Organic silicon composite material with environment self-adaptive function

Abstract

The invention discloses an organic silicon composite material with an environment self-adaptive function, which is characterized by comprising a silicon-based resin base material layer, environment-responsive dimming gel particles dispersed in the resin base material layer, an adhesive layer and a polymer protective layer, the silicon-based resin base material layer has proper water permeability and optical transparency, and the polymer protective layer has proper water permeability and optical transparency. The environment-responsive dimming gel particles have obvious temperature responsiveness, the filling amount of the environment-responsive dimming gel particles is 1-100 wt% of the total mass of the resin base material layer, the adhesive layer is hydrophobic polysiloxane, and the polymer protective layer has the characteristics of high watertightness, optical transparency and mechanical toughness. The organic silicon composite membrane material with the environment self-adaption function can adjust light transmission in a self-adaption mode along with changes of external climate, the visible light transmittance range of the organic silicon composite membrane material is 5%-90% along with seasonal changes, and the organic silicon composite membrane material has good cycling stability and therefore has wide application prospects in heat management of industries such as buildings and traffic transportation.

Description

Technical field:

[0001] The present invention belongs to the technical field of new thermal energy management materials, and in particular relates to an environmentally adaptive functional organic silicon composite material and a preparation method thereof. Background technology:

[0002] In recent years, as the global climate has fundamentally changed dramatically, the high temperature crisis caused by climate change is sweeping the world. Against the backdrop of global warming, people's desire for a comfortable living environment has increased dramatically. For this reason, high-power temperature control equipment such as air conditioners, refrigerators and electric heaters are widely used in human normal life, which greatly increases the energy consumption in thermal management. In order to alleviate this pressure, intelligent light modulation materials stand out in many new material fields. They can quickly and effectively control sunlight and mid-infrared atmospheric windows through external stimulus response, reduce the frequency of using temperature control equipment, further reduce human energy consumption, and meet human thermal management needs in areas such as construction and transportation. At present, there are many light modulation intelligent films, the more common ones include electrochromic films (such as liquid crystal molecules, organic dyes, inorganic tungsten oxides), photochromic films (such as organic conjugated structures, inorganic halogen compounds, etc.), and temperature-sensitive nano-vanadium oxide and temperature-sensitive gel films and other dimming materials.

[0003] Among them, the thermosensitive gel is a material that can self-regulate optical transmittance as the ambient temperature changes. That is, when the external temperature is lower than the response temperature of the thermosensitive gel, the film is optically transparent and light can penetrate the material itself without hindrance; when the external ambient temperature rises above the response temperature of the thermosensitive gel, it can spontaneously change the transmittance of light according to the temperature change, and this change is highly reversible. In addition, because the thermosensitive gel contains a large amount of water, it is a very good infrared heat emitter, which is beneficial to the cooling of buildings in summer. The light modulation of the gel thermosensitive material does not require the input of an additional electric field, that is, it can adaptively adjust the light. Therefore, it can achieve excellent light modulation efficiency without adding any additional energy, and truly achieve the purpose of energy saving and emission reduction. In addition, the preparation process of the thermosensitive gel is simple and the cost is low. It has irreplaceable advantages in practical application and economic benefits. Therefore, compared with other types of light modulation media, the thermosensitive gel material is of great significance to the development of smart windows and thermal energy management in the field of building transportation.

[0004] Although the preparation process of thermosensitive gel is simple and the dimming effect is excellent, most thermosensitive gels are difficult to use alone. Its dimming property depends on the water medium, and once the water evaporates, its dimming performance disappears. Therefore, the use of thermosensitive gel film needs to be compounded with glass or other polymer materials and requires complex encapsulation. Due to the high water content of hydrogel, there are problems such as poor adhesiveness and complex encapsulation process in the process of compounding with other hydrophobic materials, which easily causes water vapor leakage and short product service life; in addition, the mechanical properties of general thermosensitive gel are poor, so it is easy to produce incompatibility when compounded with polymer matrix. In actual application cases, problems in the application process caused by poor material ductility, low tensile strength and low elastic modulus will also appear. Summary of the invention:

[0005] In order to solve the problems existing in the prior art, an object of the present invention is to provide an environmentally adaptive functional organic silicon composite material. Another object of the present invention is to provide a method for preparing the above environmentally adaptive functional organic silicon radiation cooling composite film.

[0006] The present invention provides an environmentally adaptive functional organic silicon composite material, comprising a silicone-based resin substrate layer, environmentally responsive dimming gel particles dispersed in the resin substrate layer, a silicone adhesive layer and a transparent polymer protective layer, wherein the silicone-based resin substrate layer has appropriate water permeability and optical transparency, the environmentally responsive dimming gel particles have obvious temperature responsiveness, and the filling amount of the temperature-sensitive gel is 1wt%-100wt% of the total mass of the resin substrate layer, the adhesive layer is a hydrophobic polysiloxane, and the polymer protective layer has high water impermeability, optical transparency and mechanical toughness.

[0007] Preferably, the silicon-based resin substrate layer includes one or more of polydimethylsiloxane, polymethylphenylsiloxane, polyhydroxymethylsiloxane, polyaminomethylsiloxane, polysiloxane-modified polyurethane / polyvinyl alcohol / polyurea / cellulose / polymethyl methacrylate / epoxy resin, wherein the silicon content in the polysiloxane-modified polymer is 0wt%-37wt%.

[0008] Preferably, the environmentally responsive dimming gel particles include one or more of poly (N-isopropylacrylamide) hydrogels, poly (N,N-diethylacrylamide) hydrogels, hydroxypropylcellulose hydrogels, polyethylene glycol hydrogels, poly (hydroxy methacrylate) hydrogels, and poly (N,N-dimethylaminoethyl methacrylate) hydrogels.

[0009] Preferably, the transparent polymer protective layer includes one or more of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and polystyrene acrylate.

[0010] The present invention also provides a method for preparing the above-mentioned environmentally adaptive functional organic silicon composite material, and the specific steps are as follows:

[0011] (1) The polymerizable monomers and crosslinking agent of the thermosensitive gel are dissolved in water, and free radical polymerization is carried out under the presence of an initiator to obtain a thermosensitive gel with a specific phase transition temperature.

[0012] (2) The prepared thermosensitive wet gel is dried and heated to remove moisture from the gel, and then ground into powder.

[0013] (3) dispersing the dry powder of the thermosensitive gel obtained in step (2) in a silicon-based resin or a resin solution, and then polymerizing by heating or light to form a composite substrate.

[0014] (4) Soaking the composite substrate obtained in step (3) in water and allowing it to absorb water until it becomes transparent, and then removing it from the water.

[0015] (5) The composite substrate that has absorbed water in step (4) is sandwiched between two transparent polymer protective layers and bonded with a hydrophobic organic silicone adhesive, and then heated and fixed to obtain a functional organic silicone radiation cooling composite film.

[0016] In the preparation method of the functional silicone radiation cooling composite film of the present invention, the thermosensitive gel is dried and ground into powder and then effectively compounded with a resin substrate. Thereafter, the gel dispersed phase inside the composite material absorbs water to make the refractive index of the gel phase and the substrate phase consistent, thereby avoiding the incompatibility of the thermosensitive gel and the resin substrate and the opacity caused by the different refractive indices of the two. Finally, a transparent polymer film is used to sandwich it with a hydrophobic silicone adhesive, and the manufacturing process is simple and the cost is low.

[0017] Beneficial effects:

[0018] Compared with traditional dimming materials, the environmentally adaptive functional organic silicon composite film obtained by the present invention greatly simplifies the preparation process, effectively solves the problem that traditional thermosensitive hydrogels are prone to water loss and gel failure, greatly improves the stability and durable cycle capacity of the material, and realizes flexible preparation with tensile and bending resistance, meeting the needs of most practical applications. Compared with expensive liquid crystal dimming composite films and electro-responsive color-changing materials, the dimming composite film obtained by the present invention truly realizes the dimming function of adaptive intelligent light regulation without any energy consumption, and the materials are cheap and easy to obtain, which has more significant economic benefits in the market. Description of the drawings:

[0019] Figure 1The schematic diagram of the structure and working principle of the environmentally adaptive functional organic silicon composite material prepared by the present invention, wherein (1) is the silicone-based resin substrate layer, (2) is the environmentally responsive dimming gel particles, and (3) is the transparent protective layer. Specific implementation method:

[0020] The principles and features of the present invention are described below in conjunction with specific embodiments and accompanying drawings. The examples are only used to explain the present invention and are not used to limit the scope of the present invention. If specific conditions are not specified in the embodiments, they are carried out according to normal conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be purchased commercially.

[0021] Example 1

[0022] Step 1: 0.5 g of N-isopropylacrylamide, 0.05 g of N,N-methylenebisacrylamide and 0.05 g of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone were mixed in a culture dish containing 5 ml of deionized water, and the mixture was placed in an ultrasonic cleaner for ultrasonic treatment for 2 min to ensure that N-isopropylacrylamide was completely dissolved in the deionized water. The culture dish was then placed under ultraviolet light for photopolymerization for 2 min to obtain poly-N-isopropylacrylamide hydrogel;

[0023] Step 2: Preliminarily grind the poly (N-isopropylacrylamide) hydrogel and place it in an oven at 80 degrees for 2 hours to evaporate all the water. Then, place the large pieces of the pieces in a planetary ball mill, adjust the ball mill speed to 300 r / min, and grind for 3 hours to obtain poly (N-isopropylacrylamide) dry powder.

[0024] Step 3: Prepare 1g of polydimethylsiloxane (base / linker) matrix, with a base to linker ratio of 10:1, weigh 0.5g of poly (N-isopropylacrylamide) powder in step 2, mix it with polydimethylsiloxane, and apply it on the surface of a flat plastic container by spin coating. The bubbles generated in the process can be removed by solvent dilution or vacuuming. Then, the poly (N-isopropylacrylamide) powder is completely wrapped in the polydimethylsiloxane matrix by in-situ polymerization, and finally immersed in water to absorb water until it becomes transparent;

[0025] Step 4: The transparent polymer protective layer polyethylene terephthalate is cleaned by immersion in anhydrous ethanol to remove stains and dust on the surface, and 0.2g of polydimethylsiloxane is used as an adhesive with a base to linker ratio of 10:1. It is evenly coated on the upper and lower surfaces of the transparent poly (N-isopropylacrylamide)-polydimethylsiloxane temperature-sensitive matrix. Then, the cleaned polyethylene terephthalate film is respectively pasted on the upper and lower surfaces of the temperature-sensitive matrix, and the adhesive is cured.

[0026] The intelligent flexible temperature-sensitive composite film prepared in Example 1 has good light modulation ability, that is, at a temperature lower than the phase transition temperature of poly (N-isopropylacrylamide) (32°C), the film is transparent; as the external temperature rises, the film gradually becomes opaque, and the degree of opacity deepens with the increase in temperature; after multiple cycle tests, through the detection of the film transmittance, it was found that the transmittance of the film in the visible light band at room temperature only decreased from 88% to 86%, while the transmittance when heated remained at 35% without a huge floating change, which greatly confirmed that the temperature-sensitive composite film has good stability and water retention ability; at the same time, due to the adhered transparent polymer protective layer and the flexible resin as the matrix, the film is well endowed with flexibility and mechanical strength, and due to the presence of the transparent polyethylene terephthalate film, the film's anti-ultraviolet ability is improved, which adapts to most of the needs in practical applications, and provides more possibilities for thermal management and light modulation for the construction field and automotive glass industries, truly achieving the goal of energy conservation and emission reduction.

[0027] Embodiment 2:

[0028] like Figure 1 A composite structure of an intelligent flexible temperature-sensitive composite film is shown, and a method for preparing the intelligent flexible temperature-sensitive composite film comprises the following steps:

[0029] Step 1: 0.5 g of N-isopropylacrylamide, 0.05 g of N,N-methylenebisacrylamide and 0.05 g of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone were mixed in a culture dish containing 5 ml of deionized water, and the mixture was placed in an ultrasonic cleaner for ultrasonic treatment for 2 min to ensure that N-isopropylacrylamide was completely dissolved in the deionized water. The culture dish was then placed under ultraviolet light for photopolymerization for 2 min to obtain poly-N-isopropylacrylamide hydrogel;

[0030] Step 2: Preliminarily grind the poly (N-isopropylacrylamide) hydrogel and place it in an oven at 80 degrees for 2 hours to evaporate all the water. Then, place the large pieces of the pieces in a planetary ball mill, adjust the ball mill speed to 300 r / min, and grind for 3 hours to obtain poly (N-isopropylacrylamide) dry powder.

[0031] Step 3: Dissolve 1g of polymethyl methacrylate particles in 4ml of acetone by dissolution composite method, weigh 0.1g of poly (N-isopropylacrylamide) powder in step 2, mix it with the dissolved polymethyl methacrylate, and apply it on the surface of a flat glass vessel by spin coating. The bubbles generated in the process can be removed by solvent dilution or vacuuming. Then, the poly (N-isopropylacrylamide) powder is completely wrapped in the polymethyl methacrylate matrix by evaporating the solvent, and finally immersed in water to absorb water until transparent;

[0032] Step 4: The transparent polymer protective layer polycarbonate film is cleaned by immersion in anhydrous ethanol to remove stains and dust on the surface, and 0.2g of polydimethylsiloxane is used as an adhesive with a base and linker ratio of 10:0.2. It is evenly coated on the upper and lower surfaces of a transparent poly (N-isopropylacrylamide)-polymethyl methacrylate) temperature-sensitive matrix. Then, the cleaned polycarbonate film is respectively pasted on the upper and lower surfaces of the temperature-sensitive matrix, and the adhesive is allowed to solidify.

[0033] The intelligent flexible temperature-sensitive composite film prepared in Example 2 is similar to that in Example 1, except that the flexible matrix layer and the transparent polymer protective layer are changed, and the organic temperature-sensitive gel dispersed in the resin matrix is ​​not changed, so the light modulation performance thereof is basically the same; the only difference is that the protective layer is made of a polycarbonate film, which is still transparent, flexible, stable and has a certain mechanical strength, and only lacks UV resistance, but this does not affect its application in the construction field and industries such as automotive glass, and is extremely beneficial in reducing preparation costs.

[0034] Example 3

[0035] like Figure 1 A composite structure of an intelligent flexible temperature-sensitive composite film is shown, and a method for preparing the intelligent flexible temperature-sensitive composite film comprises the following steps:

[0036] Step 1: 0.5 g of N-isopropylacrylamide, 0.05 g of N,N-methylenebisacrylamide and 0.05 g of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone were mixed in a culture dish containing 5 ml of deionized water, and the mixture was placed in an ultrasonic cleaner for ultrasonic treatment for 2 min to ensure that N-isopropylacrylamide was completely dissolved in the deionized water. The culture dish was then placed under ultraviolet light for photopolymerization for 2 min to obtain poly-N-isopropylacrylamide hydrogel;

[0037] Step 2: Preliminarily grind the poly (N-isopropylacrylamide) hydrogel and place it in an oven at 80 degrees for 2 hours to evaporate all the water. Then, place the large pieces of the pieces in a planetary ball mill, adjust the ball mill speed to 300 r / min, and grind for 3 hours to obtain poly (N-isopropylacrylamide) dry powder.

[0038] Step 3: After mixing 0.5g of polyurea A component with 0.5g of polyurea B component, take 0.2g of poly N-isopropylacrylamide dry powder in step 2, mix it with polyurea AB component, and apply it on the flat surface of plastic container by spin coating. The bubbles generated in the process can be removed by solvent dilution or vacuuming. Then, the poly N-isopropylacrylamide dry powder is completely wrapped in the polyurea matrix by in-situ polymerization, and finally immersed in water to absorb water until transparent;

[0039] Step 4: The transparent polymer protective layer polyethylene terephthalate is cleaned by immersion in anhydrous ethanol to remove stains and dust on the surface, and 0.2g of polyurea is used as an adhesive with an AB component ratio of 1:1. It is evenly coated on the upper and lower surfaces of the transparent poly (N-isopropylacrylamide)-polyurea thermosensitive matrix. Then, the washed polyethylene terephthalate film is respectively pasted on the upper and lower surfaces of the thermosensitive matrix, and the adhesive is cured.

[0040] The intelligent flexible temperature-sensitive composite film prepared in Example 3 has good temperature-sensitive properties. Through changes in ambient temperature, the temperature-sensitive composite film can quickly switch between transparent and opaque, thereby affecting the transmission of sunlight to achieve regulation of indoor temperature; secondly, the temperature-sensitive composite film has good flexibility, good stability and certain mechanical strength, and has broad application prospects in the construction field and automotive glass and other industries.

[0041] Example 4

[0042] like Figure 1 A composite structure of an intelligent flexible temperature-sensitive composite film is shown, and a method for preparing the intelligent flexible temperature-sensitive composite film comprises the following steps:

[0043] Step 1: 0.5 g of N-isopropylacrylamide, 0.05 g of N,N-methylenebisacrylamide and 0.05 g of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone were mixed in a culture dish containing 5 ml of deionized water, and the mixture was placed in an ultrasonic cleaner for ultrasonic treatment for 2 min to ensure that N-isopropylacrylamide was completely dissolved in the deionized water. The culture dish was then placed under ultraviolet light for photopolymerization for 2 min to obtain poly-N-isopropylacrylamide hydrogel;

[0044] Step 2: Preliminarily grind the poly (N-isopropylacrylamide) hydrogel and place it in an oven at 80 degrees for 2 hours to evaporate all the water. Then, place the large pieces of the pieces in a planetary ball mill, adjust the ball mill speed to 300 r / min, and grind for 3 hours to obtain poly (N-isopropylacrylamide) dry powder.

[0045] Step 3: Evenly mix 1g of waterborne polyurethane with 0.05g of poly (N-isopropylacrylamide) powder in step 2, and apply it on the flat surface of a plastic container by spin coating. The bubbles generated in the process can be removed by solvent dilution, and then the waterborne polyurethane containing poly (N-isopropylacrylamide) powder is cured by heating and evaporating the solvent, and finally immersed in water to absorb water until it becomes transparent;

[0046] Step 4: The transparent polymer protective layer polyethylene terephthalate is cleaned by immersion in anhydrous ethanol to remove stains and dust on the surface, and 0.2g of polydimethylsiloxane is used as an adhesive with a base and linker ratio of 10:1. It is evenly coated on the upper and lower surfaces of the transparent poly (N-isopropylacrylamide)-aqueous polyurethane temperature-sensitive matrix. Then, the cleaned polyethylene terephthalate film is respectively pasted on the upper and lower surfaces of the temperature-sensitive matrix, and the adhesive is allowed to solidify.

[0047] The intelligent flexible temperature-sensitive composite film prepared in Example 4 has good temperature-sensitive properties. Through changes in ambient temperature, the temperature-sensitive composite film can quickly switch between transparent and opaque, thereby affecting the transmission of sunlight to achieve regulation of indoor temperature; secondly, the temperature-sensitive composite film has good flexibility, good stability and certain mechanical strength, and has broad application prospects in the construction field and automotive glass and other industries.

[0048] Example 5

[0049] like Figure 1 A composite structure of an intelligent flexible temperature-sensitive composite film is shown, and a method for preparing the intelligent flexible temperature-sensitive composite film comprises the following steps:

[0050] Step 1: 0.5 g of N-isopropylacrylamide, 0.05 g of N,N-methylenebisacrylamide and 0.05 g of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone were mixed in a culture dish containing 5 ml of deionized water, and the mixture was placed in an ultrasonic cleaner for ultrasonic treatment for 2 min to ensure that N-isopropylacrylamide was completely dissolved in the deionized water. The culture dish was then placed under ultraviolet light for photopolymerization for 2 min to obtain poly-N-isopropylacrylamide hydrogel;

[0051] Step 2: Preliminarily grind the poly (N-isopropylacrylamide) hydrogel and place it in an oven at 80 degrees for 2 hours to evaporate all the water. Then, place the large pieces of the pieces in a planetary ball mill, adjust the ball mill speed to 300 r / min, and grind for 3 hours to obtain poly (N-isopropylacrylamide) dry powder.

[0052] Step 3: Add 1g of polyvinyl alcohol 1750 to a culture dish containing 5ml of deionized water, dissolve it into liquid by heating and stirring at 60 degrees, and then mix it evenly with 0.3g of poly (N-isopropylacrylamide) dry powder in step 2, and apply it on the surface of a flat plastic container by spin coating. The bubbles generated in the process can be removed by solvent dilution or vacuuming, and then the solvent is evaporated by heating to solidify the polyvinyl alcohol 1750 containing poly (N-isopropylacrylamide) dry powder, and finally immersed in water to absorb water until transparent;

[0053] Step 4: The transparent polymer protective layer polyethylene terephthalate is cleaned by immersion in anhydrous ethanol to remove stains and dust on the surface, and 0.2g of polydimethylsiloxane is used as an adhesive with a base and linker ratio of 10:0.8. It is evenly coated on the upper and lower surfaces of a transparent poly (N-isopropylacrylamide)-polyvinyl alcohol 1750 temperature-sensitive matrix. Then, the cleaned polyethylene terephthalate film is respectively pasted on the upper and lower surfaces of the temperature-sensitive matrix, and the adhesive is allowed to solidify.

[0054] The intelligent flexible temperature-sensitive composite film prepared in this Example 5 has good temperature-sensitive properties. Through changes in ambient temperature, the temperature-sensitive composite film can quickly switch between transparent and opaque, thereby affecting the transmission of sunlight to achieve regulation of indoor temperature; secondly, the temperature-sensitive composite film has good flexibility, good stability and certain mechanical strength, and has broad application prospects in the construction field and automotive glass and other industries.

[0055] Example 6

[0056] like Figure 1 A composite structure of an intelligent flexible temperature-sensitive composite film is shown, and a method for preparing the intelligent flexible temperature-sensitive composite film comprises the following steps:

[0057] Step 1: 0.5 g of N-isopropylacrylamide, 0.05 g of N,N-methylenebisacrylamide and 0.05 g of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone were mixed in a culture dish containing 5 ml of deionized water, and the mixture was placed in an ultrasonic cleaner for ultrasonic treatment for 2 min to ensure that N-isopropylacrylamide was completely dissolved in the deionized water. The culture dish was then placed under ultraviolet light for photopolymerization for 2 min to obtain poly-N-isopropylacrylamide hydrogel;

[0058] Step 2: Preliminarily grind the poly (N-isopropylacrylamide) hydrogel and place it in an oven at 80 degrees for 2 hours to evaporate all the water. Then, place the large pieces of the pieces in a planetary ball mill, adjust the ball mill speed to 300 r / min, and grind for 3 hours to obtain poly (N-isopropylacrylamide) dry powder.

[0059] Step 3: Dissolve 0.2 g of cellulose acetate particles in 2 ml of acetone by a dissolution composite method, weigh 0.05 g of poly (N-isopropylacrylamide) powder in step 2, mix it with the dissolved cellulose acetate, and apply it on the surface of a flat glass vessel by spin coating. The bubbles generated in the process can be removed by solvent dilution, and then the cellulose acetate containing poly (N-isopropylacrylamide) powder is solidified by heating to volatilize the solvent, and finally immersed in water to absorb water until it is transparent;

[0060] Step 4: The transparent polymer protective layer polyethylene terephthalate is cleaned by immersion in anhydrous ethanol to remove stains and dust on the surface, and 0.2g of polydimethylsiloxane is used as an adhesive with a base and linker ratio of 10:0.5. It is evenly coated on the upper and lower surfaces of a transparent poly (N-isopropylacrylamide)-cellulose acetate thermosensitive matrix. Then, the cleaned polyethylene terephthalate film is respectively pasted on the upper and lower surfaces of the thermosensitive matrix, and the adhesive is allowed to solidify.

[0061] The intelligent flexible temperature-sensitive composite film prepared in Example 6 has good temperature-sensitive properties. Through changes in ambient temperature, the temperature-sensitive composite film can quickly switch between transparent and opaque, thereby affecting the transmission of sunlight to achieve regulation of indoor temperature; secondly, the temperature-sensitive composite film has good flexibility, good stability and certain mechanical strength, and has broad application prospects in the construction field and automotive glass and other industries.

[0062] Example 7

[0063] like Figure 1 A composite structure of an intelligent flexible temperature-sensitive composite film is shown, and a method for preparing the intelligent flexible temperature-sensitive composite film comprises the following steps:

[0064] Step 1: Mix 1 ml of N,N-diethylacrylamide, 0.01 g of N,N-methylenebisacrylamide and 0.01 g of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone in a culture dish containing 2 ml of deionized water, and place it in an ultrasonic cleaner for ultrasonic treatment for 2 minutes to ensure that the crosslinker and photoinitiator are completely dissolved in the deionized water. Then, place the culture dish under ultraviolet light for photopolymerization for 2 minutes to obtain poly N,N-diethylacrylamide hydrogel;

[0065] Step 2: Preliminarily grind the poly (N,N-diethylacrylamide) hydrogel and place it in an oven at 80 degrees for 1 hour to evaporate all the water. Then, place the large pieces of the fragments in a planetary ball mill, adjust the ball mill speed to 200 r / min, and grind for 2 hours to obtain poly (N,N-diethylacrylamide) dry powder.

[0066] Step 3: Add 1g of polyvinyl alcohol 1750 to a culture dish containing 5ml of deionized water, dissolve it into liquid by heating and stirring at 60 degrees, and then mix it evenly with 0.25g of poly (N,N-diethylacrylamide) dry powder in step 2, and apply it on the surface of a flat plastic vessel by spin coating. The bubbles generated in the process can be removed by solvent dilution or vacuuming, and then the solvent is evaporated by heating to solidify the polyvinyl alcohol 1750 containing poly (N,N-diethylacrylamide) dry powder, and finally immerse it in water to absorb water until it is transparent;

[0067] Step 4: The transparent polymer protective layer polyethylene terephthalate is cleaned by immersion in anhydrous ethanol to remove stains and dust on the surface, and 0.2g of polydimethylsiloxane is used as an adhesive with a base and linker ratio of 10:1. It is evenly coated on the upper and lower surfaces of a transparent poly (N, N-diethylacrylamide-polyvinyl alcohol) 1750 temperature-sensitive matrix. Then, the cleaned polyethylene terephthalate film is respectively pasted on the upper and lower surfaces of the temperature-sensitive matrix, and the adhesive is allowed to solidify.

[0068] The intelligent flexible temperature-sensitive composite film prepared in this embodiment 7 has good temperature-sensitive properties. The organic temperature-sensitive gel used in its preparation process has a phase transition temperature similar to that of the poly N-isopropylacrylamide temperature-sensitive gel used in embodiments 1, 2, 3, 4, 5, and 6. Therefore, the temperature-sensitive properties and light modulation capabilities exhibited by the temperature-sensitive composite film are basically the same. The transmission of sunlight can be adjusted by changes in ambient temperature, thereby causing corresponding changes in indoor temperature. Secondly, the intelligent film composited with poly N, N-diethylacrylamide as the organic temperature-sensitive gel still has good flexibility, good stability, and certain mechanical strength, and has broad application prospects in the construction field and automotive glass and other industries.

[0069] Example 8

[0070] like Figure 1 A composite structure of an intelligent flexible temperature-sensitive composite film is shown, and a method for preparing the intelligent flexible temperature-sensitive composite film comprises the following steps:

[0071] Step 1: Mix 1 ml of N,N-diethylacrylamide, 0.01 g of N,N-methylenebisacrylamide and 0.01 g of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone in a culture dish containing 2 ml of deionized water, and place it in an ultrasonic cleaner for ultrasonic treatment for 2 minutes to ensure that the crosslinker and photoinitiator are completely dissolved in the deionized water. Then, place the culture dish under ultraviolet light for photopolymerization for 2 minutes to obtain poly N,N-diethylacrylamide hydrogel;

[0072] Step 2: Preliminarily grind the poly (N,N-diethylacrylamide) hydrogel and place it in an oven at 80 degrees for 1 hour to evaporate all the water. Then, place the large pieces of the fragments in a planetary ball mill, adjust the ball mill speed to 200 r / min, and grind for 2 hours to obtain poly (N,N-diethylacrylamide) dry powder.

[0073] Step 3: Evenly mix 1g of waterborne polyurethane with 0.05g of poly (N,N-diethylacrylamide) powder in step 2, and apply it on the surface of a flat plastic container by spin coating. The bubbles generated in the process can be removed by solvent dilution, and then the waterborne polyurethane containing poly (N,N-diethylacrylamide) powder is cured by heating and evaporating the solvent, and finally immersed in water to absorb water until it becomes transparent;

[0074] Step 4: The transparent polymer protective layer polyethylene terephthalate is cleaned by immersion in anhydrous ethanol to remove stains and dust on the surface, and 0.2g of polydimethylsiloxane is used as an adhesive with a base and linker ratio of 10:1. It is evenly coated on the upper and lower surfaces of the transparent poly (N, N-diethylacrylamide)-aqueous polyurethane temperature-sensitive matrix. Then, the cleaned polyethylene terephthalate film is respectively pasted on the upper and lower surfaces of the temperature-sensitive matrix, and the adhesive is cured.

[0075] The intelligent flexible temperature-sensitive composite film prepared in Example 8 has good temperature-sensitive properties. Through changes in ambient temperature, the temperature-sensitive composite film can quickly switch between transparent and opaque, thereby affecting the transmission of sunlight to achieve regulation of indoor temperature; secondly, the temperature-sensitive composite film has good flexibility, good stability and certain mechanical strength, and has broad application prospects in the construction field and automotive glass and other industries.

[0076] Example 9

[0077] like Figure 1 A composite structure of an intelligent flexible temperature-sensitive composite film is shown, and a method for preparing the intelligent flexible temperature-sensitive composite film comprises the following steps:

[0078] Step 1: dissolving 2 g of N,N-dimethylaminoethyl methacrylate in 8 ml of deionized water, then adding 0.04 g of potassium persulfate and 0.2 g of N,N-methylenebisacrylamide respectively, and then placing it at room temperature with magnetic stirring until the mixed solution is clear, and the prepared mixed solution is allowed to stand at room temperature for a period of time until it finally becomes a gel, that is, poly(N,N-dimethylaminoethyl methacrylate) hydrogel;

[0079] Step 2: Preliminarily grind the poly(N,N-dimethylaminoethyl methacrylate) hydrogel and place it in an oven at 80 degrees for 2 hours to evaporate all the water. Then, place the large pieces of the pieces in a planetary ball mill, adjust the ball mill speed to 300 r / min, and grind for 3 hours to obtain poly(N,N-dimethylaminoethyl methacrylate) dry powder.

[0080] Step 3: Prepare 1g of polydimethylsiloxane (base / linker) matrix, with a base to linker ratio of 10:1, weigh 0.4g of poly (N-isopropylacrylamide) powder in step 2, mix it with polydimethylsiloxane, and apply it on the surface of a flat plastic container by spin coating. The bubbles generated in the process can be removed by solvent dilution or vacuuming. Then, the poly (N,N-dimethylaminoethyl methacrylate) powder is completely wrapped in the polydimethylsiloxane matrix by in-situ polymerization, and finally immersed in water to absorb water until it becomes transparent;

[0081] Step 4: The transparent polymer protective layer polyethylene terephthalate is cleaned by immersion in anhydrous ethanol to remove stains and dust on the surface, and 0.2g of polydimethylsiloxane is used as an adhesive with a base and linker ratio of 10:1. It is evenly coated on the upper and lower surfaces of the transparent polymethacrylate N,N-dimethylaminoethyl ester-polydimethylsiloxane temperature-sensitive matrix. Then, the cleaned polyethylene terephthalate film is respectively pasted on the upper and lower surfaces of the temperature-sensitive matrix, and the adhesive is cured.

[0082] The intelligent flexible temperature-sensitive composite film prepared in this Example 9 has good light modulation ability, that is, at a temperature lower than the phase transition temperature of poly (N,N-dimethylaminoethyl methacrylate) (55°C), the film is transparent; as the external temperature rises, the film gradually becomes opaque, and the degree of opacity deepens with the increase in temperature; after undergoing multiple cycle tests, the temperature-sensitive composite film still has a good temperature-sensitive effect, which proves that the temperature-sensitive composite film has good stability and water retention capacity; at the same time, due to the adhered transparent polymer protective layer and the flexible resin as the matrix, the film is given good flexibility and mechanical strength, and due to the presence of the transparent polyethylene terephthalate film, the film's anti-ultraviolet ability is improved, and it has broad application prospects in the construction field and automotive glass and other industries.

[0083] Example 10

[0084] like Figure 1 A composite structure of an intelligent flexible temperature-sensitive composite film is shown, and a method for preparing the intelligent flexible temperature-sensitive composite film comprises the following steps:

[0085] Step 1: 6 g of hydroxypropyl acrylate, 0.3 g of N,N-methylenebisacrylamide and 0.06 g of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone were mixed in a culture dish containing 4 ml of deionized water, and the mixture was placed in an ultrasonic cleaner for ultrasonic treatment for 2 min to ensure that the hydroxypropyl acrylate was completely dissolved in the deionized water. The culture dish was then placed under ultraviolet light for photopolymerization for 2 min to obtain a polyhydroxypropyl acrylate hydrogel;

[0086] Step 2: grind the polyhydroxypropyl acrylate hydrogel preliminarily, put it in an oven at 80 degrees for 2 hours to evaporate all the water, then put the large pieces into a planetary ball mill, adjust the ball mill speed to 400r / min, and grind for 4 hours to obtain polyhydroxypropyl acrylate dry powder;

[0087] Step 3: Prepare 1g of polydimethylsiloxane (base / linker) matrix, with a base to linker ratio of 10:1, weigh 0.2g of polyhydroxypropyl acrylate dry powder in step 2, mix it with polydimethylsiloxane thoroughly, and apply it on the surface of a flat plastic container by spin coating. The bubbles generated in the process can be removed by solvent dilution or vacuuming. Then, the polyhydroxypropyl acrylate dry powder is completely wrapped in the polydimethylsiloxane matrix by in-situ polymerization, and finally immersed in water to absorb water until it becomes transparent;

[0088] Step 4: The transparent polymer protective layer polyethylene terephthalate is cleaned by immersion in anhydrous ethanol to remove stains and dust on the surface, and 0.2g of polydimethylsiloxane is used as an adhesive with a base to linker ratio of 10:1. It is evenly coated on the upper and lower surfaces of the transparent polyhydroxypropyl acrylate-polydimethylsiloxane temperature-sensitive matrix, and then the cleaned polyethylene terephthalate film is respectively pasted on the upper and lower surfaces of the temperature-sensitive matrix, and the adhesive is cured.

[0089] The intelligent flexible temperature-sensitive composite film prepared in Example 10 has good light modulation ability, that is, at a temperature lower than the phase transition temperature of polyhydroxypropyl acrylate (45°C), the film is transparent; as the external temperature rises, the film gradually becomes opaque, and the degree of opacity deepens with the increase in temperature; after undergoing multiple cycle tests, the temperature-sensitive composite film still has a good temperature-sensitive effect, which proves that the temperature-sensitive composite film has good stability and water retention capacity; at the same time, due to the adhered transparent polymer protective layer and the flexible resin as the matrix, the film is given good flexibility and mechanical strength, and has broad application prospects in the construction field and automotive glass and other industries.

Claims

1. An environmentally adaptive functional organic silicon composite material, characterized in that: It includes a silicone-based resin substrate layer, environmentally responsive dimming gel particles dispersed in the resin substrate layer, a silicone adhesive layer and a transparent polymer protective layer. The silicone-based resin substrate layer has appropriate water permeability and optical transparency, the environmentally responsive dimming gel particles have obvious temperature responsiveness, and the temperature-sensitive gel filling amount is 1wt%-100wt% of the total mass of the resin substrate layer. The adhesive layer is hydrophobic polysiloxane, and the polymer protective layer has high water impermeability, optical transparency and mechanical toughness.

2. The environmentally adaptive functional organic silicon composite material according to claim 1, characterized in that: The silicon-based resin substrate layer includes one or more of polydimethylsiloxane, polymethylphenylsiloxane, polyhydroxymethylsiloxane, polyaminomethylsiloxane, polysiloxane-modified polyurethane / polyvinyl alcohol / polyurea / cellulose / polymethyl methacrylate / epoxy resin, wherein the silicon content in the polysiloxane-modified polymer is 0wt%-37wt%.

3. The environmentally adaptive functional organic silicon composite material according to claim 1, characterized in that: The environmentally responsive dimming gel particles include one or more of poly (N-isopropylacrylamide) hydrogels, poly (N,N-diethylacrylamide) hydrogels, hydroxypropylcellulose hydrogels, polyethylene glycol hydrogels, poly (hydroxy methacrylate) hydrogels, and poly (N,N-dimethylaminoethyl methacrylate) hydrogels.

4. The environmentally adaptive functional organic silicon composite material according to claim 1, characterized in that: The transparent polymer protective layer includes one or more of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and polystyrene acrylate.

5. A method for preparing an environmentally adaptive functional organic silicon composite material as claimed in claim 1, wherein the specific steps are as follows: (1) The polymerizable monomers and crosslinking agent of the thermosensitive gel are dissolved in water, and free radical polymerization is carried out under the presence of an initiator to obtain a thermosensitive gel with a specific phase transition temperature. (2) The prepared thermosensitive wet gel is dried and heated to remove moisture from the gel, and then ground into powder. (3) dispersing the dry powder of the thermosensitive gel obtained in step (2) in a silicon-based resin or a resin solution, and then polymerizing by heating or light to form a composite substrate. (4) Soaking the composite substrate obtained in step (3) in water and allowing it to absorb water until it becomes transparent, and then removing it from the water. (5) The composite substrate that has absorbed water in step (4) is sandwiched between two transparent polymer protective layers and bonded with a hydrophobic organic silicone adhesive, and then heated and fixed to obtain a functional organic silicone radiation cooling composite film.

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