CN113943441A - Hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature-regulating material and preparation method thereof - Google Patents
Hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature-regulating material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change temperature regulating material and a preparation method thereof, wherein the preparation method comprises the following steps: 1) preparing dialdehyde carboxymethyl cellulose; (2) preparing dialdehyde carboxymethyl cellulose solution and collagen solution respectively by using deionized water or PBS buffer solution, and then mixing and reacting the dialdehyde carboxymethyl cellulose solution and the collagen solution to prepare dialdehyde carboxymethyl cellulose-collagen aerogel; (3) preparing a dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change material by vacuum impregnation of a PEG solution; (4) PDMS is used as a hydrophobic material to prepare the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature-regulating material. The hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change temperature regulating material prepared by the invention maintains the high porosity, low thermal conductivity and light weight of the aerogel, and improves the mechanical property, thermal stability and water resistance of the aerogel.
Description
Technical Field
The invention relates to a heat insulation material, in particular to a hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change temperature regulating material and a preparation method thereof.
Background
With the development of industry and urbanization, excessive energy consumption is not negligible. The development and application of the high-efficiency heat management material are the most direct and effective energy-saving methods in the building industry, the transportation industry, outdoor tents, outdoor electronic device equipment and the like. At present, although the traditional heat insulation materials are widely applied, the defects of environmental pollution and poor heat insulation effect exist, for example, mineral wool, glass fiber and clay are the most commonly used inorganic heat insulation materials, but the mechanical property and the heat insulation property are not excellent. In addition, organic thermal insulation materials such as foam, sponge, epoxy resin and the like have good thermal insulation performance, but the main raw materials are non-renewable energy sources such as petroleum and the like, the preparation process is complex, and the degradation is not easy to cause environmental pollution. The novel aerogel insulation materials are amorphous materials having a particular three-dimensional structure and are considered to be the best solid materials for thermal insulation. It has excellent properties such as high porosity (80 to 99.8%), low apparent density (0.001 to 0.3g/cm) and low thermal conductivity (0.01 to 0.1Wm-1 k-1). With the increasing demand for green, energy-saving and high-efficiency heat-insulating materials, it is important to develop novel aerogels with low cost, high performance, safety and environmental protection.
Collagen is a biological protein widely existing in animal skin and bones, has good environmental compatibility and biodegradability, can form hydrogel, film and aerogel, and is a biological material with wide application prospect in the field of heat preservation and insulation. Leftover materials generated in the tanning process are low-cost industrial raw materials rich in collagen, a suitable and effective application way is found for the waste, products with high added values are researched and developed, resources can be fully utilized, and meanwhile, the leftover materials are necessary for environmental protection. Collagen, as a natural protein, is composed of dozens of amino acids, and the molecular chain of the collagen has stronger polar side chain groups such as carboxyl, hydroxyl and amino, so that the collagen is easy to crosslink with other active groups and easy to gel, and becomes an ideal choice for constructing macroscopic three-dimensional materials. However, the main challenge of collagen materials in thermal insulation applications is their amorphous structure and the resulting fragile mechanical properties, which are difficult to adapt to the actual application environment. To compensate for these disadvantages, the structure of the polymer skeleton can be reinforced by the crosslinking agent, and a biomass-based composite aerogel with significantly improved mechanical properties is obtained, which is also a necessary trend in the development of biomass-based composite aerogels. Therefore, solving the problem of the effective combination form between the collagen aerogel framework and the cross-linking agent and the influence on the heat preservation and insulation performance is necessary to expand the application of the collagen aerogel framework in the heat preservation and insulation material.
To date, researchers have utilized various methods to improve the properties of collagen, including crosslinking, blending, and copolymerizing it with natural fibers, high molecular polymers, and nanomaterials. Currently, the main materials in the field of biodegradable materials are various polysaccharides and their derivatives. The water-soluble carboxymethyl cellulose (CMC) has excellent environmental compatibility and biodegradability, is one of the most abundant polysaccharides in nature, and has the advantages of economy, reproducibility and environmental protection. Dialdehyde carboxymethyl cellulose is a cross-linking agent derived from natural polysaccharides. Compared with short chain aldehydes such as formaldehyde and pentanedialdehyde, the longer side chain in the dialdehyde polysaccharide cellulose can increase the reactivity and assist in improving the mechanical property. Carboxymethyl cellulose can be oxidized with periodate to obtain highly reactive dialdehyde carboxymethyl cellulose (DCMC). By periodate oxidation, CMC can specifically cleave the C2-C3 bond of 1, 4-glucan, resulting in a ring-opened product with two aldehyde groups. The presence of two aldehyde groups makes DCMC an excellent cross-linker in a wide variety of cellulose-based biomaterials. The aldehyde group in DCMC can react with the epsilon-amino group of lysine and the zeta-amino group of arginine via a-C ═ N-bond (Schiff base, i.e. azomethine, R-CH ═ NR ', R' ≠ H) to improve the properties of collagen.
In addition, the effect of heat insulation achieved by only depending on the porous structure of the aerogel is very limited, and the use under some complicated and variable conditions is difficult to meet. The heat energy storage technology is considered as a key technology for sustainable control and utilization of renewable energy sources, excess heat is collected and stored in a suitable medium or device, and is released when needed, and intermittence and unsustainability in the heat supply and demand process can be effectively solved. The heart of thermal energy storage technology is the phase change material, which absorbs and releases heat through phase change. The aerogel is a three-dimensional network porous material mainly comprising air and prepared by combining a sol-gel method with a special drying process, and a special nano porous network structure and a mesoporous capillary effect of the aerogel can be used for adsorbing a phase-change material. The porous composite material prepared by the porous carrier composite technology is called aerogel-based composite phase-change material, has the excellent heat-insulating property of aerogel and the energy-storage and temperature-regulating functions of the phase-change material, and has good application prospect in the fields of solar collection, heat preservation, heat insulation and the like. However, hydrophilic collagen has poor water vapor barrier properties, which is a major disadvantage of collagen aerogels used as thermal insulation materials. The collagen aerogel is a three-dimensional material which is light in weight, porous and large in specific surface area, and is a good solution for ensuring that the collagen aerogel still keeps water resistance and stable structure after adsorbing a phase-change material and the phase-change material does not leak, so that a hydrophobic structure is constructed on the surface. In addition, the hydrophobic surface can also enhance the stability of the phase-change material in a humid environment and the self-cleaning performance of the aerogel, so that the service life can be prolonged and the aerogel can be kept clean even if the aerogel is used as a heat insulation material in humid outdoor for a long time.
In summary, the problems of the prior art are as follows: the mechanical property of the collagen material can not meet the application requirement, and the main challenge in the application of the heat preservation and insulation field is that the mechanical property of the pure collagen aerogel is poor, and the crosslinking modification is beneficial to improving the mechanical property of the pure collagen aerogel; the heat insulation effect realized only by depending on the porous structure of the aerogel is very limited, the application under some complex and variable conditions is difficult to meet, and the application range of the aerogel can be widened by adopting the heat energy storage technology of the phase-change material; the collagen aerogel composite phase-change material obtained after freeze drying is easy to collapse when meeting water and is easy to dissolve in normal saline, the defects greatly limit the application of the collagen aerogel in the fields of heat preservation, heat insulation and the like, and hydrophobic modification is needed.
The difficulty and significance for solving the technical problems are as follows: collagen is used as a natural biological macromolecule, so that the defects of poor mechanical property, high water solubility, limited use condition and the like of the collagen are improved while the good environmental friendliness and heat insulation performance are maintained, and the collagen has important significance for expanding the application field of the collagen aerogel.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature-regulating material which has heat insulation and heat preservation performance and heat storage and temperature regulation performance and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change temperature regulating material comprises the following steps:
(1) deionized water is used as a solvent, and a sodium periodate solution containing sodium carboxymethylcellulose and sodium periodate in a mass ratio of 1: (0.5-3), adjusting the pH value of the mixed solution A to 1.5-5.0, reacting at 20-60 ℃ for 3-5 h to generate dialdehyde carboxymethyl cellulose, adding 2-7 times volume of absolute ethanol into the reacted mixed solution to precipitate the dialdehyde carboxymethyl cellulose, alternately washing with the absolute ethanol and deionized water until the washing solution is neutral, and taking out and drying for later use;
(2) deionized water or PBS buffer solution is used for respectively preparing dialdehyde carboxymethyl cellulose solution with the concentration of 0.1-1.0 mg/mL and collagen solution with the concentration of 1.0-10.0 mg/mL, and then according to the mass ratio of dialdehyde carboxymethyl cellulose to collagen of 1: (1-200), mixing the dialdehyde carboxymethyl cellulose solution with the collagen solution, reacting at 0-35 ℃ for 0.5-2 h, then injecting the reacted mixed solution into a mold, pre-freezing at-60 to-20 ℃ for 4-72 h, taking out, and freeze-drying for 24-72 h to obtain the dialdehyde carboxymethyl cellulose-collagen aerogel;
(3) preparing a PEG solution with the mass fraction of 30-60% by taking ethanol as a solvent, then carrying out vacuum impregnation on the dialdehyde carboxymethyl cellulose-collagen aerogel prepared in the step (3) in the PEG solution, taking out and drying to obtain the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change material;
(4) mixing Sylgard 184 component A, component B and an organic solvent according to a mass ratio of 10: 1: (10-1000) uniformly mixing to obtain a PDMS mixed solution, soaking the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change material prepared in the step (3) in the PDMS mixed solution, taking out, and curing and drying at 23-150 ℃ to obtain the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change temperature adjusting material.
Further, the concentration of the sodium carboxymethyl cellulose in the mixed solution A in the step (1) is 0.01-0.05 g/mL.
Further, the PEG in the PEG solution in the step (3) is a mixture of PEG with different molecular weights.
Further, the vacuum impregnation time in the step (3) is 1-10 min.
Further, the organic solvent in the step (4) is ethyl acetate, tetrahydrofuran or n-hexane.
Further, in the step (4), the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change material is soaked in the PDMS mixed solution for 5-30 min.
Further, the curing and drying time in the step (4) is 15 min-24 h.
The invention also relates to the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature-regulating material prepared by the method, wherein the microscopic pore structure of the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature-regulating material is filled with the phase-change material PEG, and the surface of the phase-change material PEG is attached with the hydrophobic material PDMS.
Wherein, PDMS (polydimethylsiloxane) is a component A of Sylgard 184 of Dow Corning, and a component B is added when the PDMS is used, wherein A, B is mixed in a mass ratio of 10: 1; wherein the component A is a basic component and belongs to double-bond end-capped polydimethylsiloxane; the component B is a curing agent, belonging to poly dimethyl siloxane containing silicon-hydrogen bond with multiple functionality.
Compared with the prior art, the invention has the following technical effects:
1. the invention successfully prepares the dialdehyde carboxymethyl cellulose by oxidizing the carboxymethyl cellulose with periodate; as an efficient biomacromolecule cross-linking agent, the biomacromolecule cross-linking agent is non-toxic and non-irritant, and can avoid the problem of micromolecule aldehyde release caused by free micromolecule aldehyde. And DCMC (dialdehyde carboxymethyl cellulose) forms Schiff base between-NH 2 on collagen and-CHO in DCMC through Schiff base reaction, so that the collagen and DCMC form a composite structure, and the chemical stability, the mechanical property and the heat insulation property of the composite aerogel are improved. The invention will greatly advance the application of collagen-based biomaterials in fields such as heat preservation, heat insulation engineering, energy conservation, environmental protection, etc.
2. The method prepares the collagen aerogel by using a freeze-drying method, the whole process is carried out at low temperature, and the whole process can not denature the collagen, so that the specific triple helical structure of the collagen can be maintained, and the excellent performance of the collagen is kept; in addition, the obtained collagen aerogel greatly increases the specific surface area of the collagen material, so that the performance of adsorbing the phase-change material is better.
3. The invention loads the phase-change material by a simple capillary adsorption method, absorbs and releases heat by utilizing the phase-change of the phase-change material, collects and stores the excess heat, releases the excess heat when needed, and can effectively solve the intermittence and unsustainability of the aerogel material in the heat supply and demand process. The obtained aerogel composite phase-change material has excellent heat-insulating property of aerogel and the function of energy storage and temperature regulation of the phase-change material, and has good application prospect in the fields of solar collection, heat preservation, heat insulation and the like.
4. The method adopts a simple dipping-coating mode to carry out hydrophobic treatment on the collagen aerogel, has simple and mild reaction conditions, and greatly simplifies the production flow. The construction of the hydrophobic structure on the surface of the aerogel is a good solution for solving the problem of leakage of solid-liquid phase change of the phase-change material. In addition, the hydrophobic surface can also enhance the stability of the phase-change material in a humid environment and the self-cleaning performance of the aerogel, so that the service life can be prolonged and the aerogel can be kept clean even if the aerogel is used as a heat insulation material in humid outdoor for a long time.
5. The main raw materials used in the invention comprise collagen and sodium carboxymethylcellulose which are all environment-friendly biomass materials, have wide sources, do not cause pollution to the environment, are green and friendly, and avoid secondary pollution in the preparation process.
6. According to the invention, the phase change temperature can be regulated and controlled by controlling the molecular weight of the PEG adopted in the step (3) and the combination ratio of the PEG with different molecular weights, so that the aerogel composite phase change material which can be used under different temperature conditions can be obtained.
7. The product obtained by the invention has good heat insulation and heat preservation performance and heat storage and temperature regulation performance, and can be applied to heat insulation and heat preservation protection under common or extreme conditions.
Drawings
FIG. 1 is a FT-IR spectrum of sodium carboxymethylcellulose used in example 1 of the present invention and a prepared dialdehyde carboxymethyl cellulose;
FIG. 2 is a FT-IR spectrum of dialdehyde carboxymethyl cellulose-collagen aerogel prepared in example 1 of the present invention and pure collagen aerogel;
fig. 3 is a mechanical property diagram of the dialdehyde carboxymethyl cellulose-collagen aerogel prepared in example 1 of the present invention: (a) compressing; (b) bending; (c) folding;
FIG. 4 is a graph showing the measurement results of the contact angle of the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change material prepared in example 1 of the invention before hydrophobic treatment and after hydrophobic treatment;
FIG. 5 is an infrared thermal imaging diagram of the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change material prepared in example 1 of the invention on a cold source at-25 ℃;
fig. 6 is an infrared thermal imaging diagram of the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change material prepared in example 1 of the invention on a heat source at 80 ℃.
Detailed Description
The present invention will be explained in further detail with reference to examples.
The embodiment provides a preparation method of a hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature-regulating material, which specifically comprises the following steps:
(1) deionized water is used as a solvent, and a sodium periodate solution containing sodium carboxymethylcellulose and sodium periodate in a mass ratio of 1: (0.5-3), adjusting the pH value of the mixed solution A to 1.5-5.0, reacting at 20-60 ℃ for 3-5 h to generate dialdehyde carboxymethyl cellulose, adding 2-7 times volume of absolute ethanol into the reacted mixed solution to precipitate the dialdehyde carboxymethyl cellulose, alternately washing with the absolute ethanol and deionized water until the washing solution is neutral, and taking out and drying for later use;
(2) deionized water or PBS buffer solution is used for respectively preparing dialdehyde carboxymethyl cellulose solution with the concentration of 0.1-1.0 mg/mL and collagen solution with the concentration of 1.0-10.0 mg/mL, and then according to the mass ratio of dialdehyde carboxymethyl cellulose to collagen of 1: (1-200), mixing the dialdehyde carboxymethyl cellulose solution with the collagen solution, reacting at 0-35 ℃ for 0.5-2 h, then injecting the reacted mixed solution into a mold, pre-freezing at-60 to-20 ℃ for 4-72 h, taking out, and freeze-drying for 24-72 h to obtain the dialdehyde carboxymethyl cellulose-collagen aerogel;
(3) preparing a PEG solution with the mass fraction of 30-60% by taking ethanol as a solvent, then carrying out vacuum impregnation on the dialdehyde carboxymethyl cellulose-collagen aerogel prepared in the step (3) in the PEG solution, taking out and drying to obtain the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change material;
(4) mixing Sylgard 184 component A, component B and an organic solvent according to a mass ratio of 10: 1: (10-1000) uniformly mixing to obtain a PDMS mixed solution, soaking the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change material prepared in the step (3) in the PDMS mixed solution, taking out, and curing and drying at 23-150 ℃ to obtain the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change temperature adjusting material.
The embodiment also relates to the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature regulating material prepared by the method, wherein the microscopic pore structure of the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature regulating material is filled with the phase-change material PEG, and the surface of the phase-change material PEG is attached with the hydrophobic material PDMS.
To further explain the technical solution of the present invention in detail, the following description will be given with reference to specific examples.
Example 1
Weighing 1.0g of sodium carboxymethylcellulose and 0.98g of sodium periodate, respectively adding into 50ml of ionized water, placing in a water bath kettle at 35 ℃ and stirring at a constant speed until the sodium carboxymethylcellulose and the sodium periodate are completely dissolved, then mixing, adjusting the pH value of the mixed solution to 3.0, reacting at 35 ℃ for 4h, pouring the reacted mixed solution into 5 times volume of absolute ethyl alcohol for precipitation, alternately washing the obtained white precipitate with the absolute ethyl alcohol and deionized water for multiple times until the washing liquid is neutral, and drying to obtain the dialdehyde carboxymethyl cellulose.
Dissolving collagen with PBS buffer solution (10mmol/L disodium hydrogen phosphate, 10mmol/L sodium dihydrogen phosphate, 100mmol/L sodium chloride, pH 7.4) to obtain collagen solution with concentration of 6.0 mg/mL; dissolving dialdehyde carboxymethyl cellulose by using PBS buffer solution to prepare dialdehyde carboxymethyl cellulose solution with the concentration of 1.0 mg/mL; then, according to the mass ratio of the dialdehyde carboxymethyl cellulose to the collagen of 1: and 6, uniformly mixing the dialdehyde carboxymethyl cellulose solution and the collagen solution, stirring in an ice water bath for reaction for 2 hours, pouring the reacted mixed solution into a mold, pre-freezing at-20 ℃ for 24 hours, and freeze-drying in a freeze-drying machine for 48 hours to obtain the dialdehyde carboxymethyl cellulose-collagen aerogel.
Dissolving 5.0g of PEG1000 and 5.0g of PEG4000 in absolute ethyl alcohol at 60 ℃ to prepare a PEG solution with the mass fraction of 40 percent; and (3) soaking the dialdehyde carboxymethyl cellulose-collagen aerogel in the obtained PEG solution for 5min in vacuum, wiping the PEG on the clean surface with filter paper, drying in the air, and repeating the soaking, wiping and drying for three times to obtain the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change material.
Respectively dissolving 0.5g of Sylgard 184 component A and 0.05g of component B in 50.0g of ethyl acetate, stirring for 10min to form a uniform PDMS mixed solution, soaking the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change material in the PDMS mixed solution for 5min, taking out, drying and curing at 65 ℃ for 4h to obtain the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change temperature regulating material.
FIG. 1 is an infrared spectrum of commercially available sodium carboxymethylcellulose (CMC) and the dialdehyde carboxymethyl cellulose (DCMC) prepared in this example; as can be seen, the depth is 3418.1cm-1The characteristic peak appeared here is attributed to the-OH stretching vibration peak in carboxyl; 1635.8cm-1The characteristic peak at (A) is assigned as C ═ O asymmetric stretching vibration peak of carboxyl. Compared with CMC, DCMC is 1109.8cm-1Is prepared from cellulose skeleton-CH2─O─CH2Characteristic peak of 1735.8cm-1The characteristic absorption peak of aldehyde group-CO is present, which accords with the infrared characteristic of dialdehyde carboxymethyl cellulose. From the infrared spectrum, it can be seen that dialdehyde carboxymethyl cellulose (DCMC) was successfully prepared by oxidizing carboxymethyl cellulose with sodium periodate.
FIG. 2 is a FT-IR spectrum of the dialdehyde carboxymethyl cellulose-collagen aerogel prepared in the present example and pure collagen aerogel; the pure collagen aerogel is completely consistent with the dialdehyde carboxymethyl cellulose-collagen aerogel except that dialdehyde carboxymethyl cellulose is not added, namely the specific preparation method is as follows: dissolving collagen with PBS buffer solution (10mmol/L disodium hydrogen phosphate, 10mmol/L sodium dihydrogen phosphate, 100mmol/L sodium chloride, pH 7.4), preparing collagen solution with concentration of 6.0mg/mL, stirring in ice water bath for reaction for 2h, pouring the reacted solution into a mold, pre-freezing at-20 deg.C for 24h, and freeze-drying in a freeze-dryer for 48h to obtain pure collagen aerogel. As can be seen, the IR spectrum of the pure collagen aerogel shows the following characteristic peaks: 1637cm-1The compound (A) represents a characteristic peak of amide I, and the characteristic peak represents the stretching vibration of C ═ O; 1538cm-1The peak represents the characteristic peak of amide II and characterizes C-N stretching vibration; 1228cm-1The site represents the characteristic peak of amide III, for the indices C-N stretch, N-H in-plane bend and-CH2-a rocking vibration. By comparison, the infrared spectra of the pure collagen aerogel and the DCMC modified collagen aerogel are found in the wave number rangeThe enclosure is 800--1There is a significant difference between them. This is due to the fact that the introduction of DCMC into collagen leads to a sharp increase in the intensity of the bands in these ranges. Located at 1030cm-1The main peak at (A) is the C-O stretching vibration and the red shift occurs due to DCMC introduction. The test result shows that the modified collagen does not lose the natural triple helix structure, and the bioactivity of the collagen is not influenced. In addition, after DCMC is modified, the absorption peaks of amide I, II and III bands of collagen are slightly reduced, which shows that DCMC and Schiff base crosslinking reaction of collagen form more stable C ═ N crosslinking bonds, thereby enhancing the structural stability of collagen molecules.
Fig. 3 is a mechanical property diagram of the dialdehyde carboxymethyl cellulose-collagen aerogel prepared in this example: (a) compressing; (b) bending; (c) folding; as shown in the figure:
(a) compressing; in turn as shown in a1、a2、a3As shown, the sheet-like round aerogel was released after being pinched hard by both the thumb and the index finger, and it was seen that it was rapidly restored to the state before the uncompressed state.
(b) Bending; in the order of b1、b2、b3After the edges of the flaky circular aerogel are lightly pinched by the two fingers, the two fingers are lightly pinched to apply force to the middle to enable the aerogel to be bent and then release the hand, and the aerogel can be observed to be rapidly restored to the state before the aerogel is bent manually.
(c) Folding; in turn as shown in c1、c2、c3As shown, the sheet-shaped round aerogel is folded twice and then put on a plane with hands loosened, and can be seen to be rapidly restored to a state before being unfolded.
The flaky round aerogel is prepared from dialdehyde carboxymethyl cellulose-collagen aerogel through a mould, and the aerogel modified by DCMC crosslinking can be rapidly recovered to the original state after being compressed, bent and folded, and has good mechanical properties. The dialdehyde carboxymethyl cellulose-collagen aerogel prepared by the embodiment has certain elastic capacity and bending resistance and has potential application value.
Fig. 4 is a graph illustrating the measurement results of the contact angle of the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change material prepared in the embodiment before and after hydrophobic treatment; the data are measured by a contact angle tester of the OCA-20 type. As can be seen from the figure, the contact angle of the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change material without PDMS hydrophobic treatment is 0 degrees, and the composite phase-change material shows hydrophilic characteristic; the contact angle of the treated hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change temperature regulating material is obviously improved, is about 140.2 degrees, and shows a hydrophobic characteristic. The result shows that the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change temperature regulating material treated by PDMS shows obvious hydrophobic property.
FIGS. 5 and 6 are two square dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature-regulating materials prepared by using a 2cm by 2cm cubic mold, which are respectively placed on a cold source at-25 ℃ and a heat source at 80 ℃ for 30min, and then are subjected to infrared thermal imaging photographs taken by an infrared thermal imaging instrument FLIR E4 (Haikang lithography sensing technology, Inc.); as shown in fig. 5, after being placed on a cold source at-25 ℃ for half an hour, the central temperature of the upper surface of the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature-regulating material is still maintained at about 23.1 ℃, which indicates that the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature-regulating material has excellent heat preservation capability; as shown in figure 6, after being placed on a heating table at 80 ℃ for 30min, the central temperature of the upper surface of the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature-regulating material is kept at about 35.1 ℃ which is far lower than the temperature of the heating table, and the heat insulation effect is excellent.
Example 2
Weighing 2.0g of sodium carboxymethylcellulose, adding the sodium carboxymethylcellulose into 200ml of deionized water to prepare a carboxymethyl cellulose solution, placing the carboxymethyl cellulose solution in a water bath kettle provided with a magnetic stirring device to stir the solution, weighing 2.94g of sodium periodate after complete dissolution, adjusting the pH value to 2.0, stirring the solution in a water bath at about 40 ℃ to react for about 5 hours, adding absolute ethyl alcohol with the volume being 3 times that of a reaction solution after the reaction is finished to precipitate dialdehyde carboxymethyl cellulose, filtering the solution after complete precipitation, alternately and repeatedly washing and centrifuging the solution by using the absolute ethyl alcohol and the deionized water, and placing the solution in a vacuum oven at 50 ℃ to dry the solution for 12 hours to obtain the dialdehyde carboxymethyl cellulose.
Weighing 0.5g of collagen, adding the collagen into 100mL of deionized water, and continuously stirring for about 8 hours at the temperature of about 5 ℃ to obtain a collagen solution with the concentration of about 5.0 mg/mL; simultaneously weighing 0.05g of dialdehyde carboxymethyl cellulose, adding the dialdehyde carboxymethyl cellulose into 100mL of deionized water, heating in a water bath at about 75 ℃ and continuously stirring for about 1h to obtain dialdehyde carboxymethyl cellulose solution with the concentration of about 0.5 mg/mL; slowly blending the collagen and the dialdehyde carboxymethyl cellulose according to the mass ratio of 20:1 at room temperature, continuously stirring and reacting for about 2 hours, then pouring the reacted mixed solution into a mould, and pre-freezing for 24 hours at the temperature of about-20 ℃; and then putting the mould into a freeze dryer for freeze drying for 48 hours to obtain the dialdehyde carboxymethyl cellulose-collagen aerogel.
Dissolving 5.0g of PEG1000 and 5.0g of PEG4000 in absolute ethyl alcohol at 60 ℃ to prepare a PEG solution with the mass fraction of 40 percent; soaking dialdehyde carboxymethyl cellulose-collagen aerogel in a PEG solution for 5min in vacuum, wiping the clean surface of the phase change material PEG solution with filter paper, naturally drying, and repeating the soaking, wiping and drying for three times to obtain the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change material.
Respectively dissolving 0.5g of Sylgard 184 component A and 0.05g of component B in 50.0g of tetrahydrofuran, stirring for 10min to form a uniform PDMS mixed solution, soaking the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change material in the PDMS mixed solution for 30min, taking out, drying and curing at 65 ℃ for 4h to obtain the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change temperature regulating material.
Example 3
Weighing 2.0g of sodium carboxymethylcellulose, adding the sodium carboxymethylcellulose into 200ml of deionized water to prepare a carboxymethyl cellulose solution, placing the carboxymethyl cellulose solution in a water bath kettle provided with a magnetic stirring device to stir the solution, weighing 4.575g of sodium periodate after the sodium carboxymethylcellulose is completely dissolved, then adjusting the pH value of the sodium periodate to 1.5, stirring the sodium periodate solution in a water bath at about 35 ℃ to react for about 4 hours, adding absolute ethyl alcohol with 4 times volume of reaction liquid after the reaction is finished to precipitate dialdehyde carboxymethyl cellulose, and filtering the solution after the precipitation is complete; and washing with absolute ethyl alcohol and deionized water alternately and repeatedly, centrifuging and drying to obtain the dialdehyde carboxymethyl cellulose.
Weighing 1.0g of collagen, adding the collagen into 100mL of deionized water, and continuously stirring for about 12 hours at the temperature of about 5 ℃ to obtain a collagen solution with the concentration of about 10.0 mg/mL; simultaneously weighing 0.01g of dialdehyde carboxymethyl cellulose, adding into 100mL of deionized water, heating in a water bath at about 75 ℃ and continuously stirring for about 0.5h to obtain dialdehyde carboxymethyl cellulose solution with the concentration of about 0.1 mg/mL; slowly blending collagen and dialdehyde carboxymethyl cellulose according to the mass ratio of 100:1 at room temperature, continuously stirring and reacting for about 2h, then pouring the reacted mixed solution into a mould, pre-freezing for 4h at about-60 ℃, then putting the mould into a freeze dryer, and freeze-drying for 48h to obtain the dialdehyde carboxymethyl cellulose-collagen aerogel.
Dissolving 2.5g of PEG1000 and 7.5g of PEG2000 in absolute ethyl alcohol at 60 ℃ to prepare a PEG solution with the mass fraction of 60 percent; soaking dialdehyde carboxymethyl cellulose-collagen aerogel in the obtained PEG solution for 10min in vacuum, wiping the phase change material on the clean surface with filter paper, naturally drying, and repeating the soaking, wiping and drying for three times to obtain the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change material.
Respectively dissolving 5g of Sylgard 184 component A and 0.5g of component B in 11.0g of n-hexane, stirring for 10min to form a uniform PDMS mixed solution, soaking the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change material in the PDMS mixed solution for 20min, taking out, and drying and curing at 23 ℃ for 24h to obtain the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change temperature regulating material.
Example 4
Weighing 2.0g of sodium carboxymethylcellulose, adding the sodium carboxymethylcellulose into 40ml of deionized water to prepare a carboxymethyl cellulose solution, placing the carboxymethyl cellulose solution in a water bath kettle provided with a magnetic stirring device to stir the solution, weighing 1.0g of sodium periodate after complete dissolution, then adjusting the pH value to 5, stirring the solution in a water bath at about 60 ℃ to react for about 3 hours, adding absolute ethyl alcohol with 2 times of volume of reaction liquid after reaction to precipitate dialdehyde carboxymethyl cellulose, and filtering the solution after complete precipitation; and washing with absolute ethyl alcohol and deionized water alternately and repeatedly, centrifuging and drying to obtain the dialdehyde carboxymethyl cellulose.
Weighing 0.1g of collagen, adding the collagen into 100mL of deionized water, and continuously stirring for about 12 hours at about 4 ℃ to obtain a collagen solution with the concentration of about 1.0 mg/mL; simultaneously weighing 0.01g of dialdehyde carboxymethyl cellulose, adding into 100mL of deionized water, heating in water bath at about 50 ℃ and continuously stirring for about 1h to obtain dialdehyde carboxymethyl cellulose solution with the concentration of about 0.1 mg/mL; slowly blending the collagen and the dialdehyde carboxymethyl cellulose according to the mass ratio of 200:1 at 35 ℃, continuously stirring and reacting for about 0.5h, then pouring the reacted mixed solution into a mould, pre-freezing for 48h at about-40 ℃, then putting the mould into a freeze dryer, and freeze-drying for 24h to obtain the dialdehyde carboxymethyl cellulose-collagen aerogel.
Dissolving 2.5g of PEG1000 and 7.5g of PEG2000 in absolute ethyl alcohol at 60 ℃ to prepare a PEG solution with the mass fraction of 30 percent; and (3) soaking the dialdehyde carboxymethyl cellulose-collagen aerogel in the obtained PEG solution for 10min in vacuum, wiping the phase change material on the clean surface with filter paper, and naturally drying to obtain the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change material.
Respectively dissolving 5g of Sylgard 184 component A and 0.5g of component B in 5.0g of n-hexane, stirring for 10min to form a uniform PDMS mixed solution, soaking the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change material in the PDMS mixed solution for 10min, taking out, and drying and curing at 100 ℃ for 1h to obtain the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change temperature regulating material.
Example 5
Weighing 2.0g of sodium carboxymethylcellulose, adding the sodium carboxymethylcellulose into 150ml of deionized water to prepare a carboxymethyl cellulose solution, placing the carboxymethyl cellulose solution in a water bath kettle provided with a magnetic stirring device to stir the solution, weighing 6.0g of sodium periodate after complete dissolution, adjusting the pH value to 2.0, stirring the solution in a water bath at about 20 ℃ to react for about 5 hours, adding 7 times volume of absolute ethyl alcohol into reaction liquid after the reaction is finished to precipitate dialdehyde carboxymethyl cellulose, filtering the solution after complete precipitation, alternately and repeatedly washing and centrifuging the solution by using the absolute ethyl alcohol and the deionized water, and placing the solution in a vacuum oven at 40 ℃ to dry the solution for 12 hours to obtain the dialdehyde carboxymethyl cellulose.
Weighing 0.3g of collagen, adding the collagen into 100mL of deionized water, and continuously stirring for about 24 hours at about 4 ℃ to obtain a collagen solution with the concentration of about 3.0 mg/mL; simultaneously weighing 0.05g of dialdehyde carboxymethyl cellulose, adding the dialdehyde carboxymethyl cellulose into 100mL of deionized water, heating in water bath at about 50 ℃ and continuously stirring for about 2h to obtain dialdehyde carboxymethyl cellulose solution with the concentration of about 0.5 mg/mL; slowly blending the collagen and the dialdehyde carboxymethyl cellulose according to the mass ratio of 1:1 at 30 ℃, continuously stirring and reacting for about 1h, then injecting the reacted mixed solution into a mould, and pre-freezing for 72h at about-30 ℃; and then putting the mould into a freeze dryer for freeze drying for 72 hours to obtain the dialdehyde carboxymethyl cellulose-collagen aerogel.
Dissolving 5.0g of PEG1000 and 5.0g of PEG4000 in absolute ethyl alcohol at 55 ℃ to prepare a PEG solution with the mass fraction of 50 percent; soaking the dialdehyde carboxymethyl cellulose-collagen aerogel in a PEG solution for 1min in vacuum, wiping the phase change material on the clean surface with filter paper, and naturally drying to obtain the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change material.
Respectively dissolving 0.5g of Sylgard 184 component A and 0.05g of component B in 5.0g of tetrahydrofuran, stirring for 10min to form a uniform PDMS mixed solution, soaking the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change material in the PDMS mixed solution for 30min, taking out, drying and curing at 150 ℃ for 15min to obtain the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change temperature regulating material.
Claims (8)
1. The preparation method of the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change temperature regulating material is characterized by comprising the following steps of:
(1) deionized water is used as a solvent, and a sodium periodate solution containing sodium carboxymethylcellulose and sodium periodate in a mass ratio of 1: (0.5-3), adjusting the pH value of the mixed solution A to 1.5-5.0, reacting at 20-60 ℃ for 3-5 h to generate dialdehyde carboxymethyl cellulose, adding 2-7 times volume of absolute ethanol into the reacted mixed solution to precipitate the dialdehyde carboxymethyl cellulose, alternately washing with the absolute ethanol and deionized water until the washing solution is neutral, and taking out and drying for later use;
(2) deionized water or PBS buffer solution is used for respectively preparing dialdehyde carboxymethyl cellulose solution with the concentration of 0.1-1.0 mg/mL and collagen solution with the concentration of 1.0-10.0 mg/mL, and then according to the mass ratio of dialdehyde carboxymethyl cellulose to collagen of 1: (1-200), mixing the dialdehyde carboxymethyl cellulose solution with the collagen solution, reacting at 0-35 ℃ for 0.5-2 h, then injecting the reacted mixed solution into a mold, pre-freezing at-60 to-20 ℃ for 4-72 h, taking out, and freeze-drying for 24-72 h to obtain the dialdehyde carboxymethyl cellulose-collagen aerogel;
(3) preparing a PEG solution with the mass fraction of 30-60% by taking ethanol as a solvent, then carrying out vacuum impregnation on the dialdehyde carboxymethyl cellulose-collagen aerogel prepared in the step (3) in the PEG solution, taking out and drying to obtain the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change material;
(4) mixing Sylgard 184 component A, component B and an organic solvent according to a mass ratio of 10: 1: (10-1000) uniformly mixing to obtain a PDMS mixed solution, soaking the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change material prepared in the step (3) in the PDMS mixed solution, taking out, and curing and drying at 23-150 ℃ to obtain the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase change temperature adjusting material.
2. The preparation method of the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature regulating material as claimed in claim 1, wherein the concentration of the sodium carboxymethyl cellulose in the mixed solution A in the step (1) is 0.01-0.05 g/mL.
3. The method for preparing the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature regulating material as claimed in claim 1, wherein the PEG in the PEG solution in the step (3) is a mixture of PEG with different molecular weights.
4. The preparation method of the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature regulating material as claimed in claim 1, wherein the vacuum impregnation time in the step (3) is 1-10 min.
5. The preparation method of the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature regulating material as claimed in claim 1, wherein the organic solvent in the step (4) is ethyl acetate, tetrahydrofuran or n-hexane.
6. The preparation method of the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature regulating material as claimed in claim 1, wherein the soaking time of the dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change material in the PDMS mixed solution in the step (4) is 5-30 min.
7. The preparation method of the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature regulating material as claimed in claim 1, wherein the curing and drying time in the step (4) is 15min to 24 h.
8. The hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature regulating material prepared by the method of claim 1, wherein the microscopic pore structure of the hydrophobic dialdehyde carboxymethyl cellulose-collagen aerogel composite phase-change temperature regulating material is filled with the phase-change material PEG, and the surface of the phase-change material PEG is attached with the hydrophobic material PDMS.
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