CN113117613A - Functional supramolecular aerogel, preparation method and application thereof - Google Patents
Functional supramolecular aerogel, preparation method and application thereof Download PDFInfo
- Publication number
- CN113117613A CN113117613A CN202110415154.7A CN202110415154A CN113117613A CN 113117613 A CN113117613 A CN 113117613A CN 202110415154 A CN202110415154 A CN 202110415154A CN 113117613 A CN113117613 A CN 113117613A
- Authority
- CN
- China
- Prior art keywords
- raw material
- aerogel
- component hydrogel
- functional
- supramolecular
- 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.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Colloid Chemistry (AREA)
- Silicon Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a functional supramolecular aerogel, a preparation method and application thereof; the functional supermolecule aerogel is prepared by freezing and freeze-drying bi-component hydrogel, and the raw materials of the bi-component hydrogel comprise a raw material A and a raw material B. In addition, the invention also provides a method for preparing the aerogel, a method for applying the aerogel, a functional supramolecular aerogel for sound insulation and a functional supramolecular aerogel for organic solvent absorption. The invention creatively obtains the supermolecule aerogel with a three-dimensional supermolecule network structure by taking organic micromolecules as the raw material of the gelling agent, and the supermolecule aerogel has the same volume as the bi-component hydrogel and has the lower limit of the density regulation range of 4mg/cm3The elastic solid material has good reversibility and stimulus responsiveness, is easy to degrade, shows great advantages in the fields of sound insulation, organic solvent absorption and the like, and has the characteristics of simple preparation method, low cost, energy conservation, environmental protection and the like.
Description
Technical Field
The invention belongs to the technical field of aerogels, and particularly relates to a functional supramolecular aerogel, and a preparation method and application thereof.
Background
The aerogel is a composite system formed by replacing liquid with gas in the pores of a gel three-dimensional network framework, is known as a super-porous material in the 21 st century world-changing miraculous material, has a unique structure, has a plurality of excellent characteristics and has wide application prospects. The aerogel can be divided into inorganic oxide aerogel, organic aerogel, metal aerogel and the like according to the component composition, most of the current researches on the aerogel are focused on carbon aerogel, silicon aerogel and high polymer aerogel, the defects of high manufacturing cost, complex method, poor product function diversity and the like are usually caused, the preparation method of the aerogel which is easier to realize and has higher functionalization degree is provided, and the method is one of important ways for pushing the industrial application process of the aerogel.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a functional supramolecular aerogel, a preparation method and an application thereof, aiming at the defects of the prior art. The invention creatively obtains the supermolecule aerogel with a three-dimensional supermolecule network structure by taking organic micromolecules as the raw material of the gelling agent, and the supermolecule aerogel has the same volume as the bi-component hydrogel and has the lower limit of the density regulation range of 4mg/cm3The elastic solid material has good reversibility and stimulus responsiveness, is easy to degrade, shows great advantages in the fields of sound insulation, organic solvent absorption and the like, and has the characteristics of simple preparation method, low cost, energy conservation, environmental protection and the like.
In order to solve the technical problems, the invention adopts the technical scheme that: the functional supramolecular aerogel is characterized in that the functional supramolecular aerogel is obtained by freezing and freeze-drying a bi-component hydrogel;
the functional supramolecular aerogel volume phase and the bi-component hydrogel volume phaseMeanwhile, the lower limit of the density regulation range of the functional supramolecular aerogel is 4mg/cm3(ii) a The bi-component hydrogel is organic micromolecule bi-component hydrogel, the raw materials of the organic micromolecule bi-component hydrogel comprise a raw material A and a raw material B, the raw material A is melamine, and the raw material B is isonicotinic acid or quinoline-4-formic acid.
In addition, the invention also provides a method for preparing the functional supramolecular aerogel, which is characterized by comprising the following steps: preparing a raw material A, a raw material B and water into a bi-component hydrogel, freezing the bi-component hydrogel, and freeze-drying the frozen bi-component hydrogel to obtain the functional supramolecular aerogel; the sum of the mass of the raw material A and the raw material B is 4-50 times of the volume of the water, the mass unit of the raw material A and the raw material B is mg, and the unit of the volume of the water is mL.
The above production method is characterized in that the ratio of the amount of the material of the raw material A to the amount of the material of the raw material B is (5-1): (1-5).
The preparation method is characterized in that the raw material A is melamine, the raw material B is isonicotinic acid, and the ratio of the amount of the raw material A to the amount of the raw material B is (3-1): (1-3).
The above-mentioned production method is characterized by a method for preparing a two-component hydrogel from a raw material A, a raw material B and water, comprising:
placing a raw material A, a raw material B and water in a glass closed container, and keeping the temperature of 85-95 ℃ for 5-10 min to obtain a double-component-containing aqueous solution;
and step two, standing the aqueous solution containing the double components obtained in the step one at room temperature until the glass closed container is turned over, wherein no liquid phase flows in the glass closed container, so that the double-component hydrogel is obtained.
The preparation method is characterized in that the method for freezing the bi-component hydrogel and freeze-drying the frozen bi-component hydrogel to obtain the functional supramolecular aerogel comprises the following steps:
step one, freezing the bi-component hydrogel for 0.1 to 12 hours at the temperature of-196 to-5 ℃ to obtain the frozen bi-component hydrogel;
and step two, freeze-drying the frozen bi-component hydrogel in the step one for 40-50 h under the conditions that the temperature is-60-50 ℃ and the vacuum degree is 1.5-10 Pa to obtain the functional supramolecular aerogel.
Furthermore, the invention also provides a functional supramolecular aerogel for sound insulation, which is characterized by comprising the functional supramolecular aerogel.
Furthermore, the invention also provides a functional supramolecular aerogel for absorbing organic solvents, which is characterized by comprising the functional supramolecular aerogel.
Furthermore, the invention also provides a method for applying the functional supramolecular aerogel.
The application method is characterized by comprising a method for performing sound insulation or adsorbing an organic solvent by using the functional supramolecular aerogel, wherein the organic solvent comprises one or more of cyclohexane, toluene, benzene, dichloromethane, tetrahydrofuran, ethyl acetate, dioxane, acetone and acetonitrile.
Compared with the prior art, the invention has the following advantages:
1. the invention creatively obtains the supermolecule aerogel with a three-dimensional supermolecule network structure by taking organic micromolecules as the raw material of the gelling agent, and the supermolecule aerogel has the same volume as the bi-component hydrogel and has the lower limit of the density regulation range of 4mg/cm3The elastic solid material has good reversibility and stimulus responsiveness, is easy to degrade, shows great advantages in the fields of sound insulation, organic solvent absorption and the like, and has the characteristics of simple preparation method, low cost, energy conservation, environmental protection and the like.
2. According to the preparation method, the organic micromolecule raw material A and the raw material B are used as gelling agent raw materials, and the supermolecule aerogel with the three-dimensional supermolecule network structure is synthesized by self-assembly under the non-covalent interaction of H bonds, pi-pi stacking and the like in a water environment.
3. Preferably, the preparation method comprises the steps of freezing the bi-component hydrogel, and freeze-drying the frozen bi-component hydrogel, and compared with the traditional supercritical drying method, the preparation method provided by the invention has the advantages of milder and safer conditions and low cost.
4. The preparation method can realize the preparation of the ultra-low density aerogel, and the prepared aerogel can have the lowest density of 4mg/cm3Greatly broadens the density control range of the aerogel, and the density of the aerogel is only the air density (1.29 mg/cm) under the standard condition3) 3.1 times of the total mass of the product, and can greatly reduce the mass on the basis of meeting the volume requirement. In addition, the aerogel can rebound to the original height under the pressure action of 1.71kPa and 3.42kPa, has good longitudinal elastic performance and high repeatability of rebound after compression, and can keep the existing elastic modulus after multiple times of compression.
5. On the other hand, in a test of isolating noise by using the supramolecular aerogel, compared with air sound transmission, the maximum sound insulation amount of the supramolecular aerogel is 31.09dB, and the average sound insulation amount is 16.80dB, so that a good sound insulation effect is achieved.
6. On the other hand, the invention also provides the functional supramolecular aerogel for organic solvent absorption, which can be absorbed by various organic solvents, and the supramolecular aerogel keeps the original volume after absorbing the organic solvents and has no structural contraction and collapse phenomena.
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and embodiments.
Drawings
FIG. 1 is a schematic flow chart of the method of example 1-1.
FIG. 2 is a DSC of two-component hydrogel of examples 1-1 to 1-3.
FIG. 3 is a graph of rheological modulus of the two-component hydrogel of examples 1-1 to 1-3.
FIG. 4 is a two-component hydrogel temperature change material of examples 1-1 to 1-31H-NMR chart.
FIG. 5 is an ultraviolet spectrum of the two-component hydrogel of examples 1-1 to 1-3.
FIG. 6 is an SEM photograph of the two-component hydrogel of examples 1-1 to 1-3.
FIG. 7 is an SEM image of the two-component hydrogel of examples 1-4.
FIG. 8 is a schematic view showing a state after standing in step two of comparative example 1 to 1.
FIG. 9 is a diagram showing gel state of comparative examples 1-2 in different pH response ranges.
FIG. 10 is an SEM photograph of comparative examples 1-2 to 1-4.
FIG. 11 is an infrared spectrum of the functional supramolecular aerogel according to examples 2-1 to 2-3.
FIG. 12 is a graph showing the density of the functional supramolecular aerogel according to examples 2-1 to 2-3.
FIG. 13 is an SEM image of the functional supramolecular aerogels of examples 2-4 to 2-6.
FIG. 14 is a TEM image of the functional supramolecular aerogels of examples 2-4 to 2-6.
Figure 15 is the compression and modulus diagrams of the functional supramolecular aerogels of examples 2-4.
FIG. 16 is an organic solvent absorption diagram of the functional supramolecular aerogels in application examples 3-1 to 3-3.
FIG. 17 is a diagram of a mold for acoustic insulation test using the functional supramolecular aerogel of example 4-1 to 4-3.
FIG. 18 is a diagram illustrating the sound insulation effect of the functional supramolecular aerogel according to application examples 4-1 to 4-3.
Detailed Description
In the following examples, the reagent sources and parameters were as follows: melamine (national chemical group chemical agents limited, M-126.12 g/mol); 2,4, 6-triaminopyrimidine (alfa aesar, M ═ 125.14 g/mol); isonicotinic acid (beijing yinoka ltd, M123.11 g/mol); nicotinic acid (beijing yinoka ltd, M123.11 g/mol); quinoline-4-carboxylic acid (beijing enokay ltd, M-173.17 g/mol); piperidine-4-carboxylic acid (beijing enokay ltd, M-129.16 g/mol); benzoic acid (national chemical group, ltd, M122.12 g/mol); caffeic acid (alatin, M180.16 g/mol); orotic acid (alatin, M. 156.10 g/mol); Fmoc-L glutamic acid (gill chemical limited, M-369.37 g/mol); 3, 4-dihydroxybenzoic acid (hadamard reagent limited, M-154.12 g/mol); cyclohexane (Guangdong Guanghua science and technology, Inc.); benzene (national chemical group chemical agents limited); toluene (national chemical group, chemical Co., Ltd.); dichloromethane (Tianjin Fuyu Fine chemical Co., Ltd.); tetrahydrofuran (Guangdong Guanghua science and technology, Inc.); dioxane (Fuchen chemical Co., Ltd.); ethyl acetate (Tianjin Fuyu Fine chemical Co., Ltd.); acetone (national chemical group chemical Co., Ltd.).
The above drugs and solvents were all analytically pure and were not further purified.
Examples 1 to 1
This example provides a method for preparing a two-component hydrogel, the process flow of which is shown in FIG. 1, comprising the steps of:
placing a raw material A, a raw material B and water in a glass closed container, and sleeving a KDM type electric heating sleeve in the closed container at the temperature of 90 ℃ for 8min to obtain a clear aqueous solution containing two components; the clear two-component-containing aqueous solution is shown as a in fig. 1; the mass sum of the raw material A and the raw material B is 10mg, the mass ratio of the raw material A to the raw material B is 3:1, the raw material A is melamine, and the raw material B is isonicotinic acid; the volume of the water is 1 mL; the KDM type electric heating jacket is purchased from Beijing Gohi laboratory instruments science and technology Limited;
step two, standing the aqueous solution containing the double components in the step one at room temperature until no liquid phase flows in the glass closed container when the glass closed container is turned over, and obtaining the homogeneous double-component hydrogel MI A31; the room temperature is 20-25 ℃, and the standing time is 45 min; the phenomenon change in the closed vessel during standing at room temperature is shown in B and C in FIG. 1.
Examples 1 to 2
This example provides a method of preparing a two-component hydrogel comprising the steps of:
placing a raw material A, a raw material B and water in a glass closed container, and maintaining the closed container at 85 ℃ for 10min by using a KDM type electric heating sleeve to obtain a water solution containing two components; the mass sum of the raw material A and the raw material B is 10mg, the mass ratio of the raw material A to the raw material B is 1:1, the raw material A is melamine, and the raw material B is isonicotinic acid; the volume of the water is 1 mL;
step two, standing the aqueous solution containing the double components in the step one at room temperature until the glass closed container is turned over, and enabling no liquid phase to flow in the glass closed container to obtain homogeneous double-component hydrogel and MI A11; the room temperature is 20-25 ℃, and the standing time is 60 min.
Examples 1 to 3
This example provides a method of preparing a two-component hydrogel comprising the steps of:
placing a raw material A, a raw material B and water in a glass closed container, and sleeving a KDM type electric heating sleeve for the closed container at the temperature of 95 ℃ for 5min to obtain a clear aqueous solution containing two components; the mass sum of the raw material A and the raw material B is 10mg, the mass ratio of the raw material A to the raw material B is 1:3, the raw material A is melamine, and the raw material B is isonicotinic acid; the volume of the water is 1 mL;
step two, standing the aqueous solution containing the double components in the step one at room temperature until no liquid phase flows in the glass closed container when the glass closed container is turned over, and obtaining the homogeneous double-component hydrogel MI A13; the room temperature is 20-25 ℃, and the standing time is 30 min.
Examples 1 to 4
Examples 1-4 the process for the preparation of a two-component hydrogel corresponds to examples 1 to 3, respectively, with the difference that starting material A is melamine, starting material B is quinoline-4-carboxylic acid, and the mass ratio of starting material A to starting material B is 1: 1.
Examples 1 to 5
This example provides a process for preparing a two-component hydrogel, which is the same as in example 1, except that the sum of the masses of raw material a and raw material B is 50mg, and the mass ratio of the materials of raw material a and raw material B is 1: 5.
The properties of the two-component hydrogel prepared in this example are substantially the same as those of example 1.
Examples 1 to 6
This example provides a process for preparing a two-component hydrogel, which is the same as in example 1, except that the sum of the masses of raw material a and raw material B is 50mg, and the mass ratio of the materials of raw material a and raw material B is 5: 1.
The properties of the two-component hydrogel prepared in this example are substantially the same as those of example 1.
Comparative examples 1 to 1
The present comparative example provides a method of preparing a two-component hydrogel comprising the steps of:
placing a raw material A, a raw material B and water in a glass closed container, and sleeving a KDM type electric heating sleeve in the closed container at the temperature of 90 ℃ for 8min to obtain a clear aqueous solution containing two components; the mass sum of the raw material A and the raw material B is 10mg, the mass ratio of the raw material A to the raw material B is 1:1, the raw material A is melamine, and the raw material B is Fmoc-L-glutamic acid; the volume of the water is 1 mL; the KDM type electric heating jacket is purchased from Beijing Gohi laboratory instruments science and technology Limited;
step two, standing the aqueous solution containing the double components in the step one at room temperature for more than 60 min; the room temperature is 20-25 ℃.
Comparative examples 1 to 2
The present comparative example provides a method of preparing a two-component hydrogel comprising the steps of:
placing a raw material A, a raw material B and water in a glass closed container, and sleeving a KDM type electric heating sleeve in the closed container at the temperature of 90 ℃ for 8min to obtain a clear aqueous solution containing two components; the mass sum of the raw material A and the raw material B is 10mg, the mass ratio of the raw material A to the raw material B is 1:1, the raw material A is melamine, and the raw material B is nicotinic acid; the volume of the water is 1 mL; the KDM type electric heating jacket is purchased from Beijing Gohi laboratory instruments science and technology Limited;
step two, dividing the aqueous solution containing the double components in the step one into N groups, and standing the first group at room temperature for more than 60min to obtain hydrogel with high compactness; the room temperature is 20-25 ℃;
and the second group to the N group respectively use 2 mu L of pH regulator/mL of bi-component water solution as an initial value and 2uL/mL of pH regulator as a gradient, wherein the pH regulator is 5mol/L of HCl (aq) or 5mol/L of NaOH (aq), standing at room temperature and naturally cooling, and observing the gelling state.
Comparative examples 1 to 3
This comparative example provides a method for preparing a two-component hydrogel, the same as comparative examples 1-2, except that the ratio of the amounts of the materials of the raw material a and the raw material B was 3: 1.
Comparative examples 1 to 4
This comparative example provides a method for preparing a two-component hydrogel, the same as comparative examples 1-2, except that the ratio of the amounts of the materials of the raw material a and the raw material B was 1: 3.
Example 2-1
The embodiment provides a functional supramolecular aerogel, which is a functional supramolecular aerogel obtained by freezing and freeze-drying a bi-component hydrogel;
the volume of the functional supramolecular aerogel is the same as that of the bi-component hydrogel, and the density of the functional supramolecular aerogel is 4mg/cm3(ii) a The bi-component hydrogel is organic micromolecule bi-component hydrogel, the raw materials of the organic micromolecule bi-component hydrogel comprise a raw material A and a raw material B, the raw material A is melamine, and the raw material B is isonicotinic acid.
The present embodiment provides a method for preparing the above functional supramolecular aerogel, which includes:
placing a raw material A, a raw material B and water in a glass closed container, and sleeving a KDM type electric heating sleeve in the closed container at the temperature of 90 ℃ for 8min to obtain a clear aqueous solution containing two components; the mass sum of the raw material A and the raw material B is 4mg, the mass ratio of the raw material A to the raw material B is 1:1, the raw material A is melamine, and the raw material B is isonicotinic acid; the volume of the water is 1 mL;
step two, standing the aqueous solution containing the double components in the step one at room temperature until no liquid phase flows in the glass closed container when the glass closed container is turned over, so as to obtain homogeneous double-component hydrogel; the standing time is 45 min; the concentration of the bi-component hydrogel is 4 mg/mL;
step three, freezing the bi-component hydrogel for 8 hours at the temperature of-25 to-20 ℃ to obtain the frozen bi-component hydrogel;
step four, freeze-drying the frozen bi-component hydrogel in the step three for 48 to 50 hours at the temperature of between 52 ℃ below zero and 50 ℃ below zero and under the vacuum degree of between 8 and 10Pa to remove the solvent water in the bi-component hydrogel; obtaining functional supermolecule aerogel; the density of the functional supermolecule aerogel is 4mg/cm3。
Examples 2 to 2
The embodiment provides a functional supramolecular aerogel, which is a functional supramolecular aerogel obtained by freezing and freeze-drying a bi-component hydrogel;
the volume of the functional supramolecular aerogel is the same as that of the bi-component hydrogel, and the density of the functional supramolecular aerogel is 4mg/cm3(ii) a The bi-component hydrogel is organic micromolecule bi-component hydrogel, the raw materials of the organic micromolecule bi-component hydrogel comprise a raw material A and a raw material B, the raw material A is melamine, and the raw material B is isonicotinic acid.
The present embodiment provides a method for preparing the above functional supramolecular aerogel, which includes:
placing a raw material A, a raw material B and water in a glass closed container, and maintaining the closed container at 85 ℃ for 10min by using a KDM type electric heating sleeve to obtain a clear double-component-containing water solution; the mass sum of the raw material A and the raw material B is 4mg, the mass ratio of the raw material A to the raw material B is 1:3, the raw material A is melamine, and the raw material B is isonicotinic acid; the volume of the water is 1 mL;
step two, standing the aqueous solution containing the double components in the step one at room temperature until no liquid phase flows in the glass closed container when the glass closed container is turned over, so as to obtain homogeneous double-component hydrogel; the standing time is 30 min; the concentration of the bi-component hydrogel is 4 mg/mL;
step three, freezing the bi-component hydrogel for 0.1h at the temperature of-196 ℃ to-190 ℃ to obtain the frozen bi-component hydrogel;
step four, freeze-drying the frozen bi-component hydrogel in the step three for 40-42 h under the conditions that the temperature is-60 to-58 ℃ and the vacuum degree is 1.5 to 3Pa to remove the solvent water; obtaining functional supermolecule aerogel; the density of the functional supermolecule aerogel is 4mg/cm3。
Examples 2 to 3
The embodiment provides a functional supramolecular aerogel, which is a functional supramolecular aerogel obtained by freezing and freeze-drying a bi-component hydrogel;
the volume of the functional supramolecular aerogel is the same as that of the bi-component hydrogel, and the density of the functional supramolecular aerogel is 4mg/cm3(ii) a The bi-component hydrogel is organic micromolecule bi-component hydrogel, the raw materials of the organic micromolecule bi-component hydrogel comprise a raw material A and a raw material B, the raw material A is melamine, and the raw material B is isonicotinic acid.
The present embodiment provides a method for preparing the above functional supramolecular aerogel, which includes:
placing a raw material A, a raw material B and water in a glass closed container, and sleeving a KDM type electric heating sleeve for the closed container at the temperature of 95 ℃ for 5min to obtain a clear aqueous solution containing two components; the mass sum of the raw material A and the raw material B is 4mg, the mass ratio of the raw material A to the raw material B is 3:1, the raw material A is melamine, and the raw material B is isonicotinic acid; the volume of the water is 1 mL;
step two, standing the aqueous solution containing the double components in the step one at room temperature until no liquid phase flows in the glass closed container when the glass closed container is turned over, so as to obtain homogeneous double-component hydrogel; the standing time is 60 min; the concentration of the bi-component hydrogel is 4 mg/mL;
step three, freezing the bi-component hydrogel for 12 hours at the temperature of-10 to-5 ℃ to obtain the frozen bi-component hydrogel;
step four, freeze-drying the frozen bi-component hydrogel in the step three for 44-46 h under the conditions that the temperature is-57-55 ℃ and the vacuum degree is 6-7 Pa to remove the solvent water; obtaining functional supermolecule aerogel; the density of the functional supermolecule aerogel is 4mg/cm3。
Examples 2 to 4
The embodiment provides a functional supramolecular aerogel, which is a functional supramolecular aerogel obtained by freezing and freeze-drying a bi-component hydrogel;
the volume of the functional supramolecular aerogel is the same as that of the bi-component hydrogel, and the density of the functional supramolecular aerogel is 10mg/cm3(ii) a The bi-component hydrogel is organic micromolecule bi-component hydrogel, the raw materials of the organic micromolecule bi-component hydrogel comprise a raw material A and a raw material B, the raw material A is melamine, and the raw material B is isonicotinic acid.
The present embodiment provides a method for preparing the above functional supramolecular aerogel, which includes:
placing a raw material A, a raw material B and water in a glass closed container, and sleeving a KDM type electric heating sleeve in the closed container at the temperature of 90 ℃ for 8min to obtain a clear aqueous solution containing two components; the mass sum of the raw material A and the raw material B is 10mg, the mass ratio of the raw material A to the raw material B is 1:1, the raw material A is melamine, and the raw material B is isonicotinic acid; the volume of the water is 1 mL;
step two, standing the aqueous solution containing the double components in the step one at room temperature until no liquid phase flows in the glass closed container when the glass closed container is turned over, so as to obtain homogeneous double-component hydrogel; the standing time is 60 min; the concentration of the bi-component hydrogel is 10 mg/mL;
step three, freezing the bi-component hydrogel for 8 hours at the temperature of-25 to-20 ℃ to obtain the frozen bi-component hydrogel;
step four, freeze-drying the frozen bi-component hydrogel in the step three for 44-46 h under the conditions that the temperature is-57-55 ℃ and the vacuum degree is 6-7 Pa to remove the solvent water; obtaining functional supermolecule aerogel; the density of the functional supermolecule aerogel is 10mg/cm3。
Examples 2 to 5
The embodiment provides a functional supramolecular aerogel, which is a functional supramolecular aerogel obtained by freezing and freeze-drying a bi-component hydrogel;
the volume of the functional supramolecular aerogel is the same as that of the bi-component hydrogel, and the density of the functional supramolecular aerogel is 10mg/cm3(ii) a The bi-component hydrogel is organic micromolecule bi-component hydrogel, the raw materials of the organic micromolecule bi-component hydrogel comprise a raw material A and a raw material B, the raw material A is melamine, and the raw material B is isonicotinic acid.
The present embodiment provides a method for preparing the above functional supramolecular aerogel, which includes:
placing a raw material A, a raw material B and water in a glass closed container, and sleeving a KDM type electric heating sleeve in the closed container at the temperature of 90 ℃ for 8min to obtain a clear aqueous solution containing two components; the mass sum of the raw material A and the raw material B is 10mg, the mass ratio of the raw material A to the raw material B is 1:3, the raw material A is melamine, and the raw material B is isonicotinic acid; the volume of the water is 1 mL;
step two, standing the aqueous solution containing the double components in the step one at room temperature until no liquid phase flows in the glass closed container when the glass closed container is turned over, so as to obtain homogeneous double-component hydrogel; the standing time is 60 min; the concentration of the bi-component hydrogel is 10 mg/mL;
step three, freezing the bi-component hydrogel for 0.1h at the temperature of-196 ℃ to-190 ℃ to obtain the frozen bi-component hydrogel;
step four, the step threeThe frozen bi-component hydrogel is frozen and dried for 44 to 46 hours under the conditions that the temperature is between 57 ℃ below zero and 55 ℃ below zero and the vacuum degree is between 6Pa and 7Pa so as to remove the solvent water in the bi-component hydrogel; obtaining functional supermolecule aerogel; the density of the functional supermolecule aerogel is 10mg/cm3。
Examples 2 to 6
The embodiment provides a functional supramolecular aerogel, which is a functional supramolecular aerogel obtained by freezing and freeze-drying a bi-component hydrogel;
the volume of the functional supramolecular aerogel is the same as that of the bi-component hydrogel, and the density of the functional supramolecular aerogel is 10mg/cm3(ii) a The bi-component hydrogel is organic micromolecule bi-component hydrogel, the raw materials of the organic micromolecule bi-component hydrogel comprise a raw material A and a raw material B, the raw material A is melamine, and the raw material B is isonicotinic acid.
The present embodiment provides a method for preparing the above functional supramolecular aerogel, which includes:
placing a raw material A, a raw material B and water in a glass closed container, and sleeving a KDM type electric heating sleeve in the closed container at the temperature of 90 ℃ for 8min to obtain a clear aqueous solution containing two components; the mass sum of the raw material A and the raw material B is 10mg, the mass ratio of the raw material A to the raw material B is 3:1, the raw material A is melamine, and the raw material B is isonicotinic acid; the volume of the water is 1 mL;
step two, standing the aqueous solution containing the double components in the step one at room temperature until no liquid phase flows in the glass closed container when the glass closed container is turned over, so as to obtain homogeneous double-component hydrogel; the standing time is 60 min; the concentration of the bi-component hydrogel is 10 mg/mL;
step three, freezing the bi-component hydrogel for 0.1h at the temperature of-10 to-5 ℃ to obtain the frozen bi-component hydrogel;
step four, freeze-drying the frozen bi-component hydrogel in the step three for 48 to 50 hours at the temperature of between 52 ℃ below zero and 50 ℃ below zero and under the vacuum degree of between 8 and 10Pa,to remove the solvent water therein; obtaining functional supermolecule aerogel; the density of the functional supermolecule aerogel is 10mg/cm3。
Examples 2 to 7
The embodiment provides a functional supramolecular aerogel, which is a functional supramolecular aerogel obtained by freezing and freeze-drying a bi-component hydrogel;
the volume of the functional supramolecular aerogel is the same as that of the bi-component hydrogel, and the density of the functional supramolecular aerogel is 15mg/cm3(ii) a The bi-component hydrogel is organic micromolecule bi-component hydrogel, the raw materials of the organic micromolecule bi-component hydrogel comprise a raw material A and a raw material B, the raw material A is melamine, and the raw material B is isonicotinic acid.
The present embodiment provides a method for preparing the above functional supramolecular aerogel, which includes:
placing a raw material A, a raw material B and water in a glass closed container, and sleeving a KDM type electric heating sleeve for the closed container at the temperature of 95 ℃ for 5min to obtain a clear aqueous solution containing two components; the mass sum of the raw material A and the raw material B is 15mg, the mass ratio of the raw material A to the raw material B is 1:1, the raw material A is melamine, and the raw material B is isonicotinic acid; the volume of the water is 1 mL;
step two, standing the aqueous solution containing the double components in the step one at room temperature until no liquid phase flows in the glass closed container when the glass closed container is turned over, so as to obtain homogeneous double-component hydrogel; the standing time is 60 min; the concentration of the bi-component hydrogel is 15 mg/mL;
step three, freezing the bi-component hydrogel for 0.1h at the temperature of-196 ℃ to-190 ℃ to obtain the frozen bi-component hydrogel;
step four, freeze-drying the frozen bi-component hydrogel in the step three for 48 to 50 hours at the temperature of between 52 ℃ below zero and 50 ℃ below zero and under the vacuum degree of between 8 and 10Pa to remove the solvent water in the bi-component hydrogel; obtaining functional supermolecule aerogel; the density of the functional supramolecular aerogel is 15mg/cm3。
Examples 2 to 8
The embodiment provides a functional supramolecular aerogel, which is a functional supramolecular aerogel obtained by freezing and freeze-drying a bi-component hydrogel;
the volume of the functional supramolecular aerogel is the same as that of the bi-component hydrogel, and the density of the functional supramolecular aerogel is 15mg/cm3(ii) a The bi-component hydrogel is organic micromolecule bi-component hydrogel, the raw materials of the organic micromolecule bi-component hydrogel comprise a raw material A and a raw material B, the raw material A is melamine, and the raw material B is isonicotinic acid.
The present embodiment provides a method for preparing the above functional supramolecular aerogel, which includes:
placing a raw material A, a raw material B and water in a glass closed container, and maintaining the closed container at 85 ℃ for 10min by using a KDM type electric heating sleeve to obtain a clear double-component-containing water solution; the mass sum of the raw material A and the raw material B is 15mg, the mass ratio of the raw material A to the raw material B is 3:1, the raw material A is melamine, and the raw material B is isonicotinic acid; the volume of the water is 1 mL;
step two, standing the aqueous solution containing the double components in the step one at room temperature until no liquid phase flows in the glass closed container when the glass closed container is turned over, so as to obtain homogeneous double-component hydrogel; the standing time is 40 min; the concentration of the bi-component hydrogel is 15 mg/mL;
step three, freezing the bi-component hydrogel for 8 hours at the temperature of-25 to-20 ℃ to obtain the frozen bi-component hydrogel;
step four, freeze-drying the frozen bi-component hydrogel in the step three for 48 to 50 hours at the temperature of between 52 ℃ below zero and 50 ℃ below zero and under the vacuum degree of between 8 and 10Pa to remove the solvent water in the bi-component hydrogel; obtaining functional supermolecule aerogel; the density of the functional supermolecule aerogel is 15mg/cm3。
Examples 2 to 9
The embodiment provides a functional supramolecular aerogel, which is a functional supramolecular aerogel obtained by freezing and freeze-drying a bi-component hydrogel;
the volume of the functional supramolecular aerogel is the same as that of the bi-component hydrogel, and the density of the functional supramolecular aerogel is 15mg/cm3(ii) a The bi-component hydrogel is organic micromolecule bi-component hydrogel, the raw materials of the organic micromolecule bi-component hydrogel comprise a raw material A and a raw material B, the raw material A is melamine, and the raw material B is isonicotinic acid.
The present embodiment provides a method for preparing the above functional supramolecular aerogel, which includes:
placing a raw material A, a raw material B and water in a glass closed container, and sleeving a KDM type electric heating sleeve in the closed container at the temperature of 90 ℃ for 8min to obtain a clear aqueous solution containing two components; the mass sum of the raw material A and the raw material B is 15mg, the mass ratio of the raw material A to the raw material B is 1:3, the raw material A is melamine, and the raw material B is isonicotinic acid; the volume of the water is 1 mL;
step two, standing the aqueous solution containing the double components in the step one at room temperature until no liquid phase flows in the glass closed container when the glass closed container is turned over, so as to obtain homogeneous double-component hydrogel; the standing time is 60 min; the concentration of the bi-component hydrogel is 15 mg/mL;
step three, freezing the bi-component hydrogel for 12 hours at the temperature of-10 to-5 ℃ to obtain the frozen bi-component hydrogel;
step four, freeze-drying the frozen bi-component hydrogel in the step three for 40-42 h under the conditions that the temperature is-60 to-58 ℃ and the vacuum degree is 1.5 to 3Pa to remove the solvent water; obtaining functional supermolecule aerogel; the density of the functional supermolecule aerogel is 15mg/cm3。
Examples 2 to 10
The embodiment provides a functional supramolecular aerogel, which is a functional supramolecular aerogel obtained by freezing and freeze-drying a bi-component hydrogel;
the volume of the functional supramolecular aerogel is the same as that of the bi-component hydrogel, and the density of the functional supramolecular aerogel is 50mg/cm3(ii) a The bi-component hydrogel is organic micromolecule bi-component hydrogel, the raw materials of the organic micromolecule bi-component hydrogel comprise a raw material A and a raw material B, the raw material A is melamine, and the raw material B is isonicotinic acid.
This example is the same as example 2-1, except that the sum of the mass of raw material a and raw material B is 50mg, and the mass ratio of raw material a to raw material B is 1: 5.
The properties of the two-component hydrogel prepared in this example were substantially the same as those of example 2-1.
Examples 2 to 11
The embodiment provides a functional supramolecular aerogel, which is a functional supramolecular aerogel obtained by freezing and freeze-drying a bi-component hydrogel;
the volume of the functional supramolecular aerogel is the same as that of the bi-component hydrogel, and the density of the functional supramolecular aerogel is 50mg/cm3(ii) a The bi-component hydrogel is organic micromolecule bi-component hydrogel, the raw materials of the organic micromolecule bi-component hydrogel comprise a raw material A and a raw material B, the raw material A is melamine, and the raw material B is isonicotinic acid.
This example is the same as example 2-1, except that the sum of the mass of raw material a and raw material B is 50mg, and the mass ratio of raw material a to raw material B is 5: 1.
The properties of the two-component hydrogel prepared in this example were substantially the same as those of example 2-1.
Examples 2 to 12
The embodiment provides a functional supramolecular aerogel, which is a functional supramolecular aerogel obtained by freezing and freeze-drying a bi-component hydrogel;
the volume of the functional supramolecular aerogel is the same as that of the bi-component hydrogel, and the density of the functional supramolecular aerogel is 10mg/cm3(ii) a The bi-component hydrogel is organic micromolecule bi-component hydrogel, the raw materials of the organic micromolecule bi-component hydrogel comprise a raw material A and a raw material B, the raw material A is melamine, and the raw material B is quinoline-4-formic acid.
The method for preparing the functional supramolecular aerogel in this example is the same as that in example 2-1, except that the sum of the mass of the raw material a and the raw material B is 10mg, and the mass ratio of the raw material a to the raw material B is 1: 1; the raw material A is melamine, and the raw material B is quinoline-4-formic acid.
The properties of the two-component hydrogel prepared in this example were substantially the same as those of example 2-1.
Comparative example 2-1
This comparative example provides a method for preparing a functional supramolecular aerogel, the same as in example 2-1, except that the ratio of the amounts of the materials of raw material a and raw material B is 1:1, raw material a is melamine, and raw material B is 3, 4-dihydroxybenzoic acid.
Comparative examples 2 to 2
This comparative example provides a method for the preparation of a functional supramolecular aerogel, identical to example 2-1, with the difference that the ratio of the amounts of substances of raw material a and raw material B is 1:1, raw material a being melamine and raw material B being piperidine-4-carboxylic acid.
Comparative examples 2 to 3
This comparative example provides a method for the preparation of a functional supramolecular aerogel, identical to example 2-1, with the difference that the ratio of the amounts of substances of raw material a and raw material B is 1:1, raw material a being melamine and raw material B being benzoic acid.
Comparative examples 2 to 4
This comparative example provides a method for the preparation of a functional supramolecular aerogel, identical to example 2-1, with the difference that the ratio of the amounts of substances of raw material a and raw material B is 1:1, raw material a being melamine and raw material B being caffeic acid.
Comparative examples 2 to 5
This comparative example provides a method for the preparation of a functional supramolecular aerogel, identical to example 2-1, with the difference that the ratio of the amounts of substances of raw material a and raw material B is 1:1, raw material a being melamine and raw material B being orotic acid.
Comparative examples 2 to 6
This comparative example provides a method for the preparation of functional supramolecular aerogels, identical to example 2-1, with the difference that the ratio of the amounts of the substances of raw material a and raw material B is 1:1, raw material a being 2,4, 6-triaminopyrimidine and raw material B being isonicotinic acid.
Comparative examples 2 to 7
This comparative example provides a method for the preparation of functional supramolecular aerogels, identical to example 2-1, with the difference that the ratio of the amounts of the substances of raw material a and raw material B is 1:3, raw material a being 2,4, 6-triaminopyrimidine and raw material B being isonicotinic acid.
Comparative examples 2 to 8
This comparative example provides a method for the preparation of functional supramolecular aerogels, identical to example 2-1, with the difference that the ratio of the amounts of the substances of raw material a and raw material B is 3:1, raw material a being 2,4, 6-triaminopyrimidine and raw material B being isonicotinic acid.
The method of comparative examples 2-1 to 2-8 cannot be used to obtain a functional supramolecular aerogel with the same volume as the bi-component hydrogel.
And (3) performance testing:
examples 1-1 to 1-3 two-component hydrogel DSC chart, rheological modulus chart, temperature Change1The H-NMR chart, the ultraviolet spectrum chart and the SEM chart are shown in FIGS. 2 to 6.
Wherein the heating temperature range of Differential Scanning Calorimetry (DSC) is 10-60 ℃. As can be seen from FIG. 2, the broad endothermic temperature of the two-component hydrogel during the first heating is about 55 ℃, the exothermic temperature during the cooling stage is about 43 ℃, and the endothermic peak temperature of the second heating is about 55 ℃, which indicates that the two-component hydrogel has certain heat resistance, the gelation temperature is lower than the gel melting temperature, and the two-component hydrogel conforms to the first-order phase transition characteristic, and indicates that the two-component hydrogel of the present invention belongs to the first-order phase transition thermoreversible gel.
As can be seen from the frequency-scanning modulus graph of fixed temperature shown in FIG. 3, the storage modulus G 'of the two-component hydrogel is always higher than the loss modulus G' and does not change with the frequency, and meets the gel standard, the graph is the temperature-scanning modulus graph of fixed frequency, the G 'and G' of the three two-component hydrogels intersect at 37.2 deg.C, 34.4 deg.C and 33.2 deg.C, respectively, which indicates that the sol-gel transition temperature of the two-component hydrogel of the present invention is 33 deg.C to 37 deg.C.
As can be seen from the temperature-variable NMR spectrum shown in FIG. 4, isonicotinic acid I decreases with temperatureATwo groups of absorption peaks of the aromatic C-H proton move to a low field, which shows that in the gelation process, the supermolecular complex generates a secondary structure through pi-pi interaction, so that the aromatic proton is shielded. In conjunction with the UV spectrum shown in FIG. 5, the red shift of the absorption peak at 203nm indicates "J-shaped" stacking.
FIG. 6 is an SEM image of a xerogel prepared by vacuum drying the two-component hydrogel of examples 1-1 to 1-3, from which the presence of fibrils dispersed in the gel is clearly seen in MI A11 two-component hydrogel and MI A13 obvious intertwined three-dimensional fiber network structures exist in the bi-component hydrogel, and the width of the fibers is between 0.5 and 2.0 mu m; and at MI A31 bicomponent hydrogels, in addition to the fibrous structure, also present a lamellar structure, indicating the presence of excess melamine.
The bicomponent hydrogels of examples 1-4 were vacuum dried to obtain xerogels, and the observation under scanning electron microscope of FIG. 7 clearly shows the presence of a three-dimensional network of fibers dispersed therein, the width of the fibers being between 0.3 μm and 1.2. mu.m.
Comparative examples 1-1, step two, the state after standing is schematically shown in fig. 8, and it can be seen from fig. 8 that the gel can be formed by the method of this comparative example, but the leakage phenomenon exists and the gel structure is destroyed by slight shaking, which indicates that the hydrogel with high solidity can not be obtained by this comparative example.
Comparative examples 1-2 different pH response ranges gel state are schematically shown in fig. 9. from fig. 9 it can be seen that no white gel, but only co-precipitation, can be obtained with the method of this comparative example, probably because changing the pH does not affect the strong forces between melamine and niacin.
Comparative examples 1-2-1-4 groups to which hcl (aq) or naoh (aq) was added showed co-precipitation in the form of macroscopic fine needle-like fibers, without forming gel, and as a result, as shown by the rigid fiber structure and the sheet-like structure formed by the fiber packing in the SEM image of fig. 10, which is probably due to strong forces between melamine and nicotinic acid molecules.
The infrared spectrum and the density display chart of the functional supramolecular aerogel in the embodiments 2-1 to 2-3 are shown in fig. 11 to 12.
As can be seen from FIG. 11, in the infrared spectrum scan of the functional supramolecular aerogels of examples 2-1 to 2-3, the stretching vibration of the isonicotinic acid C ═ O appeared at 1716cm-1And moved to 1722cm in three kinds of performance supramolecular aerogels-1The reason why the peak position of C ═ O is increased is probably NH in melamine2Hydrogen bonds are formed between the groups and C ═ O in the isonicotinic acid, so that a gel structure with higher energy is formed, and the stretching vibration of the C ═ O is transferred to the higher energy. In addition, the bending vibration of OH on carboxylic acid in isonicotinic acid is also 1337cm from the reason of hydrogen bond formation-1Moved to 1373cm-1. The melamine content is 3469cm-1And 3419cm-1Stretching vibration of the corresponding amino group at MI A11 and MI A13 the functional supramolecular aerogel moves to 3396cm-1Here, the absorption peak was clearly broadened, indicating that hydrogen bonds were formed between the amino group in melamine and C ═ O and OH in isonicotinic acid. This is also 1654cm-1Bending vibration of NH at the point is transferred to 1670cm-1The part is proved to be printed. And at MIAThe 31 functional supermolecule aerogel has excessive melamine and free amino groups, so that some original absorption peaks of the melamine remain. The original absorption peak of C-N in melamine and isonicotinic acid is 1556cm-1And 1566cm-1Transferred to 1550cm in functional supramolecular aerogels-1Here, the formation of stacking secondary structures was demonstrated.
As shown in FIG. 12, the mass was 80mg and the volume was 20cm3The functional supramolecular aerogel disclosed by the embodiment 2-1 to 2-3 is placed on the villus, and the villus is not bent, so that the functional supramolecular aerogel disclosed by the invention has the characteristic of ultralow density.
The scanning electron microscope image and the transmission electron microscope image of the functional supramolecular aerogel in examples 2-4 to 2-6 are shown in FIGS. 13 and 14.
It can be seen from the SEM image of FIG. 13 that the gel fibers become finer and more uniform after lyophilization, with an average width of about 0.4 μm, and the presence of such flexibly twisted fibers can also be seen in the TEM image of FIG. 14.
The compression resilience of the functional supramolecular aerogels in examples 2-4 is shown in figure 15.
Preparing the functional supramolecular aerogels of the examples 2 to 4 into 200mg of cylindrical aerogels, circularly compressing under the pressure of 1.71kPa and 3.42kPa, recording the height of the cylindrical aerogels before and after compression as shown in FIG. 15, and calculating the elastic modulus stored in each compression, wherein the calculation formula is as follows:
wherein F is applied pressure and has the unit of N;
s is the stress area in mm2；
Delta h is the amount of height deformation in mm;
h is the original height in mm.
As can be seen from FIG. 15, 200mg of aerogel can recover to the original height after being compressed under the pressure of 1.71kPa of a 100g weight, and can still recover to the original height after being compressed for many cycles. Increasing the pressure to 3.42kPa still showed good compression resilience with the stored modulus of elasticity remaining substantially constant per compression.
Application examples 3-1 to 3-3
The application examples 3-1 to 3-3 provide the functional supramolecular aerogel for organic solvent absorption, and the functional supramolecular aerogel for organic solvent absorption is the same as the functional supramolecular aerogel in the examples 2-4 to 2-6.
By adopting the method for absorbing the organic solvent in the application embodiment, the organic solvent can be cyclohexane, toluene, benzene, dichloromethane, tetrahydrofuran, ethyl acetate, dioxane, acetone or acetonitrile, or can be a mixture of the cyclohexane, the toluene, the benzene, the dichloromethane, the tetrahydrofuran, the ethyl acetate, the dioxane, the acetone or the acetonitrile; the method for organic solvent absorption includes:
20mg of the functional supramolecular aerogel obtained in the embodiments 2-4 to 2-6 is put into a small bottle shown in fig. 16, 2mL of cyclohexane, toluene, benzene, dichloromethane, tetrahydrofuran, ethyl acetate, dioxane, acetone or acetonitrile are respectively dropped into the small bottle, as can be seen from fig. 16, the volume of the functional supramolecular aerogel is not changed, and after the small bottle is inverted, all the organic solvents are absorbed, and no liquid leakage occurs.
Application examples 4-1 to 4-3
Application examples 4-1 to 4-3 provide functional supramolecular aerogels for sound insulation, which are the same as examples 2-7 to 2-9.
In the preparation method of the functional supramolecular aerogel for sound insulation, the glass closed container in any one of the embodiments 2-7-2-9 is replaced by the glass closed mold shown in fig. 17, the two-component hydrogel shown in the mold is obtained in the second step, and then the operation is continued according to the third step and the fourth step, so that the functional supramolecular aerogel for sound insulation is obtained.
Placing a noise source into the sealed glass mold for sound insulation, monitoring noise with a decibel meter, comparing the obtained data with air sound transmission, and evaluating the sound insulation performance, wherein the mold mass is 3g, and the cavity area is 9.43X 10-3m2Areal density of 0.32kg/m2. As shown in FIG. 18, when the sound insulation effect of the glass closed mold is compared with the sound transmission effect of air, the maximum sound insulation amount of medium and low noise is 31.09dB under 400-1300 Hz, and the sound insulation amount is determined according to the sound insulation amountThe formula is tested, the surface density required for achieving the sound insulation is 58 times of the functional supermolecule aerogel surface density for sound insulation, the average sound insulation is 16.80dB, the required surface density is 5 times of the functional supermolecule aerogel surface density for sound insulation, and the calculation formula is as follows:
R＝13.5lgm+14(m≤200kg/m2)
wherein R is the sound insulation quantity, and the unit is dB;
m is mass density, unit kg/m2；
Therefore, the functional supramolecular aerogel for sound insulation greatly reduces the surface density on the basis of meeting the requirement of sound insulation quantity, and can effectively reduce the use cost.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. The functional supramolecular aerogel is characterized in that the functional supramolecular aerogel is obtained by freezing and freeze-drying a bi-component hydrogel;
the volume of the functional supramolecular aerogel is the same as that of the bi-component hydrogel, and the lower limit of the density regulation range of the functional supramolecular aerogel is 4mg/cm3(ii) a The bi-component hydrogel is organic micromolecule bi-component hydrogel, the raw materials of the organic micromolecule bi-component hydrogel comprise a raw material A and a raw material B, the raw material A is melamine, and the raw material B is isonicotinic acid or quinoline-4-formic acid.
2. A method of preparing the functional supramolecular aerogel as claimed in claim 1, comprising: preparing a raw material A, a raw material B and water into a bi-component hydrogel, freezing the bi-component hydrogel, and freeze-drying the frozen bi-component hydrogel to obtain the functional supramolecular aerogel; the sum of the mass of the raw material A and the raw material B is 4-50 times of the volume of the water, the mass unit of the raw material A and the raw material B is mg, and the unit of the volume of the water is mL.
3. The method according to claim 2, wherein the ratio of the amount of the material of the raw material A to the amount of the material of the raw material B is (5-1): (1-5).
4. The preparation method according to claim 3, wherein the raw material A is melamine, the raw material B is isonicotinic acid, and the ratio of the amount of the raw material A to the amount of the raw material B is (3-1): (1-3).
5. The method of claim 2, wherein the step of formulating material a, material B and water into a two-component hydrogel comprises:
placing a raw material A, a raw material B and water in a glass closed container, and keeping the temperature of 85-95 ℃ for 5-10 min to obtain a double-component-containing aqueous solution;
and step two, standing the aqueous solution containing the double components obtained in the step one at room temperature until the glass closed container is turned over, wherein no liquid phase flows in the glass closed container, so that the double-component hydrogel is obtained.
6. The method of claim 2, wherein the freezing of the bi-component hydrogel and the freeze-drying of the frozen bi-component hydrogel to obtain the functional supramolecular aerogel comprises:
step one, freezing the bi-component hydrogel for 0.1 to 12 hours at the temperature of-196 to-5 ℃ to obtain the frozen bi-component hydrogel;
and step two, freeze-drying the frozen bi-component hydrogel in the step one for 40-50 h under the conditions that the temperature is-60-50 ℃ and the vacuum degree is 1.5-10 Pa to obtain the functional supramolecular aerogel.
7. A functional supramolecular aerogel for acoustic insulation comprising the functional supramolecular aerogel of claim 1.
8. A functional supramolecular aerogel for organic solvent absorption, comprising the functional supramolecular aerogel of claim 1.
9. A method of using the functional supramolecular aerogel of claim 1.
10. The method of use according to claim 9, comprising applying the functional supramolecular aerogel to sound insulation or adsorption of organic solvents comprising one or more of cyclohexane, toluene, benzene, dichloromethane, tetrahydrofuran, ethyl acetate, dioxane, acetone and acetonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110415154.7A CN113117613B (en) | 2021-04-17 | 2021-04-17 | Functional supramolecular aerogel, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110415154.7A CN113117613B (en) | 2021-04-17 | 2021-04-17 | Functional supramolecular aerogel, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113117613A true CN113117613A (en) | 2021-07-16 |
| CN113117613B CN113117613B (en) | 2022-09-27 |
Family
ID=76777085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110415154.7A Active CN113117613B (en) | 2021-04-17 | 2021-04-17 | Functional supramolecular aerogel, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113117613B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471095A (en) * | 2022-02-11 | 2022-05-13 | 苏州北美国际高级中学 | Organic aerogel desiccant and preparation method thereof |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5086085A (en) * | 1991-04-11 | 1992-02-04 | The United States Of America As Represented By The Department Of Energy | Melamine-formaldehyde aerogels |
| US5705535A (en) * | 1993-05-18 | 1998-01-06 | Hoechst Aktiengesellschaft | Method for the subcritical drying of aerogels |
| CN101376097A (en) * | 2008-10-06 | 2009-03-04 | 华东理工大学 | Method for preparing carbon aerogel desulfurizing agent |
| WO2011079909A2 (en) * | 2009-12-18 | 2011-07-07 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Method for producing encapsulated metal colloids as inorganic pigments |
| DE102013215400A1 (en) * | 2013-08-06 | 2015-02-12 | Robert Bosch Gmbh | Silicate airgel and process for its preparation |
| CN105283495A (en) * | 2013-06-14 | 2016-01-27 | 斯攀气凝胶公司 | Insulating composite materials comprising an inorganic aerogel and a melamine foam |
| CN106000366A (en) * | 2016-05-25 | 2016-10-12 | 江苏科技大学 | Graphene-melamine foam aerogel and preparation method thereof |
| WO2017074751A1 (en) * | 2015-10-30 | 2017-05-04 | Blueshift International Materials, Inc. | Highly branched non-crosslinked aerogel, methods of making, and uses thereof |
| CN107057107A (en) * | 2017-04-13 | 2017-08-18 | 昆明理工大学 | It is a kind of to be freeze-dried the method for preparing cellulose aerogels |
| CN107353406A (en) * | 2017-06-14 | 2017-11-17 | 浙江工业大学 | A kind of dendroid gelator and its preparation and application |
| CN108517042A (en) * | 2018-07-13 | 2018-09-11 | 赣南师范大学 | A kind of supramolecular hydrogel and preparation method thereof and one kind are gone out blood fluke cercaria sustained release preparation and preparation method thereof |
| CN110183716A (en) * | 2019-05-13 | 2019-08-30 | 浙江工业大学 | A kind of preparation method of fire-retardant heat insulation fiber type element base aeroge |
| US20200238263A1 (en) * | 2019-01-25 | 2020-07-30 | Nanjing University | Method for preparing bi-component, multi-network nanofibrous aerogel-supported heterojunction photocatalyst and application thereof |
| US20200399431A1 (en) * | 2018-06-27 | 2020-12-24 | Hunan Elixer Therapeutics Co., Ltd. | Covalently Cross-Linked Hyaluronic Acid Aerogel, Hydrogel, and Preparation Method Thereof |
| CN112313004A (en) * | 2018-04-26 | 2021-02-02 | 蓝移材料有限公司 | Polymer aerogels prepared by solvent-free exchange |
-
2021
- 2021-04-17 CN CN202110415154.7A patent/CN113117613B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5086085A (en) * | 1991-04-11 | 1992-02-04 | The United States Of America As Represented By The Department Of Energy | Melamine-formaldehyde aerogels |
| US5705535A (en) * | 1993-05-18 | 1998-01-06 | Hoechst Aktiengesellschaft | Method for the subcritical drying of aerogels |
| CN101376097A (en) * | 2008-10-06 | 2009-03-04 | 华东理工大学 | Method for preparing carbon aerogel desulfurizing agent |
| WO2011079909A2 (en) * | 2009-12-18 | 2011-07-07 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Method for producing encapsulated metal colloids as inorganic pigments |
| CN105283495A (en) * | 2013-06-14 | 2016-01-27 | 斯攀气凝胶公司 | Insulating composite materials comprising an inorganic aerogel and a melamine foam |
| DE102013215400A1 (en) * | 2013-08-06 | 2015-02-12 | Robert Bosch Gmbh | Silicate airgel and process for its preparation |
| WO2017074751A1 (en) * | 2015-10-30 | 2017-05-04 | Blueshift International Materials, Inc. | Highly branched non-crosslinked aerogel, methods of making, and uses thereof |
| CN106000366A (en) * | 2016-05-25 | 2016-10-12 | 江苏科技大学 | Graphene-melamine foam aerogel and preparation method thereof |
| CN107057107A (en) * | 2017-04-13 | 2017-08-18 | 昆明理工大学 | It is a kind of to be freeze-dried the method for preparing cellulose aerogels |
| CN107353406A (en) * | 2017-06-14 | 2017-11-17 | 浙江工业大学 | A kind of dendroid gelator and its preparation and application |
| CN112313004A (en) * | 2018-04-26 | 2021-02-02 | 蓝移材料有限公司 | Polymer aerogels prepared by solvent-free exchange |
| US20200399431A1 (en) * | 2018-06-27 | 2020-12-24 | Hunan Elixer Therapeutics Co., Ltd. | Covalently Cross-Linked Hyaluronic Acid Aerogel, Hydrogel, and Preparation Method Thereof |
| CN108517042A (en) * | 2018-07-13 | 2018-09-11 | 赣南师范大学 | A kind of supramolecular hydrogel and preparation method thereof and one kind are gone out blood fluke cercaria sustained release preparation and preparation method thereof |
| US20200238263A1 (en) * | 2019-01-25 | 2020-07-30 | Nanjing University | Method for preparing bi-component, multi-network nanofibrous aerogel-supported heterojunction photocatalyst and application thereof |
| CN110183716A (en) * | 2019-05-13 | 2019-08-30 | 浙江工业大学 | A kind of preparation method of fire-retardant heat insulation fiber type element base aeroge |
Non-Patent Citations (3)
| Title |
|---|
| HAIPENG ZHENG，ETAL: "Self-assembly of supramolecular complexes based on hydrogen bonding", 《SUPRAMOLECULAR SCIENCE》 * |
| PENG MENG,ETAL: "One-Minute Synthesis of a Supramolecular Hydrogel from Suspension − Gel Transition and the Derived Crystalline, Elastic, and Photoactive Aerogels", 《ACS APPLIED MATERIALS ＆ INTERFACES》 * |
| 马天慧等: "基于氢键和π-π堆积的网络化合物", 《黑龙江大学自然科学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471095A (en) * | 2022-02-11 | 2022-05-13 | 苏州北美国际高级中学 | Organic aerogel desiccant and preparation method thereof |
| CN114471095B (en) * | 2022-02-11 | 2024-02-09 | 苏州北美国际高级中学 | Organic aerogel drying agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113117613B (en) | 2022-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cao et al. | 1D/2D nanomaterials synergistic, compressible, and response rapidly 3D graphene aerogel for piezoresistive sensor | |
| Cai et al. | Fabrication and characterization of capric–lauric–palmitic acid/electrospun SiO2 nanofibers composite as form-stable phase change material for thermal energy storage/retrieval | |
| Liu et al. | Lightweight, superelastic, and hydrophobic polyimide nanofiber/MXene composite aerogel for wearable piezoresistive sensor and oil/water separation applications | |
| EP3878809B1 (en) | Flexible boron nitride nano-belt aerogel and preparation method therefor | |
| He et al. | Superelastic and superhydrophobic bacterial cellulose/silica aerogels with hierarchical cellular structure for oil absorption and recovery | |
| Yao et al. | Ultrahigh‐conductivity polymer hydrogels with arbitrary structures | |
| Zhu et al. | Thermo-responsive polymer-functionalized mesoporous carbon for controlled drug release | |
| Cheng et al. | One-step in-situ green synthesis of cellulose nanocrystal aerogel based shape stable phase change material | |
| CN107417961A (en) | A kind of anisotropy polyimide aerogels material and preparation method thereof | |
| Zong et al. | Fabrication and characterization of electrospun SiO2 nanofibers absorbed with fatty acid eutectics for thermal energy storage/retrieval | |
| Zhang et al. | A synergistic strategy for fabricating an ultralight and thermal insulating aramid nanofiber/polyimide aerogel | |
| CN113117613B (en) | Functional supramolecular aerogel, preparation method and application thereof | |
| Liu et al. | Metal–organic frameworks: a universal strategy towards super-elastic hydrogels | |
| Yang et al. | Hyperelastic and hydrophobic silica aerogels with enhanced compressive strength by using VTES/MTMS as precursors | |
| You et al. | Highly improved water tolerance of hydrogel fibers with a carbon nanotube sheath for rotational, contractile and elongational actuation | |
| Kang et al. | Compression strain-dependent tubular carbon nanofibers/graphene aerogel absorber with ultrabroad absorption band | |
| KR20110032946A (en) | Organic aerogel and composition for the organic aerogel | |
| Li et al. | Poly (vinyl alcohol) assisted regulation of aramid nanofibers aerogel structure for thermal insulation and adsorption | |
| CN113150746A (en) | Boron nitride/pea meal double-heat-conduction carbon-based aerogel and preparation method and application thereof | |
| CN110079991A (en) | A kind of polymer nanofiber-based aerogel heat-insulating material of ultra-light elastic based on Static Spinning | |
| Zhang et al. | High latent heat stearic acid impregnated in expanded graphite | |
| Cai et al. | Flexible cellulose acetate nano-felts absorbed with capric–myristic–stearic acid ternary eutectic mixture as form-stable phase-change materials for thermal energy storage/retrieval | |
| US20170173556A1 (en) | Adsorption material and method of manufacturing the same and adsorption heat pump | |
| Feng et al. | Facile and rapid synthesis of flexible PEG porous polymers as substrates for functional materials by thiol-ene click chemistry | |
| Guo et al. | Shape memory polyimide aerogel composites with high programming temperatures and exceptional shape recovery capability |
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 |