CN117025016A - VO 2 Nano particle @ PDMA, preparation method and intelligent heat-insulating coating prepared from nano particle @ PDMA - Google Patents

VO 2 Nano particle @ PDMA, preparation method and intelligent heat-insulating coating prepared from nano particle @ PDMA Download PDF

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CN117025016A
CN117025016A CN202310972806.6A CN202310972806A CN117025016A CN 117025016 A CN117025016 A CN 117025016A CN 202310972806 A CN202310972806 A CN 202310972806A CN 117025016 A CN117025016 A CN 117025016A
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pdma
reaction
preparation
powder
mass ratio
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蒋绪川
冯佳佳
马佳晨
刘桐垚
赵修贤
李文婷
吴林森
杨立凯
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University of Jinan
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University of Jinan
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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
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention provides a VO 2 PDMA nano particles, a preparation method and an intelligent heat insulation coating prepared from the nano particles, and belong to the field of functional composite materials. The preparation method of the invention comprises the following steps: (1) preparation of vanadium dioxide powder; (2) Preparation of a mercapto-terminated PDMA-SH hydrophilic polymer; (3) VO (VO) 2 Preparation of PDMA nanoparticles. The preparation method provided by the invention is simple to operate, and the prepared VO 2 Nano particle @ PDMAThe light-emitting diode has excellent stability, dispersibility and near infrared light-adjusting performance, and has great advantages when being applied to the field of coatings.

Description

VO 2 Nano particle @ PDMA, preparation method and intelligent heat-insulating coating prepared from nano particle @ PDMA
Technical Field
The invention belongs to the field of functional composite materials, and in particular relates to a VO (volatile organic compound) 2 PDMA nanoparticle, preparation method and intelligent heat insulation coating prepared from the same.
Background
Vanadium dioxide (VO) 2 ) Is a thermochromic material capable of undergoing a phase change at 68 ℃, and when the temperature is increased from room temperature to 68 ℃, the insulating phase vanadium dioxide will be converted to a metallic phase, with the change in the transmission-reflection of infrared light. The characteristic that the infrared light reflectivity is different before and after phase change is utilized, the infrared light reflection coating can be used as a coating material for intelligently regulating and controlling the transmittance of near infrared light in building doors and windows, so that the indoor temperature is intelligently regulated and controlled, the use of indoor air conditioners and cold air in a high-temperature environment is reduced, and the energy consumption is reduced, and the energy conservation and the emission reduction are realized. But VO 2 Is easily oxidized into vanadium pentoxide (V) by water, oxygen and the like 2 O 5 ) Therefore, in practical application VO 2 Poor stability in aqueous resins and VO inside functional coatings 2 Poor compatibility with organic film-forming resin, resulting in structural defects at the interface between the organic film-forming resin and the VO in the coating due to oxygen, water vapor and the like at the interface 2 Is a metal oxide semiconductor device. VO enhancement commonly used at present 2 The method for stabilizing powder and its compatibility with organic resin is to utilize organic micromolecule or inorganic oxide and other material to VO 2 Coating the nano powder, and forming a compact protective layer on the surface of the powder by a shell layer material, thereby improving VO 2 Stability of the nanopowder.
In improving VO 2 At the same time of stabilizing nano powder, how to further improve the dispersibility in aqueous system and reduce the interface structure defect due to the compatibility with organic film-forming resinOne challenge to be addressed is to solve.
Disclosure of Invention
The invention aims to provide a VO 2 The @ PDMA nano particles, the preparation method and the intelligent heat insulation coating prepared from the nano particles are used for solving the problems of poor dispersibility, poor stability and the like in the prior art. .
To achieve the above object or other objects, the present invention is achieved by the following technical solutions.
Preparation VO 2 A method of @ PDMA nanoparticles comprising the steps of:
(1) Preparing vanadium dioxide powder; (2) Preparation of a mercapto-terminated PDMA-SH hydrophilic polymer; (3) VO (VO) 2 Preparation of PDMA nanoparticles.
Specifically, the method comprises the following steps:
(1) Preparation of vanadium dioxide powder:
will V 2 O 5 Adding the solution into deionized water, stirring to obtain a dispersion liquid, heating the dispersion liquid, dropwise adding hydrazine hydrate under stirring, continuously stirring for reaction after the dropwise adding is finished, transferring the solution into a reaction kettle for continuous reaction, and performing post-treatment after the reaction is finished to obtain vanadium dioxide powder;
(2) Preparation of thiol-terminated PDMA-SH hydrophilic Polymer: a) Adding N, N-dimethylacrylamide, S-1-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -propionic acid) and azodiisobutyronitrile into a 1, 4-dioxane solvent, stirring for reaction under the protection of nitrogen after complete dissolution, precipitating and washing the solution obtained after the reaction in normal hexane, carrying out suction filtration, and vacuum drying the obtained product at 40-90 ℃ for 8-24 h to obtain trithioester-terminated poly (N, N-dimethylacrylamide), which is named as PDMA-DOPAT;
b) Adding the PDMA-DOPAT, n-hexylamine and tributylphosphine obtained in the step a) into tetrahydrofuran, stirring for reaction under the protection of nitrogen, dripping the solution into n-hexane for precipitation and washing after the reaction is finished, filtering and collecting the precipitate, and vacuum drying at 40-90 ℃ for 8-24 hours to obtain a sulfhydryl-terminated PDMA-SH hydrophilic polymer;
(3)VO 2 nano @ PDMAPreparation of the particles: dispersing the vanadium dioxide powder prepared in the step (1) in absolute ethyl alcohol by ultrasonic, dripping ammonia water to adjust the pH value, adding gamma- (methacryloyloxy) propyl trimethoxy silane, then heating the system for reaction, centrifuging after the reaction is finished, washing by absolute ethyl alcohol, and vacuum drying at 40-70 ℃ for 12-24 hours to obtain VO 2 KH-570 nanometer powder;
VO is to be provided with 2 Super-dispersing KH-570 nano powder in tetrahydrofuran, adding the PDMA-SH hydrophilic polymer prepared in the step (2), stirring until the polymer is fully dissolved, adding initiator AIBN, reacting under the protection of nitrogen, centrifuging after the reaction is finished, washing with tetrahydrofuran, and vacuum drying the washed product at 50-70 ℃ for 12-24 hours to obtain VO 2 PDMA nanoparticle.
Preferably, V in step (1) 2 O 5 The mass ratio of the deionized water to the deionized water is (1-5): (70-150).
Preferably, the dispersion in step (1) is heated to 50-80 ℃ and then hydrazine hydrate is added dropwise with stirring.
Preferably, V in step (1) 2 O 5 The mass ratio of the hydrazine hydrate to the hydrazine hydrate is (5-10): (1-5).
Further, the hydrazine hydrate selected was 40wt% hydrazine hydrate.
Preferably, the hydrazine hydrate dropping speed in the step (1) is 0.1-1 mL/min.
Preferably, the stirring reaction time is continuously 0.5-5 h after the dripping in the step (1) is finished. Preferably, the reaction temperature in the reaction kettle in the step (1) is 240-350 ℃ and the reaction time is 6-30 h.
Preferably, after the reaction in the step (1) is finished, the post-treatment sequentially comprises centrifugation at 1000-8000 rpm for 5-20 min and vacuum drying at 40-90 ℃ for 8-24 h.
Preferably, in step (2), the mass ratio of N, N-Dimethylacrylamide (DMA), S-1-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -propionic acid) (DOPAT) in step a) is (80-120): (5-15).
Preferably, in step (2), the mass ratio of S-1-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -propionic acid) (DOPAT) to Azobisisobutyronitrile (AIBN) in step a) is (15-50): (0.5-7).
Preferably, in the step (2), the mass ratio of the 1, 4-dioxane to the N, N-dimethylacrylamide in the step a) is (5-10): (0.5-5).
Preferably, in the step (2), the reaction temperature under the protection of nitrogen in the step a) is 50-70 ℃ and the reaction time is 6-24 h.
Preferably, in the step (2), the mass ratio of PDMA-DOPAT, n-hexylamine and tributylphosphine in the step b) is (90-150): (10-30): (0.5-5).
Preferably, in step (2), the mass ratio of PDMA-dotat to tetrahydrofuran in step b) is 1: (5-30).
Preferably, in the step (2), the stirring reaction temperature is 20-60 ℃ under the protection of nitrogen in the step b); the stirring reaction time is 2-12 h.
Preferably, the ultrasonic dispersion time in the step (3) is 10-40 min.
Preferably, in the step (3), the mass ratio of the vanadium dioxide powder to the absolute ethyl alcohol is (0.1-4): (60-120).
Preferably, ammonia water is added dropwise in the step (3) to adjust the pH to 8-12.
Preferably, in the step (3), the mass ratio of the vanadium dioxide powder to the gamma- (methacryloyloxy) propyl trimethoxysilane (KH-570) is (1-20): (0.2-1).
Preferably, the heating reaction temperature in the step (3) is 50-70 ℃ and the reaction time is 3-10 h.
Preferably, the unreacted KH-570 is removed by washing with absolute ethanol 3-5 times in step (3).
Preferably, VO in step (3) 2 The mass ratio of the KH-570 nano powder to the tetrahydrofuran is (0.1-10): (60-120).
Preferably, VO in step (3) 2 The mass ratio of the @ KH-570 nano-powder to the PDMA-SH hydrophilic polymer is (1-10): (0.5-2).
Preferably, VO in step (3) 2 The mass ratio of the @ KH-570 nano-powder to the AIBN is (20-50): 1.
preferably, the reaction temperature under the nitrogen condition in the step (3) is 50-70 ℃ and the reaction time is 12-24 h.
The invention also protects the VO prepared by the method 2 PDMA nanoparticle. The VO is 2 The particle size of the @ PDMA nano-particles is 30-40 nm.
The third aspect of the present invention also provides a method for using the VO 2 Intelligent heat-insulating paint prepared from the PDMA nano particles. The preparation method of the intelligent heat insulation coating comprises the following steps: VO is to be provided with 2 Dripping the aqueous dispersion of the @ PDMA nano particles into the aqueous resin, and stirring until the aqueous dispersion is uniform to obtain a system dispersion; and uniformly mixing the film forming auxiliary agent, the leveling agent and the defoaming agent, and then adding the mixture into the system dispersion liquid to uniformly stir, thus obtaining the intelligent heat insulation coating.
Further, an aqueous resin and VO 2 The mass ratio of the @ PDMA nanoparticle aqueous dispersion is (50-100): (40-60); VO (VO) 2 The mass fraction of the aqueous dispersion of @ PDMA nanoparticles was 1wt%.
Further, VO 2 The drop velocity of the aqueous dispersion of the @ PDMA nano particles is 0.5-2 mL/min. Further, the stirring speed in the dripping process is 500-2000 rpm, and the stirring time after the dripping is finished is 0.5-5 h.
Further, the aqueous resin is selected from aqueous polyurethane resin and aqueous acrylate resin.
Further, the mass ratio of the aqueous resin, the film forming auxiliary agent, the leveling agent and the defoaming agent is (50-100): (10-30): (1-5): (1-5).
Further, the film forming auxiliary agent is selected from alcohol ether film forming auxiliary agents, the leveling agent is selected from organic silicon leveling agents, and the defoaming agent is selected from silicone defoaming agents.
The intelligent heat-insulating coating prepared by the invention is uniformly coated on the surface of a common clean glass plate by a conventional roll coating method, and the wet film thickness is 45-55 mu m after the coating is finished, so that the intelligent heat-insulating glass is prepared. Specifically, the intelligent heat-insulating coating is uniformly coated on the surface of a clean glass plate through a roll coating method, and the intelligent heat-insulating glass based on vanadium dioxide is prepared by placing the intelligent heat-insulating coating in an oven at 60 ℃ to assist in the accelerated solidification of the coating.
The VO provided by the invention 2 The @ PDMA nanoparticle is a vanadium dioxide-based hybrid material with double shells, the stability of vanadium dioxide powder is improved by utilizing a hydrophobic shell layer of an internal silane coupling agent, the dispersibility of vanadium dioxide in aqueous emulsion can be improved by an external hydrophilic shell layer PDMA, meanwhile, the compatibility of a filler and a film-forming resin is improved by virtue of an interface hydrogen bond between the shell layer material and the film-forming resin, the interface structure defect inside a functional coating is reduced, and the weather resistance of the functional coating is improved. The preparation method provided by the invention is simple to operate, and the prepared VO 2 The @ PDMA nano particles have excellent stability, dispersibility and near infrared dimming performance, and have great advantages when applied to the field of coatings.
VO prepared by the invention 2 The intelligent heat-insulating coating prepared by the PDMA nano particles has excellent light-adjusting performance and can realize efficient heat insulation effect.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of PDMA-DOPAT (Avance III HD 600MHz nuclear magnetic resonance apparatus, deuterated acetone as solvent) obtained in example 1;
FIG. 2 is an ultraviolet absorption spectrum of the PDMA-DOAPT polymer prepared in example 1 before and after aminolysis (tetrahydrofuran as solvent, 0.001g/mL concentration of polymer solution, UV-3600 type ultraviolet-visible-near infrared spectrophotometer);
FIG. 3 is a scanning electron microscope image of the vanadium dioxide powder prepared in example 1;
FIG. 4 shows the vanadium dioxide powder and VO obtained in example 1 2 @KH-570 nanoparticle and VO 2 Thermal weight loss curve of PDMA nanoparticle (TGA 55 thermogravimetric analyzer at N 2 Testing the thermal weight loss of the sample under atmosphere, wherein the testing temperature is 30-700 ℃, and the heating rate is 20 ℃/min);
FIG. 5 shows the vanadium dioxide powder and VO obtained in example 1 2 XRD pattern of @ PDMA nanoparticles;
FIG. 6 shows the vanadium dioxide powder and VO obtained in example 1 2 Dispersibility test of PDMA nanoparticles in water (0.1 gVO 2 And VO (Voice over Internet protocol) 2 Dispersing @ PDMA nano particles in 8mL distilled water respectively, then performing ultrasonic dispersion for 30min by using a cell pulverizer, standing and observing the twoSettling condition);
FIG. 7 is a graph (a) showing the intelligent thermal insulation coating prepared in application example 1, application example 2 and application example 3, and a graph (b) showing the ultraviolet-visible-near infrared transmission spectrum at different temperatures (ultraviolet-visible-near infrared spectrophotometer (UV) is used for testing the optical properties of samples at 20 ℃ and 90 ℃ respectively, and the testing wavelength ranges are 250-2500 nm).
Detailed Description
The following specific examples are presented to illustrate the present invention, and those skilled in the art will readily appreciate the additional advantages and capabilities of the present invention as disclosed herein. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
It should be noted that the following embodiments and features in the embodiments may be combined with each other without conflict. It is also to be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention. The test methods in the following examples, in which specific conditions are not noted, are generally conducted under conventional conditions or under conditions recommended by the respective manufacturers.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and to which this invention belongs, and any method, apparatus, or material of the prior art similar or equivalent to the methods, apparatus, or materials described in the examples of this invention may be used to practice the invention.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention as defined in the claims.
Example 1
Preparation of vanadium dioxide powder
Will be 13.5g V 2 O 5 After adding to a beaker containing 400mL of deionized water and heating the dispersion to 75 ℃, 6.0g of hydrazine hydrate (40 wt%) was slowly added dropwise to the dispersion with stirring. After completion of the dropwise addition, stirring was continued for 1 hour, and then the dispersion was transferred to a reaction vessel and reacted at 260℃for 24 hours. And (3) centrifuging for multiple times after the reaction is finished, and vacuum drying the obtained centrifugal product to obtain vanadium dioxide powder.
Preparation of trithioester-terminated polymers by reversible-addition fragmentation chain transfer (RAFT) polymerization
10.0g of N, N-Dimethylacrylamide (DMA), 0.71g S-1-dodecyl-S '- (α, α' -dimethyl- α "-propionic acid) (DOPAT), 0.05g of Azobisisobutyronitrile (AIBN) were added to 30mL of 1, 4-dioxane for complete dissolution. The system is stirred and reacted for 18 hours at 65 ℃ under the protection of nitrogen, the obtained solution is precipitated and washed in normal hexane, the product is obtained by suction filtration, and the trithio-terminated poly (N, N-dimethylacrylamide) (PDMA-DOPAT) yellow powder is obtained by vacuum drying at 40 ℃.
Preparation of thiol-terminated PDMA-SH hydrophilic polymers
3.0g of PDMA-DOPAT, 0.539g of n-hexylamine and 0.065g of tributylphosphine are added into 5mL of tetrahydrofuran, the mixture is stirred and reacted for 6 hours at 30 ℃ under the protection of nitrogen, after the reaction is finished, the solution is dripped into n-hexane to be precipitated and washed for three times, and the upper precipitate is collected by filtration and dried in vacuum at 40 ℃ to obtain PDMA-SH white powder.
VO 2 Preparation of KH-570 nano-powder
1.0g of VO was taken 2 The nano powder is dispersed in 100mL of absolute ethanol for 30min by ultrasonic, ammonia water is slowly added dropwise to adjust the pH to 10, 0.05g of gamma- (methacryloyloxy) propyl trimethoxysilane (KH-570) is added, and then the system is heated to 60 ℃ for reaction for 6h. Reaction junctionCentrifuging after the beam, washing with absolute ethanol for multiple times to remove unreacted KH-570, and drying the centrifuged solid product in a vacuum oven at 40 ℃ to obtain VO 2 The @ KH-570 nanometer powder.
VO 2 Preparation of PDMA nanoparticles
0.50g of VO obtained in example 4 was obtained 2 The @ KH-570 nano-powder was dispersed in 20mL of tetrahydrofuran by ultrasonic treatment for 30min, then 0.50g of PDMA-SH was added and dissolved sufficiently, and then 0.02g of AIBN was added and reacted under nitrogen protection at 60℃for 24 hours. Centrifuging and washing with tetrahydrofuran for 2 times after the reaction is finished, and finally vacuum drying the washed product for 24 hours at 60 ℃ to obtain VO 2 PDMA nanoparticle.
Example 2
Preparation of vanadium dioxide powder
Will be 10.0. 10.0g V 2 O 5 After adding to a beaker containing 300mL of deionized water and heating the dispersion to 75 ℃, 5.5g of hydrazine hydrate (40 wt%) was slowly added dropwise to the dispersion with stirring. After completion of the dropwise addition, stirring was continued for 1 hour, and then the dispersion was transferred to a reaction vessel and reacted at 280℃for 24 hours. And (3) centrifuging for multiple times after the reaction is finished, and vacuum drying the obtained centrifugal product to obtain vanadium dioxide powder.
Preparation of trithioester-terminated polymers by reversible-addition fragmentation chain transfer (RAFT) polymerization
10.0g of N, N-Dimethylacrylamide (DMA), 0.55g S-1-dodecyl-S '- (α, α' -dimethyl- α "-propionic acid) (DOPAT), 0.04g of Azobisisobutyronitrile (AIBN) were added to 30mL of 1, 4-dioxane for complete dissolution. The system is stirred and reacted for 18 hours at 65 ℃ under the protection of nitrogen, the obtained solution is precipitated and washed in normal hexane, the product is obtained by suction filtration, and the trithio-terminated poly (N, N-dimethylacrylamide) (PDMA-DOPAT) yellow powder is obtained by vacuum drying at 40 ℃.
Preparation of thiol-terminated PDMA-SH hydrophilic polymers
3.0g of PDMA-DOPAT, 0.42g of n-hexylamine and 0.05g of tributylphosphine are added into 5mL of tetrahydrofuran, the mixture is stirred and reacted for 6h at 30 ℃ under the protection of nitrogen, after the reaction is finished, the solution is dripped into n-hexane to be precipitated and washed for three times, and the upper precipitate is collected by filtration and dried in vacuum at 40 ℃ to obtain PDMA-SH white powder.
VO 2 Preparation of @ KH-570 nanoparticles
1.0g of VO was taken 2 The nano powder is dispersed in 80mL absolute ethanol for 30min, ammonia water is slowly added dropwise to adjust the pH to 10, 0.07g of gamma- (methacryloyloxy) propyl trimethoxysilane (KH-570) is added, and then the system is heated to 60 ℃ for reaction for 6h. Centrifuging after the reaction is finished, washing with absolute ethyl alcohol for multiple times to remove unreacted KH-570, and drying the centrifuged solid product in a vacuum oven at 40 ℃ to obtain VO 2 The @ KH-570 nanometer powder.
VO 2 Preparation of PDMA nanoparticles
0.50g VO was taken 2 The @ KH-570 nano-powder was dispersed in 30mL of tetrahydrofuran by ultrasonic treatment for 30min, then 0.3g of PDMA-SH was added and dissolved sufficiently, and then 0.015g of AIBN was added and reacted for 14h under the protection of nitrogen at 70 ℃. Centrifuging and washing with tetrahydrofuran for 2 times after the reaction is finished, and finally vacuum drying the washed product for 24 hours at 60 ℃ to obtain VO 2 PDMA nanoparticle.
Example 3
Preparation of vanadium dioxide powder
Will be 12.5g V 2 O 5 After adding to a beaker containing 350mL of deionized water and heating the dispersion to 75 ℃, 5.8g of hydrazine hydrate (40 wt%) was slowly added dropwise to the dispersion with stirring. After completion of the dropwise addition, stirring was continued for 1 hour, and then the dispersion was transferred to a reaction vessel and reacted at 280℃for 20 hours. And (3) centrifuging for multiple times after the reaction is finished, and vacuum drying the obtained centrifugal product to obtain vanadium dioxide powder.
Preparation of trithioester-terminated polymers by reversible-addition fragmentation chain transfer (RAFT) polymerization
11.5g of N, N-Dimethylacrylamide (DMA), 0.45g S-1-dodecyl-S '- (α, α' -dimethyl- α "-propionic acid) (DOPAT), 0.03g of Azobisisobutyronitrile (AIBN) were added to 30mL of 1, 4-dioxane for complete dissolution. The system is stirred and reacted for 18 hours at 65 ℃ under the protection of nitrogen, the obtained solution is precipitated and washed in normal hexane, the product is obtained by suction filtration, and the trithio-terminated poly (N, N-dimethylacrylamide) (PDMA-DOPAT) yellow powder is obtained by vacuum drying at 40 ℃.
Preparation of thiol-terminated PDMA-SH hydrophilic polymers
5.2g of PDMA-DOPAT, 0.75g of n-hexylamine and 0.1g of tributylphosphine are added into 5mL of tetrahydrofuran, the mixture is stirred and reacted for 6h at 30 ℃ under the protection of nitrogen, after the reaction is finished, the solution is dripped into n-hexane to be precipitated and washed for three times, and the upper precipitate is collected by filtration and dried in vacuum at 40 ℃ to obtain PDMA-SH white powder.
VO 2 Preparation of @ KH-570 nanoparticles
1.5g of VO was taken 2 The nano powder is dispersed in 120mL of absolute ethanol for 30min by ultrasonic, ammonia water is slowly added dropwise to adjust the pH to 10, 0.09g of gamma- (methacryloyloxy) propyl trimethoxysilane (KH-570) is added, and then the system is heated to 60 ℃ for reaction for 6h. Centrifuging after the reaction is finished, washing with absolute ethyl alcohol for multiple times to remove unreacted KH-570, and drying the centrifuged solid product in a vacuum oven at 40 ℃ to obtain VO 2 The @ KH-570 nanometer powder.
VO 2 Preparation of PDMA nanoparticles
0.50g VO was taken 2 The @ KH-570 nano-powder was dispersed in 50mL of tetrahydrofuran by sonication for 30min, then 0.4g of PDMA-SH was added and dissolved well, and then 0.025g of AIBN was added and reacted for 18h under the protection of nitrogen at 65 ℃. Centrifuging and washing with tetrahydrofuran for 2 times after the reaction is finished, and finally vacuum drying the washed product for 24 hours at 60 ℃ to obtain VO 2 PDMA nanoparticle.
Application example 1
1g of VO obtained in example 2 was reacted 2 Uniformly dispersing the powder in 99mL of water solvent, and performing ultrasonic treatment with a cell pulverizer for 30min until the powder is uniformly dispersed to obtain VO 2 And (3) a base slurry. 7.5g of aqueous polyurethane resin (model: sanbang 9080) is taken in a 20mL beaker, 5g of the slurry is taken in a 10mL serum bottle, and the slurry is slowly added into the aqueous resin in a dropwise manner and stirred until the slurry is uniformly dispersed. 2.5g of film forming auxiliary agent, 0.3g of flatting agent and 0.3g of defoamer are weighed and uniformly mixed in a 10mL serum bottle, and slowly added into a beaker in a dropwise manner. Fully and uniformly stirring to obtain VO 2 And (3) a base intelligent heat insulation coating.
Application example 2
1g of solidVO obtained in example 3 2 Uniformly dispersing the @ KH-570 nano-powder in 99mL of water solvent, and performing ultrasonic treatment with a cell pulverizer for 30min until the powder is uniformly dispersed to obtain VO 2 @ KH-570-based slurry. 7.5g of aqueous polyurethane resin (model: sanbang 9080) is taken in a 20mL beaker, 5g of the slurry is taken in a 10mL serum bottle, and the slurry is slowly added into the aqueous resin in a dropwise manner and stirred until the slurry is uniformly dispersed. 2.5g of film forming auxiliary agent, 0.3g of flatting agent and 0.3g of defoamer are weighed and uniformly mixed in a 10mL serum bottle, and slowly added into a beaker in a dropwise manner. Fully and uniformly stirring to obtain VO 2 Intelligent heat-insulating paint based on KH-570.
Application example 3
VO 2 Preparation of @ PDMA nanoparticle-based high-weather-resistance water-based intelligent heat-insulating coating
1g of the VO obtained in example 1 was reacted 2 Uniformly dispersing @ PDMA nano particles in 99mL of water solvent, and performing ultrasonic treatment for 30min by using a cell pulverizer until powder is uniformly dispersed to obtain VO 2 @ PDMA-based slurry. 7.5g of aqueous polyurethane resin (model: sanbang 9080) is taken in a 20mL beaker, 5g of the slurry is taken in a 10mL serum bottle, and the slurry is slowly added into the aqueous resin in a dropwise manner and stirred until the slurry is uniformly dispersed. 2.5g of film forming auxiliary agent, 0.3g of flatting agent and 0.3g of defoamer are weighed and uniformly mixed in a 10mL serum bottle, and slowly added into a beaker in a dropwise manner. Fully and uniformly stirring to obtain VO 2 PDMA-based intelligent heat insulation paint.
Preparation of intelligent thermal insulation coating
4mL of VO obtained in application examples 1 to 3 were taken respectively 2 Intelligent heat-insulating paint based on KH-570 and VO 2 Intelligent heat-insulating paint based on KH-570 and VO 2 The intelligent heat-insulating paint with the @ PDMA matrix is uniformly coated on a glass substrate by a roll coating method through a wire rod with the thickness of 50 mu m, and then the substrate is rapidly placed in a 60 ℃ oven to accelerate solvent volatilization, so that VO can be obtained 2 Based intelligent thermal insulation coating and VO 2 Intelligent heat-insulating coating based on @ KH570 and VO 2 The dry film thickness of the PDMA-based intelligent thermal insulation coating after thorough drying is about 5 mu m.
Performance analysis
1. Taking the PDMA-DOPAT yellow powder prepared in example 1, dissolving with deuterated acetone solvent, and performing nuclear magnetic hydrogen spectrometry by using Avance III HD 600MHz nuclear magnetic resonance spectrometerAs a result of the test, the results are shown in FIG. 1, and it can be seen from FIG. 1 that the characteristic peaks of the PDMA polymer appear in which 1.42 to 1.91ppm is assigned to the main chain-CH 2 -,2.30 to 2.78ppm of-CH-belonging to the main chain, 2.78 to 3.27ppm of-CH belonging to the side chain 3 . In addition, there was also a characteristic chemical shift of RAFT chain transfer agent dott in the spectrum (0.95 ppm ascribed to methyl in RAFT reagent), indicating that the PDMA homo-polymerization product retained the functional group of dott, and RAFT polymerization was successfully performed to prepare a PDMA homopolymer containing trithioester end group functional group.
2. The PDMA-DOPAT yellow powder and the PDMA-SH white powder prepared in example 1 were respectively prepared into polymer solutions with a concentration of 0.001g/mL by using tetrahydrofuran as a solvent, and ultraviolet absorption test was performed by using an ultraviolet-visible-near infrared spectrophotometer model UV-3600, and the obtained results are shown in FIG. 2. As can be seen from FIG. 2, the ultraviolet absorption peak of the trithio group of the PDMA-DOPAT polymer before aminolysis appears at 308nm, and further, the trithio functional group of the DOPAT chain transfer agent is connected to the polymer chain segment, while the ultraviolet absorption peak of the PDMA-SH polymer after aminolysis at 308nm disappears, namely, the end trithio group disappears, which indicates that the aminolysis successfully converts the trithio group to generate the mercapto-terminated PDMA-SH polymer.
3. The vanadium dioxide powder prepared in the example 1 is adopted for morphological characterization by adopting a Gemini300 type scanning electron microscope, and as shown in figure 3, the obtained vanadium dioxide powder has smaller primary particle size (30-40 nm). Then the vanadium dioxide powder and VO prepared in example 1 are respectively taken 2 KH-570 nano-powder and VO 2 @ PDMA nanoparticles, using a TGA55 thermogravimetric analyzer in N 2 The thermal weight loss of the test sample is tested under the atmosphere, the test temperature is 30-700 ℃, the temperature rising rate is 20 ℃/min, the obtained result is shown in figure 4, and the unmodified VO can be seen from figure 4 2 The weight loss of the nano powder reaches the maximum value (about 0.5%) at 270 ℃, the quality is kept unchanged with the temperature rising to 700 ℃, and the VO is maintained 2 The thermal weight loss of the KH-570 nano-powder is about 1.4% when the powder is heated to 700 ℃, which shows that the silane coupling agent is successfully grafted to VO 2 Powder surface. PDMA polymerizationVO after modification of matter 2 The thermal weight loss of the PDMA nanoparticle reaches a maximum value (2.5%) at 600 ℃, and it can be seen that the weight loss of the nano powder gradually increases with further modification, indicating that the block polymer is successfully grafted to the powder surface.
4. The vanadium dioxide powder and VO obtained in example 1 were taken separately 2 XRD test is carried out on the @ PDMA nano particles at room temperature by adopting a SmartlabSE type powder diffractometer, the test range is 10-80 degrees, the test step length is 1 degree/min, the crystal form change of the particles is observed, the result is shown in figure 5, and as can be seen from figure 5, both the powder before and after modification are monoclinic phases, which indicates that the polymer is modified into VO 2 The crystal form and the dimming performance of the powder are not affected in the powder process.
5. The vanadium dioxide powder and VO obtained in example 1 were taken separately 2 0.1g of each @ PDMA nanoparticle was dispersed in 8mL of distilled water, followed by ultrasonic dispersion in a cell pulverizer for 30min, and standing for observation of sedimentation of both, as shown in FIG. 5, as can be seen from FIG. 6, unmodified VO 2 Obvious sedimentation of the powder already occurs when the powder is left to stand for 5 days, while the hydrophilic polymer modified VO 2 The sedimentation velocity of the @ PDMA nano particles is obviously slowed down, and after standing for 7 days, a certain dispersion state is maintained without obvious sedimentation. This is mainly because hydrophilic PDMA can exhibit a stretched state in an aqueous solution system, improving the suspension effect of powder in an aqueous phase, and by combining the above results, PDMA as a shell material can improve the dispersibility of powder in an aqueous phase.
6. FIG. 7 (a) is a schematic view of the heat-insulating coating layers produced in application examples 1, 2 and 3, respectively, and it can be seen from the drawing that the heat-insulating coating layers are each a brown-yellow film excellent in light transmittance, and the film coating layers are uniform in surface. The optical properties of three different thermal barrier coatings were tested at 20℃and 90℃using an ultraviolet-visible-near infrared spectrophotometer (UV), respectively, with a test wavelength range of 250 to 2500nm, and the results are shown in FIG. 7 (b), from which it can be seen that the film has excellent solar light modulation ability under the conditions of high temperature of 90℃and low temperature of 20℃in which VO of example 1 was applied 2 Solar light modulation capability delta T of base film coating sol =8.47%, and application exampleVO of 3 2 The @ PDMA-based film coating exhibits higher solar light modulation capability (Δt sol =9.58%). This is mainly because the modification of PDMA polymer promotes the dispersibility of inorganic powder, reduces the agglomeration of large powder particles, and the existence of polymer shell layer is beneficial to improving the compatibility of powder and organic resin and reducing interface defects, and the result proves that PDMA changes VO 2 The nano particles can exert more excellent dimming performance to realize efficient heat insulation effect.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.

Claims (9)

1. Preparation VO 2 A method of @ PDMA nanoparticles, comprising the steps of:
(1) Preparing vanadium dioxide powder; (2) Preparation of a mercapto-terminated PDMA-SH hydrophilic polymer; (3) VO (VO) 2 Preparation of PDMA nanoparticles.
2. The method of claim 1, comprising the steps of:
(1) Preparation of vanadium dioxide powder:
will V 2 O 5 Adding the solution into deionized water, stirring to obtain a dispersion liquid, heating the dispersion liquid, dropwise adding hydrazine hydrate under stirring, continuously stirring for reaction after the dropwise adding is finished, transferring the solution into a reaction kettle for continuous reaction, and performing post-treatment after the reaction is finished to obtain vanadium dioxide powder;
(2) Preparation of thiol-terminated PDMA-SH hydrophilic Polymer: a) Adding N, N-dimethylacrylamide, S-1-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -propionic acid) and azodiisobutyronitrile into a 1, 4-dioxane solvent, stirring for reaction under the protection of nitrogen after complete dissolution, precipitating and washing the solution obtained after the reaction in normal hexane, carrying out suction filtration, and vacuum drying the obtained product at 40-90 ℃ for 8-24 h to obtain trithioester-terminated poly (N, N-dimethylacrylamide), which is named as PDMA-DOPAT;
b) Adding the PDMA-DOPAT, n-hexylamine and tributylphosphine obtained in the step a) into tetrahydrofuran, stirring for reaction under the protection of nitrogen, dripping the solution into n-hexane for precipitation and washing after the reaction is finished, filtering and collecting the precipitate, and vacuum drying at 40-90 ℃ for 8-24 hours to obtain a sulfhydryl-terminated PDMA-SH hydrophilic polymer;
(3)VO 2 preparation of PDMA nanoparticles: dispersing the vanadium dioxide powder prepared in the step (1) in absolute ethyl alcohol by ultrasonic, dripping ammonia water to adjust the pH value, adding gamma- (methacryloyloxy) propyl trimethoxy silane, then heating the system for reaction, centrifuging after the reaction is finished, washing by absolute ethyl alcohol, and vacuum drying at 40-70 ℃ for 12-24 hours to obtain VO 2 KH-570 nanometer powder;
VO is to be provided with 2 Super-dispersing KH-570 nano powder in tetrahydrofuran, adding the PDMA-SH hydrophilic polymer prepared in the step (2), stirring until the polymer is fully dissolved, adding initiator AIBN, reacting under the protection of nitrogen, centrifuging after the reaction is finished, washing with tetrahydrofuran, and vacuum drying the washed product at 50-70 ℃ for 12-24 hours to obtain VO 2 PDMA nanoparticle.
3. The method of claim 2, further comprising one or more of the following features:
v in step (1) 2 O 5 The mass ratio of the hydrazine hydrate to the hydrazine hydrate is (5-10): (1-5);
the reaction temperature in the reaction kettle in the step (1) is 240-350 ℃ and the reaction time is 6-30 h.
4. The method of claim 2, further comprising one or more of the following features:
in the step (2), the mass ratio of the N, N-dimethylacrylamide to the S-1-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -propionic acid) in the step a) is (80-120): (5-15);
in the step (2), the mass ratio of S-1-dodecyl-S ' - (alpha, alpha ' -dimethyl-alpha ' -propionic acid) to azodiisobutyronitrile in the step a) is (15-50): (0.5-7);
a) The mass ratio of the 1, 4-dioxane to the N, N-dimethylacrylamide is (5-10): (0.5-5);
b) The mass ratio of PDMA-DOPAT, n-hexylamine and tributylphosphine is (90-150): (10-30): (0.5-5).
5. The method of claim 2, further comprising one or more of the following features:
in the step (3), the mass ratio of the vanadium dioxide powder to the gamma- (methacryloyloxy) propyl trimethoxysilane is (5-30): (0.5-3);
VO in step (3) 2 The mass ratio of the @ KH-570 nano-powder to the PDMA-SH hydrophilic polymer is (1-10): (0.2-2);
VO in step (3) 2 The mass ratio of the @ KH-570 nano-powder to the AIBN is (10-40): 1, a step of;
the reaction temperature in the step (3) under the protection of nitrogen is 50-70 ℃ and the reaction time is 12-24 h.
6. A VO prepared by the process of claims 1-5 2 PDMA nanoparticle.
7. Use of VO according to claim 6 2 The intelligent heat-insulating coating prepared by the PDMA nano particles is characterized by comprising the following steps of: VO is to be provided with 2 Uniformly dripping the aqueous dispersion of the @ PDMA nano particles into the aqueous resin, and stirring until the aqueous dispersion is uniform to obtain a system dispersion; and uniformly mixing the film forming auxiliary agent, the leveling agent and the defoaming agent, then adding the mixture into the system dispersion liquid, and uniformly stirring to obtain the intelligent heat-insulating coating.
8. The intelligent thermal insulation coating of claim 7, wherein the aqueous resin and VO 2 Aqueous dispersion of PDMA nanoparticlesThe mass ratio of (50-100): (40-60); VO (VO) 2 The mass fraction of the aqueous dispersion of the @ PDMA nanoparticles was 1wt%.
9. The intelligent thermal insulation coating of claim 7, wherein VO 2 The drop velocity of the water dispersion of the PDMA nano particles is 0.5-2 mL/min.
CN202310972806.6A 2023-08-03 2023-08-03 VO 2 Nano particle @ PDMA, preparation method and intelligent heat-insulating coating prepared from nano particle @ PDMA Pending CN117025016A (en)

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