CN108892407B - Double-shell epoxy resin microcapsule self-repairing material and preparation method thereof - Google Patents
Double-shell epoxy resin microcapsule self-repairing material and preparation method thereof Download PDFInfo
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
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Abstract
The invention belongs to the technical field of microcapsule self-repairing material preparation, and particularly relates to a double-shell epoxy resin microcapsule self-repairing material and a preparation method thereof, wherein the microcapsule self-repairing material adopts epoxy resin as a repairing agent core material, firstly, a single-shell microcapsule self-repairing material with melamine-urea-formaldehyde resin as an inner wall material is prepared by an in-situ polymerization method, and then, a double-shell microcapsule self-repairing material with inorganic SiO2 polymer as an outer wall material is prepared by a sol-gel method; the graphene oxide is used as the epoxy resin emulsifier, and compared with the traditional emulsifier, the epoxy resin emulsifier has the characteristics of no toxicity and environmental protection; the invention utilizes the good biocompatibility and the excellent acid and alkali resistance of the inorganic SiO2 polymer as the outer wall material to improve the compatibility of the microcapsule self-repairing material and the cement concrete material, so that the microcapsule self-repairing material can better exert the self-repairing performance in the cement concrete material.
Description
Technical Field
The invention belongs to the technical field of microcapsule self-repairing material preparation, and particularly relates to a double-shell epoxy resin microcapsule self-repairing material and a preparation method thereof.
Background
The concrete material is a main structural material in infrastructure construction in China, but due to the fact that the concrete material is high in brittleness, micro cracks can be generated in the long-term service process, and if the micro cracks are not repaired in time, the micro cracks can be developed into macro visible cracks, and structural durability of the concrete material is affected. The epoxy resin is a polymer material with good repairing performance, and is microencapsulated and embedded into the cement concrete material, so that when cracks appear in the cement concrete material, the microcapsule material can crack under the stress action generated by the cracks, the repairing agent flows out, and the repairing of the micro cracks of the cement concrete material is achieved.
At present, urea resin or melamine-formaldehyde resin is used as a wall material to coat epoxy resin by an in-situ polymerization method, so that a core-shell structure microcapsule self-repairing material with excellent coating performance and epoxy resin as a core material can be formed. The urea-formaldehyde resin or melamine-formaldehyde resin polymer wall material has poor acid and alkali resistance, so that the wall material has poor stability in the alkaline environment of cement concrete for a long time, and the organic wall material and the cement-based material have poor compatibility, thereby bringing adverse effects to the stability of the wall material in the cement-based material for a long time. SiO22The microcapsule wall material has good biocompatibility, excellent acid and alkali resistance and chemical stability, and good compatibility with cement-based materials, and is a good substitute material for organic microcapsule wall materials. Therefore, by using the inorganic wall material coating technology, through SiO2The wall material carries out secondary coating on the organic wall material microcapsule epoxy resin self-repairing material, so that the microcapsule self-repairing material with good compatibility with the cement concrete material can be prepared, the microcapsule self-repairing material is easier to combine with the cement concrete material, and the repairing performance of the epoxy resin microcapsule self-repairing material is better exerted.
At present, Chinese patent CN104772086A discloses an epoxy resin microcapsule and a preparation method thereof; epoxy resin is mainly used as a capsule core raw material, inorganic particles for adsorbing a curing agent are used as a capsule wall raw material, the capsule core and the capsule wall materials are dispersed in an aqueous solution, and the adsorption of the capsule core materials to the inorganic particles and the curing agent are utilized to initiate the polymerization reaction on the surface of the capsule core under proper conditions, so that the epoxy microcapsule with the epoxy resin film and the inorganic particles as the capsule wall components is formed. The preparation method of the microcapsule has the characteristics of high yield, simple process, low cost, no solvent volatilization and the like, and the synthesized microcapsule has excellent heat resistance and potential value in the field of self-repairing materials.
Disclosure of Invention
In order to overcome the defects of the prior art,the invention aims to provide a preparation method of a double-shell epoxy resin microcapsule self-repairing material, which comprises the steps of coating epoxy resin with melamine-urea-formaldehyde resin to form the epoxy resin microcapsule self-repairing material with a core-shell structure by an in-situ polymerization method, and hydrolyzing tetraethyl orthosilicate by a sol-gel method to generate SiO through polymerization2The inorganic polymer is used as an outer wall material to prepare the double-shell epoxy resin microcapsule self-repairing material, so that the prepared epoxy resin microcapsule self-repairing material has better acid and alkali resistance and better compatibility with inorganic cement concrete materials, and the repairing performance of the microcapsule self-repairing material in cement-based materials is better exerted.
Aiming at the problems, the invention provides a double-shell epoxy resin microcapsule self-repairing material and a preparation method thereof. According to the method, graphene oxide is used as an epoxy resin emulsifier, the graphene oxide has a large specific surface area, the structure contains rich oxygen-containing hydrophilic groups, and the amphiphilic property of the graphene oxide enables the graphene oxide to be used as the epoxy resin emulsifier, while the traditional epoxy resin emulsifier (such as sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, Span80, Tween80, glyceryl stearate and the like) often has certain toxicity and is difficult to degrade, and a large amount of graphene oxide is used to cause serious environmental pollution. Therefore, the graphene oxide is used as the epoxy resin emulsifier, so that the excellent dispersion effect can be achieved under the condition of a small mixing amount, and the problem of environmental pollution is avoided.
In order to achieve the purpose, the method is realized by the following technical scheme:
the preparation process comprises two stages of preparation of the single-shell epoxy resin microcapsule self-repairing material and preparation of the double-shell microcapsule self-repairing material, wherein the preparation process of the single-shell microcapsule self-repairing material comprises the following three steps:
(1) mixing a graphene oxide emulsifier, epoxy resin and a diluent, dropwise adding deionized water, emulsifying, shearing and stirring at 2000-4000 r/min to obtain uniform and stable epoxy resin emulsion, and adjusting the pH value of the emulsion to 3-4 by using an acidic regulator;
(2) mixing and stirring melamine, urea, formaldehyde and deionized water uniformly to obtain a low-molecular-weight water-soluble prepolymer solution, obtaining an aqueous solution prepolymer solution, and adjusting the pH value of the mixed solution to 9-10 by using an alkaline regulator;
(3) slowly dripping a low-molecular-weight water-soluble prepolymer solution into the epoxy resin emulsion, stirring for 1-2 hours, slowly dripping an acid regulator, adjusting the pH of the mixed solution to 2-3, continuously stirring for 2 hours to obtain a microcapsule phase change material suspension, and filtering, washing and drying the suspension to obtain the single-shell epoxy resin microcapsule self-repairing material taking melamine-urea-formaldehyde resin as a wall material.
Preferably, the graphene oxide used is an aqueous graphene oxide dispersion prepared by a Hummers method, the GO content is 7.4g/L, the thickness of the lamella is about 1.027nm, and the length and width are about 600 nm.
Preferably, the epoxy resin emulsion is composed of the following raw materials in parts by weight: 100 parts of epoxy resin, 8-15 parts of diluent, 10-15 parts of graphene oxide aqueous solution and 150-300 parts of deionized water, wherein the low-molecular-weight water-soluble prepolymer solution is composed of 15-60 parts of melamine, 45-180 parts of urea and 125-500 parts of formaldehyde solution.
Preferably, the epoxy resin is composed of one or more of epoxy vinyl ester resin, glycidyl epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol a type epoxy resin, polyfunctional glycidyl ether resin, amino epoxy resin, glycidyl ester type epoxy resin, epoxidized olefin, novolac epoxy vinyl ester resin.
Preferably, the diluent is composed of one or more of acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, n-butanol, styrene, butyl glycidyl ether, ethylene glycol glycidyl ether and diethylene glycol glycidyl ether, and the doping amount is 8-15% of the mass of the epoxy resin.
A double-shell epoxy resin microcapsule self-repairing material and a preparation method thereof are provided, the double-shell microcapsule self-repairing material is prepared on the basis of the preparation of the single-shell microcapsule self-repairing material, and the preparation process comprises the following two steps:
(1) weighing a certain amount of tetraethyl orthosilicate, deionized water and absolute ethyl alcohol, adding a certain amount of alkaline regulator to regulate the pH value to 10, fully stirring to hydrolyze the tetraethyl orthosilicate, and uniformly mixing the prepared microcapsule self-repairing material with a hexadecyl trimethyl ammonium bromide aqueous solution with the mass fraction of 2% according to the mass ratio of 1:3 to uniformly disperse microcapsule particles in the aqueous solution;
(2) adding the tetraethyl orthosilicate hydrolysate into the microcapsule dispersion liquid, fully stirring for 24 hours, washing, filtering and drying the obtained solid powder to obtain the inorganic polymer SiO taking the melamine-urea-formaldehyde resin as the inner wall material and the inorganic polymer2Is a double-shell microcapsule self-repairing material of an outer-layer wall material.
Preferably, the alkaline regulator is any one of an aqueous ammonia solution and a silane coupling agent.
Preferably, the double-shell microcapsule self-repairing material comprises the following raw materials in parts by weight: 100 parts of tetraethyl orthosilicate, 50-200 parts of deionized water, 50-200 parts of absolute ethyl alcohol, 10-20 parts of alkaline regulator, 30-100 parts of single-shell epoxy resin microcapsule self-repairing material and 100 parts of hexadecyl trimethyl ammonium bromide aqueous solution.
Preferably, the silane coupling agent is one or more of vinyl silane, amino silane, epoxy silane, mercapto silane and methacryloxy silane.
By adopting the technical scheme, the invention has the following beneficial effects:
(1) the graphene oxide is used as an emulsifier, is an oxide of graphene, has a layered structure, and has excellent mechanical, acoustic, optical and electrical properties. After oxidation treatment, the graphene oxide contains rich oxygen-containing functional groups such as hydroxyl, carboxyl, carbonyl, epoxy and the like, so that the graphene oxide is more active in chemical property than graphene, shows hydrophilic and hydrophobic amphiphilic performances, has excellent dispersibility in water, and can be used as an amphiphilic surfactant;
(2) according to the invention, the melamine-urea-formaldehyde resin is used as an inner wall material, and the epoxy resin is coated by using an organic wall material, so that the epoxy resin microcapsule self-repairing material with compact structure and excellent coating performance is obtained; with SiO2As an outer-layer wall material, the problem of poor compatibility of the traditional single organic-wall material microcapsule self-repairing material and a cement-based material is solved, and secondly, the outer-layer SiO is2The inorganic polymer wall material has good chemical stability and thermal stability, has better compatibility with matrix media (cement, concrete and the like), and enables the microcapsule self-repairing material to be better compounded in a cement-based material.
Drawings
FIG. 1-1 is SEM photograph of self-repairing material of melamine-urea-formaldehyde resin single-shell epoxy resin microcapsule prepared in example 1 of the present invention, and FIG. 1-2 is SEM photograph of self-repairing material prepared in example 1 of the present invention and prepared by using melamine-urea-formaldehyde resin inner shell layer and inorganic SiO2SEM (scanning electron microscope) picture of double-shell microcapsule self-repairing material with polymer as shell;
FIG. 2-1 is a SEM photograph of a melamine-urea-formaldehyde resin single-shell epoxy resin microcapsule self-repairing material prepared in example 2 of the present invention, and FIG. 2-2 is a SEM photograph of an inorganic SiO solid solution prepared in example 2 of the present invention, in which the melamine-urea-formaldehyde resin is used as an inner shell layer2SEM (scanning electron microscope) picture of double-shell microcapsule self-repairing material with polymer as shell;
FIG. 3-1 is a SEM photograph of a melamine-urea-formaldehyde resin single-shell epoxy resin microcapsule self-repairing material prepared in example 3 of the present invention, and FIG. 3-2 is a SEM photograph of an inorganic SiO solid solution prepared in example 3 of the present invention, in which the melamine-urea-formaldehyde resin is used as an inner shell layer2SEM (scanning electron microscope) picture of double-shell microcapsule self-repairing material with polymer as shell;
FIG. 4-1 is a SEM photograph of a melamine-urea-formaldehyde resin single-shell epoxy resin microcapsule self-repairing material prepared in example 4 of the present invention, and FIG. 4-2 is a SEM photograph of a melamine-urea-formaldehyde resin prepared in example 4 of the present invention as an inner shell layer and inorganic SiO2Double-shell microcapsule self-repairing material SEM taking polymer as shellA photo;
FIG. 5 shows a core material of epoxy resin, a single-layer shell of melamine-urea-formaldehyde resin, and inorganic SiO prepared in example 1 of the present invention2FTIR spectra of the polymer shell double-shell microcapsule self-repairing material. The characteristic peaks at 1469.1cm-1 and 1517.6 cm-1 are C-C stretching vibration peaks on a benzene ring, and the special vibration peaks at 822.1cm-1 and 961.8cm-1 are epoxy groups, so that the existence of the epoxy resin is proved; the peak at 460.3cm-1 is the bending vibration peak of Si-O-Si, indicating SiO2Presence of (a); the peak in the range of 2929.4-2963.2 cm-1 is a symmetric stretching vibration peak of C-H, and the strong absorption peaks at 3429.4cm-1 are stretching vibration peaks of N-H and O-H, so that the existence of melamine-formaldehyde-urea-formaldehyde resin is proved. Thus, the description shows that the epoxy resin is coated with melamine-formaldehyde-urea-formaldehyde resin and inorganic SiO2The polymer is coated well, and the microcapsule self-repairing material with a double-shell structure is formed.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1:
a double-shell epoxy resin microcapsule self-repairing material and a preparation method thereof comprise the following steps:
(1) emulsifying, shearing and stirring 30g of bisphenol A epoxy resin (E51), 4.5g of butyl glycidyl ether and 15ml of graphene oxide aqueous dispersion at the water bath temperature of 80 ℃ at 3000r/min for 30min, dripping 60ml of deionized water in the process to form epoxy resin emulsion, and adjusting the pH value of the emulsion to 3-4 by using 10% citric acid solution in mass concentration;
(2) mixing 4g of melamine, 8g of urea and 27g of formaldehyde solution, magnetically stirring at 70 ℃ water bath temperature, adjusting the pH value of a mixed solution system to 9-10 by using 10% sodium hydroxide solution, adding 30ml of deionized water, and stirring for 1h to obtain a viscous and transparent urea-formaldehyde prepolymer, thereby generating a low-molecular-weight water-soluble prepolymer solution;
(3) pouring the emulsion into a three-neck flask, dripping the prepared prepolymer solution into the three-neck flask at the water bath temperature of 70 ℃, mixing and stirring for 1h, adding a 10 mass percent hydrochloric acid solution to adjust the pH value of the system to 2-3 to obtain a microcapsule phase change material suspension, filtering, washing and drying the suspension to obtain the single-shell epoxy resin microcapsule self-repairing material with melamine-urea-formaldehyde resin as the wall material;
(4) mixing 10g of tetraethyl orthosilicate, 40g of deionized water and 40ml of absolute ethyl alcohol, adding an epoxy silane coupling agent KH560 to adjust the pH value to 10-11, and magnetically stirring for 30min at the temperature of 35 ℃ to fully hydrolyze the tetraethyl orthosilicate to form silica sol; mixing and stirring 40g of the prepared single-shell epoxy resin microcapsule self-repairing material and 120g of hexadecyl trimethyl ammonium bromide solution for 30min to form microcapsule phase change material dispersion liquid, dripping the prepared silica sol into the dispersion liquid, fully stirring for 24h, washing, filtering and drying the obtained solid powder to obtain the inorganic polymer SiO with the melamine-urea-formaldehyde resin as the inner wall material and the melamine-urea-formaldehyde resin as the inner wall material2Is a double-shell microcapsule self-repairing material of an outer-layer wall material.
Example 2:
a double-shell epoxy resin microcapsule self-repairing material and a preparation method thereof comprise the following steps:
(1) emulsifying, shearing and stirring 20g of bisphenol A epoxy resin (E44), 2.4g of butyl glycidyl ether and 15ml of graphene oxide aqueous dispersion at the water bath temperature of 85 ℃ at 2000r/min for 30min, dripping 60ml of deionized water in the process to form epoxy resin emulsion, and adjusting the pH value of the emulsion to 3-4 by using 10% hydrochloric acid in mass concentration;
(2) mixing 3g of melamine, 9g of urea and 27g of formaldehyde solution, magnetically stirring at 70 ℃ water bath temperature, adjusting the pH value of a mixed solution system to 9-10 by using 10% triethanolamine solution, adding 30ml of deionized water, and stirring for 1h to obtain a viscous and transparent urea-formaldehyde prepolymer, thereby generating a low-molecular-weight water-soluble prepolymer solution;
(3) pouring the emulsion into a three-neck flask, dripping the prepared prepolymer solution into the three-neck flask at 70 ℃ water bath temperature, mixing and stirring for 1h, adding 10% acetic acid solution with mass concentration to adjust the pH value of the system to 2-3 to obtain microcapsule phase change material suspension, filtering, washing and drying the suspension to obtain the single-shell epoxy resin microcapsule self-repairing material with melamine-urea-formaldehyde resin as the wall material;
(4) mixing 10g of tetraethyl orthosilicate, 20g of deionized water and 20g of absolute ethyl alcohol, adding an ammonia water solution to adjust the pH value to 10-11, and magnetically stirring at the temperature of 35 ℃ for 30min to fully hydrolyze the tetraethyl orthosilicate to form silica sol; mixing and stirring 20g of the prepared single-shell epoxy resin microcapsule self-repairing material and 60g of hexadecyl trimethyl ammonium bromide solution for 30min to form microcapsule phase change material dispersion liquid, dripping the prepared silica sol into the dispersion liquid, fully stirring for 24h, washing, filtering and drying the obtained solid powder to obtain the inorganic polymer SiO with the melamine-urea-formaldehyde resin as an inner wall material and the melamine-urea-formaldehyde resin as an inner wall material2Is a double-shell microcapsule self-repairing material of an outer-layer wall material.
Example 3:
a double-shell epoxy resin microcapsule self-repairing material and a preparation method thereof comprise the following steps:
(1) emulsifying, shearing and stirring 10g of bisphenol A epoxy resin (E51), 1.5g of butyl glycidyl ether and 15ml of graphene oxide aqueous dispersion at the water bath temperature of 75 ℃ for 30min at 4000r/min, dripping 60ml of deionized water in the process to form epoxy resin emulsion, and adjusting the pH value of the emulsion to 3-4 by using a 10 mass percent citric acid solution;
(2) mixing 2g of melamine, 10g of urea and 27g of formaldehyde solution, magnetically stirring at 70 ℃ water bath temperature, adjusting the pH value of a mixed solution system to 9-10 by using 10% sodium carbonate solution, adding 30ml of deionized water, and stirring for 1h to obtain a viscous and transparent urea-formaldehyde prepolymer so as to generate a low-molecular-weight water-soluble prepolymer solution;
(3) pouring the emulsion into a three-neck flask, dripping the prepared prepolymer solution into the three-neck flask at the water bath temperature of 70 ℃, mixing and stirring for 1h, adding a 10 mass percent hydrochloric acid solution to adjust the pH value of the system to 2-3 to obtain a microcapsule phase change material suspension, filtering, washing and drying the suspension to obtain the single-shell epoxy resin microcapsule self-repairing material with melamine-urea-formaldehyde resin as the wall material;
(4) mixing 10g of tetraethyl orthosilicate, 10g of deionized water and 10g of absolute ethyl alcohol, adding an amino functional group silane coupling agent KH550 to adjust the pH value to 10-11, and magnetically stirring for 30min at the temperature of 35 ℃ to fully hydrolyze the tetraethyl orthosilicate to form silica sol; mixing and stirring 10g of the prepared single-shell epoxy resin microcapsule self-repairing material and 30g of hexadecyl trimethyl ammonium bromide solution for 30min to form microcapsule phase change material dispersion liquid, dripping the prepared silica sol into the dispersion liquid, fully stirring for 24h, washing, filtering and drying the obtained solid powder to obtain the inorganic polymer SiO with the melamine-urea-formaldehyde resin as an inner wall material and the melamine-urea-formaldehyde resin as an inner wall material2Is a double-shell microcapsule self-repairing material of an outer-layer wall material.
Example 4:
a double-shell epoxy resin microcapsule self-repairing material and a preparation method thereof comprise the following steps:
(1) emulsifying, shearing and stirring 5g of bisphenol F type epoxy resin (NPEF-170), 0.5g of butyl glycidyl ether and 15ml of graphene oxide aqueous dispersion at the water bath temperature of 75 ℃ at 3000r/min for 30min, dripping 60ml of deionized water in the process to form epoxy resin emulsion, and adjusting the pH value of the emulsion to 3-4 by using 10% citric acid solution in mass concentration;
(2) mixing 4g of melamine, 8g of urea and 27g of formaldehyde solution, magnetically stirring at 70 ℃ water bath temperature, adjusting the pH value of a mixed solution system to 9-10 by using 10% sodium hydroxide solution, adding 30ml of deionized water, and stirring for 1h to obtain a viscous and transparent urea-formaldehyde prepolymer, thereby generating a low-molecular-weight water-soluble prepolymer solution;
(3) pouring the emulsion into a three-neck flask, dripping the prepared prepolymer solution into the three-neck flask at 70 ℃ water bath temperature, mixing and stirring for 1h, adding a citric acid solution with the mass concentration of 10% to adjust the pH value of the system to 2-3 to obtain a microcapsule phase change material suspension, and filtering, washing and drying the suspension to obtain the single-shell epoxy resin microcapsule self-repairing material with the melamine-urea-formaldehyde resin as the wall material;
(4) mixing 10g of tetraethyl orthosilicate, 10g of deionized water and 10g of absolute ethyl alcohol, adding a vinyltrimethoxysilane coupling agent A171 to adjust the pH value to 10-11, and magnetically stirring for 30min at the temperature of 35 ℃ to fully hydrolyze the tetraethyl orthosilicate to form silica sol; mixing and stirring 2.5g of the prepared single-shell epoxy resin microcapsule self-repairing material and 7.5g of hexadecyl trimethyl ammonium bromide solution for 30min to form microcapsule phase-change material dispersion liquid, dripping the prepared silica sol into the dispersion liquid, fully stirring for 24h, washing, filtering and drying the obtained solid powder to obtain the inorganic polymer SiO and the melamine-urea-formaldehyde resin which are used as inner-layer wall materials2Is a double-shell microcapsule self-repairing material of an outer-layer wall material.
The above examples are intended only to illustrate the technical solution of the invention, and not to limit it; although the invention of the present application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (7)
1. The preparation method of the double-shell epoxy resin microcapsule self-repairing material is characterized in that the preparation process comprises two stages of preparation of the single-shell epoxy resin microcapsule self-repairing material and preparation of the double-shell microcapsule self-repairing material, wherein the preparation process of the single-shell microcapsule self-repairing material comprises the following three steps:
(1) the epoxy resin emulsion comprises the following raw materials in parts by weight: 100 parts of epoxy resin, 8-15 parts of diluent, 10-15 parts of graphene oxide aqueous solution and 150 parts of deionized water; mixing a graphene oxide emulsifier, epoxy resin and a diluent, dropwise adding deionized water, emulsifying, shearing and stirring at 2000-4000 r/min to obtain uniform and stable epoxy resin emulsion, and adjusting the pH value of the emulsion to 3-4 by using an acidic regulator;
(2) mixing and stirring melamine, urea, formaldehyde and deionized water uniformly to obtain a low-molecular-weight water-soluble prepolymer solution to obtain an aqueous solution prepolymer solution, and adjusting the pH value of the mixed solution to 9-10 by using an alkaline regulator, wherein the low-molecular-weight water-soluble prepolymer solution is composed of 15-60 parts of melamine, 45-180 parts of urea and 125-500 parts of formaldehyde solution;
(3) slowly dripping a low-molecular-weight water-soluble prepolymer solution into the epoxy resin emulsion, stirring for 1-2 hours, slowly dripping an acid regulator, adjusting the pH of the mixed solution to 2-3, continuously stirring for 2 hours to obtain a microcapsule phase change material suspension, filtering, washing and drying the suspension to obtain a single-shell epoxy resin microcapsule self-repairing material taking melamine-urea-formaldehyde resin as a wall material;
on the basis of the preparation of the single-shell microcapsule self-repairing material, the double-shell microcapsule self-repairing material is prepared, and comprises the following raw materials in parts by weight: 100 parts of tetraethyl orthosilicate, 50-200 parts of deionized water, 50-200 parts of absolute ethyl alcohol, 10-20 parts of alkaline regulator, 30-100 parts of single-shell epoxy resin microcapsule self-repairing material and 100 parts of hexadecyl trimethyl ammonium bromide aqueous solution; the preparation process comprises the following two steps:
(1) weighing a certain amount of tetraethyl orthosilicate, deionized water and absolute ethyl alcohol, adding a certain amount of alkaline regulator to regulate the pH value to 10, fully stirring to hydrolyze the tetraethyl orthosilicate, and uniformly mixing the prepared microcapsule self-repairing material with a hexadecyl trimethyl ammonium bromide aqueous solution with the mass fraction of 2% according to the mass ratio of 1:3 to uniformly disperse microcapsule particles in the aqueous solution;
（2) Adding the tetraethyl orthosilicate hydrolysate into the microcapsule dispersion liquid, fully stirring for 24 hours, washing, filtering and drying the obtained solid powder to obtain the inorganic polymer SiO taking the melamine-urea-formaldehyde resin as the inner wall material and the inorganic polymer2Is a double-shell microcapsule self-repairing material of an outer-layer wall material.
2. The preparation method of the double-shell epoxy resin microcapsule self-repairing material as claimed in claim 1, wherein the graphene oxide used is graphene oxide aqueous dispersion prepared by Hummers method, GO content is 7.4g/L, thickness of lamella is about 1.027nm, length and width are about 600 nm.
3. The method for preparing the double-shell epoxy resin microcapsule self-repairing material as claimed in claim 1, wherein the epoxy resin is composed of one or more of epoxy vinyl ester resin, glycidyl epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, multifunctional glycidyl ether resin, amino epoxy resin, glycidyl ester type epoxy resin, epoxidized olefin and novolac epoxy vinyl ester resin.
4. The preparation method of the double-shell epoxy resin microcapsule self-repairing material as claimed in claim 1, wherein the diluent is composed of one or more of acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, n-butanol, styrene, butyl glycidyl ether, ethylene glycol glycidyl ether and diethylene glycol glycidyl ether, and the doping amount is 8-15% of the mass of the epoxy resin.
5. The preparation method of the double-shell epoxy resin microcapsule self-repairing material as claimed in claim 1, wherein the acid regulator is any one of a hydrochloric acid solution, an acetic acid solution and a citric acid solution with a mass concentration of 10%.
6. The preparation method of the double-shell epoxy resin microcapsule self-repairing material as claimed in claim 1, wherein the alkaline regulator is any one of an ammonia solution or a silane coupling agent.
7. The preparation method of the double-shell epoxy resin microcapsule self-repairing material as claimed in claim 6, wherein the silane coupling agent is one or more of vinyl silane, amino silane, epoxy silane, mercapto silane and methacryloxy silane.
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| CN117645430A (en) * | 2023-11-30 | 2024-03-05 | 吉林省水利科学研究院(吉林省水利科技推广总站、吉林省水利水电工程质量检测中心、吉林省灌溉试验中心站) | Double microcapsule preparation method for self-repairing concrete freeze-thawing damage |
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