CN113024723A - Glass intelligent window and preparation method thereof - Google Patents

Glass intelligent window and preparation method thereof Download PDF

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Publication number
CN113024723A
CN113024723A CN202110323618.1A CN202110323618A CN113024723A CN 113024723 A CN113024723 A CN 113024723A CN 202110323618 A CN202110323618 A CN 202110323618A CN 113024723 A CN113024723 A CN 113024723A
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glass
hydrogel
mass
pieces
polymerization
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Inventor
徐文龙
孙泽乾
李正浩
张志文
陈坤
谢新敏
欧阳佳慧
陈孟军
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Ludong University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56Acrylamide; Methacrylamide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/22Emulsion polymerisation
    • C08F2/24Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/30Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • EFIXED CONSTRUCTIONS
    • E06DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06BFIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B9/00Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
    • E06B9/24Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
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Abstract

The invention discloses a glass intelligent window and a preparation method thereof, wherein the preparation method comprises the steps of providing two pieces of glass; sequentially cleaning and drying the glass; adding hydrogel prepolymer liquid between two pieces of dried glass for sealing, and carrying out in-situ polymerization reaction on the hydrogel prepolymer liquid between the two pieces of glass to obtain the glass intelligent window; the hydrogel pre-polymerization liquid is prepared by the following preparation steps: adding an alkene monomer, a cross-linking agent, a catalyst and a nonionic surfactant into deionized water for dissolving, and then adding an initiator for mixing to obtain a hydrogel pre-polymerization liquid. The glass intelligent window prepared by the method has rapid response to temperature and stable performance.

Description

Glass intelligent window and preparation method thereof
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a glass intelligent window and a preparation method thereof.
Background
About 40% of the global energy consumption comes from the building industry, the annual building energy consumption of China is as high as about 20%, and the energy is applied to refrigeration, heating, illumination and the like. Nowadays, the energy problem is increasingly prominent, and how to reduce energy loss on the basis of meeting the daily life needs of people becomes a key problem. "intelligence window" can the dynamic adjustment solar radiation energy transmissivity, not only can let indoor people feel comfortable, can reduce the required energy consumption of indoor refrigeration, heating moreover, reduces the energy loss from the source.
At present, the mature technology in the field of intelligent windows comprises an electrochromic intelligent window, a photochromic intelligent window and a thermochromic intelligent window, but the electrochromic intelligent window needs extra electric energy to be supplied, so that the loss of another energy source is caused, the photochromic intelligent window is limited by the characteristics of complex process, high cost and the like, and the traditional material VO commonly used for the thermochromic intelligent window2The phase transition temperature is too high (68 ℃), which also makes it difficult to apply to daily life, so that it is urgent to develop an intelligent window with simple and safe process and appropriate response temperature.
Disclosure of Invention
The invention aims to provide a glass intelligent window and a preparation method thereof, wherein the preparation method is safe and quick in reaction.
In order to achieve the above object, in a first aspect, an embodiment of the present invention provides a method for manufacturing a glass smart window, including: providing two pieces of glass; sequentially cleaning and drying the glass; adding hydrogel prepolymer liquid between two pieces of dried glass for sealing, and carrying out in-situ polymerization reaction on the hydrogel prepolymer liquid between the two pieces of glass to obtain the glass intelligent window; the hydrogel pre-polymerization liquid is prepared by the following preparation steps: adding the nonionic surfactant, the vinyl monomer, the cross-linking agent and the catalyst into deionized water for dissolving, and then adding the initiator for mixing to obtain the hydrogel pre-polymerization liquid.
According to the embodiment of the invention, the hydrogel pre-polymerization liquid is subjected to in-situ polymerization reaction between two pieces of glass to form hydrogel, and the two pieces of glass are bonded into the glass intelligent window through the hydrogel; wherein, the nonionic surfactant enables the synthesized hydrogel prepolymer liquid to have temperature response property, and the preparation method is safe and has quick reaction.
In any of the preceding embodiments of the first aspect of the present invention, the polymerization time of the hydrogel pre-polymerization solution between two sheets of glass is 15min to 30min, and the polymerization temperature is 20 ℃ to 70 ℃. The reaction condition is mild, and the preparation is rapid.
In any one of the preceding embodiments of the first aspect of the present invention, the mass fraction of the nonionic surfactant is 0.5% to 5% based on the total mass 1 of the hydrogel pre-polymerization solution. The transparent-opaque transition temperature of the hydrogel can be controlled by varying the amount of the nonionic surfactant, which has the property of cloud point, and the light transmittance of the hydrogel decreases as the temperature increases. When the mass fraction of the nonionic surfactant is 0.5-5%, the temperature for the transparent-opaque hydrogel to start to transform is 25-50 ℃. The lower the temperature at which the clear-opaque transition of the gel begins with increasing nonionic surfactant mass fraction.
In any one of the preceding embodiments of the first aspect of the present invention, based on the total mass 1 of the hydrogel pre-polymerization solution to be prepared, the mass fraction of the vinyl monomer is 5% to 15%, the mass fraction of the crosslinking agent is 0.05% to 0.2%, the mass fraction of the catalyst is 0.05% to 0.1%, and the mass fraction of the initiator is 0.05% to 0.2%. The transparent-opaque transition temperature of the hydrogel can be controlled by changing the dosage of the vinyl monomer and the cross-linking agent, and the temperature for starting the transparent-opaque transition of the prepared glass intelligent window can be reduced by increasing the dosage of the vinyl monomer and the cross-linking agent in the hydrogel pre-polymerization liquid. The glass intelligent window prepared by the method has rapid response to temperature and stable performance.
In any of the preceding embodiments of the first aspect of the invention, the cleaning process comprises: and cleaning the glass by using water or absolute ethyl alcohol to remove stains on the surface of the glass. The cleaning solvent has little harm to the environment.
In any of the preceding embodiments of the first aspect of the present disclosure, the nonionic surfactant comprises at least one of poly (propylene glycol) -block-poly (ethylene glycol) -block-poly (propylene glycol), lauryl diethanol amide, and polyethylene glycol ether. The nonionic surfactant does not participate in the free radical polymerization reaction, has no influence on the free radical polymerization reaction, but can control the light transmittance change of the intelligent window. The nonionic surfactant has stable cloud point property, is dissolved in the gel at low temperature, and the hydrogel is clear and transparent; the gel is uniformly precipitated at high temperature, resulting in a decrease in the transmittance of the hydrogel.
In any of the preceding embodiments of the first aspect of the present disclosure, the ethylenic monomer includes at least one of acrylamide, acrylic acid, and vinyl acetate. The vinyl monomer can be subjected to radical polymerization to form the main structure of the hydrogel.
In any of the preceding embodiments of the first aspect of the invention, the crosslinker comprises N, N' -methylenebisacrylamide and/or polyethylene glycol diacrylate. The crosslinking agent has a diene structure, and can crosslink chain polymer chains into a three-dimensional network structure in radical polymerization, thereby preventing solvent flow.
The catalyst comprises N, N, N ', N', -tetramethylethylenediamine and/or sodium bisulfite. The catalyst has certain reducibility, and can reduce an initiator into a primary free radical, thereby accelerating the speed of free radical polymerization reaction.
The initiator comprises ammonium persulfate and/or potassium persulfate. The initiator has oxidizing property and can react with a reducing agent to generate a stable primary free radical for initiating the polymerization reaction of the vinyl monomer.
In a second aspect, embodiments of the present disclosure provide a glass smart window obtained by the manufacturing method of any one of the embodiments of the first aspect. The glass intelligent window provided by the embodiment of the invention has the advantages of rapid response to temperature and stable performance.
Drawings
Fig. 1 is a graph of the uv-vis absorption spectra of the glass smart windows prepared in examples 1 and 2 of the present invention.
Fig. 2 is a representation of the glass smart window prepared in example 1 of the present invention at different temperatures.
Detailed Description
In order to make the purpose, technical solution and advantageous technical effects of the present invention clearer, the present invention is described in detail with reference to specific embodiments below. It should be understood that the embodiments described in this specification are only for the purpose of explaining the present application and are not intended to limit the present application.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Thus, each point or individual value can form a range not explicitly recited as its own lower or upper limit in combination with any other point or individual value or in combination with other lower or upper limits.
In the description herein, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive, and "one or more" means "a plurality of" is two or more.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through a list of embodiments that can be used in various combinations. In each instance, the list is merely a representative group and should not be construed as exhaustive.
The inventors have found that nonionic surfactants have a unique temperature response property, the cloud point, and that when temperatures are below their cloud point, nonionic surfactants are completely dissolved in water and when temperatures are above their cloud point, nonionic surfactants will precipitate in water.
The non-ionic surfactant is introduced into the free radical polymerization hydrogel, and is dissolved in the hydrogel by utilizing a large amount of water in a unique three-dimensional network structure network of the hydrogel, so that the synthesized hydrogel has unique temperature response property, the hydrogel is transparent due to complete dissolution of the non-ionic surfactant at low temperature, and is changed into milky opaque due to partial precipitation of the non-ionic surfactant at high temperature, and the hydrogel has a good temperature response effect when applied to an intelligent window.
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
In this embodiment, a synthetic glass smart window is prepared by using poly (propylene glycol) -block-poly (ethylene glycol) -block-poly (propylene glycol), acrylamide, N '-methylenebisacrylamide, N', -tetramethylethylenediamine, ammonium persulfate, and deionized water as raw materials, and the light transmittance begins to decrease at 27 ℃ as the temperature increases, and the specific implementation process is as follows:
(1) cleaning two pieces of glass with water, removing stains, and drying;
(2) 10g of hydrogel prepolymer solution was prepared. Wherein the mass of poly (propylene glycol) -block-poly (ethylene glycol) -block-poly (propylene glycol) is 0.2g, the mass of acrylamide is 1g, the mass of N, N ' -methylenebisacrylamide is 0.015g, the mass of N, N, N ', N ' -tetramethylethylenediamine is 0.008g, the mass of ammonium persulfate is 0.016g and the mass of deionized water is 8.761 g.
(3) And respectively carrying out in-situ polymerization and sealing on the hydrogel prepolymerization solution between two pieces of glass, and reacting for 20 minutes to obtain the glass intelligent window starting opaque transformation at 27 ℃.
Example 2
In this example, a synthetic glass smart window is prepared by using poly (propylene glycol) -block-poly (ethylene glycol) -block-poly (propylene glycol), acrylamide, N '-methylenebisacrylamide, N', -tetramethylethylenediamine, ammonium persulfate, and deionized water as raw materials, and starts opaque transition at 32 ℃, and the specific implementation process is as follows:
(1) cleaning two pieces of glass with water, removing stains, and drying;
(2) 10g of hydrogel prepolymer solution was prepared. Wherein the mass of poly (propylene glycol) -block-poly (ethylene glycol) -block-poly (propylene glycol) is 0.2g, the mass of acrylamide is 0.5g, the mass of N, N ' -methylenebisacrylamide is 0.015g, the mass of N, N, N ', N ', -tetramethylethylenediamine is 0.008g, the mass of ammonium persulfate is 0.016g and the mass of deionized water is 9.261 g.
(3) And respectively carrying out in-situ polymerization and sealing on the hydrogel prepolymerization solution between two pieces of glass, and reacting for 20 minutes to obtain the glass intelligent window starting opaque transformation at 32 ℃.
Example 3
In this example, a synthetic glass smart window is prepared by using poly (propylene glycol) -block-poly (ethylene glycol) -block-poly (propylene glycol), acrylamide, N '-methylenebisacrylamide, N', -tetramethylethylenediamine, ammonium persulfate, and deionized water as raw materials, and starts opaque transition at 40 ℃, and the specific implementation process is as follows:
(1) cleaning two pieces of glass with water, removing stains, and drying;
(2) preparation of hydrogel prepolymerization 10 g. Wherein the mass of the poly (propylene glycol) -block-poly (ethylene glycol) -block-poly (propylene glycol) is 0.05g, the mass of the acrylamide is 1g, the mass of the N, N ' -methylene bisacrylamide is 0.015g, the mass of the N, N, N ', N ' -tetramethyl ethylenediamine is 0.008g, the mass of the ammonium persulfate is 0.016g, and the mass of the deionized water is 8.911 g.
(3) And polymerizing the hydrogel pre-polymerization liquid in situ between two pieces of glass, sealing, and reacting for 20 minutes to obtain the glass intelligent window starting to be subjected to opaque transformation at 40 ℃.
Example 4
In the embodiment, the synthesized glass intelligent window is prepared by taking lauroyl diethanolamine, acrylic acid, polyethylene glycol diacrylate, sodium bisulfite, potassium persulfate and deionized water as raw materials, wherein the synthesized glass intelligent window starts opaque transformation at 35 ℃, and the specific implementation process is as follows:
(1) cleaning two pieces of glass with water, removing stains, and drying;
(2) preparation of hydrogel prepolymerization 10 g. Wherein the mass of the lauroyl diethanolamine is 0.1g, the mass of the acrylic acid is 1g, the mass of the polyethylene glycol diacrylate is 0.015g, the mass of the sodium bisulfite is 0.008g, the mass of the potassium persulfate is 0.016g and the mass of the deionized water is 8.861 g.
(3) And polymerizing the hydrogel pre-polymerization liquid in situ between two pieces of glass, sealing, and reacting for 20 minutes to obtain the glass intelligent window starting opaque transformation at 35 ℃.
Example 5
In the embodiment, the synthetic glass intelligent window is prepared by taking polyethylene glycol ether, vinyl acetate, polyethylene glycol diacrylate, sodium bisulfite and potassium persulfate deionized water as raw materials, and the opaque transformation starts at 45 ℃, and the specific implementation process is as follows:
(1) cleaning two pieces of glass with water, removing stains, and drying;
(2) preparation of hydrogel prepolymerization 10 g. Wherein the mass of the polyethylene glycol ether is 0.05g, the mass of the vinyl acetate is 0.5g, the mass of the polyethylene glycol diacrylate is 0.015g, the mass of the sodium bisulfite is 0.008g, the mass of the potassium persulfate is 0.016g and the mass of the deionized water is 9.411 g.
(3) And polymerizing the hydrogel pre-polymerization solution between two pieces of glass in situ and sealing, and reacting for 20 minutes to obtain the glass intelligent window starting to be subjected to opaque transformation at the temperature of 45 ℃.
As shown in fig. 1, the temperature responsive glass smart windows prepared in examples 1 and 2 were characterized and analyzed. The glass smart window prepared in example 1 (10% by weight acrylamide) begins to decrease in light transmittance at 27 ℃ and undergoes a transparent-opaque transition. The glass smart window prepared in example 2 (5% by mass of acrylamide) starts to decrease in light transmittance at 32 ℃ and undergoes a transparent-opaque transition.
As shown in fig. 2, the glass smart window prepared in example 1 becomes transparent at 25 ℃, becomes opaque at 35 ℃, and becomes transparent again after being cooled (fig. 2).
The present invention has been described in further detail with reference to the specific embodiments thereof, and it should be understood that the foregoing is only illustrative of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, but rather that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.

Claims (9)

1. A preparation method of a glass intelligent window is characterized by comprising the following steps:
providing two pieces of glass;
sequentially cleaning and drying the glass;
adding hydrogel prepolymer liquid between two pieces of dried glass for sealing, and carrying out in-situ polymerization reaction on the hydrogel prepolymer liquid between the two pieces of glass to obtain the glass intelligent window; the hydrogel pre-polymerization liquid is prepared by the following preparation steps: adding the nonionic surface active agent, the alkene monomer, the cross-linking agent and the catalyst into deionized water for dissolving, and then adding the initiator for mixing to obtain the hydrogel pre-polymerization liquid.
2. The preparation method according to claim 1, wherein the polymerization time of the hydrogel pre-polymerization solution between two pieces of glass is 15min to 30min, and the polymerization temperature is 20 ℃ to 70 ℃.
3. The production method according to claim 1, wherein the mass fraction of the nonionic surfactant is 0.5 to 5% based on the total mass 1 of the hydrogel prepolymer solution.
4. The production method according to claim 1, wherein the vinyl monomer is 5 to 15% by mass, the crosslinking agent is 0.05 to 0.2% by mass, the catalyst is 0.05 to 0.1% by mass, and the initiator is 0.05 to 0.2% by mass, based on the total mass 1 of the hydrogel prepolymer solution.
5. The production method according to claim 1, wherein the cleaning treatment includes: and cleaning the glass by using water or absolute ethyl alcohol to remove stains on the surface of the glass.
6. The method of claim 1, wherein the nonionic surfactant comprises at least one of poly (propylene glycol) -block-poly (ethylene glycol) -block-poly (propylene glycol), lauryl diethanol amide, and polyethylene glycol ether.
7. The method of claim 1, wherein the vinyl monomer comprises at least one of acrylamide, acrylic acid, and vinyl acetate.
8. The production method according to claim 1,
the cross-linking agent comprises N, N' -methylene bisacrylamide and/or polyethylene glycol diacrylate;
the catalyst comprises N, N, N ', N', -tetramethylethylenediamine and/or sodium bisulfite;
the initiator comprises ammonium persulfate and/or potassium persulfate.
9. A glass smart window, characterized in that it is obtained by the manufacturing process according to any one of claims 1 to 8.
CN202110323618.1A 2021-03-26 2021-03-26 Glass intelligent window and preparation method thereof Pending CN113024723A (en)

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