CN116212754A - Photoinitiated self-repairing microcapsule containing carbon quantum dots and preparation method thereof - Google Patents
Photoinitiated self-repairing microcapsule containing carbon quantum dots and preparation method thereof Download PDFInfo
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- CN116212754A CN116212754A CN202111462539.5A CN202111462539A CN116212754A CN 116212754 A CN116212754 A CN 116212754A CN 202111462539 A CN202111462539 A CN 202111462539A CN 116212754 A CN116212754 A CN 116212754A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000003094 microcapsule Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000011162 core material Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 68
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 36
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- 239000012952 cationic photoinitiator Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002736 nonionic surfactant Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract description 21
- 230000006378 damage Effects 0.000 abstract description 6
- 230000008439 repair process Effects 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002775 capsule Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000007850 fluorescent dye Substances 0.000 abstract description 2
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- VGHOWOWLIXPTOA-UHFFFAOYSA-N cyclohexane;toluene Chemical compound C1CCCCC1.CC1=CC=CC=C1 VGHOWOWLIXPTOA-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002073 fluorescence micrograph Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
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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
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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
- C09D7/65—Additives macromolecular
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
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- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention belongs to a photoinitiated self-repairing microcapsule containing carbon quantum dots and a preparation method thereof, belonging to the field of microcapsule self-repairing. The invention discloses a method for preparing a silicon oxide film by SiO 2 The invention relates to a photoinitiated self-repairing microcapsule with wall material, which takes epoxy resin, photoinitiator and carbon quantum dots as core materials, wherein the invention takes citric acid as carbon source to prepare oil-soluble carbon quantum dots, the carbon quantum dots are taken as fluorescent probes to be introduced into a mixture of epoxy resin, photoinitiator and tetraethyl orthosilicate as silicon source precursors, and the photoinitiated self-repairing microcapsule with carbon quantum dots is prepared by combining interface and in-situ polymerization, wherein the good fluorescence characteristic of the carbon quantum dots endows the microcapsule with damage tracing capability, namely, loaded microgelThe composite material of the capsule not only can self-repair the crack through the repair substance in the microcapsule, but also can display the damaged area through ultraviolet irradiation.
Description
Technical Field
The invention belongs to the field of microcapsule self-repairing, and particularly relates to a photoinitiated self-repairing microcapsule containing carbon quantum dots and a preparation method thereof.
Background
The coating material inevitably generates microcracks of different sizes on its surface or inside during service due to erosion by internal factors and external environment. These cracks (in the micrometer scale) are often difficult to detect, and in particular damage to the coating by external impacts can reduce not only the mechanical properties of the coating itself, but also the mechanical properties of the substrate.
Modern coating technology has evolved from simple primary substrate surface protection to intelligent coating technology with a variety of new functions, including self-healing, self-cleaning, and stimulus response. The self-repairing technology is helpful for autonomously repairing surface damage caused by external impact, so that the service life of the material is prolonged, but the self-repairing capability of the material is deteriorated with the lapse of time, and meanwhile, the self-repaired surface can not completely recover the integrity of the coating, so that the detection of the existence and the repairing position of cracks during self-repairing is very important for guiding the subsequent repairing work. Inspired by the organism not only being able to self-recover from injury, but also being able to self-report on the damaged area, researchers have studied smart composites with dual functions of self-repair and self-reporting.
Disclosure of Invention
In order to solve the defects in the prior art, the invention adopts the following technical scheme:
a photoinitiated self-repairing microcapsule containing carbon quantum dots is characterized in that the microcapsule is prepared by SiO 2 The wall material is made of epoxy resin, photoinitiator and carbon quantum dots as core materials.
Further, the carbon quantum dots are oil-soluble carbon quantum dots.
Further, the epoxy resin includes bisphenol a type epoxy resin and alicyclic epoxy resin;
further, the photoinitiator is a cationic photoinitiator.
Further, the carbon quantum dots account for 0.03-0.5 wt% of the epoxy resin and the photoinitiator.
A preparation method of a photoinitiated self-repairing microcapsule containing carbon quantum dots comprises the following steps:
(1) Dispersing carbon quantum dots in an organic solvent to obtain a carbon quantum dot dispersion liquid;
(2) Mixing epoxy resin, a photoinitiator, tetraethyl orthosilicate and carbon quantum dot dispersion liquid to form an oil phase mixture, adding an aqueous solution of a nonionic surfactant into the oil phase mixture, and emulsifying to form O/W emulsion;
(3) Adding hydrochloric acid solution 1 into the O/W emulsion in the step (2), stirring for reaction, and hydrolyzing and condensing tetraethyl orthosilicate in the oil phase on the surface of the oil phase under the action of hydrochloric acid to generate a layer of SiO 2 Thin shell, tetraethyl orthosilicate 1 and hydrochloric acid solution 2 are added, stirred and reacted, siO is obtained 2 SiO production is continued outside the thin shell 2 And (3) repeatedly adding the hydrochloric acid solution 3 into the shell layer to obtain the photoinitiated self-repairing microcapsule containing the carbon quantum dots.
Further, the carbon quantum dots in the step (1) are oil-soluble carbon quantum dots;
preferably, the organic solvent is one of cyclohexane or toluene;
preferably, the mass volume ratio of the carbon quantum dots to the organic solvent is 1-10:100 mg/mu L.
Further, the epoxy resin in step (2) includes bisphenol a type epoxy resin and alicyclic epoxy resin;
further, the photoinitiator is a cationic photoinitiator;
preferably, in the step (2), the mass ratio of the bisphenol a epoxy resin, the cycloaliphatic epoxy resin, the cationic photoinitiator, the tetraethyl orthosilicate and the carbon quantum dots is 1000:1000:600:600:1-10;
preferably, the bisphenol A type epoxy resin is E-51;
preferably, the cycloaliphatic epoxy resin is a1815;
preferably, the cationic photoinitiator is PI6992.
Further, the concentration of the nonionic surfactant aqueous solution in the step (2) is 18-19.5g/L;
preferably, the nonionic surfactant is F127;
preferably, the volume mass ratio of the nonionic surfactant aqueous solution to the oil phase mixture is 40:3.2mL/mg.
Further, the temperature of the stirring reaction in the step (3) is 50 ℃, and the rotating speed is 300-400rpm;
further, the time for adding the tetraethyl orthosilicate and the hydrochloric acid solution 2 is 3-5 hours after the reaction is started;
further, the time interval of repeatedly adding the hydrochloric acid solution 3 is 4 hours from the last time of adding the hydrochloric acid;
further, the repeated addition of hydrochloric acid solution 3 times is 2 times;
further, the repeated addition of the hydrochloric acid solution 3 is finished and then the reaction is continued for 12 hours;
further, the concentration of the hydrochloric acid solution is 2mol/L;
further, the volume of the hydrochloric acid solution 1 is 0.6-0.9mL, the volume of the hydrochloric acid solution 2 is 0.3-0.6mL, and the volume of the hydrochloric acid solution 3 is 0.6mL;
further, the volume of the tetraethyl orthosilicate 1 is 2-2.3mL.
Further, the emulsifying operation in the step (2) is as follows: the rotation speed was increased to 7000rpm at 500rpm, and the stirring time was 10min.
Further, the preparation method further comprises the preparation of the carbon quantum dots, and specifically comprises the following steps: grinding citric acid and hexadecylamine, heating to obtain a carbonized mixture, grinding and dispersing in water again, filtering, vacuum drying to obtain powder, dispersing in toluene cyclohexane as an organic solvent, centrifuging, taking supernatant, and rotary evaporating to obtain carbon quantum dots;
further, the organic solvent in which the carbon quantum dots are dispersed is selected from one of cyclohexane or toluene;
further, the mass volume ratio of the carbon quantum dots to the organic solvent is 1-10mg: 100. Mu.L;
further, after the carbon quantum dots are dispersed in the organic solvent, ultrasonic dispersion is carried out for 15-30min.
Further, the organic solvent is selected from one of toluene or cyclohexane;
further, the mass ratio of the citric acid to the hexadecylamine is 1.5:2.5;
further, the heating temperature of the obtained carbonized mixture is 160 ℃, and the heating time is 5 hours;
further, the filter membrane used in the filtration is a 0.22 μm filter membrane;
further, the temperature of the vacuum drying is 40 ℃ and the time is 48 hours;
further, the temperature of the centrifugation was 4 ℃, the centrifugation speed was 10000rpm, and the centrifugation time was 20min.
The beneficial effects obtained by the invention are as follows:
the invention discloses a method for preparing a silicon oxide film by SiO 2 The photoinitiated self-repairing microcapsule with carbon quantum dots takes epoxy resin, photoinitiator and carbon quantum dots as core materials as wall materials, and the photoinitiated self-repairing microcapsule is prepared by introducing the carbon quantum dots into a photoinitiated self-repairing microcapsule system for the first time. When the micro-crack microcapsule of the coating is mechanically broken, the repairing agent fills the micro-crack, the self-repairing of the crack can be realized after ultraviolet irradiation, meanwhile, the carbon quantum dots mixed into the capsule core as fluorescent probes can perform fluorescent indication on the crack, the position of the crack is distinguished, and the repaired coating is subjected to simple ultraviolet irradiationThe light irradiation can identify the damage region by observing the color of the damage region without using a color developer or an expensive catalyst.
Drawings
FIG. 1 is an SEM image of microcapsules;
fig. 2 is an SEM image of the coating repair effect of the microcapsules, (a) is the effect before repair, (b) is the effect after repair, and (c) is a fluorescence microscope image of cracks when the coating is applied to a glass slide.
Detailed Description
For a clearer understanding of the present invention, the present invention will now be further described with reference to the following examples and drawings. The examples are for illustration only and are not intended to limit the invention in any way. In the examples, each of the starting reagent materials is commercially available, and the experimental methods without specifying the specific conditions are conventional methods and conventional conditions well known in the art, or according to the conditions recommended by the instrument manufacturer.
Example 1:
(1) 1.5g of citric acid and 2.5g of hexadecylamine are taken and placed in a nickel crucible, and after being ground and uniformly mixed, the mixture is placed in a 160 ℃ oven for heating for 5 hours, and a carbonized mixture is obtained. Grinding, dispersing in distilled water, filtering with 0.22 μm filter membrane, and vacuum drying at 40deg.C for 24 hr; transferring the dried powder into toluene, centrifuging (10000 rpm) at 4 ℃ for 20min, obtaining supernatant which is toluene dispersion liquid containing carbon quantum dots, and obtaining carbon quantum dot solid after rotary evaporation.
(2) And adding 100 mu L of toluene into 1mg of the carbon quantum dots, and performing ultrasonic dispersion for 15min to obtain a dispersion liquid of the carbon quantum dots.
(3) 0.72g of a nonionic surfactant F127 was dissolved in 40mL of deionized water, followed by addition of an oil phase mixture composed of 1.0g of bisphenol A type epoxy resin (E-51), 1.0g of alicyclic epoxy resin (A1815), 0.6g of cationic photoinitiator (PI 6992), carbon quantum dots dispersed in toluene, and 0.6g of tetraethyl orthosilicate. Emulsifying by a high-speed homogenizer, slowly increasing the rotation speed to 7000rpm, and stirring for 10min to form uniform O/W emulsion. Subsequently, the O/W emulsion was transferred to a three-necked flask, 0.9mL of a diluted hydrochloric acid solution having a concentration of 2mol/L prepared in advance was added dropwise thereto, the temperature was raised to 50℃and the rotation speed was 300rpm, and the reaction was started. After 4h, 2.3mL of tetraethyl orthosilicate and 0.3mL of dilute hydrochloric acid solution were added dropwise. And then, dropwise adding 0.6mL of 2mol/L dilute hydrochloric acid solution every 4h for 2 times, continuing to react for 12h, washing with deionized water after the reaction is completed, and placing the obtained precipitate in a 60 ℃ oven for drying to obtain the photoinitiated self-repairing microcapsule containing the carbon quantum dots.
Example 2:
(1) 1.5g of citric acid and 2.5g of hexadecylamine are taken and placed in a nickel crucible, and after being ground and uniformly mixed, the mixture is placed in a 160 ℃ oven for heating for 5 hours, and a carbonized mixture is obtained. After grinding, dispersing in distilled water, filtering with a 0.22 μm filter membrane, and vacuum drying at 40℃for 24 hours. Transferring the dried powder into toluene, centrifuging (10000 rpm) at 4 ℃ for 20min, obtaining supernatant which is toluene dispersion liquid containing carbon quantum dots, and obtaining carbon quantum dot solid after rotary evaporation.
(2) And adding 3mg of carbon quantum dots into 100 mu L of cyclohexane, and performing ultrasonic dispersion for 15min to obtain a dispersion liquid of the carbon quantum dots.
(3) 0.74g of a nonionic surfactant F127 was dissolved in 40mL of deionized water, followed by addition of an oil phase mixture composed of 1.0g of bisphenol A type epoxy resin (E-51), 1.0g of alicyclic epoxy resin (A1815), 0.6g of cationic photoinitiator (PI 6992), carbon quantum dots dispersed in toluene, and 0.6g of tetraethyl orthosilicate. Emulsifying by a high-speed homogenizer, slowly increasing the rotation speed to 7000rpm, and stirring for 10min to form uniform O/W emulsion. Subsequently, the O/W emulsion was transferred to a three-necked flask, 0.9mL of a diluted hydrochloric acid solution having a concentration of 2mol/L prepared in advance was added dropwise thereto, the temperature was raised to 50℃and the rotation speed was 300rpm, and the reaction was started. After 4h, 2.3mL of tetraethyl orthosilicate and 0.3mL of dilute hydrochloric acid solution were added dropwise. And then, dropwise adding 0.6mL of 2mol/L dilute hydrochloric acid solution every 4h for 2 times, continuing to react for 12h, washing with deionized water after the reaction is completed, and placing the obtained precipitate in a 60 ℃ oven for drying to obtain the photoinitiated self-repairing microcapsule containing the carbon quantum dots.
Example 3:
(1) 1.5g of citric acid and 2.5g of hexadecylamine are taken and placed in a nickel crucible, and after being ground and uniformly mixed, the mixture is placed in a 160 ℃ oven for heating for 5 hours, and a carbonized mixture is obtained. After grinding, dispersing in distilled water, filtering with a 0.22 μm filter membrane, and vacuum drying at 40℃for 24 hours. Transferring the dried powder into toluene, centrifuging (10000 rpm) at 4 ℃ for 20min, obtaining supernatant which is toluene dispersion liquid containing carbon quantum dots, and obtaining carbon quantum dot solid after rotary evaporation.
(2) And adding 100 mu L of toluene into 5mg of the carbon quantum dots, and performing ultrasonic dispersion for 15min to obtain a dispersion liquid of the carbon quantum dots.
(3) 0.76g of a nonionic surfactant F127 was dissolved in 40mL of deionized water, followed by addition of an oil phase mixture composed of 1.0g of bisphenol A type epoxy resin (E-51), 1.0g of alicyclic epoxy resin (A1815), 0.6g of cationic photoinitiator (PI 6992), carbon quantum dots dispersed in toluene, and 0.6g of tetraethyl orthosilicate. Emulsifying by a high-speed homogenizer, slowly increasing the rotation speed to 7000rpm, and stirring for 10min to form uniform O/W emulsion. Subsequently, the O/W emulsion was transferred to a three-necked flask, 0.9mL of a diluted hydrochloric acid solution having a concentration of 2mol/L prepared in advance was added dropwise thereto, the temperature was raised to 50℃and the rotation speed was 300rpm, and the reaction was started. After 4h, 2.3mL of tetraethyl orthosilicate and 0.3mL of dilute hydrochloric acid solution were added dropwise. And then, dropwise adding 0.6mL of 2mol/L dilute hydrochloric acid solution every 4h for 2 times, continuing to react for 12h, washing with deionized water after the reaction is completed, and placing the obtained precipitate in a 60 ℃ oven for drying to obtain the photoinitiated self-repairing microcapsule containing the carbon quantum dots.
Example 4:
(1) 1.5g of citric acid and 2.5g of hexadecylamine are taken and placed in a nickel crucible, and after being ground and uniformly mixed, the mixture is placed in a 160 ℃ oven for heating for 5 hours, and a carbonized mixture is obtained. After grinding, dispersing in distilled water, filtering with a 0.22 μm filter membrane, and vacuum drying at 40℃for 24 hours. Transferring the dried powder into toluene, centrifuging (10000 rpm) at 4 ℃ for 20min, obtaining supernatant which is toluene dispersion liquid containing carbon quantum dots, and obtaining carbon quantum dot solid after rotary evaporation.
(2) Taking 10mg of carbon quantum dots, adding 100 mu L of cyclohexane, and performing ultrasonic dispersion for 15min to obtain a dispersion liquid of the carbon quantum dots.
(3) 0.78g of nonionic surfactant F127 was dissolved in 40mL of deionized water. An oil phase mixture of 1.0g bisphenol A type epoxy resin (E-51), 1.0g alicyclic epoxy resin (A1815), 0.6g cationic photoinitiator (PI 6992), carbon quantum dots dispersed in toluene, and 0.6g tetraethyl orthosilicate was added. Emulsifying by a high-speed homogenizer, slowly increasing the rotation speed to 7000rpm, and stirring for 10min to form uniform O/W emulsion. Subsequently, the O/W emulsion was transferred to a three-necked flask, 0.9mL of a diluted hydrochloric acid solution having a concentration of 2mol/L prepared in advance was added dropwise thereto, the temperature was raised to 50℃and the rotation speed was 300rpm, and the reaction was started. After 4h, 2.3mL of tetraethyl orthosilicate and 0.3mL of dilute hydrochloric acid solution were added dropwise. Then, 0.6mL of 2mol/L dilute hydrochloric acid solution was added dropwise every 4 hours, and the reaction was continued for 12 hours 2 times. And after the reaction is completed, washing the reaction product by using deionized water, and placing the obtained precipitate in a 60 ℃ oven for drying to obtain the photoinitiated self-repairing microcapsule containing the carbon quantum dots.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. A photoinitiated self-repairing microcapsule containing carbon quantum dots is characterized in that the microcapsule is prepared by SiO 2 The wall material is made of epoxy resin, photoinitiator and carbon quantum dots as core materials.
2. The carbon quantum dot-containing photoinitiated self-healing microcapsule according to claim 1, wherein the carbon quantum dot is an oil-soluble carbon quantum dot.
3. The carbon quantum dot-containing photoinitiated self-healing microcapsule according to claim 1, wherein the epoxy resin comprises bisphenol a type epoxy resin and cycloaliphatic epoxy resin;
the photoinitiator is a cationic photoinitiator.
4. The carbon quantum dot-containing photoinitiated self-healing microcapsule according to claim 1, wherein the carbon quantum dot is present in an amount of 0.03wt% to 0.5wt% in the epoxy resin and photoinitiator.
5. The preparation method of the photoinitiated self-repairing microcapsule containing the carbon quantum dots is characterized by comprising the following steps of:
(1) Dispersing carbon quantum dots in an organic solvent to obtain a carbon quantum dot dispersion liquid;
(2) Mixing epoxy resin, a photoinitiator, tetraethyl orthosilicate and carbon quantum dot dispersion liquid to form an oil phase mixture, adding an aqueous solution of a nonionic surfactant into the oil phase mixture, and emulsifying to form O/W emulsion;
(3) Adding hydrochloric acid solution 1 into the O/W emulsion in the step (2), stirring for reaction, and hydrolyzing and condensing tetraethyl orthosilicate in the oil phase on the surface of the oil phase under the action of hydrochloric acid to generate a layer of SiO 2 Thin shell, adding tetraethyl orthosilicate 1 and hydrochloric acid solution 2, continuing the reaction, and adding SiO 2 SiO production is continued outside the thin shell 2 And continuing the reaction of the shell layer, repeatedly adding the hydrochloric acid solution 3, and reacting to obtain the photoinitiated self-repairing microcapsule containing the carbon quantum dots.
6. The method of claim 5, wherein the carbon quantum dots in step (1) are oil-soluble carbon quantum dots;
preferably, the organic solvent is selected from one of cyclohexane or toluene;
preferably, the mass volume ratio of the carbon quantum dots to the organic solvent is 1-10:100 mg/mu L.
7. The method of claim 5, wherein the epoxy resin in step (2) comprises bisphenol a epoxy resin and cycloaliphatic epoxy resin;
the photoinitiator is a cationic photoinitiator;
preferably, in the step (2), the mass ratio of the bisphenol a epoxy resin, the cycloaliphatic epoxy resin, the cationic photoinitiator, the tetraethyl orthosilicate and the carbon quantum dots is 1000:1000:600:600:1-10;
preferably, the bisphenol A type epoxy resin is E-51;
preferably, the cycloaliphatic epoxy resin is a1815;
preferably, the cationic photoinitiator is PI6992.
8. The method according to claim 5, wherein the concentration of the nonionic surfactant aqueous solution in the step (2) is 18 to 19.5g/L;
preferably, the nonionic surfactant is F127;
preferably, the volume mass ratio of the nonionic surfactant aqueous solution to the oil phase mixture is 40:3.2mL/g.
9. The process according to claim 5, wherein the temperature of the stirring reaction in the step (3) is 50℃and the rotation speed is 300 to 400rpm;
the time for adding the tetraethyl orthosilicate and the hydrochloric acid solution 2 is 3-5 hours after the reaction is started;
the time for adding the hydrochloric acid solution 3 is 4 hours after the tetraethyl orthosilicate and the hydrochloric acid solution 2 are added;
the time interval of repeatedly adding the hydrochloric acid solution 3 is 4 hours from the last time of adding the hydrochloric acid;
the repeated addition of hydrochloric acid solution is carried out for 3 times for 2 times;
the repeated addition of the hydrochloric acid solution 3 is finished and then the reaction is continued for 12 hours;
the concentration of the hydrochloric acid solution is 2mol/L;
the volume of the hydrochloric acid solution 1 is 0.6-0.9mL, the volume of the hydrochloric acid solution 2 is 0.3-0.6mL, and the volume of the hydrochloric acid solution 3 is 0.6mL;
the volume of the tetraethyl orthosilicate 1 is 2-2.3mL.
10. A method according to claim 3, wherein the emulsification operation in step (2) is: the rotation speed was increased to 7000rpm at 500rpm, and the stirring time was 10min.
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