CN111363188A - Preparation method of ultralight cellulose nanocrystal aerogel material - Google Patents
Preparation method of ultralight cellulose nanocrystal aerogel material Download PDFInfo
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- 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
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- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- 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
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- 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
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- 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
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- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
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/cm3. 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 most of the solvent is removed from the gel, the liquid content is less than the solid content, or the space network of the gel is filled with a gas, and thus the density is very low. Common aerogels are prepared from tin oxide, silicon dioxide, chromium oxide and carbon. The aerogels have excellent properties, such as high porosity (99%) and low density (4-500 mg/cm)3) And a high surface area (100 to 1000 m)2In 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, particulate 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 many 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 with the weight more than 200 times of the self weight can be adsorbed in a very short time, so that the aerogel has potential application value in the aspect of solving the offshore oil leakage problem.
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 a larger initial concentration 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 made 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 number 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 surfactants remaining in the porous material after polymerization can affect the properties of the porous material, causing a substantial reduction in the mechanical properties of the material, while the use of large amounts of surfactants 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 are irreversibly adsorbed on an emulsion interface due to high adsorption energy, so that the obtained emulsion is extremely stable and can exist stably for months or even 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 method for preparing ternary composite enhanced aerogel by preparing ternary composite solution from cellulose nanocrystals, graphene and polyvinyl alcohol, inducing by inorganic salt, replacing by alcoholic solution, and freeze-drying. The method comprises the following steps: grinding graphene, uniformly mixing the ground graphene with cellulose nanocrystals according to a certain proportion, adding a certain amount of polyvinyl alcohol into deionized water, stirring and dissolving to prepare a polyvinyl alcohol aqueous solution, uniformly mixing the polyvinyl alcohol aqueous solution, the graphene and the cellulose nanocrystals in an ultrasonic manner, sucking the prepared suspension by using a glass syringe, and dripping CaCl2And standing the solution for 24 hours to obtain hydrogel spheres, and placing the formed hydrogel spheres in an alcohol solution for replacement, and then freezing and drying the hydrogel spheres 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, a hydrogel is formed through gelation through electrostatic interaction between nanocellulose and a cationic polymer, a functional additive is loaded in the gelation 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 nano-cellulose/polymer composite aerogel, which comprises the steps of firstly gelling a Pickering emulsion containing a polymer in a nano-cellulose stable oil phase, and then obtaining the nano-cellulose/polymer composite aerogel through freeze drying. 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 0.20-0.30 mol/g relative to the cellulose nanocrystal.
Furthermore, the dosage of the ammonia water is 3-10 ml/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 is in a range of 9-12.
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 nanocrystals 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 according to the volume ratio of 1: 30-1: 3 and then emulsified.
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 10-30 ℃ for 5-10 hours to form hydrogel, and then the hydrogel is freeze-dried for 2-3 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 a dispersion phase droplet 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 at 60 ℃ for 1h, centrifuging, taking out the lower-layer precipitate, dissolving the lower-layer precipitate in 100ml of water, adjusting the pH 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 ℃. 9.5g 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, freeze-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 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 size of the porous material obtained in this example was 60 μm.
Respectively measuring the quality of the obtained porous material by adopting a balance and a vernier caliperThe density of the porous material obtained in this example was 1.5 mg/cm, the volume and the density were calculated3。
Example 2
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 at 60 ℃ for 1h, centrifuging, taking out the lower-layer precipitate, dissolving the lower-layer precipitate in 100ml of water, adjusting the pH 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, 0.04g 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 ℃. 9.5g 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, freeze-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 droplets of the high internal phase emulsion were observed by inverted microscopy to have an average diameter of 33 microns.
And observing the morphology of the porous material by adopting a scanning electron microscope (SEM, S-3400N, JEOL), wherein the pore diameter of the obtained porous material is 37 microns.
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/cm3。
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 at 60 ℃ for 1h, centrifuging, taking out the lower-layer precipitate, dissolving the lower-layer precipitate in 100ml of water, adjusting the pH 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 ℃. 9.5g 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, freeze-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 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.
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 4.2 mg/cm3。
Example 4
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 at 60 ℃ for 1h, centrifuging, taking out the lower-layer precipitate, dissolving the lower-layer precipitate in 100ml of water, adjusting the pH 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, 0.04g 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, freeze-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/cm3。
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. 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 improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (6)
1. The preparation method of the ultralight cellulose nanocrystal aerogel material is characterized by comprising the following steps:
performing epoxy modification on the cellulose nanocrystal by using epoxy chloropropane;
carrying out amination modification on the epoxy-modified cellulose nanocrystal by using ammonia water;
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 a water phase at one time, fully emulsifying by a certain stirring mode to prepare a high internal phase emulsion, and freeze-drying the obtained high internal phase emulsion to obtain the cellulose nanocrystalline aerogel with regular and adjustable pore structure.
2. The method according to claim 1, wherein the amount of epichlorohydrin used is 0.20 to 0.30 mol/g relative to the amount of the cellulose nanocrystals, and the amount of ammonia water used is 3 to 10 ml/g relative to the amount of the cellulose nanocrystals.
3. The method according to claim 1, wherein the pH value of the epoxy modification reaction of the cellulose nanocrystals with epichlorohydrin is in the range of 9-12, and the substance for creating the alkaline environment is selected from one or more of the following substances: sodium hydroxide, sodium carbonate, triethylamine, calcium hydroxide or potassium hydroxide.
4. The process according to claim 1, wherein the water-insoluble organic solvent is selected from the group consisting of mixtures of one or more of the following: cyclohexane, paraffin oil, hexadecane, tetradecane, benzene, toluene or styrene.
5. The method according to claim 1, wherein the mass fraction of the amino modified cellulose nanocrystals in the water phase is 0.1% -2.0%, and the water phase and the oil phase are mixed in a volume ratio of 1: 30-1: 3 and then emulsified.
6. The method according to claim 1, wherein the emulsion is mixed in the following manner: the temperature of the oil phase and the water phase in the emulsification process is controlled to be 20-40 ℃.
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| CN113501973A (en) * | 2021-07-12 | 2021-10-15 | 江南大学 | Pickering emulsion stabilized by nano-cellulose hydrogel |
| CN113683790A (en) * | 2021-08-24 | 2021-11-23 | 塔里木大学 | Porous hydrogel and preparation method and application thereof |
| 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 |
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