CN111303608B - Temperature-change dimming fireproof material and preparation method and application thereof - Google Patents
Temperature-change dimming fireproof material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of inorganic/high-molecular composite materials, and particularly relates to a temperature-variable light-dimming fireproof material, and a preparation method and application thereof. The invention also provides temperature-control sun-shading fireproof glass containing the temperature-change dimming fireproof material and a preparation method thereof.
Description
Technical Field
The invention belongs to the technical field of inorganic/polymer composite materials, and particularly relates to a temperature-change dimming fireproof material as well as a preparation method and application thereof.
Background
Research shows that the ultraviolet UV-B in sunlight has serious harm effect on human health, potential risks comprise the initiation and aggravation of eye diseases, skin cancer and infectious diseases, and the research shows that the long-term exposure to strong ultraviolet radiation can cause the change of DNA in cells, the hypofunction of the human immune system, the reduction of the disease resistance of human bodies, and the attention of people for ultraviolet radiation prevention is paid to, and simultaneously, the penetration rate of infrared rays in the sunlight is high, the infrared rays convert light energy into heat energy under the condition of the sunlight, the indoor temperature is increased in summer and the indoor ultraviolet resistance function is increased, in order to increase the indoor ultraviolet resistance function and the infrared resistance, people begin to research materials with the color change effect, the color change glass is produced by transportation, and the transmittance of the color change glass changes along with the change of the external conditions under the conditions of illumination, temperature, electric field, current, surface pressure and the like, when external conditions do not exist, the glass is restored to the glass in the initial state, the color-changing glass can effectively control the solar radiation, the requirements of more and more people are met, along with the continuous increase of the requirements of people on the comfort degree of a use space, the application field of the dimming glass with the functions of shading sun and insulating heat is increasingly wide, and the development potential of the dimming glass is huge
At present, dimming glass on the market is almost all of an electric control type, and the transmission and the obstruction of the glass to sunlight are realized through a switching power supply. The electrically controlled dimming glass is divided into an organic liquid crystal type and an inorganic coating type, and the organic liquid crystal type has poor weather resistance and can only be used for indoor partition; the inorganic coating type is expensive, and the dimming function can be realized only by electrifying, so that the problems of design, installation, maintenance and the like exist. In addition, the existing dimming glass cannot resist high temperature, can explode and crack when a fire disaster happens, and is difficult to stop the spread of the fire. Therefore, light-dimming fireproof glass comes to be produced, for example, chinese patents 201520976334, 201610088495, 201120270512, 201621182192 and the like disclose information of light-dimming fireproof glass respectively, and the above patents all adopt cesium potassium fireproof glass as an assembly to realize the fireproof function. Chinese patent 201510564895 discloses a fire-proof liquid, and the fire-proof glass prepared by the fire-proof liquid has no dimming function.
The prior arts such as patents 03800722.3, 94190152.1, 98106929.0 and the like respectively disclose a temperature-control light-dimming material as an interlayer for preparing temperature-control light-dimming glass, but they do not have a fire-proof function. Simultaneously, this control by temperature change light control glass can change glass's luminousness, adjust indoor temperature, but along with the influence of temperature, this kind of regulation mode process is slow, and can't realize the initiative regulatory function under the low temperature condition, and it is less to ultraviolet ray light and infrared ray effect, and temperature-sensitive color change laminated glass is though there is the effect of blockking to the noise, but the effect is relatively poor, people still receive noise interference deeply, influence daily rest, the intermediate layer among the temperature-sensitive color change laminated glass produces the bubble easily in the manufacture process, the intermediate layer film of coating on glass is difficult to the dispersion, cause and paint inhomogeneously, and high temperature resistant, low temperature resistance can be poor, and can produce electrostatic action, cause harm to the human body.
Therefore, it is urgently needed to develop a temperature-variable light-adjusting fireproof material, which can adjust the transmittance of the material by the ambient temperature and sunlight, and has the advantages of high color-changing speed, long service life, good fireproof performance and the like.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a temperature-variable light-adjusting fireproof material, which can adjust the transmittance of the material by the ambient temperature and sunlight, and has the advantages of high color-changing speed, long service life and good fireproof performance. The temperature-variable dimming fireproof material can be applied to preparing temperature-control sun-shading fireproof glass, the transmittance of light can be automatically adjusted according to the ambient temperature and the solar irradiation intensity through the fireproof glass, the color change is sensitive, the service life is long, the fireproof performance is achieved, and the use is safer. Meanwhile, the invention also provides a preparation method of the temperature-control sunshade fireproof glass, which has the advantages of strong practicability, high production efficiency and good production quality.
The temperature-change dimming fireproof material comprises the following raw material components in parts by weight of 100 parts: 3.0-12 parts of temperature-sensitive substance, 2.0-12 parts of photo-curing monomer, 0.02-0.5 part of photoinitiator, 1.2-3.0 parts of light stabilizer, 0.05-0.5 part of cross-linked water-absorbent resin, 40-45 parts of nano-silicon solution, 0.3-1 part of curing agent, 10-20 parts of polyhydroxy solvent and the balance of water;
the nano silicon solution is an aqueous solution containing 30-50% by mass of nano silicon dioxide particles;
the pH value of the nano silicon solution is 9.0-10.5;
the particle size of the nano silicon solution is 5 nm-20 nm.
Further, the temperature-change dimming fireproof material comprises the following raw material components in parts by weight of 100: 10 parts of temperature-sensitive substance, 10 parts of light-cured monomer, 0.2 part of photoinitiator, 2.0 parts of light stabilizer, 0.4 part of cross-linked water-absorbent resin, 42 parts of nano-silicon solution, 0.8 part of curing agent, 18 parts of polyhydroxy solvent and 16.6 parts of water.
Further, the temperature-sensitive substance is an amphiphilic substance with an HLB value of 10-18.5, and the temperature-sensitive substance is composed of block polyether, dodecyl phenol polyoxyethylene ether and polyoxyethylene fatty acid ester according to a weight ratio of 3-8: 1-6: 10-15.
Furthermore, the temperature-sensitive substance is an amphiphilic substance with the HLB value of 10-18.5, and the temperature-sensitive substance is composed of block polyether, dodecyl phenol polyoxyethylene ether and polyoxyethylene fatty acid ester according to the weight ratio of 5:3: 12.
Further, the light-cured monomer is one or more of a monofunctional light-cured monomer or a polyfunctional light-cured monomer;
the monofunctional photocuring monomer has one of the following structures:
the multifunctional photocuring monomer has the following structure:
Still further, the photo-curable monomer may be one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, acrylic acid, hydroxypropyl acrylate, methylolacrylamide, methacrylamide, acrylamide, dimethylacrylamide, N-isopropylacrylamide, polyethylene glycol monoacrylate, polyethylene glycol diacrylate, and the like.
Further, the light stabilizer is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, vanadium dioxide and dibutyl hydroxy toluene according to a weight ratio of 8-15: 6-11: 1 to 5.
Further, the light stabilizer is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, vanadium dioxide and dibutyl hydroxy toluene according to a weight ratio of 12: 10: 3, and (3).
Further, the photoinitiator is one or more of benzophenone, 4-phenyl-benzophenone, benzoin and benzoin dimethyl ether;
furthermore, the cross-linked water-absorbing resin is one or more of starch grafted potassium acrylate, polyacrylamide, cross-linked carboxymethyl cellulose grafted acrylamide, cross-linked hydroxyethyl cellulose grafted acrylamide and acrylic acid cross-linked resin;
furthermore, the polyhydroxy solvent is one or two of ethylene glycol, propylene glycol, glycerol, polyethylene glycol, polypropylene glycol and polyglycerol, wherein the molecular weight of the polyethylene glycol, the polypropylene glycol and the polyglycerol is 200-600; the polyhydric alcohol is used as a solvent, so that the high and low temperature resistance of the temperature-variable dimming fireproof material can be improved, and the fireproof performance of the temperature-variable dimming fireproof material can be further improved.
The curing agent is one or more of sodium pyrophosphate, potassium fluosilicate and sodium fluosilicate.
In addition, the invention also provides a preparation method of the temperature-change dimming fireproof material, which comprises the following steps:
step 1: weighing the raw materials except the crosslinking water-absorbing resin and the water according to the proportion, and then putting the raw materials into a high-speed mixer to stir for 30-60 minutes to obtain a mixture;
step 2: and (3) adding the cross-linked water-absorbent resin and water into the mixture obtained in the step (1), and stirring for 60-90 minutes to obtain the water-absorbent resin.
The invention also provides temperature-control sunshade fireproof glass which comprises the temperature-change dimming fireproof material.
In addition, the invention also provides a preparation method of the temperature-controlled sun-shading fireproof glass, which comprises the following steps:
s1, bonding a large piece of glass and a small piece of cleaned glass in parallel along the edges of the small pieces of glass by using glue, and leaving a closed gap with a glue filling opening and an exhaust hole between the two pieces of glass;
s2, filling the temperature-change dimming fireproof material into the closed gap between the two pieces of glass through the glue filling port;
and S3, rolling and shaping the filled glass by using a roller press, carrying out photocuring shaping, and sealing the glue to obtain the glass.
According to the temperature-variable dimming fireproof material provided by the invention, the adopted temperature-sensitive substances are amphiphilic substances with the HLB value of 10-18.5, and the amphiphilic substances have the functions of dissolving and precipitating in water under certain temperature and concentration conditions, so that sunlight generates light scattering, the material is converted from transparent to white and turbid in a sun-shading state, the function is used for realizing the sun-shading and color-changing functions, and the temperature point of which the visible light transmittance is reduced by 10% within 0.1 ℃ is defined as the color-changing temperature. The inventor of the application finds that when the block polyether, the dodecylphenol polyoxyethylene ether and the polyoxyethylene fatty acid ester are composed according to the weight ratio of 3-8: 1-6: 10-15, the temperature-change dimming fireproof material has a rapid color change speed and excellent sun shading performance.
The cross-linked water-absorbent resin adopted by the temperature-variable dimming fireproof material provided by the invention is a polymer material with wide application, but the water-absorbent resin applicable to the temperature-variable dimming fireproof material-containing temperature-variable sunshade fireproof glass is selective. The cross-linked water-absorbent resin has a high water absorption function of absorbing water which is hundreds to thousands times heavier than the self-water-absorbent resin, and has excellent water retention performance, once the water-absorbent resin expands into hydrogel, a three-dimensional space framework with certain strength is formed, so that on one hand, the viscosity of the aqueous solution can be increased, and the phenomenon of bulging caused by the action of gravity when the temperature-controlled sun-shading fireproof glass after being filled is used is prevented; on the other hand, when the temperature response of the temperature-sensitive amphiphilic substance in the aqueous solution generates volume shrinkage, the size stability of the whole system is favorably maintained, the phenomena of edge shrinkage, nonuniform color change, cracking and the like of the temperature-controlled sun-shading fireproof glass can be prevented, and the whole system has a wide environment working range, wherein the effective working range is between minus 20 ℃ and plus 80 ℃.
According to the temperature-variable dimming fireproof material provided by the invention, a certain amount of dibutyl hydroxy toluene is added into a light stabilizer, so that the absorption of ultraviolet rays, infrared rays and visible light can be increased, the transmittance of the ultraviolet rays, the infrared rays and the visible light is reduced, the body safety of people is protected, meanwhile, the solid content of the material is effectively improved due to the added nano silicon solution, the fireproof performance of glass can be obviously improved due to the characteristics of non-combustion and high melting point, the use effect of the glass is enhanced, and the service life is prolonged.
Compared with the prior art, the invention has the beneficial effects that:
(1) the temperature-variable dimming fireproof material is a novel intelligent material with the transmittance adjusted by temperature and sunlight, and has the advantages of high color-changing speed, long service life, simple preparation method, safety, no pollution, environmental friendliness and good fireproof performance;
(2) the temperature-control sun-shading fireproof glass containing the temperature-variable dimming fireproof material is intelligent glass for adjusting ultraviolet, visible light and infrared light transmittance under the dual conditions of temperature and solar radiation intensity, and achieves the purpose of sun shading and dimming without manually giving signals (such as electrification), so that the temperature-variable sun-shading fireproof glass is an intelligent product in the true sense;
(3) the preparation method of the temperature-control sunshade fireproof glass is a high-efficiency and practical production process which can continuously, automatically and cleanly produce large-size light-dimming fireproof glass;
(4) the temperature-control sunshade fireproof glass can automatically adjust the sunlight transmittance, eliminate indoor sunlight burning sensation in summer, reduce air conditioner refrigeration energy consumption, and keep indoor brightness while shading sun, and indoor light is soft and cool; the light-transmitting glass has high light transmittance in winter, can collect light and supplement energy, can reduce heating energy consumption, and reduces environmental pollution caused by power production; excellent fireproof performance and safer use.
Detailed Description
The present invention is further illustrated by the following description of specific embodiments, which are not intended to limit the invention, and various modifications and improvements can be made by those skilled in the art based on the basic idea of the invention, but the invention is within the protection scope of the invention.
Wherein, the reagents used in the invention are all common reagents and can be purchased from common reagent production and sale companies.
Embodiment 1 temperature-controlled sun-shading fireproof glass
The temperature-change dimming fireproof material comprises the following raw materials in parts by weight of 100: 3.0 parts of temperature-sensitive substances, 2.0 parts of hydroxyethyl acrylate, 0.02 part of 4-phenyl-benzophenone, 1.2 parts of light stabilizer, 0.05 part of polyacrylamide, 40 parts of nano-silicon solution, 0.3 part of sodium pyrophosphate, 10 parts of polyethylene glycol 60010 and 43.43 parts of water.
The nano silicon solution is an aqueous solution containing 30% of nano silicon dioxide particles by mass;
the pH value of the nano silicon solution is 9.0;
the particle size of the nano silicon solution is 5 nm.
The temperature-sensitive substance is an amphiphilic substance with an HLB value of 10, and the temperature-sensitive substance is composed of block polyether, dodecyl phenol polyoxyethylene ether and polyoxyethylene fatty acid ester according to a weight ratio of 3:1: 15.
The light stabilizer is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, vanadium dioxide and dibutyl hydroxy toluene according to a weight ratio of 8: 6: 5.
The temperature-change dimming fireproof material is prepared by the following steps:
step 1: weighing the raw materials except the polyacrylamide and the water according to the proportion, and then putting the raw materials into a high-speed mixer to stir for 30 minutes to obtain a mixture;
step 2: and (3) adding polyacrylamide and water into the mixture obtained in the step (1), and stirring for 60-90 minutes to obtain the polyacrylamide gel.
The preparation method of the temperature-control sun-shading fireproof glass comprises the following steps:
s1, bonding a large piece of glass and a small piece of cleaned glass in parallel along the edges of the small pieces of glass by using glue, and leaving a closed gap with a glue filling opening and an exhaust hole between the two pieces of glass;
s2, filling the temperature-change dimming fireproof material into the closed gap between the two pieces of glass through the glue filling port;
and S3, rolling and shaping the filled glass by using a roller press, carrying out photocuring shaping, and sealing the glue to obtain the glass.
Embodiment 2 temperature-controlled sunshade fireproof glass
The temperature-change dimming fireproof material comprises the following raw materials in parts by weight of 100: 10 parts of temperature-sensitive substance, 10 parts of light-cured monomer, 0.2 part of photoinitiator, 2.0 parts of light stabilizer, 0.4 part of cross-linked water-absorbent resin, 42 parts of nano-silicon solution, 0.8 part of curing agent, 18 parts of polyhydroxy solvent and 39.6 parts of water.
The nano silicon solution is an aqueous solution containing 40% of nano silicon dioxide particles by mass;
the pH value of the nano silicon solution is 10;
the particle size of the nano silicon solution is 12 nm.
The temperature-sensitive substance is an amphiphilic substance with the HLB value of 12, and the temperature-sensitive substance is composed of block polyether, dodecyl phenol polyoxyethylene ether and polyoxyethylene fatty acid ester according to the weight ratio of 5:3: 12.
The light-cured monomer can be hydroxyethyl methacrylate, methacrylamide and polyethylene glycol monoacrylate according to the weight ratio of 1:1: 1.
The light stabilizer is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, vanadium dioxide and dibutyl hydroxy toluene according to the weight ratio of 12: 10: 3, and (3).
The photoinitiator is composed of benzophenone and 4-phenyl-benzophenone according to the weight ratio of 1: 1;
the cross-linked water-absorbing resin is composed of cross-linked carboxymethyl cellulose, cross-linked carboxymethyl cellulose grafted acrylamide and acrylic cross-linked resin according to the weight ratio of 1:1: 1;
the polyhydroxy solvent is composed of propylene glycol, polyethylene glycol and polypropylene glycol according to the weight ratio of 1:2: 1.
The curing agent consists of potassium fluosilicate and sodium fluosilicate according to the weight ratio of 1: 1;
the temperature-change dimming fireproof material is prepared by the following steps:
step 1, weighing the raw materials except the cross-linking water-absorbent resin and water according to a ratio, and then putting the raw materials into a high-speed mixer to stir for 50 minutes to obtain a mixture;
step 2: and (3) adding the cross-linked water-absorbent resin and water into the mixture obtained in the step (1), and stirring for 70 minutes to obtain the water-absorbent resin.
The preparation method of the temperature-control sun-shading fireproof glass comprises the following steps:
s1, bonding a large piece of glass and a small piece of cleaned glass in parallel along the edges of the small pieces of glass by using glue, and leaving a closed gap with a glue filling opening and an exhaust hole between the two pieces of glass;
s2, filling the temperature-change dimming fireproof material into the closed gap between the two pieces of glass through the glue filling port;
and S3, rolling and shaping the filled glass by using a roller press, carrying out photocuring shaping, and sealing the glue to obtain the glass.
Embodiment 3 temperature-controlled sunshade fireproof glass
The temperature-change dimming fireproof material comprises the following raw materials in parts by weight of 100: 12 parts of temperature-sensitive substance, 12 parts of light-cured monomer, 0.5 part of benzoin dimethyl ether, 3.0 parts of light stabilizer, 0.5 part of cross-linked water-absorbent resin, 45 parts of nano-silicon solution, 1 part of curing agent, 20 parts of polyhydroxy solvent and 6 parts of water.
The nano silicon solution is an aqueous solution containing 50% of nano silicon dioxide particles by mass;
the pH value of the nano silicon solution is 10.5;
the particle size of the nano silicon solution is 20 nm.
The temperature-sensitive substance is an amphiphilic substance with the HLB value of 18.5, and the temperature-sensitive substance is composed of block polyether, dodecyl phenol polyoxyethylene ether and polyoxyethylene fatty acid ester according to the weight ratio of 8:1: 10.
The light-cured monomer can be hydroxypropyl acrylate and N-isopropyl acrylamide according to the weight ratio of 1: 1.
The light stabilizer is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, vanadium dioxide and dibutyl hydroxy toluene according to a weight ratio of 15: 6: 1.
The cross-linked water-absorbing resin is composed of cross-linked carboxymethyl cellulose and acrylic cross-linked resin according to the weight ratio of 1: 1;
the temperature-change dimming fireproof material is prepared by the following steps:
step 1, weighing the raw materials except the cross-linking water-absorbent resin and water according to a ratio, and then putting the raw materials into a high-speed mixer to stir for 60 minutes to obtain a mixture;
step 2: and (3) adding the cross-linked water-absorbent resin and water into the mixture obtained in the step (1), and stirring for 90 minutes to obtain the water-absorbent resin.
The preparation method of the temperature-control sun-shading fireproof glass comprises the following steps:
s1, bonding a large piece of glass and a small piece of cleaned glass in parallel along the edges of the small pieces of glass by using glue, and leaving a closed gap with a glue filling opening and an exhaust hole between the two pieces of glass;
s2, filling the temperature-change dimming fireproof material into the closed gap between the two pieces of glass through the glue filling port;
and S3, rolling and shaping the filled glass by using a roller press, carrying out photocuring shaping, and sealing the glue to obtain the glass.
Comparative example 1 temperature-controlled sun-shading fireproof glass
The temperature-change dimming fireproof material comprises the following raw material components in parts by weight of 100: 10 parts of temperature-sensitive substance, 10 parts of light-cured monomer, 0.2 part of photoinitiator, 2.0 parts of light stabilizer, 0.4 part of cross-linked water-absorbent resin, 42 parts of nano-silicon solution, 0.8 part of curing agent, 18 parts of polyhydroxy solvent and 39.6 parts of water.
The nano silicon solution is an aqueous solution containing 40% of nano silicon dioxide particles by mass;
the pH value of the nano silicon solution is 10;
the particle size of the nano silicon solution is 12 nm.
The temperature-sensitive substance is an amphiphilic substance with the HLB value of 12, and the temperature-sensitive substance is composed of block polyether, dodecyl phenol polyoxyethylene ether and polyoxyethylene fatty acid ester according to the weight ratio of 5:3: 12.
The light-cured monomer can be hydroxyethyl methacrylate, methacrylamide and polyethylene glycol monoacrylate according to the weight ratio of 1:1: 1.
The light stabilizer is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and dibutyl hydroxy toluene according to the weight ratio of 12: 3, and (3).
The photoinitiator is composed of benzophenone and 4-phenyl-benzophenone according to the weight ratio of 1: 1;
the cross-linked water-absorbing resin is composed of cross-linked carboxymethyl cellulose, cross-linked carboxymethyl cellulose grafted acrylamide and acrylic cross-linked resin according to the weight ratio of 1:1: 1;
the polyhydroxy solvent is composed of propylene glycol, polyethylene glycol and polypropylene glycol according to the weight ratio of 1:2: 1.
The curing agent consists of potassium fluosilicate and sodium fluosilicate according to the weight ratio of 1: 1;
the temperature-change dimming fireproof material is prepared by the steps similar to those of example 2.
The preparation method of the temperature-controlled sun-shading fireproof glass is similar to that of the embodiment 2.
The difference from example 2 is that no vanadium dioxide is added to the light stabilizer.
Comparative example 2 temperature-controlled sun-shading fireproof glass
The temperature-change dimming fireproof material comprises the following raw material components in parts by weight of 100: 10 parts of temperature-sensitive substance, 10 parts of light-cured monomer, 0.2 part of photoinitiator, 2.0 parts of light stabilizer, 0.4 part of cross-linked water-absorbent resin, 42 parts of nano-silicon solution, 0.8 part of curing agent, 18 parts of polyhydroxy solvent and 39.6 parts of water.
The nano silicon solution is an aqueous solution containing 40% of nano silicon dioxide particles by mass;
the pH value of the nano silicon solution is 10;
the particle size of the nano silicon solution is 12 nm.
The temperature-sensitive substance is an amphiphilic substance with the HLB value of 12, and the temperature-sensitive substance is composed of block polyether, dodecyl phenol polyoxyethylene ether and polyoxyethylene fatty acid ester according to the weight ratio of 5:3: 12.
The light-cured monomer can be hydroxyethyl methacrylate, methacrylamide and polyethylene glycol monoacrylate according to the weight ratio of 1:1: 1.
The light stabilizer is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and vanadium dioxide according to the weight ratio of 12: 10.
The photoinitiator is composed of benzophenone and 4-phenyl-benzophenone according to the weight ratio of 1: 1;
the cross-linked water-absorbing resin is composed of cross-linked carboxymethyl cellulose, cross-linked carboxymethyl cellulose grafted acrylamide and acrylic cross-linked resin according to the weight ratio of 1:1: 1;
the polyhydroxy solvent is composed of propylene glycol, polyethylene glycol and polypropylene glycol according to the weight ratio of 1:2: 1.
The curing agent consists of potassium fluosilicate and sodium fluosilicate according to the weight ratio of 1: 1;
the temperature-change dimming fireproof material is prepared by the steps similar to those of example 2.
The preparation method of the temperature-controlled sun-shading fireproof glass is similar to that of the embodiment 2.
The difference from example 2 is that no dibutylhydroxytoluene is added to the light stabilizer.
Comparative example 3 temperature-controlled sun-shading fireproof glass
The temperature-change dimming fireproof material comprises the following raw materials in parts by weight of 100: 10 parts of temperature-sensitive substance, 10 parts of light-cured monomer, 0.2 part of photoinitiator, 2.0 parts of light stabilizer, 0.4 part of cross-linked water-absorbent resin, 42 parts of nano-silicon solution, 0.8 part of curing agent, 18 parts of polyhydroxy solvent and 39.6 parts of water.
The nano silicon solution is an aqueous solution containing 40% of nano silicon dioxide particles by mass;
the pH value of the nano silicon solution is 10;
the particle size of the nano silicon solution is 12 nm.
The temperature-sensitive substance is an amphiphilic substance with the HLB value of 12, and the temperature-sensitive substance is composed of block polyether, dodecyl phenol polyoxyethylene ether and polyoxyethylene fatty acid ester according to the weight ratio of 5:3: 12.
The light-cured monomer can be hydroxyethyl methacrylate, methacrylamide and polyethylene glycol monoacrylate according to the weight ratio of 1:1: 1.
The light stabilizer is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, vanadium dioxide and dibutyl hydroxy toluene according to a weight ratio of 1:1: 1.
The photoinitiator is composed of benzophenone and 4-phenyl-benzophenone according to the weight ratio of 1: 1;
the cross-linked water-absorbing resin is cross-linked carboxymethyl cellulose, cross-linked carboxymethyl cellulose grafted acrylamide and acrylic acid cross-linked resin according to a weight ratio of 1:1:1, preparing a composition;
the polyhydroxy solvent is composed of propylene glycol, polyethylene glycol and polypropylene glycol according to the weight ratio of 1:2: 1.
The curing agent consists of potassium fluosilicate and sodium fluosilicate according to the weight ratio of 1: 1;
the temperature-change dimming fireproof material is prepared by the steps similar to those of example 2.
The preparation method of the temperature-controlled sun-shading fireproof glass is similar to that of the embodiment 2.
The difference from the example 2 is that the light stabilizer is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, vanadium dioxide and dibutyl hydroxy toluene according to the weight ratio of 1:1: 1.
Comparative example 4 temperature-controlled sun-shading fireproof glass
The temperature-change dimming fireproof material comprises the following raw materials in parts by weight of 100: 10 parts of temperature-sensitive substance, 10 parts of light-cured monomer, 0.2 part of photoinitiator, 2.0 parts of light stabilizer, 0.4 part of cross-linked water-absorbent resin, 42 parts of nano-silicon solution, 0.8 part of curing agent, 18 parts of polyhydroxy solvent and 39.6 parts of water.
The nano silicon solution is an aqueous solution containing 40% of nano silicon dioxide particles by mass;
the pH value of the nano silicon solution is 10;
the particle size of the nano silicon solution is 12 nm.
The temperature-sensitive substance is an amphiphilic substance with HLB value of 12, and the temperature-sensitive substance is composed of block polyether and polyoxyethylene fatty acid ester according to the weight ratio of 5: 12.
The light-cured monomer can be hydroxyethyl methacrylate, methacrylamide and polyethylene glycol monoacrylate according to the weight ratio of 1:1: 1.
The light stabilizer is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, vanadium dioxide and dibutyl hydroxy toluene according to the weight ratio of 12: 10: 3, and (3).
The photoinitiator is composed of benzophenone and 4-phenyl-benzophenone according to the weight ratio of 1: 1;
the cross-linked water-absorbing resin is composed of cross-linked carboxymethyl cellulose, cross-linked carboxymethyl cellulose grafted acrylamide and acrylic cross-linked resin according to the weight ratio of 1:1: 1;
the polyhydroxy solvent is composed of propylene glycol, polyethylene glycol and polypropylene glycol according to the weight ratio of 1:2: 1.
The curing agent consists of potassium fluosilicate and sodium fluosilicate according to the weight ratio of 1: 1;
the temperature-change dimming fireproof material is prepared by the steps similar to those of example 2.
The preparation method of the temperature-controlled sun-shading fireproof glass is similar to that of the embodiment 2.
The difference from the example 2 is that the temperature sensitive substance is not added with dodecylphenol polyoxyethylene ether.
Comparative example 5 temperature-controlled sun-shading fireproof glass
The temperature-change dimming fireproof material comprises the following raw materials in parts by weight of 100: 10 parts of temperature-sensitive substance, 10 parts of light-cured monomer, 0.2 part of photoinitiator, 2.0 parts of light stabilizer, 0.4 part of cross-linked water-absorbent resin, 42 parts of nano-silicon solution, 0.8 part of curing agent, 18 parts of polyhydroxy solvent and 39.6 parts of water.
The nano silicon solution is an aqueous solution containing 40% of nano silicon dioxide particles by mass;
the pH value of the nano silicon solution is 10;
the particle size of the nano silicon solution is 12 nm.
The temperature-sensitive substance is an amphiphilic substance with the HLB value of 12, and the temperature-sensitive substance is composed of block polyether, dodecyl phenol polyoxyethylene ether and polyoxyethylene fatty acid ester according to the weight ratio of 1:1: 1.
The light-cured monomer can be hydroxyethyl methacrylate, methacrylamide and polyethylene glycol monoacrylate according to the weight ratio of 1:1: 1.
The light stabilizer is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, vanadium dioxide and dibutyl hydroxy toluene according to the weight ratio of 12: 10: 3, and (3).
The photoinitiator is composed of benzophenone and 4-phenyl-benzophenone according to the weight ratio of 1: 1;
the cross-linked water-absorbing resin is composed of cross-linked carboxymethyl cellulose, cross-linked carboxymethyl cellulose grafted acrylamide and acrylic cross-linked resin according to the weight ratio of 1:1: 1;
the polyhydroxy solvent is composed of propylene glycol, polyethylene glycol and polypropylene glycol according to the weight ratio of 1:2: 1.
The curing agent consists of potassium fluosilicate and sodium fluosilicate according to the weight ratio of 1: 1;
the temperature-change dimming fireproof material is prepared by the steps similar to those of example 2.
The preparation method of the temperature-controlled sun-shading fireproof glass is similar to that of the embodiment 2.
The difference from the embodiment 2 is that the temperature-sensitive substance is composed of block polyether, dodecyl phenol polyoxyethylene ether and polyoxyethylene fatty acid ester according to the weight ratio of 1:1: 1.
Comparative example 6 temperature-control sun-shading fireproof glass
The temperature-change dimming fireproof material comprises the following raw materials in parts by weight of 100: 10 parts of temperature-sensitive substance, 10 parts of light-cured monomer, 0.2 part of photoinitiator, 2.0 parts of light stabilizer, 0.4 part of cross-linked water-absorbent resin, 42 parts of nano-silicon solution, 0.8 part of curing agent, 18 parts of polyhydroxy solvent and 39.6 parts of water.
The nano silicon solution is an aqueous solution containing 10% of nano silicon dioxide particles by mass;
the pH value of the nano silicon solution is 10;
the particle size of the nano silicon solution is 12 nm.
The temperature-sensitive substance is an amphiphilic substance with the HLB value of 12, and the temperature-sensitive substance is composed of block polyether, dodecyl phenol polyoxyethylene ether and polyoxyethylene fatty acid ester according to the weight ratio of 5:3: 12.
The light-cured monomer can be hydroxyethyl methacrylate, methacrylamide and polyethylene glycol monoacrylate according to the weight ratio of 1:1: 1.
The light stabilizer is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, vanadium dioxide and dibutyl hydroxy toluene according to the weight ratio of 12: 10: 3, and (3).
The photoinitiator is composed of benzophenone and 4-phenyl-benzophenone according to the weight ratio of 1: 1;
the cross-linked water-absorbing resin is composed of cross-linked carboxymethyl cellulose, cross-linked carboxymethyl cellulose grafted acrylamide and acrylic cross-linked resin according to the weight ratio of 1:1: 1;
the polyhydroxy solvent is composed of propylene glycol, polyethylene glycol and polypropylene glycol according to the weight ratio of 1:2: 1.
The curing agent consists of potassium fluosilicate and sodium fluosilicate according to the weight ratio of 1: 1;
the temperature-change dimming fireproof material is prepared by the steps similar to those of example 2.
The preparation method of the temperature-controlled sun-shading fireproof glass is similar to the preparation method of the temperature-controlled sun-shading fireproof glass in example 2.
The difference from example 2 is that the nano silicon solution is an aqueous solution containing nano silica particles in a mass fraction of 10%.
Test example I, weather resistance test
1. Test materials: temperature controlled sun-shading fire resistant glasses prepared in examples 1-3.
2. Test methods the temperature-controlled sunshade fireproof glass manufactured in examples 1 to 3 of the present invention was subjected to a weather resistance test according to the following table 1.
TABLE 1 weather resistance test of temperature-controlled sunshade fireproof glass
Through the tests of the items, the temperature-control sun-shading fireproof glass prepared in the embodiments 1 to 3 can reach the standards of the table above, has stable service performance and long service life in the environment of-20 ℃ to 80 ℃, has excellent weather resistance and fireproof performance, and does not have the phenomena of water seepage, air bubbles, degumming, blooming, shrinkage and delamination.
Test example two, test of fire resistance
1. Test materials: the temperature-controlled sun-shading fireproof glass prepared in the examples 1 to 3 and the comparative examples 1 to 6.
2. The test method comprises the following steps: and (3) carrying out a fire resistance detection experiment on the 3 pieces of fireproof glass according to the GB/T12513-2006 standard to obtain the fire resistance time of each piece of composite fireproof glass, wherein 3 parallel samples are taken in the experiment, and the average value of the data is taken as an experiment result.
3. Test results
The test results are shown in table 2.
TABLE 2 fireproof performance parameter table of temperature-controlled sunshade fireproof glass
| Test specimen | Time to fire/min |
| Example 1 | 68 |
| Example 2 | 71 |
| Example 3 | 67 |
| Comparative example 1 | 58 |
| Comparative example 2 | 57 |
| Comparative example 3 | 60 |
| Comparative example 4 | 55 |
| Comparative example 5 | 58 |
| Comparative example 6 | 18 |
As can be seen from Table 2: the temperature-control sun-shading fireproof glass prepared in the embodiments 1-3 of the invention can obviously improve the fireproof performance of the glass, simultaneously improve the use effect of the glass and prolong the service life. The group in the embodiment 2 has the best effect, and the fireproof time reaches 71min, which is the best embodiment of the invention. The test results of the comparative example 6 and the example group show that the aqueous solution of the nano silicon dioxide particles with the mass fraction of 30-50% added in the temperature-controlled sun-shading fireproof glass provided by the invention is reasonable in proportion to the rest components, the synergistic effect is obvious, the fireproof performance of the temperature-controlled sun-shading fireproof glass provided by the invention is effectively enhanced, and the fireproof time is prolonged.
Test example three, optical Property test
1. Test materials: example 2, comparative examples 1-3.
2. The test method comprises the following steps: the optical performance tests of the temperature-controlled sun-shading fireproof glass of the embodiment 2 and the comparative examples 1 to 3 are carried out under the same environmental conditions.
3. Test results
The test results are shown in table 3.
TABLE 3 optical Property test results
As can be seen from table 3: compared with the data of the comparative examples 1 to 3, the temperature-controlled sun-shading fireproof glass prepared in the embodiment 2 can automatically adjust the sunlight irradiation intensity, eliminate the scorching sensation of indoor sunlight in summer, reduce the refrigeration energy consumption of an air conditioner, keep the indoor brightness while shading sun, and ensure that the indoor light is soft and cool; high light transmission in winter, lighting and energy supplement, and reduced heating energy consumption. When the components and contents of the light stabilizer are changed in comparative examples 1 to 3, the prepared temperature-controlled sun-shading fireproof glass cannot achieve the automatic dimming function with the remarkable effect as in example 2, the infrared transmittance and the visible light transmittance are both reduced as compared with the data in example 2 when the light is weak or the temperature is low, and the infrared transmittance and the visible light transmittance are both increased as compared with the data in example 2 when the light is strong or the temperature is high.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Those skilled in the art can modify or change the above-described embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (8)
1. The temperature-change dimming fireproof material is characterized by comprising the following raw material components in parts by weight of 100: 3.0-12 parts of temperature-sensitive substance, 2.0-12 parts of photo-curing monomer, 0.02-0.5 part of photoinitiator, 1.2-3.0 parts of light stabilizer, 0.05-0.5 part of cross-linked water-absorbent resin, 40-45 parts of nano-silicon solution, 0.3-1 part of curing agent, 10-20 parts of polyhydroxy solvent and the balance of water;
the nano silicon solution is an aqueous solution containing 30-50% by mass of nano silicon dioxide particles;
the pH value of the nano silicon solution is 9.0-10.5;
the particle size of the nano silicon solution is 5 nm-20 nm;
the temperature-sensitive substance is an amphiphilic substance with an HLB (hydrophile-lipophile balance) value of 10-18.5, and the temperature-sensitive substance is composed of block polyether, dodecyl phenol polyoxyethylene ether and polyoxyethylene fatty acid ester according to a weight ratio of 3-8: 1-6: 10-15;
the light stabilizer is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, vanadium dioxide and dibutyl hydroxy toluene according to a weight ratio of 8-15: 6-11: 1-5;
the preparation method of the temperature-change dimming fireproof material comprises the following preparation steps:
step 1: weighing the raw materials except the crosslinking water-absorbing resin and the water according to the proportion, and then putting the raw materials into a high-speed mixer to stir for 30-60 minutes to obtain a mixture;
step 2: and (3) adding the cross-linked water-absorbent resin and water into the mixture obtained in the step (1), and stirring for 60-90 minutes to obtain the water-absorbent resin.
2. The temperature-change dimming fireproof material as claimed in claim 1, which comprises the following raw materials in parts by weight, based on 100 parts by weight: 10 parts of temperature-sensitive substance, 10 parts of light-cured monomer, 0.2 part of photoinitiator, 2.0 parts of light stabilizer, 0.4 part of cross-linked water-absorbent resin, 42 parts of nano-silicon solution, 0.8 part of curing agent, 18 parts of polyhydroxy solvent and 16.6 parts of water.
3. The temperature-sensitive dimming fireproof material according to claim 1 or 2, wherein the light-curing monomer is one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, acrylic acid, hydroxypropyl acrylate, hydroxymethyl acrylamide, methacrylamide, acrylamide, dimethylacrylamide, N-isopropylacrylamide, polyethylene glycol monoacrylate and polyethylene glycol diacrylate.
4. The temperature-change dimming fireproof material according to claim 1, wherein the light stabilizer is 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, vanadium dioxide and dibutyl hydroxy toluene in a weight ratio of 12: 10: 3, and (3).
5. The temperature-change dimming fireproof material according to claim 1 or 2, wherein the photoinitiator is one or more of benzophenone, 4-phenyl-benzophenone, benzoin and benzoin dimethyl ether;
the cross-linked water-absorbing resin is one or more of polyacrylamide, cross-linked carboxymethyl cellulose grafted acrylamide, cross-linked hydroxyethyl cellulose grafted acrylamide and acrylic cross-linked resin;
the polyhydroxy solvent is one or two of ethylene glycol, propylene glycol, glycerol, polyethylene glycol, polypropylene glycol and polyglycerol, wherein the molecular weight of the polyethylene glycol, the polypropylene glycol and the polyglycerol is 200-600; the curing agent is one or more of sodium pyrophosphate, potassium fluosilicate and sodium fluosilicate.
6. A method for preparing a temperature-variable light-adjusting fireproof material according to any one of claims 1 to 5, wherein the preparation steps are as follows:
step 1: weighing the raw materials except the crosslinking water-absorbing resin and the water according to the proportion, and then putting the raw materials into a high-speed mixer to stir for 30-60 minutes to obtain a mixture;
step 2: and (3) adding the cross-linked water-absorbent resin and water into the mixture obtained in the step (1), and stirring for 60-90 minutes to obtain the water-absorbent resin.
7. A temperature-controlled sun-shading fireproof glass, characterized by comprising the temperature-variable light-dimming fireproof material according to any one of claims 1 to 5.
8. A method for preparing the temperature-controlled sun-shading fireproof glass as claimed in claim 7, which comprises the following steps:
s1, bonding a large piece of glass and a small piece of cleaned glass in parallel along the edges of the small pieces of glass by using glue, and leaving a closed gap with a glue filling opening and an exhaust hole between the two pieces of glass;
s2, filling the temperature-change dimming fireproof material into the closed gap between the two pieces of glass through the glue filling port;
and S3, rolling and shaping the filled glass by using a rolling machine, carrying out photocuring shaping, and sealing the glue to obtain the glass.
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| US6020989A (en) * | 1997-05-14 | 2000-02-01 | Affinity Co., Ltd. | Laminated bodies and windows using them |
| DE60319285T2 (en) * | 2003-05-22 | 2009-02-12 | Affinity Co. Ltd. | SELF LIGHT ABSORPTION REGULATING LAMINATE AND WINDOW WITH THE SAME |
| CN101608021B (en) * | 2009-07-09 | 2011-09-14 | 西南大学 | Preparation method of N-isopropyl acrylamide polymer/polyvinyl alcohol composite hydrogel and product thereof |
| US9256010B2 (en) * | 2010-06-25 | 2016-02-09 | Tokyo Institute Of Technology | Thermochromic resin composite, method for adjusting clouding point of thermochromic resin composite, and dimmer |
| CN102585674B (en) * | 2011-12-23 | 2014-01-15 | 武汉康桥伟业高新科技有限公司 | Temperature-sensitive color-changing coating |
| CN102816340B (en) * | 2012-09-06 | 2017-05-17 | 北京理工大学 | Intelligent light adjusting film based on temperature-sensitive polymer hydrogel and preparation method of intelligent light adjusting film |
| CN102796267A (en) * | 2012-09-06 | 2012-11-28 | 北京理工大学 | Sodium-alginate-based temperature-sensitive polymer aquagel smart dimming film and preparation method thereof |
| CN103085393B (en) * | 2013-01-09 | 2015-03-04 | 付国东 | Thermo-sensitive type intelligent composite optical glass based on renewable resources |
| CN104062776B (en) * | 2014-07-04 | 2017-02-15 | 苏州珀力玛高分子材料有限公司 | Intelligent hollow dimming glass and preparing method thereof |
| CN104086928B (en) * | 2014-07-04 | 2016-09-07 | 苏州珀力玛高分子材料有限公司 | A kind of composition of intelligent dimming glass |
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| CN107216638A (en) * | 2017-07-12 | 2017-09-29 | 苏州珀力玛高分子材料有限公司 | A kind of temperature becomes light modulation fire proofing material, temperature control sunshade flame resistant glass and preparation method thereof |
| CN107353622A (en) * | 2017-07-12 | 2017-11-17 | 苏州珀力玛高分子材料有限公司 | Temperature becomes light control material, becomes temperature control sunshade photo chromic glass of light control material and preparation method thereof containing temperature |
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