Composite material capable of releasing negative oxygen ions as well as preparation method and application of composite material

Abstract

The invention belongs to the technical field of negative oxygen ion materials, and particularly relates to a composite material capable of releasing negative oxygen ions as well as a preparation method and application thereof. The composite material capable of releasing the negative oxygen ions is prepared from the following raw materials: polypropylene, modified titanium dioxide, modified cerium dioxide and modified microcapsule salt, the modified titanium dioxide is obtained by treating silicon dioxide coated titanium dioxide by adopting a coupling agent and plasma in sequence; the modified cerium dioxide is obtained by treating cerium dioxide with a coupling agent; the cerium dioxide comprises cerium dioxide containing oxygen vacancies; the modified microcapsule salt is obtained by treating microcapsule salt by adopting plasma; the microcapsule salt has a core-shell structure, a core material of the core-shell structure comprises calcium salt, and a shell layer of the core-shell structure comprises silicon dioxide. Specific modified titanium dioxide, modified cerium dioxide and modified microcapsule salt are adopted and have a synergistic effect, so that efficient, continuous and stable release of negative oxygen ions can be realized.

Description

Technical Field

[0001] This invention belongs to the field of negative oxygen ion materials technology, and specifically relates to a composite material that releases negative oxygen ions, its preparation method, and its application. Background Technology

[0002] Negative oxygen ions, as negatively charged oxygen molecules or atoms, play an important role in improving air quality, promoting human health, and inhibiting the growth of bacteria and mold. Numerous studies have shown that the concentration of negative oxygen ions in the air is closely related to human comfort; they can regulate the nervous system, improve blood circulation, and enhance immunity, demonstrating broad prospects for health applications.

[0003] Currently, the main pathways for generating negative oxygen ions include the following: 1) Natural release: In environments such as forests, waterfalls, and beaches, a certain concentration of negative oxygen ions can be generated due to water vapor collisions or sunlight. However, this method is limited by the natural environment, and the concentration and duration are uncontrollable. 2) Corona discharge or high-voltage ionization: Air molecules are ionized by an external electric field, instantly generating a high concentration of negative oxygen ions. However, this method requires complex equipment, consumes a lot of energy, and may produce byproducts such as ozone, which is not conducive to long-term use. 3) Release from functional materials: In recent years, natural minerals such as tourmaline and radium have been widely used as negative oxygen ion releasing materials due to their spontaneous polarization and piezoelectric effect. These materials can release negative oxygen ions at room temperature, but the release amount is limited.

[0004] Therefore, it is of great significance to provide a composite material with good negative oxygen ion release capability. Summary of the Invention

[0005] The present invention aims to solve one or more technical problems existing in the prior art, and at least provide a beneficial solution. Specifically, the present invention provides a composite material for releasing negative oxygen ions, which has good negative oxygen ion release quantity and release stability.

[0006] The inventive concept of this invention: The raw materials for preparing the composite material that releases negative oxygen ions include polypropylene, modified titanium dioxide, modified cerium dioxide, and modified microcapsule salt; the modified titanium dioxide is obtained by sequentially treating titanium dioxide coated with silica using a coupling agent and plasma; the modified cerium dioxide is obtained by treating cerium dioxide with a coupling agent; the cerium dioxide includes cerium dioxide containing oxygen vacancies; the modified microcapsule salt is obtained by treating microcapsule salt with plasma; the microcapsule salt has a core-shell structure, the core material of the core-shell structure is composed of calcium salt, and the shell layer of the core-shell structure is composed of silica.

[0007] This invention utilizes specific modified titanium dioxide, modified cerium dioxide, and modified microcapsule salt. Through the synergistic effect of these three components, a continuous electron generation-transfer-migration pathway can be formed, thereby achieving efficient and sustained release of negative oxygen ions.

[0008] First, the cerium dioxide in the modified cerium dioxide is cerium dioxide containing oxygen vacancies (CeO). 2-x The presence of oxygen vacancies creates electron-rich states in the crystal lattice, which can release active electrons under thermal disturbances or weak light conditions. These electrons can combine with oxygen molecules in the air to generate O2. - Cerium dioxide, containing a single oxygen vacancy, is the main source of electrons for negative oxygen ions in the system. However, electrons in cerium dioxide with a single oxygen vacancy are prone to rapid recombination, have limited migration paths, and are difficult to release continuously and stably.

[0009] Secondly, after SiO2 coating, coupling agent treatment, and plasma treatment, the modified titanium dioxide forms an activated layer rich in polar groups and surface defects. On the one hand, the SiO2 coating structure can inhibit electron-hole recombination on the TiO2 surface and improve electron lifetime; on the other hand, the surface defects and polar functional groups introduced by plasma help to build electron hopping channels between the filler and the polymer matrix, thereby promoting electron transfer between the inorganic phase and the polymer interface. This modified titanium dioxide mainly plays a role in electron transfer and amplification in the system, enabling electrons released from oxygen-vacant cerium dioxide to migrate more effectively to the material surface to participate in oxygen molecule reduction reactions.

[0010] Furthermore, the modified microcapsule salt consists of calcium salt microcapsules coated with a SiO2 shell. CaCl2 exhibits significant hygroscopicity, forming a stable adsorbed water layer at the material's micro-interface when ambient humidity increases. This water layer, acting as an ion transport medium, significantly reduces the interfacial barrier for electron migration, increasing the efficiency of electron migration to the material surface and enhancing electron migration. Simultaneously, the SiO2 shell, on the one hand, restricts the direct dissolution of the calcium salt, ensuring structural stability, and on the other hand, provides a polar interface, facilitating the formation of continuous charge transport paths, further enhancing electron migration.

[0011] Therefore, under the coupled effects of ambient light, heat, and humidity, modified cerium dioxide provides the electron source, modified titanium dioxide constructs the electron transport pathway, and modified microencapsulated salt further reduces the migration barrier through the interfacial water film formed by hygroscopic absorption. These three components form a synergistic electron migration network within the material, making it easier for electrons to reach the material surface and combine with oxygen molecules to generate negative oxygen ions. This multiphase synergistic mechanism significantly improves the peak release and sustained stability of negative oxygen ions, demonstrating superior performance compared to single-component systems.

[0012] Therefore, a first aspect of the present invention provides a composite material that releases negative oxygen ions.

[0013] Specifically, the raw materials for preparing the composite material that releases negative oxygen ions include polypropylene, modified titanium dioxide, modified cerium dioxide, and modified microcapsule salt; The modified titanium dioxide is obtained by sequentially treating titanium dioxide coated with silica with a coupling agent and plasma. The modified cerium dioxide was obtained by treating cerium dioxide with a coupling agent; The cerium dioxide includes cerium dioxide containing oxygen vacancies; The modified microcapsule salt was obtained by treating the microcapsule salt with plasma; The microcapsule salt has a core-shell structure, wherein the core material of the core-shell structure comprises calcium salt, and the shell layer of the core-shell structure comprises silicon dioxide.

[0014] Preferably, the coupling agent comprises a silane coupling agent.

[0015] Preferably, the plasma includes oxygen plasma.

[0016] Preferably, the calcium salt comprises calcium chloride.

[0017] Preferably, the raw materials for preparing the composite material that releases negative oxygen ions include, by mass percentage, 70-85% polypropylene, 4-10% modified titanium dioxide, 6-10% modified cerium dioxide, and 4-10% modified microencapsulated salt.

[0018] Preferably, the raw materials for preparing the composite material that releases negative oxygen ions also include a lubricant.

[0019] Preferably, the raw materials for preparing the composite material that releases negative oxygen ions include, by mass percentage, 70-85% polypropylene, 4-10% modified titanium dioxide, 6-10% modified cerium dioxide, 4-10% modified microencapsulated salt, and 1-3% lubricant.

[0020] Preferably, the lubricant comprises zinc stearate (ZnSt).

[0021] A second aspect of the present invention provides a method for preparing the composite material that releases negative oxygen ions as described in the first aspect of the present invention.

[0022] Specifically, the preparation method of the composite material that releases negative oxygen ions includes the following steps: The raw materials are mixed, melt-blended, and extruded to obtain the final product.

[0023] Preferably, a twin-screw extruder is used for the melt blending and extrusion.

[0024] Preferably, the melt blending temperature is 180-250℃, and the melt blending time is 20-60 min.

[0025] Preferably, the extrusion temperature is 180-250°C.

[0026] Preferably, the screw speed of the twin-screw extruder is 10-30 r / min.

[0027] Preferably, the extrusion process further includes a pelletizing process.

[0028] Preferably, the method for preparing the modified titanium dioxide includes the following steps: (1) Mix titanium dioxide and solvent; then add organosilicon compound, water and catalyst, react to obtain titanium dioxide coated with silica; (2) The titanium dioxide coated with silicon dioxide and the coupling agent are mixed and then subjected to plasma treatment to obtain the product.

[0029] Preferably, in step (1), the solvent includes ethanol; more preferably, the ethanol is anhydrous ethanol.

[0030] Preferably, in step (1), the particle size of the titanium dioxide is 50-200 nm.

[0031] Preferably, in step (1), the solid-liquid mass ratio of the titanium dioxide and the solvent is 1:(10-15); for example, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, etc.

[0032] Preferably, in step (1), the mixture is ultrasonically dispersed for 10-15 minutes.

[0033] Preferably, in step (1), the organosilicon compound includes alkoxysilane; more preferably, the alkoxysilane includes tetraethoxysilane (TEOS).

[0034] Preferably, in step (1), the volume ratio of the organosilicon compound to the solvent is 1:(8-12); for example, 1:8, 1:9, 1:10, 1:11, 1:12, etc.

[0035] Preferably, in step (1), the molar ratio of water to organosilicon compound is (2-4):1; for example, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, etc.

[0036] Preferably, in step (1), the catalyst comprises an acid catalyst; more preferably, the acid catalyst comprises hydrochloric acid.

[0037] Preferably, an acid catalyst is added to adjust the pH to 2-3.

[0038] Preferably, in step (1), the reaction is carried out under magnetic stirring, the reaction temperature is room temperature, and the reaction time is 30-60 min; for example, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, etc.

[0039] Preferably, the reaction is followed by a drying process.

[0040] Preferably, the drying temperature is 80-100℃ and the drying time is 1-2 hours; for example, the drying temperature is 80℃, 85℃, 90℃, 95℃, 100℃, etc., and the drying time is 1 hour, 1.5 hours, 2 hours, etc.

[0041] Specifically, after the reaction, the silica sol undergoes in-situ hydrolysis and condensation on the surface of titanium dioxide to form a continuous coating layer, resulting in titanium dioxide coated with silica.

[0042] Preferably, in step (2), the coupling agent includes a silane coupling agent; more preferably, the silane coupling agent includes γ-(2,3-epoxypropoxy)propyltrimethoxysilane (KH-560).

[0043] Preferably, in step (2), the amount of the coupling agent is 0.5-1 wt% of the amount of titanium dioxide coated with silica obtained in step (1); for example, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, etc.

[0044] Preferably, in step (2), the silica-coated titanium dioxide and the coupling agent are mixed, stirred in an organic solvent, and then dried; finally, plasma treatment is performed.

[0045] Preferably, the organic solvent includes ethanol.

[0046] Preferably, the mixing and stirring time in the organic solvent is 15-20 minutes.

[0047] Preferably, the plasma treatment power is 90-110W, and the plasma treatment time is 45-60s; for example, the plasma treatment power is 90W, 95W, 100W, 105W, 110W, etc., and the plasma treatment time is 45s, 50s, 55s, 60s, etc.

[0048] Specifically, plasma treatment enhances the surface polarity of the powder and its interfacial affinity with the polymer matrix, thereby constructing a continuous interfacial charge transfer channel between the inorganic filler and the polypropylene matrix. This reduces the migration barrier of electrons at the phase interface, improves the electron transfer efficiency from semiconductor particles to the material surface, and thus enhances the stability of negative oxygen ion generation and release.

[0049] Preferably, the method for preparing the modified cerium dioxide includes the following steps: Cerium dioxide and solvent are mixed; then a coupling agent is added, and the mixture is reacted to obtain the product.

[0050] Preferably, in the preparation process of the modified cerium dioxide, the solvent includes ethanol; more preferably, the ethanol includes anhydrous ethanol.

[0051] Preferably, the solid-liquid mass ratio of cerium dioxide to solvent is 1:(10-15); for example, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, etc.

[0052] Preferably, the mixture is then ultrasonically dispersed for 5-10 minutes; for example, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, etc. Preferably, the coupling agent comprises a silane coupling agent; more preferably, the silane coupling agent comprises 3-aminopropyltriethoxysilane (KH550).

[0053] Preferably, the amount of the coupling agent is 0.8-1.2 wt% of the amount of cerium dioxide; for example, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, 1.2 wt%, etc.

[0054] Preferably, in the preparation process of the modified cerium dioxide, the reaction temperature is room temperature and the reaction time is 20-30 min; for example, 20 min, 25 min, 30 min, etc.

[0055] Specifically, the reaction is stirred during the process to allow the coupling agent to be fully adsorbed and undergo a condensation reaction.

[0056] Preferably, the preparation process of the modified cerium dioxide further includes a separation and drying process after the reaction.

[0057] Preferably, the separation is performed by either centrifugation or filtration.

[0058] Preferably, the drying temperature is 55-65℃ and the drying time is 1-2 hours; for example, the drying temperature is 55℃, 60℃, or 65℃, and the drying time is 1 hour, 1.5 hours, or 2 hours, etc.

[0059] Specifically, through modification treatment, the dispersion and response stability of cerium dioxide in the polymer matrix can be improved without destroying the oxygen vacancy structure. This increases the effective exposure ratio of oxygen vacancy active sites in the material, improves electron release efficiency, and reduces the probability of electron recombination between particles, thereby enhancing the generation capacity and continuous output stability of negative oxygen ions.

[0060] Preferably, the method for preparing the modified microcapsule salt includes the following steps: (1) Mix calcium salt and organic solvent, add organosilicon compound and water, react to obtain silica-coated calcium salt; (2) The calcium salt coated with silica is prepared by plasma treatment.

[0061] Preferably, in step (1), the organic solvent includes ethanol; more preferably, the ethanol includes anhydrous ethanol.

[0062] Preferably, in step (1), the solid-liquid mass ratio of the calcium salt and the organic solvent is 1:(10-15); for example, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, etc.

[0063] Preferably, in step (1), the volume ratio of the organosilicon compound to the organic solvent is 1:(6-10); for example, 1:6, 1:7, 1:8, 1:9, 1:10, etc.

[0064] Preferably, in step (1), the organosilicon compound includes alkoxysilane; more preferably, the alkoxysilane includes TEOS.

[0065] Preferably, in step (1), water is added under stirring conditions.

[0066] Preferably, the molar ratio of water to organosilicon compound is (3-5):1; for example, 3:1, 4:1, 5:1, etc.

[0067] Preferably, in step (1), after adding water, the pH is adjusted to 2-4.

[0068] Preferably, in step (1), the reaction temperature is room temperature and the reaction time is 40-90 min; for example, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, etc.

[0069] Specifically, the reaction is continuously stirred during the process, and through stirring, silicon dioxide is gradually deposited on the surface of the calcium salt to form a continuous coating layer.

[0070] Preferably, in step (1), after the reaction is completed, drying is carried out at a temperature of 55-65°C and a drying time of 1.5-2.5h; for example, the drying temperature is 55°C, 60°C, 65°C, etc., and the drying time is 1.5h, 2h, 2.5h, etc.

[0071] Preferably, in step (2), the plasma treatment includes oxygen plasma treatment.

[0072] Preferably, the plasma treatment power is 80-120W, and the plasma treatment time is 30-60s; for example, the plasma treatment power is 80W, 90W, 100W, 110W, 120W, etc.; and the plasma treatment time is 30s, 40s, 50s, 60s, etc.

[0073] Specifically, plasma treatment enhances the surface wettability of microcapsule salts and their interfacial bonding with the polymer matrix, while maintaining the humidity-responsive characteristics of the internal calcium salts. This results in a more uniform and stable humidity-responsive interface region within the material, promoting the continuous distribution of adsorbed water layers at the interface when ambient humidity increases. Consequently, it reduces the migration barrier of electrons at the phase interface, improves the electron transfer efficiency to the material surface, and enhances the release intensity and stability of negative oxygen ions.

[0074] A third aspect of the present invention provides a device for releasing negative oxygen ions.

[0075] Specifically, the device for releasing negative oxygen ions includes the composite material for releasing negative oxygen ions described in the first aspect of the present invention.

[0076] Compared with the prior art, the beneficial effects of the technical solution provided by the present invention are as follows: (1) This invention uses specific modified titanium dioxide, modified cerium dioxide and modified microcapsule salt, which work synergistically to form a complete negative oxygen ion generation and migration pathway, so that the material exhibits a high negative oxygen ion release peak under environmental stimulation and shows good release stability.

[0077] (2) The preparation process of the composite material of the present invention is simple and easy to promote and apply in industrial applications. Attached Figure Description

[0078] Figure 1 These are scanning electron microscope images of the composite materials that release negative oxygen ions in Examples 1-4 of this invention; Figure 2 The elemental distribution diagram of Ca, Ce, and O in the composite material that releases negative oxygen ions in Example 1 of the present invention is shown. Figure 3 The graph shows the mechanical property test results of the composite materials that release negative oxygen ions in Examples 1-4 of this invention; Figure 4 Thermogravimetric analysis results of the composite materials that release negative oxygen ions in Examples 1-4 of this invention are shown in the figure. Figure 5 The negative oxygen ion release peak diagrams of the composite materials of Examples 1-4 and Comparative Examples 1-6 of the present invention that release negative oxygen ions are shown under the conditions of 25℃, low light environment, and humidity of 25%RH, 60%RH and 85%RH respectively. Figure 6 The temperature was 25℃, the humidity was 60%RH, and the light intensity was 10mW / cm². 2 100mW / cm 2 Under the conditions described, the negative oxygen ion release peak diagrams of the composite materials that release negative oxygen ions in Examples 1-4 and Comparative Examples 1-6 of the present invention are shown. Figure 7 At 25℃, in a low-light environment (10mW / cm²), 2 Figure 1 shows the results of the negative oxygen ion release stability test of the composite materials of Examples 1-4 and Comparative Examples 1-6 under the condition of 85%RH humidity. Detailed Implementation

[0079] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.

[0080] Unless otherwise specified, the raw materials, reagents or devices used in the following examples are available from conventional commercial sources or can be obtained by existing known methods.

[0081] For cerium dioxide (CeO) containing oxygen vacancies in the embodiments of the present invention 2-x As long as cerium dioxide with oxygen vacancies of x greater than 0 and less than 2 is used, the same effect can be achieved, thus realizing the present invention.

[0082] Example 1 This embodiment provides a composite material that releases negative oxygen ions. By mass percentage, the raw materials for its preparation consist of 78% PP, 6% modified titanium dioxide, 10% modified cerium dioxide, 4% modified microcapsule salt, and 2% ZnSt.

[0083] This embodiment also provides a method for preparing the above-mentioned composite material that releases negative oxygen ions, the specific steps of which are as follows: The raw materials are mixed, melt-blended in a twin-screw extruder, extruded, and pelletized to obtain the final product. The melt blending temperature was 220℃, the time was 40 min, the extrusion temperature was 220℃, and the screw speed of the twin-screw extruder was 20 r / min.

[0084] A thin layer of titanium dioxide coated on the surface of TiO2 was formed using the sol-gel method. Specifically, the preparation process of the modified titanium dioxide is as follows: (1) TiO2 powder (particle size 50-200nm) was added to anhydrous ethanol, the solid-liquid mass ratio was controlled at 1:12, and ultrasonically dispersed for 12min; then tetraethoxysilane (TEOS) was added as a sol precursor, the volume ratio of TEOS to ethanol was 1:10, and deionized water was added to make the molar ratio of deionized water to TEOS in the system 3:1. At the same time, a small amount of hydrochloric acid (pH adjusted to 3) was added dropwise as a catalyst. The mixture was magnetically stirred at room temperature for 45min to allow the sol to undergo in-situ hydrolysis and condensation reaction on the TiO2 surface to form a continuous coating layer; after the reaction was completed, the mixture was dried at 90℃ for 1.5h to obtain TiO2 composite powder with silica coating on the surface. (2) Add KH-560 silane coupling agent to the TiO2 composite powder obtained in step (1), the amount of which accounts for 0.8% of the mass of the TiO2 composite powder with silica coating obtained in step (1), stir in ethanol for 18 min and dry again; finally, place the dried powder in an oxygen plasma device and treat it at 100W power for 50s to obtain the product.

[0085] The preparation process of modified cerium dioxide is as follows: Cerium dioxide (CeO) containing oxygen vacancies 2-x The powder was added to anhydrous ethanol at a solid-liquid mass ratio of 1:12. After ultrasonic dispersion for 8 minutes, KH-550 silane coupling agent was added to the system at a concentration of 1 wt% (based on CeO2). 2-x The mixture was stirred at room temperature for 25 min to allow the coupling agent to be fully adsorbed and undergo a condensation reaction. The mixture was then centrifuged and dried at 60 °C for 1.5 h to obtain surface-modified cerium dioxide.

[0086] The modified microcapsule salt uses CaCl2 as the core material and forms a SiO2 shell through a sol-gel method. Specifically, the preparation process of the modified microcapsule salt is as follows: (1) CaCl2 powder was dispersed in anhydrous ethanol, with the solid-liquid mass ratio controlled at 1:12. After uniform dispersion, TEOS was added to make the volume ratio of TEOS to anhydrous ethanol 1:8. Deionized water was added under stirring to make the molar ratio of deionized water to TEOS 4:1, and the pH of the solution was adjusted to 3. Stirring was continued at room temperature for 65 min to allow SiO2 to be gradually deposited on the surface of CaCl2, forming a continuous SiO2 coating shell. After the reaction was completed, the mixture was filtered and dried at 60℃ for 2 h to obtain CaCl2@SiO2 microcapsules. (2) The dried CaCl2@SiO2 microcapsules obtained in step (1) were subjected to short-time oxygen plasma treatment with a power of 100W and a time of 45s to obtain the product.

[0087] Example 2 This embodiment provides a composite material that releases negative oxygen ions. By mass percentage, the raw materials for its preparation consist of 78% PP, 4% modified titanium dioxide, 6% modified cerium dioxide, 10% modified microcapsule salt, and 2% ZnSt.

[0088] Example 2 describes the preparation methods of the composite material that releases negative oxygen ions, the preparation methods of modified titanium dioxide, modified cerium dioxide, and modified microcapsule salt, which are the same as in Example 1.

[0089] Example 3 This embodiment provides a composite material that releases negative oxygen ions. By mass percentage, the raw materials for its preparation consist of 78% PP, 10% modified titanium dioxide, 6% modified cerium dioxide, 4% modified microcapsule salt, and 2% ZnSt.

[0090] Example 3 describes the preparation methods of the composite material that releases negative oxygen ions, the preparation methods of modified titanium dioxide, modified cerium dioxide, and modified microcapsule salt, which are the same as in Example 1.

[0091] Example 4 This embodiment provides a composite material that releases negative oxygen ions. By mass percentage, the raw materials for its preparation consist of 78% PP, 6% modified titanium dioxide, 6% modified cerium dioxide, 8% modified microcapsule salt, and 2% ZnSt.

[0092] Example 4 describes the preparation methods of the composite material that releases negative oxygen ions, the preparation methods of modified titanium dioxide, modified cerium dioxide, and modified microcapsule salt, which are the same as in Example 1.

[0093] Comparative Example 1 The only difference between Comparative Example 1 and Example 3 is that Comparative Example 1 uses modified cerium dioxide to replace the modified microcapsule salt in equal amounts, i.e., it does not contain modified microcapsule salt. Both modified titanium dioxide and modified cerium dioxide are 10%, and the rest is the same as in Example 3.

[0094] Comparative Example 2 The only difference between Comparative Example 2 and Example 3 is that Comparative Example 2 uses modified microcapsule salt to replace modified cerium dioxide in equal amounts, i.e., it does not contain modified cerium dioxide. Both modified titanium dioxide and modified microcapsule salt are 10%, and the rest is the same as in Example 3.

[0095] Comparative Example 3 The only difference between Comparative Example 3 and Example 3 is that Comparative Example 3 uses 4% modified cerium dioxide and 6% modified microcapsule salt to replace 10% modified titanium dioxide, i.e. it does not contain modified titanium dioxide. Both modified cerium dioxide and modified microcapsule salt are 10%, and the rest is the same as Example 3.

[0096] Comparative Example 4 The only difference between Comparative Example 4 and Example 3 is that Comparative Example 4 contains 20% modified titanium dioxide and does not contain modified cerium dioxide or modified microcapsule salt; otherwise, it is the same as Example 3.

[0097] Comparative Example 5 The only difference between Comparative Example 5 and Example 3 is that Comparative Example 5 contains 20% modified cerium dioxide and does not contain modified titanium dioxide or modified microcapsule salt; otherwise, it is the same as Example 3.

[0098] Comparative Example 6 The only difference between Comparative Example 6 and Example 3 is that Comparative Example 6 contains 20% modified microcapsule salt and does not contain modified titanium dioxide or modified cerium dioxide; otherwise, it is the same as Example 3.

[0099] Performance testing Test samples were prepared from the composite materials of Examples 1-4 and Comparative Examples 1-6 using a hot-pressing process. The hot-pressing temperature was 185°C, the hot-pressing pressure was 1 MPa, and the holding time was 10 min. The cooling method was to cool the samples to below 60°C while maintaining the pressure before demolding. The test samples were then subjected to the following tests.

[0100] 1. Scanning electron microscopy observation The composite materials prepared in Examples 1-4 were observed by scanning electron microscopy, and the results are as follows: Figure 1 As shown. Among them, Figure 1 Figures (a)-(d) are scanning electron microscope images of the composite materials of Examples 1-4, respectively.

[0101] Depend on Figure 1 It can be seen that in the composite materials prepared in Examples 1-4, the modified cerium dioxide, modified titanium dioxide, and modified microcapsule salt are relatively uniformly distributed in the polymer matrix, and no obvious large-size agglomeration was observed. The modified inorganic particles exhibit good dispersion, and the interface between the particle surface and the matrix is ​​tight with a clear interface outline, indicating that after surface modification and melt blending, the filler and the polypropylene matrix have good compatibility.

[0102] Despite variations in the proportions of functional fillers in each embodiment, the overall microstructure of the composite material remained consistent, with no obvious structural defects or phase separation observed. This indicates that the preparation process can achieve stable construction of the composite system under different proportions, providing a good structural basis for the subsequent release of negative oxygen ions.

[0103] 2. Energy dispersive spectroscopy (EDS) analysis Energy dispersive spectroscopy (EDS) analysis was performed on the composite material prepared in Example 1. The elemental distribution of Ca, Ce, and O in the composite material of Example 1 is shown in the figure below. Figure 2 As shown.

[0104] Depend on Figure 2 It can be seen that Ca, Ce, and O elements are all clearly distributed in the composite material of Example 1, and the distribution of each element is relatively uniform in the observation area, without obvious local enrichment or deficiency. Among them, the presence of Ca element indicates that the calcium salt component was successfully introduced into the composite system, the distribution of Ce element indicates that the cerium dioxide filler is well dispersed in the material, and the O element comes from the silica coating structure and oxide filler.

[0105] 3. Mechanical property testing Mechanical properties were tested in accordance with GB / T 1040.2-2006. The specimen type was dumbbell-shaped, the gauge length was 25 mm, the thickness was 1-2 mm, and the tensile test was carried out at room temperature with a tensile rate of 10 mm / min.

[0106] The mechanical property test results of the composite materials that release negative oxygen ions in Examples 1-4 are as follows: Figure 3 As shown.

[0107] Depend on Figure 3 It can be seen that the composite materials prepared in Examples 1-4 all exhibit good mechanical properties and show relatively continuous stress-strain response characteristics during the tensile process, indicating that the introduction of modified cerium dioxide, modified titanium dioxide and modified microcapsule salt did not significantly damage the overall mechanical integrity of the polypropylene matrix.

[0108] The tensile strength and elongation at break varied among the different embodiments, indicating that the ratio of modified cerium dioxide, modified titanium dioxide, and modified microencapsulated salt has a certain impact on the mechanical properties of the composite material. Specifically, with changes in the content and ratio of inorganic fillers, the strength and ductility of the composite material exhibited varying degrees of balance, but overall, it maintained good formability and reliability in use.

[0109] 4. Thermogravimetric analysis Thermogravimetric analysis was performed on the composite materials that released negative oxygen ions in Examples 1-4, and the results are as follows: Figure 4 As shown.

[0110] Depend on Figure 4It can be seen that the composite materials prepared in Examples 1-4 all exhibited similar thermal decomposition behavior during the heating process, and their thermogravimetric curves were basically consistent, indicating that the composite materials have good thermal stability under different formulation conditions. The main thermal decomposition stages of each example were concentrated in similar temperature ranges, and no obvious premature decomposition or abnormal weight loss was observed, indicating that the introduction of modified cerium dioxide, modified titanium dioxide, and modified microencapsulated salt and their ratio changes did not adversely affect the thermal stability of the polypropylene matrix.

[0111] As can be seen from the weight loss rate (DTG) curves, the peak positions of the maximum weight loss rates in each embodiment are close, further indicating that the composite material has similar thermal decomposition characteristics under different formulation conditions, which provides a guarantee for its stable application in the conventional processing and operating temperature range.

[0112] 5. Negative oxygen ion release capacity test (1) At 25℃, in a low-light environment (10mW / cm²), 2 Under conditions of 60% RH, the negative oxygen ion release capacity of the composite materials of Examples 1-4 and Comparative Examples 1-6 was tested. The specific test methods are as follows: The composite material sample to be tested was placed in a sealed space to reduce the influence of external air flow and environmental ion fluctuations on the test results. Then, the sampling port of the negative oxygen ion detector was connected to the sealed space and allowed to stand for pre-equilibrium under the same environmental conditions. After the sealed space was closed, the detector was run continuously for about 1 hour to allow the internal environment of the chamber and the detector readings to stabilize. When the detector readings stabilized, the negative oxygen ion concentration data was recorded and continuously collected within a certain time range (1 hour). The readings obtained during the stable phase were taken as the negative oxygen ion release level (or release peak) of the sample under the corresponding conditions. Five samples were tested in each group, and the average value was taken as the release peak.

[0113] The peak values ​​of negative oxygen ion release from the composite materials of Examples 1-4 and Comparative Examples 1-6 are shown in Table 1.

[0114] Table 1: Peak release values ​​of negative oxygen ions from composite materials in Examples 1-4 and Comparative Examples 1-6

[0115] As shown in Table 1, the composite material prepared in this invention has good negative oxygen ion release capacity, with a room temperature release peak of 13,800 ions / cm³. 3 / g. This is because in the composite material system of the present invention, modified titanium dioxide, modified cerium dioxide and modified microcapsule salt form a synergistic electron generation and migration network under the structural design and interface regulation, which enables the material to effectively maintain the electron supply and transport process when environmental conditions change, thereby obtaining a high negative oxygen ion release peak.

[0116] Comparative Example 1 used an equal amount of modified cerium dioxide to replace the modified microcapsule salt, i.e., it contained no modified microcapsule salt. As a result, the peak value of negative oxygen ion release in Comparative Example 1 was significantly lower than that in Example 3. This is because Comparative Example 1 lacked the humidity regulation pathway of modified microcapsule salt, resulting in an incomplete carrier migration chain and a significantly lower release peak value than the ternary system with the synergistic effect of modified titanium dioxide, modified cerium dioxide, and modified microcapsule salt.

[0117] Comparative Example 2 used a modified microcapsule salt to replace the modified cerium dioxide in equal amounts, i.e., it did not contain modified cerium dioxide. As a result, the peak value of negative oxygen ion release in Comparative Example 2 was significantly lower than that in Example 3. This is because Comparative Example 2 lacks the oxygen vacancy regulation ability of CeO2, resulting in insufficient overall stability and limited continuous output capability, thus its peak value of negative oxygen ion release is worse than that in Example 3.

[0118] Comparative Example 3 replaced 10% modified titanium dioxide with 4% modified cerium dioxide and 6% modified microencapsulated salt, meaning it contained no modified titanium dioxide. This resulted in a significantly lower room-temperature release peak value of negative oxygen ions in Comparative Example 3 compared to Example 3. This is because Comparative Example 3 lacked the synergistic effect of modified titanium dioxide. Although it produced a certain response improvement, the overall peak value was still significantly lower than the ternary system with the synergistic effect of modified titanium dioxide, modified cerium dioxide, and modified microencapsulated salt.

[0119] Comparative Examples 1-3 demonstrate the synergistic effect between modified titanium dioxide, modified cerium dioxide, and modified microcapsule salt. Only through the combined action of these three components can the composite material exhibit good negative oxygen ion release capability.

[0120] Comparative Examples 4-6, containing only modified titanium dioxide, modified cerium dioxide, and modified microencapsulated salt respectively, showed lower release peak values. This indicates that a single-response system cannot effectively improve the release peak value of negative oxygen ions.

[0121] (2) At 25℃, in a low-light environment (10mW / cm²), 2 The negative oxygen ion release capacity of the composite materials of Examples 1-4 and Comparative Examples 1-6 was tested under humidity conditions of 25%RH, 60%RH and 85%RH, respectively, and the test method was the same as above.

[0122] 25℃, low light environment (10mW / cm²) 2 Under humidity conditions of 25%RH, 60%RH, and 85%RH respectively, the average peak values ​​of negative oxygen ion release from the composite materials of Examples 1-4 and Comparative Examples 1-6 are as follows: Figure 5 As shown.

[0123] Depend on Figure 5 It can be seen that the release peak of the composite material increases significantly with increasing humidity.

[0124] Taking Example 2 as an example, the average peak value of negative oxygen ion release under different humidity conditions (25%RH, 60%RH, 85%RH) at 25℃ and in a low light environment is shown in Table 2.

[0125] Table 2: Peak negative oxygen ion release of the composite material in Example 2 under different humidity conditions at 25℃ and low light environment.

[0126] As shown in Table 2, the peak value of negative oxygen ion release gradually increases as the humidity increases from 25%RH to 85%RH. This is because the hygroscopic polarity and microscopic water film effect of CaCl2 are enhanced, and the surface charge migration efficiency of the material is improved, resulting in a significant increase in the peak value.

[0127] (3) At 25℃, 60%RH humidity, and a light intensity of 10mW / cm², 2 100mW / cm 2 Under the same conditions, the negative oxygen ion release capacity of the composite materials of Examples 1-4 and Comparative Examples 1-6 was tested, and the test method was the same as above.

[0128] At 25℃, 60%RH humidity, and a light intensity of 10mW / cm², 2 100mW / cm 2 Under the conditions, the average peak value of negative oxygen ion release of the composite materials of Examples 1-4 and Comparative Examples 1-6 is as follows: Figure 6 As shown.

[0129] Depend on Figure 6 It can be seen that the release peak of the composite material increases significantly with the increase of light intensity.

[0130] Taking Example 3 as an example, at 25°C and 60% RH, under different light intensity conditions (10mW / cm²), 2 100mW / cm 2 Under the following conditions: 50℃, 60% humidity, and low light (10mW / cm²). 2 The peak values ​​of negative oxygen ion release are shown in Table 3.

[0131] Table 3: 25℃, 60%RH, different light intensities, and 50℃, 60%RH, low light (10mW / cm²). 2 The average peak value of negative oxygen ion release from the composite material in Example 3 below

[0132] As shown in Table 3, the peak value of negative oxygen ion release gradually increases with increasing light intensity and temperature. This is because under illumination, TiO2 in the material system generates significant photogenerated carriers, leading to a rapid increase in the peak value. Furthermore, as the light intensity increases, the number of photogenerated carriers increases, further enhancing the peak value. When the temperature rises to approximately 50℃, the local electron transition process accelerates further, similarly enhancing the peak value. This also indicates that the material system is extremely sensitive to the light field, and modified titanium dioxide plays a key regulatory role in the ternary synergistic system, being a crucial factor in achieving a high peak response.

[0133] (4) Release stability test At 25℃, in a low-light environment (10mW / cm²), 2 The release of negative oxygen ions from the composite materials of Examples 1-4 and Comparative Examples 1-6 was tested under different placement time conditions (e.g., 1 hour, 24 hours, 7 days, 30 days, and 3 years for Example 3) at 85% RH to evaluate their release stability. The test method for the peak release of negative oxygen ions was the same as above. The test results of the negative oxygen ion release stability of the composite materials of Examples 1-4 and Comparative Examples 1-6 are as follows: Figure 7 As shown.

[0134] Figure 7 Test results show that the negative oxygen ion release of the composite materials in Examples 1-4 remained stable after 30 days of storage, and the negative oxygen ion release of the composite material in Example 3 remained high and stable after 3 years of storage, indicating that the composite material of the present invention has good release stability.

[0135] Although the release amount of the composite materials in Comparative Examples 1-6 was low after 7 days, the release was relatively stable. However, after 30 days, the release amount showed a decreasing trend, indicating that the release stability of negative oxygen ions of the composite materials in Comparative Examples 1-6 was worse than that of the composite materials in Examples 1-4 of this invention.

[0136] In summary, this invention utilizes specific modified titanium dioxide, modified cerium dioxide, and modified microcapsule salt, which work synergistically to form a continuous electron generation-transfer-migration pathway, thereby achieving efficient and continuous release of negative oxygen ions.

[0137] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A composite material, characterized in that, The raw materials for preparing the composite material include polypropylene, modified titanium dioxide, modified cerium dioxide, and modified microencapsulated salt; The modified titanium dioxide is obtained by sequentially treating titanium dioxide coated with silica with a coupling agent and plasma. The modified cerium dioxide was obtained by treating cerium dioxide with a coupling agent; The cerium dioxide includes cerium dioxide containing oxygen vacancies; The modified microcapsule salt was obtained by treating the microcapsule salt with plasma; The microcapsule salt has a core-shell structure, wherein the core material of the core-shell structure comprises calcium salt, and the shell layer of the core-shell structure comprises silicon dioxide.

2. The composite material according to claim 1, characterized in that, The coupling agent includes a silane coupling agent; And / or, the plasma includes oxygen plasma; And / or, the calcium salt includes calcium chloride.

3. The composite material according to claim 1, characterized in that, The raw materials for preparing the composite material, by mass percentage, include 70-85% polypropylene, 4-10% modified titanium dioxide, 6-10% modified cerium dioxide, and 4-10% modified microencapsulated salt.

4. The composite material according to claim 1, characterized in that, The raw materials for preparing the composite material also include lubricants.

5. The composite material according to claim 4, characterized in that, The raw materials for preparing the composite material, by mass percentage, include 70-85% polypropylene, 4-10% modified titanium dioxide, 6-10% modified cerium dioxide, 4-10% modified microencapsulated salt, and 1-3% lubricant.

6. A method for preparing the composite material according to any one of claims 1-5, characterized in that, The preparation method includes the following steps: The raw materials are mixed, melt-blended, and extruded to obtain the final product.

7. The preparation method according to claim 6, characterized in that, The method for preparing the modified titanium dioxide includes the following steps: (1) Mix titanium dioxide and solvent; then add organosilicon compound, water and catalyst, react to obtain titanium dioxide coated with silica; (2) The titanium dioxide coated with silicon dioxide and the coupling agent are mixed and then subjected to plasma treatment to obtain the product.

8. The preparation method according to claim 6, characterized in that, The method for preparing the modified cerium dioxide includes the following steps: Cerium dioxide and solvent are mixed; then a coupling agent is added, and the mixture is reacted to obtain the product.

9. The preparation method according to claim 6, characterized in that, The preparation method of the modified microcapsule salt includes the following steps: (1) Mix calcium salt and organic solvent, add organosilicon compound and water, react to obtain silica-coated calcium salt; (2) The calcium salt coated with silica is prepared by plasma treatment.

10. A device for releasing negative oxygen ions, characterized in that, Includes the composite material described in any one of claims 1-5.

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