Aerogel with orange segment pores and preparation method and application thereof

Abstract

The present invention belongs to the field of material science and technology, and relates to an aerogel with orange peel pores, and a preparation method and application thereof. Preparation method: a hydrophilic fiber material and a hydrophobic fiber material are dispersed in water, and after being sheared by a shearing machine to obtain a fiber suspension, the fiber suspension is frozen until completely frozen, and the aerogel is obtained after freeze drying; the water contact angle of the hydrophilic fiber material is 20° to 90°, the shear stiffness is 10 to 20, and the aspect ratio is ≤10; the water contact angle of the hydrophobic fiber material is 100° to 150°, the shear stiffness is 10 to 20, and the aspect ratio is ≥40; the mass ratio of the hydrophilic fiber material to the hydrophobic fiber material is 2 to 4:1; the shear rate of the shearing machine is 15000 to 25000 rpm; the supercooling degree during freezing is ≥5.5°C; the aerogel with orange peel pores is prepared by the method; the aerogel with orange peel pores is used as a drug sustained release material, etc. The method of the present invention is simple, and an aerogel with orange peel pores can be prepared.

Description

Technical Field

[0001] The invention belongs to the technical field of material science and relates to an aerogel with orange segment pores and a preparation method and application thereof. Background Art

[0002] In the field of materials science, porous structures have attracted much attention due to their unique physical and chemical properties. Among them, the orange-segment structure, as a special porous structure, has a small core area in the center surrounded by multiple petal-like structures, showing a series of unique performance advantages. This structure has potential application value in adsorption, filtration and separation, catalysis and energy storage, slow-descent and slow-release performance, etc.

[0003] Specifically, the orange-peel structure gives the aerogel the characteristics of light weight and adjustable multi-level pore size, which enables it to show excellent performance as a lightweight thermal insulation material in the aviation and aerospace fields, or as a thermal insulation material in the construction field. At the same time, its high specific surface area and high porosity also make it an ideal candidate material for solar collectors in the energy field, which is expected to improve energy conversion efficiency. In addition, the ordered multi-level pore structure enables the orange-peel channel aerogel to be used as a catalyst carrier, improving the utilization rate and reaction efficiency of the catalyst, while also improving the permeability of the aerogel, which is conducive to the improvement of filtration and separation effects.

[0004] More importantly, the aerodynamic properties of the orange peel-shaped structure enable it to suspend in the air or slowly land, providing new possibilities for atmospheric samplers in the field of environmental monitoring. In addition, this structure is also suitable as a material for micro-aircraft, for aerodynamic research or as a carrier for micro-sensors. In the field of biomedicine, orange peel porous aerogel can also be used as a drug delivery system or bionic template, providing a new solution for tissue engineering.

[0005] However, despite the many potential advantages and application prospects of orange segment pore aerogel, existing technologies are still unable to produce aerogels with this specific structure. The multi-level pore orientation distribution problem is the key technical difficulty in preparing orange segment pore aerogels. The current technical methods cannot accurately control the formation and distribution of aerogel pores, making it difficult to obtain aerogels with regular orange segment-shaped structures.

[0006] Therefore, developing a new technology that can prepare aerogels with orange-peel pore structures is of great significance for promoting the development of materials science and expanding the application scope of aerogels. Summary of the invention

[0007] The purpose of the present invention is to solve the problems existing in the prior art and to provide an aerogel with orange segment pores and a preparation method and application thereof.

[0008] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] A method for preparing an aerogel with orange segment pores, comprising dispersing a hydrophilic fiber material and a hydrophobic fiber material in water, shearing the fiber suspension with a shearing machine, freezing the fiber suspension until it is completely frozen, and freeze-drying the aerogel.

[0010] The water contact angle of the hydrophilic fiber material is 20°~90°, the shear stiffness is 10~20, and the aspect ratio is ≤10; the water contact angle of the hydrophobic fiber material is 100°~150°, the shear stiffness is 10~20, and the aspect ratio is ≥40; the mass ratio of the hydrophilic fiber material to the hydrophobic fiber material is 2~4:1; the shear rate of the shearing machine is 15000~25000rpm; the supercooling degree during freezing (supercooling degree is the difference between the theoretical crystallization temperature of the crystal and the actual given crystallization field temperature, the magnitude of supercooling degree is closely related to the cooling rate, the faster the cooling rate, the lower the actual crystallization temperature, the greater the supercooling degree; conversely, the slower the cooling rate, the smaller the supercooling degree, and the actual crystallization temperature is closer to the theoretical crystallization temperature) ≥5.5℃.

[0011] As the preferred technical solution:

[0012] In the method for preparing an aerogel with orange-segment pores as described above, the aspect ratio of the hydrophilic fiber material is 1-10; and the aspect ratio of the hydrophobic fiber material is 40-80.

[0013] In the method for preparing an aerogel having segmented pores as described above, the hydrophilic fiber material is cellulose fiber, cellulose derivative fiber (such as cellulose acetate fiber) or nylon.

[0014] In the method for preparing an aerogel having orange segment pores as described above, the hydrophobic fiber material is thermoplastic polyurethane fiber, polylactic acid fiber or polycaprolactone fiber.

[0015] In the method for preparing an aerogel having orange segment pores as described above, the content of the hydrophilic fiber material in the fiber suspension is 0.67-0.8 wt %.

[0016] In the method for preparing an aerogel having orange segment pores as described above, the fiber suspension also contains 0.25-2 wt % of a surfactant, so that the surface energy can be adjusted, and the size of the pore structure can be regulated.

[0017] In the method for preparing an aerogel having orange-peel pores as described above, freezing the fiber suspension until it is completely frozen means leaving the fiber suspension at -50 to -196°C for 0.2 to 8 hours.

[0018] The present invention also provides an aerogel with orange segment pores, which is prepared by using the preparation method of an aerogel with multi-oriented pores as described in any one of the above items.

[0019] The present invention also provides an application of the aerogel having orange segment pores as described above, which is used as a drug sustained-release material, a catalytic carrier, a bone repair material or a gas separation material;

[0020] Aerogels with orange peel pore structure have pores arranged radially, with different pore sizes and generally decreasing in size. This unique structure gives aerogels high connectivity and high specific surface area, making them exhibit excellent performance in many fields.

[0021] In the field of drug sustained-release materials, aerogels with orange-peel pore structures can be used to make nanocapsules or microcapsules, thereby achieving precise control of drug release rate and location. This structure helps to achieve precise drug delivery and sustained-release effects, thereby improving the overall effect of drug treatment.

[0022] As a catalytic carrier, the orange segment pore structure is not only conducive to the transport of substances along the pore direction, but also can regulate the diffusion path of reactants and products by providing pores of different sizes, which helps to optimize the catalytic process and significantly improve the catalytic efficiency.

[0023] In the field of bone repair materials, the pore structure of orange peels matches the microstructure of bones, which helps to provide the required mechanical strength and lightweight properties. By adjusting the pore size, the material can be customized for different types of bone defects and more accurately match the bone defect area, thereby promoting bone regeneration and repair.

[0024] In addition, the unique connectivity of the orange peel pore structure makes it have potential application value in the field of gas separation materials. The small pores help the selective adsorption of gas molecules in the pores, thereby improving the gas separation efficiency, such as achieving the effective separation of gases such as oxygen and nitrogen.

[0025] In the field of environmental testing, because materials with this structure can fall steadily in the air and slow down the descent speed, they are suitable for application scenarios that require long-term suspension or slow descent. Their suspension characteristics can be used to collect samples in the atmosphere as an atmospheric sampler.

[0026] In summary, aerogels with orange peel pore structure have broad application prospects in many fields such as drug sustained release, catalytic carrier, bone repair, gas separation, environmental testing, etc. due to their unique structure and properties.

[0027] Principle of the invention:

[0028] Under high-speed shear, hydrophilic fiber materials with small aspect ratios are greatly affected by the shear flow, and their arrangement direction near the wall is close to parallel to the Z axis. Hydrophobic fiber materials with large aspect ratios are less affected by the shear flow. All fiber materials are distributed in a circular pattern from the periphery to the inner circle. The more hydrophilic the hydrophilic fiber material is, the more it is arranged in the outer circle (such as Figure 1 As shown, the outermost circle is the hydrophilic fiber layer 1), and the closer the angle with the Z axis is to 0°, the more hydrophobic the hydrophobic fiber material is and the closer it is to the central axis (such as Figure 1 As shown in the figure, the innermost circle is the hydrophobic fiber layer 2), and the angle with the Z axis is closer to 90°. Under high supercooling, ice crystals grow vertically on the surface of the fiber material, and the hydrophilic and hydrophobic gradient formed by the hydrophilic and hydrophobic fiber material pulls the ice crystals to extend and grow from the periphery to the central axis, thus forming a Figure 1 The orange segment-shaped ice crystals 3 shown are freeze-dried to obtain orange segment channels.

[0029] Beneficial effects:

[0030] The preparation method of the aerogel with the orange segment pore structure of the present invention is simple. The prepared aerogel with the orange segment pore structure has broad application prospects in multiple fields such as drug sustained release, catalytic carrier, bone repair and gas separation due to its unique structure. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 Schematic diagram of aerogel with orange segment pores;

[0032] Figure 2 This is a top view of the aerogel with orange segment pores prepared in Example 1 (the lines in the figure represent the distribution of orange segment pores);

[0033] Figure 3 This is a front view of the aerogel with orange segment pores prepared in Example 1 (the lines in the figure represent the distribution of orange segment pores);

[0034] Among them, 1-hydrophilic fiber layer, 2-hydrophobic fiber layer, 3-orange-segment-shaped ice crystals. DETAILED DESCRIPTION

[0035] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0036] Example 1

[0037] A method for preparing an aerogel having orange segment pores, the specific steps are as follows:

[0038] (1) Preparation of raw materials;

[0039] Hydrophilic fiber material: cellulose acetate fiber, water contact angle of 30° to 80°, shear stiffness of 10 to 20, aspect ratio of 1 to 10;

[0040] Hydrophobic fiber material: thermoplastic polyurethane fiber, water contact angle of 100° to 150°, shear stiffness of 10 to 20, aspect ratio of 40 to 80;

[0041] Surfactant: blocked water-based isocyanate, manufactured by China Changzhou Houding Chemical Co., Ltd., model number HD-8035;

[0042] water;

[0043] (2) The hydrophilic fiber material, the hydrophobic fiber material and the surfactant are dispersed in water, and the fiber suspension is obtained by shearing with a shearing machine (shear rate of 15000 rpm), and the fiber suspension is allowed to stand at -50°C (supercooling degree of 5.5°C) for 8 hours, and freeze-dried (temperature of -45°C, pressure of 15 Pa, time of 24 hours) to obtain an aerogel;

[0044] The mass ratio of the hydrophilic fiber material to the hydrophobic fiber material is 2:1; the content of the hydrophilic fiber material in the fiber suspension is 0.67wt%, and the content of the surfactant is 0.25wt%.

[0045] The aerogel with orange segment pores finally obtained is as follows Figure 2 , Figure 3 As shown; aerogels with orange peel pores can be used as drug sustained-release materials, catalytic carriers, bone repair materials or gas separation materials.

[0046] Example 2

[0047] A method for preparing an aerogel having orange segment pores, the specific steps are as follows:

[0048] (1) Preparation of raw materials;

[0049] Hydrophilic fiber material: cellulose fiber, water contact angle of 20° to 90°, shear stiffness of 10 to 20, aspect ratio of 1 to 10;

[0050] Hydrophobic fiber material: polycaprolactone fiber, water contact angle of 130° to 150°, shear stiffness of 10 to 12, aspect ratio of 40 to 80;

[0051] Surfactant: potassium lauryl ether phosphate, CAS number 58318-92-6;

[0052] water;

[0053] (2) The hydrophilic fiber material, the hydrophobic fiber material and the surfactant are dispersed in water, and the fiber suspension is obtained by shearing with a shearing machine (shear rate of 20000 rpm), and the fiber suspension is allowed to stand at -70°C (supercooling degree of 7°C) for 6 hours, and freeze-dried (temperature of -50°C, pressure of 20 Pa, time of 36 hours) to obtain an aerogel;

[0054] The mass ratio of the hydrophilic fiber material to the hydrophobic fiber material is 3:1; the content of the hydrophilic fiber material in the fiber suspension is 0.75wt%, and the content of the surfactant is 1wt%.

[0055] The aerogel with orange segment pores finally prepared can be used as a drug sustained-release material, a catalytic carrier, a bone repair material or a gas separation material.

[0056] Example 3

[0057] A method for preparing an aerogel having orange segment pores, the specific steps are as follows:

[0058] (1) Preparation of raw materials;

[0059] Hydrophilic fiber material: nylon, water contact angle is 30°~75°, shear stiffness is 10~15, aspect ratio is 5~10;

[0060] Hydrophobic fiber material: polylactic acid fiber, water contact angle of 100° to 130°, shear stiffness of 10 to 15, aspect ratio of 40 to 80;

[0061] Surfactant: Lauramidopropyl hydroxysulfobetaine, CAS No. 13197-76-7;

[0062] water;

[0063] (2) The hydrophilic fiber material, the hydrophobic fiber material and the surfactant are dispersed in water, and the fiber suspension is obtained by shearing with a shearing machine (shear rate of 25000 rpm), and the fiber suspension is allowed to stand at -196 ° C (supercooling degree of 8 ° C) for 0.2 h, and freeze-dried (temperature of -60 ° C, pressure of 40 Pa, time of 48 h) to obtain an aerogel;

[0064] The mass ratio of the hydrophilic fiber material to the hydrophobic fiber material is 4:1; the content of the hydrophilic fiber material in the fiber suspension is 0.8wt%, and the content of the surfactant is 2wt%.

[0065] The aerogel with orange segment pores finally prepared can be used as a drug sustained-release material, a catalytic carrier, a bone repair material or a gas separation material.

[0066] Example 4

[0067] A method for preparing an aerogel having orange segment pores is basically the same as that in Example 3, except that no surfactant is added in step (2).

[0068] The aerogel with orange segment pores finally prepared can be used as a drug sustained-release material, a catalytic carrier, a bone repair material or a gas separation material.

Claims

1. A method for preparing an aerogel having orange segment pores, characterized in that: The hydrophilic fiber material and the hydrophobic fiber material are dispersed in water, and after being sheared by a shearing machine to obtain a fiber suspension, the fiber suspension is frozen until completely frozen, and then freeze-dried to obtain an aerogel; The fiber suspension also contains 0.25 to 2 wt% of a surfactant; The water contact angle of the hydrophilic fiber material is 20° to 90°, the shear stiffness is 10 to 20, and the aspect ratio is ≤10; the water contact angle of the hydrophobic fiber material is 100° to 150°, the shear stiffness is 10 to 20, and the aspect ratio is ≥40; the mass ratio of the hydrophilic fiber material to the hydrophobic fiber material is 2 to 4:1; the shear rate of the shearing machine is 15000 to 25000 rpm; the supercooling degree during freezing is ≥5.5°C.

2. The method for preparing an aerogel having orange segment pores according to claim 1, characterized in that: The aspect ratio of the hydrophilic fiber material is 1-10; the aspect ratio of the hydrophobic fiber material is 40-80.

3. The method for preparing an aerogel having orange segment pores according to claim 1, characterized in that: The hydrophilic fiber material is cellulose fiber, cellulose derivative fiber or nylon.

4. The method for preparing an aerogel having orange segment pores according to claim 1, characterized in that: The hydrophobic fiber material is thermoplastic polyurethane fiber, polylactic acid fiber or polycaprolactone fiber.

5. The method for preparing an aerogel having orange segment pores according to claim 1, characterized in that: In the fiber suspension, the content of the hydrophilic fiber material is 0.67-0.8wt%.

6. The method for preparing an aerogel having orange segment pores according to claim 1, characterized in that: Freezing the fiber suspension until it is completely frozen means leaving the fiber suspension at -50 to -196°C for 0.2 to 8 hours.

7. An aerogel having orange segment pores, characterized in that: The aerogel is prepared by the method for preparing an aerogel having orange segment pores as described in any one of claims 1 to 6.

8. The use of an aerogel having orange segment pores as claimed in claim 7, characterized in that: Used as drug sustained-release material, catalytic carrier, bone repair material or gas separation material.

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