Acoustic compounding material, preparation method thereof, loudspeaker module and electronic device

Abstract

The application provides an acoustic capacity-increasing material, a preparation method thereof, a loudspeaker module and electronic equipment. The acoustic capacity-increasing material comprises a host carrier and a COF material, the host carrier has mesopores and macropores; the COF material is loaded in and / or embedded in the pore structure of the host carrier; the COF material has three-dimensional channels with a pore diameter not less than 0.4 nm, and the channels are interconnected. The COF material and the host carrier have good bonding force, which can improve the mechanical properties of the host material and greatly reduce the water absorption of the host carrier. The application also provides a preparation method of the acoustic capacity-increasing material, which comprises immersing the host carrier in a solution of a COF material precursor, crystallizing, and obtaining the acoustic capacity-increasing material; the method does not include a calcination step. The acoustic capacity-increasing material provided by the application has a hierarchical pore structure, has good acoustic capacity-increasing effect, and can effectively improve the low-frequency effect of a loudspeaker.

Description

Technical Field

[0001] This invention relates to the field of loudspeaker manufacturing technology, and in particular to an acoustic capacity-enhancing material, its preparation method, and loudspeaker modules and electronic devices. Background Technology

[0002] COF material is one of the commonly used porous materials, but the water absorption and low-frequency improvement performance of COF material still need to be improved.

[0003] In the prior art, inorganic agglomerates can be used to make acoustically active products. These agglomerates have an average size of 50 μm-2 mm and contain a network of carbon or silicon dioxide and metal oxide particles embedded in the network. They can reduce the resonant frequency of acoustic devices in the frequency range of 50 Hz to about 1500 Hz.

[0004] There are also existing technologies for preparing virtual acoustic materials through in-situ emulsion synthesis. These methods typically use silicone as the silicon source and binder, alumina, aluminum hydroxide, fumed silica, etc., as structure modifiers, and nano- to micron-sized carbon black as a pore-forming agent. The silicone and other components are dissolved or uniformly dispersed using a low-boiling-point solvent, and then microspheres with a particle size ranging from 50 μm to 2 mm are prepared by suspension polymerization in an aqueous system containing surfactants. After high-temperature calcination in an aerobic environment to remove the pore-forming agent and hydrocarbon components, a white porous composite inorganic microsphere material is obtained. The resulting microsphere products with a particle size range of 50 μm to 1000 μm can significantly reduce the actual volume of loudspeakers without affecting their acoustic performance.

[0005] However, the aforementioned acoustic improvement materials have the following problems: In the above methods, the raw materials for preparing the improvement materials are usually porous oxide materials such as alumina and carbon dioxide. These porous materials are formed by carbonizing organic carbon under aerobic or anaerobic conditions to form a porous structure. During the carbonization process, the distribution of organic carbon is uncontrollable, and the formation of pores is greatly affected by the distribution of organic carbon. Therefore, the above methods cannot precisely control the distribution and orientation of the pore structure. In addition, oxides such as alumina and silicon dioxide cannot form crystalline substances during the above preparation process, and there is a lack of regularly distributed pore structure within these oxide structures. Summary of the Invention

[0006] To address the aforementioned problems, the present invention aims to provide an acoustic compatibility enhancement material, its preparation method, a speaker module, and electronic equipment. This acoustic compatibility enhancement material has a hierarchical porous structure, exhibiting good acoustic compatibility enhancement effects and effectively improving the low-frequency performance of the speaker.

[0007] To achieve the above objectives, the present invention provides an acoustic compatibilizing material comprising a host carrier and a COF (covalent organic framework compound) material, wherein the host carrier has a porous structure including mesopores and macropores, and the COF material is loaded in and / or embedded in the porous structure of the host carrier.

[0008] The COF material has three-dimensional channels, the pore size of which is not less than (greater than or equal to) 0.4 nm, and the channels are interconnected.

[0009] The aforementioned acoustic compatibilizer material has a parasitic structure. The COF material can be loaded and / or embedded in the porous structure of a parasitic carrier to form a parasitic structure. Because the COF material is loaded or embedded in the porous structure of the parasitic carrier, it provides support within the mesopores and macropores of the carrier, resulting in an acoustic compatibilizer material with higher mechanical strength than the parasitic carrier itself. Simultaneously, due to the relatively low atomic mass and well-developed porosity of its main elements, the COF does not significantly affect the density of the parasitic structure. Furthermore, the polar groups involved in the COF material can combine with the hydroxyl groups in the porous carbon of the parasitic carrier, increasing the bonding force between the COF and the carrier while reducing the water absorption rate of the parasitic structure. This parasitic structure allows the porous structures in the carrier and the COF material to synergistically enhance the adsorption and desorption capacity of the acoustic compatibilizer material for gas molecules, thereby significantly improving low-frequency performance. Moreover, the acoustic compatibilizer material with the parasitic structure already possesses a moldable appearance and suitable dimensions, eliminating the need for molding adhesives to form the acoustic compatibilizer material.

[0010] In some specific embodiments, the compressive strength of the acoustic compressive material is greater than or equal to 0.1N; further, the compressive strength can reach 1.4N or more.

[0011] In some specific embodiments, the density of the acoustic compatibilizing material is less than or equal to 0.8 g / cm³. 3 .

[0012] In some specific embodiments, the water absorption rate of the acoustic compatibilizing material is less than or equal to 11%, and may further be less than or equal to 5.0%.

[0013] In some specific implementations, the specific surface area of ​​the acoustic compatibilizing material is 2500-2900 m². 2 / g, which can be further increased to 2600-2900m 2 / g, and even further, it can be 2700-2900m 2 / g.

[0014] In the aforementioned acoustic compatibilizing materials, the host carrier generally has a porous structure, possessing at least mesopores and macropores. The mesopores provide channels for the flow of gas molecules and can also be used for the adsorption and desorption of gas molecules; the macropores can be used to load or grow COF materials, and can also work together with the mesopores to adsorb and desorb gas molecules to achieve a sound absorption effect, thus synergistically achieving acoustic compatibilization with the porous material. In some specific embodiments, the pore size of the mesopores of the host carrier is 2nm-50nm, and the pore size of the macropores of the host carrier is typically 50nm-20μm.

[0015] In the aforementioned acoustic compatibilizing materials, the host carrier may include porous carbon materials. Further, the porous carbon material may include one or more of the following: carbonized coconut shell, soft carbon, hard carbon (such as lignite), carbon molecular sieves, and functionalized activated carbon (such as alkaline-modified activated carbon), wherein the functionalized activated carbon may include alkaline-modified activated carbon.

[0016] In the aforementioned acoustic compatibilizing material, the host carrier can withstand temperatures above 200°C, thereby enabling the host carrier to withstand the crystallization temperature and crystallization process of the COF material, and preventing the structure of the host carrier from being affected by the crystallization process.

[0017] Among the aforementioned acoustic enhancement materials, COF materials with three-dimensional channel structures have a more developed pore structure. When the external pressure changes, they can quickly adsorb and desorb air, thereby expanding the virtual volume of the loudspeaker for acoustic enhancement and improving low-frequency acoustic performance.

[0018] In the aforementioned acoustic compatibilizing material, the COF material has three-dimensional channels, and the channels are interconnected.

[0019] In the aforementioned acoustic compatibilizing material, the COF material has micropores and / or mesopores, and the pore size in the COF material is greater than or equal to 0.4 nm; and the pores are interconnected, allowing gas molecules (mainly nitrogen molecules) to freely enter and exit the pores of the COF material, thereby achieving the acoustic compatibilizing effect.

[0020] Among the aforementioned acoustic compatibilizing materials, the COF material can possess a high specific surface area and a high air adsorption capacity. In some specific embodiments, the specific surface area of ​​the COF material can reach 300 m². 2 / g or higher, and can further reach 400m 2 / g or more or 500m 2 / g or higher, and even higher up to 800m 2 / g or more.

[0021] In the aforementioned acoustic compatibilizing materials, the COF material used in this invention generally has a high degree of crystallinity. Therefore, compared with amorphous materials, the COF material of this invention has a higher degree of structural order and more regularly distributed pores. In some specific embodiments, the crystallinity of the COF material can reach over 80%. The crystallinity is a relative crystallinity, which can be calculated based on the ratio of the total area of ​​the crystalline peaks to the total area of ​​all eluting peaks (the sum of the areas of crystalline peaks and amorphous peaks). The calculation formula is as follows:

[0022] Crystallinity (%) = ∑A crystalline / (∑A crystalline +∑A amorphous ), where A crystalline For the area of ​​the crystallization peak, A amorphous The area of ​​the amorphous peak.

[0023] In the aforementioned acoustic compatibilizing material, the COF has three-dimensional channels connected by N building nodes, where N ≥ 4. Specifically, N can be 4, 6, or 8, meaning the COF can include a three-dimensional channel structure constructed from four-, six-, or eight-connected building nodes. More specifically, the COF material includes, but is not limited to, one or more combinations of COF-102, COF-103, COF-105, COF-108, COF-202, COF-300, COF-302, and COF-505.

[0024] According to specific embodiments of the present invention, the mass ratio of the host carrier to the COF material can be 4:1 to 1:4, for example, specific values ​​such as 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, etc., and a range with any two of the above specific values ​​as endpoints. In some specific embodiments, the mass ratio of the host carrier to the COF material can be 2:1 to 1:2.

[0025] According to a specific embodiment of the present invention, the aforementioned acoustic capacitance-enhancing material can be used as a capacitance-enhancing material in a loudspeaker. This acoustic capacitance-enhancing material can increase the virtual volume within the loudspeaker and improve low-frequency performance.

[0026] The present invention also provides a method for preparing the above-mentioned acoustic compatibilizing material, comprising immersing a host carrier in a solution of a COF material precursor and crystallizing it to obtain the acoustic compatibilizing material; wherein, the preparation method does not include a calcination step.

[0027] In the above preparation method, the COF material precursor is the COF mother liquor, which contains raw materials for forming the COF material.

[0028] In the above preparation method, the COF material precursor generally includes a reagent with N-connected building blocks (or: multi-connected building block reagent), where N ≥ 4, for example, N can be 4, 6, or 8. Specifically, the reagent with N-connected building blocks may include two or more of the following: tetra(4-borate-phenyl)methane, n-butylsilanetriol, tetra(4-phenylamino)methane, 3,3',5,5'-tetraaldehyde-biphenyl, [1,1:3,1-terphenyl]-3,3,5,5-tetraaldehyde, aminotetraphenylporphyrin, 2,3,6,7,14,15-hexaaldehyde-phenyltriptene, tetra(4-pinarate-phenyl)methane, tetra(4-borate-phenyl)ethylene, and 3,3',5,5'-tetra(p-aminophenyl)-biphenyl.

[0029] In the above preparation method, the COF material precursor may further include a ligand, which reacts with a reagent having building blocks to form a COF. Specifically, the ligand may include one or a combination of two or more of the following: p-phenylenediamine, terephthalaldehyde, terephthalic acid, benzylenediamine, benzylenedialdehyde, 1,4-diiodo-2,5-dimethylbenzene, 4,4-dibromo-2,2-bipyridine, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, 1,3,5-tris(4-ethynylphenyl)benzene, 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine, and tris(4-ethynylphenyl)amine.

[0030] In the above preparation method, the particle size of the host carrier is usually controlled to be 30-50 mesh, for example, 30-40 mesh.

[0031] In the above preparation method, before immersing the COF material precursor solution, the preparation method may include a pretreatment operation on the host carrier.

[0032] When the host carrier is carbonized coconut shell, the pretreatment process may include: treating the host carrier at a high temperature of 450℃-800℃ for more than 2 hours (e.g., 4 hours) in a protective atmosphere. The protective atmosphere may be nitrogen, helium, etc. This pretreatment process will not significantly affect the distribution and orientation of the pores within the host carrier, but it can reduce the amount of water adsorbed by the host carrier and ensure that the host carrier is fully carbonized. The fully carbonized host carrier has a high degree of pore openness, almost completely open, and the porosity and surface area of ​​the host carrier are also improved, which is beneficial to increasing the loading capacity of the host carrier on the COF material. In some specific embodiments, the above pretreatment may further include: before the high-temperature treatment, subjecting the host carrier to a first sieving, ball milling, a second sieving, and drying process.

[0033] In the above preparation method, when the host carrier is hard carbon, the pretreatment process of the host carrier may include: drying the hard carbon (lignite, etc.) to remove moisture and volatile components, carbonizing it at high temperature in a protective atmosphere (such as nitrogen or helium), the carbonization temperature may be 1500℃ and the carbonization time may be 12h, crushing the carbonization product, first screening, ball milling, second screening, drying, and completing the pretreatment.

[0034] During the pretreatment process described above, the particle size of the colonized carrier obtained after ball milling can reach 30-50 mesh, and the irregular edges of the colonized carrier after ball milling are removed, resulting in an ellipsoidal or spherical shape. After the first sieving, particles with a particle size of 20-40 mesh can be obtained, and after the second sieving, particles with a particle size of 30-40 mesh can be obtained.

[0035] In the above preparation method, the crystallization conditions can be adjusted according to the type and degree of crystallinity of the COF material. The crystallization conditions can be 80℃-160℃ for 36h-120h. Generally, the crystallization temperature should not exceed 200℃ (i.e., the crystallization temperature is less than or equal to 200℃) to avoid changes in the pore structure of the host carrier during the crystallization process.

[0036] According to a specific embodiment of the present invention, the above preparation method may include:

[0037] Step 1, Pretreatment: The parasitic carrier is first sieved and then ball-milled. During the ball milling process, the shape of the carrier tends to be regular (such as spherical or ellipsoidal). The ball-milled parasitic carrier is then sieved a second time to obtain a parasitic carrier with a particle size of 30-50 mesh, and then dried (the conditions can be drying at 60℃ for 12 hours). The dried parasitic carrier is then subjected to high-temperature treatment at 450-800℃ for more than 2 hours (e.g., 4 hours) to obtain the pretreated parasitic carrier.

[0038] Step 2: Immerse the pretreated host carrier in a solution of the COF material precursor, stir to fully wet the host carrier, and crystallize at 80℃-160℃ for 36h-120h to obtain the acoustic compatibilizer material. No high-temperature treatment such as calcination is performed in step 2 of the above preparation process.

[0039] The present invention also provides a loudspeaker module comprising the aforementioned acoustic compatibility enhancement material. In some specific embodiments, the acoustic compatibility enhancement material can be filled, sprayed, or coated onto any location of the loudspeaker module to achieve multiple functions such as sound absorption and vibration damping.

[0040] According to a specific embodiment of the present invention, the acoustic compatibility enhancement material can be filled inside the speaker module. More specifically, a speaker can be disposed inside the resonant cavity of the speaker module, and the acoustic compatibility enhancement material is filled inside the resonant cavity of the speaker module. By filling the cavity of the speaker module with this acoustic compatibility enhancement material, the adsorption and desorption capacity for air can be improved, the virtual volume of the speaker can be expanded, and the low-frequency effect can be improved.

[0041] The appearance of the acoustic compressive material provided by this invention can be adjusted according to actual needs (such as the shape of the cavity filled by the material), specifically it can be granular, blocky, sheet-like, etc. For example, the appearance of the acoustic compressive material can be changed by means of bonding, etc., to present granular, blocky, sheet-like shapes, etc.

[0042] The present invention also provides an electronic device comprising the aforementioned speaker module. In some specific embodiments, the electronic device may be a smartphone, smartwatch, tablet computer, smart glasses, VR glasses, smart speaker, or laptop computer (especially a thin and light laptop computer), etc.

[0043] According to a specific embodiment of the present invention, the electronic device is provided with a sound output opening and a sound output channel, and the speaker module is acoustically coupled to the sound output opening through the sound output channel.

[0044] According to a specific embodiment of the present invention, the speaker module is integrally formed with the electronic device; or, the electronic device further includes a housing, and the speaker module is disposed within the internal space formed by the housing.

[0045] The beneficial effects of this invention include:

[0046] The acoustic compatibilizing material provided by this invention combines the advantages of the carrier material (light weight and high air adsorption capacity) and the regular channels and pore structure of the COF material by loading COF material into a porous host carrier. Because the COF material is loaded or embedded in the pore structure of the carrier, it provides support in the mesopores and macropores, resulting in higher mechanical strength than the host carrier. Simultaneously, due to the low atomic number of the main element and the well-developed porosity of COF, it does not significantly increase the density of the host structure. Furthermore, the polar groups involved in the COF material can combine with the hydroxyl groups in the porous carbon, increasing the bonding force between the host and the carrier while reducing the water absorption rate of the host structure. This acoustic compatibilizing material has a hierarchical pore structure, which facilitates air adsorption and desorption, significantly increasing the virtual volume of devices such as loudspeakers, thus providing acoustic compatibilization and improving low-frequency performance. It can replace existing zeolite materials as sound-absorbing materials. Moreover, the acoustic compatibilizing material provided by this invention is itself a molding material, eliminating the need for adhesives, improving the product's resistance to VOCs (volatile organic compounds), and making it environmentally friendly and safe. Attached Figure Description

[0047] Figure 1 This is a schematic diagram of the preparation process of the acoustic compatibilizing materials in Examples 1 to 3.

[0048] Figure 2 SEM image of the carbonized coconut shell used in Example 1.

[0049] Figure 3 The mesopore distribution diagram of the carbonized coconut shell in Example 1 is shown.

[0050] Figure 4 The macropore distribution diagram of the carbonized coconut shell used in Example 1.

[0051] Figure 5 This is a SEM image of the acoustic compatibilizing material in Example 1.

[0052] Figure 6 This is a mesoporous diagram of the acoustic compatibilizing material in Example 1.

[0053] Figure 7 This is a macropore distribution diagram of the acoustic compatibilizing material in Example 1.

[0054] Figure 8 The nitrogen adsorption-desorption curves and pore size distribution curves of the COF material in Comparative Example 1 are shown.

[0055] Figure 9 The image shows the XRD pattern of the COF material prepared in Comparative Example 1. Detailed Implementation

[0056] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0057] The commercially available carbonized coconut shells used in the following experiments were manufactured by Huayu Zhengda, and the model number was 1000 iodine value.

[0058] Preparation Example 1

[0059] This embodiment prepared a near-spherical carbonized coconut shell, and the preparation method is as follows:

[0060] Purchased carbonized coconut shells (also known as coconut shell charcoal) are sieved using a screen to obtain carbonized coconut shells with a particle size of 20-40 mesh. The 20-40 mesh carbonized coconut shells are then transferred to a stainless steel ball mill jar for ball milling. During the ball milling process, the irregular edges of the carbonized coconut shell particles are removed by friction and collision between the carbonized coconut shells, resulting in ellipsoidal or spherical carbonized coconut shell particles. The ball-milled carbonized coconut shells are then sieved again to obtain approximately spherical carbonized coconut shell particles with a particle size of 30-40 mesh. These particles are then dried in a 60℃ forced-air oven for 12 hours. The dried nearly spherical carbonized coconut shell particles are then placed in a room temperature desiccator for later use.

[0061] Preparation Example 2

[0062] This embodiment prepared a near-spherical carbonized coconut shell, and the preparation method is as follows:

[0063] Purchased carbonized coconut shells (also known as coconut shell charcoal) are sieved to obtain carbonized coconut shells with a particle size of 20-40 mesh. The 20-40 mesh carbonized coconut shells are then transferred to a stainless steel ball mill jar for ball milling. During the ball milling process, the irregular edges of the carbonized coconut shell particles are removed by friction and collision between the carbonized coconut shells, resulting in ellipsoidal or spherical carbonized coconut shell particles. The ball-milled carbonized coconut shells are then sieved to obtain approximately spherical carbonized coconut shell particles with a particle size of 30-40 mesh, and then dried in a 60℃ forced-air oven for 12 hours.

[0064] The dried, nearly spherical carbonized coconut shell particles were subjected to high-temperature nitrogen carbonization treatment under the following conditions: constant temperature of 800℃ with flowing nitrogen for 4 hours. High-temperature nitrogen carbonization treatment can remove adsorbed water molecules and small molecules from the carbonized coconut shell, and at the same time, it can fully carbonize the uncarbonized tissue. The carbonized coconut shells obtained by high-temperature nitrogen carbonization treatment were placed in a room temperature desiccator for later use.

[0065] Preparation Example 3

[0066] This embodiment prepares a near-spherical hard carbon material, and the preparation method is as follows:

[0067] Weigh 500.0g of lignite and bake it in a 120℃ forced-air oven for 6 hours to remove moisture and volatile components. Then, place it in a high-temperature roasting furnace and carbonize it in a nitrogen atmosphere at 1500℃ for 12 hours. After carbonization, crush it to obtain irregular hard carbon blocks. Sieve the irregular hard carbon blocks to obtain hard carbon particles with a particle size of 20-40 mesh. Transfer the 20-40 mesh hard carbon particles to a stainless steel ball mill jar for ball milling. During ball milling, the friction and collision between the hard carbon particles remove irregular edges, resulting in ellipsoidal or spherical hard carbon particles. Sieve the ball-milled hard carbon particles again to obtain approximately spherical hard carbon particles with a particle size of 30-40 mesh, and then dry them in a 60℃ forced-air oven for 12 hours. Place the dried hard carbon particles in a room-temperature desiccator for later use.

[0068] Example 1

[0069] This embodiment provides an acoustic compatibilizing material, such as Figure 1 As shown, the preparation method of this acoustic compatibilizer material includes:

[0070] All experimental operations in this embodiment were carried out in a vacuum glove box and nitrogen environment, with a borosilicate glass tube used as the reaction vessel.

[0071] The specific experimental procedure includes:

[0072] 1. Weigh 200.0 mg of carbonized coconut shell from Preparation Example 1 and place it in a borosilicate glass tube with an outer diameter of 20 mm and a wall thickness of 3 mm.

[0073] 2. Weigh 0.25 mmol (125.0 mg) of tetra(4-boratephenyl)methane and place it in the borosilicate glass tube from step 1; then, add 0.625 mmol (83.5 mg) of n-butylsilanetriol and 4.2 mL of a mixed solution of toluene and dioxane as solvents (volume ratio of the two is 2:1);

[0074] 3. The mixed reaction materials in the glass tube were flash-frozen using liquid nitrogen (-77K) and pressurized to about 20Pa. The glass tube was then sealed at high temperature, and the length of the sealed glass tube was about 12cm. The glass tube was then placed in a 30℃ water bath to thaw and stir. After stirring for 10 minutes, the glass tube was placed in a 120℃ oven for crystallization for 3 days.

[0075] 4. After crystallization, the reaction system was centrifuged and washed with 50 ml of acetone. The centrifugation and washing operations were repeated twice. Then, vacuum was applied to remove the acetone. The acoustic compatibilizer material inhabited by COF-202 was obtained.

[0076] In this embodiment, the mass percentage of COF material can be calculated by the mass change of carbonized coconut shell before and after crystallization. The COF material is calculated to account for 47.34% wt of the acoustic compatibilizer material product. Based on XRD characterization results, the crystallinity of COF-202 is calculated to be 95%.

[0077] Example 2

[0078] This embodiment provides an acoustic compatibilizing material. The preparation method of this embodiment is basically the same as that of Example 1, except that 200.0 mg of carbonized coconut shell from Preparation Example 2 is used instead of 200.0 mg of carbonized coconut shell from Preparation Example 1. In this embodiment, the COF material accounts for 47.31% wt% of the acoustic compatibilizing material product. The crystallinity of COF-202 is calculated to be 96% based on XRD characterization results.

[0079] Example 3

[0080] This embodiment provides an acoustic compatibilizing material. The preparation method of this embodiment is basically the same as that of Example 1, except that 200.0 mg of near-spherical hard carbon from Preparation Example 3 is used instead of 200.0 mg of carbonized coconut shell from Preparation Example 1. In this embodiment, the COF material accounts for 47.54% wt% of the acoustic compatibilizing material product. Based on the XRD characterization results, the crystallinity of COF-202 is 96%.

[0081] Tests showed that the densities of the acoustic compatibilizing materials in Examples 1, 2, and 3 were 0.692 g / cm³. 3 0.687 g / cm 3 0.701 g / cm 3 The specific surface areas of the acoustic compatibilizing materials in Examples 1, 2, and 3 are 2763 m², respectively. 2 / g、2797m 2 / g、2650m 2 / g.

[0082] Comparative Example 1

[0083] This comparative example provides a method for preparing COF-202 material. The material preparation process (including the reagents and amounts used, and crystallization conditions) is the same as steps 1 to 4 in Example 1, but without introducing carbonized coconut shell. According to... Figure 8 The BET test results shown indicate that the specific surface area of ​​COF-202 material is 2643 m². 2 / g.

[0084] The porous carbon prepared in Preparation Example 1, Preparation Example 2, and Preparation Example 3, as well as the porous carbon (carbonized coconut shell, hard carbon) used in Examples 1 to 3, all have mesopores and macropores. The mesopore pore size is 2nm-50nm, and the macropore pore size is 50nm-20μm.

[0085] Figure 1 The flowcharts for the preparation of parasitic acoustic compatibilizers in Examples 1 to 3 are shown.

[0086] Figure 2 The image shows a SEM image of the carbonized coconut shell from Example 1. It can be seen that after ball milling, the carbonized coconut shell exhibits a near-spherical shape and a porous structure with both mesopores and macropores on its surface.

[0087] Figure 3 The image shows the mesopore size distribution of the carbonized coconut shell used in Example 1. It can be seen that the mesopore size is clearly distributed in the range of 10 nm to 20 nm.

[0088] Figure 4 The image shows the macropore size distribution of the carbonized coconut shell used in Example 1. It can be seen that the macropore size is clearly distributed in the range of 0.6 μm to 5 μm.

[0089] The above data proves that the carbonized coconut shell in the preparation example has macropores and mesopores.

[0090] Figure 5 The image shows a SEM image of the parasitic acoustic compatibilizer material from Example 1. It can be seen that after the COF material enters the carbonized coconut shell, the mesopores and macropores on the surface of the carbonized coconut shell become smaller or disappear. This is because after the COF material crystallizes, it fills these pores, causing the mesopores and macropores on the surface of the carbonized coconut shell to become smaller or disappear.

[0091] Figure 6 The image shows the mesopore size distribution of the acoustic compatibilizer material in Example 1. It can be seen that the mesopore size is clearly distributed in the range of 2nm-20nm, and there are ultramicroporous structures near the 1.6nm pore size.

[0092] Figure 7 This is a diagram showing the macropore size distribution of the acoustic compatibilizer material in Example 1. It can be seen that the macropore size is clearly distributed in the range of 0.1 μm to 5 μm.

[0093] Figure 8 The nitrogen adsorption-desorption curve and micropore size distribution curve are for the crystallized product COF-202 in Comparative Example 1. Figure 8 It can be seen that the COF-202 material has a high specific surface area, reaching 2560 m². 2 The content is above / g, and the micropore size is around 1.1nm.

[0094] Figure 9 The image shows the XRD pattern of the crystallized product, COF-202, in Comparative Example 1. "COF-202" in the image represents the simulated structural XRD result from the literature. It can be seen that this COF material possesses a typical COF-202 topology and high crystallinity, exceeding 90%.

[0095] Test Example 1

[0096] This test example provides acoustic test results for the products prepared in Preparation Examples 1 to 3, Examples 1 to 3, and Comparative Example 1.

[0097] The test samples were filled into a standard acoustic cavity for acoustic performance testing. The filling amount for each test sample was 300 mg, and the volume of the standard acoustic cavity was 1.0 cubic centimeter. The structure of the standard acoustic cavity was the acoustic material testing fixture assembly described in CN215072984U (Invention title "An Acoustic Material Testing Fixture Assembly", application number 202120796674.2), the full text of which is incorporated herein by reference. The test signal was the analog program signal or pink noise signal specified in GB / T 12060.1 "Acoustic System Equipment Part 1: Overview". The test results are summarized in Table 1.

[0098] Table 1

[0099]

[0100] As shown in Table 1, compared to porous carbon alone and COF material alone, the porous carbon loaded with COF material in this invention, as an acoustic compatibilizer, exhibits better improvement in low-frequency performance. This indicates that porous carbon and COF material can synergistically improve low-frequency performance.

[0101] Furthermore, compared to acoustic compatibilizers made from carbonized coconut shells that have not undergone high-temperature treatment, acoustic compatibilizers prepared using high-temperature treated carbonized coconut shells as a carrier have a better effect on improving low-frequency performance.

[0102] Test Example 2

[0103] This test example provides test results for the mechanical strength of the products prepared in Preparation Examples 1 to 3 and Examples 1 to 3.

[0104] The test was conducted using a computer-controlled spring tension and compression testing machine. Before the test, the range of the testing equipment was adjusted to 0.005N to 5N, and the accuracy was 0.001N. At room temperature, five samples of the same particle size were placed in the test pressure plate. The particle deformation was set to 5% of the particle size, and the descent speed was 5mm / min. After the set deformation was reached, the test was ended, and the data was saved. The compressive strength results are shown in Table 2.

[0105] Table 2

[0106] sample Preparation Example 1 Preparation Example 2 Preparation Example 3 Example 1 Example 2 Example 3 Test 1 1.052 1.063 1.088 1.452 1.561 1.564 Test 2 1.061 1.064 1.091 1.456 1.562 1.571 Test 3 1.060 1.057 1.087 1.458 1.565 1.567 Test 4 1.052 1.049 1.092 1.454 1.547 1.562 Test 5 1.049 1.055 1.090 1.449 1.553 1.553 Average / N 1.055 1.058 1.090 1.454 1.558 1.563

[0107] As shown in Table 2, porous carbon loaded with COF exhibits higher mechanical strength compared to porous carbon materials alone. This is mainly because the COF material, after entering the macropores or mesopores of the porous carbon, can act as a filler and support, thereby enhancing the mechanical strength of the parasitic structure. The pores of coconut shell carbon treated with high-temperature nitrogen are even more open, allowing more COF material to fill and embed within the macropores of the coconut shell carbon, resulting in a greater increase in mechanical strength.

[0108] Test Example 3

[0109] This test example provides the test results for the water absorption rate of the prepared products in Preparation Examples 1 to 3, Examples 1 to 3, and Comparative Example 1.

[0110] Before the test, weigh 2g ± 0.001g (M1) of the sample to be tested and spread it evenly in a petri dish; adjust the test chamber to 85℃ and humidity to 85%RH, maintain for 24h, remove the sample, weigh it using an analytical balance (M2) and record it; calculate the water absorption rate of the sample to be tested based on the change in mass before and after the test. The test results are shown in Table 3.

[0111] Table 3

[0112]

[0113]

[0114] As shown in Table 3, porous carbon loaded with COF material exhibits a lower water absorption rate compared to porous carbon materials alone. This is mainly because the COF material (Comparative Example 1) itself has a very low water absorption rate. After the COF material enters the macropores or mesopores of the porous carbon, it not only fills and supports the porous carbon material but also enhances the hydrophobicity of the porous carbon surface. The water absorption rate of coconut shell carbon treated with high-temperature nitrogen gas (Preparation Example 2) is higher than that of carbonized coconut shell without high-temperature treatment (Preparation Example 1). This is mainly because after high-temperature nitrogen gas treatment, the adsorbed water molecules are removed, exposing the adsorption sites. Under high humidity, more water molecules are adsorbed, thus exhibiting a higher water absorption rate. The water absorption rate of porous carbon materials of different types all showed a significant reduction after the introduction of COF material.

[0115] The above results show that by loading COF material with three-dimensional channels into porous carbon material, the present invention can combine the advantages of carrier material with light weight, large air adsorption capacity and low water absorption rate, as well as the advantages of porous material with regular channels and pore structure, thus systematically improving the low-frequency acoustic effect.

Claims

1. An acoustic compatibilizing material, comprising a host carrier and a COF material, wherein the host carrier has a porous structure comprising mesopores and macropores; The COF material is loaded and / or embedded in the porous structure of the host carrier; the COF material has three-dimensional channels, the pore size of the three-dimensional channels in the COF material is greater than or equal to 0.4 nm, and the three-dimensional channels are interconnected. The mesopores of the host carrier have a pore size of 2 nm-50 nm, and the macropores of the host carrier have a pore size of 50 nm-20 μm; the macropores of the host carrier are used for loading or growing COF materials. The host carrier includes porous carbon materials; The porous carbon material includes one or more of the following: carbonized coconut shell, soft carbon, hard carbon, carbon molecular sieve, functionalized activated carbon, and alkaline-modified activated carbon. The host carrier is a pre-treated host carrier, and the pre-treatment process includes: The host carrier was treated at a high temperature of 450℃-800℃ for more than 2 hours in an inert atmosphere.

2. The acoustic compatibilizer material according to claim 1, wherein, The host carrier can withstand temperatures above 200°C.

3. The acoustic compatibilizer material according to claim 1, wherein, The COF material has micropores and / or mesopores.

4. The acoustic compatibilizer material according to claim 1, wherein, The COF material has three-dimensional channels connected by N construction nodes, where N≥4.

5. The acoustic compatibilizer material according to claim 4, wherein, N is 4, 6, or 8.

6. The acoustic compatibilizer material according to claim 4, wherein, The COF material includes one or more of COF-102, COF-103, COF-105, COF-108, COF-202, COF-300, COF-302, and COF-505.

7. The acoustic compatibilizer material according to claim 1, wherein, The mass ratio of the host carrier to the COF material is 4:1 to 1:

4.

8. The acoustic compatibilizer material according to claim 7, wherein, The mass ratio of the host carrier to the COF material is 2:1 to 1:

2.

9. The acoustic compatibilizer material according to claim 1, wherein, The compressive strength of the acoustic compressive material is greater than or equal to 0.1 N.

10. The acoustic compatibilizer material according to claim 9, wherein, The compressive strength of the acoustic compressive material is greater than or equal to 1.4 N.

11. The acoustic compatibilizer material according to claim 1, wherein, The density of the acoustic compatibilizing material is less than or equal to 0.8 g / cm³. 3 ; And / or, the specific surface area of ​​the acoustic compatibilizing material is 2500-2900 m². 2 / g.

12. The acoustic compatibilizer material according to claim 1, wherein, The water absorption rate of the acoustic compatibilizing material is less than or equal to 5.0%.

13. A method for preparing the acoustic compatibilizing material according to any one of claims 1-12, comprising: The host carrier is immersed in a solution of COF material precursor and crystallized to obtain the acoustic compatibilizing material. The preparation method does not include a calcination step.

14. The preparation method according to claim 13, wherein, The COF material precursor includes a reagent with N-connected building blocks, where N ≥ 4.

15. The preparation method according to claim 14, wherein, The COF material precursor includes two or more combinations of tetra(4-boronylphenyl)methane, n-butylsilanetriol, tetra(4-phenylamino)methane, 3,3',5,5'-tetraaldehyde biphenyl, [1,1:3,1-terphenyl]-3,3,5,5-tetraaldehyde, aminotetraphenylporphyrin, 2,3,6,7,14,15-hexaaldehyde phenyltriptene, tetra(4-pinarate phenyl)methane, tetra(4-boronylphenyl)ethylene, and 3,3',5,5'-tetra(p-aminophenyl)-biphenyl.

16. A loudspeaker module, wherein, The speaker module includes the acoustic compressive material as described in any one of claims 1-12.

17. The loudspeaker module according to claim 16, wherein, The acoustic enhancement material is filled inside the speaker module.

18. The loudspeaker module according to claim 16, wherein, The speaker module has a speaker installed in its resonant cavity, and the acoustic capacity-enhancing material is filled in the resonant cavity of the speaker module.

19. An electronic device comprising the speaker module according to any one of claims 16-18.

20. The electronic device according to claim 19, wherein, The electronic device is a smartphone, smartwatch, tablet, smart glasses, VR glasses, smart speaker, or laptop.

21. The electronic device according to claim 19, wherein, The electronic device is provided with a sound output opening and a sound output channel, and the speaker module is acoustically coupled to the sound output opening through the sound output channel.

22. The electronic device according to claim 19, wherein, The speaker module is integrally formed with the electronic device; or, the electronic device further includes a housing, and the speaker module is disposed within the internal space formed by the housing.

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