High-toughness, antibacterial, self-healing, and high-transmittance flexible sensor materials and their preparation methods
By introducing polysulfide polymers and silver nanoparticles into flexible sensors, the antibacterial and self-healing problems of flexible sensors are solved, achieving high toughness, antibacterial properties, self-healing capabilities, and high transmittance, making them suitable for applications such as wearable devices and artificial skin.
Patent Information
- Application Number
- CN202510001890.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-02
- Publication Date
- 2025-10-31
- Estimated Expiration
- 2045-01-02
AI Technical Summary
Existing flexible sensors are susceptible to bacterial contamination during long-term use, leading to performance degradation and shortened lifespan. Additionally, their sensitivity decreases after wear and tear, making self-repair difficult.
By combining polysulfide polymers with silver nanoparticles, the antibacterial and conductive properties are enhanced by introducing polysulfide bonds and silver nanoparticles into the polymer chain segments. The interaction between polysulfide bonds and hydrogen bonds is utilized to achieve self-healing, thus preparing a flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance.
The material possesses strong antibacterial properties, effectively preventing the growth of microorganisms, maintaining high sensitivity, and achieving self-repair of mechanical damage at temperatures suitable for the human body. It also has high permeability, making it suitable for wearable devices and artificial skin.
Smart Images
Figure CN119798965B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of polymer materials technology, specifically relating to a flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance, and its preparation method. Background Technology
[0002] With the advent of the intelligent era, flexible electronic products, characterized by their flexibility and stretchability, have demonstrated enormous market potential. As a core component of these products, flexible sensors can sensitively detect a variety of stimuli related to specific environments or organisms, playing a crucial role in fields such as motion monitoring, electronic skin, and clinical diagnostics. Their unique flexibility, conformability, and lightweight properties make them an important component of next-generation electronic technology.
[0003] Flexible sensors are commonly used in wearable devices, medical devices, and other applications requiring prolonged skin contact. However, bacteria, sweat, and other microorganisms can easily adhere to the sensor surface in these environments, and long-term accumulation can lead to decreased device performance, signal distortion, and even shortened lifespan. Particularly in medical and health monitoring, the area where the sensor contacts the skin is more susceptible to bacterial contamination, which can not only affect the device's detection accuracy but also potentially threaten human health. Therefore, using materials with antibacterial properties to fabricate flexible sensors is an effective strategy that helps improve the sensor's safety and durability.
[0004] Depending on the detection direction, flexible sensors can be categorized into strain, pressure, temperature, humidity, and pH sensors, among others. However, these sensors inevitably experience wear and tear during use, leading to decreased sensitivity and a shortened lifespan. Therefore, the development of flexible sensor materials with self-healing properties at room temperature and high sensitivity is of significant application value. Summary of the Invention
[0005] To address the shortcomings of flexible sensors in terms of antibacterial and self-healing capabilities, this invention provides a flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance, along with its preparation method. This invention discovers that by adding an appropriate amount of elemental sulfur to the polymerization of polyols and polyisocyanates, polysulfide bonds are introduced into the polymer chains by abstracting hydrogen from the polyurethane, enhancing the stability of the polymer structure. The resulting material retains high sensitivity even after prolonged use. Furthermore, the addition of nano-silver particles allows for complexation with sulfur, resulting in uniform dispersion along the polymer chains. The abundant sulfur and nano-silver particles improve the material's antibacterial and electrical conductivity properties. The interaction between polysulfide and hydrogen bonds enables the material to repair mechanical damage within a temperature range suitable for human use. This flexible sensor material also exhibits high transmittance, making it suitable for applications in artificial skin, wearable devices, and other fields.
[0006] To achieve the above objectives, the present invention is implemented through the following technical solution:
[0007] A flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance is prepared using polysulfide polymers as raw materials. The formulation composition by mass percentage is: 95-99 wt% polysulfide polymer and 1-5 wt% nano-silver particles.
[0008] The polysulfide polymer is composed of 10-20 wt% elemental sulfur, 25-50 wt% hydroxyl monomers and 30-60 wt% isocyanate monomers.
[0009] The hydroxyl monomers in the polysulfide polymers are: polytetrahydrofuran PTMG-2000, polyethylene glycol PEG-600, polycaprolactone diol PCLDO-530, and tris(pentaerythritol)TPT.
[0010] The isocyanate monomers in the polysulfide polymers are: pentamethylene diisocyanate (PDI) and isophorone diisocyanate (IPDI).
[0011] The preparation method of polysulfide polymer is as follows: hydroxyl monomer, isocyanate monomer and elemental sulfur are added to a reaction flask according to the mass percentage, a catalyst is added, and the reaction is carried out at 80℃ for 12 hours. After the reaction is completed, the sample is washed with n-hexane solvent until the solvent is clear and transparent, the sample is dried, and the polysulfide polymer is obtained.
[0012] The fabrication process of a flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance involves the following steps:
[0013] A. Place the dried polysulfide polymer and nano-silver particles in a flask according to the mass percentage, mix and stir at 80°C for 8 hours. After the reaction is complete, wash with ethanol solvent until the solvent is clear and transparent, and finally dry in a vacuum oven.
[0014] B. The dried mixture is hot-pressed to obtain a flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance. The hot-pressing temperature is 90-100℃, and the hot-pressing time is 3-4 minutes.
[0015] Beneficial technical effects:
[0016] (1) In this invention, the raw material elemental sulfur and nano silver particles provide the material with strong antibacterial ability, which can prevent the growth of microorganisms during the use of the material and affect its use.
[0017] (2) The polymer network of the present invention contains a large number of SS bonds and hydrogen bonds, which endow the material with the ability to self-repair efficiently at a suitable temperature for the human body.
[0018] (3) The material of the present invention has high optical transmittance and can be used in wearable devices, artificial skin and other fields.
[0019] (4) The material of the present invention has long-lasting durability and retains high sensitivity even after long-term use.
[0020] (5) The material preparation method of the present invention is simple, the raw materials are inexpensive, and the production cycle is short, which greatly reduces the production cost. Attached Figure Description
[0021] Figure 1 The FTIR spectra of the products from Examples 1, 2, 3 and 4 are shown.
[0022] Figure 2 XPS curve of the product of Example 1.
[0023] Figure 3 The stress-strain curves of the products obtained in Example 1, Example 2, Comparative Example 1, Example 3 and Example 4 are shown.
[0024] Figure 4 The transmittance curves of the products from Examples 1 and 2 are compared with those from Examples 1, 3, 4 and 5.
[0025] Figure 5 The conductivity curves of the products of Example 1, Example 2, Example 3 and Comparative Example 1 after immediate molding, 1 month, 6 months and 12 months are shown.
[0026] Figure 6 The stress-strain curves of Example 3 before and after self-healing at room temperature are shown. Detailed Implementation
[0027] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.
[0028] Example 1
[0029] 100g of a polysulfide polymer containing 30wt% pentamethylene diisocyanate (PDI), 60wt% polytetrahydrofuran (PTMG-2000), and 10wt% sulfur, along with 5g of silver nanoparticles, was placed in a 250ml flask and stirred at 80℃ for 8 hours. After the reaction, the mixture was washed with ethanol until the solvent was clear and transparent. The mixture was then dried in a vacuum oven for 4 hours. The dried mixture was then hot-pressed at 90℃ for 3 minutes to obtain a flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance.
[0030] The preparation method of polysulfide polymer is as follows: hydroxyl monomer, isocyanate monomer, and elemental sulfur are added to a reaction flask according to the mass percentage, and 0.5 wt% of sodium hydroxide (NaOH) catalyst is added. The reaction is carried out at 80℃ for 12 h. After the reaction is completed, the sample is washed with n-hexane solvent until the solvent is clear and transparent, and then dried and stored.
[0031] Example 2
[0032] 100g of a polysulfide polymer containing 28wt% pentamethylene diisocyanate (PDI), 57wt% polytetrahydrofuran (PTMG-2000), and 15wt% sulfur, along with 5g of silver nanoparticles, was placed in a 250ml flask and stirred at 80℃ for 8 hours. After the reaction, the mixture was washed with ethanol until the solvent was clear and transparent. The mixture was then dried in a vacuum oven for 4 hours. The dried mixture was then hot-pressed at 90℃ for 3 minutes to obtain a flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance.
[0033] The preparation method of the polysulfide polymer is the same as in Example 1.
[0034] Comparative Example 1
[0035] 100g of a polymer containing 35wt% pentamethylene diisocyanate (PDI) and 65wt% polytetrahydrofuran (PTMG-2000) after impurity removal and drying was placed in a 250ml flask and mixed and stirred at 80℃ for 8h. After the reaction was completed, the mixture was washed with ethanol solvent until the solvent was clear and transparent. The mixture was then dried in a vacuum oven for 4h. The dried mixture was hot-pressed at 90℃ for 3min to obtain the flexible sensor material.
[0036] The polymer was prepared using the same method as in Example 1.
[0037] Example 3
[0038] 100g of a polysulfide polymer containing 25wt% isophorone diisocyanate (IPDI), 55wt% polytetrahydrofuran (PTMG-2000), and 20wt% sulfur, and 5g of silver nanoparticles were placed in a 250ml flask and mixed and stirred at 80℃ for 8h. After the reaction was completed, the mixture was washed with ethanol solvent until the solvent was clear and transparent. The mixture was then dried in a vacuum oven for 4h. The dried mixture was then hot-pressed at 100℃ for 4min to obtain a flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance.
[0039] The preparation method of the polysulfide polymer is the same as in Example 1.
[0040] Comparative Example 2
[0041] 100g of a polysulfide polymer containing 25wt% isophorone diisocyanate (IPDI), 55wt% polytetrahydrofuran (PTMG-2000), and 20wt% sulfur after impurity removal and drying was placed in a 250ml flask and mixed and stirred at 80℃ for 8h. After the reaction was completed, the mixture was washed with ethanol solvent until the solvent was clear and transparent. The mixture was then dried in a vacuum oven for 4h. The dried mixture was then hot-pressed at 100℃ for 4min to obtain the flexible sensor material.
[0042] The preparation method of the polysulfide polymer is the same as in Example 1.
[0043] Example 4
[0044] 100g of a polysulfide polymer containing 35wt% isophorone diisocyanate (IPDI), 45wt% polytetrahydrofuran (PTMG-2000), and 20wt% sulfur, and 5g of silver nanoparticles were placed in a 250ml flask and mixed and stirred at 80℃ for 8h. After the reaction was completed, the mixture was washed with ethanol solvent until the solvent was clear and transparent. The mixture was then dried in a vacuum oven for 4h. The dried mixture was hot-pressed at 100℃ for 4min to obtain a flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance.
[0045] The preparation method of the polysulfide polymer is the same as in Example 1.
[0046] Comparative Example 3
[0047] Take 100g of polymer containing 40wt% isophorone diisocyanate (IPDI) and 60wt% polytetrahydrofuran (PTMG-2000) after impurity removal and drying, and 5g of silver nanoparticles, and place them in a 250ml flask. Mix and stir at 80℃ for 8h. After the reaction is complete, wash with ethanol solvent until the solvent is clear and transparent. Dry in a vacuum oven for 4h. Hot press the dried mixture at 100℃ for 4min to obtain the flexible sensor material.
[0048] The polymer was prepared using the same method as in Example 1.
[0049] Example 5
[0050] 100g of a polysulfide polymer containing 48wt% isophorone diisocyanate (IPDI), 32wt% polyethylene glycol (PEG-600), and 20wt% sulfur after impurity removal and drying, and 5g of silver nanoparticles were placed in a 250ml flask and mixed and stirred at 80℃ for 8h. After the reaction was completed, the mixture was washed with ethanol solvent until the solvent was clear and transparent, and dried in a vacuum oven for 4h. The dried mixture was then hot-pressed at 100℃ for 4min to obtain a flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance.
[0051] The preparation method of the polysulfide polymer is the same as in Example 1.
[0052] Example 6
[0053] 100g of a polysulfide polymer containing 50wt% isophorone diisocyanate (IPDI), 30wt% polycaprolactone diol (PCLDO-530), and 20wt% sulfur, and 5g of silver nanoparticles were placed in a 250ml flask and mixed and stirred at 80℃ for 8h. After the reaction was completed, the mixture was washed with ethanol solvent until the solvent was clear and transparent. The mixture was then dried in a vacuum oven for 4h. The dried mixture was then hot-pressed at 100℃ for 4min to obtain a flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance.
[0054] The preparation method of the polysulfide polymer is the same as in Example 1.
[0055] Example 7
[0056] 100g of a polysulfide polymer containing 35wt% isophorone diisocyanate (IPDI), 45wt% tris(pentaerythritol) TPT, and 20wt% sulfur, and 5g of silver nanoparticles were placed in a 250ml flask and mixed and stirred at 80℃ for 8h. After the reaction was completed, the mixture was washed with ethanol solvent until the solvent was clear and transparent. The mixture was then dried in a vacuum oven for 4h. The dried mixture was then hot-pressed at 100℃ for 4min to obtain a flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance.
[0057] The preparation method of the polysulfide polymer is the same as in Example 1.
[0058] Example 8
[0059] 100g of a polysulfide polymer containing 25wt% isophorone diisocyanate (IPDI), 55wt% polytetrahydrofuran (PTMG-2000), and 20wt% sulfur, and 2.5g of silver nanoparticles were placed in a 250ml flask and mixed and stirred at 80℃ for 8h. After the reaction was completed, the mixture was washed with ethanol solvent until the solvent was clear and transparent. The mixture was then dried in a vacuum oven for 4h. The dried mixture was then hot-pressed at 100℃ for 4min to obtain a flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance.
[0060] The preparation method of the polysulfide polymer is the same as in Example 1.
[0061] Performance testing: Tensile properties were tested at 25℃ (GB / T 1040.1-2006), and the data are shown in Table 1.
[0062] Table 1. Tensile properties and self-healing efficiency of the flexible sensors in the embodiments.
[0063]
[0064]
[0065] Note: Mechanical performance testing; three sets of control experiments were established for each test example.
[0066] As shown in Table 1, the flexible sensor material synthesized in this invention possesses high toughness, meeting the basic requirements for the use of flexible sensors. The flexible sensor material prepared in this invention can repair mechanical damage within 30 minutes at 35°C while still maintaining good mechanical properties. Furthermore, the properties of this material can be controlled by changing the monomer input and monomer type, and it also has broad adaptability for fixing materials with specific requirements.
[0067] The antibacterial properties of the flexible sensor material, characterized by high toughness, antibacterial properties, self-healing ability, and high transmittance, are shown in Table 2. Tests conducted according to the GB / T4789.2-2010 standard demonstrate that this flexible sensor material exhibits excellent antibacterial properties.
[0068] Table 2 shows the antibacterial performance of the flexible sensors in the embodiments.
[0069]
[0070] This invention produces a flexible sensor material that exhibits excellent plasticity at a suitable human body temperature, high antibacterial properties, high toughness, and high transparency. The abundant sulfur content in the material provides superior antibacterial properties, preventing the material from increasing the risk of human infection due to bacterial growth. Simultaneously, the material possesses high transparency, making it suitable for applications such as artificial skin and wearable devices.
[0071] The electrical conductivity of the flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance is shown in Table 3.
[0072] Table 3. Conductivity of the flexible sensor in the embodiments
[0073]
[0074] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.
Claims
1. A flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance, characterized in that: The flexible sensor material is composed of the following composition by mass percentage: 95-99 wt% polysulfide polymer and 1-5 wt% silver nanoparticles. The polysulfide polymer has the following composition by mass percentage: 10-20 wt% elemental sulfur, 25-50 wt% hydroxyl monomer, and 30-60 wt% isocyanate monomer. The hydroxyl monomers are: polytetrahydrofuran PTMG-2000, polyethylene glycol PEG-600, polycaprolactone diol PCLDO-530, and tris(pentaerythritol)TPT.
2. The flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance according to claim 1, characterized in that, The isocyanate monomers are: pentamethylene diisocyanate (PDI) and isophorone diisocyanate (IPDI).
3. The flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance according to claim 1, characterized in that, The preparation method of the polysulfide polymer is as follows: hydroxyl monomer, isocyanate monomer, and elemental sulfur are added to a reaction flask according to the mass percentage, a catalyst is added to react, after the reaction is completed, the mixture is washed until the solvent is clear and transparent, and then dried to obtain the polysulfide polymer.
4. A method for preparing a flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance according to claim 1, characterized in that, The preparation method steps are as follows: A. Place the dried polysulfide polymer and nano-silver particles in a flask according to the mass percentage, mix and stir at 80°C for 8 h. After the reaction is complete, wash with ethanol until the solvent is clear and transparent, and finally dry in a vacuum oven. B. The dried mixture is hot-pressed to obtain a flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance.
5. The method for preparing the flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance according to claim 4, characterized in that, The hot-pressing temperature in step B is 90-100℃, and the hot-pressing time is 3-4 min.
6. An application of the flexible sensor material with high toughness, antibacterial properties, self-healing ability, and high transmittance as described in claim 1, characterized in that, The flexible sensor material is used in the fields of artificial skin and wearable devices.