 40g of N, N-dimethylcyclohexylamine, mixing, stirring for 3min at 200r/min until the glycerol tribenzoate is completely dissolved, adding 7g of ethyl cellulose, mixing, stirring for 10min at 200r/min until the ethyl cellulose is completely dissolved, then adding 3g of span-80, mixing, stirring for 1min at 200r/min until the span-80 is completely dissolved, and obtaining an oil phase solution; adding 7g of tween-80 into 60g of deionized water, mixing, and stirring for 1min at 200r/min until tween-80 is completely dissolved to obtain an aqueous phase solution; mixing the oil phase solution and the water phase solution and completely emulsifying to obtain emulsion; adding 31g H to the emulsion2SO4(sulfuric acid content 50%), adjusting pH to6.3, demulsifying the emulsion to generate a precipitate, standing the emulsion, performing suction filtration, and drying the precipitate obtained by filtration at 50 ℃ for 2 hours to obtain a product of glycerol tribenzoate/ethyl cellulose microcapsule; and adding 12.70g of NaOH (solid) into the filtrate obtained by suction filtration, adjusting the pH value of the filtrate to 13.5, centrifuging by using a centrifugal machine, and separating to obtain 34.5g of N, N-dimethylcyclohexylamine, wherein the recovery rate is 86.3%.
Example 2:
adding 4g of glycerol tribenzoate into 50g of N, N-dimethylcyclohexylamine, mixing, stirring for 3min at 200r/min until the glycerol tribenzoate is completely dissolved, adding 6g of ethyl cellulose, mixing, stirring for 10min at 200r/min until the ethyl cellulose is completely dissolved, then adding 5g of span-80, mixing, stirring for 1min at 200r/min until the span-80 is completely dissolved, and obtaining an oil phase solution; adding 5g of tween-80 into 50g of deionized water, mixing, stirring for 1min at 200r/min until tween-80 is completely dissolved to obtain an aqueous phase solution; mixing the oil phase solution and the water phase solution and completely emulsifying to obtain emulsion; adding 38.60g H to the emulsion2SO4(50% by mass of sulfuric acid), adjusting the pH value to 6.5, demulsifying the emulsion, generating a precipitate, standing the emulsion, performing suction filtration, and drying the precipitate obtained by filtration at 50 ℃ for 2 hours to obtain the product of glyceryl tribenzoate/ethyl cellulose microcapsule; adding 15.80g of NaOH (solid) into the filtrate obtained by suction filtration, adjusting the pH value of the filtrate to 13.0, centrifuging by using a centrifugal machine, and separating to obtain 42.3g of N, N-dimethylcyclohexylamine, wherein the recovery rate is 84.6%.
Second, performance test
(1) Determination of effective content of glyceryl tribenzoate in glyceryl tribenzoate/ethylcellulose microcapsules:
a, obtaining a relation standard curve of the concentration and the absorbance of the glyceryl tribenzoate
Weighing glycerol tribenzoate with different masses, and dissolving with absolute ethanol respectively to obtain ethanol solutions of the glycerol tribenzoate with the concentrations of 0.001g/L, 0.002g/L, 0.003g/L, 0.004g/L, 0.005g/L, 0.006g/L, 0.007g/L, 0.008g/L and 0.009 g/L. The absorbance of the ethanol solutions of the respective glycerol tribenzoates was measured by an ultraviolet spectrophotometer (UV-1800, ShumdZU, Japan) and the data were processed to obtain the relationship between the absorbance and the concentration of the glycerol tribenzoate, as shown in FIG. 1.
As can be seen from FIG. 1, the standard curve equation of the absorbance and the concentration of glycerol tribenzoate is that Y is 99.1960X +0.0012,
wherein X is the concentration of glyceryl tribenzoate, g/L; y is absorbance.
B measurement of Glycerol tribenzoate content in Glycerol tribenzoate/ethylcellulose microcapsules prepared in examples
Taking 0.01g of the glyceryl tribenzoate/ethyl cellulose microcapsule prepared in example 1, completely dissolving the 0.01g of the microcapsule with 40mL of absolute ethyl alcohol, transferring the solution into a 1000mL volumetric flask, fixing the volume to the scale mark of the 1000mL volumetric flask with the absolute ethyl alcohol, and shaking up; measuring the absorbance of the solution to 0.3216 by using an ultraviolet spectrophotometer; the concentration of the glyceryl tribenzoate in the solution is obtained to be 0.00323g/L by using a standard curve equation of the absorbance and the concentration of the glyceryl tribenzoate, and then the mass of the glyceryl tribenzoate is calculated to be 0.00323g, and the effective content of the glyceryl tribenzoate in the microcapsule can be calculated to be 32.3% by using the mass of the glyceryl tribenzoate and the glyceryl tribenzoate/ethyl cellulose microcapsule.
Taking 0.01g of the glyceryl tribenzoate/ethyl cellulose microcapsule prepared in example 2, completely dissolving the 0.01g of the microcapsule with 40mL of absolute ethyl alcohol, transferring the solution into a 100mL volumetric flask, then fixing the volume to the scale mark of the 100mL volumetric flask with the absolute ethyl alcohol, and shaking up; measuring the absorbance of the solution to 0.4129 by using an ultraviolet spectrophotometer; the concentration of the glyceryl tribenzoate in the solution is 0.00415g/L by using a standard curve equation of the absorbance and the concentration of the glyceryl tribenzoate, the mass 0.00415 of the glyceryl tribenzoate is further calculated, and the effective content of the glyceryl tribenzoate in the microcapsule can be calculated to be 41.5% by using the masses of the glyceryl tribenzoate and the glyceryl tribenzoate/ethyl cellulose microcapsule.
(2) Determination of embedding rate of glycerin tribenzoate/ethyl cellulose microcapsules:
1.00g of the glycerol tribenzoate/ethylcellulose microcapsules prepared in example 1 was taken, the microcapsules were washed with 100mL of cyclohexane, then suction-filtered, dried to a constant weight, and weighed again to 0.94g, and the encapsulation ratio thereof was calculated by using the formula 1-1. The entrapment of glyceryl tribenzoate in the microcapsules was calculated to be 81.42%.
1.00g of the glyceryl tribenzoate/ethylcellulose microcapsule prepared in example 2 was taken, and the microcapsule was washed with 100mL of cyclohexane, then suction-filtered, dried to a constant weight, and weighed again to 0.93g, and the encapsulation ratio thereof was calculated by using the formula 1-1. The entrapment rate of glyceryl tribenzoate in the microcapsules was calculated to be 83.13%.
Figure BDA0002184895530000041
Wherein m isaInitial microcapsule mass, g; m isbG, the mass of the microcapsule which is dried to constant weight after washing; a is the effective content of the microcapsule.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (3)

1. A method for preparing microcapsules based on a pH response type switch solvent emulsion method is characterized by comprising the following steps:
(1) sequentially dissolving glyceryl tribenzoate, ethyl cellulose and span-80 in N, N-dimethylcyclohexylamine, and stirring during the dissolving process to obtain an oil phase solution;
(2) dissolving tween-80 in deionized water, and stirring during the dissolving process to obtain an aqueous phase solution;
(3) mixing the oil phase solution prepared in the step (1) with the water phase solution prepared in the step (2), and stirring until the oil phase solution and the water phase solution are completely emulsified to obtain an emulsion;
(4) adding a pH value regulator A into the emulsion prepared in the step (3) to regulate the pH value to 6-7, completely demulsifying the emulsion to generate precipitates, standing the emulsion, performing suction filtration to obtain filtrate and precipitates, and drying the precipitates to obtain the glyceryl tribenzoate/ethyl cellulose microcapsules;
(5) and (3) adding a pH value regulator B into the filtrate obtained in the step (4) to regulate the pH value to 12-14, then carrying out centrifugal separation, and separating out N, N-dimethylcyclohexylamine and water, wherein the N, N-dimethylcyclohexylamine can be recycled in the step (1).
2. The method for preparing microcapsule according to claim 1, wherein the microcapsule is prepared by emulsion process based on pH-responsive switch solvent,
the mass ratio of the glyceryl tribenzoate to the N, N-dimethylcyclohexylamine in the step (1) is 1: 4-20, the mass ratio of the ethyl cellulose to the glyceryl tribenzoate is 1-5: 1, and the mass ratio of the span-80 to the N, N-dimethylcyclohexylamine in the step (1) is 1: 4-20;
the mass ratio of the Tween-80 to the deionized water in the step (2) is 1: 5-10;
the mass ratio of the oil phase solution to the water phase solution in the step (3) is 3: 2-7.
3. The method for preparing microcapsules according to claim 1, wherein the pH regulator A in step (4) is one of sulfuric acid and hydrochloric acid, and the pH regulator B in step (5) is one of sodium hydroxide and potassium hydroxide.
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