CN107352549A - A kind of preparation method of hollow glass micropearl - Google Patents
A kind of preparation method of hollow glass micropearl Download PDFInfo
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- CN107352549A CN107352549A CN201710763425.1A CN201710763425A CN107352549A CN 107352549 A CN107352549 A CN 107352549A CN 201710763425 A CN201710763425 A CN 201710763425A CN 107352549 A CN107352549 A CN 107352549A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/66—Hue (H*)
Abstract
The present invention relates to a kind of preparation method of hollow glass micropearl.This method is the emulsifying agent using nano-cellulose as pickering emulsion, the presoma of silica is added in the oil phase of emulsion, using pickering emulsion as template, solgel reaction is occurred by the presoma of silica under acid or alkaline conditions, so as to prepare hollow glass micropearl.The method is simple and convenient, and particle diameter is adjustable, can carry out at room temperature, reduces the cost of hollow glass micropearl preparation.
Description
Technical field
The present invention relates to material preparation and application field, specifically a kind of preparation method of hollow glass micropearl.
Background technology
Hollow glass micropearl is a kind of hollow glass spheroid of size in micron level.Usual particle diameter is at 10~200 microns
Between, bulk density is 0.1~0.5g/cm3.Because the component of uniqueness is formed and structure, hollow glass micropearl have light, lead
Heating rate is low, sound insulation, favorable dispersibility, is a kind of widely used, property that new development is got up the advantages that insulating properties and good heat endurance
The excellent new material of energy.
Hollow glass micropearl has advantages below：(1) white color, can be widely applied to the material that is required to outward appearance or
Product；(2) density is small, due to the hollow-core construction of glass microballoon, its density very little, be several points of Conventional filling material density it
One, therefore filled articles are used as, the density of product or product can be mitigated significantly, substitute or save more matrix materials, from
And reduce cost；(3) good dispersiveness, hollow glass micropearl are dispersed in most of resins, such as polyester, polychlorostyrene second
Alkene, epoxy resin, polyurethane etc.；(4) good fluidity, hollow glass micropearl are micron-sized spheroids, in liquid resin than
The inserts of sheet, needle-like or irregular shape has more preferable mobility, so punch die excellent performance；(5) isotropism, it is empty
Heart glass microballoon is isotropic, therefore will not be produced because different parts shrinkage factor is inconsistent caused by orientation the problem of, is ensured
The dimensionally stable of product, will not warpage；(6) heat-insulated, sound insulation and good insulation preformance, what hollow glass micropearl was internally hollow,
Therefore it is all kinds of sound insulations, the excellent packing material of insulating product, its excellent thermal insulation is special with sound insulation, heat-insulated and insulation characteristic
Property be used to protecting product to be subjected to anxious heat and chilling condition that directly alternately stress variation caused by change, its insulating properties can to make it should
For cable insulation material etc..
Due to its excellent performance, hollow glass micro-ball is with a wide range of applications.It can apply in following several big necks
Domain：(1) rubber plastic product, in terms of rubber, hollow glass micropearl as filler, its loading up to 40~80%,
The intensity of rubber can be improved, wearability increase, main performance is better than other fillers；(2) syntactic foam, will be hollow
Glass microballoon is added in liquid thermosetting resin and syntactic foam is made, and its density is low, intensity is high, good heat-insulation effect.(3) people
Make marble, artificial marble production in fill appropriate hollow glass micropearl, can improve artificial marble texture layout and
The continuity of color, hardening time is reduced, improve impact strength, improve freedom from cracking ability, reduce breakage rate, while improve machinery
Processability, reduces the abrasion of post processing instrument, and is easy to carry and installs；(4) adhesive and encapsulant, hollow glass micropearl
With noninflammability, thermal insulation, electrical insulating property and chemical inertness, microballoon adhesive or microballoon sealant are configured to, available for aircraft
The sealing of floor or enging cabin fire wall in cabin, or the sealing of the adiabatic burn-out proof as aerospace systems such as guided missile, rockets；(5)
Emulsion, density, particle diameter, compression strength and the chemical composition adjustable of hollow glass micropearl, are that other emulsions are close
Degree conditioning agent can not accomplish that hollow glass micropearl can effectively improve the degree of controllability and detonation property of explosive, significantly improve explosive
Storage period and storage stability；(6) coating, efficient fillibility, low oil absorption ferric, density is low, adds 5% (percentage by weight)
Finished product can be made to increase 25%~35% coated area percentage, so as to reduce the volume cost of coating；(7) other field,
Hollow glass micropearl powder density is smaller, after carrying out metalized to its surface, can substitute the larger metal-powder of density
Preparation for electro-magnetic wave absorption or electromagnetic shielding material.
Hollow glass micropearl international market demand amount is huge.At present, the preparation method of conventional hollow glass micropearl includes
Glass powder method, spraying pelletizing process, sessile drop method and desiccant gel method, but often step is complicated for these methods, production cost is high,
Size tunable is poor, often needs the conditions such as high temperature, therefore the hollow glass that urgent need is a kind of easily, inexpensive, controllability is strong
The preparation method of glass microballoon.In recent years, novel hollow glass micropearl preparation method is also to emerge in an endless stream, but these method advantages
It is not particularly evident, still can not substitutes existing technology.
Emulsifying agent of the present invention by the use of nano-cellulose as Pickering (pik woods) emulsion, is made with pickering emulsion
For template, hollow glass micropearl is prepared by the solgel reaction of silica precursor at room temperature.The hollow glass prepared
Glass microballon has that particle diameter is adjustable, and good mechanical performance is simple to operate, and reaction condition is gentle, and cost is low to wait remarkable advantage.It is described to receive
Rice cellulose is the cellulose of nanometer and micron order size, and its a diameter of 1 to 100 nanometers, its length is 5 nanometers micro- to 100
Rice.As the nano material of a new generation, nano-cellulose causes great concern in recent years.Nano-cellulose is from natural micro-
The nano material extracted in crystalline cellulose, such as wood pulp, stalk and cotton etc. (Chinese patent CN105419012 A,
CN104762845 B)。
Nano-cellulose is divided into three classes generally according to size, preparation method and source difference：It is cellulose nano-fibrous
(cellulose nanofiber, CNF), nano-cellulose (cellulose nanocrystal, CNC) and Nano bacteria
Plain (bacterial nanocellulose, BNC).Nano-cellulose has many good performances, such as excellent mechanical property
Energy, the biocompatibility that specific surface area is big, good, environment-friendly, wide material sources, it is renewable, can volume production and cost it is low the features such as.
The density of nano-cellulose only has the 1/5 of steel, and intensity is but much better than steel.The mechanical property of nano-cellulose even better than makes anti-
Play the kevlar fiber of clothing.Due to these excellent performances, in terms of nano-cellulose can be used in a lot, such as reinforcing material,
Plastic additive, oil-gas mining, solar cell, cosmetics, packaging for foodstuff, catalyst, wastewater treatment, aeroge, hydrogel,
Coating, anti-biotic material and pickering emulsion etc. (Chinese patent CN106280911 A).Unmodified nano-cellulose is usually parent
Water-based, pass through small molecule reaction or the macromolecular grafted surface hydrophilic and hydrophobic property that can regulate and control nano-cellulose.It is hydrophilic
Nano-cellulose can be dispersed in aqueous phase, oil-in-water pickering emulsion can be emulsified；Hydrophobic nano-cellulose can
To be dispersed in oil phase, can emulsify to obtain the pickering emulsion of Water-In-Oil.
The content of the invention
Present invention solves the technical problem that it is to provide a kind of preparation method of easily hollow glass micropearl, this method step
Rapid simple, easy to operate, particle diameter is adjustable, is reacted at room temperature, and cost is low, the step of overcoming existing preparation method
Complexity, production cost are high, and size tunable is poor, the shortcomings that often needing the conditions such as high temperature.
To reach above-mentioned purpose, it is a feature of the present invention that being used as Pickering (pik woods) breasts by the use of nano-cellulose
The emulsifying agent of liquid, in the oil phase in emulsion dissolving add silica precursor, using pickering emulsion as template, pass through oil
The solgel reaction of silica precursor at room temperature in phase system prepares hollow glass micropearl.
Non-modified nano-cellulose is usually hydrophilic, by small molecule reaction or macromolecular grafted can regulate and control to receive
The surface hydrophilic and hydrophobic property of rice cellulose.Hydrophilic nano-cellulose can be dispersed in aqueous phase, can be with as emulsifying agent
Emulsification forms oil-in-water pickering emulsion, and aqueous phase is continuous phase in described oil-in-water pickering emulsion, and oil phase is discontinuous
Phase.Hydrophobic nano-cellulose can be dispersed in the oil phases such as toluene or chloroform, can be with during emulsifying agent as pickering emulsion
The pickering emulsion of Water-In-Oil is formed, in the pickering emulsion of described Water-In-Oil, oil phase is continuous phase, and aqueous phase is discontinuous
Phase.Therefore, hollow glass micropearl can be prepared by two kinds of pickering emulsion systems of oil-in-water and Water-In-Oil.
The aqueous phase of the pickering emulsion refers to the phase using water as solvent.The oil phase of the pickering emulsion refers in emulsion
Prepare it is stable under be in a liquid state and oil phase solvent that is not soluble in water and dissolving silica precursor, such as atoleine, styrene,
Toluene, chloroform, dichloromethane, n-hexane, hexamethylene and edible oil etc..
The presoma of the silica is the compound containing-Si-O- keys, can be sent out under conditions of acid or alkalescence
The solgel reaction of unboiled water solution esterification.Silica precursor in pickering emulsion in oil phase can be in profit circle of emulsion
Solgel reaction occurs for face, so as to form layer of silicon dioxide shell on the interface of emulsion, and then obtains hollow glass
Microballon.
The oil-in-water pickering emulsion emulsified using hydrophilic nano-cellulose prepares hollow glass micropearl as template
Embodiment and step are as follows：
1) hydrophilic nano-cellulose is dispersed in water the aqueous phase A as pickering emulsion, the pH value of wherein aqueous phase is big
In 9 or less than 5, concentration of the nano-cellulose in aqueous phase is 0.5-10mg/mL.
2) presoma of silica is dissolved in oil phase B of the oil phase solvent as pickering emulsion, wherein described two
Siliconoxide precursor is that the compound of solgel reaction can be carried out with-Si-O- keys, wherein described oil phase solvent can be with
It is atoleine, styrene, toluene, chloroform, dichloromethane, n-hexane, hexamethylene or edible oil.
3) above-mentioned aqueous phase A and oil phase B is mixed, pickering emulsion is prepared by ultrasound or homogenizer, stands a couple of days
Afterwards, washing, which is dried, can obtain hollow glass microballoon.
The pickering emulsion of the Water-In-Oil emulsified using hydrophobic nano-cellulose prepares hollow glass micropearl as template
Embodiment and step are as follows：
1) hydrophobic nanofiber element is dispersed in oil phase solvent, the presoma dissolving for adding silica is used as pik
The oil phase A of woods emulsion, wherein concentration of the modified nano-cellulose in oil phase A is 0.25~4mg/mL, wherein described two
Siliconoxide precursor is the compound that solgel reaction can be carried out with-Si-O- keys, wherein described oil phase solvent is liquid
One kind in body paraffin, styrene, toluene, chloroform, dichloromethane, n-hexane, hexamethylene and edible oil.
2) using pH value be more than 9 or the water less than 5 as pickering emulsion aqueous phase B
3) above-mentioned oil phase A and aqueous phase B are mixed, pickering emulsion is prepared by ultrasound or homogenizer, stands a couple of days
Washing, which is dried, afterwards can obtain hollow glass microballoon.
Beneficial effects of the present invention：The pickering emulsion that the present invention is prepared using nano-cellulose as emulsifying agent is used as template
Prepare, using the collosol and gel exchange reaction of the silica precursor in oil phase at room temperature come hollow glass micropearl, wherein
Nano-cellulose wide material sources, the usage amount as emulsifying agent is less, and cost is relatively low, and obtained pickering emulsion is also more stable；
The particle diameter of pickering emulsion can be adjusted by dosage of nano-cellulose etc., and then the grain of conveniently adjusted hollow glass micropearl
Footpath；The solgel reaction of silica precursor can be carried out at room temperature, it is not necessary to the reaction condition such as high temperature；The sky of preparation
Heart glass microballoon is strengthened due to the introducing of nano-cellulose, its mechanical performance；The system of the hollow glass micropearl of the present invention
Preparation Method one-step method can be achieved, and preparation process is simple, and cost is relatively low.
Brief description of the drawings
Fig. 1 is the optical microscope photograph of the hollow glass micropearl prepared in embodiment 1 under different sodium chloride concentrations；
Fig. 2 is the tendency chart that the diameter of hollow glass micropearl in embodiment 1 changes with sodium chloride concentration；
Fig. 3 is the light microscope of the hollow glass micropearl prepared in embodiment 1 under different nano-cellulose concentration
Photo；
Fig. 4 is the diameter of hollow glass micropearl in embodiment 1 with the tendency chart of nano-cellulose change in concentration；
Fig. 5 is that the optics of the hollow glass micropearl prepared in embodiment 3 under different hydrophobic nanofiber element concentration shows
Micro mirror photo；
Fig. 6 is the diameter of hollow glass micropearl in embodiment 3 with the trend of the nano-cellulose change in concentration of hydrophobically modified
Figure；
Fig. 7 is the electron scanning micrograph of hollow glass micropearl in embodiment 3.
Specific implementation method
In order that the technical means, the inventive features, the objects and the advantages of the present invention are easy to understand, tie below
Instantiation and diagram are closed, the present invention is expanded on further, but these examples are not intended to limit protection scope of the present invention.
Embodiment 1
The oil-in-water pickering emulsion emulsified using hydrophilic nano-cellulose prepares hollow glass micropearl as template
Specific embodiment is as follows：
The pH value of water is transferred to 2.0, is then dispersed in hydrophilic nano-cellulose in the water that the pH is 2.0, and add
Enter aqueous phase A of the sodium chloride as pickering emulsion.
By toluene and methyl silicate according to volume ratio 1:1 ratio mixes the oil phase B as pickering emulsion.
By above-mentioned aqueous phase A and oil phase B according to volume ratio 7:3 ratio is mixed, and then ultrasound is i.e. available after 2 minutes
Pickering emulsion.Above-mentioned pickering emulsion is stood 5 days at room temperature, dried after being washed with acetone or alcohol, you can obtain sky
Heart glass microballoon.The size of hollow glass micropearl can by the concentration of sodium chloride, the concentration of nano-cellulose and aqueous phase with
The volume ratio regulation of oil phase.
Each test parameters and result of the test are summarized as follows：
According to experiment 1~experiment 7, the diameter and sodium chloride of hollow glass micropearl are closely related in the concentration of aqueous phase.By
Nano-cellulose surface prepared by sulphuric acid hydrolysis is with very strong negative electrical charge, it is necessary to add certain salt to neutralize the negative electricity on surface
Lotus.When concentration of the nano-cellulose in aqueous phase is 5mg/mL, when the concentration of the sodium chloride of addition is 1mg/mL, hollow glass
A diameter of 27.1 microns of microballon, when the concentration of sodium chloride is 20mg/mL, a diameter of 5 microns of hollow glass micropearl.
When concentration of the nano-cellulose in aqueous phase is 5mg/mL, the hollow glass micropearl that is prepared under different sodium chloride concentrations
Optical microscope photograph is as shown in figure 1, the concentration of sodium chloride is followed successively by the engineer's scale in 1,2,4,6,8,10 and 20mg/mL, Fig. 1
For 50 microns.Therefore the diameter of hollow glass micropearl is gradually reduced with the concentration increase of sodium chloride, hollow glass micropearl
Diameter is as shown in Figure 2 with the change of sodium chloride concentration.
According to experiment 8~experiment 14, when concentration of the sodium chloride in aqueous phase is 5mg/mL, nano-cellulose is in aqueous phase
Concentration also contribute to the diameter of glass microballoon；As the concentration as little as 0.5mg/mL of nano-cellulose, hollow glass micropearl
A diameter of 18.6 microns, when the brilliant concentration of nano-cellulose increases to 8mg/mL, it is micro- that the diameter of hollow glass micropearl is reduced to 7
Rice.When concentration of the sodium chloride in aqueous phase is 5mg/mL, the hollow glass micropearl that is prepared under different nano-cellulose concentration
Optical microscope photograph as shown in figure 3, concentration of the nano-cellulose in aqueous phase is followed successively by 0.5,1,2,4,6 and 8mg/mL,
Engineer's scale in Fig. 3 is 50 microns.Therefore the diameter of hollow glass micropearl increases and is gradually reduced with the concentration of nano-cellulose,
The diameter of hollow glass micropearl is as shown in Figure 4 with the change of nano-cellulose concentration.
Obtained hollow glass micropearl is white, can be dispersed in water, dimethylformamide, tetrahydrofuran, toluene and
In the different solvents such as chloroform, and after ultrasound 10 minutes, hollow glass micropearl has remained in that good integrality, therefore has
There is good mechanical performance.
Embodiment 2
The shadow to hollow glass micropearl such as this case study different silica precursors, pH value and organic phase solvent
Ring.
Hydrophilic nano-cellulose is dispersed in the water of certain pH value, and adds water of the sodium chloride as pickering emulsion
Phase A.
By oil phase solvent and silica precursor according to volume ratio 1:1 ratio mixes the oil phase as pickering emulsion
B。
By above-mentioned aqueous phase A and oil phase B according to volume ratio 7:3 ratio is mixed, and ultrasound can obtain pik after 2 minutes
Woods emulsion.Above-mentioned pickering emulsion is stood 5 days at room temperature, dried after being washed with acetone or alcohol, you can obtain hollow glass
Glass microballon.
Each test parameters and result of the test overall test knot is as follows：
Methyl silicate in embodiment 1 can be substituted by other silica precursors.According to experiment 15 and 16,
Methyl silicate in above-described embodiment 1 is replaced as during silica precursor by tetraethyl orthosilicate, collosol and gel it is anti-
The hollow glass micropearl that can just obtain that there is certain mechanical strength for 7 days should be extended between seasonable, if the sol gel time is less than 7
It when, when being washed with acetone or alcohol, glass microballoon can be damaged.The diameter of hollow glass micropearl and above-mentioned experimental result class
Seemingly.
According to experiment 17~experiment 25, gamma-aminopropyl-triethoxy-silane, γ-aminopropyl three are have also been attempted in this example
Methoxy silane, VTES, vinyltrimethoxy silane, diethylenetriamine base propyl trimethoxy silicon
Alkane, γ-glycidyl ether oxygen propyl trimethoxy silicane, sodium metasilicate, γ-methacryloxypropyl trimethoxy silane and
γ-methacryloxypropyl, hollow glass micropearl, the diameter of specific grain glass microballoon can be obtained
Experiment 17~experiment 25 in being shown in Table.
According to experiment 26~experiment 28, the pH value of the aqueous phase in above-described embodiment 1 is adjusted to 0.1mol/L hydrochloric acid
1, it is only necessary to which the collosol and gel time of 4 days is the hollow glass micropearl that can obtain having certain mechanical strength；Work as above-described embodiment
, it is necessary to the sol gel time of 7 days when the pH value of middle aqueous phase is 3；When the pH value of aqueous phase in above-described embodiment is 5, it is necessary to 10
The collosol and gel time of it or so.Therefore when pH is less than 5, pH value is smaller, and the required collosol and gel time is shorter, Er Qiekong
The diameter of heart glass microballoon is smaller.
According to experiment 29~experiment 31, the pH value regulation of the aqueous phase in above-described embodiment 1 to alkalescence when pH is 9, needs
Take the hollow glass micropearl that the collosol and gel time of 11 days can just obtain having certain mechanical strength；When pH is 12, it is necessary to extremely
Few 5 days collosol and gel time.Therefore when pH is more than 9, pH value is bigger, and the required collosol and gel time is shorter, and space
The diameter of glass microballoon is smaller.
According to experiment 32~experiment 38, by oil phase solvent such as atoleine, styrene, the chlorine in above-described embodiment 1
When imitative, dichloromethane, n-hexane, hexamethylene and edible oil replace, due to the difference of solvent polarity, the diameter of hollow glass micropearl
It is slightly different, specific particle diameter see the above table in experiment 32~experiment 38.
Embodiment 3
The pickering emulsion of the Water-In-Oil emulsified using hydrophobic nano-cellulose prepares hollow glass micropearl as template
Specific embodiment is as follows：
Hydrophobically modified is carried out to hydrophilic nano-cellulose first, can be reacted or macromolecular grafted waited just by small molecule
Method introduces hydrophobic substrates on nano-cellulose and prepares modified hydrophobic nanofiber element.This example is using butyl chloride to Nanowire
Dimension element carries out hydrophobically modified.1 gram of nano-cellulose is distributed in 100 milliliters of dimethylformamides, adds 1 milliliter of triethylamine, 1
Gram DMAP and 1 gram of butyl chloride, when reacting 24 at room temperature, that is, obtain the nano-cellulose of hydrophobically modified.
It is distributed to the fiber of above-mentioned hydrophobically modified is nanocrystalline in oil-based solvent, according still further to volume ratio 1:1 ratio adds
Oil phase A of the silica precursor methyl silicate as pickering emulsion.
Using pH value be 2 the aqueous solution as pickering emulsion aqueous phase B.Then by above-mentioned oil phase A and aqueous phase B with volume ratio
7:3 ratio mixing, ultrasound prepare pickering emulsion for 2 minutes, 5 days are stood, after being washed with acetone or alcohol, you can obtain hollow
Glass microballoon.
Each test parameters and result of the test are summarized as follows：
According to experiment 39~experiment 43, the size of hollow glass micropearl and the Nanowire of hydrophobically modified prepared by methods described
The concentration for tieing up element is closely related.As the nano-cellulose of hydrophobically modified concentration as little as 0.25mg/mL in oil phase, hollow glass
The diameter of microballon is about 61.9 microns, empty when concentration of the nano-cellulose of hydrophobically modified in oil phase increases to 4mg/mL
The diameter of heart glass microballoon is reduced to 7 microns.The optical microscope photograph of the hollow glass micropearl prepared according to methods described is such as
Shown in Fig. 5, concentration of the hydrophobically modified nano-cellulose in oil phase is followed successively by the ratio in 0.25,0.5,1,2 and 4mg/mL, Fig. 5
Example chi is 50 microns.The diameter of hollow glass micropearl is gradually reduced with the concentration increase of the nano-cellulose of hydrophobically modified,
The diameter of hollow glass micropearl is as shown in Figure 6 with the change of the nano-cellulose concentration of hydrophobically modified.
Obtained hollow glass micropearl is white, can be dispersed in water, dimethylformamide, tetrahydrofuran, toluene and
In the different solvents such as chloroform, and after ultrasound 10 minutes, hollow glass micropearl has remained in that good integrality, therefore makes
Standby hollow glass micropearl has good mechanical performance.
The hollow glass micropearl carries out morphology analysis with SEM, as shown in Figure 7.Hollow glass micropearl exhibition
Spherical structure is showed, by showing that the wall thickness of hollow glass micropearl probably exists to the debris analysis of a hollow glass micropearl
1.2 microns.
Claims (10)
1. a kind of preparation method of hollow glass micropearl, it is characterised in that this method is using nano-cellulose as pickering emulsion
Emulsifying agent, in the oil phase of emulsion dissolving add the presoma of silica, using this pickering emulsion as template, pass through two
In emulsion interface solgel reaction occurs for the presoma of silica under acid or alkaline conditions, micro- so as to prepare hollow glass
Pearl.
2. the preparation method of a kind of hollow glass micropearl according to claim 1, it is characterised in that with hydrophilic Nanowire
For the oil-in-water pickering emulsion of dimension element emulsification as template, embodiment and the step for preparing hollow glass micropearl are as follows：
1) hydrophilic nano-cellulose is dispersed in as the aqueous phase A of pickering emulsion in acid or alkalescence water, wherein described
Acid or alkalescence pH value is less than 5 or more than 9；
2) presoma of silica is dissolved in oil phase B of the oil phase solvent as pickering emulsion；
3) above-mentioned aqueous phase A and oil phase B is mixed, pickering emulsion is prepared by ultrasound or homogenizer, after standing a couple of days i.e.
It can obtain hollow glass microballoon.
3. the preparation method of a kind of hollow glass micropearl according to claim 1, it is characterised in that with hydrophobic Nanowire
For the pickering emulsion of the Water-In-Oil of dimension element emulsification as template, embodiment and the step for preparing hollow glass micropearl are as follows：
1) hydrophobic nano-cellulose is dispersed in oil phase solvent, the presoma for adding silica is dissolved in oil phase solvent
In, the oil phase A as pickering emulsion；
2) using pH value be more than 9 or the water less than 5 as pickering emulsion aqueous phase B；
3) above-mentioned oil phase A and aqueous phase B are mixed, pickering emulsion is prepared by ultrasound or homogenizer, after standing a couple of days i.e.
It can obtain hollow glass microballoon.
A kind of 4. preparation method of hollow glass micropearl according to claim 1, it is characterised in that the nano-cellulose
For the cellulose of nanometer and micron order size, its a diameter of 1 to 100 nanometers, its length is 5 nanometers to 100 microns, described to receive
Concentration of the rice cellulose in aqueous phase is 0.25-10mg/mL.
A kind of 5. preparation method of hollow glass micropearl according to claim 1, it is characterised in that the pickering emulsion
In aqueous phase pH be more than 9.
A kind of 6. preparation method of hollow glass micropearl according to claim 1, it is characterised in that the pickering emulsion
In aqueous phase pH be less than 5.
A kind of 7. preparation method of hollow glass micropearl according to claim 1, it is characterised in that the pickering emulsion
In oil phase solvent be atoleine, styrene, toluene, chloroform, dichloromethane, n-hexane, hexamethylene and edible oil in one
Kind.
A kind of 8. preparation method of hollow glass micropearl according to claim 1, it is characterised in that described silica
Presoma for be methyl silicate, tetraethyl orthosilicate, gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane,
VTES, vinyltrimethoxy silane, diethylenetriamine base propyl trimethoxy silicane, γ-shrink are sweet
Oily ether oxygen propyl trimethoxy silicane, sodium metasilicate, γ-methacryloxypropyl trimethoxy silane or γ-metering system
One kind of acryloxypropylethoxysilane triethoxysilane.
A kind of 9. preparation method of hollow glass micropearl according to claim 1, it is characterised in that described silica
Presoma is methyl silicate.
A kind of 10. preparation method of hollow glass micropearl according to claim 1, it is characterised in that the hollow glass of preparation
Glass bead diameter is 5~100 microns, and can be dispersed in water, dimethylformamide, tetrahydrofuran, toluene and chloroform.
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| CN107868161A (en) * | 2017-12-07 | 2018-04-03 | 张振 | A kind of preparation method of polymeric hollow microcapsules and its application |
| 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 |
| CN109925985A (en) * | 2019-03-15 | 2019-06-25 | 湖州闪思新材料科技有限公司 | A kind of methods and applications of phase-change material micro-capsule cladding |
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| CN111205515A (en) * | 2020-03-13 | 2020-05-29 | 中国科学技术大学 | Light composite rubber and preparation method thereof |
| CN112375536A (en) * | 2020-11-25 | 2021-02-19 | 郑州中原思蓝德高科股份有限公司 | Waterproof elastic sealing material |
| CN112375536B (en) * | 2020-11-25 | 2021-08-20 | 郑州中原思蓝德高科股份有限公司 | Waterproof elastic sealing material |
| CN114181411A (en) * | 2021-12-10 | 2022-03-15 | 成都德斐生物科技有限公司 | Hydrogel material with high cold/heat insulation effect |
| CN114181411B (en) * | 2021-12-10 | 2023-12-08 | 马素德 | Hydrogel material with high cold/heat insulation effect |
| CN114230238A (en) * | 2021-12-13 | 2022-03-25 | 东莞市科惠工业材料有限公司 | Elastic rock plate paving adhesive and preparation method thereof |
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