Thermal insulation composite glass material and preparation method and application thereof

Abstract

The present application relates to the technical field of heat insulation glass material preparation, and particularly relates to a heat insulation composite glass material, a preparation method and application thereof. The present application uses hydrogel material and non-toxic water-phase quantum dot material or noble metal nanomaterial to realize the balance of high heat insulation performance and high visible light transmittance, and has high heat insulation capacity and ultraviolet light resistance while realizing high transparency. The heat insulation composite glass material provided by the present application, as a layered hydrogel material, has significant advantages in smart glass, and has great potential in energy saving and environmental protection by reducing air conditioning and lighting energy consumption, and provides an efficient and multifunctional material solution for smart buildings and green development, and is suitable for various building scene requirements. The ultraviolet light resistant heat insulation glass and temperature-reducing glass assembly provided by the present application can better meet the functional requirements of various application scenes, and have significant economic and social benefits.

Description

Technical Field

[0001] This invention relates to the field of heat-insulating glass material preparation technology, and in particular to a heat-insulating composite glass material, its preparation method and application. Background Technology

[0002] Reducing energy loss is a key issue for economic development and daily life. For example, cooling during hot seasons consumes a large amount of energy, and heat transfer within the space further increases energy consumption. Insulation materials can effectively reduce energy loss, thus their development has attracted considerable attention. In cities and residential areas, transparent glass is widely used in buildings and is a key factor in improving energy efficiency and living comfort. Improving the insulation performance of transparent glass can not only reduce energy consumption but also improve indoor environmental quality.

[0003] Currently, commonly used transparent thermal insulation materials in buildings mainly include vacuum glass, gas-filled (inert gas) glass, metallic coatings, and metal oxide coatings. Vacuum glass and gas-filled glass offer excellent thermal insulation performance, but require high sealing integrity, are heavy, and have high production costs. Metallic coatings and metal oxide coatings can effectively reduce heat transfer, but they reduce visible light transmittance, exhibit angle-dependent optical properties, and their thermal insulation durability is affected over time. Prolonged exposure to sunlight and ultraviolet radiation accelerates material aging, leading to performance degradation, yellowing, and reduced durability. Importantly, these transparent thermal insulation materials typically lack stimulus-responsive characteristics, limiting their smart functionality.

[0004] Therefore, how to balance thermal insulation and visual comfort, and develop a highly intelligent thermal insulation material with high transparency and high UV blocking rate, is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0005] In view of this, the present invention provides a heat-insulating composite glass material, its preparation method and application. The heat-insulating composite glass material provided by the present invention achieves a balance between high heat insulation performance and high visible light transmittance, while also having strong ultraviolet blocking ability.

[0006] This invention provides a thermally insulating composite glass material prepared from free radical polymerization raw materials or freeze-thaw raw materials. The free radical polymerization raw materials include the following components in parts by weight: 0.1-1 parts acrylic acid, 1-2 parts acrylamide, 1-2 parts zwitterionic compound, 0.0001-0.5 parts modified material, 0.02-0.04 parts crosslinking agent, 0.35-0.45 parts initiator, 0.5-1 parts co-initiator, and 10-30 parts water. The modified material is an aqueous quantum dot material or a noble metal nanomaterial. The freeze-thaw raw materials include the following components in parts by weight: 0.1-1 parts acrylic acid, 1-2 parts hydrogel monomer, 1-2 parts zwitterionic compound, 0.0001-0.5 parts modified material, and 10-30 parts water. The hydrogel monomer is acrylamide or polyethylene glycol, and the modified material is an aqueous quantum dot material or a noble metal nanomaterial.

[0007] Preferably, the zwitterionic compound in the free radical polymerization raw material or freeze-thaw raw material includes one or more of betaine, polysulfonate betaine, sulfobetaine and amino acids.

[0008] Preferably, in the free radical polymerization raw material or freeze-thaw raw material, the aqueous quantum dot material includes one or more of carbon quantum dots and indium phosphide quantum dots.

[0009] Preferably, in the free radical polymerization raw material or freeze-thaw raw material, the noble metal nanomaterial includes one or more of nano-gold, nano-silver and nano-platinum; the morphology of the noble metal nanomaterial includes one or more of nanorods and nanospheres.

[0010] The present invention also provides a method for preparing the heat-insulating composite glass material described above, including free radical polymerization or freeze-thaw method; The free radical polymerization method includes the following steps: mixing acrylamide, acrylic acid, zwitterionic compound, modifying material and water to obtain a precursor solution; mixing the precursor solution, initiator, crosslinking agent and co-initiator to carry out a gelation reaction to obtain the heat-insulating composite glass material; The freeze-thaw method includes the following steps: mixing hydrogel monomer, acrylic acid, zwitterionic compound, modifier and water to obtain a precursor solution, and then freezing and thawing the precursor solution in sequence, repeating the freezing and thawing more than 5 times to obtain the heat-insulating composite glass material.

[0011] The present invention also provides the application of the thermally insulating composite glass material described in the above-described scheme or the thermally insulating composite glass material obtained by the preparation method described in the above-described scheme in functional glass components.

[0012] The present invention also provides a UV-resistant heat-insulating glass, comprising a heat-insulating composite glass material and quartz glass covering both sides of the heat-insulating composite glass material, wherein the heat-insulating composite glass material and the quartz glass are encapsulated as a whole; the heat-insulating composite glass material is the heat-insulating composite glass material described in the above scheme or the heat-insulating composite glass material obtained by the preparation method described in the above scheme.

[0013] The present invention also provides a method for preparing the UV-resistant heat-insulating glass described above, comprising the following steps: The heat-insulating composite glass material is placed between two layers of quartz glass and sealed with glue to obtain the UV-resistant heat-insulating glass.

[0014] The present invention also provides a cooling glass assembly, comprising a first glass, a heat-insulating composite glass material, a second glass, a cavity layer and a third glass stacked sequentially, wherein the first glass, the heat-insulating composite glass material, the second glass, the cavity layer and the third glass are encapsulated into a whole.

[0015] Preferably, the first cavity layer and the second cavity layer are provided with a liquid inlet and a liquid outlet.

[0016] Compared with the prior art, the thermally insulating composite glass material, its preparation method, and its application provided by the present invention have achieved the following beneficial effects: The thermally insulating composite glass material provided by this invention utilizes hydrogel materials and non-toxic aqueous quantum dot materials or noble metal nanomaterials to achieve a balance between high thermal insulation performance and high visible light transmittance. While achieving high transparency, it also possesses extremely high thermal insulation and UV protection capabilities. As a layered hydrogel material, the thermally insulating composite glass material provided by this invention exhibits significant advantages in smart glass, demonstrating outstanding potential in energy conservation and environmental protection by reducing air conditioning and lighting energy consumption. It provides an efficient and multifunctional material solution for smart buildings and green development, adaptable to various building scenario requirements.

[0017] The UV-resistant heat-insulating glass provided by this invention further improves the UV protection capability based on the heat-insulating composite glass material, and has excellent overall performance.

[0018] The cooling glass assembly provided by this invention has a cooling function, which can better meet the functional requirements of various application scenarios, and has significant economic and social benefits.

[0019] Existing methods for preparing transparent heat-insulating materials are complex, requiring high-precision control and specialized materials, resulting in high production costs and limiting large-scale applications. The heat-insulating composite glass material preparation method provided by this invention is simple in procedure, convenient to operate, highly safe, and cost-controllable, possessing the potential for large-scale industrial production. Attached Figure Description

[0020] To more clearly illustrate the technical solutions of this invention, the accompanying drawings used in the embodiments of this invention or in the prior art are briefly described below. For those skilled in the art, other drawings can be derived from the following drawings without creative effort, and all such drawings are within the protection scope of this invention.

[0021] Figure 1 The transmittance test results are shown for the heat-insulating composite glass material prepared in Example 2 of the present invention; the inset shows the actual light transmittance of the UV-resistant heat-insulating glass used in architectural glass. Figure 2 The temperature difference and heat source temperature (red line) curves of the test device (a) and the heat-insulating composite glass material prepared in Example 1 of the present invention and the control group are shown in Figure (b); where 1 is the sample, 2 is the foam, and 3 is the thermocouple. Figure 3 The image shows the ultraviolet blocking performance of the heat-insulating composite glass material prepared in Example 1 of this invention; where 1 is the heat-insulating composite glass material and 2 is the heat-insulating composite glass material without modified materials. Figure 4 The temperature response and sensing performance of the thermally insulating composite glass material prepared in Example 1 of this invention are shown in the figure. Detailed Implementation

[0022] This invention provides a thermally insulating composite glass material prepared from free radical polymerization raw materials or freeze-thaw raw materials. The free radical polymerization raw materials include the following components in parts by weight: 0.1-1 parts acrylic acid, 1-2 parts acrylamide, 1-2 parts zwitterionic compound, 0.0001-0.5 parts modified material, 0.02-0.04 parts crosslinking agent, 0.35-0.45 parts initiator, 0.5-1 parts co-initiator, and 10-30 parts water. The modified material is an aqueous quantum dot material or a noble metal nanomaterial. The freeze-thaw raw materials include the following components in parts by weight: 0.1-1 parts acrylic acid, 1-2 parts hydrogel monomer, 1-2 parts zwitterionic compound, 0.0001-0.5 parts modified material, and 10-30 parts water. The hydrogel monomer is acrylamide or polyethylene glycol, and the modified material is an aqueous quantum dot material or a noble metal nanomaterial.

[0023] In this invention, the free radical polymerization raw material comprises the following components in parts by mass: 0.1-1 parts acrylic acid, 1-2 parts acrylamide, 1-2 parts zwitterionic compound, 0.0001-0.5 parts modifier, 0.02-0.04 parts crosslinking agent, 0.35-0.45 parts initiator, 0.5-1 parts co-initiator, and 10-30 parts water, wherein the modifier is an aqueous quantum dot material or a noble metal nanomaterial.

[0024] The free radical polymerization raw material for the heat-insulating composite glass material provided by the present invention includes 0.1 to 1 part of acrylic acid, preferably 0.3 to 0.7 parts, and more preferably 0.5 parts.

[0025] The free radical polymerization raw material of the heat-insulating composite glass material provided by the present invention includes 1 to 2 parts of acrylamide, preferably 1.2 to 1.8 parts, and more preferably 1.4 to 1.6 parts.

[0026] The free radical polymerization raw material for the heat-insulating composite glass material provided by the present invention includes 1 to 2 parts of zwitterionic compound, preferably 1.3 to 1.7 parts, and more preferably 1.5 parts.

[0027] In this invention, the zwitterionic compound preferably includes one or more of betaine, polysulfonated betaine, sulfobetaine, and amino acids; the betaine is preferably anhydrous betaine; and the amino acid preferably includes one or more of glycine and alanine.

[0028] The free radical polymerization raw material for the heat-insulating composite glass material provided by the present invention includes 0.0001 to 0.5 parts of modified material, preferably 0.002 to 0.4 parts, and more preferably 0.05 to 0.3 parts.

[0029] In this invention, the aqueous quantum dot material preferably includes one or more of carbon quantum dots and indium phosphide quantum dots.

[0030] In this invention, the method for preparing the carbon quantum dots preferably includes the following steps: mixing citric acid, polyethyleneimine, o-phenylenediamine and water (denoted as the first mixture), reacting the mixture, and then freeze-drying it to obtain the carbon quantum dots.

[0031] In this invention, the mass ratio of citric acid to polyethyleneimine is preferably 1:0.2 to 0.8, more preferably 1:0.3 to 0.7, and even more preferably 1:0.4 to 0.6.

[0032] In this invention, the mass ratio of citric acid to o-phenylenediamine is preferably 1:0.2 to 0.8, more preferably 1:0.3 to 0.7, and even more preferably 1:0.4 to 0.6.

[0033] In this invention, the water is preferably deionized water; the mass ratio of citric acid to water is preferably 1:10~30, more preferably 1:15~25, and even more preferably 1:20.

[0034] In this invention, the first mixing is preferably ultrasonic; the first mixing time is preferably 10-60 minutes, more preferably 30-40 minutes.

[0035] In this invention, the reaction temperature is preferably 170~190℃, more preferably 180℃, and the holding time is preferably 4~8h, more preferably 6h; the reaction equipment preferably includes a Teflon high-pressure reactor.

[0036] In this invention, the reaction preferably further includes sequentially cooling, filtering, and dialysis of the resulting product.

[0037] In this invention, the cooling is preferably natural cooling; the final temperature of the cooling is preferably room temperature.

[0038] In this invention, the pore size of the membrane filter used for filtration is preferably 0.22 μm. This invention removes large molecular particles through filtration, yielding a yellow filtrate.

[0039] In this invention, the dialysis preferably includes the following steps: mixing the filtrate obtained from filtration with deionized water and soaking it in a dialysis bag.

[0040] In this invention, the mass ratio of the filtrate to deionized water is preferably 1:500.

[0041] In this invention, the preferred specification of the dialysis bag is 500 Da.

[0042] In this invention, the soaking time is preferably 24-48 hours, more preferably 36 hours; during the soaking process, the deionized water is preferably changed every 8 hours. This invention removes small molecule particles through dialysis.

[0043] In this invention, the freeze-drying temperature is preferably -22 to -18°C, more preferably -20°C, and the holding time is preferably 11 to 13 hours, more preferably 12 hours.

[0044] In this invention, the preferred method for preparing indium phosphide quantum dots includes the following steps: mixing oleylamine, 1-octadecene, indium phosphide and indium chloride to obtain a precursor solution, then mixing the precursor solution with tridimethylaminophosphine for nucleation to obtain a nucleation solution, then mixing the nucleation solution with n-dodecyl mercaptan for reaction and purification to obtain indium phosphide quantum dots.

[0045] In this invention, the volume ratio of oleylamine to 1-octadecene is preferably 5 to 7:4, more preferably 6:4.

[0046] In this invention, the molar ratio of indium phosphide to indium chloride is preferably 2.8 to 3.2:1, and more preferably 3:1.

[0047] In this invention, the volume ratio of oleylamine to indium phosphide is preferably 6 mL:(1~2) mmol, more preferably 6 mL:1.2 mmol.

[0048] In this invention, the method for mixing oleylamine, 1-octadecene, indium phosphide, and indium chloride is preferably magnetic stirring. The mixing temperature is preferably 105-115°C, more preferably 110°C. The mixing is preferably carried out in a protective atmosphere, a degassing device, and a reflux condenser. The protective atmosphere is preferably nitrogen, which is introduced once every 4 minutes. The mixing time is preferably 30-35 minutes, more preferably 30 minutes. Through the above mixing, the solute is completely dissolved, forming a homogeneous and transparent precursor solution.

[0049] In this invention, the volume ratio of oleylamine to tridimethylaminophosphine is preferably 5~7:0.4, more preferably 6:0.4.

[0050] In this invention, the process of mixing the precursor solution and tridimethylaminophosphine preferably includes heating; the target temperature for heating is preferably 205~215℃, more preferably 210℃, and the heating time is preferably no more than 10 minutes.

[0051] In this invention, the nucleation temperature is preferably 205~215℃, more preferably 210℃, and the holding time is preferably 10~12min, more preferably 10min.

[0052] In this invention, the volume ratio of oleylamine to n-dodecyl mercaptan is preferably 1.8 to 2.2:1, more preferably 2:1.

[0053] In this invention, the nucleating solution and n-dodecyl mercaptan are preferably mixed under heating conditions. The target temperature for heating is preferably 255~265°C, more preferably 260°C, and the heating time is preferably no more than 3 minutes, more preferably 2~3 minutes.

[0054] In this invention, the reaction temperature is preferably 255~265℃, more preferably 260℃, and the holding time is preferably 110~130min, more preferably 120min.

[0055] In this invention, the purification preferably includes sequential cooling, centrifugation, and drying.

[0056] In this invention, the cooling is preferably natural cooling; the final temperature of the cooling is preferably room temperature.

[0057] In this invention, the centrifugation preferably includes the following steps: mixing the cooled product and n-hexane with anhydrous ethanol, and centrifuging at 8000 rpm for 8 min.

[0058] In this invention, the volume ratio of oleylamine to n-hexane is preferably 5.5~6.5:5, more preferably 6:5; the volume ratio of n-hexane to anhydrous ethanol is preferably 1:1.8~2.2, more preferably 1:2.

[0059] In this invention, the number of centrifugations is preferably 4 to 5 times.

[0060] In this invention, the drying temperature is preferably 85~95℃, more preferably 90℃, and the heat preservation time is preferably 4.5~5.5h, more preferably 5h.

[0061] In this invention, the noble metal nanomaterial preferably includes one or more of nano-gold, nano-silver, and nano-platinum; the morphology of the noble metal nanomaterial preferably includes one or more of nanorods and nanospheres.

[0062] The free radical polymerization raw material for the thermal insulation composite glass material provided by the present invention includes 0.02 to 0.04 parts of crosslinking agent, preferably 0.03 parts.

[0063] In this invention, the crosslinking agent is preferably N,N′-methylenebisacrylamide.

[0064] The free radical polymerization raw material for the heat-insulating composite glass material provided by the present invention includes 0.35 to 0.45 parts of initiator, preferably 0.4 parts.

[0065] In this invention, the initiator is preferably a persulfate; the persulfate preferably includes one or more of ammonium persulfate and potassium persulfate.

[0066] The free radical polymerization raw material for the heat-insulating composite glass material provided by the present invention includes 0.5 to 1 part of a co-initiator, preferably 0.6 to 0.9 parts, and more preferably 0.7 to 0.8 parts.

[0067] In this invention, the co-initiator is preferably an ethylenediamine-substituted product; the ethylenediamine-substituted product is preferably N,N,N′,N′-tetramethylethylenediamine.

[0068] The free radical polymerization raw material for the heat-insulating composite glass material provided by the present invention includes 10-30 parts of water, preferably 15-25 parts, and more preferably 20 parts.

[0069] In this invention, the water is preferably deionized water.

[0070] In this invention, the freeze-thaw raw material comprises the following components in parts by mass: 0.1-1 parts acrylic acid, 1-2 parts hydrogel monomer, 1-2 parts zwitterionic compound, 0.0001-0.5 parts modified material, and 10-30 parts water. The hydrogel monomer is acrylamide or polyethylene glycol, and the modified material is aqueous quantum dot material or noble metal nanomaterial.

[0071] The freeze-thaw raw material for the heat-insulating composite glass material provided by the present invention includes 0.1 to 1 part of acrylic acid, preferably 0.3 to 0.7 parts, and more preferably 0.5 parts.

[0072] The freeze-thaw raw material for the thermal insulation composite glass material provided by the present invention includes 1 to 2 parts of hydrogel monomer, preferably 1.5 parts.

[0073] The freeze-thaw raw material for the heat-insulating composite glass material provided by the present invention includes 1 to 2 parts of a zwitterionic compound, preferably 1.5 parts.

[0074] In this invention, the zwitterionic compound preferably includes one or more of betaine, polysulfonated betaine, sulfobetaine, and amino acids; the betaine is preferably anhydrous betaine; the amino acids preferably include one or more of glycine, alanine, valine, and leucine.

[0075] The freeze-thaw raw material for the heat-insulating composite glass material provided by the present invention includes 0.0001 to 0.5 parts of modified material, preferably 0.003 to 0.4 parts, more preferably 0.05 to 0.3 parts, and even more preferably 0.1 to 0.2 parts.

[0076] In this invention, the aqueous quantum dot material or noble metal nanomaterial is the same as that obtained by free radical polymerization, and will not be described again here.

[0077] The freeze-thaw raw material for the heat-insulating composite glass material provided by the present invention includes 10 to 30 parts of water, preferably 15 to 25 parts, and more preferably 20 parts.

[0078] In this invention, the water is preferably deionized water.

[0079] The present invention also provides a method for preparing the heat-insulating composite glass material described above, including free radical polymerization or freeze-thaw method; The free radical polymerization method includes the following steps: mixing acrylamide, acrylic acid, zwitterionic compound, modifying material and water to obtain a precursor solution; mixing the precursor solution, initiator, crosslinking agent and co-initiator to carry out a gelation reaction to obtain the heat-insulating composite glass material; The freeze-thaw method includes the following steps: mixing hydrogel monomer, acrylic acid, zwitterionic compound, modifier and water to obtain a precursor solution, and then freezing and thawing the precursor solution in sequence, repeating the freezing and thawing more than 5 times to obtain the heat-insulating composite glass material.

[0080] In the free radical polymerization method, this invention mixes acrylamide, acrylic acid, a zwitterionic compound, a modifier, and water (referred to as the second mixture) to obtain a precursor solution. In this invention, the second mixture is preferably stirred, with a stirring speed preferably of 300-800 rpm; the stirring time is preferably 5-20 min.

[0081] After obtaining the precursor solution, the present invention mixes the precursor solution, initiator, crosslinking agent, and co-initiator (denoted as the third mixture) and carries out a gelation reaction to obtain the heat-insulating composite glass material. In the present invention, the third mixture is preferably stirred, and the stirring speed is preferably 300~800 rpm; the third mixture time is preferably 1~10 min.

[0082] In this invention, the temperature of the gelation reaction is preferably room temperature (20~30℃), the holding time is preferably 0.5~15min, more preferably 1~10min, and even more preferably 5min.

[0083] In the freeze-thaw process, the present invention mixes hydrogel monomer, acrylic acid, zwitterionic compound, modifier and water (referred to as the fourth mixture) to obtain a precursor solution, and then freezes and thaws the precursor solution in sequence, repeating the freezing and thawing process more than 5 times to obtain the heat-insulating composite glass material.

[0084] In this invention, the fourth mixing is preferably stirring mixing, and the stirring speed is preferably 300~800 rpm; the fourth mixing time is preferably 5~60 min.

[0085] In this invention, the freezing temperature is preferably -20°C, more preferably -20°C, and the heat preservation time is preferably 11~13h, more preferably 12h.

[0086] In this invention, the thawing temperature is preferably room temperature (20~30℃), more preferably 25℃, and the heat preservation time is preferably 6~7h, more preferably 6h.

[0087] The present invention also provides the application of the thermally insulating composite glass material described in the above-described scheme or the thermally insulating composite glass material obtained by the preparation method described in the above-described scheme in functional glass components.

[0088] The present invention also provides a UV-resistant heat-insulating glass, comprising a heat-insulating composite glass material and quartz glass covering both sides of the heat-insulating composite glass material, wherein the heat-insulating composite glass material and the quartz glass are encapsulated as a whole; the heat-insulating composite glass material is the heat-insulating composite glass material described in the above scheme or the heat-insulating composite glass material obtained by the preparation method described in the above scheme.

[0089] In this invention, the thickness of the quartz glass is preferably 0.8~1.2mm, more preferably 1mm.

[0090] In this invention, the thickness of the heat-insulating composite glass material is preferably 1-2 mm, and more preferably 1.5 mm.

[0091] The present invention also provides a method for preparing the UV-resistant heat-insulating glass described above, comprising the following steps: The heat-insulating composite glass material is placed between two layers of quartz glass and sealed with glue to obtain the UV-resistant heat-insulating glass.

[0092] In this invention, the adhesive is preferably a waterproof and heat-insulating adhesive. In a specific embodiment of this invention, the adhesive is preferably Dow Corning 795 Silicone Building Sealant, Permatex High-Temp Red RTV Silicone Gasket Maker, or Loctite SI 596 Superflex Red High Temp RTV Silicone.

[0093] The present invention also provides a cooling glass assembly, comprising a first glass, a heat-insulating composite glass material, a second glass, a cavity layer and a third glass stacked sequentially, wherein the first glass, the heat-insulating composite glass material, the second glass, the cavity layer and the third glass are encapsulated into a whole.

[0094] In this invention, the first glass, the second glass, and the third glass are each preferably tempered glass or polyolefin film (PO film); when polyolefin film is used, it is preferred to use a steel structure for fixing.

[0095] In this invention, the thickness of the first glass, the second glass and the third glass is preferably 1 to 2 mm, more preferably 1.5 mm.

[0096] In this invention, the thickness of the heat-insulating composite glass material is preferably 1-5 mm, more preferably 2-4 mm, and even more preferably 3 mm.

[0097] In this invention, the thickness of the cavity layer is preferably 1-5 mm, more preferably 2-4 mm, and even more preferably 3 mm.

[0098] In this invention, the cavity layer preferably has a liquid inlet and a liquid outlet. The cavity layer has a liquid inlet and a liquid outlet for the flow of cooling medium (e.g., condensate).

[0099] In this invention, the encapsulation material is preferably a waterproof material, specifically Stormguard EPDMRubber E Strip 73216 or a one-component room temperature vulcanizing deacidified silicone surface sealant (Loctite SI 596 Superflex Red High Temp RTV Silicone).

[0100] To further illustrate the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and embodiments.

[0101] It should be noted that the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion, for example, a process, method, system, product, or device that includes a series of steps or units is not necessarily limited to those steps or units that are explicitly listed, but may include other steps or units that are not explicitly listed or that are inherent to such process, method, product, or device.

[0102] In the specific embodiments and comparative examples of the present invention, the parts of raw materials are all parts by mass.

[0103] Example 1: This embodiment prepares a heat-insulating composite glass material, the preparation of which includes the following steps: (1) Preparation of aqueous quantum dot powder, the specific steps are as follows: Dissolve 1 part citric acid, 0.5 parts polyethyleneimine, and 0.5 parts o-phenylenediamine in 20 parts deionized water, and sonicate for 40 minutes to obtain a mixed solution. The obtained mixed solution was added to a Teflon high-pressure reactor and heated at 180°C for 6 hours. After cooling to room temperature, the macromolecular particles were filtered through a 0.22 μm membrane filter to obtain a yellow solution. The obtained yellow solution and deionized water were placed together in a 500Da dialysis bag with a mass ratio of yellow liquid to deionized water of 1:500. The solution was soaked for 40 hours to remove small molecule particles. The deionized water was changed every 8 hours. The product obtained by dialysis was freeze-dried and kept at -20℃ for 12 hours to obtain carbon quantum dot powder.

[0104] (2) Take 1 part acrylamide, 0.5 part acrylic acid, 1 part anhydrous betaine, and 0.3 parts of the prepared carbon quantum dot powder, add them to 20 parts deionized water, stir at 500 rpm for 15 min, and stir thoroughly to obtain a precursor solution; add 0.4 parts ammonium persulfate, 0.03 parts crosslinking agent N,N′-methylenebisacrylamide, and 0.8 parts co-initiator N,N,N′,N′-tetramethylethylenediamine to the prepared precursor solution, stir at 700 rpm for 5 min, and then pour it into a mold while stirring. React at room temperature for 1 min to form a gel to obtain a heat-insulating composite glass material.

[0105] Example 2: This embodiment prepares a highly transparent UV-resistant heat-insulating glass for use as a building window material. The specific steps for preparing a cooling glass assembly are as follows: (1) Raw material preparation: Acrylamide, acrylic acid, betaine, ammonium persulfate, N,N′-methylenebisacrylamide, N,N,N′,N′-tetramethylethylenediamine, citric acid, polyethyleneimine, o-phenylenediamine, and deionized water.

[0106] (2) Preparation process: Preparation of carbon quantum dots: First, 1g of citric acid, 0.5g of polyethyleneimine, and 0.5g of o-phenylenediamine were dissolved in 20mL of deionized water and sonicated for 30 minutes. Then, the resulting solution was added to a Teflon high-pressure reactor and heated at 180℃ for 6 hours. After cooling to room temperature, the solution was filtered through a 0.22μm membrane filter to obtain a yellow solution. The yellow solution and deionized water were then placed together in a dialysis bag (500Da), with a mass ratio of yellow liquid to deionized water of 1:500, and soaked for 48 hours, changing the deionized water every 8 hours. Finally, the dialysis product was freeze-dried and incubated at -20℃ for 12 hours to obtain carbon quantum dot powder.

[0107] Preparation of thermally insulating composite glass material: Using free radical polymerization, 2g of acrylamide, 1mL of acrylic acid, 2g of betaine, and 0.1g of prepared carbon quantum dot powder were added to 10mL of deionized water and stirred at 300rpm for 20min until fully stirred to obtain a precursor solution. 0.4g of initiator ammonium persulfate, 0.03g of crosslinking agent N,N′-methylenebisacrylamide, and 200μL of co-initiator N,N,N′,N′-tetramethylethylenediamine were added to the prepared precursor solution and stirred at 800rpm for 3min. The mixture was then poured into a mold while stirring to prepare a hydrogel. The mixture was allowed to react at room temperature for 1min to form a gel, thus obtaining the thermally insulating composite glass material.

[0108] Preparation of UV-resistant heat-insulating glass: Place a 2mm thick heat-insulating composite glass material between two 1mm thick quartz glass pieces, and seal it with commercially available Loctite SI 596 Superflex Red High Temp RTV Silicone waterproof and heat-insulating adhesive to obtain UV-resistant heat-insulating glass, which can be used as a heat-insulating window material.

[0109] Fabrication of a cooling glass module: Three layers of 1mm thick tempered glass are used. Between two adjacent layers of tempered glass, a 2mm thick layer of thermally insulating composite glass is sandwiched. Between another two adjacent layers of tempered glass, a 2mm thick water-filled cavity layer is sandwiched. The entire assembly is sealed with commercially available Stormguard EPDM Rubber E Strip 73216 high-temperature waterproof material, resulting in a cooling glass module suitable for use as a building window. A pair of outlets are provided in the condensate-filled cavity layer of the cooling glass module to allow condensate flow. A pump continuously circulates the condensate into the cooling glass module system, while waste heat can be used for other purposes. Solar panels are used to meet the pump's energy requirements, enabling the cooling glass module system to operate automatically in high-temperature environments.

[0110] The heat-reducing glass assembly prepared in this embodiment achieves high optical transparency, high ultraviolet protection, intelligent thermal radiation management, lightweight and safety features, and high durability. Specifically: The thermally insulating composite glass material prepared in this embodiment achieves a light transmittance of over 90% (close to ordinary glass) through molecular structure optimization, while maintaining low haze to ensure ample natural indoor lighting and a clear, distortion-free field of vision. In strong light environments, the hydrogel material dynamically adjusts its light scattering characteristics to avoid glare and improve visual comfort. The hydrophilic network structure and some chemical bonds in the hydrogel material selectively reflect or absorb infrared light, blocking over 70% of solar radiation heat, significantly reducing air conditioning energy consumption in summer. The built-in ultraviolet absorber or nano-coating (i.e., aqueous quantum dot materials or precious metal nanomaterials) can block over 90% of the ultraviolet band, protecting human skin from UV damage. It also possesses certain sensing functions to detect glass temperature and pressure, and can interact with other cooling equipment within the building to achieve an intelligent indoor environment.

[0111] Example 3: This embodiment prepares a highly transparent, UV-resistant, and heat-insulating glass for use as a material for automotive sunroofs. The specific steps are as follows: (1) Raw material preparation: The mixture contained silver nanorods in aqueous solution, acrylamide, acrylic acid, sulfonated betaine, ammonium persulfate, N,N′-methylenebisacrylamide, N,N,N′,N′-tetramethylethylenediamine, urea, polyethyleneimine, o-phenylenediamine, and deionized water.

[0112] Silver nanorods were prepared: the radius of the silver nanorods was distributed in the range of 20~30nm, the length was distributed in the range of 120~180nm, and the aspect ratio (the aspect ratio is the ratio of length to radius) was distributed in the range of 5~6. They had a relatively uniform size distribution and stable morphological characteristics.

[0113] (2) Preparation process: Preparation of thermally insulating composite glass material: Using free radical polymerization, 2g of acrylamide, 1mL of acrylic acid, 2g of sulfobetaine, and 1mL of 0.1mg / mL silver nanorod aqueous solution were added to 10mL of deionized water and stirred at 400rpm for 12min to obtain a precursor solution. 0.4g of ammonium persulfate initiator, 0.03g of N,N′-methylenebisacrylamide crosslinking agent, and 200μL of N,N,N′,N′-tetramethylethylenediamine co-initiator were added to the precursor solution and stirred at 500rpm for 5min. The mixture was then poured into a mold while stirring and allowed to react at room temperature for 5min to form a gel, thus obtaining the thermally insulating composite glass material.

[0114] A 2mm thick heat-insulating composite glass material is sandwiched between two 1mm thick laminated glass pieces and encapsulated using a commercially available Permatex High-Temp Red RTV Silicone Gasket Maker to form a single unit, resulting in UV-resistant heat-insulating glass for use in car sunroofs.

[0115] Example 4: This embodiment produces a highly transparent, UV-resistant, and heat-insulating glass that can be used as a glass material for museum display cases. The specific steps are as follows: (1) Raw material preparation: Polyvinyl alcohol, acrylic acid, polysulfonate betaine, citric acid, polyethyleneimine, p-phenylenediamine, and deionized water.

[0116] (2) Preparation process: Preparation of carbon quantum dots: First, 1g of citric acid, 0.4g of polyethyleneimine, and 0.5g of p-phenylenediamine were dissolved in 20mL of deionized water and sonicated for 30 minutes. Then, the resulting solution was added to a Teflon high-pressure reactor and heated at 180℃ for 6 hours. After cooling to room temperature, the solution was filtered through a 0.22μm membrane filter to obtain a yellow solution. The solution and deionized water were then placed together in a dialysis bag (500Da), with a mass ratio of yellow liquid to deionized water of 1:500, and soaked for 48 hours, changing the deionized water every 8 hours. The dialysis product was freeze-dried and incubated at -20℃ for 12 hours to obtain carbon quantum dot powder.

[0117] Preparation of thermally insulating composite glass material: Using the freeze-thaw method, 2g of polyvinyl alcohol, 1mL of acrylic acid, 2g of polysulfonate betaine, and 0.1g of the prepared carbon quantum dot powder were added to 10mL of deionized water and stirred at 600rpm for 40min until fully stirred to obtain a precursor solution. The prepared precursor solution was poured into a mold and frozen at -20℃ for 12h, and then moved to room temperature (25℃) to thaw for 6h. The freeze-thaw process was repeated 5 times to obtain the thermally insulating composite glass material.

[0118] UV-resistant heat-insulating glass: Two 1mm thick quartz glass pieces sandwich a 1mm thick heat-insulating composite glass material, which is then encapsulated using commercially available Dow Corning 795 Silicone Building Sealant to form a whole, resulting in UV-resistant heat-insulating glass for use in display cases.

[0119] Example 5: This embodiment prepares a highly transparent, cooling glass component for use as a material in agricultural greenhouses. The specific steps are as follows: (1) Raw material preparation: Acrylamide, acrylic acid, polysulfonated betaine, ammonium persulfate, N,N′-methylenebisacrylamide, N,N,N′,N′-tetramethylethylenediamine, 1-octadecene, oleylamine, indium phosphide, indium chloride, tridimethylaminophosphide, anhydrous ethanol, n-hexane, and deionized water.

[0120] (2) Preparation process: Preparation of Indium Phosphide Quantum Dots (taking the representative (Zn:In=3) hot-injection method as an example): 6 mL of oleylamine and 4 mL of 1-octadecene were placed in a 50 mL three-necked flask. 1.2 mmol of indium phosphide and 0.4 mmol of indium chloride were then weighed into the flask. A high-temperature magnetic stir bar was added, and a nitrogen-filled reflux condenser was connected. The mixture was stirred thoroughly at 110 °C and degassed for 30 min, with nitrogen gas introduced every 4 min until all the solute dissolved to form a homogeneous and transparent precursor solution. The system temperature was then raised to 210 °C within 10 min, and 0.4 mL of tris(2,4-dimethylaminophosphide) was rapidly injected into the three-necked flask and maintained for 10 min to complete the nucleation process. The system temperature was then raised to 260 °C within 3 min, with 3 mL of n-dodecyl mercaptan slowly injected during the heating process. The temperature was maintained at 260 °C for 120 min to obtain the InP / ZnS quantum dot stock solution. After naturally cooling to room temperature, the InP / ZnS quantum dot stock solution was placed in a centrifuge tube, 5 mL of n-hexane and 10 mL of anhydrous ethanol were added, and the mixture was centrifuged at 8000 rpm for 8 min. The precipitate was sampled and dissolved again in 5 mL of n-hexane to obtain a liquid sample for subsequent characterization. The remaining precipitate was then collected, and n-hexane and ethanol were added again for centrifugation. The above steps were repeated 3 to 4 times. Finally, the solid precipitate was placed in a vacuum drying oven and kept at 90 °C for 5 h to obtain indium phosphide quantum dot powder.

[0121] Preparation of thermally insulating composite glass material: Using the freeze-thaw method, 2g of acrylamide, 1mL of acrylic acid, 2g of polysulfonate betaine, and 0.1g of the prepared indium phosphide quantum dot powder were added to 10mL of deionized water and stirred at 700rpm for 30min until fully stirred to obtain a precursor solution. 0.4g of initiator ammonium persulfate, 0.03g of crosslinking agent N,N′-methylenebisacrylamide, and 200μL of co-initiator N,N,N′,N′-tetramethylethylenediamine were added to the prepared precursor solution, stirred, poured into a mold, and reacted at room temperature for 10min to form a gel, thus obtaining the thermally insulating composite glass material.

[0122] Fabrication of the cooling glass module: Three 1mm thick PO films are used, arranged in the following order: PO film, thermal insulation composite glass material layer, PO film, cavity layer, and PO film again. These films then wrap around a 2mm thick thermal insulation composite glass material layer and a 1mm thick water-filled cavity layer. The entire perimeter is sealed with commercially available Loctite SI 596 Superflex Red High Temp RTV Silicone high-temperature waterproof material and secured with a steel frame structure. A pair of outlets are provided in the cavity layer for condensate flow. A pump continuously circulates the condensate into the cooling glass module system, while waste heat can be used for other purposes. Solar panels are used to meet the pump's energy requirements, enabling the cooling glass module system to operate automatically in high-temperature environments.

[0123] Test Example 1: The transmittance and absorptivity of the heat-insulating composite glass material prepared in Example 2 were tested, and the results are as follows: Figure 1 As shown.

[0124] Figure 1 The transmittance τ (red line) and absorptivity α (blue line) spectra of the thermally insulating composite glass material are displayed, along with the AM1.5 global solar reference spectrum (yellow spectrum). Figure 1 It can be seen that the heat-insulating composite glass material has extremely high transmittance in the visible light band (>91%), and has a relatively obvious blocking effect in the ultraviolet band (<20%) and near-infrared band (<30%).

[0125] Test Example 2: The thermal insulation performance of the thermal insulation composite glass material prepared in Example 1 was tested using the following method: Figure 2 As shown in Figure a, a 10cm × 10cm × 10cm black box was constructed as a simulated greenhouse, with light-blocking and heat-insulating treatment (foam) on all four sides to reduce the effects of heat conduction and convection. An infrared heat source (wavelength range 760~5000nm) was used for irradiation and heating, and the temperature was measured using thermocouples. The ambient temperature at 10cm below the experimental setup was recorded. The heat-insulating composite glass material prepared in Example 1 was used as the experimental group, and ordinary vacuum glass was used as the control group. The results are as follows: Figure 2 As shown in b in the figure.

[0126] according to Figure 2 As shown in b, the effective heat preservation time of the heat-insulating composite glass material reaches 2 hours; during the initial heating stage, the temperatures of both the control group and the experimental group increased. However, when the heat source stabilized at 85℃ and the infrared radiation intensity was 450W / m², the temperature remained stable. 2 Significant differences were observed. Compared to the control group, the thermally insulated composite glass material maintained a stable temperature difference of 11°C (range 10–14°C), and this effect lasted for up to 2 hours. These results indicate that the thermally insulated composite glass material has good long-term thermal stability and strong potential for practical applications.

[0127] Test Example 3: The ultraviolet blocking performance of the heat-insulating composite glass material prepared in Example 1 was tested, and the results are as follows: Figure 3 As shown. According to Figure 3 As can be seen directly, the heat-insulating composite glass material of this invention has extremely high absorption performance for ultraviolet light (200~400nm).

[0128] Test Example 4: Electrical signals of the heat-insulating composite glass material prepared in Example 1 were detected at different temperatures (30~100℃), and the results are as follows:Figure 4 As shown.

[0129] according to Figure 4 It can be seen that the ΔR / R signal of the thermal insulation composite glass material of the present invention exhibits a stable change at different temperatures, which provides the most intuitive support for the temperature sensor.

[0130] The embodiments of the present invention have been described above; however, these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. All other embodiments obtained by those skilled in the art based on the above embodiments of the present invention without inventive effort are within the protection scope of the present invention.

Claims

1. A heat-insulating composite glass material, characterized in that, Prepared from free radical polymerization raw materials or freeze-thaw raw materials; The free radical polymerization raw material comprises the following components in parts by weight: 0.1-1 parts acrylic acid, 1-2 parts acrylamide, 1-2 parts zwitterionic compound, 0.0001-0.5 parts modifier, 0.02-0.04 parts crosslinking agent, 0.35-0.45 parts initiator, 0.5-1 parts co-initiator, and 10-30 parts water, wherein the modifier is an aqueous quantum dot material or a noble metal nanomaterial; The freeze-thaw raw material comprises the following components in parts by weight: 0.1-1 parts acrylic acid, 1-2 parts hydrogel monomer, 1-2 parts zwitterionic compound, 0.0001-0.5 parts modified material, and 10-30 parts water. The hydrogel monomer is acrylamide or polyethylene glycol, and the modified material is aqueous quantum dot material or noble metal nanomaterial.

2. The heat-insulating composite glass material according to claim 1, characterized in that, The zwitterionic compounds in the free radical polymerization raw materials or freeze-thaw raw materials include one or more of betaine, polysulfonated betaine, sulfobetaine, and amino acids.

3. The heat-insulating composite glass material according to claim 1, characterized in that, In the free radical polymerization raw materials or freeze-thaw raw materials, the aqueous quantum dot material includes one or more of carbon quantum dots and indium phosphide quantum dots.

4. The heat-insulating composite glass material according to claim 1, characterized in that, In the free radical polymerization raw material or freeze-thaw raw material, the noble metal nanomaterials include one or more of nano gold, nano silver and nano platinum; The morphology of the noble metal nanomaterials includes one or more of nanorods and nanospheres.

5. A method for preparing a heat-insulating composite glass material, characterized in that, The heat-insulating composite glass material is the heat-insulating composite glass material according to any one of claims 1 to 4, including free radical polymerization or freeze-thaw method; The free radical polymerization method includes the following steps: mixing acrylamide, acrylic acid, zwitterionic compound, modifying material and water to obtain a precursor solution; mixing the precursor solution, initiator, crosslinking agent and co-initiator to carry out a gelation reaction to obtain the heat-insulating composite glass material; The freeze-thaw method includes the following steps: mixing hydrogel monomer, acrylic acid, zwitterionic compound, modifier and water to obtain a precursor solution, and then freezing and thawing the precursor solution in sequence, repeating the freezing and thawing more than 5 times to obtain the heat-insulating composite glass material.

6. The application of a thermally insulating composite glass material in functional glass components, characterized in that, The heat-insulating composite glass material is the heat-insulating composite glass material according to any one of claims 1 to 4 or the heat-insulating composite glass material obtained by the preparation method according to claim 5.

7. A UV-resistant heat-insulating glass, characterized in that, It includes a heat-insulating composite glass material and quartz glass covering both sides of the heat-insulating composite glass material, wherein the heat-insulating composite glass material and quartz glass are encapsulated as a whole; The heat-insulating composite glass material is the heat-insulating composite glass material according to any one of claims 1 to 4 or the heat-insulating composite glass material obtained by the preparation method according to claim 5.

8. A method for preparing ultraviolet-proof heat-insulating glass, characterized in that, The UV-resistant heat-insulating glass is the UV-resistant heat-insulating glass as described in claim 7, comprising the following steps: The heat-insulating composite glass material is placed between two layers of quartz glass and sealed with glue to obtain the UV-resistant heat-insulating glass.

9. A cooling glass assembly, characterized in that, It includes a first glass, a heat-insulating composite glass material, a second glass, a cavity layer and a third glass stacked in sequence, and the first glass, the heat-insulating composite glass material, the second glass, the cavity layer and the third glass are encapsulated into a whole; The heat-insulating composite glass material is the heat-insulating composite glass material according to any one of claims 1 to 4 or the heat-insulating composite glass material obtained by the preparation method according to claim 5.

10. The cooling glass assembly according to claim 9, characterized in that, The cavity layer is provided with a liquid inlet and a liquid outlet.

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