CN116970302A - VO 2 PHFBMA-b-PDMA nano-particle, preparation method and application - Google Patents

VO 2 PHFBMA-b-PDMA nano-particle, preparation method and application Download PDF

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CN116970302A
CN116970302A CN202310972807.0A CN202310972807A CN116970302A CN 116970302 A CN116970302 A CN 116970302A CN 202310972807 A CN202310972807 A CN 202310972807A CN 116970302 A CN116970302 A CN 116970302A
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pdma
phfbma
reaction
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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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

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Abstract

The invention provides a VO 2 PHFBMA-b-PDMA nano-particles, a preparation method and application thereof, belonging to the field of functional composite materials. The VO is 2 The particle size of the PHFBMA-b-PDMA nano particle is 30-40 nm, and the preparation method comprises the following steps: (1) preparation of vanadium dioxide powder; (2) Preparing a sulfhydryl-terminated PDMA-b-PHFBMA-SH amphiphilic block polymer; (3) VO (VO) 2 Preparation of PHFBMA-b-PDMA nanoparticles. The VO provided by the invention 2 VO prepared from@PHFBMA-b-PDMA nano particles 2 The PHFBMA-b-PDMA nanoparticle has excellent stability, dispersibility and near infrared dimming performance, and has great advantages when being applied to the field of coatings.

Description

VO 2 PHFBMA-b-PDMA nano-particle, preparation method and application
Technical Field
The invention belongs to the field of functional composite materials, and in particular relates to a VO (volatile organic compound) 2 PHFBMA-b-PDMA nanoparticle, and its preparation method and application are provided.
Background
Vanadium dioxide (VO) 2 ) The thermochromic material can generate phase change at 68 ℃, has the characteristic of difference in infrared light reflectivity before and after phase change, and can be used as a coating material for intelligently regulating and controlling the transmittance of near infrared light in building door and window glass, so that the indoor temperature is intelligently regulated and controlled, the use of indoor air conditioning and cold air in a high-temperature environment is reduced, and the energy consumption is reduced, thereby being beneficial to energy conservation and emission reduction. But in practical application VO 2 Is easily oxidized into vanadium pentoxide (V) by water, oxygen and the like in the air 2 O 5 ) The poor stability of this disadvantage limits its practical application. VO enhancement commonly used at present 2 The strategy of powder stability is to carry out surface modification and construct a core-shell structure pair VO 2 The nano powder is coated, and a compact protective layer is formed on the surface of the powder by a shell layer material, wherein the common shell layer material mainly comprises organic micromolecules (silane coupling agents), inorganic oxides (silicon dioxide, titanium dioxide and the like) and organic polymers (such as polydopamine, polystyrene and the like). Although the method for improving the stability of vanadium dioxide can improve the weather resistance of vanadium dioxide powder to a certain extent, the common shell materials are inorganic materials or hydrophobic organic materials, the inorganic shell materials cannot simultaneously solve the dispersibility of the powder in aqueous emulsion, and the shell materials of non-fluorine-containing polymers are easy to decompose under the irradiation of sunlight and cannot meet the long-time application requirements of the powder and the coating.
Disclosure of Invention
The invention aims to provide a VO 2 PHFBMA-b-PDMA nano particles, a preparation method and application thereof are used for solving the problems of poor powder dispersibility, poor stability, poor dimming performance 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.
VO (Voice over Internet protocol) 2 PHFBMA-b-PDMA nanoparticle, said VO 2 The particle size of the @ PHFBMA-b-PDMA nano-particles is 30-40 nm.
Preparation of VO 2 A method of @ PHFBMA-b-PDMA nanoparticles comprising the steps of:
(1) Preparing vanadium dioxide powder; (2) Preparing a sulfhydryl-terminated PDMA-b-PHFBMA-SH amphiphilic block polymer; (3) VO (VO) 2 Preparation of PHFBMA-b-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-b-PHFBMA-SH amphiphilic block 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 30-60 ℃ for 8-24 h to obtain trithioester-terminated poly (N, N-dimethylacrylamide), which is named as PDMA-DOPAT;
b) Adding the PDMA-DOPAT, hexafluorobutyl methacrylate and azodiisobutyronitrile obtained in the step a) into tetrahydrofuran, stirring until the materials are completely dissolved, stirring the materials under the protection of nitrogen for reaction, dripping the solution into N-hexane for precipitation and washing after the reaction is finished, filtering and collecting the precipitate, and vacuum drying the precipitate at 30-60 ℃ for 8-24 hours to obtain poly (N, N-dimethylacrylamide-b-hexafluorobutyl methacrylate), which is named as PDMA-b-PHFBMA-DOPAT;
c) Adding the PDMA-b-PHFBMA-DOPAT, n-hexylamine and tributylphosphine prepared in the step b) into tetrahydrofuran, stirring for reaction under the protection of nitrogen, adding the reaction solution into n-hexane for precipitation and washing after the reaction is finished to obtain a solid product, and vacuum drying at 30-60 ℃ for 8-24 hours to obtain a mercapto-terminated PDMA-b-PHFBMA-SH amphiphilic block polymer;
(3)VO 2 preparation of PHFBMA-b-PDMA nanoparticles:
a) 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 30-60 ℃ for 12-24 hours to obtain VO 2 KH-570 nanometer powder;
b) VO is to be provided with 2 Ultra-dispersing KH-570 nano powder in tetrahydrofuran, adding the PDMA-b-PHFBMA-SH amphiphilic block polymer prepared in the step (2), stirring until the amphiphilic block polymer is fully dissolved, adding an initiator AIBN, reacting under the protection of nitrogen, centrifuging after the reaction is finished, washing with tetrahydrofuran, and vacuum drying the washed product at 30-60 ℃ for 12-24 hours to obtain VO 2 PHFBMA-b-PDMA nanoparticle.
Preferably, V in step (1) 2 O 5 The mass ratio of the deionized water to the deionized water is (1-7): (60-160).
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.
Further, the hydrazine hydrate dropping speed in the step (1) is 0.1-1 mL/min. 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 220-350 ℃ and the reaction time is 6-32 h.
Preferably, after the reaction in the step (1) is finished, the post-treatment sequentially comprises centrifugation at 1000-8000 rpm for 10-30 min and vacuum drying at 30-60 ℃ 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 stirring reaction temperature is 55-70 ℃ under the protection of nitrogen in the step a), and the reaction time is 12-24 h.
Preferably, in the step (2), the mass ratio of PDMA-DOPAT, hexafluorobutyl methacrylate (HFBMA) and Azobisisobutyronitrile (AIBN) in the step (b) is (260-350): (150-240): (0.5-5).
Preferably, in step (2), the mass ratio of PDMA-dotat to tetrahydrofuran in b) is 1: (3-20).
Preferably, in the step (2), the stirring reaction temperature is 55-70 ℃ under the protection of nitrogen in the step b), and the reaction time is 12-24 h.
Preferably, in step (2), the amount of n-hexane in processes a), b), c) should be such that it is sufficient to complete the precipitation.
Preferably, in the step (2), the mass ratio of PDMA-b-PHFBMA-DOPAT, n-hexylamine and tributylphosphine in the step (c) is (250-450): (45-90): (2-12).
Preferably, in step (2), the mass ratio of PDMA-b-PHFBMA-dotat to tetrahydrofuran in c) is 1: (2-10).
Preferably, in the step (2), the stirring reaction temperature is 25-45 ℃ under the protection of nitrogen in the step c), and the reaction time is 3-12 h.
Preferably, in step (3), the ultrasonic dispersion time in a) is 20 to 40 minutes.
Preferably, in the step (3), the mass ratio of the vanadium dioxide powder to the absolute ethyl alcohol in the step a) is (0.1-4): (60-120).
Preferably, in the step (3), ammonia water is added dropwise to adjust the pH to 8-12.
Preferably, in the step (3), the mass ratio of the vanadium dioxide powder in the step a) to the gamma- (methacryloyloxy) propyl trimethoxysilane (KH-570) is (5-30): (0.5-3).
Preferably, in step (3), a) the heating reaction temperature is 50-70 ℃ and the reaction time is 3-12 h.
Preferably, in step (3), the unreacted KH-570 is removed by washing with absolute ethanol 3 to 5 times.
Preferably, in step (3), VO in b) 2 The mass ratio of the KH-570 nano powder to the tetrahydrofuran is (0.1-10): (60-120).
Preferably, in step (3), VO in b) 2 The mass ratio of the @ KH-570 nano-powder to the AIBN is (20-50): 1.
preferably, in the step (3), the reaction temperature is 55-70 ℃ under the protection of nitrogen in the step b), and the reaction time is 12-24 h.
Preferably, in step (3), THF is washed 3 to 5 times to remove unreacted amphiphilic block polymer in step (3).
The invention also protects a method for utilizing the VO 2 Intelligent heat-insulating paint prepared from PHFBMA-b-PDMA nano particles.
The preparation method of the intelligent heat insulation coating comprises the following steps: VO is to be provided with 2 Uniformly dripping the aqueous dispersion of the PHFBMA-b-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.
Further, an aqueous resin and VO 2 Quality of aqueous dispersion of PHFBMA-b-PDMA nanoparticlesThe ratio is (50-100): (40-60); VO (VO) 2 The mass percentage of the aqueous dispersion of the PHFBMA-b-PDMA nano particles is 1wt%.
Further, VO 2 The dropping speed of the aqueous dispersion of the PHFBMA-b-PDMA nano particles is 0.5-2 mL/min. Further, the stirring speed in the dripping process is 4000-8000 rpm, and the stirring time after the dripping is completed 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): (0.5-5): (1-3).
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 PHFBMA-b-PDMA nanoparticle is a vanadium dioxide-based hybrid material with double shells, the high stability and hydrophobicity of the inner fluoropolymer PHFBMA are utilized to improve the weather resistance of vanadium dioxide powder in aqueous resin, the outer hydrophilic shell PDMA can effectively improve the dispersibility of vanadium dioxide in aqueous emulsion, prevent sedimentation and agglomeration, and meanwhile, the interface hydrogen bond between the shell material and film-forming resin is beneficial to improving the compatibility of filler and resin, reducing the interface structural defect inside the functional coating and improving the weather resistance of the functional coating. The preparation method provided by the invention has certain universality, and the prepared VO 2 The PHFBMA-b-PDMA nanoparticle has excellent stability, dispersibility and near infrared dimming performance, and has great advantages in the field of intelligent heat-insulating coatings.
VO prepared by the invention 2 The intelligent heat-insulating coating prepared by the PHFBMA-b-PDMA nano particles has excellent light-adjusting performance and can realize efficient heat insulation effect.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a PDMA-b-PHFBMA-DOPAT block polymer prepared in example 1;
FIG. 2 is a nuclear magnetic resonance spectrum of the PDMA-b-PHFBMA-DOPAT block polymer obtained in example 1;
FIG. 3 is an ultraviolet absorption spectrum of PDMA-b-PHFBMA-DOPAT, PDMA-b-PHFBMA-SH prepared in example 1;
FIG. 4 shows the VO obtained in example 1 2 SEM picture of powder;
FIG. 5 shows the VO obtained in example 1 2 Powder, VO 2 XRD pattern of @ PHFBMA-b-PDMA nanoparticles;
FIG. 6 shows the VO obtained in example 1 2 Powder, VO 2 @KH-570、VO 2 Thermal weight loss curve of @ PHFBMA-b-PDMA nanoparticles;
FIG. 7 shows the VO obtained in example 1 2 Powder, VO 2 @KH-570 and VO 2 The dispersibility test result of the @ PHFBMA-b-PDMA nanoparticle in the water phase (VO is arranged from left to right 2 Powder, VO 2 PHFBMA-b-PDMA nanoparticle and VO 2 @KH-570)；
FIG. 8 shows the VO obtained in example 1 2 Powder, VO 2 @KH-570 and VO 2 Acid resistance and oxidation resistance test results (VO in order from left to right 2 Powder, VO 2 @KH-570、VO 2 PHFBMA-b-PDMA nanoparticle);
FIG. 9 is a graph of the thermal barrier coating obtained in application example 1, application example 2, application example 3, and the ultraviolet-visible-near infrared transmission spectrum at different temperatures, wherein (a) is VO 2 Based intelligent thermal insulation coating, (b) VO 2 Intelligent heat-insulating coating based on @ KH570, (c) VO 2 And (d) the PHFBMA-b-PDMA-based intelligent thermal insulation coating is an ultraviolet-visible-near infrared transmission spectrum chart at different temperatures.
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 10gV 2 O 5 After adding to a beaker containing 300mL of deionized water and heating the dispersion to 65 ℃, 5.0g of hydrazine hydrate (40 wt%) was added dropwise to the dispersion at a rate of 0.5mL/min 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. Centrifuging for multiple times after the reaction is finished, and vacuum drying the obtained centrifugal product to obtain the dioxygenVanadium powder.
Preparation of PDMA-DOPAT hydrophilic polymer 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 16 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 amphiphilic block polymer PDMA-b-PHFBMA-DOPAT
3.0g of PDMA-DOPAT, 2.1g of hexafluorobutyl methacrylate (HFBMA) and 0.02g of AIBN are added into 24mL of Tetrahydrofuran (THF) to be completely dissolved, the mixture is stirred and reacted for 20h under the protection of nitrogen at 60 ℃, after the reaction is finished, the precipitate is washed in normal hexane, and after suction filtration, the solid product is dried in vacuum at 45 ℃ to obtain poly (N, N-dimethylacrylamide-b-hexafluorobutyl methacrylate) (PDMA-b-PHFBMA-DOPAT) as light yellow powder.
Preparation of mercapto-terminated PDMA-b-PHFBMA-SH
3.0g of PDMA-b-PHFBMA-DOPAT, 0.55g of n-hexylamine and 0.065g of tributylphosphine are added into 10mL of tetrahydrofuran, the mixture is stirred and reacted for 8 hours at 25 ℃ under the protection of nitrogen, the mixture is precipitated and washed three times in n-hexane after the reaction is finished, and the obtained solid product is dried in vacuum at 40 ℃ to obtain PDMA-b-PHFBMA-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 absolute ethanol for 40min, ammonia water is added dropwise to adjust the pH to 10, 0.2g gamma- (methacryloyloxy) propyl trimethoxysilane (KH-570) is added, and then the system is heated to 50 ℃ for reaction for 8h. Centrifuging after the reaction, washing with absolute ethanol for multiple times to remove unreacted KH-570, and vacuum drying the centrifuged solid product at 60deg.C to obtain VO 2 The @ KH-570 nanometer powder.
VO 2 Preparation of @ PHFBMA-b-PDMA nanoparticles
0.50g VO was taken 2 The @ KH-570 nano-powder was dispersed in 20mL THF by sonication for 30min, then 0.25g PDMA-b-PHFBMA-SH was added and dissolved well, and then 0.02g AIBN was added and reacted at 60℃under nitrogen protection for 24h. Centrifuging and washing with THF for 3 times after the reaction is finished, and finally vacuum drying the washed product for 24 hours at 40 ℃ to obtain VO 2 PHFBMA-b-PDMA nanoparticle.
Example 2
Preparation of vanadium dioxide powder
Will be 10gV 2 O 5 After adding to a beaker containing 400mL of deionized water and heating the dispersion to 70 ℃, 6.0g of hydrazine hydrate (40 wt%) was added dropwise to the dispersion at a rate of 0.5mL/min with stirring. After completion of the dropwise addition, stirring was continued for 2 hours, and then the dispersion was transferred to a reaction vessel and reacted at 260℃for 22 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 PDMA-DOPAT hydrophilic polymer by reversible-addition fragmentation chain transfer (RAFT) polymerization
8.0g 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 12 hours at 70 ℃ 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 50 ℃.
Preparation of amphiphilic block polymer PDMA-b-PHFBMA-DOPAT
4.0g of PDMA-DOPAT, 2.0g of hexafluorobutyl methacrylate (HFBMA) and 0.04g of AIBN are added into 30mL of Tetrahydrofuran (THF) to be completely dissolved, the mixture is stirred and reacted for 16h under the protection of nitrogen at 65 ℃, after the reaction is finished, the precipitate is washed in normal hexane, and after suction filtration, the solid product is dried in vacuum at 55 ℃ to obtain poly (N, N-dimethylacrylamide-b-hexafluorobutyl methacrylate) (PDMA-b-PHFBMA-DOPAT) as light yellow powder.
Preparation of mercapto-terminated PDMA-b-PHFBMA-SH
3.0g of PDMA-b-PHFBMA-DOPAT, 0.612g of n-hexylamine and 0.075g of tributylphosphine are added into 15mL of tetrahydrofuran, the mixture is stirred and reacted for 6 hours at 35 ℃ under the protection of nitrogen, the mixture is precipitated and washed three times in n-hexane after the reaction is finished, and the obtained solid product is dried in vacuum at 60 ℃ to obtain PDMA-b-PHFBMA-SH white powder.
VO 2 Preparation of KH-570 nano-powder
2.0g VO was taken 2 The nano powder is dispersed in 160mL absolute ethanol for 30min, ammonia water is added dropwise to adjust the pH to 11, 0.3g gamma- (methacryloyloxy) propyl trimethoxysilane (KH-570) is added, and then the system is heated to 60 ℃ for reaction for 6h. Centrifuging after the reaction, washing with absolute ethanol for multiple times to remove unreacted KH-570, and vacuum drying the centrifuged solid product at 40deg.C to obtain VO 2 The @ KH-570 nanometer powder.
VO 2 Preparation of @ PHFBMA-b-PDMA nanoparticles
0.70g VO was taken 2 The @ KH-570 nano-powder was dispersed in 20mL THF by sonication for 20min, then 0.50g PDMA-b-PHFBMA-SH was added and dissolved well, and then 0.03g AIBN was added and reacted at 70℃under nitrogen protection for 12h. Centrifuging and washing with THF for 4 times after the reaction is finished, and finally vacuum drying the washed product for 24 hours at 50 ℃ to obtain VO 2 PHFBMA-b-PDMA nanoparticle.
Example 3
Preparation of vanadium dioxide powder
Will be 8gV 2 O 5 After adding to a beaker containing 350mL of deionized water and heating the dispersion to 75 ℃, 5.5g of hydrazine hydrate (40 wt%) was added dropwise to the dispersion at a rate of 0.5mL/min 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 26 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 PDMA-DOPAT hydrophilic polymer by reversible-addition fragmentation chain transfer (RAFT) polymerization
8.0g of N, N-Dimethylacrylamide (DMA), 0.75g of g S-1-dodecyl-S '- (α, α' -dimethyl- α "-propionic acid) (DOPAT), 0.06g of Azobisisobutyronitrile (AIBN) were added to 30mL of 1, 4-dioxane for complete dissolution. The system is stirred and reacted for 20 hours at 60 ℃ 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 55 ℃.
Preparation of amphiphilic block polymer PDMA-b-PHFBMA-DOPAT
3.5g of PDMA-DOPAT, 1.8g of hexafluorobutyl methacrylate (HFBMA) and 0.03g of AIBN are added into 20mL of Tetrahydrofuran (THF) to be completely dissolved, the mixture is stirred and reacted for 12h under the protection of nitrogen at 70 ℃, after the reaction is finished, the precipitate is washed in normal hexane, and after suction filtration, the solid product is dried in vacuum at 60 ℃ to obtain poly (N, N-dimethylacrylamide-b-hexafluorobutyl methacrylate) (PDMA-b-PHFBMA-DOPAT) as light yellow powder.
Preparation of mercapto-terminated PDMA-b-PHFBMA-SH
4.0g of PDMA-b-PHFBMA-DOPAT, 0.72g of n-hexylamine and 0.083g of tributylphosphine are added into 20mL of tetrahydrofuran, the mixture is stirred and reacted for 4 hours at 45 ℃ under the protection of nitrogen, the mixture is precipitated and washed three times in n-hexane after the reaction is finished to obtain a solid product, and finally the solid product is dried in vacuum at 60 ℃ to obtain PDMA-b-PHFBMA-SH white powder.
VO 2 Preparation of KH-570 nano-powder
1.0g of VO was taken 2 The nano powder is dispersed in 150mL of absolute ethanol for 30min, ammonia water is added dropwise to adjust the pH to 12, 0.15g of gamma- (methacryloyloxy) propyl trimethoxysilane (KH-570) is added, and then the system is heated to 45 ℃ for reaction for 12h. Centrifuging after the reaction, washing with absolute ethanol for multiple times to remove unreacted KH-570, and vacuum drying the centrifuged solid product at 50deg.C to obtain VO 2 The @ KH-570 nanometer powder.
VO 2 Preparation of @ PHFBMA-b-PDMA nanoparticles
0.50g VO was taken 2 The @ KH-570 nano-powder was dispersed in 30mL THF by sonication for 40min, then 0.15g PDMA-b-PHFBMA-SH was added and dissolved well, and after 0.02g AIBN was added, reacted at 65℃under nitrogen protection for 18h. Centrifuging and washing with THF for 3 times after the reaction is finished, and finally vacuum drying the washed product at 60 ℃ for 24 hours to obtain VO 2 PHFBMA-b-PDMA nanoparticle.
Application example 1
1g of VO obtained in example 2 2 Uniformly dispersing the powder in 99mL distilled water, 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 beaker, 5g of the slurry is taken and added into the aqueous resin dropwise at the speed of 0.8mL/min, and the mixture is 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 VO obtained in example 3 was reacted 2 Uniformly dispersing the @ KH-570 nano-powder in 99mL of water solvent, and performing ultrasonic treatment with a cell pulverizer for 40min 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, 4g of the slurry is taken and added into the aqueous resin dropwise at the speed of 1.2mL/min, and the mixture is 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 PHFBMA-b-PDMA nanoparticle-based high-weather-resistance water-based intelligent heat-insulating paint
1g of the VO obtained in example 1 was reacted 2 Uniformly dispersing the @ PHFBMA-b-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 PHFBMA-b-PDMA based slurry. 7.5g of aqueous polyurethane resin (model: sanbang 9080) is taken in a 20mL beaker, 7g of the slurry is taken and added into the aqueous resin dropwise at the speed of 1.8mL/min, and the mixture is 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 PHFBMA-b-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 Base intelligent heat insulation paint and VO 2 Intelligent heat-insulating paint based on KH-570 and VO 2 PHFBMA-b-PDMA-based intelligent heat insulation paint, uniformly coating a glass substrate by using a wire rod with the thickness of 50 mu m by adopting a roll coating method, and then rapidly placing the substrate in a 60 ℃ oven to accelerate solvent volatilization, thus obtaining VO 2 、VO 2 @KH570、VO 2 PHFBMA-b-PDMA-based intelligent thermal barrier coating, dry film thickness after thorough drying was about 5. Mu.m.
Characterization of Performance
1. FIG. 1 is a schematic diagram of the synthesis reaction of a PDMA-b-PHFBMA-DOPAT block polymer, and it can be seen from the figure that the synthesis of a mercapto-terminated PDMA-b-PHFBMA-SH block polymer is mainly divided into three steps, wherein DMA is firstly a monomer, DOPAT is a chain transfer agent to prepare a PDMA-DOPAT homopolymer, then the PDMA-DOPAT homopolymer is further polymerized with HFBMA monomer as a macromolecular chain transfer agent to prepare a PDMA-b-PHFBMA-DOPAT amphiphilic block polymer with a trithioate group at the end group, and finally the trithioate group is converted into the mercapto group through an aminolysis reaction to prepare the PDMA-b-PHFBMA-SH block polymer.
2. The PDMA-b-PHFBMA-dott block polymer prepared in example 1 was dissolved in deuterated dimethyl sulfoxide as a solvent, and nuclear magnetic hydrogen spectrum was measured by using Avance III HD 600MHz nuclear magnetic resonance, and the obtained results are shown in fig. 2, and it can be seen from fig. 2: 0.8ppm of-CH belonging to the polymer backbone 3 1.42 to 1.91ppm ascribed to the backbone-CH 2 -,2.30 to 2.78ppm of a characteristic peak ascribed to the main chain-CH-. Meanwhile, the characteristic proton signal of methyl in the RAFT reagent appears at 0.95ppm of PDMA-b-PHFBMA-DOPAT, which indicates that the polymer product retains the functional group of DOPAT, and the PDMA-b-PHFBMA-DOPAT block polymer is successfully prepared.
3. The polymer solutions with the concentration of 0.001g/mL were prepared by taking PDMA-b-PHFBMA-DOPAT and PDMA-b-PHFBMA-SH prepared in example 1 and tetrahydrofuran as solvents, respectively, and ultraviolet absorption test was performed by using a UV-3600 type ultraviolet-visible-near infrared spectrophotometer, and the obtained results are shown in FIG. 3. As can be seen from FIG. 3, the ultraviolet absorption peak of the trithio group of the PDMA-b-PHFBMA-DOPAT block polymer before the aminolysis appears at 308nm, which proves that the DOPAT chain transfer agent is contained on the polymer chain segment, and the absorption peak of the polymer at 308nm disappears after the aminolysis reaction, which proves that the trithio group in the block polymer disappears, and the trithio group is successfully converted into a mercapto group, so as to prepare the PDMA-b-PHFBMA-SH block polymer.
4. The vanadium dioxide powder prepared in the example 1 is adopted for morphology characterization by adopting a Gemini300 type scanning electron microscope, as shown in fig. 4, the obtained vanadium dioxide powder has smaller primary particle size (30-40 nm) and no obvious agglomeration among particles.
5. The vanadium dioxide powder and VO obtained in example 1 were taken separately 2 XRD test is carried out on the PHFBMA-b-PDMA nano particles at room temperature by adopting a SmartlabSE powder diffractometer, the test range is 10-80 degrees, the test step length is 1 degree/min, the crystal form change of the PHFBMA-b-PDMA nano particles is observed, the result is shown in figure 5, and the powder before and after modification is monoclinic phase, which shows that the polymer modified VO 2 The crystal form and the dimming performance of the powder are not affected in the powder process.
6. The vanadium dioxide powder and VO obtained in example 1 were taken separately 2 KH-570 nano-powder and VO 2 PHFBMA-b-PDMA nanoparticle, TGA55 thermogravimetric analyzer was used in N 2 The thermal weight loss of the test sample is tested under the atmosphere, the test temperature is 30-800 ℃, the temperature rising rate is 10 ℃/min, the obtained result is shown in figure 6, and as can be seen from figure 6, VO 2 The nano powder hardly decomposes weight loss at 700 ℃, has good thermal stability, and the VO modified by KH-570 2 When the temperature of the hybrid particles is increased to 700 ℃, the weight loss of the powder is about 2.8%, which proves that KH-570 is successfully grafted to the surface of the powder, the grafting amount is about 2.8%, and the VO coated by the PDMA-b-PHFBMA polymer is obtained 2 PHFBMA-b-PDMA nanoparticles having a thermal weight loss of about 13.9% at 700℃indicating successful grafting of the click-reaction block polymer onto the powder surface.
7. The vanadium dioxide powder and VO obtained in example 1 were taken separately 2 0.1g of @ PDMA nano particles are respectively dispersed in 8mL of distilled water, then are ultrasonically dispersed for 30min in a cell pulverizer, and are stood for observing sedimentation conditions of the two,as a result, as shown in FIG. 7, it can be seen from FIG. 7 that VO was observed on day 4 2 Obvious sedimentation of powder and VO appear 2 @KH-570 and VO 2 The @ PHFBMA-b-PDMA powder still keeps better dispersity, and is VO after standing for 5 days 2 Partial sedimentation also starts to occur at @ KH-570, mainly because although the hydroxyl groups after hydrolysis of the silane coupling agent can increase VO 2 Dispersibility in water, but small organic molecules in the coupling agent exhibit hydrophobicity, so VO is observed with prolonged standing time 2 Sedimentation also occurs at KH-570. And after standing for 7 days VO 2 The @ PHFBMA-b-PDMA powder still keeps a good dispersion state, which indicates VO 2 PHFBMA-b-PDMA powder shows excellent dispersing effect in aqueous system, which is mainly attributed to the fact that the hydrophilic block of the outermost PDMA can keep a stretching state in water, so that the powder keeps good suspension stability in the aqueous phase.
8. The VO obtained in example 1 was taken 2 Powder, VO 2 @KH-570 and VO 2 PHFBMA-b-PDMA nanoparticles 0.1g each, dispersed in 0.5mol/L H 2 SO 4 Performing ultrasonic dispersion in the solution for 30min to perform an acid resistance test, and observing the color change of the dispersion liquid; 0.1g of VO was taken separately 2 Powder, VO 2 @KH-570 and VO 2 PHFBMA-b-PDMA nanoparticle dispersed in 0.5mol/L H 2 O 2 Performing ultrasonic dispersion in the solution for 30min for oxidation resistance test, and observing the oxidation condition of the powder; the results are shown in FIG. 8, wherein (a) in FIG. 8 is the result of the powder acid resistance test and (b) is the powder oxidation resistance test (VO in order from left to right 2 、VO 2 @KH-570、VO 2 @PHFBMA-b-PDMA)。
In the powder acid resistance test (FIG. 8 (a)), VO 2 The nano-powder is quickly turned blue by the acid-etched decomposition solution, mainly because of unmodified VO 2 The powder is directly dissolved by dilute sulfuric acid to generate blue VO 2+ Ions. And VO is 2 After 2 days of standing, the dispersion of KH-570 started to appear light blue, while VO 2 The PHFBMA-b-PDMA dispersion still keeps a good dispersion state at the 5 th day and has no color change, which shows that the powder modified by the block polymer has the best acid resistance.
In the powder oxidation resistance test (fig. 8 (b)), unmodified VO was found by observation 2 The dispersion quickly turned into a brown solution due to VO 2 Oxidized to brown [ V ] 4 O 9 ] 2- 、[VO 4 ] 4- The ions, which illustrate the worst stability of unmodified vanadium dioxide. And for VO 2 The dispersion @ KH-570 had not changed color after 2 days of rest and VO had been observed when the rest time was extended to 5 days 2 Only the dispersion at KH-570 starts to turn yellow, while VO 2 The PHFBMA-b-PDMA dispersion still keeps a good dispersion state and has no color change, which indicates that the powder modified by the block polymer shows excellent oxidation resistance and improves the stability of the powder.
9. FIG. 9 is a schematic diagram of the thermal barrier coatings prepared in application example 1, application example 2 and application example 3, respectively, and it can be seen from the figure that the thermal barrier coatings are brown yellow with excellent light transmittance and the film coating surface is uniform. 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. 9 (d), 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 was calculated 2 Solar light modulation capability delta T of film sol ＝8.28％，VO 2 Sunlight modulation Capacity DeltaT of @ KH-570 film sol =9.82%, and VO 2 The sunlight modulation capability of the PHFBMA-b-PDMA film is increased to delta T sol =10.84%, indicating that the modification of the block polymer is beneficial to improve the light-modulating properties of the film. The hydrophilic PDMA chain segment of the outermost layer of the powder promotes the dispersibility of inorganic powder, reduces the agglomeration of large powder particles, and the fluorine-containing PHFBMA of the inner layer improves the stability of the powder, so that the coated VO of the block polymer is finally realized 2 The nanoparticles exhibit optimal dimming properties enabling efficient near infrared light dimming capabilities.
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. VO (Voice over Internet protocol) 2 PHFBMA-b-PDMA nanoparticle characterized in that the VO 2 The particle size of the @ PHFBMA-b-PDMA nano-particles is 30-40 nm.
2. Preparation of VO according to claim 1 2 A method of @ PHFBMA-b-PDMA nanoparticles comprising the steps of:
(1) Preparing vanadium dioxide powder; (2) Preparing a sulfhydryl-terminated PDMA-b-PHFBMA-SH amphiphilic block polymer; (3) VO (VO) 2 Preparation of PHFBMA-b-PDMA nanoparticles.
3. The method of claim 2, 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-b-PHFBMA-SH amphiphilic block 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 30-60 ℃ for 8-24 h to obtain trithioester-terminated poly (N, N-dimethylacrylamide), which is named as PDMA-DOPAT;
b) Adding the PDMA-DOPAT, hexafluorobutyl methacrylate and azodiisobutyronitrile obtained in the step a) into tetrahydrofuran, stirring until the materials are completely dissolved, stirring the materials under the protection of nitrogen for reaction, dripping the solution into N-hexane for precipitation and washing after the reaction is finished, filtering and collecting the precipitate, and vacuum drying the precipitate at 30-60 ℃ for 8-24 hours to obtain poly (N, N-dimethylacrylamide-b-hexafluorobutyl methacrylate), which is named as PDMA-b-PHFBMA-DOPAT;
c) Adding the PDMA-b-PHFBMA-DOPAT, n-hexylamine and tributylphosphine prepared in the step b) into tetrahydrofuran, stirring for reaction under the protection of nitrogen, adding the reaction solution into n-hexane for precipitation and washing after the reaction is finished to obtain a solid product, and vacuum drying at 30-60 ℃ for 8-24 hours to obtain a mercapto-terminated PDMA-b-PHFBMA-SH amphiphilic block polymer;
(3)VO 2 preparation of PHFBMA-b-PDMA nanoparticles:
a) 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 30-60 ℃ for 12-24 hours to obtain VO 2 KH-570 nanometer powder;
b) VO is to be provided with 2 Ultra-dispersing KH-570 nano powder in tetrahydrofuran, adding the PDMA-b-PHFBMA-SH amphiphilic block polymer prepared in the step (2), stirring until the amphiphilic block polymer is fully dissolved, adding an initiator AIBN, reacting under the protection of nitrogen, centrifuging after the reaction is finished, washing with tetrahydrofuran, and vacuum drying the washed product at 30-60 ℃ for 12-24 hours to obtain VO 2 PHFBMA-b-PDMA nanoparticle.
4. A method as claimed in claim 3, further comprising one or more of the following technical features:
v in step (1) 2 O 5 The mass ratio of the deionized water to the deionized water is (1-7): (60-160);
v in step (1) 2 O 5 The mass ratio of the hydrazine hydrate to the hydrazine hydrate is (5-10): (1-5).
5. A method as claimed in claim 3, further comprising one or more of the following technical 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);
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);
in the step (2), the mass ratio of PDMA-DOPAT, hexafluorobutyl methacrylate and azodiisobutyronitrile in the step b) is (260-350): (150-240): (0.5-5);
in the step (2), the mass ratio of PDMA-DOPAT to tetrahydrofuran in the step b) is 1: (3-20);
in the step (2), the mass ratio of PDMA-b-PHFBMA-DOPAT, n-hexylamine and tributylphosphine in the step c) is (250-450): (45-90): (2-12).
6. A method as claimed in claim 3, further comprising one or more of the following technical features:
in the step (3), the mass ratio of the vanadium dioxide powder to the absolute ethyl alcohol in the step a) is (0.1-4): (60-120);
in the step (3), the mass ratio of the vanadium dioxide powder to the gamma- (methacryloyloxy) propyl trimethoxysilane in the step a) is (5-30): (0.5-3);
in step (3), VO in b) 2 The mass ratio of the KH-570 nano powder to the tetrahydrofuran is (0.1-10): (60-120).
7. Use of VO according to claim 1 2 PHFBMA-b-PDMA nanoparticle or VO prepared by the method of any one of claims 2 to 6 2 The intelligent heat-insulating coating prepared by the PHFBMA-b-PDMA nano-particles is characterized by comprising the following preparation method: VO is to be provided with 2 Uniformly dripping the aqueous dispersion of the PHFBMA-b-PDMA nano particles into the aqueous resin, and stirring until the aqueous dispersion is uniform to obtainObtaining a system dispersion liquid; 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 The mass ratio of the aqueous dispersion of the PHFBMA-b-PDMA nano particles is (50-100): (40-60); VO (VO) 2 The mass percentage of the aqueous dispersion of the PHFBMA-b-PDMA nano particles is 1wt%.
9. The intelligent thermal insulation coating of claim 7, wherein VO 2 The dropping speed of the aqueous dispersion of the PHFBMA-b-PDMA nano particles is 0.5-2 mL/min.
CN202310972807.0A 2023-08-03 2023-08-03 VO 2 PHFBMA-b-PDMA nano-particle, preparation method and application Pending CN116970302A (en)

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