CN111363188B - Preparation method of ultralight cellulose nanocrystal aerogel material - Google Patents
Preparation method of ultralight cellulose nanocrystal aerogel material Download PDFInfo
- Publication number
- CN111363188B CN111363188B CN201911301022.0A CN201911301022A CN111363188B CN 111363188 B CN111363188 B CN 111363188B CN 201911301022 A CN201911301022 A CN 201911301022A CN 111363188 B CN111363188 B CN 111363188B
- Authority
- CN
- China
- Prior art keywords
- water
- phase
- aerogel
- cellulose nanocrystal
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/048—Elimination of a frozen liquid phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Colloid Chemistry (AREA)
Abstract
The invention discloses a preparation method of an ultralight cellulose nanocrystal aerogel material. Taking water dispersion of cellulose nanocrystals as a water phase; taking a water-insoluble organic solvent as an oil phase; pouring the oil phase into the water phase at one time, and emulsifying to obtain a high internal phase emulsion; freeze-drying the emulsion to obtain the porous aerogel material with adjustable pore structure and extremely low density which can be as low as 0.5 mg/cm 3 . The method is simple, convenient and easy to implement, green and environment-friendly, and the ultralow-density cellulose nanocrystal aerogel can be obtained.
Description
Technical Field
The invention belongs to the technical field of aerogel material preparation, and particularly relates to a preparation method of cellulose nanocrystal aerogel based on an amino modified stable pickering emulsion technology.
Background
Aerogel is a three-dimensional nanoporous material with ultra-high porosity. Since the gel removes most of the solvent, the liquid content is less than the solid content, or the space network of the gel is filled with a gas, and thus has a very low density. Common aerogels are prepared from tin oxide, silicon dioxide, chromium oxide and carbon. The aerogel has excellent performance, such as high porosity (99 percent) and low density (4 to 500 mg/cm) 3 ) And a high surface area (100 to 1000 m) 2 In terms of/g). The unique properties of aerogels, especially their ultra-light weight, have led to their wide use in applications such as catalysts, electronics, particle filters, and thermal and acoustic insulation.
Aerogel prepared from inorganic nanoparticles, carbon nanotubes, graphene and other particles has excellent performance, but is a non-degradable material, and causes pollution to the environment after long-term use. Cellulose is produced in abundant and renewable quantities on earth making it a major chemical resource in the future. With the increasing demand for environmental protection, many aerogel-based products are being derived. Tan et al found that after the cellulose gel skeleton was crosslinked with a crosslinking agent, the aerogel was more easily formed, and the mechanical properties were significantly improved. The cellulose aerogel can be physically and chemically modified to prepare materials with different functions and shapes, for example, a block can be used as a heat insulation material, a membrane material can be applied to the aspects of adsorption, drug slow release and the like, and other functionalized molecules can be embedded in a circular spheroid material to prepare a gel material with functions of magnetism and the like. In addition, the aerogel has other excellent performances, such as the thermal conductivity coefficient of the aerogel is close to that of air at room temperature, the aerogel has a strong adsorption function, and liquid pollutants which are more than 200 times of the weight of the aerogel can be adsorbed in a very short time, so that the aerogel has potential application value in the aspect of solving the problem of offshore oil leakage.
The traditional aerogel preparation method is mainly characterized in that water in the hydrogel is replaced by ethanol and dried to obtain the aerogel. Lindy Heat and Wim Thielemans by using larger initial concentrations of CNCs (C:)>8 wt%) and high power sonication to produce an initial hydrogel structure, followed by a critical drying process to produce the aerogel. The aerogels they produce have very low densities (78 mg/cm) 3 ). Dash et al prepared CNC aerogels by directional freeze casting CNC suspensions. The pore size of aerogels produced by this method depends on the size of the ice crystals formed during freezing (pore size)>5 μm). Here we intend to combine high internal phase emulsions to make hydrogels, which are directly freeze dried to give aerogels. At the same time, the high internal phase emulsion has an extremely high internal phase, so that the aerogel with extremely low density is obtained after freeze drying.
High Internal Phase Emulsions (HIPE), also known as super concentrated emulsions, refer to emulsions having an internal phase volume fraction of greater than 74.05%. A wide variety of surfactants are used to stabilize HIPEs, such as Tween85, span80, and block copolymer surfactants. The use of surfactants to stabilize high internal phase emulsions generally requires the addition of 30% of the external phase, and the residual surfactant in the porous material after polymerization can affect the properties of the porous material, thereby greatly reducing the mechanical properties of the material, and simultaneously, the use of a large amount of surfactant can cause environmental pollution.
The Pickering emulsion is an emulsion without a surfactant, is stabilized by solid amphiphilic particles, and the particles preferentially migrate to an oil-water interface and self-assemble at the oil-water interface, thereby hindering droplet coalescence. Compared with the traditional high internal phase emulsion, the Pickering emulsion has the following advantages: firstly, in the Pickering emulsion, solid particles irreversibly adsorb on an emulsion interface due to higher adsorption energy, so that the obtained emulsion is extremely stable and can stably exist for several months or even several years; meanwhile, as the solid particles have higher adsorption energy, the high internal phase emulsion with extremely high internal phase can be stabilized only by few particles, and the toxicity of the final porous material is reduced, so that the porous material can be used as a biological material; finally, the solid particles can be subjected to functional modification, so that the surfaces of the solid particles have functional groups, and the finally prepared porous material can be subjected to functional application. The use of particles instead of surfactants in the production process is a very promising direction of research, especially in the synthesis of porous materials for support, membrane or bio-related applications.
The hydrogel prepared by stabilizing the high internal phase emulsion by adopting the amino modified cellulose nanocrystal has the characteristics of degradability and good environmental friendliness, and meanwhile, the aerogel prepared after freeze drying has extremely low density due to the extremely high internal phase of the high internal phase emulsion.
Chinese patent CN108579626A discloses a preparation method of a ternary composite enhanced aerogel, which is prepared by preparing a ternary composite solution from cellulose nanocrystals, graphene and polyvinyl alcohol, inducing by inorganic salt, replacing by an alcoholic solution, and freeze-drying. The method comprises the following steps: grinding graphene according to a certain proportionUniformly mixing with cellulose nanocrystals, adding a certain amount of polyvinyl alcohol into deionized water, stirring and dissolving to obtain a polyvinyl alcohol aqueous solution, ultrasonically mixing a certain amount of polyvinyl alcohol aqueous solution with graphene and cellulose nanocrystals uniformly, sucking the prepared suspension by using a glass syringe, and dripping CaCl 2 And standing the solution for 24 hours to obtain hydrogel pellets, placing the formed hydrogel pellets in an alcohol solution for replacement, and then freezing and drying to obtain the aerogel.
Chinese patent CN107556495B discloses a preparation method of a functional nanocellulose composite aerogel combining physical crosslinking and chemical enhancement, firstly, in an aqueous solution, the nanocellulose and a cationic polymer are gelled through electrostatic interaction to form hydrogel, functional additives are loaded in the gelling process, the obtained hydrogel adsorbs a crosslinking agent for chemical crosslinking, and the nanocellulose composite aerogel is obtained after drying. The method comprises the following steps: placing a certain amount of nano cellulose solution and polyethyleneimine aqueous solution in a mold, uniformly stirring, placing at room temperature for 48 hours to obtain hydrogel, soaking the hydrogel in glyoxal aqueous solution to react for 2 hours in an acidic environment, placing in deionized water to soak and wash cleanly to remove unreacted reagents after the reaction is finished, and freeze-drying to obtain the aerogel.
Chinese patent CN106117592B discloses a method for preparing a nanocellulose/polymer composite aerogel, which comprises the steps of firstly gelling a Pickering emulsion containing a polymer in a nanocellulose-stabilized oil phase, and then carrying out freeze drying to obtain the nanocellulose/polymer composite aerogel. The method comprises the following steps: mixing the nano-cellulose aqueous dispersion with the polymer solution, performing ultrasonic treatment to obtain a Pickering emulsion gel with stable gelation nano-cellulose, and performing freeze drying to obtain the aerogel.
All three patents are related to the preparation of aerogel by cellulose nanocrystals, and all three patents utilize polymer additives or other reinforcing materials to stabilize the system, and the technology of preparing aerogel by stabilizing Pickering emulsion by amino-modified cellulose nanocrystals has not been reported. The invention has another innovation point that the method is simple, convenient and easy to implement, green and environment-friendly, and the obtained material is ultra-light.
Disclosure of Invention
The invention relates to a method for preparing aerogel by stabilizing Pickering emulsion by using amino modified cellulose nano-crystals.
The purpose of the invention can be realized by the following technical scheme:
the invention firstly provides a method for modifying cellulose nanocrystals by amino, which comprises the following steps:
performing epoxy modification on the cellulose nanocrystal by using epoxy chloropropane;
and carrying out amination modification on the epoxy-modified cellulose nanocrystal by using ammonia water.
Furthermore, the dosage of the epichlorohydrin is 0.20 to 0.30mol/g relative to the cellulose nanocrystal.
Furthermore, the dosage of the ammonia water is 3 to 10ml/g relative to the cellulose nanocrystal.
Further, in the process of modifying the cellulose nanocrystals with the amino group, the pH value of the reaction environment ranges from 9 to 12.
Further, the substance used for creating the alkaline environment in the amino modified cellulose nanocrystal process is selected from one or more of the following substances: sodium hydroxide, ammonia, sodium carbonate, triethylamine, calcium hydroxide or potassium hydroxide.
Further, protective gas is required to be used for atmosphere protection in the amination modification process of the epoxy-modified cellulose nanocrystal by using ammonia water, and the protective gas is nitrogen.
The invention also provides a method for stabilizing Pickering emulsion by using the amino modified cellulose nanocrystals, which comprises the following steps:
dispersing amino modified cellulose nano crystals in water as a water phase;
taking a water-insoluble organic solvent as an oil phase;
adding an organic solvent into the water phase at one time, and fully emulsifying by a certain stirring mode to prepare the high internal phase emulsion.
Further, the water-insoluble organic solvent is selected from one or more of the following substances: cyclohexane, paraffin oil, hexadecane, tetradecane, benzene, toluene or styrene.
Further, the mass fraction of the amino modified cellulose nanocrystals in the water phase is 0.1% -2.0%.
Further, the water phase and the oil phase are mixed at a volume ratio of 1 to 1.
Further, the emulsion mixing mode is as follows: magnetic stirrers, high-speed shear emulsification, high-speed oscillators or sonicators.
Further, the temperature of the oil phase and the water phase in the emulsification process is controlled to be 20-40 ℃.
Further, the high internal phase emulsion is placed at 10 to 30 ℃ for 5 to 10 hours to form hydrogel, and then the hydrogel is freeze-dried for 2 to 3 days to obtain the aerogel.
The invention relates to a method for preparing aerogel with biocompatibility and biodegradability by using amino modified cellulose nanocrystals.
The size of dispersed phase droplets of the high internal phase emulsion is observed by an inverted microscope, the morphology of the bulk aerogel porous material is observed by a scanning electron microscope (SEM, S-3400N, JEOL company, japan), the surface morphology of the bulk material is shot by a digital camera, the mass and the volume of the bulk aerogel open-cell material are respectively measured by a balance and a vernier caliper, and the density of the porous material is calculated.
The emulsion obtained by the method has controllable properties such as the size of dispersed phase droplets, the pore diameter of the porous material, the density of the porous material and the like.
The invention is environment-friendly and simple and convenient to operate, the high internal phase emulsion is prepared after emulsification, and the biodegradable aerogel with extremely low density and extremely high aperture ratio and complete appearance can be obtained by directly freeze-drying.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
Dissolving 1g of cellulose nanocrystal in 40ml of water, adding 100ml of 1M sodium hydroxide solution and 24ml of epichlorohydrin, carrying out water bath reaction for 1h at 60 ℃, centrifuging, taking out the lower-layer precipitate, dissolving the lower-layer precipitate in 100ml of water, adjusting the pH value to 12, adding 60ml of ammonia water, reacting for 3h under the protection of protective gas at 60 ℃, and washing with water for three times to obtain the amino modified cellulose nanocrystal.
4g of water is used as a solvent, 0.02g of amino modified cellulose nanocrystals are used as a solute, and the cellulose nanocrystals are uniformly dispersed in the aqueous solution by ultrasonic treatment for 5min at the room temperature of 25 ℃. To the aqueous solution was added 9.5g of cyclohexane. Shearing and emulsifying for 3min to obtain uniform oil-in-water high internal phase emulsion. And (3) placing the prepared high internal phase emulsion in liquid nitrogen for freezing for 2 to 3min, taking out, placing in a freeze drier for freeze drying for 24h, and taking out to obtain the amino modified cellulose nanocrystal aerogel with extremely low density, extremely high porosity, biocompatibility and biodegradability.
The dispersed phase droplet size of the high internal phase emulsion was observed by an inverted microscope and the emulsion obtained in this example had a droplet mean diameter of 48 microns.
The morphology of the porous material was observed by scanning electron microscopy (SEM, S-3400N, JEOL), and the pore diameter of the porous material obtained in this example was 60 μm.
The mass and volume of the obtained porous material were measured by a balance and a vernier caliper, respectively, and the density of the porous material obtained in this example was 1.5 mg/cm 3 。
Example 2
Dissolving 1g of cellulose nanocrystal in 40ml of water, adding 100ml of 1M sodium hydroxide solution and 24ml of epichlorohydrin, reacting for 1 hour at 60 ℃ in a water bath, centrifuging, taking out the lower precipitate, dissolving in 100ml of water, adjusting the pH value to 12, adding 60ml of ammonia water, reacting for 3 hours under the protection of 60 ℃ protective gas, and washing with water for three times to obtain the amino modified cellulose nanocrystal.
4g of water is used as a solvent, 0.04g of amino modified cellulose nanocrystals are used as a solute, and the cellulose nanocrystals are uniformly dispersed in an aqueous solution by ultrasonic treatment for 15min at room temperature and 25 ℃. To the aqueous solution was added 9.5g of cyclohexane. Shearing and emulsifying for 3min to obtain uniform oil-in-water high internal phase emulsion. And (3) placing the prepared high internal phase emulsion in liquid nitrogen for freezing for 2 to 3min, taking out, placing in a freeze drier for freeze drying for 24h, and taking out to obtain the amino modified cellulose nanocrystal aerogel with extremely low density, extremely high porosity, biocompatibility and biodegradability.
The dispersed phase droplets of the high internal phase emulsion were observed by inverted microscopy to have an average diameter of 33 microns.
The morphology of the porous material was observed by scanning electron microscopy (SEM, S-3400N, JEOL), and the pore size of the porous material was 37 μm.
The mass and volume of the obtained porous material were measured by a balance and a vernier caliper, respectively, and the density of the porous material obtained in this example was 2.8 mg/cm 3 。
Example 3
Dissolving 1g of cellulose nanocrystal in 40ml of water, adding 100ml of 1M sodium hydroxide solution and 24ml of epichlorohydrin, carrying out water bath reaction for 1h at 60 ℃, centrifuging, taking out the lower-layer precipitate, dissolving the lower-layer precipitate in 100ml of water, adjusting the pH value to 12, adding 60ml of ammonia water, reacting for 3h under the protection of protective gas at 60 ℃, and washing with water for three times to obtain the amino modified cellulose nanocrystal.
4g of water is used as a solvent, 0.06g of amino modified cellulose nanocrystals are used as a solute, and the cellulose nanocrystals are uniformly dispersed in the aqueous solution by ultrasonic treatment for 15min at the room temperature of 25 ℃. To the aqueous solution was added 9.5g of cyclohexane. Shearing and emulsifying for 3min to obtain uniform oil-in-water high internal phase emulsion. And (3) placing the prepared high internal phase emulsion in liquid nitrogen for freezing for 2 to 3min, taking out, placing in a freeze drier for freeze drying for 24h, and taking out to obtain the amino modified cellulose nanocrystal aerogel with extremely low density, extremely high porosity, biocompatibility and biodegradability.
The high internal phase emulsion obtained in this example had a droplet mean diameter of 26 microns as observed by inverted microscopy for the dispersed phase droplet size of the high internal phase emulsion.
The morphology of the porous material was observed by scanning electron microscopy (SEM, S-3400N, JEOL), and the pore diameter of the porous material obtained in this example was 36 μm.
Respectively measuring with balance and vernier caliperThe mass and volume of the porous material were calculated, and the density of the porous material obtained in this example was 4.2 mg/cm 3 。
Example 4
Dissolving 1g of cellulose nanocrystal in 40ml of water, adding 100ml of 1M sodium hydroxide solution and 24ml of epichlorohydrin, reacting for 1 hour at 60 ℃ in a water bath, centrifuging, taking out the lower precipitate, dissolving in 100ml of water, adjusting the pH value to 12, adding 60ml of ammonia water, reacting for 3 hours under the protection of 60 ℃ protective gas, and washing with water for three times to obtain the amino modified cellulose nanocrystal.
4g of water is used as a solvent, 0.04g of amino modified cellulose nanocrystals are used as a solute, and the cellulose nanocrystals are uniformly dispersed in the aqueous solution by ultrasonic treatment for 15min at the room temperature of 25 ℃. 12.5g of cyclohexane were added to the aqueous solution. Shearing and emulsifying for 3min to obtain uniform oil-in-water high internal phase emulsion. And (3) freezing the prepared high internal phase emulsion in liquid nitrogen for 2-3 min, taking out, freezing and drying in a freeze dryer for 24h, and taking out to obtain the amino modified cellulose nanocrystal aerogel with extremely low density, extremely high porosity, biocompatibility and biodegradability.
The dispersed phase droplet size of the high internal phase emulsion was observed by an inverted microscope and the average diameter of the high internal phase emulsion droplets obtained in this example was 38 microns.
The morphology of the porous material was observed by scanning electron microscopy (SEM, S-3400N, JEOL), and the pore diameter of the porous material obtained in this example was 42 μm.
The mass and volume of the obtained porous material were measured by a balance and a vernier caliper, respectively, and the density of the porous material obtained in this example was 2.3 mg/cm 3 。
The embodiments described above are intended to facilitate a person of ordinary skill in the art in understanding and using the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (2)
1. The preparation method of the ultralight cellulose nanocrystal aerogel material is characterized by comprising the following steps:
epoxy modification is carried out on the cellulose nanocrystal by using epoxy chloropropane, the pH value range of the epoxy modification reaction carried out on the cellulose nanocrystal by using the epoxy chloropropane is 9-12, and substances used for creating an alkaline environment are selected from one or more of the following substances: sodium hydroxide, sodium carbonate, triethylamine, calcium hydroxide or potassium hydroxide;
carrying out amination modification on the epoxy-modified cellulose nanocrystal by using ammonia water;
dispersing amino modified cellulose nanocrystals in water as an aqueous phase;
taking a water-insoluble organic solvent as an oil phase, wherein the water-insoluble organic solvent is cyclohexane;
adding an organic solvent into the water phase at one time, fully emulsifying by a certain stirring mode to prepare a high internal phase emulsion, wherein the emulsion mixing mode is high-speed shearing emulsification, the temperature in the emulsification process of the oil phase and the water phase is controlled to be 20-40 ℃, and freeze-drying the obtained high internal phase emulsion to obtain the cellulose nanocrystalline aerogel with regular and adjustable pore structure;
the mass fraction of the amino modified cellulose nanocrystal in a water phase is 0.1-2.0%, and the water phase and an oil phase are mixed according to the volume ratio of 1.
2. The process according to claim 1, characterized in that epichlorohydrin is used in an amount of 0.20 to 0.30mol/g relative to the amount of cellulose nanocrystals and aqueous ammonia is used in an amount of 3 to 10ml/g relative to the amount of cellulose nanocrystals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911301022.0A CN111363188B (en) | 2019-12-17 | 2019-12-17 | Preparation method of ultralight cellulose nanocrystal aerogel material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911301022.0A CN111363188B (en) | 2019-12-17 | 2019-12-17 | Preparation method of ultralight cellulose nanocrystal aerogel material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111363188A CN111363188A (en) | 2020-07-03 |
| CN111363188B true CN111363188B (en) | 2022-11-11 |
Family
ID=71202064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911301022.0A Active CN111363188B (en) | 2019-12-17 | 2019-12-17 | Preparation method of ultralight cellulose nanocrystal aerogel material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111363188B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112552553B (en) * | 2020-12-09 | 2022-06-17 | 桂林理工大学 | Composite foam porous material and preparation method and application thereof |
| CN113120879B (en) * | 2021-04-25 | 2023-03-28 | 桂林理工大学 | Carbon aerogel material and preparation method and application thereof |
| CN113415800B (en) * | 2021-06-23 | 2022-12-27 | 桂林理工大学 | Carbon foam material and preparation method and application thereof |
| CN113501973B (en) * | 2021-07-12 | 2022-08-23 | 江南大学 | Pickering emulsion stabilized by nano-cellulose hydrogel |
| CN113683790B (en) * | 2021-08-24 | 2023-12-22 | 塔里木大学 | Porous hydrogel and preparation method and application thereof |
| CN114214035A (en) * | 2021-11-29 | 2022-03-22 | 苏州大学 | Photoelectric-driven cellulose-based flexible phase change material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558212A (en) * | 2015-01-29 | 2015-04-29 | 海南光宇生物科技有限公司 | Preparation method of aminated bio-cellulose |
| CN106117592A (en) * | 2016-07-21 | 2016-11-16 | 桂林理工大学 | A kind of preparation method of nanofiber cellulose/polymer composite aerogel |
| CN108295265A (en) * | 2018-02-01 | 2018-07-20 | 华东师范大学 | Cellulose nanocrystal is the acidic environment sensitivity nano prodrug system and preparation method of carrier |
| CN108530649A (en) * | 2018-03-05 | 2018-09-14 | 浙江工业大学 | A kind of preparation method for the High Internal Phase Emulsion that Cellulose nanocrystal is stablized |
-
2019
- 2019-12-17 CN CN201911301022.0A patent/CN111363188B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558212A (en) * | 2015-01-29 | 2015-04-29 | 海南光宇生物科技有限公司 | Preparation method of aminated bio-cellulose |
| CN106117592A (en) * | 2016-07-21 | 2016-11-16 | 桂林理工大学 | A kind of preparation method of nanofiber cellulose/polymer composite aerogel |
| CN108295265A (en) * | 2018-02-01 | 2018-07-20 | 华东师范大学 | Cellulose nanocrystal is the acidic environment sensitivity nano prodrug system and preparation method of carrier |
| CN108530649A (en) * | 2018-03-05 | 2018-09-14 | 浙江工业大学 | A kind of preparation method for the High Internal Phase Emulsion that Cellulose nanocrystal is stablized |
Non-Patent Citations (1)
| Title |
|---|
| Thermal Superinsulating Materials Made from Nanofibrillated Cellulose-Stabilized Pickering Emulsions;Clara Jiménez-Saelices et al.;《ACS Appl. Mater. Interfaces》;20180423;第10卷;第16193-16202页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111363188A (en) | 2020-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111363188B (en) | Preparation method of ultralight cellulose nanocrystal aerogel material | |
| Maleki et al. | Compressible, thermally insulating, and fire retardant aerogels through self-assembling silk fibroin biopolymers inside a silica structure—an approach towards 3D printing of aerogels | |
| Li et al. | Facile fabrication of mechanically-strong and flame retardant alginate/clay aerogels | |
| Qiao et al. | Ultralight aerogels with hierarchical porous structures prepared from cellulose nanocrystal stabilized Pickering high internal phase emulsions | |
| JP6760841B2 (en) | Method for producing porous cellulose medium | |
| Shen et al. | Nanocellulose-based composite phase change materials for thermal energy storage: status and challenges | |
| CN110606992A (en) | Preparation method and application of porous foam material based on biomass nano material | |
| Blaker et al. | Ice-microsphere templating to produce highly porous nanocomposite PLA matrix scaffolds with pores selectively lined by bacterial cellulose nano-whiskers | |
| Zhang et al. | Novel and wet-resilient cellulose nanofiber cryogels with tunable porosity and improved mechanical strength for methyl orange dyes removal | |
| Salimian et al. | Water-glass based silica aerogel: unique nanostructured filler for epoxy nanocomposites | |
| Liu et al. | Recent advances in the direct fabrication of millimeter-sized hierarchical porous materials | |
| Huo et al. | Ceramic particle-stabilized foams/emulsions with UV light response and further synthesis of ceramic capsules | |
| Yao et al. | Preparation of cellulose-based chromatographic medium for biological separation: A review | |
| Madhavan et al. | Porous ceramics via processable Pickering emulsion stabilized by oppositely charged colloids | |
| Beaumont et al. | Cellulose nanofibrils: From hydrogels to aerogels | |
| KR20180104472A (en) | Hierarchically Microporous and Mesoporous Carbon Spheres and Method of Preparing the Same | |
| Tu et al. | Pore structure of macroporous polymers using polystyrene/silica composite particles as pickering stabilizers | |
| Wang et al. | Templated synthesis and assembly with sustainable cellulose nanomaterial for functional nanostructure | |
| Tian et al. | An antimicrobial bio-based polymer foam from ZnO-stabilised pickering emulsion templated polymerisation | |
| Xie et al. | Pickering emulsions stabilized by mesoporous nanoparticles with different morphologies in combination with DTAB | |
| Budtova | Bio‐based Aerogels: A New Generation of Thermal Superinsulating Materials | |
| Fitzpatrick et al. | Protein-based aerogels: processing and morphology | |
| ES2342871B1 (en) | RIGID FOAMS OF COMPOSITE TYPE BASED ON BIOPOLYMERS COMBINED WITH FIBER CLAYS AND THEIR PREPARATION METHOD. | |
| US11083820B2 (en) | Elastic macro porous scaffold and a process for the preparation thereof | |
| CN111875939B (en) | Method for preparing porous material by regulating and controlling HAp stable emulsion characteristics with inorganic electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |