Organic fluorosilicone synthetic leather, preparation method and application of organic fluorosilicone synthetic leather in field of intelligent wearing

Abstract

The invention relates to organic fluorosilicone synthetic leather, a preparation method and application in the field of intelligent wearing. Under the action of the catalyst, the vinyl silicone oil, the hydrogen-containing silicone oil, the vinyl fluorine-containing silicone oil and the conductive carbon paste react to prepare a series of organic fluorine-silicon synthetic leather with different fluorine contents, the reaction process is green, the synthetic leather has lower surface energy, the service life of oil-resistant and solvent-resistant products is prolonged, and the comfort of the synthetic leather is improved. Based on good chemical stability, stretchability and wearing comfort, the organic fluorosilicone synthetic leather can meet the basic physical and chemical performance requirements of synthetic leather, and the application range of the materials in the field of flexible wearable sensing is widened. The organic fluorosilicone synthetic leather material is applied to the fields of health monitoring, human motion detection, electronic skin, human-computer interfaces, soft robots, implantable biosensors and the like, and a material basis is provided for producing flexible wearable sensors with high sensitivity, high stretchability and excellent mechanical properties.

Description

Technical Field

[0001] The invention relates to organic fluorine-silicon synthetic leather, a preparation method and applications in the field of smart wearables, and belongs to the field of new materials. Background Art

[0002] From the perspective of structural composition, synthetic leather can be divided into five parts: surface layer (surface effect layer), surface layer, intermediate foaming layer, bonding layer and substrate. Synthetic leather materials have high mechanical strength, hydrolysis resistance, wear resistance, scratch resistance, aging resistance, bending resistance, etc., and have been widely used in the fields of shoe uppers, bags, clothing, etc., and have occupied an important position in people's daily life. So far, solvent-based polyurethane is mainly used for coatings in traditional synthetic leather manufacturing processes, and China's annual consumption is about 2 million tons. For example: CN109454942A discloses a high-density high-peeling deer fiber velvet synthetic leather, which includes a base fabric layer, the upper end face of the base fabric layer is set as a dry polyurethane layer, the upper end face of the dry polyurethane layer is provided with an elastic layer, the elastic layer includes an elastic epidermis layer and an internal cavity layer, the dry polyurethane layer and the elastic layer have a structure, the upper end of the elastic layer is coated with a nano-organic fluorosilicone film layer, the upper surface of the nano-organic fluorosilicone film layer is provided with a waterproof film, and the upper surface of the waterproof film is a feel treatment layer. However, the use and discharge of a large amount of organic solvents not only cause carbon emissions, but also bring serious environmental pollution. The main raw materials of polyurethane, diisocyanate and polyol, are derivatives of the petroleum industry. With the increasing depletion of petroleum resources, the global petrochemical industry chain faces huge challenges. Therefore, how to develop new coating materials to replace carbon-based and petroleum-based raw materials according to the demand for carbon peak and carbon emission reduction strategy has become an inevitable trend in the development of the synthetic leather industry.

[0003] Organic silicon synthetic leather coating has unique resource advantages. Silicon content is the most abundant raw material in the earth's crust resources, which can reduce the consumption of carbon-based materials. Organic silicon synthetic leather coating is mainly formed by mixing, coating and thermal curing of components such as base polymer (vinyl silicone oil), crosslinking agent (hydrogen-containing silicone oil), reinforcing filler (white carbon black), platinum catalyst and inhibitor. The preparation process mainly adopts addition type liquid silicone rubber system, which reduces the emission and use of solvents, and the reaction process is relatively green. For example: CN113737539A discloses organic silicon synthetic leather for ship and yacht furniture decoration and its preparation method, and CN114263048A discloses organic silicon synthetic leather surface layer, preparation method and organic silicon synthetic leather. Fluorosilicone polymer is an important branch of organic silicon material. On the basis of the good performance of organic silicon, it has lower surface energy and more stable chemical resistance. It can reduce the surface tension of the coating fabric interface and extend the service life of oil-resistant and solvent-resistant products. Therefore, organic fluorosilicone synthetic leather materials can be prepared. Organic fluorosilicone synthetic leather can meet the market demand for high-quality ecological synthetic leather today and has great development prospects. With the continuous development of society and technology and the growing diversified demands of consumers, it is of great significance to explore and develop more functional and intelligent organic fluorosilicone synthetic leathers.

[0004] Smart flexible wearable products are increasingly being shown in real life and are deeply loved by people. Smart flexible wearable health monitoring devices can accurately detect human health parameters in real time. They are light and portable, have excellent electrical performance and high integration, and are increasingly entering people's field of vision. Traditional sensing devices based on metals or semiconductors can only sense tiny deformations of small strains, and the inherent rigidity affects the comfort of wearing. Synthetic leather has become a hot topic in the field of flexible wearable sensing due to its good flexibility and comfort. For example: CN117103812A discloses a synthetic leather for smart wearable silicone gloves and its preparation method. In the field of flexible wearable health monitoring, how to improve the sensitivity, stretchability and mechanical properties of materials while ensuring flexibility and comfort has become an urgent problem to be solved.

[0005] Based on good chemical stability, stretchability and wearing comfort, organic fluorosilicone synthetic leather can not only meet the basic physical and chemical performance requirements of synthetic leather, but also can be used in fields such as health monitoring, human motion detection, electronic skin, human-machine interface, soft robots and implantable biosensors, providing a material basis for the production of flexible wearable sensors with high sensitivity, high stretchability and excellent mechanical properties. Organic fluorosilicone synthetic leather is a solvent-free process for green production, and its process is more environmentally friendly than traditional polyurethane solvent production. Organic fluorosilicone synthetic leather has good hydrophobic and oleophobic effects, and retains the high air permeability of the polymer network structure, which alleviates the problem of synthetic leather materials being stuffy and uncomfortable to wear. Therefore, the preparation of organic fluorosilicone synthetic leather has very important practical value. For this reason, the present invention is proposed. Summary of the invention

[0006] In view of the above-mentioned technical status, especially the problems of serious pollution of solvent-based synthetic leather in the prior art, blank of ultra-low temperature applicability, weak high-performance anti-fouling performance, poor wearing comfort and the need to improve the usability of wearable electronic sensors, the present invention provides organic fluorosilicone synthetic leather, preparation method and application in the field of smart wear. The present invention adopts vinyl silicone oil, hydrogen-containing silicone oil and vinyl fluorine-containing silicone oil to synthesize organic fluorosilicone polymer synthetic leather through addition reaction, thereby avoiding the problem of pollution caused by the use of solvents and improving the low temperature resistance, anti-fouling and breathability of synthetic leather. The present invention combines conductive carbon slurry with organic fluorosilicone synthetic leather, which can be used to prepare flexible wearable products with human health monitoring and motion tracking functions.

[0007] Therefore, an object of the present invention is to provide an organic fluorine-silicone synthetic leather and a method for preparing the same.

[0008] The second object of the present invention is to provide the use of the above-mentioned organic fluorine-silicone synthetic leather in the field of smart wearables.

[0009] The third object of the present invention is to provide a flexible smart wearable material.

[0010] The fourth object of the present invention is to provide a method for health monitoring and human motion detection.

[0011] The technical solution for achieving the above-mentioned invention object can be summarized as follows:

[0012] An organic fluorine-silicone synthetic leather comprises: a base fabric and an organic fluorine-silicone polymer layer on the surface of the base fabric, wherein a conductive material layer is arranged between the base fabric and the organic fluorine-silicone polymer layer;

[0013] The organic fluorine-silicone polymer layer is a catalytic reaction copolymer of vinyl silicone oil, hydrogen-containing silicone oil and vinyl fluorine-containing silicone oil;

[0014] The conductive material is carbon paste.

[0015] According to the present invention, preferably, the molecular structure of the vinyl silicone oil is organofunctional group-R-polydisiloxane, and more preferably at least one of vinyl-terminated polydimethylsiloxane (Vi-PDMS) and vinyl-terminated polymethylvinylsiloxane (Vi-PMVS).

[0016] According to the present invention, preferably, the molecular structure of the hydrogen-containing silicone oil is an organic functional group -R-SiH(OR)2, and more preferably polymethylhydrogensiloxane (PMHS).

[0017] According to the present invention, preferably, the vinyl fluorinated silicone oil is a vinyl terminated polymer, and more preferably, it is obtained by catalytic reaction of D3F, D4 and vinyl silane;

[0018] Preferably, the catalyst for preparing the vinyl fluorinated silicone oil is an alkaline compound, more preferably tetramethylammonium hydroxide.

[0019] According to the present invention, preferably, the catalyst for the catalytic reaction of the organic fluorosilicone polymer layer is a platinum compound, and more preferably a Karstedt catalyst.

[0020] According to the present invention, preferably, the molar ratio of vinyl silicone oil to hydrogen silicone oil in the organic fluorosilicone polymer layer is 9:1;

[0021] Preferably, the content of the vinyl fluorine-containing silicone oil in the organic fluorine-silicone polymer layer accounts for 0.1-20% of the total weight of the vinyl silicone oil and the hydrogen-containing silicone oil.

[0022] According to the present invention, preferably, the organic fluorine-silicone polymer layer is a structural layer formed by coating a catalytic reaction copolymer of vinyl silicone oil, hydrogen-containing silicone oil and vinyl fluorine-containing silicone oil on release paper.

[0023] According to the present invention, the use of the catalytic reaction copolymer of the above-mentioned vinyl silicone oil, hydrogen-containing silicone oil and vinyl fluorine-containing silicone oil in the preparation of organic fluorine-silicone synthetic leather is further preferably used in the preparation of smart wearable product materials.

[0024] According to the present invention, the method for preparing the above-mentioned organic fluorine-silicone synthetic leather comprises the following steps:

[0025] After the vinyl silicone oil, hydrogen-containing silicone oil and vinyl fluorine-containing silicone oil are mixed evenly, vacuum drying is performed, a catalyst is added and stirred evenly, and the mixture is coated on a release paper to obtain an organic fluorine-silicone polymer layer;

[0026] The carbon slurry is dissolved in dichloromethane (CH2Cl2), sprayed on the surface of the obtained organic fluorosilicone polymer layer, and completely cured at room temperature; then a base cloth is attached to the surface to obtain the organic fluorosilicone synthetic leather.

[0027] According to the present invention, also provided are applications of the above-mentioned organic fluorine-silicone synthetic leather in health monitoring, human motion detection, soft robots, ionic skin, human-machine interface and flexible electronic devices.

[0028] According to the present invention, a flexible intelligent wearable material is also provided, and the material is the above-mentioned organic fluorine-silicone synthetic leather.

[0029] According to the present invention, a method for health monitoring and human motion detection is also provided, comprising using the above-mentioned organic fluorine-silicone synthetic leather to monitor human health and detect human motion, comprising the following steps:

[0030] Cut the organic fluorosilicone synthetic leather into appropriate sizes, connect the resistance tester to both ends of the conductive material layer, monitor the heart pulse, detect the movements of knee bending, neck bending, and elbow bending, detect smiling, laughing, and surprised facial expressions, collect resistance change data, and draw a resistance change graph to complete the human health monitoring and human movement detection.

[0031] The beneficial effects of the present invention are as follows:

[0032] 1. The method for preparing the organic fluorine-silicone synthetic leather in the present invention is simple and feasible, has strong designability, a high success rate and is easy to scale up. The prepared organic fluorine-silicone synthetic leather has a wide range of high and low temperature applications and excellent stain resistance.

[0033] 2. The hydrophobic effect of the organic fluorine-silicone synthetic leather material prepared by the present invention is increased compared with the synthetic leather without fluorine, and the surface hydrophobic effect can be increased from the contact angle of 105° of the synthetic leather to the contact angle of 128°. At the same time, in the tensile performance test, the tensile strength of the synthetic leather material is also increased, from the stress of 9.95MPa to the stress of 14.83MPa.

[0034] 3. The organic fluorine-silicone synthetic leather prepared by the present invention has the advantages of high sensitivity, fast response speed, good long-term stability and good durability for human health monitoring and human motion detection. Based on these advantages, the application prospects of this type of material in health monitoring, human motion detection, soft robots, ionic skin, human-machine interface and other flexible electronic devices are expanded.

[0035] 4. The present invention does not require any organic solvents, consumes no water, and produces no by-products during the preparation process, thus alleviating the problems of long process flow and high emission of volatile organic compounds (VOCs) in traditional synthetic leather. The content of vinyl fluorinated silicone oil introduced into synthetic leather can be adjusted by adjusting the modification process and the content of selected silicone oil; the molecular structure of fluorinated silicone oil and the finishing and modification process of synthetic leather materials can be adjusted according to specific needs to meet actual needs, with strong flexibility. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is the infrared spectrum of the organic fluorine-silicon synthetic leather material obtained during the reaction process in Example 2 of the present invention.

[0037] Figure 2 This is a thermogravimetric analysis diagram of organic fluorine-silicone synthetic leather materials with different fluorine contents in Test Example 1 of the present invention.

[0038] Figure 3 This is a macroscopic photograph of the product in Example 2 of the present invention.

[0039] Figure 4 This is a resistance change diagram of the organic fluorosilicone synthetic leather material for human health monitoring and human movement detection in Test Example 2 of the present invention, pulse monitoring (top), larger movements such as knee bending, neck bending, elbow bending (middle), and small movement detection of facial expressions such as smiling, laughing, and surprise (bottom).

[0040] Figure 5 This is the DSC graph of the organic fluorine-silicone synthetic leather material with different fluorine contents in Test Example 3 of the present invention.

[0041] Figure 6 This is a graph showing the hydrophobic properties of an organic fluorine-silicone synthetic leather material with a fluorine content of 20% in Test Example 4 of the present invention.

[0042] Figure 7 This is a test diagram of the mechanical properties of organic fluorine-silicone synthetic leather materials with different fluorine contents in Test Example 5 of the present invention. DETAILED DESCRIPTION

[0043] An organic fluorine-silicone synthetic leather comprises: a base fabric and an organic fluorine-silicone polymer layer on the surface of the base fabric, wherein a conductive material layer is arranged between the base fabric and the organic fluorine-silicone polymer layer;

[0044] The organic fluorine-silicone polymer layer is a catalytic copolymer of vinyl silicone oil, hydrogen-containing silicone oil and vinyl fluorine-containing silicone oil;

[0045] The conductive material is carbon paste.

[0046] According to the present invention, the molecular structure of the vinyl silicone oil is generally organic functional group-R-polydisiloxane;

[0047] In one or more preferred embodiments, the vinyl silicone oil is vinyl-terminated polydimethylsiloxane (Vi-PDMS), vinyl-terminated polymethylvinylsiloxane (Vi-PMVS), etc.

[0048] In one or more preferred embodiments, the viscosity of the vinyl silicone oil at 25° C. is 5000-60000 mPa.s, and the molar content of vinyl is 0.2-5%.

[0049] According to the present invention, the molecular structure of the hydrogen-containing silicone oil is generally an organic functional group -R-SiH(OR)2, which can be cross-linked at an appropriate temperature under the action of a metal catalyst to form a waterproof film on the surface of various substrates, and is widely used as a waterproofing agent, anti-adhesive agent or anti-corrosion agent for fabrics, fire extinguishing agents, paper, metals, wood, leather, glass, cement, ceramics, and marble;

[0050] In one or more preferred embodiments, the hydrogen-containing silicone oil is polymethyl hydrogen siloxane (PMHS);

[0051] In one or more preferred embodiments, the hydrogen-containing silicone oil has a viscosity of 100-10000 mPa.s at 25° C. and a hydrogen molar content of 1-5%.

[0052] According to the present invention, the vinyl fluorinated silicone oil is generally a vinyl terminated polymer;

[0053] In one or more preferred embodiments, the vinyl fluorinated silicone oil is obtained by catalytic reaction of D3F, D4 and vinyl silane through a catalyst;

[0054] Preferably, the catalyst for preparing vinyl fluorinated silicone oil is an alkaline compound, such as tetramethylammonium hydroxide.

[0055] In one or more preferred embodiments, the catalyst for the catalytic reaction of preparing the organic fluorosilicone polymer layer is a platinum compound, preferably a Karstedt catalyst;

[0056] In one or more preferred embodiments, the molar fluorine content of the vinyl fluorinated silicone oil is 2-20%.

[0057] In one or more preferred embodiments, the viscosity of the vinyl fluorinated silicone oil at 25° C. is 5000-50000 mPa.s.

[0058] According to the present invention, the molar ratio of vinyl silicone oil to hydrogen silicone oil in the organic fluorosilicone polymer layer is 9:1;

[0059] In one or more preferred embodiments, the content of vinyl fluorine-containing silicone oil in the organic fluorine-silicone polymer layer is 0.1-20% of the total weight of vinyl silicone oil and hydrogen-containing silicone oil, for example: 1%, 3%, 6%, 9%, 12%, 15%, 20%.

[0060] In one or more preferred embodiments, the organic fluorine-silicone polymer layer is a structural layer formed by coating a catalytic reaction copolymer of vinyl silicone oil, hydrogen-containing silicone oil and vinyl fluorine-containing silicone oil on release paper.

[0061] According to the present invention, the use of the catalytic reaction copolymer of the above-mentioned vinyl silicone oil, hydrogen-containing silicone oil and vinyl fluorine-containing silicone oil in the preparation of organic fluorine-silicone synthetic leather is further preferably used in the preparation of smart wearable product materials.

[0062] According to the present invention, the method for preparing the above-mentioned organic fluorine-silicone synthetic leather comprises the following steps:

[0063] After the vinyl silicone oil, hydrogen-containing silicone oil and vinyl fluorine-containing silicone oil are mixed evenly, vacuum drying is performed, a catalyst is added and stirred evenly, and the mixture is coated on a release paper to obtain an organic fluorine-silicone polymer layer;

[0064] The carbon slurry is dissolved in dichloromethane (CH2Cl2), sprayed on the surface of the obtained organic fluorosilicone polymer layer, and completely cured at room temperature; then a base cloth is attached to the surface to obtain the organic fluorosilicone synthetic leather.

[0065] According to the present invention, a preferred embodiment of the method for preparing the above-mentioned organic fluorine-silicone synthetic leather comprises the following steps:

[0066] Vinyl silicone oil, hydrogen-containing silicone oil and vinyl fluorine-containing silicone oil are mixed evenly in a beaker, and placed in a vacuum drying oven to evacuate for 15 minutes, platinum catalyst is added to the mixture and stirred evenly, and the mixture is scraped and coated on a release paper using a coating rod to obtain an organic fluorine-silicone polymer layer;

[0067] The carbon slurry is dissolved in dichloromethane (CH2Cl2), and the carbon slurry solution is sprayed on the surface of the organic fluorosilicone polymer when it is semi-cured, and completely cured at room temperature; then, the organic silicone adhesive is coated, and the coating rod is used to scrape it on the cured release paper and the base cloth is pasted on the surface of the release paper to obtain the organic fluorosilicone synthetic leather material.

[0068] According to the present invention, also provided are applications of the above-mentioned organic fluorine-silicone synthetic leather in health monitoring, human motion detection, soft robots, ionic skin, human-machine interface and flexible electronic devices.

[0069] According to the present invention, a flexible intelligent wearable material is also provided, and the material is the above-mentioned organic fluorine-silicone synthetic leather.

[0070] According to the present invention, a method for health monitoring and human motion detection is also provided, comprising using the above-mentioned organic fluorine-silicone synthetic leather to monitor human health and detect human motion, comprising the following steps:

[0071] Cut the organic fluorosilicone synthetic leather into appropriate sizes, connect the resistance tester to both ends of the conductive material layer, monitor the heart pulse, detect the movements of knee bending, neck bending, and elbow bending, detect smiling, laughing, and surprised facial expressions, collect resistance change data, and draw a resistance change graph to complete the human health monitoring and human movement detection.

[0072] According to the present invention, human health monitoring mainly monitors pulse changes;

[0073] According to the present invention, human body motion detection mainly includes detection of larger movements such as knee bending, neck bending, elbow bending, and smaller movements of facial expressions such as smiling, laughing, and surprise.

[0074] Principle of the present invention:

[0075] The present invention is to prepare an organic fluorine-silicone synthetic leather material by using vinyl silicone oil, hydrogen-containing silicone oil, conductive carbon paste and vinyl fluorine-containing silicone oil under the action of a catalyst. In the present invention, for example, a series of organic fluorine-silicone synthetic leathers are generated by reacting vinyl silicone oil (Vi-PMVS), hydrogen-containing silicone oil (PMHS), conductive carbon paste and vinyl fluorine-containing silicone oil with different contents. The reaction process is relatively mild and the reaction success rate is high.

[0076] In the preparation process of the organic fluorine-silicone synthetic leather material of the present invention, vinyl silicone oil (Vi-PMVS) (vinyl polymethylvinyl siloxane), hydrogen-containing silicone oil (PMHS) (polymethylhydrogen siloxane), conductive carbon paste and vinyl fluorine-containing silicone oil with different contents are used as raw materials, and Karstedt catalyst is used as a catalyst. The organic fluorine-silicone synthetic leather material is obtained by copolymerization through a hydrosilylation reaction.

[0077] Taking Vi-PMVS, PMHS and vinyl fluorinated silicone oil as examples, the reaction technology route is as follows:

[0078]

[0079]

[0080] The invention adopts vinyl silicone oil, hydrogen-containing silicone oil, conductive carbon paste and vinyl fluorine-containing silicone oil with different contents to prepare organic fluorine-silicone synthetic leather materials with different fluorine contents.

[0081] The present invention is described in detail below by means of specific examples, but is not limited thereto.

[0082] The raw materials used in the examples are all conventional commercially available raw materials, and the equipment used are all conventional equipment. The vinyl silicone oil used is Vi-PMVS, the hydrogen-containing silicone oil is PMHS, and the vinyl fluorine-containing silicone oil is obtained by reacting D3F, D4 and vinyl silane.

[0083] Embodiment 1:

[0084] The organic fluorine-silicone synthetic leather comprises: a base fabric and an organic fluorine-silicone polymer layer on the surface of the base fabric, wherein a conductive material layer is arranged between the base fabric and the organic fluorine-silicone polymer layer;

[0085] The organic fluorine-silicone polymer layer is a catalytic copolymer of vinyl silicone oil, hydrogen-containing silicone oil and vinyl fluorine-containing silicone oil;

[0086] The conductive material is carbon paste.

[0087] The preparation process includes the following steps:

[0088] Weigh 9.000 g of vinyl silicone oil, 1.000 g of hydrogen-containing silicone oil and 0.300 g of catalyst, mix the vinyl silicone oil, hydrogen-containing silicone oil and vinyl fluorine-containing silicone oil evenly in a beaker, put it into a vacuum drying oven and evacuate for 15 minutes, add the platinum catalyst to the mixture and stir evenly, use a coating rod to scrape the mixture on the release paper to obtain an organic fluorine-silicone polymer layer;

[0089] The carbon slurry is dissolved in dichloromethane (CH2Cl2), and the carbon slurry solution is sprayed on the surface of the organic fluorosilicone polymer when it is semi-cured, and completely cured at room temperature; then, the organic silicone adhesive is coated, and the coating rod is used to scrape it on the cured release paper and the base cloth is pasted on the surface of the release paper to obtain the organic fluorosilicone synthetic leather material.

[0090] Embodiment 2:

[0091] Weigh 9.000 g of vinyl silicone oil, 1.000 g of hydrogen-containing silicone oil, 0.300 g of vinyl fluorine-containing silicone oil and 0.700 g of catalyst, mix the vinyl silicone oil, hydrogen-containing silicone oil and vinyl fluorine-containing silicone oil evenly in a beaker, put it into a vacuum drying oven and evacuate for 15 minutes, add the platinum catalyst to the mixture and stir evenly, use a coating rod to scrape the mixture on the release paper to obtain an organic fluorine-silicone polymer layer;

[0092] The carbon slurry is dissolved in dichloromethane (CH2Cl2), and the carbon slurry solution is sprayed on the surface of the organic fluorosilicone polymer when it is semi-cured, and completely cured at room temperature; then, the organic silicone adhesive is coated, and the coating rod is used to scrape it on the cured release paper and the base cloth is pasted on the surface of the release paper to obtain the organic fluorosilicone synthetic leather material.

[0093] The infrared spectrum of the organic fluorine-silicon synthetic leather material obtained during the reaction in this embodiment is as follows Figure 1 As shown, multiple stretching vibration absorption peaks can be seen, including 2970cm -1 The CH stretching vibration absorption peak, 1262 cm -1 The Si-O stretching vibration absorption peak and 2161cm -1 The Si-H stretching vibration absorption peak at 802cm -1 The C=C bending vibration absorption peak at 1631.8cm -1The infrared characteristic absorption peak of the C=C double bond was also observed. In addition, 1012.6cm -1 The CF stretching vibration absorption peak at 802 cm -1 and 2161cm -1 At , the characteristic absorption peaks of the C=C bond in the vinyl silicone oil and the Si-H bond in the hydrogen-containing silicone oil were significantly reduced, indicating that in the presence of the platinum catalyst, a hydrosilylation reaction occurred between the C=C bond in the vinyl silicone oil and the Si-H bond in the hydrogen-containing silicone oil. In summary, the reaction was successful and the structure of the obtained product was in line with expectations.

[0094] Embodiment 3:

[0095] Weigh 9.000 g of vinyl silicone oil, 1.000 g of hydrogenated silicone oil, 0.600 g of vinyl fluorinated silicone oil and 1.000 g of catalyst, mix the vinyl silicone oil, hydrogenated silicone oil and vinyl fluorinated silicone oil evenly in a beaker, put the mixture into a vacuum drying oven and evacuate for 15 min, add the platinum catalyst into the mixture and stir evenly, and use a coating rod to scrape the mixture onto a release paper to obtain an organic fluorinated silicone polymer layer;

[0096] The carbon slurry is dissolved in dichloromethane (CH2Cl2), and the carbon slurry solution is sprayed on the surface of the organic fluorosilicone polymer when it is semi-cured, and completely cured at room temperature; then, the organic silicone adhesive is coated, and the coating rod is used to scrape it on the cured release paper and the base cloth is pasted on the surface of the release paper to obtain the organic fluorosilicone synthetic leather material.

[0097] Embodiment 4:

[0098] Weigh 9.000 g of vinyl silicone oil, 1.000 g of hydrogenated silicone oil, 0.900 g of vinyl fluorinated silicone oil and 1.300 g of catalyst, mix the vinyl silicone oil, hydrogenated silicone oil and vinyl fluorinated silicone oil evenly in a beaker, put the mixture into a vacuum drying oven and evacuate for 15 min, add the platinum catalyst into the mixture and stir evenly, and use a coating rod to scrape the mixture onto a release paper to obtain an organic fluorinated silicone polymer layer;

[0099] The carbon slurry is dissolved in dichloromethane (CH2Cl2), and the carbon slurry solution is sprayed on the surface of the organic fluorosilicone polymer when it is semi-cured, and completely cured at room temperature; then, the organic silicone adhesive is coated, and the coating rod is used to scrape it on the cured release paper and the base cloth is pasted on the surface of the release paper to obtain the organic fluorosilicone synthetic leather material.

[0100] Embodiment 5:

[0101] Weigh 9.000 g of vinyl silicone oil, 1.000 g of hydrogenated silicone oil, 1.200 g of vinyl fluorinated silicone oil and 1.600 g of catalyst, mix the vinyl silicone oil, hydrogenated silicone oil and vinyl fluorinated silicone oil evenly in a beaker, put it into a vacuum drying oven and evacuate for 15 min, add the platinum catalyst to the mixture and stir evenly, and use a coating rod to scrape the mixture onto a release paper to obtain an organic fluorinated silicone polymer layer;

[0102] The carbon slurry is dissolved in dichloromethane (CH2Cl2), and the carbon slurry solution is sprayed on the surface of the organic fluorosilicone polymer when it is semi-cured, and completely cured at room temperature; then, the organic silicone adhesive is coated, and the coating rod is used to scrape it on the cured release paper and the base cloth is pasted on the surface of the release paper to obtain the organic fluorosilicone synthetic leather material.

[0103] Embodiment 6:

[0104] Weigh 9.000 g of vinyl silicone oil, 1.000 g of hydrogenated silicone oil, 1.500 g of vinyl fluorinated silicone oil and 1.900 g of catalyst, mix the vinyl silicone oil, hydrogenated silicone oil and vinyl fluorinated silicone oil evenly in a beaker, put it into a vacuum drying oven and evacuate for 15 min, add the platinum catalyst to the mixture and stir evenly, and use a coating rod to scrape the mixture onto a release paper to obtain an organic fluorinated silicone polymer layer;

[0105] The carbon slurry is dissolved in dichloromethane (CH2Cl2), and the carbon slurry solution is sprayed on the surface of the organic fluorosilicone polymer when it is semi-cured, and completely cured at room temperature; then, the organic silicone adhesive is coated, and the coating rod is used to scrape it on the cured release paper and the base cloth is pasted on the surface of the release paper to obtain the organic fluorosilicone synthetic leather material.

[0106] Embodiment 7:

[0107] Weigh 9.000 g of vinyl silicone oil, 1.000 g of hydrogenated silicone oil, 2.000 g of vinyl fluorinated silicone oil and 2.100 g of catalyst, mix the vinyl silicone oil, hydrogenated silicone oil and vinyl fluorinated silicone oil evenly in a beaker, put it into a vacuum drying oven and evacuate for 15 min, add the platinum catalyst to the mixture and stir evenly, and use a coating rod to scrape the mixture onto a release paper to obtain an organic fluorinated silicone polymer layer;

[0108] The carbon slurry is dissolved in dichloromethane (CH2Cl2), and the carbon slurry solution is sprayed on the surface of the organic fluorosilicone polymer when it is semi-cured, and completely cured at room temperature; then, the organic silicone adhesive is coated, and the coating rod is used to scrape it on the cured release paper and the base cloth is pasted on the surface of the release paper to obtain the organic fluorosilicone synthetic leather material.

[0109] Embodiment 8:

[0110] Organic fluorine-silicone synthetic leather for human health monitoring and human motion detection, including the following steps:

[0111] Cut the organic fluorosilicone synthetic leather into appropriate sizes, connect the resistance tester to both ends of the conductive material layer, monitor the heart pulse, detect the movements of knee bending, neck bending, and elbow bending, detect smiling, laughing, and surprised facial expressions, collect resistance change data, and draw a resistance change graph to complete the human health monitoring and human movement detection.

[0112] Comparative Example 1:

[0113] Fabrication of high-performance flexible pressure sensors using ACNT / graphene (ACNT / G) hybrid films as active materials and microstructured PDMS (m-PDMS) films molded directly from natural leaves as flexible substrates. Two layers of ACNT / G hybrid films on m-PDMS films were placed face to face to construct a flexible pressure sensor. Silver paste was coated on one side of each ACNT / G film to serve as an electrode. In the original state, the top and bottom ACNT / G films contacted each other to form a conductive path. After pressure was applied, the contact area between the two ACNT / G films would increase, resulting in an increase in the conductive path and a change in current.

[0114] Comparative Example 2:

[0115] First, a 275 μm thick silicon substrate is laser cut into test structures. The pattern resolution required for the sensor electrodes can be achieved by laser cutting a sticker mask attached to both sides of the silicon substrate.

[0116] The masked substrate is placed on one side in an atmospheric plasma cleaner to allow plasma access to both sides of the silicone, rendering the unmasked areas hydrophilic. After removal from the chamber, the mask is removed and the substrate is ready to receive the nanotubes. The SWNTs are dispersed in a surfactant solution by ultrasound, followed by vacuum filtration and collection on a filter membrane with a pore size of 20nm. The result of this process is a percolation network on top of the filter membrane. By contacting both sides of the plasma-treated silicone with these percolation networks, direct transfer of the nanotubes to untreated areas of the silicone is achieved and the overlapping electrodes required for parallel plate capacitors are produced. If sub-millimeter features are required, the masking film can be replaced by a photoresist layer that can be removed by acetone soaking after the plasma treatment. Between the two masking techniques, serpentine patterns ranging from centimeter sizes to 100μm wide have been successfully demonstrated.

[0117] As a final step to protect and stabilize the newly transferred nanotube layer, a thin layer of silicone is applied to the substrate using a spray gun while avoiding the ends of the spray device (the contact pads).

[0118] Comparative Example 3:

[0119] 4gCNTs and 1.6gDBPH vulcanizing agent were added in sequence. A 2000 mesh screen with a size of 60mm*60mm was cut out, ultrasonically cleaned in a KQ-500DE CNC ultrasonic cleaning machine for 20 minutes, and then preheated in a vulcanizer at 175°C. The kneaded silicone rubber sheet was placed in a mold, a release agent was sprayed on the 2000 mesh screen, and it was pressed against the MVQ surface, and then placed in a vulcanizer for vulcanization for 10 minutes to obtain a conductive hydrophobic silicone rubber composite material. Finally, a layer of CNTs solution with a mass fraction of 6.25% was sprayed on the surface of the vulcanized silicone rubber using a spray gun. Thus, a conductive super-hydrophobic silicone rubber composite material was prepared.

[0120] Comparative Example 4:

[0121] Use a delicate and clean silk scarf (10*10cm 2 ) is used as a mold, a mixture of PDMS substrate and cross-linking agent is applied to the silk mold, and after curing, it is peeled off from the silk mold, and the opposite textile surface pattern can be easily molded on the flexible PDMS surface. In order to make the micro-patterned PDMS surface conductive, an independent SWNTs ultra-thin film (about 30nm thick) is transferred to its patterned surface and then annealed in air at 200℃ for 30 minutes. The E-skin is composed of two layers of SWNTs / PDMS films, whose patterned surfaces are placed face to face, and silver paste is placed on the edges of the two films as source-drain.

[0122] Comparative Example 5:

[0123] The process of monitoring human health and detecting human motion using the conductive composite materials prepared in Comparative Examples 1-4 is as follows:

[0124] Take an appropriate amount of the conductive composite material synthesized in Comparative Examples 1-4, connect the resistance tester to both ends of the conductive material layer, monitor the heart pulse, detect the movements of knee bending, neck bending, and elbow bending, detect smiling, laughing, and surprised facial expressions, collect resistance change data, and draw a resistance change graph, thereby completing the human health monitoring and human movement detection.

[0125] The resistance graph after detection has a certain regularity, but does not have a good effect in terms of repeatability. Therefore, the conductive composite materials in Examples 1-4 are difficult to effectively demonstrate the repeatability in the process of human health monitoring and human movement detection, and it is difficult to achieve the repeatability effect of the material.

[0126] Test Example 1:

[0127] The organic fluorine-silicone synthetic leather obtained in Examples 1, 2, 3, 4, and 6 was tested. In order to study the effect of different fluorine contents on the products, the products were subjected to thermogravimetric analysis. The thermal stability of the synthesized organic fluorine-silicone synthetic leather materials was detected by using a thermogravimetric analyzer. Figure 2 As shown. In the experiment, the temperature was set between 30℃ and 800℃, and the experimental results were analyzed according to the chart of the thermogravimetric analyzer. It can be seen from the chart that when the thermal weight loss is 10%, the corresponding thermal weight loss temperature is 514℃, the fastest thermal weight loss temperature is 470℃, and at 680℃, the organic fluorine silicon synthetic leather material completely loses weight. This shows that the organic fluorine silicon synthetic leather material has extremely strong thermal stability and good high temperature resistance.

[0128] Test Example 2:

[0129] The organic fluorine-silicon synthetic leather material obtained in Test Example 8 is used to monitor human health, detect resistance change diagrams of human movement, monitor heart pulse, detect knee bending, neck bending, elbow bending movements, and detect smiling, laughing, and surprised facial expressions. Figure 4 shown. Figure 4 For pulse monitoring, the resistance change graphs for larger movements such as knee bending, neck bending, elbow bending, and small movements of facial expressions such as smiling, laughing, and surprise are shown. The upper part is a conductive material layer fixed to the radial artery on the wrist, which is used as a pulse monitor by recording the frequency of the resistance signal. The pulse was monitored for 1 minute, and the shape of the signal curve can reflect complex blood flow and heartbeat information. The middle and lower parts are resistance change graphs for larger movements such as knee bending, neck bending, elbow bending, and small movements of facial expressions such as smiling, laughing, and surprise. The shape of the signal curve has good repeatability, stability, and responsiveness, and can detect large-scale movements of various joints and small-scale movements of facial expressions. Organic fluorosilicone synthetic leather materials are expected to become wearable devices for real-time monitoring of human health and body movement.

[0130] Test Example 3:

[0131] The DSC analysis of the organic fluorine-silicon synthetic leather materials with different fluorine contents in Test Examples 1, 2 and 4 is as follows: Figure 5 As shown in the figure, the low temperature stability of the synthesized organic fluorine-silicon synthetic leather material was detected by using a DSC analyzer. In the experiment, the temperature was set between -30°C and 0°C, and the experimental results were analyzed according to the chart of the DSC analyzer. It can be seen from the chart that the glass transition temperature (T g ) are -85.14℃, -82.13℃ and -79.61℃ respectively. T of commonly used PU and plasticized PVC synthetic leather gIt is around -50℃, which shows that synthetic leather materials with different fluorine contents have better stability at low temperatures.

[0132] Test example 4:

[0133] The hydrophobic properties in test example 7 and blank synthetic leather materials are as follows: Figure 6 As shown. The hydrophobicity of blank synthetic leather and the organic fluorine-silicone synthetic leather material with a fluorine content of 20% in Example 7 was measured. It can be seen that the contact angle of the synthetic leather is 105.6 degrees, which is greater than 90 degrees, indicating that the surface of the synthetic leather without any treatment has good hydrophobicity. The contact angle of the synthesized organic fluorine-silicone synthetic leather material with a fluorine content of 20% is 128.3 degrees, which is greater than 90 degrees and greater than the contact angle of the synthetic leather material without any treatment, indicating that the synthesized organic fluorine-silicone synthetic leather material with a fluorine content of 20% has good hydrophobicity. According to the contact angle measured by the optical contact angle meter, it can be seen that vinyl fluorine-containing silicone oil can improve the hydrophobicity of synthetic leather.

[0134] Test Example 5:

[0135] The organic fluorine-silicone synthetic leather obtained in Examples 1, 2, 3, 4, and 6 was tested for mechanical properties. In order to study the effect of different fluorine contents on the mechanical properties of the products, a tensile test was performed on the products. The mechanical properties of the synthesized organic fluorine-silicone synthetic leather materials were tested by using a tensile machine. Figure 7 As shown in the figure, with the increase of fluorine content, the elongation at break and tensile strength of organic fluorine-silicone synthetic leather materials first increase and then decrease. When the fluorine content is 6%, the organic fluorine-silicone synthetic leather material has a good elongation at break and tensile strength, which are 296.25% and 14.83MPa respectively, which is higher than the elongation at break and tensile strength of synthetic leather materials without fluorine. This shows that vinyl fluorine-containing silicone oil can improve the mechanical properties of synthetic leather.

[0136] The content of the present invention is not limited to the embodiments listed, and any equivalent changes made to the technical solution of the present invention by ordinary technicians in the field after reading the description of the present invention are covered by the claims of the present invention.

Claims

1. An organic fluorine-silicone synthetic leather, characterized in that: The synthetic leather comprises: a base fabric and an organic fluorine-silicon polymer layer on the surface of the base fabric, and a conductive material layer is arranged between the base fabric and the organic fluorine-silicon polymer layer; The organic fluorine-silicone polymer layer is a catalytic reaction copolymer of vinyl silicone oil, hydrogen-containing silicone oil and vinyl fluorine-containing silicone oil; The conductive material is carbon paste.

2. The organic fluorine-silicone synthetic leather according to claim 1, characterized in that: The vinyl silicone oil is at least one of vinyl-terminated polydimethylsiloxane and vinyl-terminated polymethylvinylsiloxane; Preferably, the hydrogen-containing silicone oil is polymethyl hydrogen siloxane; Preferably, the vinyl fluorine-containing silicone oil is a vinyl-terminated polymer, and more preferably is obtained by catalytic reaction of D3F, D4 and vinyl silane.

3. The organic fluorine-silicone synthetic leather according to claim 1, characterized in that: The catalyst for the catalytic reaction of the organic fluorosilicone polymer layer is a platinum compound, preferably a Karstedt catalyst.

4. The organic fluorine-silicone synthetic leather according to claim 1, characterized in that: The molar ratio of vinyl silicone oil to hydrogen silicone oil in the organic fluorosilicone polymer layer is 9:1; Preferably, the content of the vinyl fluorine-containing silicone oil in the organic fluorine-silicone polymer layer accounts for 0.1-20% of the total weight of the vinyl silicone oil and the hydrogen-containing silicone oil.

5. The organic fluorine-silicone synthetic leather according to claim 1, characterized in that: The organic fluorine-silicone polymer layer is a structural layer formed by coating a catalytic reaction copolymer of vinyl silicone oil, hydrogen-containing silicone oil and vinyl fluorine-containing silicone oil on release paper.

6. Use of the catalytic reaction copolymer of vinyl silicone oil, hydrogen silicone oil and vinyl fluorine silicone oil according to any one of claims 1 to 5 in the preparation of organic fluorine silicone synthetic leather, preferably in the preparation of smart wearable product materials.

7. The method for preparing the organic fluorine-silicone synthetic leather according to any one of claims 1 to 5, comprising the following steps: After the vinyl silicone oil, hydrogen-containing silicone oil and vinyl fluorine-containing silicone oil are mixed evenly, vacuum drying is performed, a catalyst is added and stirred evenly, and the mixture is coated on a release paper to obtain an organic fluorine-silicone polymer layer; The carbon slurry is dissolved in dichloromethane, sprayed on the surface of the obtained organic fluorosilicone polymer layer, and completely cured at room temperature; then a base cloth is attached to the surface to obtain the organic fluorosilicone synthetic leather.

8. Application of the organic fluorine-silicone synthetic leather according to any one of claims 1 to 5 in health monitoring, human motion detection, soft robots, ionic skin, human-machine interface and flexible electronic devices.

9. A flexible smart wearable material, characterized in that: The material is the organic fluorine-silicone synthetic leather as described in any one of claims 1 to 5.

10. A method for health monitoring and human motion detection, comprising using the organic fluorine-silicone synthetic leather according to any one of claims 1 to 5 to monitor human health and detect human motion, comprising the following steps: Cut the organic fluorosilicone synthetic leather into appropriate sizes, connect the resistance tester to both ends of the conductive material layer, monitor the heart pulse, detect the movements of knee bending, neck bending, and elbow bending, detect smiling, laughing, and surprised facial expressions, collect resistance change data, and draw a resistance change graph to complete the human health monitoring and human movement detection.

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