Silica gel and rare earth compounded broad-spectrum antibacterial material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of medical materials, in particular to a silica gel and rare earth compounded broad-spectrum antibacterial material and a preparation method and application thereof.The antibacterial material comprises silica gel, a rare earth additive, nano-silver particles, a dispersing agent, a rare earth complex with fluorescence characteristics and a polymer with temperature sensitivity, the rare earth complex with the fluorescence characteristic is an organic complex of europium or an organic complex of terbium, and the polymer with the temperature sensitivity comprises one or more of poly (N-isopropylacrylamide), poly (N-vinyl caprolactam) and poly (N, N-diethyl acrylamide). The silica gel anti-bacterial silica gel material with good double anti-microbial performance and intelligent response performance is prepared, and the problems that in an existing preparation method, additives and silica gel are not evenly mixed, combination is not stable, and product performance is insufficient are solved.

Description

Technical Field

[0001] The present invention relates to the technical field of medical materials, and in particular to a broad-spectrum antibacterial material composited with silica gel and rare earth, and a preparation method and application thereof. Background Art

[0002] In the modern medical field, medical-grade silicone, as a high-performance polymer material, is widely used in products such as pharmaceutical packaging materials, auxiliary oxygen masks, positive pressure masks, medical gloves, and various types of operating room pipes due to its excellent biocompatibility. However, with the increasingly stringent hygiene standards in the medical environment, especially since the epidemic, medical institutions and professional associations have placed extremely high requirements on the sterilization control of medical devices. Although traditional medical-grade silicone has many advantages, it has obvious shortcomings in microbial control. It is very easy to breed bacteria and cannot meet the needs of high-hygiene scenarios, which limits its application in food preservation, high-end medical care and other fields.

[0003] Rare earth elements (REEs) have attracted significant attention in the field of material modification in recent years due to their exceptional and broad-spectrum antibacterial properties. Combining rare earth elements with medical-grade silicone has the potential to impart self-cleaning capabilities to medical devices, effectively addressing the microbial growth issues associated with traditional silicone. However, existing preparation processes face numerous challenges in achieving this fusion. Limited mixing equipment and processes make it difficult to ensure uniform dispersion of the rare earth elements within the silicone matrix, resulting in unstable product performance and an inability to fully utilize the rare earth elements' antibacterial properties. Furthermore, the insufficient stability of the rare earth-silicone bond can lead to separation during use, severely impacting the product's lifespan and reliability. Therefore, developing a rare earth-modified silicone with both excellent self-cleaning capabilities and stable chemical properties is key to improving the self-cleaning capabilities of medical devices and meeting the demands of modern healthcare. Summary of the Invention

[0004] The purpose of the present invention is to provide a broad-spectrum antibacterial material composited with silica gel and rare earth, and its preparation method and application, to prepare a silica gel antibacterial silica gel material with good dual antimicrobial properties and intelligent response performance, thereby solving the problems of uneven mixing of additives and silica gel, unstable bonding and insufficient product performance in the existing preparation method.

[0005] To achieve the above objectives, the present invention provides a broad-spectrum antibacterial material composited with silica gel and rare earth elements. The antibacterial material comprises silica gel, a rare earth additive, nanosilver particles, a dispersant, a rare earth complex with fluorescent properties, and a thermosensitive polymer. The rare earth complex with fluorescent properties is an organic complex of europium or an organic complex of terbium, and the thermosensitive polymer comprises one or more of poly (N-isopropylacrylamide), poly (N-vinylcaprolactam), and poly (N,N-diethylacrylamide).

[0006] Preferably, based on the percentage of each raw material in the mass of the silica gel, the rare earth additive is 0.5%-3%, the nano silver particles are 0.1%-0.5%, the dispersant is 0.5%-2%, the rare earth complex with fluorescent properties is 1%-5%, and the temperature-sensitive polymer is 3%-8%.

[0007] Preferably, the silicone rubber includes one or more of methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber.

[0008] Preferably, the rare earth additive includes one or more of lanthanum chloride, cerium nitrate, lanthanum oxide, and cerium oxide.

[0009] Preferably, the dispersant is oleic acid.

[0010] The present invention also provides a method for preparing the above-mentioned broad-spectrum antibacterial material composited with silica gel and rare earth, comprising the following steps:

[0011] S1. Pre-treat the silica gel: crush or grind the silica gel into particles and then perform surface activation treatment;

[0012] S2. Pre-treating the rare earth additive: grinding the rare earth additive into nano-scale or submicron-scale powder;

[0013] S3. Surface modification of the silver nanoparticles: using polyvinyl pyrrolidone to coat the surface of the silver nanoparticles;

[0014] S4, preparing a rare earth complex solution with fluorescent properties and a temperature-sensitive polymer solution;

[0015] S5, putting the silica gel particles pretreated in S1 into a high-speed blender, and then slowly adding the rare earth additive powder in S2, the surface-modified nanosilver particles in S3, the dispersant, the rare earth complex solution with fluorescent properties and the temperature-sensitive polymer solution in S4, and preliminarily mixing them to obtain a mixture;

[0016] S6. Transfer the mixture obtained in S5 to an ultrasonic dispersion device, apply a magnetic field at the same time, and perform ultrasonic treatment on the mixture. After the ultrasonic treatment, transfer the mixture to a vulcanization mold, pre-vulcanize it at a temperature of 110°C-120°C, and then heat it to 140°C-170°C for formal vulcanization. After the vulcanization is completed, an antibacterial material is obtained.

[0017] Preferably, the surface activation treatment in S1 is first plasma treatment and then immersion treatment in a weak alkaline solution.

[0018] Preferably, in S3, polyvinyl pyrrolidone is dissolved in an organic solvent such as toluene or dimethylformamide to form a uniform solution, and then nanosilver particles are dispersed in the solution. Ultrasonic treatment is performed to allow the polyvinyl pyrrolidone to adsorb on the surface of the nanosilver particles, so that the average particle size of the surface-modified nanosilver particles is 20-50 nm.

[0019] Preferably, the ultrasonic treatment in S6 uses ultrasonic waves with a frequency of 25-45 kHz and a magnetic field strength of 0.1-0.3T.

[0020] The present invention also provides an application of the above-mentioned broad-spectrum antibacterial material composited with silica gel and rare earth for preparing medical devices.

[0021] Beneficial effects of the present invention:

[0022] (1) The broad-spectrum antibacterial material of silica gel and rare earth composite provided by the present invention exhibits excellent inhibitory effect on common bacteria such as Escherichia coli and Staphylococcus aureus. From the performance test results, it can be seen that Examples 1-3 can control the bacterial growth at a low level throughout the experimental period, greatly reducing the risk of bacterial contamination of medical devices. In the antibacterial performance test, the optical density value (OD 600 ) found that the OD of Examples 1-3 600 The value increased slowly, which was much lower than that of the blank control group, indicating that the growth and reproduction of bacteria was effectively curbed; in the bactericidal performance test, the colony count of Examples 1-3 decreased significantly over time and dropped to a low level within 3.5 hours, which strongly demonstrated the powerful bactericidal ability of the material, ensuring the hygienic safety of medical devices and providing patients with more reliable medical protection.

[0023] (2) The present invention provides a method for preparing a broad-spectrum antibacterial material composited with silica gel and rare earth elements. The raw materials are pretreated, the silica gel is crushed and ground to activate its surface, the rare earth additive is ground into a nanometer or submicron powder, and the surface is modified with nanosilver particles. High-speed stirring, ultrasonic dispersion, and application of a magnetic field are also used to uniformly disperse the rare earth additive, nanosilver particles, etc. in the silica gel matrix and stably bond with the silica gel. This uniform dispersion and stable bonding avoids the problems of unstable product performance and separation during use, fully utilizes the antibacterial properties of the rare earth elements, and at the same time ensures the reliability and service life of the material during use.

[0024] (3) The present invention provides a broad-spectrum antibacterial material composed of silica gel and rare earth elements, which has fluorescent rare earth complexes and temperature-sensitive polymers that give the product intelligent response performance. Within the temperature range of 25°C-40°C, the fluorescence intensity of the antibacterial materials of Examples 1-3 shows a clear linear enhancement trend, successfully establishing a quantitative correlation between temperature and fluorescence signals. This characteristic enables it to be used in the manufacture of wearable healthcare products, such as real-time monitoring of human body temperature changes through changes in fluorescence intensity, expanding the material's scope of application.

[0025] (4) The present invention provides a broad-spectrum antibacterial material composed of a composite of silica gel and rare earth elements. The raw materials used are medical-grade silica gels such as methyl vinyl silicone rubber and methylphenyl vinyl silicone rubber, combined with appropriate amounts of rare earth additives and nanosilver particles. While ensuring antibacterial properties, the material maintains the inherent properties of silica gel, such as good flexibility, stability, and biocompatibility. While exerting its antibacterial effects, it does not adversely affect human tissue, meeting the strict biocompatibility requirements of medical devices and can be safely used in the medical field.

[0026] (5) The present invention provides a broad-spectrum antibacterial material composed of silica gel and rare earth, which incorporates rare earth additives, nanosilver particles, rare earth complexes with fluorescent properties, and thermosensitive polymers into silica gel, so that the product has good dual antimicrobial properties and intelligent response performance. Compared with traditional medical-grade silica gel, the comprehensive performance is significantly improved, which can better meet the stringent requirements of the modern medical field for medical devices in terms of hygiene standards and functional diversity, and has broad application prospects in fields with high requirements for hygiene conditions such as food preservation and high-end medical care.

[0027] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 Schematic diagram of the effect of the antibacterial materials prepared in Examples 1-3 of the present invention on the bacterial growth curve; Figure 1 (a) is a schematic diagram of the growth curve of Escherichia coli. Figure 1 (b) is a schematic diagram of the growth curve of Staphylococcus aureus;

[0029] Figure 2 Schematic diagram of the bactericidal effect of the antibacterial material prepared in Examples 1-3 of the present invention on bacteria; Figure 2 (a) is a schematic diagram of the number of Escherichia coli colonies. Figure 2 (b) is a schematic diagram of the colony count of Staphylococcus aureus;

[0030] Figure 33 is a graph showing the fluorescence intensity change rate of the antibacterial materials prepared in Examples 1-3 of the present invention at 25-40°C. DETAILED DESCRIPTION

[0031] The present invention is further described below with reference to the accompanying drawings and examples. Unless otherwise defined, technical or scientific terms used herein shall have the same meanings as those commonly understood by persons of ordinary skill in the art to which the present invention pertains. The above-mentioned features or features described in the specific examples of the present invention may be combined in any manner. These specific examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention.

[0032] The present invention provides a broad-spectrum antibacterial material composited with silica gel and rare earth. The antibacterial material comprises silica gel, rare earth additives, nano-silver particles, a dispersant, a rare earth complex with fluorescent properties, and a thermosensitive polymer. The rare earth complex with fluorescent properties is an organic complex of europium or an organic complex of terbium, and the thermosensitive polymer comprises one or more of poly (N-isopropylacrylamide), poly (N-vinylcaprolactam), and poly (N,N-diethylacrylamide).

[0033] In some embodiments of the present invention, the organic complex of europium is a dibenzoylmethane complex of europium, and the organic complex of terbium is a phenanthroline complex of terbium.

[0034] Preferably, based on the percentage of each raw material in the mass of the silica gel, the rare earth additive is 0.5%-3%, the nano silver particles are 0.1%-0.5%, the dispersant is 0.5%-2%, the rare earth complex with fluorescent properties is 1%-5%, and the temperature-sensitive polymer is 3%-8%.

[0035] The rare earth additive dosage in the present invention is within the aforementioned range, ensuring relatively uniform dispersion within the silica gel matrix, fully exerting its antibacterial properties, such as disrupting bacterial cell membranes and interfering with bacterial metabolism, while maintaining the silica gel's inherent properties of good flexibility, stability, and biocompatibility. When the dosage is less than 0.5% by weight of the silica gel, the rare earth additive's antibacterial active sites are insufficient, making it difficult to form an effective antibacterial network within the silica gel matrix, resulting in a weak inhibitory effect against common bacteria. Furthermore, when the dosage exceeds 3% by weight of the silica gel, rare earth particles may aggregate within the silica gel, disrupting the silica gel's originally uniform microstructure and affecting its mechanical properties and biocompatibility. Furthermore, excessive rare earth content may significantly increase material costs, which is not economically viable.

[0036] The nanosilver particles used in the present invention within the aforementioned range effectively enhance the antibacterial properties of the silica gel. Within this ratio, the nanosilver particles can be evenly dispersed throughout the silica gel system, fully exerting their antibacterial activity while maintaining the flexibility and mechanical strength of the silica gel itself. When the addition amount is less than 0.1% by weight of the silica gel, the antibacterial effect is weak and ineffective against common pathogens. When the addition amount exceeds 0.5% by weight of the silica gel, the nanosilver particles tend to agglomerate, reducing their antibacterial efficiency and degrading the silica gel's physical properties, such as decreased flexibility and brittleness.

[0037] In the present invention, the dispersant is used to promote the mixing of the nano silver particles, the rare earth additive and the silica gel and prevent agglomeration.

[0038] In the present invention, the amount of the rare earth complex with fluorescent properties is within the above range, which can effectively impart fluorescent properties to silica gel, causing it to emit bright and stable fluorescence under specific wavelength excitation, while not causing intermolecular aggregation due to excessive addition, avoiding fluorescence quenching, and ensuring that the fluorescence intensity and stability are optimally balanced.

[0039] In the present invention, the amount of the thermosensitive polymer used is within the above range, which gives the silica gel excellent thermosensitive response characteristics. If it is less than 3% of the mass of the silica gel, the thermosensitive effect is weak; if it is higher than 8% of the mass of the silica gel, it may cause excessive aggregation of the polymer and destroy the original performance of the silica gel.

[0040] Preferably, the silicone rubber includes one or more of methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber.

[0041] Preferably, the rare earth additive includes one or more of lanthanum chloride, cerium nitrate, lanthanum oxide, and cerium oxide.

[0042] Preferably, the dispersant is oleic acid.

[0043] The present invention also provides a method for preparing the above-mentioned broad-spectrum antibacterial material composited with silica gel and rare earth, comprising the following steps:

[0044] S1. Pre-treat the silica gel: crush or grind the silica gel into particles and then perform surface activation treatment;

[0045] S2. Pre-treating the rare earth additive: grinding the rare earth additive into nano-scale or submicron-scale powder;

[0046] S3. Surface modification of the silver nanoparticles: using polyvinyl pyrrolidone to coat the surface of the silver nanoparticles;

[0047] S4. preparing a rare earth complex solution having fluorescent properties and a temperature-sensitive polymer solution;

[0048] S5, putting the silica gel particles pretreated in S1 into a high-speed blender, and then slowly adding the rare earth additive powder in S2, the surface-modified nanosilver particles in S3, the dispersant, the rare earth complex solution with fluorescent properties and the temperature-sensitive polymer solution in S4, and preliminarily mixing them to obtain a mixture;

[0049] S6. Transfer the mixture obtained in S5 to an ultrasonic dispersion device, apply a magnetic field at the same time, and perform ultrasonic treatment on the mixture. After the ultrasonic treatment, transfer the mixture to a vulcanization mold, pre-vulcanize it at a temperature of 110°C-120°C, and then heat it to 140°C-170°C for formal vulcanization. After the vulcanization is completed, an antibacterial material is obtained.

[0050] Preferably, the surface activation treatment in S1 is first plasma treatment and then immersion treatment in a weak alkaline solution.

[0051] In some embodiments of the present invention, the silica gel particles of S1 have a particle size range of 100-400 mesh;

[0052] Plasma treatment involves placing silica gel particles in a vacuum chamber, introducing argon gas into the vacuum chamber, setting the power to 350W, and treating for 20 minutes to form a large number of active free radical sites on the silica gel surface; weak alkaline solution immersion treatment involves immersing the plasma-treated silica gel particles in a 3% sodium carbonate solution for 15 minutes to further adjust the surface chemical properties and enhance the surface's adsorption capacity for different additives.

[0053] In some embodiments of the present invention, the particle size of the rare earth additive powder in S2 is 30-150 nm. In the present invention, the rare earth additive is ground into powder so that the rare earth additive is evenly dispersed in the silica gel matrix, increasing the contact area with bacteria and improving the antibacterial efficiency.

[0054] Preferably, in S3, polyvinyl pyrrolidone is dissolved in an organic solvent such as toluene or dimethylformamide to form a uniform solution, and then nanosilver particles are dispersed in the solution. Ultrasonic treatment is performed to allow the polyvinyl pyrrolidone to adsorb on the surface of the nanosilver particles, so that the average particle size of the surface-modified nanosilver particles is 20-50 nm.

[0055] In some embodiments of the present invention, the nanosilver particles in S3 are prepared using a sodium citrate reduction method, and the surface modification is performed by dissolving 0.5-2 g of polyvinyl pyrrolidone in 10-20 mL of toluene or N,N-dimethylformamide to form a uniform solution, then dispersing nanosilver particles in a ratio of 0.5% to 2% of the total volume of the solution into the solution, and adsorbing the polyvinyl pyrrolidone molecules onto the surface of the nanosilver particles by ultrasonic treatment. A stable protective layer is formed on the surface of the nanosilver particles, making them more stable during subsequent mixing processes.

[0056] In some embodiments of the present invention, an organic solvent is used in S4 to prepare the rare earth complex solution with fluorescent properties and the temperature-sensitive polymer solution, and the organic solvent is one or more of toluene, xylene, acetone, and butanone.

[0057] In some embodiments of the present invention, the raw materials are added in S5 as follows: first, the pretreated silica gel particles are placed in a high-speed blender at a speed of 900-1300 rpm. Then, the rare earth additive powder is slowly added and stirred for 20-30 minutes to initially disperse the rare earth additive powder in the silica gel particles. The surface-modified nanosilver particles are then added and stirred for a further 15-20 minutes. During this stirring process, a dispersant is added to promote mixing of the nanosilver particles, the rare earth additive, and the silica gel and prevent agglomeration. Subsequently, an appropriate amount of a solution containing a fluorescent rare earth complex is calculated and measured based on the mass of the silica gel. This solution is slowly added dropwise to the blender at a rate of 3-5 drops per minute while stirring continuously for 10-15 minutes. After the addition is complete, stirring is continued for an additional 10-15 minutes to ensure uniform dispersion of the complex. Finally, an appropriate amount of a temperature-sensitive polymer solution is calculated and measured based on the mass of the silica gel and stirred for 15-20 minutes.

[0058] Preferably, the ultrasonic treatment in S6 uses ultrasonic waves with a frequency of 25-45kHz and an intensity of the magnetic field of 0.1-0.3T. In the present invention, the cavitation effect of the ultrasonic wave combined with the effect of the magnetic field can produce more complex physical effects inside the material. On the one hand, the strong impact force generated by the rupture of the cavitation bubbles of the ultrasonic wave further refines the nanosilver particles and rare earth particles, and promotes them to be more evenly dispersed in the silica gel matrix; on the other hand, the magnetic field can guide the additives with magnetism or paramagnetism (such as some rare earth ions, nanosilver particles) to be oriented in the silica gel, strengthen the interaction between them, and also help the rare earth complexes with fluorescent properties and thermosensitive polymers to be evenly distributed, promote the synergistic effect between different additives, and enhance physical adsorption and initial chemical bonding.

[0059] In some embodiments of the present invention, the pre-vulcanization time in S6 is 15-20 minutes, and the formal vulcanization time is 40-100 minutes.

[0060] In the present invention, pre-sulfurization is first performed at a relatively low temperature to initially form a stable structure of chemical bonding and physical adsorption between the nano-silver particles, rare earth additives and silica gel, while the rare earth complex with fluorescent properties and the thermosensitive polymer also begin to interact with the silica gel matrix.

[0061] In the present invention, during the formal vulcanization process, silanol groups undergo dehydration condensation to form a silicon-oxygen bond network structure. Rare earth ions further form covalent bonds with oxygen atoms in the silicon-oxygen bonds. Nanosilver particles undergo chemical reactions or physical adsorption with active groups such as hydroxyl (-OH), carboxyl (-COOH), and amino (-NH2) on the surface of the silica gel, firmly binding to the silica gel matrix. At the same time, the rare earth complex and thermosensitive polymer with fluorescent properties are stably embedded in the three-dimensional network structure of the silica gel during the vulcanization process, achieving multi-dimensional modification of the silica gel, giving the product excellent dual antimicrobial properties and intelligent response performance.

[0062] The present invention also provides an application of the above-mentioned broad-spectrum antibacterial material composited with silica gel and rare earth for preparing medical devices.

[0063] Example 1

[0064] The present invention provides a broad-spectrum antibacterial material composited with silica gel and rare earth elements, comprising silica gel, lanthanum chloride (0.5% by weight of the silica gel), nanosilver particles (0.1% by weight of the silica gel), oleic acid (0.5% by weight of the silica gel), a dibenzoylmethane complex of europium (1% by weight of the silica gel), and poly (N-isopropylacrylamide) (3% by weight of the silica gel). The silica gel is methyl vinyl silicone rubber.

[0065] Example 2

[0066] The present invention provides a broad-spectrum antibacterial material composited with silica gel and rare earth elements, comprising silica gel, cerium oxide accounting for 1.5% of the silica gel mass, nanosilver particles accounting for 0.3% of the silica gel mass, oleic acid accounting for 1.0% of the silica gel mass, a dibenzoylmethane complex of europium accounting for 3% of the silica gel mass, and poly(N-vinylcaprolactam) accounting for 5% of the silica gel mass. The silica gel is methylphenylvinyl silicone rubber.

[0067] Example 3

[0068] The present invention provides a broad-spectrum antibacterial material composited with silica gel and rare earth elements, comprising silica gel, lanthanum oxide accounting for 3% of the silica gel mass, nanosilver particles accounting for 0.5% of the silica gel mass, oleic acid accounting for 2% of the silica gel mass, a terbium-o-phenanthroline complex accounting for 5% of the silica gel mass, and poly(N,N-diethylacrylamide) accounting for 8% of the silica gel mass. The silica gel is methyl vinyl silicone rubber.

[0069] Example 4

[0070] The present invention provides a method for preparing a broad-spectrum antibacterial material composite of silica gel and rare earth according to Example 1, comprising the following steps (weighing the raw materials according to the amounts and types of the raw materials in Example 1):

[0071] S1. Methyl vinyl silicone rubber is selected as the silicone matrix. The silicone is crushed or ground into particles with a particle size range of 100-400 mesh, and then transferred to a vacuum chamber. Argon gas is introduced into the vacuum chamber, and the power is set to 350W. Plasma treatment is performed for 20 minutes. The plasma-treated silicone particles are immersed in a sodium carbonate solution with a mass fraction of 3% for 15 minutes to complete the surface activation treatment of the silicone.

[0072] S2. Grind lanthanum chloride into powder with a particle size of 30-150 nm.

[0073] S3. Surface modification of the silver nanoparticles was performed by dissolving 1 g of polyvinyl pyrrolidone in 15 mL of toluene to form a uniform solution. Then, silver nanoparticles were weighed and dispersed in the solution at a ratio of 2% of the total volume of the solution. The silver nanoparticles were adsorbed on the surface of the silver nanoparticles by ultrasonic treatment.

[0074] S4. Dissolve the dibenzoylmethane complex of europium in acetone to prepare a solution with a concentration of 0.6 mol / L, and dissolve poly (N-isopropylacrylamide) in acetone to prepare a solution with a concentration of 0.5 mol / L.

[0075] S5, the pretreated silica gel particles of S1 are dropped into a high-speed stirrer, rotating speed 1000 rev / min is set, then the lanthanum chloride powder of S2 is slowly added, stirred for 30min, and lanthanum chloride powder is tentatively dispersed in the silica gel particles. Then S3 is added to carry out the surface-modified nano silver particles, and the stirring process is continued for 20min. Oleic acid is added, and subsequently, according to the quality of silica gel, the dibenzoylmethane complex solution of an amount of europium is calculated and measured, and under continuous stirring, the speed of 3-5 drops per minute is slowly added drop-wise to the stirrer, and the dropping process continues for 10-15min. After being added dropwise, it is stirred for 15min again, and it is guaranteed that the complex is uniformly dispersed. Finally, according to the quality of silica gel, the dibenzoylmethane complex solution of an amount of europium is calculated and measured, and the mixture is uniformly dispersed.

[0076] S6. Transfer the mixture obtained in S5 to an ultrasonic dispersion device, apply a magnetic field (the strength of the magnetic field is 0.1-0.3T) at the same time, and use ultrasonic waves with a frequency of 30kHz to ultrasonically treat the mixture. After ultrasonication for 35 minutes, transfer it to a vulcanization mold, pre-vulcanize it at 110°C for 20 minutes, and then heat it to 150°C for formal vulcanization for 100 minutes. After vulcanization, the antibacterial material is obtained.

[0077] Example 5

[0078] The present invention provides a method for preparing a broad-spectrum antibacterial and antimicrobial composite material of silica gel and rare earth according to Example 2. The method differs from Example 4 in that the raw materials are weighed according to the amounts and types of raw materials in Example 2. In S6, the pre-vulcanization temperature is 120° C., the pre-vulcanization time is 15 minutes, the main vulcanization temperature is 160° C., and the main vulcanization time is 80 minutes.

[0079] Example 6

[0080] The present invention provides a method for preparing a broad-spectrum antibacterial and antimicrobial composite material of silica gel and rare earth according to Example 3. The method differs from Example 4 in that the raw materials are weighed according to the amounts and types of raw materials in Example 3. In S6, the pre-vulcanization temperature is 120°C, the pre-vulcanization time is 15 minutes, the main vulcanization temperature is 170°C, and the main vulcanization time is 60 minutes.

[0081] Performance Testing

[0082] Escherichia coli and Staphylococcus aureus were selected as experimental bacteria to test the antibacterial and bactericidal properties of the anti-bacterial materials of Examples 1-3 of the present invention.

[0083] The bacteria were cultured to the logarithmic growth phase, 100 μL of the bacterial solution was added to Luria-Bertani liquid medium (LB medium, 12.5% ​​yeast powder, 25% tryptone, 25% sodium chloride and 37.5% agar), and the antibacterial material of Examples 1-3 was added (the amount of the antibacterial material added was 60 mg / mL). A group without the antibacterial material was taken as a blank control, and then placed in a constant temperature shaker at 37°C for shaking culture. The bacterial solution was taken every 1 hour, and its optical density value (OD600) at a wavelength of 600 nm was measured using a UV-visible spectrophotometer to detect the growth of the test bacteria. The results are shown as follows: Figure 1 As shown, Examples 1-3 have significant inhibitory effects on Escherichia coli and Staphylococcus aureus, and the growth of bacteria can be controlled at a low level throughout the experimental period. It can be seen that the anti-bacterial material prepared by the present invention has efficient antibacterial ability, greatly reducing the risk of bacterial contamination of medical devices, ensuring the hygiene and safety of medical devices, and providing patients with more reliable medical protection.

[0084] The antibacterial materials of Examples 1-3 were dispersed in an aqueous solution to prepare a mixed solution with a concentration of 60 mg / mL, and the solution was shaken on a constant temperature shaker. The supernatant was taken every 0.5 h, and then the bacterial solution diluted to a CFU of 1.2×106 cells / mL was added to the supernatant. A group without antibacterial materials was taken as a blank control and placed in a constant temperature shaker at 37°C for shaking culture. Finally, 100 μL of the solution was spread on a plate and cultured in a constant temperature incubator at 37°C for 18 to 24 h. The number of colonies was recorded. The results are shown in FIG. Figure 2 As shown, the colony counts of Example 1, Example 2 and Example 3 all showed a significant downward trend over time. Within 3.5 hours, the colony counts all dropped to a low level, indicating that the prepared antibacterial material had a significant inhibitory effect on Escherichia coli.

[0085] In terms of intelligent response performance, the present invention uses spectral analysis technology to test the antibacterial materials of Examples 1-3 in the temperature range of 25°C-40°C. By adjusting the wavelength of the xenon lamp excitation light source to 450nm and maintaining its intensity at 100mW / cm 2 , monitor the fluorescence intensity of the antibacterial material. The results are as follows Figure 3 As shown, the fluorescence intensity of the anti-bacterial materials of Examples 1-3 showed an obvious linear enhancement trend, and a quantitative correlation between temperature and fluorescence signal was successfully established, so that the anti-bacterial materials have good intelligent response performance, so that they can be used to make wearable health care products and expand their scope of application.

[0086] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the same. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solutions of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A broad-spectrum antibacterial material composited with silica gel and rare earth, characterized by: The antibacterial material includes silica gel, rare earth additives, nanosilver particles, dispersants, rare earth complexes with fluorescent properties and thermosensitive polymers. The rare earth complexes with fluorescent properties are organic complexes of europium or organic complexes of terbium. The thermosensitive polymers include one or more of poly N-isopropylacrylamide, poly (N-vinylcaprolactam) and poly (N,N-diethylacrylamide).

2. The broad-spectrum antibacterial material of silica gel and rare earth composite according to claim 1, characterized in that: Calculated by the percentage of each raw material in the mass of the silica gel, the rare earth additive is 0.5%-3%, the nano silver particles are 0.1%-0.5%, the dispersant is 0.5%-2%, the rare earth complex with fluorescent properties is 1%-5%, and the temperature-sensitive polymer is 3%-8%.

3. The broad-spectrum antibacterial material of silica gel and rare earth composite according to claim 1, characterized in that: The silicone rubber includes one or more of methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber.

4. The broad-spectrum antibacterial material of silica gel and rare earth composite according to claim 1, characterized in that: The rare earth additive includes one or more of lanthanum chloride, cerium nitrate, lanthanum oxide, and cerium oxide.

5. The broad-spectrum antibacterial material composed of silica gel and rare earth according to claim 1, characterized in that: The dispersant is oleic acid.

6. A method for preparing a broad-spectrum antibacterial material composite of silica gel and rare earth as claimed in any one of claims 1 to 5, characterized in that: The following steps are included: S1. Pre-treat the silica gel: crush or grind the silica gel into particles and then perform surface activation treatment; S2. Pre-treating the rare earth additive: grinding the rare earth additive into nano-scale or submicron-scale powder; S3. Surface modification of the silver nanoparticles: using polyvinyl pyrrolidone to coat the surface of the silver nanoparticles; S4, preparing a rare earth complex solution with fluorescent properties and a temperature-sensitive polymer solution; S5, putting the silica gel particles pretreated in S1 into a high-speed blender, and then slowly adding the rare earth additive powder in S2, the surface-modified nanosilver particles in S3, the dispersant, the rare earth complex solution with fluorescent properties and the temperature-sensitive polymer solution in S4, and preliminarily mixing them to obtain a mixture; S6. Transfer the mixture obtained in S5 to an ultrasonic dispersion device, apply a magnetic field at the same time, and perform ultrasonic treatment on the mixture. After the ultrasonic treatment, transfer the mixture to a vulcanization mold, pre-vulcanize it at a temperature of 110°C-120°C, and then heat it to 140°C-170°C for formal vulcanization. After the vulcanization is completed, an antibacterial material is obtained.

7. The method for preparing a broad-spectrum antibacterial material composite of silica gel and rare earth according to claim 6, characterized in that: The surface activation treatment in S1 is first plasma treatment and then immersion treatment in a weak alkaline solution.

8. The method for preparing a broad-spectrum antibacterial material composite of silica gel and rare earth according to claim 6, characterized in that: In S3, polyvinyl pyrrolidone is dissolved in an organic solvent such as toluene or dimethylformamide to form a uniform solution, and then nanosilver particles are dispersed in the solution. Ultrasonic treatment is performed to allow the polyvinyl pyrrolidone to adsorb on the surface of the nanosilver particles, and the average particle size of the surface-modified nanosilver particles obtained is 20-50 nm.

9. The method for preparing a broad-spectrum antibacterial material composite of silica gel and rare earth according to claim 6, characterized in that: The ultrasonic treatment in S6 uses ultrasonic waves with a frequency of 25-45 kHz and a magnetic field strength of 0.1-0.3T.

10. An application of a broad-spectrum antibacterial material composited with silica gel and rare earth as claimed in any one of claims 1 to 5, characterized in that: Used in the preparation of medical devices.

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