CN112194941B - Antibacterial and ultraviolet-resistant color temperature-adjusting coating containing iron oxide-coated paraffin phase-change microcapsules and preparation method thereof - Google Patents

Antibacterial and ultraviolet-resistant color temperature-adjusting coating containing iron oxide-coated paraffin phase-change microcapsules and preparation method thereof Download PDF

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CN112194941B
CN112194941B CN202010970471.0A CN202010970471A CN112194941B CN 112194941 B CN112194941 B CN 112194941B CN 202010970471 A CN202010970471 A CN 202010970471A CN 112194941 B CN112194941 B CN 112194941B
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paraffin
iron oxide
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CN112194941A (en
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黄金谦
韦正煌
黄锡
马勇军
连城
徐国才
徐斌
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Xiao Holdings Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Abstract

The invention relates to the field of paint, and discloses an antibacterial ultraviolet-resistant color temperature-adjusting paint containing iron oxide-coated paraffin phase-change microcapsules and a preparation method thereof, wherein the paint comprises 45-50% of silicone-acrylic emulsion (with the concentration of 35-40 wt%), 25-35% of iron oxide-coated paraffin phase-change microcapsules, 1-2% of ethylene glycol, 1-3% of decaglycol ester, 0.1-1% of a thickening agent, and the balance of water. The coating contains the iron oxide-coated paraffin phase change microcapsule, the microcapsule takes the iron oxide as a wall material to directly coat the paraffin, on one hand, the phase change material can be effectively coated to prevent leakage, the heat conductivity of the phase change material is improved, and the obtained microcapsule has excellent antibacterial property, ultraviolet resistance and stability, so that the coating also has the performances; on the other hand, the iron oxide can be used as a pigment and can endow the paint with rich colors after being combined with the traditional paint.

Description

Antibacterial and ultraviolet-resistant color temperature-adjusting coating containing iron oxide-coated paraffin phase-change microcapsules and preparation method thereof
Technical Field
The invention relates to the field of coatings, in particular to an antibacterial and anti-ultraviolet color temperature-adjusting coating containing iron oxide-coated paraffin phase-change microcapsules and a preparation method thereof.
Background
Along with the improvement of living standard of people, the requirement on the comfort level of the indoor environment is higher and higher, the corresponding building energy consumption is increased, the energy consumption is overlarge, and the environmental pollution is aggravated. Finding reasonable balance points in comfort, energy and environment becomes a permanent theme in the fields of building design and building energy conservation. In recent years, many building energy saving technologies have been developed, and the application of phase change energy storage materials to building materials has become a hot spot of research and attention. The combination of phase change energy storage materials with the rational utilization of solar energy provides an effective way to increase building comfort and reduce energy consumption and environmental negative effects. Unlike the conventional thermal energy storage material, as a latent heat storage material, a phase change material can maintain its temperature within a certain range by absorbing or releasing latent heat, so the phase change material is considered as a renewable energy material having high energy utilization efficiency.
Paraffin as a traditional phase change material has large phase change latent heat and low price, and is widely applied to serve as a phase change microcapsule core. The microcapsule wall material generally comprises high polymers such as polystyrene, polyurea-formaldehyde resin, polymethyl methacrylate and polyurethane. Researches find that the novel temperature-regulating coating prepared by adding the paraffin microcapsules into the traditional coating can obviously regulate the indoor environment temperature. For example, Chinese patent [ CN201910247457.5]The patent discloses a heat-storage temperature-regulating interior wall water-based paint and a preparation method thereof, wherein paraffin/cenosphere-organic silicon resin phase change microcapsules are added into the traditional paint, so that the paint has the advantages of large phase change latent heat, high energy storage capacity, strong temperature regulating capacity and the like. However, the paraffin microcapsules using a high polymer as a wall material have disadvantages such as low mechanical strength, poor thermal and chemical stability, and low thermal conductivity. More importantly, the phase change microcapsule coating taking the high polymer with low thermal conductivity as the wall material has very slow thermal response speed to the ambient temperature. This results in the disadvantage of poor weather resistance, poor heat resistance and slow temperature control speed of the temperature control coating containing microcapsules. Iron oxide as a conventional inorganic pigment has excellent thermal stability and resistanceUltraviolet performance. For example: rufus et al [ Rufus A, Sreeju N, Vilas V, et al biosynthesis of hectite (. alpha. -Fe)2O3)nanostructures：Size effects on applications in thermal conductivity， catalysis，and antibacterial activity[J].Journal of Molecular Liquids，2017，242.]A simple, efficient and environment-friendly iron oxide nanoparticle synthesis scheme is developed, and performance researches such as heat conduction, antibiosis and catalysis are carried out on the iron oxide nanoparticle, and the results show that the iron oxide can improve the heat conduction coefficient of the traditional base solution, can degrade pollutants such as methyl red and yellow in a short time, and can obviously inhibit the growth of escherichia coli and staphylococcus aureus.
Chinese patent No. CN201110367192.6 discloses a preparation method of a color temperature-regulating paint, which is characterized in that besides a basic formula of the paint, phase-change paraffin microcapsules and nano iron oxide are added, so that the paint has an automatic temperature-regulating function. However, the method for preparing the color temperature-adjusting coating by simply doping the nano iron oxide and the paraffin microcapsules in the traditional coating has the defects that the nano iron oxide serving as the nano particles has very high surface energy, is easy to agglomerate, has poor dispersibility in the coating, causes phase separation among the nano iron oxide, the paraffin phase-change microcapsules and the coating, and cannot better play a role of improving the thermal conductivity of the coating, so that the actual temperature-adjusting effect of the coating is not obvious.
Disclosure of Invention
In order to solve the technical problems, the invention provides an antibacterial ultraviolet-resistant color temperature-regulating coating containing iron oxide-coated paraffin phase-change microcapsules and a preparation method thereof, wherein the coating contains the iron oxide-coated paraffin phase-change microcapsules, and the microcapsules directly coat paraffin by taking iron oxide as a wall material, so that on one hand, the phase-change material can be effectively coated to prevent leakage, the heat conductivity of the phase-change material is improved, and the obtained microcapsules have excellent antibacterial property, ultraviolet resistance and stability, so that the coating also has the performances; on the other hand, the iron oxide can be used as a pigment and can endow the paint with rich colors after being combined with the traditional paint.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides an antibacterial and ultraviolet-resistant color temperature-regulating paint containing an iron oxide-coated paraffin phase-change microcapsule, which comprises the following raw materials in percentage by mass:
45-50% of silicone-acrylic emulsion with the concentration of 35-40wt%,
25 to 35 percent of iron oxide coated paraffin phase change microcapsule,
1 to 2 percent of ethylene glycol,
1 to 3 percent of decaglycol ester,
0.1 to 1 percent of thickening agent,
the balance of water.
The coating contains the iron oxide-coated paraffin phase change microcapsule, the microcapsule takes the iron oxide as a wall material to directly coat the paraffin, on one hand, the phase change material can be effectively coated to prevent leakage, the heat conductivity of the phase change material is improved, and the obtained microcapsule has excellent antibacterial property, ultraviolet resistance and stability, so that the coating also has the performances; on the other hand, the iron oxide can be used as a pigment and can endow the paint with rich colors after being combined with the traditional paint.
Preferably, the coating comprises the following raw materials in percentage by mass:
45-50% of silicone-acrylic emulsion with the concentration of 35-40wt%,
25 to 35 percent of iron oxide coated paraffin phase change microcapsule,
2 percent of ethylene glycol,
2.5 percent of decaglycol ester,
0.5 percent of thickening agent,
the balance of water.
Preferably, the thickener is a hydrophobically modified ethylene oxide polyurethane.
In a second aspect, the invention provides a preparation method of an antibacterial and ultraviolet-resistant color temperature-adjusting coating containing iron oxide-coated paraffin phase-change microcapsules, which comprises the following steps:
(1) placing paraffin, n-butanol, sodium oleate and water in a container, heating and stirring to form microemulsion; dropwise adding ferric chloride solution into the microemulsion, and continuously heating and stirring to obtain a reactant; the mass ratio of the paraffin, the n-butyl alcohol, the sodium oleate, the water and the ferric chloride is 0.3-0.8: 0.1-0.4: 0.5-1: 5-10: 0.1-0.3.
(2) And placing the reactants in a reaction container, heating at 180-200 ℃ for 20-35 hours, after natural cooling, centrifugally separating the solution obtained by the reaction to obtain a precipitate, washing with water and anhydrous n-butyl alcohol in sequence, and drying to obtain the iron oxide-coated paraffin phase-change microcapsule.
(3) Adding the iron oxide coated paraffin phase change microcapsule into a pre-mixed mixture of silicone-acrylic emulsion, ethylene glycol, lauryl ester, a thickening agent and water, and uniformly mixing to obtain the coating.
In the preparation process, paraffin is mixed with sodium oleate, n-butyl alcohol and deionized water, heating and stirring are carried out to form oil-in-water type microemulsion of which the oil phase is paraffin, then ferric chloride solution is dropwise added into the microemulsion, sodium oleate adsorbed on the interface of the microemulsion reacts with ferric chloride to generate precipitate ferric oleate, and thereby the microcapsule taking the ferric oleate as the wall material and the paraffin as the core material is obtained. Finally, the wall material iron oleate is further reacted to generate iron oxide by a hydrothermal method, so that the iron oxide which is used as the wall material and paraffin wax which is used as the core material is obtained, namely, the iron oxide-coated paraffin wax microcapsule (paraffin @ Fe)2O3). The chemical reaction principle is as follows:
FeCl3+Na(oleate)→Fe(oleate)3
Fe(oleate)3+H2O→Fe(OH)3
Fe(OH)3→FeOOH→Fe2O3
in conclusion, the invention innovatively uses the iron oxide as the wall material to coat the paraffin to form the microcapsule, which can effectively prevent the paraffin from leaking and can improve the heat conductivity of the microcapsule, in addition, the obtained microcapsule has excellent antibacterial property, ultraviolet resistance and stability, can effectively improve the antibacterial property, thermal stability and weather resistance of the coating, and the iron oxide can be used as a pigment to be mixed with the traditional coating to endow the coating with rich colors.
Preferably, in the step (1), the melting point of the paraffin is 25-35 ℃; the paraffin is single melting point paraffin or mixed paraffin compounded by multiple kinds of single melting point paraffin.
Preferably, in the step (1), the temperature of the two-time heating and stirring is 70-85 ℃, the stirring speed is 4000-.
Preferably, in the step (1), the dropping rate of the ferric chloride solution is 1.5 to 2.5 drops/second.
Preferably, in the step (1), the mass ratio of the paraffin, the n-butanol, the sodium oleate, the water and the ferric chloride is 0.5-0.8: 0.3-0.4: 0.6-0.8: 8-10: 0.2-0.3.
The material is controlled within the range, so that stable oil-in-water microemulsion can be obtained, and the subsequent coating process is facilitated. Under the proportion of the sodium oleate and the ferric chloride, the reactant of the sodium oleate and the ferric chloride can effectively coat the paraffin, and the coating effect is ideal.
Preferably, in the step (2), the reaction temperature is 180 ℃ and the reaction time is 30 hours.
Preferably, in the step (2), the drying temperature is 35 to 45 ℃ and the drying time is 10 to 15 hours.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, iron oxide is innovatively used for replacing a high polymer as a wall material, and paraffin is directly coated to form the microcapsule, so that the microcapsule has higher thermal conductivity, and the response speed of the temperature-regulating coating to the environmental temperature is improved.
(2) The iron oxide coated paraffin microcapsule has excellent antibacterial property, ultraviolet resistance and stability, and can effectively improve the antibacterial property, thermal stability and weather resistance of the temperature-regulating coating.
(3) The iron oxide can be used as a pigment and mixed with the traditional coating, and can endow the temperature-adjusting coating with rich colors.
Drawings
The following are all the profiles or experimental data tested in example 1:
FIG. 1 is an XRD pattern of iron oxide coated paraffin microcapsules;
FIG. 2 is an SEM image and a TEM image of an iron oxide-coated paraffin microcapsule;
FIG. 3 is a bar graph of the thermal conductivity of paraffin, iron oxide coated paraffin microcapsules;
FIG. 4 is a DSC chart of the iron oxide coated paraffin microcapsules;
FIG. 5 is an ultraviolet absorption spectrum of paraffin and iron oxide coated paraffin microcapsules;
FIG. 6 is a time temperature profile of the same mass of paraffin and iron oxide coated paraffin microcapsules;
FIG. 7 is an infrared thermal imaging diagram of the iron oxide coated paraffin microcapsule antibacterial ultraviolet resistant color temperature regulating coating under simulated illumination conditions.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
An antibacterial and ultraviolet-resistant color temperature-adjusting coating containing iron oxide-coated paraffin phase-change microcapsules comprises the following raw materials in percentage by mass:
45-50% of silicone-acrylic emulsion with the concentration of 35-40wt%,
25 to 35 percent of iron oxide coated paraffin phase change microcapsule,
1-2% (preferably 2%) of ethylene glycol,
1-3% (preferably 2.5%) of a decaglycol ester,
0.1 to 1% of a thickener (preferably 0.5%, preferably hydrophobically modified ethylene oxide polyurethane),
the balance of water.
A preparation method of an antibacterial and ultraviolet-resistant color temperature-regulating coating containing iron oxide-coated paraffin phase-change microcapsules comprises the following steps:
(1) placing paraffin, n-butanol, sodium oleate and water in a container, and stirring at 70-85 deg.C (4000-; dropwise adding the ferric chloride solution into the microemulsion at 1.5-2.5 drops/second, and continuously stirring at 70-85 ℃ (4000-; the mass ratio of the paraffin, the normal butanol, the sodium oleate, the water and the ferric chloride is 0.3-0.8: 0.1-0.4: 0.5-1: 5-10: 0.1-0.3 (preferably 0.5-0.8: 0.3-0.4: 0.6-0.8: 8-10: 0.2-0.3). The melting point range of the paraffin is 25-35 ℃; the paraffin is single melting point paraffin or mixed paraffin compounded by multiple kinds of single melting point paraffin.
(2) And (3) placing the reactants in a reaction container, heating for 20-35 hours (preferably 30 hours) at 180-200 ℃ (preferably 180 ℃), after natural cooling, centrifugally separating the solution obtained by the reaction to obtain a precipitate, washing with water and anhydrous n-butyl alcohol in sequence, and drying for 10-15 hours at 35-45 ℃ to obtain the iron oxide-coated paraffin phase-change microcapsule.
(3) Adding the iron oxide coated paraffin phase change microcapsule into a pre-mixed mixture of silicone-acrylic emulsion, ethylene glycol, lauryl ester, a thickening agent and water, and uniformly mixing to obtain the coating.
Example 1
(1) 5g of paraffin, 3g of n-butanol, 6g of sodium oleate and 60ml of deionized water were placed in a beaker and stirred at high speed for 40 minutes at 75 ℃ at 6000 rpm to form a microemulsion. 2g of ferric chloride was dissolved in 20ml of deionized water to prepare a 0.62mol/L ferric chloride solution, which was then added dropwise to the microemulsion at 1.5 drops/sec and stirred at 6000 rpm at 75 ℃ for 60 minutes to obtain a reaction product.
(2) The above reactants were placed in a stainless steel reactor lined with polytetrafluoroethylene and heated at 180 ℃ for 30 hours. And after the reaction kettle is naturally cooled, carrying out centrifugal separation on the solution after reaction to obtain a precipitate, sequentially washing the precipitate with deionized water and anhydrous n-butyl alcohol for three times, and drying the precipitate in an oven at 40 ℃ for 12 hours to obtain the iron oxide-coated paraffin phase-change microcapsule.
(3) Adding the iron oxide coated paraffin phase change microcapsule into a mixed system of pre-mixed silicone-acrylate emulsion, ethylene glycol, glycol tridecyl ester, a thickening agent and deionized water, and uniformly mixing to obtain the antibacterial ultraviolet-resistant color temperature-regulating coating. Wherein, the silicone-acrylic emulsion (with the concentration of 40 wt%) is 45 percent, the ferric oxide coated paraffin phase-change microcapsule is 25 percent, the glycol is 2 percent, the dodecanol ester is 2.5 percent, the thickening agent is 0.5 percent, and the deionized water is 25 percent
Example 2
(1) 8g of paraffin, 4g of n-butanol, 8g of sodium oleate and 80ml of deionized water were placed in a beaker and stirred at 75 ℃ for 60 minutes at 8000 rpm, forming a microemulsion. 3g of ferric chloride was dissolved in 20ml of deionized water to prepare a 0.93mol/L ferric chloride solution, and then the ferric chloride solution was added dropwise to the microemulsion at 2.5 drops/sec, and stirring was continued at 75 ℃ at 8000 rpm for 60 minutes to obtain a reaction product.
(2) The above reactants were placed in a stainless steel reactor lined with polytetrafluoroethylene and heated at 180 ℃ for 30 hours. And after the reaction kettle is naturally cooled, carrying out centrifugal separation on the solution after reaction to obtain a precipitate, sequentially washing the precipitate with deionized water and anhydrous n-butyl alcohol for three times, and drying the precipitate in an oven at 40 ℃ for 12 hours to obtain the iron oxide-coated paraffin phase-change microcapsule.
(3) Adding the iron oxide coated paraffin phase change microcapsule into a mixed system of pre-mixed silicone-acrylate emulsion, ethylene glycol, glycol tridecyl ester, a thickening agent and deionized water, and uniformly mixing to obtain the antibacterial ultraviolet-resistant color temperature-regulating coating. Wherein, the silicone-acrylic emulsion (with the concentration of 40 wt%) is 50%, the ferric oxide coated paraffin phase-change microcapsule is 35%, the ethylene glycol is 2%, the dodecanol ester is 2.5%, the hydrophobic modified ethylene oxide polyurethane is 0.5%, and the deionized water is 10%.
Example 3
(1) 6g of paraffin, 3g of n-butanol, 6.5g of sodium oleate and 80ml of deionized water were placed in a beaker and stirred at high speed for 60 minutes at 75 ℃ at 6000 rpm to form a microemulsion. 2g of ferric chloride was dissolved in 20ml of deionized water to prepare a 0.62mol/L ferric chloride solution, and then the ferric chloride solution was added dropwise to the microemulsion at 2 drops/sec, and stirring was continued at 6000 rpm at 75 ℃ for 60 minutes to obtain a reaction product.
(2) The above reactants were placed in a stainless steel reactor lined with polytetrafluoroethylene and heated at 180 ℃ for 30 hours. And after the reaction kettle is naturally cooled, carrying out centrifugal separation on the solution after reaction to obtain a precipitate, sequentially washing the precipitate with deionized water and anhydrous n-butyl alcohol for three times, and drying the precipitate in an oven at 40 ℃ for 12 hours to obtain the iron oxide-coated paraffin phase-change microcapsule.
(3) Adding the iron oxide coated paraffin phase change microcapsule into a mixed system of pre-mixed silicone-acrylate emulsion, ethylene glycol, glycol tridecyl ester, a thickening agent and deionized water, and uniformly mixing to obtain the antibacterial ultraviolet-resistant color temperature-regulating coating. Wherein, the silicone-acrylic emulsion (with the concentration of 40 wt%) is 50%, the ferric oxide coated paraffin phase-change microcapsule is 35%, the ethylene glycol is 2%, the dodecanol ester is 2.5%, the hydrophobic modified ethylene oxide polyurethane is 0.5%, and the deionized water is 10%.
Example 4
(1) 5.5g of paraffin, 2.5g of n-butanol, 7.5g of sodium oleate and 55ml of deionized water were placed in a beaker and stirred at 4000 rpm for 70 minutes at 70 ℃ to form a microemulsion. 2g of ferric chloride was dissolved in 20ml of deionized water to prepare a 0.62mol/L ferric chloride solution, and then the ferric chloride solution was added dropwise to the microemulsion at 2 drops/sec, and stirring was continued at 4000 rpm at 70 ℃ for 70 minutes to obtain a reaction product.
(2) The above reactants were placed in a stainless steel reactor lined with polytetrafluoroethylene and heated at 200 ℃ for 20 hours. And after the reaction kettle is naturally cooled, carrying out centrifugal separation on the solution after reaction to obtain a precipitate, sequentially washing the precipitate with deionized water and anhydrous n-butyl alcohol for three times, and drying the precipitate in an oven at 35 ℃ for 15 hours to obtain the iron oxide-coated paraffin phase-change microcapsule.
(3) Adding the iron oxide coated paraffin phase change microcapsule into a mixed system of pre-mixed silicone-acrylate emulsion, ethylene glycol, glycol tridecyl ester, a thickening agent and deionized water, and uniformly mixing to obtain the antibacterial ultraviolet-resistant color temperature-regulating coating. Wherein, the silicone-acrylic emulsion (with the concentration of 40 wt%) is 48%, the ferric oxide coated paraffin phase-change microcapsule is 30%, the glycol is 1.5%, the dodecanol ester is 2%, the thickening agent is 0.5%, and the deionized water is 18%.
Example 5
(1) 6.5g of paraffin, 3.5g of n-butanol, 7g of sodium oleate and 60ml of deionized water were placed in a beaker and stirred at 85 ℃ for 40 minutes at 8000 rpm at a high speed to form a microemulsion. 2g of ferric chloride was dissolved in 20ml of deionized water to prepare a 0.62mol/L ferric chloride solution, and then the ferric chloride solution was added dropwise to the microemulsion at 2.5 drops/sec, and stirring was continued at 85 ℃ at 8000 rpm for 40 minutes to obtain a reaction product.
(2) The above reactants were placed in a stainless steel reactor lined with polytetrafluoroethylene and heated at 190 ℃ for 30 hours. And after the reaction kettle is naturally cooled, carrying out centrifugal separation on the solution after reaction to obtain a precipitate, sequentially washing the precipitate with deionized water and anhydrous n-butyl alcohol for three times, and drying the precipitate in an oven at 45 ℃ for 10 hours to obtain the iron oxide-coated paraffin phase-change microcapsule.
(3) Adding the iron oxide coated paraffin phase change microcapsule into a mixed system of pre-mixed silicone-acrylate emulsion, ethylene glycol, glycol tridecyl ester, a thickening agent and deionized water, and uniformly mixing to obtain the antibacterial ultraviolet-resistant color temperature-regulating coating. Wherein, the silicone-acrylic emulsion (with the concentration of 40 wt%) is 45%, the ferric oxide coated paraffin phase-change microcapsule is 30%, the ethylene glycol is 2%, the dodecanol ester is 3%, the thickening agent is 1%, and the deionized water is 19%.
Example 6
(1) 6.5g of paraffin, 3.5g of n-butanol, 7g of sodium oleate and 60ml of deionized water were placed in a beaker and stirred at 80 ℃ for 60 minutes at 5000 rpm, forming a microemulsion. 2g of ferric chloride was dissolved in 20ml of deionized water to prepare a 0.62mol/L ferric chloride solution, and then the ferric chloride solution was added dropwise to the microemulsion at 2 drops/sec, and stirring was continued at 80 ℃ at 5000 rpm for 60 minutes to obtain a reaction product.
(2) The above reactants were placed in a stainless steel reactor lined with polytetrafluoroethylene and heated at 200 ℃ for 20 hours. And after the reaction kettle is naturally cooled, carrying out centrifugal separation on the solution after reaction to obtain a precipitate, sequentially washing the precipitate with deionized water and anhydrous n-butyl alcohol for three times, and drying the precipitate in an oven at 40 ℃ for 12 hours to obtain the iron oxide-coated paraffin phase-change microcapsule.
(3) Adding the iron oxide coated paraffin phase change microcapsule into a mixed system of pre-mixed silicone-acrylate emulsion, ethylene glycol, glycol tridecyl ester, a thickening agent and deionized water, and uniformly mixing to obtain the antibacterial ultraviolet-resistant color temperature-regulating coating. Wherein, the silicone-acrylic emulsion (with the concentration of 35 wt%) is 50%, the ferric oxide coated paraffin phase-change microcapsule is 25%, the ethylene glycol is 2%, the dodecanol ester is 1%, the thickening agent is 0.1%, and the deionized water is 21.9%.
Performance detection
FIGS. 1-7 are all graphs or experimental data tested in example 1, wherein:
fig. 1 is an XRD pattern of the paraffin microcapsule coated with iron oxide, and it can be seen from the graph that diffraction angles at 2 θ of 12.24 °, 16.56 °, 20.51 °, 21.49 °, 24.15 °, 20.51 °, and 29.51 ° correspond to (008), (0010), (0012), (110), (0014), and (0114) crystal planes of paraffin, respectively (JCPDF 36-1591). Diffraction angles at 2 θ of 33.15 °, 35.78 °, 40.83 °, 49.53 ° and 54.19 ° correspond to (104), (110), (113), (024) and (116) planes of iron oxide, respectively (JCPDF 99-0060). The synthetic microcapsules are illustrated to consist of paraffin and iron oxide.
Fig. 2 is SEM and TEM images of iron oxide coated paraffin microcapsules. As seen from the SEM image, the particle size of the microcapsule is about 800nm, and the surface of the capsule is rough. As can be seen from the TEM image, a typical core-shell structure is presented, with a wall thickness of about 150 nm.
Figure 3 is a bar graph of the thermal conductivity of paraffin and iron oxide coated paraffin microcapsules. As can be seen from the figure, the thermal conductivities of the paraffin and the iron oxide-coated paraffin microcapsules are respectively 0.290 W.m-1K-1And 0.357 W.m-1K-1Compared with paraffin, the thermal conductivity of the iron oxide coated paraffin microcapsule is improved by 23.10%.
Figure 4 is a DSC profile of paraffin and iron oxide coated paraffin microcapsules. As shown in the figure, the curve at the lower half part of the graph is a temperature rise process, and the composite material absorbs heat to generate melting enthalpy; the upper half curve is a cooling process, and the composite material releases heat to generate crystallization enthalpy. Because the phase change enthalpy exists, a phase change peak appears, and the phase change peak position comprises two peaks, wherein one peak is a solid-solid phase change peak, and the solid-liquid phase change peak is the largest and is a main phase change enthalpy source. The DSC spectra were analyzed by computer software for the physical parameters of the thermal properties of the samples available, see table 1.
TABLE 1-thermal Properties and physical parameters of Paraffin and iron oxide coated Paraffin microcapsules
Sample Tm(℃) Tf℃) ΔHm(J/g) ΔHf(J/g) E(％)
paraffin 34.26 26.07 202.97 201.32 -
paraffin@Fe2O3 31.97 25.62 77.89 76.52 38.55％
Through analysis, the melting points of the paraffin wax and the iron oxide coated paraffin wax microcapsule are respectively 34.26 ℃ and 31.97 ℃, and the crystallization points are respectively 26.07 ℃ and 25.62 ℃, so that the existence of the shell layer of the microcapsule reduces the melting point and the crystallization point of the paraffin wax, and the phase change material is subjected to phase change at a lower temperature, because the shell layer material has a higher thermal conductivity coefficient, the heat transfer speed between the interiors of the paraffin wax is improved, meanwhile, the heat transfer process between the phase change materials is further accelerated by the small particle size of the microcapsule, the heat transfer efficiency is improved, and the phase change material has a lower melting point and a lower crystallization point. By calculation, the melting enthalpy of the iron oxide-coated paraffin microcapsule is 77.89J/g, and the crystallization enthalpy is 76.52J/g. The melting enthalpy and crystallization enthalpy of paraffin were 202.97J/g and 201.32J/g, respectively. The encapsulation rate of the paraffin in the iron oxide-coated paraffin microcapsule can be calculated to be 38.55 percent through the melting enthalpy and the crystallization enthalpy.
Fig. 5 is an ultraviolet absorption spectrum of paraffin and iron oxide-coated paraffin microcapsules. As can be seen from the figure, the microcapsule has a significant absorption effect on ultraviolet light compared to paraffin, because the iron oxide wall material significantly improves the absorption of ultraviolet light by the microcapsule material.
Fig. 6 is a time-temperature curve of paraffin and iron oxide coated paraffin microcapsules. As can be seen from the figure, the melting process of the paraffin and iron oxide coated paraffin microcapsules is divided into three stages, namely a solid-phase sensible heat storage stage (AB stage) and a phase-change latent heat storage stage (BC stage)1，BC2Stage) and liquid phase sensible heat storage stage (C)1D1，C2D2Segment). The phase-change latent heat storage stage (BC1, BC 2) is caused by slow temperature change due to phase-change heat absorption caused by heating and melting of phase-change material paraffin.
Table 2 shows the bacteriostatic rate of the microcapsules, which were diluted to an appropriate concentration by a tenfold gradient dilution method using escherichia coli as an experimental strain, the microcapsules were dispersed in a culture solution, uniformly coated on a culture medium by a plate coating method, placed in a 37 ℃ illumination incubator, cultured for 24 hours by visible light, and the antibacterial ability of the microcapsules was calculated by a plate counting method. As can be seen from the data in Table 2, the prepared iron oxide-coated paraffin microcapsule has a bacteriostasis rate of 87.3%, which indicates that the iron oxide-coated paraffin microcapsule has remarkable antibacterial performance.
TABLE 2 bacteriostatic ratio of iron oxide coated paraffin microcapsules
Bacteriostatic agent Antibacterial rate of Escherichia coli
paraffin@Fe2O3 87.3％
FIG. 7 is an infrared thermal imaging image of the iron oxide-coated paraffin microcapsule-containing antibacterial ultraviolet-resistant color temperature-regulating coating under simulated illumination conditions. In the figure, part A is a temperature-adjusting coating containing iron oxide coated paraffin phase-change microcapsules, part B is iron oxide particles and a general coating mixed with the coating, a substrate is high-transparency silica glass, an irradiation light source is a xenon lamp, and the ambient temperature is 28 ℃. An infrared thermal imaging graph after 1min after illumination shows that the temperature of the part B is obviously higher than that of the part A, which indicates that the coating of the part A has the functions of heat absorption and temperature regulation.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (9)

1. An antibacterial and ultraviolet-resistant color temperature-adjusting coating containing an iron oxide-coated paraffin phase-change microcapsule is characterized by comprising the following raw materials in percentage by mass:
45-50% of silicone-acrylic emulsion with the concentration of 35-40wt%,
25 to 35 percent of ferric oxide coated paraffin phase change microcapsule,
1 to 2 percent of ethylene glycol,
1 to 3 percent of decaglycol ester,
0.1 to 1 percent of thickening agent,
the balance of water;
the preparation method of the coating comprises the following steps:
(1) placing paraffin, n-butanol, sodium oleate and water in a container, heating and stirring to form microemulsion; dropwise adding ferric chloride solution into the microemulsion, and continuously heating and stirring to obtain a reactant; the mass ratio of the paraffin, the n-butyl alcohol, the sodium oleate, the water and the ferric chloride is 0.3-0.8: 0.1-0.4: 0.5-1: 5-10: 0.1-0.3;
(2) placing the reactants in a reaction container, heating at 180-200 ℃ for 20-35 hours, after natural cooling, centrifugally separating the solution obtained by the reaction to obtain a precipitate, washing with water and anhydrous n-butyl alcohol in sequence, and drying to obtain the iron oxide-coated paraffin phase-change microcapsule;
(3) adding the iron oxide coated paraffin phase change microcapsule into a pre-mixed mixture of silicone-acrylic emulsion, ethylene glycol, lauryl ester, a thickening agent and water, and uniformly mixing to obtain the coating.
2. The coating of claim 1, characterized by comprising the following raw materials in percentage by mass:
45-50% of silicone-acrylic emulsion with the concentration of 35-40wt%,
25 to 35 percent of ferric oxide coated paraffin phase change microcapsule,
2 percent of ethylene glycol,
2.5 percent of decaglycol ester,
0.5 percent of thickening agent,
the balance of water.
3. The coating of claim 1 or 2, wherein the thickener is a hydrophobically modified ethylene oxide polyurethane.
4. The coating of claim 1, wherein in step (1), the paraffin wax has a melting point in the range of 25 to 35 ℃.
5. The coating of claim 1, wherein in step (1), the temperature of the two-time heating and stirring is 70-85 ℃, the stirring speed is 4000-.
6. The paint according to claim 1, wherein the ferric chloride solution is dropped at a rate of 1.5 to 2.5 drops/sec in the step (1).
7. The dope of claim 1, wherein in the step (1), the mass ratio of the paraffin, n-butanol, sodium oleate, water and ferric chloride is 0.5 to 0.8: 0.3-0.4: 0.6-0.8: 8-10: 0.2-0.3.
8. The coating of claim 1, wherein in step (2), the reaction temperature is 180 ℃ and the reaction time is 30 hours.
9. The coating of claim 1 or 7, wherein in step (2), the drying temperature is 35 to 45 ℃ and the drying time is 10 to 15 hours.
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Denomination of invention: An antibacterial and UV resistant color temperature regulating coating containing iron oxide coated paraffin phase change microcapsules and its preparation method

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