CN109550465B - Preparation method of composite polymer microcapsule for slow release of dye - Google Patents
Preparation method of composite polymer microcapsule for slow release of dye Download PDFInfo
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- 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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/0004—General aspects of dyeing
- D06P1/0016—Dye baths containing a dyeing agent in a special form such as for instance in melted or solid form, as a floating film or gel, spray or aerosol, or atomised dyes
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Abstract
The invention provides a preparation method of a composite polymer microcapsule for hydrophilic/hydrophobic dye slow release, which takes methylene dichloride in which high molecular polymers are dissolved as an oil phase, disperses nano silicon dioxide for absorbing dyes in the oil phase, forms a stable oil-in-water miniemulsion system under the action of a surfactant and a cosolvent, and diffuses the methylene dichloride into ethanol to form a hollow microcapsule with an inner cavity coated with nano silicon dioxide spheres during phase inversion, wherein the introduction of the silicon dioxide is beneficial to further enhancing the hydrophobic dye coating and slow release capability of the polymer microcapsule, realizes the coating and slow release of the hydrophilic dye, and greatly widens the application range of the polymer microcapsule dye slow release.
Description
(I) technical field
The invention relates to a preparation method of a composite polymer microcapsule for slow release of a dye.
(II) background of the invention
The microcapsule technology is a technology in which a polymer film-forming material is used as a wall material, and solid particles, liquid droplets or gas of a core material are wrapped in the wall material of the polymer capsule. The microcapsules generally have the functions of protecting the physicochemical state of the core material, isolating the influence of the external environment and controlling the sustainable release thereof. The microcapsule is used as a novel functional material which develops rapidly, and is widely applied to the fields of functional coatings, food industry, daily chemical products, aerospace, medicine and the like.
The use of microcapsules stems from their ability to slowly and efficiently release the core active agent to the external system over a period of time. The key point of preparing the effective microcapsule is the selection of wall materials, and the selection of proper wall materials is particularly important for different core materials and application fields. The microcapsule wall material mainly comprises three main types of natural polymer materials, semi-synthetic polymer materials and synthetic polymer materials. Generally the choice of wall material follows the following principle: no chemical reaction occurs between the wall material and the core material; the outer wall of the capsule has certain mechanical strength; the wall material can flow, dissolve and emulsify, and has permeability, stability and the like. The common membrane material high molecular polymer monomer has the advantages of easy dissolution in various organic solvents, quick membrane formation, adjustable membrane formation structure, high mechanical strength and the like, so the common membrane material high molecular polymer monomer can be used as a wall material of microcapsules. Compared with the solvent evaporation and spray drying method for preparing the hollow microcapsule, the method for preparing the hollow microcapsule based on the phase inversion technology has the advantages of short time consumption, low energy consumption, regular capsule shape, uniform size and the like.
Disclosure of the invention
The invention aims to provide a preparation method of a composite polymer microcapsule for hydrophilic/hydrophobic dye slow release, which is based on that a high-molecular oil-in-water microemulsion system is quickly subjected to phase conversion in ethanol to form a capsule wall, and mass transfer is carried out between the ethanol and an oil phase to form a capsule cavity, thereby preparing hollow microcapsules with regular shapes and uniform sizes. Because the surface of the nano silicon dioxide sphere contains a large number of hydroxyl functional groups, the introduction of the nano silicon dioxide sphere expands the dye slow release application range of the composite microcapsule and can be used for a plurality of hydrophilic or hydrophobic dye slow release processes.
The technical scheme of the invention is as follows:
a preparation method of composite polymer microcapsules for slow release of dyes comprises the following steps:
(1) adding a dye into ethanol, performing ultrasonic dissolution to obtain a dye solution, then adding hydrophobic nano silicon dioxide microspheres into the dye solution, stirring and adsorbing (2h), then centrifuging (5000rpm, 5min), washing (with ethanol), drying (60 ℃) to obtain silicon spheres adsorbing the dye;
the volume dosage of the ethanol is 2L/g calculated by the mass of the dye;
the volume dosage of the dye solution is 200mL/g based on the mass of the hydrophobic nano silicon dioxide microspheres;
the dyes include hydrophilic dyes such as: methylene blue, methyl orange, rhodamine B, and the hydrophobic dye specifically includes: solvent red 24, solvent black, Lilaihong;
the size of the hydrophobic nano silicon dioxide microspheres is 10-50 nm, and the hydrophobic nano silicon dioxide microspheres can be obtained commercially by a conventional way;
(2) adding a high molecular polymer into a solvent dichloromethane, stirring until the high molecular polymer is completely dissolved (4-8 h) to obtain an oil phase, adding the dye-adsorbing silica spheres obtained in the step (1) into the oil phase, then adding dodecyl glucoside, and stirring until the mixture is uniformly dispersed (30min) to obtain an oil phase mixed solution;
the mass ratio of the high molecular polymer to dichloromethane serving as a solvent, silicon spheres for adsorbing dye and dodecyl glucoside is 1: 10-20: 0.1-1: 0.4-0.6;
the high molecular polymer is, for example: polysulfone (PSF), Polyethersulfone (PES), polyurethane elastomer (TPU), or Plexiglass (PMMA);
(3) adding the oil phase mixed solution obtained in the step (2) into solvent deionized water at room temperature (20-30 ℃) under the condition of stirring (1000rpm), adding cosolvent and sodium dodecyl benzene sulfonate, stirring (30 min-2 h), and performing ultrasonic treatment (30min) to obtain an oil-in-water miniemulsion system;
the volume ratio of the solvent deionized water to the solvent dichloromethane in the step (2) is 2-5: 1;
the mass ratio of the cosolvent to the dichloromethane solvent in the step (2) is 1: 3-10;
such as: n-butanol, isooctyl alcohol, PEG-200, PEG-400, PEG-600, glycerol, n-hexadecane or styrene;
compounding the dosage of the sodium dodecyl benzene sulfonate according to the dosage of the dodecyl glucoside in the step (2) to ensure that the HLB value of the obtained oil-in-water miniemulsion system is 14.5;
(4) adding ethanol into the oil-in-water miniemulsion system obtained in the step (3) under the condition of uniform stirring (100rpm), carrying out phase inversion (4-8 h) at room temperature, then centrifuging (5000rpm, 5min), washing (washing with ethanol for 3 times), and drying (60 ℃) to obtain the composite polymer microcapsule for slow release of the dye;
the volume ratio of the ethanol to the dichloromethane solvent in the step (2) is 10-20: 1.
further, when the dye is a hydrophobic dye, in the step (2), the hydrophobic dye is added into the obtained oil phase mixed solution, the adding mass of the hydrophobic dye is 0.5-5% of that of the high-molecular polymer, and the subsequent steps are unchanged; this is not necessary when the dye is a hydrophilic dye.
The composite polymer microcapsule for dye slow release prepared by the invention can be slowly released in various solvents, wherein the solvents include but are not limited to methanol, ethanol, food oil, benzene, diethyl ether, acetone and chloroform; in particular, the composite polymer microcapsule coated with the hydrophilic dye can be slowly released in water.
Specifically, the slow release steps of the composite polymer microcapsule are as follows:
adjusting the pH value of a solvent to 3-7, adding the composite polymer microcapsule, oscillating at the temperature of 20-50 ℃ for 4 hours, sampling 0.22 mu m PVDF membrane at intervals of 20min, and measuring and calculating the content of the dye by using an ultraviolet spectrophotometer;
the volume dosage of the solvent is 2000mL/g based on the mass of the composite polymer microcapsule;
the solvent is water, ethanol, methanol, edible vegetable oil or chloroform;
the dye coated in the composite polymer microcapsule is Methylene Blue (MB) or solvent red 24.
The invention has the beneficial effects that: the invention takes methylene dichloride dissolved with high molecular polymer as an oil phase, disperses nanometer silicon dioxide absorbing dye in the oil phase, forms a stable oil-in-water miniemulsion system under the action of a surfactant and a cosolvent, and at the same time of phase inversion, the methylene dichloride is diffused into ethanol to form a hollow microcapsule with an inner cavity coated with nanometer silicon dioxide spheres. The introduction of the silicon dioxide is beneficial to further enhancing the hydrophobic dye coating and slow release capability of the polymer microcapsule, and the hydrophilic dye coating and slow release are realized, so that the application range of the polymer microcapsule dye slow release is greatly widened.
(IV) description of the drawings
FIG. 1 is an SEM image of composite polymeric microcapsules of example 1;
FIG. 2 is a graph of the sustained release performance of the composite polymer microcapsules of application example 1 to MB in different solvents;
fig. 3 is a graph of the sustained release performance of the composite polymer microcapsule of application example 2 in different solvents to the solvent red 24.
(V) detailed description of the preferred embodiments
The present invention is further illustrated by the following specific examples, but the scope of the invention is not limited thereto.
Example 1:
(1) dissolving 0.05g of Methylene Blue (MB) dye in 100ml of ethanol by ultrasonic, adding 0.5g of hydrophobic nano-silica microspheres (Tianxing New Material Co., Ltd.), stirring for 2h for full adsorption, centrifuging (5000rpm) for 5min, washing (with ethanol), and drying at 60 ℃ for later use.
(2) Adding 1g of high molecular polymer PSF into a dichloromethane solvent with the mass of 20 times that of the PSF, stirring for 6 hours until the high molecular polymer is completely dissolved to prepare an oil phase, adding 0.3g of the silicon spheres obtained in the step (1) into the oil phase, and adding 0.5g of dodecyl glucoside to uniformly disperse the silicon spheres;
(3) adding the oil phase into deionized water with a volume ratio of 2:1 to dichloromethane under rapid (1000rpm) stirring, adding 3ml of cosolvent n-butyl alcohol under a cold water bath, adding sodium dodecyl benzene sulfonate for compounding until the emulsion is semitransparent or clear, and performing ultrasonic treatment for half an hour after continuously stirring for 2 hours to prepare a stable oil-in-water miniemulsion system;
(4) adding ethanol with the volume of 20 times that of dichloromethane slowly into the oil-in-water miniemulsion in the step (3) under uniform stirring, and performing phase inversion at room temperature for 6 hours to prepare a composite polymer microcapsule;
(5) after the steps are finished, washing the microcapsule for 3 times by using ethanol after centrifugal separation, and drying the microcapsule at the temperature of 60 ℃ to obtain the microcapsule.
Example 2:
(1)0.05g of solvent red 24 dye is dispersed in 100ml of ethanol by ultrasonic, 0.5g of hydrophobic nano silicon dioxide microspheres (Tianxing New Material Co., Ltd.) are added, the mixture is stirred for 2 hours for full adsorption, and then the mixture is centrifuged (5000rpm) for 5 minutes, washed (by ethanol) for 3 times and dried at 60 ℃ for standby.
(2) Adding 1g of high molecular polymer PMMA into a dichloromethane solvent with the mass of 20 times that of PMMA, stirring for 4 hours until the high molecular polymer is completely dissolved to prepare an oil phase, adding 0.3g of the silicon spheres obtained in the step (1) into the oil phase, and then adding 0.6g of dodecyl glucoside to uniformly disperse the silicon spheres; adding 0.01g of solvent red 24 into the oil phase for coating;
(3) adding the oil phase into deionized water with a volume ratio of 5:1 to dichloromethane under rapid (1000rpm) stirring, adding 4ml of cosolvent n-butyl alcohol under cold water bath, adding sodium dodecyl benzene sulfonate for compounding until the emulsion is semitransparent or clear, and performing ultrasonic treatment for half an hour after continuously stirring for 2 hours to prepare a stable oil-in-water miniemulsion system;
(4) and (3) adding ethanol with the volume of 20 times that of the dichloromethane slowly into the oil-in-water miniemulsion in the step (3) under uniform stirring, and performing phase inversion for 4 hours at room temperature to prepare the composite polymer microcapsule.
(5) After the steps are finished, washing the microcapsule for 3 times by using ethanol after centrifugal separation, and drying the microcapsule at the temperature of 60 ℃ to obtain the microcapsule.
Application example 1:
the slow release effect of the composite polymer microcapsule on MB in different solvents is explored at room temperature and pH of 6.
Accurately weighing 0.05g (3 parts) of the composite polymer microcapsule in example 1, respectively adding 100ml of water, ethanol and edible vegetable oil, placing the mixture into a shaker at 25 ℃, shaking the shaker at the frequency of 120 times per minute, respectively sampling the solution every 20min, and measuring and calculating the content of the dye by using an ultraviolet spectrophotometer after passing through a PVDF film with the thickness of 0.22 mu m. As can be seen from FIG. 2, the sustained release of MB in each solvent of the composite microcapsule is up to about 200min, wherein the maximum sustained release amount of MB in ethanol is up to 15.4 mg/L.
Application example 2:
the slow release effect of the composite polymer microcapsule on solvent red in different solvents is researched at room temperature and pH of 6.
Accurately weighing 0.05g (3 parts) of the composite polymer microcapsule in the embodiment 2, respectively adding the microcapsule into 100ml of ethanol, methanol and edible vegetable oil, placing the microcapsule into a shaker at 25 ℃, shaking the microcapsule at the frequency of 120 times per minute, respectively sampling the solution every 20min, and measuring and calculating the content of the dye by using an ultraviolet spectrophotometer after passing through a PVDF film with the thickness of 0.22 mu m. As can be seen from FIG. 3, the sustained release of the solvent red 24 in each solvent of the composite microcapsule can reach about 180min, wherein the maximum sustained release amount of the solvent red 24 in ethanol reaches 55.3 mg/L.
Claims (7)
1. A preparation method of composite polymer microcapsules for slow release of dyes is characterized by comprising the following steps:
(1) adding a dye into ethanol, ultrasonically dissolving to obtain a dye solution, then adding hydrophobic nano silicon dioxide microspheres into the dye solution, stirring and adsorbing, then centrifuging, washing and drying to obtain silicon spheres adsorbing the dye;
the dye is a hydrophilic dye or a hydrophobic dye;
(2) adding a high molecular polymer into a solvent dichloromethane, stirring until the high molecular polymer is completely dissolved to obtain an oil phase, adding the dye-adsorbing silica spheres obtained in the step (1) into the oil phase, then adding dodecyl glucoside, and stirring until the mixture is uniformly dispersed to obtain an oil phase mixed solution;
the mass ratio of the high molecular polymer to dichloromethane serving as a solvent, silicon spheres for adsorbing dye and dodecyl glucoside is 1: 10-20: 0.1-1: 0.4 to 0.6;
(3) adding the oil phase mixed solution obtained in the step (2) into solvent deionized water at room temperature under the stirring condition, adding cosolvent and sodium dodecyl benzene sulfonate, stirring and performing ultrasonic treatment to obtain an oil-in-water miniemulsion system;
the volume ratio of the deionized water solvent to the dichloromethane solvent in the step (2) is 2-5: 1;
the mass ratio of the cosolvent to the dichloromethane solvent in the step (2) is 1: 3-10;
the cosolvent is selected from: n-butanol, isooctyl alcohol, PEG-200, PEG-400, PEG-600, glycerol, n-hexadecane or styrene;
compounding the dosage of the sodium dodecyl benzene sulfonate according to the dosage of the dodecyl glucoside in the step (2) to ensure that the HLB value of the obtained oil-in-water miniemulsion system is 14.5;
(4) and (3) under the condition of uniform stirring, adding ethanol into the oil-in-water miniemulsion system obtained in the step (3), carrying out phase inversion at room temperature, and then centrifuging, washing and drying to obtain the composite polymer microcapsule for slow release of the dye.
2. The method for preparing the composite polymer microcapsule for sustained release of the dye according to claim 1, wherein when the dye is a hydrophobic dye, in the step (2) of the preparation method, the hydrophobic dye is added to the obtained oil-phase mixed solution, the mass of the hydrophobic dye added is 0.5-5% of that of the high-molecular polymer, and the subsequent steps are not changed.
3. The method for preparing a composite polymer microcapsule for sustained release of dye according to claim 1, wherein in the step (1), the volume amount of ethanol is 2L/g based on the mass of the dye.
4. The method for preparing a composite polymer microcapsule for sustained release of dye according to claim 1, wherein in the step (1), the volume usage amount of the dye solution is 200mL/g based on the mass of the hydrophobic nano-silica microspheres.
5. The method for preparing a composite polymer microcapsule for dye sustained release according to claim 1, wherein in the step (1), the hydrophilic dye is: methylene blue, methyl orange or rhodamine B, wherein the hydrophobic dye is: solvent red 24, solvent black or Lilaihong.
6. The method for preparing composite polymer microcapsules for sustained release of dye according to claim 1, wherein in the step (2), the high molecular polymer is selected from: polysulfone, polyethersulfone, polyurethane elastomer or plexiglass.
7. The preparation method of the composite polymer microcapsule for sustained release of the dye according to claim 1, wherein in the step (4), the volume ratio of the ethanol to the solvent dichloromethane in the step (2) is 10-20: 1.
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| CN1925908A (en) * | 2003-08-22 | 2007-03-07 | 丹尼斯科有限公司 | Microcapsules |
| CN107138104A (en) * | 2017-05-22 | 2017-09-08 | 天津晶润锐拓科技发展有限公司 | A kind of preparation method of the microcapsules of common cladding hindered amines stabilizer, Hinered phenols stabilizer and organic dyestuff |
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| CN1925908A (en) * | 2003-08-22 | 2007-03-07 | 丹尼斯科有限公司 | Microcapsules |
| CN107138104A (en) * | 2017-05-22 | 2017-09-08 | 天津晶润锐拓科技发展有限公司 | A kind of preparation method of the microcapsules of common cladding hindered amines stabilizer, Hinered phenols stabilizer and organic dyestuff |
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