CN107352549B - Preparation method of hollow glass beads - Google Patents
Preparation method of hollow glass beads Download PDFInfo
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- CN107352549B CN107352549B CN201710763425.1A CN201710763425A CN107352549B CN 107352549 B CN107352549 B CN 107352549B CN 201710763425 A CN201710763425 A CN 201710763425A CN 107352549 B CN107352549 B CN 107352549B
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/10—Forming beads
- C03B19/107—Forming hollow beads
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
- C03C11/002—Hollow glass particles
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- C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2006/66—Hue (H*)
Abstract
The invention relates to a preparation method of hollow glass beads. The method takes nano-cellulose as an emulsifier of Pickering emulsion, adds a precursor of silicon dioxide into an oil phase of the emulsion, takes the Pickering emulsion as a template, and generates sol-gel reaction under acidic or alkaline conditions through the precursor of the silicon dioxide, thereby preparing the hollow glass microspheres. The method is simple and convenient, has adjustable particle size, can be carried out at room temperature, and reduces the preparation cost of the hollow glass microspheres.
Description
Technical Field
The invention relates to the field of material preparation and application, in particular to a preparation method of hollow glass beads.
Background
The hollow glass microspheres are hollow glass spheres with the size of micron grade. Usually, the particle diameter is 10 to 200 μm, and the bulk density is 0.1 to 0.5g/cm3. Due to the unique component composition and structure, the hollow glass microsphere has the advantages of light weight, low thermal conductivity, sound insulation, good dispersibility, good insulativity and thermal stability and the like, and is a new material which is newly developed and has wide application and excellent performance.
The hollow glass beads have the following advantages: (1) the color is white, and the paint can be widely applied to materials or products with requirements on appearance; (2) the density is small, and the density of the glass beads is small and is a fraction of that of the traditional filling material due to the hollow structure of the glass beads, so that the glass beads can be used as a filling product, the density of the product or the product can be greatly reduced, and more base materials can be replaced or saved, so that the cost is reduced; (3) the hollow glass microspheres can be dispersed in most resins, such as polyester, polyvinyl chloride, epoxy resin, polyurethane and the like; (4) the hollow glass microspheres are micron-sized spheres, and have better fluidity in liquid resin than flaky, needle-shaped or irregularly-shaped fillers, so that the stamping die has excellent performance; (5) the hollow glass beads are isotropic, so that the problem of inconsistent shrinkage of different parts due to orientation is avoided, the size stability of the product is ensured, and the product is not warped; (6) the hollow glass microspheres have good heat insulation, sound insulation and insulating properties, are hollow, have the characteristics of sound insulation, heat insulation and insulation, are excellent filling materials for various sound insulation and heat preservation products, have excellent heat insulation properties for protecting the products from stress changes caused by direct and alternate change of sharp heat and rapid cooling conditions, and have insulativity for being applied to cable insulating materials and the like.
Due to the excellent performance, the hollow glass microsphere has wide application prospect. The method can be applied to the following fields: (1) in the aspect of rubber products, the hollow glass beads are used as a filler, the filling amount of the hollow glass beads reaches 40-80%, the strength of the rubber products can be improved, the wear resistance of the rubber products is increased, and the main performance of the rubber products is superior to that of other fillers; (2) the composite foamed plastic is prepared by adding the hollow glass beads into liquid thermosetting resin, and has the advantages of low density, high strength and good heat insulation effect. (3) The artificial marble is filled with appropriate hollow glass beads in the production of the artificial marble, so that the texture layout and color continuity of the artificial marble can be improved, the curing time is shortened, the impact strength is improved, the anti-cracking capability is improved, the breakage rate is reduced, the machinability is improved, the abrasion of a post-processing tool is reduced, and the artificial marble is convenient to carry and install; (4) the hollow glass beads have incombustibility, heat insulation, electric insulation and chemical inertness, are prepared into a microsphere adhesive or a microsphere sealant, and can be used for sealing floors in aircraft cabins or fire walls of engine cabins or heat insulation and ablation prevention sealing of aerospace systems such as missiles, rockets and the like; (5) the density, the grain diameter, the compressive strength and the chemical composition adjustability of the hollow glass beads of the emulsion explosive cannot be achieved by other emulsion explosive density regulators, the hollow glass beads can effectively improve the controllability and the detonation performance of the explosive, and the storage period and the storage stability of the explosive are obviously improved; (6) the coating has high filling efficiency, low oil absorption and low density, and the addition of 5 percent (by weight) can increase the coating area percentage of a finished product by 25 to 35 percent, thereby reducing the unit volume cost of the coating; (7) in other fields, the density of the hollow glass bead powder is low, and the hollow glass bead powder can replace metal powder with high density to be used for electromagnetic wave absorption or electromagnetic shielding material preparation after the surface of the hollow glass bead powder is subjected to metallization treatment.
The international market demand of the hollow glass beads is huge. At present, the commonly used preparation methods of hollow glass microspheres comprise a glass powder method, a spray granulation method, a liquid drop method and a dry gel method, but the methods are complex in steps, high in production cost, poor in particle size controllability and often require high temperature and other conditions, so that a convenient, low-cost and strong-controllability preparation method of the hollow glass microspheres is urgently needed. In recent years, novel methods for preparing hollow glass beads are also diversified, but the advantages of the methods are not particularly obvious and cannot replace the prior art.
The invention utilizes nano-cellulose as an emulsifier of Pickering emulsion, takes Pickering emulsion as a template, and prepares the hollow glass beads through sol-gel reaction of silicon dioxide precursors at room temperature. The prepared hollow glass bead has the obvious advantages of adjustable grain size, excellent mechanical property, simple operation, mild reaction condition, low cost and the like. The nanocellulose is nano-sized and micro-sized cellulose, the diameter of which is 1 to 100 nanometers, and the length of which is 5 nanometers to 100 micrometers. Nanocellulose has attracted considerable attention in recent years as a new generation of nanomaterials. The nano-cellulose is a nano-material extracted from natural microcrystalline cellulose, such as wood pulp, straw, cotton and the like (Chinese patent CN 105419012A, CN 104762845B).
Nanocellulose is generally divided into three categories depending on size, preparation method and source: cellulose Nanofibers (CNF), nanocellulose (CNC) and Bacterial Nanocellulose (BNC). The nano-cellulose has many good properties, such as excellent mechanical properties, large specific surface area, good biocompatibility, environmental friendliness, wide sources, reproducibility, mass production, low cost and the like. The density of the nano-cellulose is only 1/5 of steel, but the strength is far better than that of the steel. The mechanical property of the nano-cellulose is even better than that of Kevlar fiber for manufacturing body armor. Due to these excellent properties, nanocellulose can be used in many areas, such as reinforcement materials, plastic additives, oil and gas mining, solar cells, cosmetics, food packaging, catalysts, waste water treatment, aerogels, hydrogels, paints, antibacterial materials, pickering emulsions, etc. (chinese patent CN 106280911A). Unmodified nanocellulose is generally hydrophilic, and the surface hydrophilic and hydrophobic properties of nanocellulose can be regulated and controlled through small molecule reaction or macromolecular grafting. The hydrophilic nano-cellulose can be dispersed in a water phase and can emulsify an oil-in-water pickering emulsion; the hydrophobic nano-cellulose can be dispersed in an oil phase and can be emulsified to obtain a water-in-oil pickering emulsion.
Disclosure of Invention
The invention solves the technical problem of providing a convenient preparation method of hollow glass beads, which has the advantages of simple steps, convenient operation, adjustable particle size, reaction at room temperature, low cost and capability of overcoming the defects of complicated steps, high production cost, poor particle size controllability, frequent need of high temperature and the like of the conventional preparation method.
In order to achieve the purpose, the invention is characterized in that nanocellulose is used as an emulsifier of Pickering emulsion, a silica precursor is dissolved and added into an oil phase in the emulsion, the Pickering emulsion is used as a template, and the hollow glass beads are prepared by the sol-gel reaction of the silica precursor in an oil phase system at room temperature.
Unmodified nanocellulose is generally hydrophilic, and the surface hydrophilic and hydrophobic properties of nanocellulose can be regulated and controlled through small molecule reaction or macromolecular grafting. The hydrophilic nanocellulose can be dispersed in an aqueous phase and used as an emulsifier to emulsify to form an oil-in-water pickering emulsion in which the aqueous phase is the continuous phase and the oil phase is the discontinuous phase. The hydrophobic nanocellulose can be dispersed in an oil phase such as toluene or chloroform, and when used as an emulsifier for a pickering emulsion, a water-in-oil pickering emulsion can be formed in which the oil phase is a continuous phase and the aqueous phase is a discontinuous phase. Thus, hollow glass microspheres can be prepared by both oil-in-water and water-in-oil pickering emulsion systems.
The water phase of the pickering emulsion refers to a phase taking water as a solvent. The oil phase of the pickering emulsion refers to an oil phase solvent which is liquid under the stable preparation of the emulsion and is insoluble in water and dissolves a silicon dioxide precursor, such as liquid paraffin, styrene, toluene, chloroform, dichloromethane, n-hexane, cyclohexane, edible oil and the like.
The precursor of the silicon dioxide is a compound containing a-Si-O-bond, and can perform a sol-gel reaction of hydrolytic esterification under an acidic or alkaline condition. The silica precursor in the oil phase in the Pickering emulsion generates sol-gel reaction at the oil-water interface of the emulsion, so that a silica shell layer is formed on the interface of the emulsion, and the hollow glass beads are obtained.
The embodiment and the steps for preparing the hollow glass microspheres by using the hydrophilic nanocellulose emulsified oil-in-water pickering emulsion as a template are as follows:
1) dispersing hydrophilic nano-cellulose in water to be used as an aqueous phase A of a Pickering emulsion, wherein the pH value of the aqueous phase is more than 9 or less than 5, and the concentration of the nano-cellulose in the aqueous phase is 0.5-10 mg/mL.
2) Dissolving a precursor of silicon dioxide in an oil phase solvent to be used as an oil phase B of the Pickering emulsion, wherein the precursor of the silicon dioxide is a compound which has-Si-O-bonds and can carry out sol-gel reaction, and the oil phase solvent can be liquid paraffin, styrene, toluene, chloroform, dichloromethane, n-hexane, cyclohexane or edible oil.
3) And mixing the water phase A and the oil phase B, stirring by an ultrasonic or homogenizer to prepare a Pickering emulsion, standing for several days, and washing and drying to obtain the hollow glass microspheres.
The embodiment and the steps for preparing the hollow glass beads by using the water-in-oil Pickering emulsion emulsified by the hydrophobic nano cellulose as a template are as follows:
1) dispersing hydrophobic nano-cellulose in an oil phase solvent, adding a precursor of silicon dioxide to dissolve the hydrophobic nano-cellulose to form an oil phase A of Pickering emulsion, wherein the concentration of the modified nano-cellulose in the oil phase A is 0.25-4 mg/mL, the precursor of the silicon dioxide is a compound with a-Si-O-bond capable of carrying out sol-gel reaction, and the oil phase solvent is one of liquid paraffin, styrene, toluene, chloroform, dichloromethane, n-hexane, cyclohexane and edible oil.
2) Taking water with pH value more than 9 or less than 5 as water phase B of Pickering emulsion
3) And mixing the oil phase A and the water phase B, stirring by an ultrasonic or homogenizer to prepare a Pickering emulsion, standing for several days, washing and drying to obtain the hollow glass microspheres.
The invention has the beneficial effects that: the method takes the Pickering emulsion prepared by taking the nano-cellulose as the emulsifier as the template for preparation, and utilizes the sol-gel alternating-current reaction of the silicon dioxide precursor in the oil phase at room temperature to prepare the hollow glass beads, wherein the nano-cellulose has wide sources, less using amount as the emulsifier and lower cost, and the obtained Pickering emulsion is more stable; the particle size of the Pickering emulsion can be adjusted by the dosage of the nano-cellulose and the like, so that the particle size of the hollow glass microspheres can be conveniently adjusted; the sol-gel reaction of the silicon dioxide precursor can be carried out at room temperature without reaction conditions such as high temperature and the like; the mechanical property of the prepared hollow glass bead is enhanced due to the introduction of the nano-cellulose; the preparation method of the hollow glass bead can be realized by a one-step method, and has simple preparation process and lower cost.
Drawings
FIG. 1 is an optical micrograph of hollow glass microspheres prepared at different sodium chloride concentrations in example 1;
FIG. 2 is a graph showing the tendency of the diameter of hollow glass microspheres to vary with the concentration of sodium chloride in example 1;
FIG. 3 is an optical microscope photograph of hollow glass microspheres prepared in example 1 at different nanocellulose concentrations;
FIG. 4 is a graph showing the trend of the diameter of hollow glass microspheres in example 1 as a function of the concentration of nanocellulose;
FIG. 5 is an optical micrograph of hollow glass microspheres prepared at different concentrations of hydrophobic nanocellulose in example 3;
FIG. 6 is a graph of the trend of the diameter of hollow glass microspheres in example 3 as a function of the concentration of hydrophobically modified nanocellulose;
FIG. 7 is a scanning electron micrograph of hollow glass beads in example 3.
Detailed description of the invention
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described below by combining the specific examples and the drawings, but the examples do not limit the protection scope of the invention.
Example 1
The specific examples of the preparation of hollow glass microspheres using an oil-in-water pickering emulsion emulsified with hydrophilic nanocellulose as a template are as follows:
the pH of the water was adjusted to 2.0, then the hydrophilic nanocellulose was dispersed in said water with pH 2.0, and sodium chloride was added as aqueous phase a of the pickering emulsion.
Toluene and methyl orthosilicate are mixed according to the volume ratio of 1:1 to be used as an oil phase B of the Pickering emulsion.
And mixing the water phase A and the oil phase B according to the volume ratio of 7:3, and then carrying out ultrasonic treatment for 2 minutes to obtain the Pickering emulsion. And standing the pickering emulsion at room temperature for 5 days, washing with acetone or ethanol, and drying to obtain the hollow glass microspheres. The size of the hollow glass microspheres can be adjusted by the concentration of sodium chloride, the concentration of nanocellulose and the volume ratio of the water phase to the oil phase.
The individual test parameters and test results are summarized below:
according to tests 1 to 7, the diameter of the hollow glass microspheres is closely related to the concentration of sodium chloride in the aqueous phase. The surface of the nano-cellulose prepared by sulfuric acid hydrolysis has strong negative charges, and certain salt needs to be added to neutralize the negative charges on the surface. When the concentration of the nano-cellulose in the water phase is 5mg/mL, the diameter of the hollow glass microsphere is 27.1 micrometers when the concentration of the added sodium chloride is 1mg/mL, and the diameter of the hollow glass microsphere is about 5 micrometers when the concentration of the sodium chloride is 20 mg/mL. Optical micrographs of hollow glass microspheres prepared at different sodium chloride concentrations, as shown in figure 1, when the concentration of nanocellulose in the aqueous phase was 5mg/mL, the sodium chloride concentrations were 1, 2, 4, 6, 8, 10 and 20mg/mL in that order, with the scale bar in figure 1 being 50 microns. Therefore, the diameter of the hollow glass microspheres gradually decreases with the increase of the concentration of sodium chloride, and the change of the diameter of the hollow glass microspheres with the concentration of sodium chloride is shown in fig. 2.
According to tests 8 to 14, when the concentration of sodium chloride in the aqueous phase is 5mg/mL, the concentration of the nanocellulose in the aqueous phase also affects the diameter of the glass microspheres; when the concentration of the nano-cellulose is as low as 0.5mg/mL, the diameter of the hollow glass microsphere is 18.6 microns, and when the concentration of the nano-cellulose crystal is increased to 8mg/mL, the diameter of the hollow glass microsphere is reduced to 7 microns. When the concentration of sodium chloride in the aqueous phase is 5mg/mL, the optical micrographs of the hollow glass microspheres prepared at different nanocellulose concentrations are shown in fig. 3, the nanocellulose concentrations in the aqueous phase are 0.5, 1, 2, 4, 6 and 8mg/mL in sequence, and the scale bar in fig. 3 is 50 μm. Therefore, the diameter of the hollow glass microspheres gradually decreases with the increase of the concentration of the nanocellulose, and the change of the diameter of the hollow glass microspheres with the concentration of the nanocellulose is shown in fig. 4.
The obtained hollow glass microspheres are white, can be dispersed in different solvents such as water, dimethylformamide, tetrahydrofuran, toluene, chloroform and the like, and still keep good integrity after being subjected to ultrasonic treatment for 10 minutes, so that the hollow glass microspheres have good mechanical properties.
Example 2
The present example investigated the effect of different silica precursors, pH values, organic phase solvents, etc. on hollow glass microspheres.
Dispersing hydrophilic nano cellulose in water with certain pH value, and adding sodium chloride as a water phase A of the Pickering emulsion.
And mixing the oil phase solvent and the silicon dioxide precursor according to the volume ratio of 1:1 to obtain an oil phase B of the Pickering emulsion.
And mixing the water phase A and the oil phase B according to the volume ratio of 7:3, and carrying out ultrasonic treatment for 2 minutes to obtain the Pickering emulsion. And standing the pickering emulsion at room temperature for 5 days, washing with acetone or ethanol, and drying to obtain the hollow glass microspheres.
The overall test results for each test parameter and test result are as follows:
the methyl orthosilicate in example 1 is substituted with other silica precursors. According to tests 15 and 16, when methyl orthosilicate was replaced with ethyl orthosilicate in the above example 1 as a silica precursor, the sol-gel reaction time should be extended to 7 days to obtain hollow glass beads having a certain mechanical strength, and if the solvent gel time is less than 7 days, the glass beads may be broken when washed with acetone or ethanol. The diameter of the hollow glass microspheres was similar to the experimental results described above.
According to the tests 17 to 25, the present example also tried gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, diethylenetriaminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, sodium silicate, gamma-methacryloxypropyltrimethoxysilane and gamma-methacryloxypropyltriethoxysilane, all of which gave hollow glass beads, and the diameters of the specific glass beads were shown in the tests 17 to 25 in the table.
According to tests 26 to 28, the pH value of the aqueous phase in the above example 1 is adjusted to 1 by 0.1mol/L hydrochloric acid, and the hollow glass beads with a certain mechanical strength can be obtained only by 4 days of sol-gel time; when the pH of the aqueous phase in the above example was 3, a solvent gel time of 7 days was required; when the pH of the aqueous phase in the above examples is 5, a sol-gel time of about 10 days is required. Therefore, when the pH is less than 5, the smaller the pH value, the shorter the sol-gel time required, and the smaller the diameter of the hollow glass microspheres.
According to tests 29 to 31, the pH value of the aqueous phase in the above example 1 is adjusted to be alkaline, and when the pH value is 9, a sol-gel time of 11 days is required to obtain hollow glass beads with certain mechanical strength; at a pH of 12, a sol gel time of at least 5 days is required. Thus, when the pH is greater than 9, the larger the pH, the shorter the sol-gel time required and the smaller the diameter of the voided glass microspheres.
When the oil phase solvent in example 1 is replaced with, for example, liquid paraffin, styrene, chloroform, methylene chloride, n-hexane, cyclohexane and edible oil according to tests 32 to 38, the diameters of the hollow glass beads are slightly different due to the difference in polarity of the solvent, and the specific particle diameters are shown in tests 32 to 38 in the above table.
Example 3
The specific examples of the preparation of hollow glass beads using a water-in-oil pickering emulsion emulsified with hydrophobic nanocellulose as a template are as follows:
firstly, hydrophobic modification is carried out on hydrophilic nano-cellulose, and the modified hydrophobic nano-cellulose can be prepared by introducing a hydrophobic matrix on the nano-cellulose through methods such as small molecule reaction or macromolecular grafting and the like. This example hydrophobically modified nanocellulose with butyryl chloride. Dispersing 1 g of nano-cellulose into 100 ml of dimethylformamide, adding 1 ml of triethylamine, 1 g of 4-dimethylaminopyridine and 1 g of butyryl chloride, and reacting at room temperature for 24 hours to obtain the hydrophobically modified nano-cellulose.
Dispersing the hydrophobically modified fiber nanocrystals into an oily solvent, and adding a silicon dioxide precursor methyl orthosilicate according to the volume ratio of 1:1 to obtain an oil phase A of the Pickering emulsion.
The aqueous solution with a pH value of 2 was used as the aqueous phase B of the Pickering emulsion. And then mixing the oil phase A and the water phase B according to the volume ratio of 7:3, carrying out ultrasonic treatment for 2 minutes to prepare a Pickering emulsion, standing for 5 days, and washing with acetone or ethanol to obtain the hollow glass microspheres.
The individual test parameters and test results are summarized below:
according to tests 39 to 43, the size of the hollow glass microspheres prepared by the method is closely related to the concentration of the hydrophobically modified nanocellulose. The diameter of the hollow glass microspheres was about 61.9 microns when the concentration of the hydrophobically modified nanocellulose in the oil phase was as low as 0.25mg/mL, and the diameter of the hollow glass microspheres was reduced to 7 microns when the concentration of the hydrophobically modified nanocellulose in the oil phase was increased to 4 mg/mL. An optical microscope photograph of the hollow glass microspheres prepared according to the method is shown in fig. 5, the concentrations of the hydrophobically modified nanocellulose in the oil phase are 0.25, 0.5, 1, 2 and 4mg/mL in this order, and the scale bar in fig. 5 is 50 micrometers. The diameter of the hollow glass microspheres gradually decreased with the increase of the concentration of the hydrophobically modified nanocellulose, and the change of the diameter of the hollow glass microspheres with the concentration of the hydrophobically modified nanocellulose is shown in fig. 6.
The obtained hollow glass microspheres are white, can be dispersed in different solvents such as water, dimethylformamide, tetrahydrofuran, toluene, chloroform and the like, and still keep good integrity after being subjected to ultrasonic treatment for 10 minutes, so that the prepared hollow glass microspheres have good mechanical properties.
The hollow glass beads were subjected to morphology analysis using a scanning electron microscope, as shown in fig. 7. The hollow glass microspheres exhibit a spherical structure, and the wall thickness of the hollow glass microspheres is approximately 1.2 microns or so by fragment analysis of one hollow glass microsphere.
Claims (10)
1. A preparation method of hollow glass microspheres is characterized in that nanocellulose is used as an emulsifier of Pickering emulsion, a precursor of silicon dioxide is dissolved in an oil phase of the emulsion, the Pickering emulsion is used as a template, and the precursor of the silicon dioxide is subjected to sol-gel reaction on an emulsion interface under acidic or alkaline conditions to prepare the hollow glass microspheres.
2. The method for preparing hollow glass microspheres according to claim 1, wherein the hydrophilic nanocellulose emulsified oil-in-water pickering emulsion is used as a template to prepare the hollow glass microspheres according to the following embodiments and steps:
1) dispersing hydrophilic nanocellulose in acidic or basic water as the aqueous phase a of a pickering emulsion, wherein the acidic or basic pH is less than 5 or greater than 9;
2) dissolving a precursor of silicon dioxide in an oil phase solvent to be used as an oil phase B of the Pickering emulsion;
3) and mixing the water phase A and the oil phase B, stirring by an ultrasonic or homogenizer to prepare a Pickering emulsion, and standing for several days to obtain the hollow glass microspheres.
3. The method for preparing hollow glass microspheres according to claim 1, wherein the hydrophobic nanocellulose emulsified water-in-oil pickering emulsion is used as a template, and the embodiment and steps for preparing the hollow glass microspheres are as follows:
1) dispersing hydrophobic nano-cellulose in an oil phase solvent, adding a precursor of silicon dioxide, and dissolving the precursor in the oil phase solvent to obtain an oil phase A of the Pickering emulsion;
2) taking water with the pH value of more than 9 or less than 5 as a water phase B of the Pickering emulsion;
3) mixing the oil phase A and the water phase B, stirring by an ultrasonic or homogenizer to prepare a Pickering emulsion, and standing for several days to obtain the hollow glass microspheres.
4. The method for preparing hollow glass microspheres according to claim 1, wherein the nanocellulose is nano-sized and micro-sized cellulose with a diameter of 1 to 100 nm and a length of 5 nm to 100 μm, and the concentration of the nanocellulose in the aqueous phase is 0.25-10 mg/mL.
5. The method of claim 1, wherein the pH of the aqueous phase of the Pickering emulsion is greater than 9.
6. The method of claim 1, wherein the pH of the aqueous phase of the Pickering emulsion is less than 5.
7. The method for preparing hollow glass microspheres according to claim 1, wherein the oil phase solvent in the pickering emulsion is one of liquid paraffin, toluene, chloroform, dichloromethane, n-hexane, cyclohexane and edible oil.
8. The method for preparing hollow glass microspheres according to claim 1, wherein the precursor of silica is one of methyl orthosilicate, ethyl orthosilicate, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, diethylenetriaminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, sodium silicate, gamma-methacryloxypropyltrimethoxysilane, or gamma-methacryloxypropyltriethoxysilane.
9. The method according to claim 1, wherein the precursor of silica is methyl orthosilicate.
10. A method for preparing hollow glass microspheres according to claim 1, wherein the hollow glass microspheres have a diameter of 5 to 100 μm and can be dispersed in water, dimethylformamide, tetrahydrofuran, toluene and chloroform.
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| CN107868161B (en) * | 2017-12-07 | 2020-06-05 | 张振 | Preparation method and application of polymer hollow microcapsule |
| CN108690206A (en) * | 2018-05-09 | 2018-10-23 | 上海应用技术大学 | A kind of citral pickering emulsion and preparation method thereof that nano-cellulose is stablized |
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