CN108947319B

CN108947319B - Externally-repaired and internally-fixed self-repairing microcapsule with cellular structure and preparation method thereof

Info

Publication number: CN108947319B
Application number: CN201810838496.8A
Authority: CN
Inventors: 马衍轩; 张颖锐; 徐亚茜; 张建鑫; 张群; 王晓慧; 吴睿; 乔广轩
Original assignee: Qingdao University of Technology
Current assignee: Qingdao University of Technology
Priority date: 2018-07-27
Filing date: 2018-07-27
Publication date: 2021-01-15
Anticipated expiration: 2038-07-27
Also published as: CN108947319A

Abstract

Aiming at the problems of a self-repairing system in the prior art, the invention provides a silane functional self-repairing microcapsule with a cellular structure and a preparation method thereof. The externally-repaired internally-fixed self-repairing microcapsule with the cellular structure comprises a capsule wall and a repairing agent coated by the capsule wall, wherein a series of micro-nano microcapsules are dispersed in the repairing agent to form the cellular structure; the micro-nano microcapsule is coated with a curing agent. The externally-repaired and internally-fixed self-repairing microcapsule system has a micro-nano multi-core coating structure, so that the stability of the microcapsule is improved, the probability of contact of a repairing agent and a curing agent is increased, and the repairing efficiency is improved. In addition, the capsule wall of the self-repairing microcapsule system is modified by silane, the unhydrolyzed silane emulsion after the microcapsule is broken can form a hydrophobic film in concrete capillary holes to prevent further diffusion of water, and the hydrolyzed silane emulsion can participate in the synthesis of the wall material to improve the performance of the microcapsule.

Description

Externally-repaired and internally-fixed self-repairing microcapsule with cellular structure and preparation method thereof

Technical Field

The invention belongs to the field of organic composite materials, relates to a self-repairing material, and particularly relates to a silane functional self-repairing microcapsule with a cellular structure and a preparation method thereof.

Background

With the continuous development of society, the building industry is also rapidly developed, and various high-rise buildings, bridges and roads are dug successively. Concrete is widely used in the construction field due to its excellent properties such as wide source, high compressive strength, easy construction, and high durability. However, due to inherent defects of low tensile strength, large brittleness and the like of concrete, micro cracks are easily generated to reduce the mechanical property of the concrete and influence the durability of the structure under the changes of external load and environmental temperature and humidity in the process of construction and later service. With the change of the load and the passage of time, the cracks gradually expand into cracks and even extend to the surface to cause the cracking of the concrete material. After the through cracks are formed, the concrete is easily corroded and damaged by the external environment and various harmful factors, such as steel bar corrosion, carbonization, chloride ion corrosion, sulfate corrosion and the like, and finally the concrete material is cracked and damaged, so that the durability of the concrete material is seriously influenced, and even the irrecoverable loss of people and property caused by sudden building damage can be caused.

Therefore, the effect of micro-cracks on durability has received increasing attention and importance. In order to prolong the service life of the concrete structure, the cracks need to be repaired in time. The traditional repair methods mainly have two types: surface treatment and grouting. The former is mainly to brush anti-seepage and anti-corrosion organic paint on the surface of the concrete structure, but the organic paint is easy to age, and the coating can be peeled off after a period of time; and the latter can not accurately judge the grouting point and the grouting amount. In addition, the traditional repairing methods not only need a large amount of manpower and material resources, but also have the defects of addressing symptoms and not addressing causes, the crack propagation cannot be inhibited, and tiny cracks existing in the structure cannot be repaired, so that potential safety hazards are left for the construction engineering.

Since 1925 Abrams discovered that the concrete test piece can be self-repaired, the self-repairing concrete technology begins to develop. In recent years, self-repairing technology based on bionics becomes a hot spot of research in the field of concrete self-repairing. The bionic self-repairing method of concrete is developed according to the principle that organisms in the nature secrete certain substances after being injured so as to enable the injured parts to heal in time, is an intelligent repairing method, and does not need to depend on manual assistance. In order to form an intelligent self-healing system in concrete, a carrier containing a repairing agent needs to be embedded into a concrete matrix in advance, when a micro crack is generated on the matrix, the carrier is broken under the action of the tip of the crack, the repairing agent flows out, and the carrier penetrates into the crack to repair the crack in time. The technology carries out targeted repair on concrete cracks, is pre-embedded in the concrete in advance, does not need secondary maintenance, and can greatly reduce the engineering maintenance cost.

Currently, microcapsule self-repair systems mainly include single-wall microcapsule repair systems, single-wall double-microcapsule repair systems, and double-wall microcapsule systems. Single wall microcapsule repair systems suffer from the following problems: (1) the thermochemical stability of the microcapsule is poor; (2) the reaction curing film forming speed is slow, and cracks cannot be effectively filled; (3) the catalyst is expensive and easy to deactivate; (4) the self-repairing system has a narrow application range and can only be limited in a certain base material. The single-wall double-microcapsule system comprises two microcapsules, namely a coating repairing agent and a coating curing agent. The single-wall double-microcapsule system solves the problem of the single-wall microcapsule system to a certain extent, but still has the problems that the repairing agent and the curing agent cannot be contacted simultaneously, the repairing cannot be carried out quickly, the response mechanism to cracks is complex and the like. The double-wall microcapsule system has better stability, and reduces the probability of inactivation of the repairing agent and the curing agent; greatly increasing the contact probability of the repairing agent and the catalyst and avoiding the adverse effect of excessive adding of the repairing agent and the catalyst on the concrete performance.

The invention patent application 201711236097.6 discloses an externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule and a preparation method thereof. The externally-repaired and internally-fixed polyurea double-wall self-repairing microcapsule is a double-wall microcapsule system which takes aliphatic isocyanate-amino-terminated polyether polymer as a repairing agent and takes an amino chain extender as a curing agent. The repairing agent and the curing agent are respectively stored in the outer-layer capsule core and the inner-layer capsule core, so that the problem that the contact rate of the repairing agent and the curing agent is low is solved, the repairing agent and the curing agent react quickly, and the cracks are repaired quickly. However, the self-repairing microcapsules with micron-sized structures are easy to break in the process of stirring and vibrating the concrete test block, so that the quantity of the remaining microcapsules in the concrete is small, and the timely response to cracks cannot be realized.

The invention patent application 201710331413.1 discloses a surface modified self-repairing microcapsule and a preparation method thereof. The surface modified self-repairing microcapsule selects a silane coupling agent as a surface treating agent of the microcapsule, and carbon nano tubes are grafted on the surface of the microcapsule through amidation reaction of amino and carboxyl, so that the surface modified self-repairing microcapsule has an antistatic function while the interface performance of the microcapsule and a resin matrix is improved. However, the function of the silane coupling agent is different from that of the silane emulsion, the silane coupling agent is mainly used for bonding organic and inorganic interfaces, and the silane coupling agent emphasizes the function of preventing water molecules from diffusing to form protection on a substrate.

Disclosure of Invention

Aiming at the problems of a self-repairing system in the prior art, the invention provides a silane functional self-repairing microcapsule with a cellular structure and a preparation method thereof. The externally-repaired and internally-fixed self-repairing microcapsule system has a micro-nano multi-core coating structure, so that the stability of the microcapsule is improved, the probability of contact of a repairing agent and a curing agent is increased, and the repairing efficiency is improved. In addition, the capsule wall of the self-repairing microcapsule system is modified by silane, the unhydrolyzed silane emulsion after the microcapsule is broken can form a hydrophobic film in concrete capillary holes to prevent further diffusion of water, and the hydrolyzed silane emulsion can participate in the synthesis of the wall material to improve the performance of the microcapsule.

The technical scheme of the invention is as follows:

the externally-repaired internally-fixed self-repairing microcapsule with a cellular structure comprises a capsule wall and a repairing agent coated by the capsule wall, wherein a series of micro-nano microcapsules are dispersed in the repairing agent to form the cellular structure; the micro-nano microcapsule is coated with a curing agent. The repairing agent is isocyanate emulsion, and the curing agent is hydroxyl compound emulsion or amino compound emulsion. The capsule wall of the self-repairing microcapsule is a silane modified capsule wall obtained by reacting a repairing agent coated by the self-repairing microcapsule, a curing agent outside the self-repairing microcapsule and a silane emulsion. The capsule wall of the micro-nano microcapsule is obtained by the reaction of a curing agent coated by the micro-nano microcapsule and a repairing agent outside the micro-nano microcapsule.

The preparation method of the externally-repaired internally-fixed self-repairing microcapsule with the cellular structure comprises the following steps:

(1) preparation of oil-in-water silane emulsion 1:

(1a) weighing a proper amount of silane, an emulsifying agent and a dispersing agent, wherein the weight ratio of the silane to the emulsifying agent to the dispersing agent is 80:1:1-120:5:1, and stirring at the normal temperature at the rotation speed of 2000-4000rpm for 15-30min to obtain an oil phase with uniform dispersion; (1b) weighing a proper amount of emulsifier and water, wherein the weight ratio of the emulsifier to the water is 1:80-1:120, and stirring for 15-30min at the normal temperature under the conditions of 1000-3000rpm to obtain a composite water phase; (1c) gradually dripping the oil phase into the water phase, wherein the weight ratio of the oil phase to the water phase is 1:0.8-1:1.5, and stirring at 5000-10000rpm for 4-5h at 40-60 ℃ to obtain the uniform and stable oil-in-water type composite emulsion, namely the silane emulsion 1.

(2) Preparing micro-nano microcapsule emulsion:

(2a) weighing a proper amount of isocyanate repairing agent, solvent and emulsifier, and stirring for 80-120min at the normal temperature of 6000-9000rpm to obtain isocyanate repairing agent emulsion 2a 1; the weight ratio of the isocyanate repairing agent to the solvent to the emulsifier is 1 (10-15) to 0.10-0.18. (2b) Weighing a proper amount of curing agent, solvent and emulsifier, and stirring at the normal temperature of 4000-7000rpm for 60-100min to obtain curing agent emulsion 2b 1; the weight ratio of the curing agent to the solvent to the emulsifier is 1 (15-20) to 0.08-0.15. (2c) Dropwise adding the isocyanate repairing agent emulsion 2a1 into the curing agent emulsion 2b1, and stirring at the normal temperature of 2000-6000rpm for 1-2h to obtain the micro-nano microcapsule emulsion 2 coated with the curing agent. The curing agent emulsion 2b1 and the repairing agent in the isocyanate repairing agent emulsion 2a1 are subjected to interface reaction to generate a capsule wall, so that the micro-nano microcapsule emulsion 2 coated with the curing agent is obtained; the weight ratio of the isocyanate repair agent emulsion 2a1 to the curing agent emulsion 2b1 is 1:1-5: 1. In the step, the micro-nano microcapsule emulsion can be obtained only by adopting high-speed rotation; and the droplets of the isocyanate are relatively larger than those of the curing agent emulsion, so that the droplets of the curing agent emulsion are dispersed on the surfaces of the droplets of the isocyanate emulsion to generate an interfacial reaction to form the capsule wall.

(3) Preparing an external-repairing and internal-fixing type silane functionalized self-repairing microcapsule with a cellular structure:

(3a) weighing a proper amount of curing agent, emulsifier and solvent, and uniformly stirring at the normal temperature of 4000-6000rpm for 70-100min to obtain curing agent emulsion 3a 2; the weight ratio of the curing agent to the solvent to the emulsifier is 1 (10-15) to 0.06-0.15.

(3b) Weighing a proper amount of isocyanate repairing agent, dispersant and solvent, and stirring at the normal temperature of 3000-5000rpm for 50-70min to obtain isocyanate dispersion liquid 3b 2; the weight ratio of the isocyanate repairing agent to the solvent to the dispersant is 1 (15-20) to 0.06-0.12.

(3c) Adding a certain amount of silane emulsion 1, micro-nano microcapsule emulsion 2 and an emulsifier into isocyanate dispersion liquid 3b2, and emulsifying at the normal temperature at the rotating speed of 1500-; then, dripping a curing agent emulsion 3a2 into the composite emulsion, stirring for 2-3h under the temperature condition of 50-70 ℃ and the rotating speed of 1000-2500rpm, and carrying out interface reaction on the curing agent emulsion 3a2 and a repairing agent emulsion droplet containing a plurality of micro-nano microcapsules to generate a capsule wall; obtaining the externally-modified and internally-fixed silane functionalized self-repairing microcapsule emulsion with a cellular structure. The weight ratio of the isocyanate dispersion liquid 3b2, the silane emulsion 1, the nano microcapsule emulsion 2 and the emulsifier to curing agent ester emulsion 3a2 is 1 (0.5-0.8): (0.5-0.8): (0.06-0.15): 1-3.

(3d) And (4) centrifuging, washing and drying the emulsion obtained in the step (3c) to obtain the externally-modified and internally-fixed silane functionalized self-repairing microcapsule with a cellular structure. When the microcapsule is broken, the crack can be repaired, and a hydrophobic film can be formed in pores of concrete, so that the further permeation of water is effectively prevented.

Preferably, in the step (3c), when the curing agent emulsion 3a2 is added dropwise to the mixed solution, an appropriate amount of acid is added dropwise to adjust the pH value of the system to 4-6. Aims to accelerate the hydrolysis of the silane emulsion to generate silicon dioxide to participate in the preparation of the wall material. SiO 2₂The nano particles participate in the synthesis process of the capsule wall, and the mechanical property and the response capability of the capsule wall and the adhesive force of the microcapsule and the concrete base material are improved to a certain extent.

Wherein the silane is one or more of vinyl triethoxysilane, vinyl trimethoxysilane, ethyl orthosilicate, isobutyl triethoxysilane, trimethylsiloxy silane and octyl triethoxysilane.

The emulsifier is one or more of Op-10, polyvinyl alcohol, span 80, Arabic gum, sodium dodecyl benzene sulfonate and stearyl alcohol polyoxyethylene ether.

The dispersing agent is one or more of polyethylene glycol, potassium citrate, sodium silicate, sodium linoleate and sodium ethylene oxide orthophosphate.

The isocyanate repairing agent is one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, 2, 5-trimethylhexane diisocyanate and tetramethylm-xylylene diisocyanate. The solvent is one or more of ethyl acetate, ethylene glycol dimethyl ether, cyclohexane, cyclopentane, cyclohexanol, toluene, xylene and chlorobenzene.

The curing agent is a hydroxyl compound or an amino compound; the hydroxyl compound is one or more of 1, 4-butanediol, n-butanol, pentanediol, 1, 6-hexanediol, cyclohexanedimethanol, pentaerythritol, polyoxypropylene polyol and polytetrahydrofuran polyol; the amino compound is diethyl toluene diamine, dimethyl sulfur toluene diamine, N ' -dialkyl methyl diphenylamine, cyclohexane diamine, chlorinated MDH, ethylene diamine, 1, 3-diaminopropane, 1, 4-diaminobutane, diethylene amine, pentaethylene hexamine, hexaethylene diamine, tetraethylene pentamine, pentaethylene hexamine, polyether amine D400, polyether amine D230, ethylene diamine or 3,3' -4,4' -diamino-diphenylmethane MOCA.

The self-repairing system of the externally-repaired internally-fixed self-repairing microcapsule with the cell structure is adopted, and the mass fraction of the externally-repaired internally-fixed silane functionalized self-repairing microcapsule with the cell structure in the self-repairing system is 5-18%; the self-repairing system is self-repairing concrete or a self-repairing coating.

The invention has the beneficial effects that:

(1) according to the externally-repaired internally-fixed self-repairing microcapsule with the cellular structure, a series of micro-nano microcapsules are dispersed in the repairing agent coated by the capsule wall, namely the size of the multi-core microcapsule is nano, so that the probability of breakage of the microcapsules in the concrete manufacturing process can be greatly reduced, and the self-repairing efficiency is greatly improved.

(2) The externally-repaired and internally-fixed self-repairing microcapsule is a silane modified microcapsule; therefore, when the microcapsules are broken, the unhydrolyzed silane emulsion can form a hydrophobic film in concrete pores while crack repair is completed, further penetration of water is effectively prevented, and the problem that the corrosion of the concrete is accelerated due to water vapor intrusion in the service process of marine concrete is effectively solved.

(3) In the preparation process of the externally-repaired and internally-fixed self-repairing microcapsule, SiO generated by hydrolysis of silane emulsion₂The nano particles participate in the synthesis process of the capsule wall, and the mechanical property and the response capability of the capsule wall and the adhesive force of the microcapsule and the concrete base material are improved to a certain extent.

(4) Compared with the existing double-wall microcapsule, the externally-repaired internally-fixed self-repairing microcapsule with the cellular structure has the advantages that the repairing agent and the curing agent react more quickly; in addition, the repairing agent can also react with external water vapor to repair cracks; therefore, the repairing effect is greatly accelerated, the timely repairing of the cracks is realized, and more serious consequences and higher repairing cost are avoided.

Drawings

FIG. 1 is a schematic structural diagram of an external-modified internal-fixed self-repairing microcapsule with a cellular structure; wherein A is a repairing agent microcapsule, and B is a curing agent microcapsule.

FIG. 2 is a photoscope diagram of the externally-modified internally-fixed self-repairing microcapsule with a cellular structure prepared in example 6.

Detailed Description

The present invention will be further described with reference to the following examples.

Example 1:

(1) preparation of oil-in-water silane emulsion 1:

(1a) weighing a proper amount of silane, an emulsifying agent and a dispersing agent, wherein the weight ratio of the silane to the emulsifying agent to the dispersing agent is 80:1:1, and stirring at the normal temperature at the rotating speed of 2000rpm for 30min to obtain an oil phase with uniform dispersion; the silane is vinyl triethoxysilane, the emulsifier is Op-10, and the dispersant is polyethylene glycol.

(1b) Weighing a proper amount of emulsifier Op-10 and water, wherein the weight ratio of the emulsifier to the water is 1:110, and stirring at the normal temperature at 1400rpm for 26min to obtain a composite water phase;

(1c) gradually dripping the oil phase into the water phase, wherein the weight ratio of the oil phase to the water phase is 1:1.2, and stirring at 7000rpm at 44 ℃ for 4h to obtain uniform and stable oil-in-water type composite emulsion, namely silane emulsion 1.

(2) Preparing micro-nano microcapsule emulsion:

(2a) weighing a proper amount of isocyanate repairing agent, solvent and emulsifier, and stirring at 7800rpm for 100min at normal temperature to obtain isocyanate repairing agent emulsion 2a 1; the weight ratio of the isocyanate repairing agent to the solvent to the emulsifier is 1:10: 0.10. The isocyanate repairing agent is diphenylmethane diisocyanate, the solvent is ethyl acetate, and the emulsifier is Op-10.

(2b) Weighing a proper amount of curing agent, solvent and emulsifier, and stirring for 60min at the normal temperature of 5200rpm to obtain curing agent emulsion 2b 1; the weight ratio of the curing agent to the solvent to the emulsifier is 1:15: 0.12. The curing agent is a hydroxyl compound, and the hydroxyl compound is 1, 4-butanediol; the solvent is ethyl acetate; the emulsifier is Op-10.

(2c) Dropwise adding the isocyanate repairing agent emulsion 2a1 into the curing agent emulsion 2b1, stirring at 6000rpm at normal temperature for 1h, and carrying out interface reaction on the curing agent emulsion 2b1 and a repairing agent in the isocyanate repairing agent emulsion 2a1 to generate a capsule wall, so as to obtain the micro-nano microcapsule emulsion 2 coated with the curing agent. The weight ratio of the isocyanate repair agent emulsion 2a1 to the curing agent emulsion 2b1 is 2: 1.

(3a) weighing a proper amount of curing agent, emulsifier and solvent, and uniformly stirring at the normal temperature at 4000rpm for 100min to obtain curing agent emulsion 3a 2; the weight ratio of the curing agent to the solvent to the emulsifier is 1:10: 0.06. The isocyanate repairing agent is diphenylmethane diisocyanate; the emulsifier is Op-10; the solvent is ethyl acetate.

(3b) Weighing a proper amount of isocyanate repairing agent, dispersant and solvent, and stirring at 3400rpm for 60min at normal temperature to obtain isocyanate dispersion liquid 3b 2; the weight ratio of the isocyanate repairing agent to the solvent to the dispersing agent is 1:15: 0.06. The curing agent is a hydroxyl compound, and the hydroxyl compound is 1, 4-butanediol; the dispersing agent is polyethylene glycol; the solvent is ethyl acetate.

(3c) Adding a certain amount of silane emulsion 1, micro-nano microcapsule emulsion 2 and an emulsifier into isocyanate dispersion liquid 3b2, and emulsifying at the normal temperature at the rotating speed of 2200rpm for 1.5h to obtain a composite emulsion containing a plurality of emulsified droplets of micro-nano microcapsules; the emulsifier is Op-10. Then, a proper amount of acid is dripped to ensure that the pH value of the system is 5; then, dripping a curing agent emulsion 3a2 into the composite emulsion, stirring for 2h at the temperature of 65 ℃ and the rotating speed of 2000rpm, and carrying out interface reaction on the curing agent emulsion 3a2 and a repairing agent emulsion drop containing a plurality of micro-nano microcapsules to generate a capsule wall; obtaining the externally-modified and internally-fixed silane functionalized self-repairing microcapsule emulsion with a cellular structure. The weight ratio of the isocyanate dispersion liquid 3b2, the silane emulsion 1, the nano microcapsule emulsion 2 and the emulsifier to curing agent ester emulsion 3a2 is 1:0.5:0.5:0.06: 1. The key steps of the application are as follows: firstly, micro-nano microcapsules are dripped, and then a curing agent is emulsified to obtain a composite system, so that emulsified liquid drops containing a plurality of micro-nano microcapsules can be formed. The purpose of dripping acid into the composite solution is to accelerate the hydrolysis of the silane emulsion to generate silicon dioxide so as to participate in the preparation of the wall material. SiO 2₂The nano particles participate in the synthesis process of the capsule wall, and the mechanical property and the response capability of the capsule wall and the adhesive force of the microcapsule and the concrete base material are improved to a certain extent.

The self-repairing concrete adopting the externally-repaired and internally-fixed self-repairing microcapsule with the cellular structure has the advantages that the mass percentage of the self-repairing microcapsule in the self-repairing concrete is 10%.

Example 2:

different from the embodiment 1, the preparation method of the externally-repaired internally-fixed self-repairing microcapsule with the cellular structure comprises the following steps:

(1) preparation of oil-in-water silane emulsion 1:

(1a) weighing a proper amount of silane, an emulsifying agent and a dispersing agent, wherein the weight ratio of the silane to the emulsifying agent to the dispersing agent is 100:2:1, and stirring at the normal temperature at the rotating speed of 2400rpm for 26min to obtain an oil phase which is uniformly dispersed; the silane is vinyl trimethoxy silane, the emulsifier is polyvinyl alcohol, and the dispersing agent is potassium citrate.

(1b) Weighing appropriate amount of emulsifier polyvinyl alcohol and water, wherein the weight ratio of the emulsifier to the water is 1:120, and stirring at 1800rpm for 22min at normal temperature to obtain a composite water phase;

(1c) gradually dripping the oil phase into the water phase, wherein the weight ratio of the oil phase to the water phase is 1:1.4, and stirring at 8000rpm at 48 ℃ for 4h to obtain uniform and stable oil-in-water type composite emulsion, namely silane emulsion 1.

(2) Preparing micro-nano microcapsule emulsion:

(2a) weighing a proper amount of isocyanate repairing agent, solvent and emulsifier, and stirring at 8400rpm for 110min at normal temperature to obtain isocyanate repairing agent emulsion 2a 1; the weight ratio of the isocyanate repairing agent to the solvent to the emulsifier is 1:12: 0.10. The isocyanate repairing agent is toluene diisocyanate, the solvent is ethylene glycol dimethyl ether, and the emulsifier is polyvinyl alcohol.

(2b) Weighing a proper amount of curing agent, solvent and emulsifier, and stirring at 7000rpm at normal temperature for 70min to obtain curing agent emulsion 2b 1; the weight ratio of the curing agent to the solvent to the emulsifier is 1:15: 0.15. The curing agent is a hydroxyl compound, and the hydroxyl compound is a mixture of n-butyl alcohol and pentanediol; the solvent is ethylene glycol dimethyl ether, and the emulsifier is span 80.

(2c) Dropwise adding the isocyanate repairing agent emulsion 2a1 into the curing agent emulsion 2b1, stirring at the normal temperature of 2000rpm for 2h, and carrying out interface reaction on the curing agent emulsion 2b1 and the repairing agent in the isocyanate repairing agent emulsion 2a1 to generate a capsule wall, thereby obtaining the curing agent-coated micro-nano microcapsule emulsion 2. The weight ratio of the isocyanate repair agent emulsion 2a1 to the curing agent emulsion 2b1 is 3: 1.

(3a) weighing a proper amount of curing agent, emulsifier and solvent, and uniformly stirring at 4400rpm at normal temperature for 95min to obtain curing agent emulsion 3a 2; the weight ratio of the curing agent to the solvent to the emulsifier is 1:12: 0.06. The isocyanate repairing agent is isophorone diisocyanate, the emulsifier is polyvinyl alcohol, and the solvent is cyclohexane.

(3b) Weighing a proper amount of isocyanate repairing agent, dispersant and solvent, and stirring at 3800rpm for 65min at normal temperature to obtain isocyanate dispersion liquid 3b 2; the weight ratio of the isocyanate repairing agent to the solvent to the dispersing agent is 1:15: 0.08. The curing agent is a hydroxyl compound, and the hydroxyl compound is n-butyl alcohol; the dispersing agent is sodium silicate, and the solvent is cyclohexane and cyclopentane.

(3c) Adding a certain amount of silane emulsion 1, micro-nano microcapsule emulsion 2 and an emulsifier into isocyanate dispersion liquid 3b2, and emulsifying at the normal temperature and the rotating speed of 2600rpm for 1.5h to obtain a composite emulsion containing a plurality of emulsified droplets of micro-nano microcapsules; the emulsifier is span 80. Then, a proper amount of acid is dripped to ensure that the pH value of the system is 6; then, dripping a curing agent emulsion 3a2 into the composite emulsion, stirring for 2.5h at the temperature of 70 ℃ and the rotating speed of 2300rpm, and carrying out interface reaction on the curing agent emulsion 3a2 and a repairing agent emulsion drop containing a plurality of micro-nano microcapsules to generate a capsule wall; obtaining the externally-modified and internally-fixed silane functionalized self-repairing microcapsule emulsion with a cellular structure. The weight ratio of the isocyanate dispersion liquid 3b2, the silane emulsion 1, the nano microcapsule emulsion 2 and the emulsifier to curing agent ester emulsion 3a2 is 1:0.65:0.5:0.09: 1.

(3d) And (4) centrifuging, washing and drying the emulsion obtained in the step (3c) to obtain the externally-modified and internally-fixed silane functionalized self-repairing microcapsule with a cellular structure.

The self-repairing coating of the externally-repaired internally-fixed self-repairing microcapsule with the cellular structure is adopted, and the mass percentage of the self-repairing microcapsule in the self-repairing coating is 15%.

Example 3:

(1) preparation of oil-in-water silane emulsion 1:

(1a) weighing a proper amount of silane, an emulsifier and a dispersant, wherein the weight ratio of the silane to the emulsifier to the dispersant is 120:2.5:1, and stirring at the normal temperature at the rotating speed of 2800rpm for 22min to obtain an oil phase with uniform dispersion; the silane is isobutyl triethoxy silane, the emulsifier is sodium dodecyl benzene sulfonate, and the dispersant is sodium linoleate.

(1b) Weighing a proper amount of emulsifier sodium dodecyl benzene sulfonate and water, wherein the weight ratio of the emulsifier to the water is 1:105, and stirring for 20min at the normal temperature under 2200rpm to obtain a composite water phase;

(1c) gradually dripping the oil phase into the water phase, wherein the weight ratio of the oil phase to the water phase is 1:1.5, and stirring at 9000rpm at 52 ℃ for 4.5h to obtain uniform and stable oil-in-water type composite emulsion, namely silane emulsion 1.

(2) Preparing micro-nano microcapsule emulsion:

(2a) weighing a proper amount of isocyanate repairing agent, solvent and emulsifier, and stirring at 9000rpm for 120min at normal temperature to obtain isocyanate repairing agent emulsion 2a 1; the weight ratio of the isocyanate repairing agent to the solvent to the emulsifier is 1:15: 0.10. The isocyanate repairing agent is 1, 6-hexamethylene diisocyanate, the solvent is cyclohexanol, and the emulsifier is sodium dodecyl benzene sulfonate.

(2b) Weighing a proper amount of curing agent, solvent and emulsifier, and stirring at normal temperature at 6400rpm for 100min to obtain curing agent emulsion 2b 1; the weight ratio of the curing agent to the solvent to the emulsifier is 1:20: 0.15. The curing agent is a hydroxyl compound, and the hydroxyl compound is pentaerythritol; the amino compound is cyclohexane diamine, the solvent is cyclopentane, and the emulsifier is Arabic gum.

(2c) Dropwise adding the isocyanate repair agent emulsion 2a1 into the curing agent emulsion 2b1, stirring at 2800rpm at normal temperature for 2h, and carrying out interface reaction on the curing agent emulsion 2b1 and the repair agent in the isocyanate repair agent emulsion 2a1 to generate a capsule wall, so as to obtain the curing agent-coated micro-nano microcapsule emulsion 2. The weight ratio of the isocyanate repair agent emulsion 2a1 to the curing agent emulsion 2b1 is 4: 1.

(3a) weighing a proper amount of curing agent, emulsifier and solvent, and uniformly stirring at the normal temperature of 4800rpm for 90min to obtain curing agent emulsion 3a 2; the weight ratio of the curing agent to the solvent to the emulsifier is 1:15: 0.06. The isocyanate repairing agent is 1, 6-hexamethylene diisocyanate, the emulsifying agent is Arabic gum, and the solvent is cyclohexane.

(3b) Weighing a proper amount of isocyanate repairing agent, dispersant and solvent, and stirring for 70min at the normal temperature of 4200rpm to obtain isocyanate dispersion liquid 3b 2; the weight ratio of the isocyanate repairing agent to the solvent to the dispersing agent is 1:15: 0.10. The amino compound of the curing agent is diethyl toluene diamine; the dispersing agent is sodium linoleate, and the solvent is cyclohexane.

(3c) Adding a certain amount of silane emulsion 1, micro-nano microcapsule emulsion 2 and an emulsifier into isocyanate dispersion liquid 3b2, and emulsifying at the normal temperature at the rotating speed of 3000rpm for 1.0h to obtain a composite emulsion containing a plurality of emulsified droplets of micro-nano microcapsules; the emulsifier is sodium dodecyl benzene sulfonate. Then, a proper amount of acid is dripped to ensure that the pH value of the system is 6; then, adding the curing agent emulsion 3a2 dropwise into the composite emulsion, stirring for 2.5h at the temperature of 50 ℃ and the rotating speed of 2500rpm, and allowing the curing agent emulsion 3a2 and the repair agent emulsion liquid drop containing a plurality of micro-nano microcapsules to perform interface reaction to generate a capsule wall; obtaining the externally-modified and internally-fixed silane functionalized self-repairing microcapsule emulsion with a cellular structure. The weight ratio of the isocyanate dispersion liquid 3b2, the silane emulsion 1, the nano microcapsule emulsion 2 and the emulsifier to curing agent ester emulsion 3a2 is 1:0.8:0.5:0.12: 1.

The self-repairing concrete adopting the externally-repaired and internally-fixed self-repairing microcapsule with the cellular structure has the advantages that the mass percentage of the self-repairing microcapsule in the self-repairing concrete is 18%.

Example 4:

(1) preparation of oil-in-water silane emulsion 1:

(1a) weighing a proper amount of silane, an emulsifying agent and a dispersing agent, wherein the weight ratio of the silane to the emulsifying agent to the dispersing agent is 90:3:1, and stirring for 20min at the normal temperature at the rotating speed of 3200rpm to obtain an oil phase with uniform dispersion; the silane is trimethylsiloxy silane, the emulsifier is octadecyl alcohol polyoxyethylene ether, and the dispersant is sodium silicate.

(1b) Weighing a proper amount of emulsifier octadecanol-based polyoxyethylene ether and water, wherein the weight ratio of the emulsifier to the water is 1:80, and stirring for 18min at the normal temperature and 2600rpm to obtain a composite water phase;

(1c) gradually dripping the oil phase into the water phase, wherein the weight ratio of the oil phase to the water phase is 1:1.1, stirring at 56 ℃ and 10000rpm for 4.5h to obtain uniform and stable oil-in-water type composite emulsion, namely silane emulsion 1.

(2) Preparing micro-nano microcapsule emulsion:

(2a) weighing a proper amount of isocyanate repairing agent, solvent and emulsifier, and stirring for 80min at the normal temperature of 6000rpm to obtain isocyanate repairing agent emulsion 2a 1; the weight ratio of the isocyanate repairing agent to the solvent to the emulsifier is 1:15: 0.18. The isocyanate repairing agent is 1, 6-hexamethylene diisocyanate, the solvent is toluene, and the emulsifier is octadecyl alcohol polyoxyethylene ether.

(2b) Weighing a proper amount of curing agent, solvent and emulsifier, and stirring for 90min at room temperature at 4600rpm to obtain curing agent emulsion 2b 1; the weight ratio of the curing agent to the solvent to the emulsifier is 1:15: 0.08. The curing agent is an amino compound, and the amino compound is ethylenediamine; the solvent is dimethylbenzene, and the emulsifier is octadecyl alcohol polyoxyethylene ether.

(2c) Dropwise adding the isocyanate repair agent emulsion 2a1 into the curing agent emulsion 2b1, stirring at 3600rpm at normal temperature for 1.5h, and carrying out interface reaction on the curing agent emulsion 2b1 and the repair agent in the isocyanate repair agent emulsion 2a1 to generate a capsule wall, so as to obtain the micro-nano microcapsule emulsion 2 coated with the curing agent. The weight ratio of the isocyanate repair agent emulsion 2a1 to the curing agent emulsion 2b1 is 5: 1.

(3a) weighing a proper amount of curing agent, emulsifier and solvent, and uniformly stirring for 85min at the normal temperature of 5200rpm to obtain curing agent emulsion 3a 2; the weight ratio of the curing agent to the solvent to the emulsifier is 1:10: 0.09. The isocyanate repairing agent is 1, 6-hexamethylene diisocyanate, the emulsifying agent is Arabic gum, and the solvent is cyclohexanol.

(3b) Weighing a proper amount of isocyanate repairing agent, dispersant and solvent, and stirring for 60min at room temperature at 4600rpm to obtain isocyanate dispersion liquid 3b 2; the weight ratio of the isocyanate repairing agent to the solvent to the dispersing agent is 1:15: 0.12. The curing agent is an amino compound, the amino compound is cyclohexane diamine, the dispersing agent is sodium silicate, and the solvent is chlorobenzene.

(3c) Adding a certain amount of silane emulsion 1, micro-nano microcapsule emulsion 2 and an emulsifier into isocyanate dispersion liquid 3b2, and emulsifying at the normal temperature at the rotating speed of 3500rpm for 1.0h to obtain a composite emulsion containing a plurality of emulsified droplets of micro-nano microcapsules; the emulsifier is span 80. Then, a proper amount of acid is dripped to ensure that the pH value of the system is 4; then, dripping a curing agent emulsion 3a2 into the composite emulsion, stirring for 3h at the temperature of 55 ℃ and the rotating speed of 1000rpm, and carrying out interface reaction on the curing agent emulsion 3a2 and a repairing agent emulsion drop containing a plurality of micro-nano microcapsules to generate a capsule wall; obtaining the externally-modified and internally-fixed silane functionalized self-repairing microcapsule emulsion with a cellular structure. The weight ratio of the isocyanate dispersion liquid 3b2, the silane emulsion 1, the nano microcapsule emulsion 2 and the emulsifier to curing agent ester emulsion 3a2 is 1:0.5:0.65:0.15: 2.

The self-repairing coating of the externally-repaired internally-fixed self-repairing microcapsule with the cellular structure is adopted, and the mass percentage of the self-repairing microcapsule in the self-repairing coating is 10%.

Example 5:

(1) preparation of oil-in-water silane emulsion 1:

(1a) weighing a proper amount of silane, an emulsifier and a dispersant, wherein the weight ratio of the silane to the emulsifier to the dispersant is 110:4:1, and stirring at the normal temperature at the rotating speed of 3600rpm for 18min to obtain an oil phase with uniform dispersion; the silane is trimethylsiloxy silane, the emulsifier is octadecyl alcohol polyoxyethylene ether, and the dispersant is sodium silicate.

(1b) Weighing a proper amount of emulsifier octadecanol-based polyoxyethylene ether and water, wherein the weight ratio of the emulsifier to the water is 1:90, and stirring at the normal temperature at 3000rpm for 15min to obtain a composite water phase;

(1c) gradually dripping the oil phase into the water phase, wherein the weight ratio of the oil phase to the water phase is 1:0.8, and stirring at 5000rpm at 60 ℃ for 5h to obtain uniform and stable oil-in-water type composite emulsion, namely silane emulsion 1.

(2) Preparing micro-nano microcapsule emulsion:

(2a) weighing a proper amount of isocyanate repairing agent, solvent and emulsifier, and stirring at 6600rpm for 90min at normal temperature to obtain isocyanate repairing agent emulsion 2a 1; the weight ratio of the isocyanate repairing agent to the solvent to the emulsifier is 1:20: 0.15. The isocyanate repairing agent is tetramethylm-xylylene diisocyanate, the solvent is chlorobenzene, and the emulsifier is octadecyl alcohol polyoxyethylene ether.

(2b) Weighing a proper amount of curing agent, solvent and emulsifier, and stirring for 80min at the normal temperature at 4000rpm to obtain curing agent emulsion 2b 1; the weight ratio of the curing agent to the solvent to the emulsifier is 1:18: 0.08. The curing agent is an amino compound, the amino compound is tetraethylenepentamine, the solvent is cyclohexane, and the emulsifier is Arabic gum.

(2c) Dropwise adding the isocyanate repairing agent emulsion 2a1 into the curing agent emulsion 2b1, stirring for 1.5h at room temperature and 4600rpm, and carrying out interface reaction on the curing agent emulsion 2b1 and the repairing agent in the isocyanate repairing agent emulsion 2a1 to generate a capsule wall, so as to obtain the curing agent-coated micro-nano microcapsule emulsion 2. The weight ratio of the isocyanate repair agent emulsion 2a1 to the curing agent emulsion 2b1 is 1:1.

(3a) weighing a proper amount of curing agent, emulsifier and solvent, and uniformly stirring at 5600rpm for 80min at normal temperature to obtain curing agent emulsion 3a 2; the weight ratio of the curing agent to the solvent to the emulsifier is 1:10: 0.12. The isocyanate repairing agent is isophorone diisocyanate, the emulsifier is sodium dodecyl benzene sulfonate, and the solvent is cyclohexane.

(3b) Weighing a proper amount of isocyanate repairing agent, dispersant and solvent, and stirring for 50min at the normal temperature at 5000rpm to obtain isocyanate dispersion liquid 3b 2; the weight ratio of the isocyanate repairing agent to the solvent to the dispersing agent is 1:18: 0.10. The curing agent is an amino compound, the amino compound is diethyleneamine, the dispersing agent is sodium silicate, and the solvent is cyclohexanol.

(3c) Adding a certain amount of silane emulsion 1, micro-nano microcapsule emulsion 2 and an emulsifier into isocyanate dispersion liquid 3b2, and emulsifying at the normal temperature at the rotating speed of 1500rpm for 2h to obtain a composite emulsion containing a plurality of micro-nano microcapsule emulsified droplets; the emulsifier is sodium dodecyl benzene sulfonate. Then, a proper amount of acid is dripped to ensure that the pH value of the system is 4.5; then, dripping a curing agent emulsion 3a2 into the composite emulsion, stirring for 3h at the temperature of 60 ℃ and the rotating speed of 1300rpm, and carrying out interface reaction on the curing agent emulsion 3a2 and a repairing agent emulsion drop containing a plurality of micro-nano microcapsules to generate a capsule wall; obtaining the externally-modified and internally-fixed silane functionalized self-repairing microcapsule emulsion with a cellular structure. The weight ratio of the isocyanate dispersion liquid 3b2, the silane emulsion 1, the nano microcapsule emulsion 2 and the emulsifier to curing agent ester emulsion 3a2 is 1:0.5:0.8:0.06: 1.

The self-repairing concrete adopting the externally-repaired and internally-fixed self-repairing microcapsule with the cellular structure has the advantages that the mass percentage of the self-repairing microcapsule in the self-repairing concrete is 15%.

Example 6:

(1) preparation of oil-in-water silane emulsion 1:

(1a) weighing a proper amount of silane, an emulsifier and a dispersant, wherein the weight ratio of the silane to the emulsifier to the dispersant is 100:5:1, and stirring at the normal temperature at the rotation speed of 4000rpm for 15min to obtain an oil phase with uniform dispersion; the silane is octyl triethoxysilane, the emulsifier is octadecyl alcohol polyoxyethylene ether, and the dispersant is sodium orthophosphate polyoxyethylene ether.

(1b) Weighing a proper amount of emulsifier octadecanol polyoxyethylene ether and water, wherein the weight ratio of the emulsifier to the water is 1:100, and stirring the mixture for 30min at the normal temperature and 1000rpm to obtain a composite water phase;

(1c) gradually dripping the oil phase into the water phase, wherein the weight ratio of the oil phase to the water phase is 1:0.8, and stirring at 6000rpm at 50 ℃ for 5h to obtain uniform and stable oil-in-water type composite emulsion, namely silane emulsion 1.

(2) Preparing micro-nano microcapsule emulsion:

(2a) weighing a proper amount of isocyanate repairing agent, solvent and emulsifier, and stirring at 7200rpm for 95min at normal temperature to obtain isocyanate repairing agent emulsion 2a 1; the weight ratio of the isocyanate repairing agent to the solvent to the emulsifier is 1:15: 0.12. The isocyanate repairing agent is 2, 2, 5-trimethylhexane diisocyanate, the solvent is xylene, and the emulsifier is sodium dodecyl benzene sulfonate.

(2b) Weighing a proper amount of curing agent, solvent and emulsifier, and stirring at the normal temperature of 5800rpm for 75min to obtain curing agent emulsion 2b 1; the weight ratio of the curing agent to the solvent to the emulsifier is 1:20: 0.08. The curing agent is a hydroxyl compound, the hydroxyl compound is polyoxypropylene polyol, the solvent is toluene, and the emulsifying agent is Arabic gum.

(2c) Dropwise adding the isocyanate repairing agent emulsion 2a1 into the curing agent emulsion 2b1, stirring at the normal temperature of 5000rpm for 1h, and carrying out interface reaction on the curing agent emulsion 2b1 and a repairing agent in the isocyanate repairing agent emulsion 2a1 to generate a capsule wall, so as to obtain the curing agent-coated micro-nano microcapsule emulsion 2. The weight ratio of the isocyanate repair agent emulsion 2a1 to the curing agent emulsion 2b1 is 2.5: 1.

(3a) weighing a proper amount of curing agent, emulsifier and solvent, and uniformly stirring at the normal temperature of 6000rpm for 70min to obtain curing agent emulsion 3a 2; the weight ratio of the curing agent to the solvent to the emulsifier is 1:15: 0.15. The isocyanate repairing agent is toluene diisocyanate, the emulsifying agent is Arabic gum, and the solvent is cyclohexanol.

(3b) Weighing a proper amount of isocyanate repairing agent, dispersant and solvent, and stirring at the normal temperature of 3000rpm for 55min to obtain isocyanate dispersion liquid 3b 2; the weight ratio of the isocyanate repairing agent to the solvent to the dispersing agent is 1:20: 0.12. The curing agent is a hydroxyl compound, the hydroxyl compound is polyoxypropylene polyol, the dispersing agent is sodium silicate, and the solvent is cyclohexane.

(3c) Adding a certain amount of silane emulsion 1, micro-nano microcapsule emulsion 2 and an emulsifier into isocyanate dispersion liquid 3b2, and emulsifying at the normal temperature at the rotation speed of 1800rpm for 2h to obtain a composite emulsion containing a plurality of micro-nano microcapsule emulsified droplets; the emulsifier is sodium dodecyl benzene sulfonate. Then, a proper amount of acid is dripped to ensure that the pH value of the system is 5; then, dripping a curing agent emulsion 3a2 into the composite emulsion, stirring for 2h at the temperature of 65 ℃ and the rotating speed of 1600rpm, and carrying out interface reaction on the curing agent emulsion 3a2 and a repairing agent emulsion drop containing a plurality of micro-nano microcapsules to generate a capsule wall; obtaining the externally-modified and internally-fixed silane functionalized self-repairing microcapsule emulsion with a cellular structure. The weight ratio of the isocyanate dispersion liquid 3b2, the silane emulsion 1, the nano microcapsule emulsion 2 and the emulsifier to curing agent ester emulsion 3a2 is 1:0.8:0.8:0.15: 3.

The self-repairing coating of the externally-repaired internally-fixed self-repairing microcapsule with the cellular structure is adopted, and the mass percentage of the self-repairing microcapsule in the self-repairing coating is 18%.

Table 1 micro-morphological characterization of the microcapsules prepared in examples 1-6

Table 2 characterization of mechanical properties of the microcapsules prepared in examples 1 to 6

As is apparent from the characterization results in tables 1 and 2, the microcapsules prepared in examples 1 to 6 had a particle size of 10 to 200. mu.m, a tensile strength of 9.27 to 11.64MPa, an elongation at break of 218.28 to 233.85%, and a Shore hardness (A) of 52 to 63.

As shown in FIG. 2, the microcapsules of the present invention have a cellular structure, i.e., a series of micro-nano microcapsules are dispersed in the curing agent coated on the capsule wall, such that the probability of the microcapsules breaking during the concrete manufacturing process can be substantially reduced, and the self-repairing efficiency can be substantially improved.

Example 7: strength determination after repair of self-repair system

The microcapsules prepared in examples 1,3 and 5 were incorporated into cement for the preparation of self-healing concrete. After 28 days of maintenance, taking a group of self-repairing concrete (each group contains 3 test blocks) to test the initial compressive strength; and (3) lightly pressing the self-repairing concrete by using a pressure testing machine to generate cracks in the self-repairing concrete by using another group (each group contains 3 test blocks), and testing the compressive strength of the self-repairing concrete after half a month. The microcapsules prepared in examples 2, 4 and 6 were incorporated into coatings for the preparation of self-healing coatings. And (3) taking one group (each group contains 3 coatings) of self-repairing coatings to test the initial tensile strength, taking the other group (each group contains 3 coatings) of self-repairing coatings to stretch the self-repairing soil layer by adopting a tensile testing machine to generate cracks in the self-repairing soil layer, and testing the tensile strength of the group of self-repairing coatings after half a month to obtain the data shown in the table 3.

Table 3 determination of strength after repair of self-healing systems of microcapsules prepared in examples 1-6

As can be seen from Table 3, the compressive strength of the repaired concrete is 46.34-46.92MPa, and the average value is 46.71 MPa; compared with the prior art, the repair efficiency is improved by 9.88 percent. The repaired epoxy coating is 17.47-17.74MPa, and the average value is 17.57 MPa; compared with the prior art, the repair efficiency is improved by 13.33%.

Example 8: determination of Water absorption after repair of self-healing System

The microcapsules prepared in examples 1-6 were incorporated into cement to prepare self-healing concrete (microcapsule content 8%) while preparing a set of blank concrete test blocks. After curing for 28 days, the self-repairing concrete is lightly pressed by a pressure tester to generate cracks inside the self-repairing concrete, and after half a month, the self-repairing concrete is dried to constant weight by an oven, and then the water absorption of the group of self-repairing concrete is tested. The weight gain method is used for testing the water absorption increment of the sample at 2, 4, 8, 12 and 24 hours.

Table 4 examples 1-6 preparation of water absorption test after repair of microcapsule self-healing systems

As can be seen from Table 4, the water absorption capacity of the repaired concrete for 24 hours was 583.4-596.4g/m³Compared with a blank sample, the reduction is 5.1-7.1%.

In conclusion, the external-repair internal-fixation self-repairing microcapsule with the cellular structure has good morphology in the aspect of microscopic morphology, and the particle size is mainly distributed between 10 and 200 mu m. Mechanical tests show that the cured microcapsule is an elastic material (the elongation at break is 218.28-233.85%) with certain strength (the tensile strength is 9.27-11.64MPa) and hardness (Shore A52-63). This is due to the SiO produced by hydrolysis of the silane emulsion₂The nano particles participate in the synthesis process of the capsule wall, and the mechanical property of the capsule wall is improved to a certain extent.

The externally repaired and internally fixed self-repairing microcapsules with cellular structures are doped into concrete and an epoxy coating, and a pre-pressing crack experiment shows that the microcapsules have a certain repairing effect on cracks, the compressive strength improvement rate of the repaired concrete is 9.88%, and the tensile strength improvement rate of the repaired epoxy coating is 13.33%. The multi-core microcapsule has the size of nanometer level, so that the probability of the microcapsule breaking in the concrete making process is greatly reduced, and the self-repairing efficiency is greatly improved. In addition, the repairing agent can also react with external water vapor to repair cracks; further quickening the repair effect and realizing the timely repair of the cracks.

The externally repaired and internally fixed self-repairing microcapsules with cellular structures are doped into concrete, and a water absorption test shows that the microcapsules have a certain repairing effect on cracks, and the water absorption reduction rate of the repaired concrete is 5.1-7.1%. When the microcapsule is broken, the unhydrolyzed silane emulsion can form a hydrophobic film in concrete pores while the crack is repaired, so that the further permeation of water is effectively prevented.

Claims

1. The preparation method of the externally-repaired and internally-fixed self-repairing microcapsule with the cellular structure is characterized by comprising the following steps of: the method comprises the following steps:

(1) preparation of oil-in-water silane emulsion 1: (1a) weighing a proper amount of silane, an emulsifying agent and a dispersing agent, wherein the weight ratio of the silane to the emulsifying agent to the dispersing agent is 80:1:1-120:5:1, and stirring at the normal temperature at the rotation speed of 2000-4000rpm for 15-30min to obtain an oil phase with uniform dispersion; (1b) weighing a proper amount of emulsifier and water, wherein the weight ratio of the emulsifier to the water is 1:80-1:120, and stirring for 15-30min at the normal temperature under the conditions of 1000-3000rpm to obtain a composite water phase; (1c) gradually dripping the oil phase into the water phase, wherein the weight ratio of the oil phase to the water phase is 1:0.8-1:1.5, and stirring at 5000-10000rpm at 40-60 ℃ for 4-5h to obtain uniform and stable oil-in-water type composite emulsion, namely silane emulsion 1;

(2) preparing a nano microcapsule emulsion: (2a) weighing a proper amount of isocyanate repairing agent, solvent and emulsifier, and stirring for 80-120min at the normal temperature of 6000-9000rpm to obtain isocyanate repairing agent emulsion 2a 1; the weight ratio of the isocyanate repairing agent to the solvent to the emulsifier is 1 (10-15) to 0.10-0.18; (2b) weighing a proper amount of curing agent, solvent and emulsifier, and stirring at the normal temperature of 4000-7000rpm for 60-100min to obtain curing agent emulsion 2b 1; the weight ratio of the curing agent, the solvent and the emulsifier is 1 (15-20) to 0.08-0.15; (2c) dropwise adding the isocyanate repairing agent emulsion 2a1 into the curing agent emulsion 2b1, and stirring at the normal temperature of 2000-6000rpm for 1-2h to obtain the curing agent coated nano-microcapsule emulsion 2; the weight ratio of the isocyanate repair agent emulsion 2a1 to the curing agent emulsion 2b1 is 1:1-5: 1;

(3) preparing an external-repairing and internal-fixing type silane functionalized self-repairing microcapsule with a cellular structure: (3a) weighing a proper amount of curing agent, emulsifier and solvent, and uniformly stirring at the normal temperature of 4000-6000rpm for 70-100min to obtain curing agent emulsion 3a 2; the weight ratio of the curing agent, the solvent and the emulsifier is 1 (10-15) to 0.06-0.15; (3b) weighing a proper amount of isocyanate repairing agent, dispersant and solvent, and stirring at the normal temperature of 3000-5000rpm for 50-70min to obtain isocyanate dispersion liquid 3b 2; the weight ratio of the isocyanate repairing agent to the solvent to the dispersant is 1 (15-20) to 0.06-0.12; (3c) adding a certain amount of silane emulsion 1, nano microcapsule emulsion 2 and emulsifier into the isocyanate dispersion liquid 3b2, and emulsifying at the normal temperature at the rotation speed of 1500-; then, dropwise adding a curing agent emulsion 3a2 into the composite emulsion, and stirring for 2-3h under the temperature condition of 50-70 ℃ and the rotating speed of 1000-2500rpm to obtain an external-repair and internal-cure type silane functionalized self-repairing microcapsule emulsion with a cellular structure; the weight ratio of the isocyanate dispersion liquid 3b2, the silane emulsion 1, the nano microcapsule emulsion 2 and the emulsifier and curing agent ester emulsion 3a2 is 1 (0.5-0.8): (0.5-0.8): (0.06-0.15): (1-3); (3d) and (4) centrifuging, washing and drying the emulsion obtained in the step (3c) to obtain the externally-modified and internally-fixed silane functionalized self-repairing microcapsule with a cellular structure.

2. The method for preparing the externally-repaired and internally-fixed self-repairing microcapsule with the cellular structure as set forth in claim 1, wherein the method comprises the following steps: in the step (3c), when the curing agent emulsion 3a2 is dripped into the mixed solution, a proper amount of acid is dripped simultaneously, so that the pH value of the system is 4-6.

3. The method for preparing the externally-repaired and internally-fixed self-repairing microcapsule with the cellular structure as set forth in claim 2, wherein the method comprises the following steps: the silane is one or more of vinyl triethoxysilane, vinyl trimethoxysilane, isobutyl triethoxysilane, trimethylsiloxy silane and octyl triethoxysilane;

the emulsifier is one or more of Op-10, polyvinyl alcohol, span 80, Arabic gum, sodium dodecyl benzene sulfonate and octadecyl alcohol polyoxyethylene ether;

the dispersant is one or more of polyethylene glycol, potassium citrate, sodium silicate and sodium linoleate;

the isocyanate repairing agent is one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate and 2, 2, 5-trimethylhexane diisocyanate;

the solvent is one or more of ethyl acetate, ethylene glycol dimethyl ether, cyclohexane, cyclopentane, cyclohexanol, toluene, xylene and chlorobenzene;

the curing agent is a hydroxyl compound or an amino compound; the hydroxyl compound is one or more of 1, 4-butanediol, n-butanol, pentanediol, 1, 6-hexanediol, cyclohexanedimethanol, pentaerythritol, polyoxypropylene polyol and polytetrahydrofuran polyol; the amino compound is diethyl toluene diamine, dimethyl sulfur toluene diamine, N ' -dialkyl methyl diphenylamine, cyclohexane diamine, chlorinated MDH, ethylene diamine, 1, 3-diaminopropane, 1, 4-diaminobutane, diethylene amine, pentaethylene hexamine, hexaethylene diamine, tetraethylene pentamine, polyether amine D400, polyether amine D230, ethylene diamine or 3,3' -4,4' -diamino-diphenylmethane MOCA.

4. An externally-repaired, internally-fixed, self-repairing microcapsule having a cellular structure prepared by the process of any one of claims 1-3, the self-repairing microcapsule comprising a wall and a wall-coated repairing agent, wherein: a series of nano-scale microcapsules are dispersed in the repairing agent, so that a cellular structure is formed; the nano-scale microcapsule is coated with a curing agent.

5. The externally-modified and internally-fixed self-repairing microcapsule with a cell structure according to claim 4, wherein: the capsule wall of the self-repairing microcapsule is a silane modified capsule wall obtained by reacting a repairing agent coated by the self-repairing microcapsule with a curing agent and a silane emulsion outside the self-repairing microcapsule; the curing agent is hydroxyl compound emulsion or amino compound emulsion, and the repairing agent is isocyanate emulsion.

6. The externally-modified and internally-fixed self-repairing microcapsule with a cellular structure according to claim 5, wherein: the capsule wall of the nano-scale microcapsule is obtained by the reaction of a curing agent coated by the nano-scale microcapsule and a repairing agent outside the nano-scale microcapsule.

7. A self-repairing system using the externally-repaired internally-cured self-repairing microcapsules having a cell structure according to any one of claims 4 to 6, wherein: the mass fraction of the external-repair and internal-fixation type silane functionalized self-repairing microcapsule with the cellular structure in a self-repairing system is 5-18%; the self-repairing system is self-repairing concrete or a self-repairing coating.