CN108975759A - With repairing outer curable type graphene functionalized self-repairing microcapsule and preparation method thereof in cell structure - Google Patents
With repairing outer curable type graphene functionalized self-repairing microcapsule and preparation method thereof in cell structure Download PDFInfo
- Publication number
- CN108975759A CN108975759A CN201810838460.XA CN201810838460A CN108975759A CN 108975759 A CN108975759 A CN 108975759A CN 201810838460 A CN201810838460 A CN 201810838460A CN 108975759 A CN108975759 A CN 108975759A
- Authority
- CN
- China
- Prior art keywords
- emulsion
- curing agent
- agent
- emulsifier
- self
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
Abstract
For the problems of self-healing system in the prior art, the present invention provides the graphene functionalized self-repairing microcapsules and preparation method thereof with cell structure.With outer curable type graphene functionalized self-repairing microcapsule is repaired in cell structure, including the curing agent that cyst wall and cyst wall coat, graphene is dispersed in the cyst wall；Serial micro/nano level microcapsules are dispersed in the curing agent, to constitute cell structure；Renovation agent is coated in the micro/nano level microcapsules.The self-repairing microcapsule system has the multicore clad structure of micro/nano level, not only increases the stability of microcapsules, while increasing the probability that renovation agent is contacted with curing agent, improves remediation efficiency.Furthermore, the cyst wall of the self-repairing microcapsule system is using silane-modified, unhydrolysed silane emulsion can form hydrophobic film in concrete capillary hole after microcapsules rupture, prevent the further diffusion of moisture, and the silane emulsion hydrolyzed can participate in the synthesis of wall material, improve the performance of microcapsules.
Description
Technical field
The invention belongs to organic composite material fields, are related to a kind of self-repair material, and in particular to one kind has born of the same parents' shape knot
Graphene functionalized self-repairing microcapsule of structure and preparation method thereof.
Background technique
With the continuous development of society, building trade is also quickly grown, various high buildings and large mansions, bridge road pick up successively and
It rises.Concrete is because its is from a wealth of sources, compression strength is high, easy construction and the excellent properties such as durability is higher due tos are widely used in
Building field.However, due to the concrete inherent shortcomings such as that there are tensile strength is low, brittleness is big, in construction and later period military service process
In, by the variation of external loads and ambient temperature and humidity, being also easy to produce micro-crack makes the reduction of its mechanical property, influences the durable of structure
Property.With the variation of load and the passage of time, crackle can gradually be extended to crack, or even extends into surface and lead to concrete material
Material cracking.After forming through crack, concrete is subject to the erosion and destruction of external environment and various adverse factors, such as steel
Muscle corrosion, carbonization, Chloride Attack and sulfate attack etc. eventually lead to the cracking of concrete material, destroy, seriously affect mixed
The durability of solidifying soil material, in some instances it may even be possible to cause sudden building destruction that the people's wealth that can not be retrieved is caused to lose.
Therefore, influence of the micro crack to durability is more and more widely paid close attention to and is paid attention to.To extend concrete
The service life of structure needs to repair crackle in time.There are two main classes for traditional restorative procedure: surface preparation and filling
Slurry processes.The former is mainly in the erosion-resisting organic coating of concrete structural surface brushing antiseepage, but organic coating is easy aging, and one
Coating can peel off after the section time；And the latter is then unable to judge accurately slip casting point and grouting quantity.In addition, these traditional restorative procedures
A large amount of man power and material is not only needed, but also there are palliative drawbacks, can not inhibit crack propagation, cannot repair knot
Fine crack existing for inside structure, will leave security risk to architectural engineering.
Have found that concrete sample can be after selfreparing from nineteen twenty-five Abrams, self-repair concrete technology starts to develop.
In recent years, become the hot spot of concrete selfreparing area research based on bionic self-repair technology.The bionical of concrete is reviewed one's lessons by oneself
Be again according to the principle that biology is injured in nature after secrete certain substance, so that wound site is healed and is developed in time, be one
The method for repairing and mending of kind intelligence, without relying on human assistance.To form intelligent self-healing system in concrete, need that reparation will be contained
In the preparatory Transducers Embedded in Concrete matrix of the carrier of agent, when matrix generates fine crack, under crack tip effect, carrier rupture is repaired
Multiple agent outflow, gos deep into the timely mended crack in crack.The technology carries out " targeting " for concrete cracks and repairs, and is embedded in advance in advance mixed
Solidifying soil is internal, is not necessarily to secondary maintenance, maintenance of works cost can be greatly reduced.
Currently, microcapsules self-healing system mainly includes that single wall microcapsules repair the double microcapsules reparation systems of system, single wall
With double-walled microcapsule systems.Single wall microcapsules are repaired system and had the following problems: (1) microcapsules thermo-chemical stability is poor；(2) anti-
Answer film-forming speed slow, it cannot effective filling cracks；(3) catalyst is expensive, is easy inactivation；(4) self-healing system is answered
It is relatively narrow with range, it can only be confined in certain substrate.The double microcapsule systems of single wall include two kinds of microcapsules, a kind of cladding reparation
Agent, a kind of cladding curing agent.The double microcapsule systems of single wall solve the problems, such as single wall microcapsule systems to a certain extent, but still
There are renovation agents can not contact simultaneously with curing agent, cannot quickly carry out repairing and manage the problems such as complicated to crackle answering machine.
Double-walled microcapsule systems have better stability, reduce the probability of renovation agent and curing agent inactivation；Considerably increase reparation
The contact probability of agent and catalyst avoids and adds excessive renovation agent and catalyst to the adverse effect of concrete performance.
Application for a patent for invention 201711236671.8 disclose " inside repair outer curable type polyureas base double-walled self-repairing microcapsule and its
Preparation method ".Outer curable type polyureas base double-walled self-repairing microcapsule is repaired in described, with aliphatic category isocyanates-amine terminated polyether
Polymer is as renovation agent, using amido chain extender as the double-walled microcapsule systems of curing agent.The renovation agent and curing agent are distinguished
It is stored in internal layer capsule-core and outer layer capsule-core, not only solves the problems, such as that the contact rate of renovation agent and curing agent is relatively low, Er Qiexiu
Multiple agent and curing agent rapid reaction, to realize the quick reparation of crackle.However, the self-repairing microcapsule of micron scale construction exists
Concrete test block stirring easily ruptures during vibrating, and causes remaining microcapsules negligible amounts in concrete, can not
Realization timely responds to crackle.
Application for a patent for invention 201710331413.1 discloses " modified self-repairing microcapsule in surface and preparation method thereof ".Institute
The surface treating agent that the modified self-repairing microcapsule in surface selects silane coupling agent as microcapsules is stated, the acyl of amino and carboxyl is passed through
Aminating reaction grafting carbon nanotube on surface of microcapsule has while improving the interface performance of microcapsules and resin matrix
Anti-static function.But the effect of silane coupling agent differs widely with silane emulsion effect, the former is mainly used for organic-inorganic interface
Bonding, the latter more emphasize its prevent water diffusion to substrate formed protection in terms of effect.
In addition, being modified to the wall material of microcapsules becomes the emphasis that researcher pays close attention in recent years to improve its performance also；
Wherein, graphene is favored as a kind of functional material with excellent thermodynamic property.Application for a patent for invention
2017100094514.1 disclosing a kind of modified graphene phase-change microcapsule and preparation method, ethylenediamine reduced graphene is utilized
The modification of amido grafting is carried out to its surface, the effect microcapsule wall made is more uniform, and effectively improves its thermally conductive system
Number.Application for a patent for invention 201510274641.0 discloses a kind of preparation side's valve of the phase-change microcapsule of modified wall material of graphene,
Mainly graphene oxide is dispersed by sonic oscillation, and it is mixed with wall material prepolymer, is realized micro- to phase transformation
The modification of capsule wall material thermal conductivity and mechanical property reduces the permeability of wall material.But the graphite oxide in foregoing invention
Alkene price is more expensive, limits the industrialized production of the technology to a certain extent.
Summary of the invention
For the problems of self-healing system in the prior art, the present invention provides the graphenes with cell structure
Functionalization self-repairing microcapsule and preparation method thereof.The self-repairing microcapsule system has the multicore cladding knot of micro/nano level
Structure, not only increases the stability of microcapsules, while increasing the probability that renovation agent is contacted with curing agent, improves reparation effect
Rate.In addition, the cyst wall of the self-repairing microcapsule system, using silane-modified, unhydrolysed silane emulsion can after microcapsules rupture
To form hydrophobic film in concrete capillary hole, the further diffusion of moisture is prevented, and the silane emulsion hydrolyzed can
To participate in the synthesis of wall material, the performance of microcapsules is improved.
Technical solution of the present invention:
With repairing outer curable type graphene functionalized self-repairing microcapsule in cell structure, the self-repairing microcapsule includes
The curing agent of cyst wall and cyst wall cladding, is dispersed with graphene in the cyst wall；Serial micro/nano level is dispersed in the curing agent
Microcapsules, to constitute cell structure；Renovation agent is coated in the micro/nano level microcapsules.The curing agent is hydroxy compounds
Lotion or amine compound lotion, the renovation agent are isocyanate emulsion.
Wherein, the curing agent for being dispersed with graphene that the cyst wall of the self-repairing microcapsule is coated by self-repairing microcapsule with
The silane-modified cyst wall that isocyanate emulsion, silane emulsion outside self-repairing microcapsule react；The micro/nano level
The cyst wall of microcapsules is reacted to obtain by the renovation agent of micro/nano level microcapsule coated with the curing agent outside micro/nano level microcapsules
Cyst wall, the graphene be oxygen plasma modified graphene.
With the preparation method for repairing outer curable type graphene functionalized self-repairing microcapsule in cell structure, including following step
It is rapid:
(1) oil-in-water type silane emulsion 1 is prepared:
(1a) weighs appropriate silane, emulsifier and dispersing agent, the weight ratio 80:1:1- of silane, emulsifier and dispersing agent
120:5:1, room temperature stir 15-30min under the revolving speed of 2000-4000rpm and obtain finely dispersed oily phase；(1b) is weighed in right amount
The weight ratio of emulsifier and water, emulsifier and water is 1:80-1:120, and room temperature stirs 15-30min at 1000-3000rpm and obtains
To compound water phase；(1c) is mutually gradually dripped to oily in water phase, and oil is mutually and the weight ratio of water phase is 1:0.8-1:1.5, at 40-60 DEG C
5000-10000rpm stirs 4-5h, obtains uniform and stable oil-in-water type multiple emulsion, i.e. silane emulsion 1.
(2) micro/nano level microcapsule emulsion is prepared:
(2a) weighs appropriate isocyanates renovation agent, solvent and emulsifier, and room temperature stirs 60- at 3000-7000rpm
100min obtains isocyanates and repairs agent emulsion 2a1；The weight ratio of the isocyanates renovation agent, solvent and emulsifier is
1:(15-20):(0.08-0.15).(2b) weighs appropriate curing agent, solvent and emulsifier, and room temperature is stirred at 5000-9000rpm
80-120min is mixed, curing agent emulsion 2b1 is obtained；The weight ratio of curing agent, solvent and emulsifier is 1:(10-15): (0.08-
0.18).Curing agent emulsion 2b1 is added dropwise isocyanates and repaired in agent emulsion 2a1 by (2c), and room temperature is at 2000-6000rpm
1-2h is stirred, isocyanates repairs the curing agent in agent emulsion 2a1 and curing agent emulsion 2b1 and interfacial reaction occurs, cyst wall is generated,
To obtain the micro/nano level microcapsule emulsion 2 of cladding renovation agent；The isocyanates repairs agent emulsion 2a1 and curing agent cream
The weight ratio 1:1-1:5 of liquid 2b1.In this step, it is necessary to use high speed rotation, can just obtain micro/nano level microcapsule emulsion；And
And the drop of isocyanates is opposite bigger than the drop of curing agent emulsion, to make curing agent emulsion droplet distribution in isocyanates
Interfacial reaction occurs for the surface of emulsion droplet, generates cyst wall.
(3) preparation of the modifies graphene emulsion of oxygen plasma: appropriate graphene powder is taken to be placed in oxygen plasma instrument
In device, it is vacuum-treated 3-5min under conditions of 200mTorr-400Torr, is then introduced into the oxygen 3-5min of 3-5ml/min,
Make to connect carbonyl, hydroxy or carboxy functional group on graphene surface, obtains modified graphene powder；Modified graphene powder is molten
It in appropriate solvent, is stirred evenly at 1000-2000rpm, obtains modified graphene lotion 3.
(4) there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule for preparation:
(4a) weighs appropriate isocyanates reagent, emulsifier and solvent, room temperature uniform stirring at 3000-6000rpm
70-100min obtains isocyanate emulsion 4a2；The weight ratio of isocyanates reagent, emulsifier and solvent is 1:(15-20):
(0.06-0.12)。
(4b) weighs appropriate curing agent, modified graphene lotion 3, dispersing agent and solvent, and room temperature is at 2000-5000rpm
50-70min is stirred, curing agent-graphene dispersing solution 4b2 is obtained；Curing agent, modified graphene lotion 3, solvent and dispersing agent
Weight ratio is 1:(0.4-0.8): (10-15): (0.06-0.15).
Appropriate silane emulsion 1, micro/nano level microcapsules cream is added in (4c) into curing agent-graphene dispersing solution 4b2 first
Liquid 2 and emulsifier, then in the emulsified 1-2h of revolving speed of room temperature, 1500-3500rpm, being formed includes the micro- glue of multiple micro/nano levels
The composite solution of the emulsion droplet of capsule；Then isocyanate emulsion 4a2 is added dropwise into composite solution, in 50-70 DEG C of temperature strip
2-3h, isocyanate emulsion 4a2 and consolidating comprising multiple micro/nano level microcapsules are stirred under the revolving speed of part and 1000-2500rpm
Interfacial reaction occurs for agent emulsion droplet, generates cyst wall；Obtain that there is the interior of cell structure to repair outer curable type graphene functionalized certainly
Repair microcapsule emulsion；The curing agent-graphene dispersing solution 4b2, silane emulsion 1, nanometer-sized microcapsules lotion 2, emulsifier
Weight ratio with isocyanate emulsion 4a2 is 1:(0.5-0.8): (0.5-0.8): (0.15-0.25): (1-3).The pass of the application
Key step is: micro-nano microcapsules being added dropwise first, then emulsifies curing agent and obtains compound system, it includes multiple for could being formed in this way
The emulsion droplet of micro-nano microcapsules.
The lotion that (4d) obtains (4c) is centrifuged, washs, is dry, obtains that there is the interior of cell structure to repair outer curable type graphene
Functionalization self-repairing microcapsule.Graphene functionalized self-repairing microcapsule of the present invention, is completed when the micro capsules are broken
Hydrophobic film can be formed while to crack forming mechanism in concrete pore again, effectively prevent the further infiltration of moisture.
Preferably, it in the step (4c), when to mixed solution and dripping isocyanate emulsion 4a2, while being added dropwise suitable
Amount acid, makes the pH value 4-6 of system；Purpose is to speed up silane emulsion hydrolysis and generates silica, to participate in the preparation of wall material.
SiO2Nanoparticle participates in the synthesis process of cyst wall, improve to a certain extent mechanical property, the responding ability of cyst wall with
And the adhesive force of microcapsules and concrete substrate.
Wherein, the silane be vinyltriethoxysilane, it is vinyltrimethoxysilane, ethyl orthosilicate, different
One or more of butyl triethoxysilane, trimethylsiloxy silane and octyltri-ethoxysilane.
The emulsifier is Op-10, polyvinyl alcohol, Span 80, Arabic gum, neopelex and octadecanol
One or more of base polyoxyethylene ether.
The dispersing agent is in polyethylene glycol, potassium citrate, sodium metasilicate, linoleic acid sodium and orthophosphoric acid acid sodium ethylene oxide ether
It is one or more of.
The isocyanates renovation agent is that '-diphenylmethane diisocyanate, toluene di-isocyanate(TDI), different Fu Er ketone two are different
Cyanate, 1,6- hexamethylene diisocyanate, 2,2,5- trimethylhexane diisocyanates and tetramethyl are for m-phenylenedimethylim-
One or more of diisocyanate.The solvent is ethyl acetate, glycol dimethyl ether, hexamethylene, pentamethylene, hexamethylene
One or more of alcohol, toluene, dimethylbenzene and chlorobenzene.
The curing agent is hydroxy compounds or amine compound；The hydroxy compounds is 1,4-butanediol, positive fourth
Alcohol, pentanediol, 1,6- hexylene glycol, cyclohexanedimethanol, pentaerythrite, polyoxypropylene polyol and polytetrahydrofuran polyol
One or more of；The amine compound is diethyl toluene diamine, dimethythiotoluene diamine, N, N'- dialkyl group first
Base diphenylamines, cyclohexane diamine, chlorination MDH, ethylenediamine, 1,3- diaminopropanes, 1,4- diaminobutane, diethylidene amine,
Penten, six ethylene diamines, tetren, penten, polyetheramine D400, polyetheramine D230, second
Diamines or 3,3'-4,4'- diamino-diphenyl-methane MOCA.
Using described with the self-healing system for repairing outer curable type graphene functionalized self-repairing microcapsule in cell structure,
It is described that there is the interior of cell structure to repair mass fraction of the outer curable type graphene functionalized self-repairing microcapsule in self-healing system
For 5%-18%；The self-healing system is self-repair concrete or coatings.
Beneficial effects of the present invention:
(1) of the present invention that there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule, cyst wall
Serial micro/nano level microcapsules are dispersed in the curing agent of cladding --- i.e. multicore capsule size is nanoscale, so as to big
Width reduces the probability that microcapsules rupture during concrete for making, greatly improves self-repair efficiency；And the cyst wall
In be dispersed with plasma modification graphene, not only further enhance the performance of cyst wall, and used method of modifying is simple
It is easy to operate, production cost is greatly reduced, industrialized production is conducive to.
(2) repairing outer curable type graphene functionalized self-repairing microcapsule in of the present invention is silane-modified microcapsules；Cause
This, when the micro capsules are broken, while completing to crack forming mechanism, unhydrolysed silane emulsion can be in concrete pore
Formed hydrophobic film, effectively prevent the further infiltration of moisture, thus efficiently solve maritime concrete during military service by
In steam invade and harass and the problem of accelerate concrete erosion.
(3) it is repaired in the preparation process of outer curable type graphene functionalized self-repairing microcapsule in of the present invention, silane cream
The SiO that liquid hydrolysis generates2Nanoparticle participates in the synthesis process of cyst wall, improves the mechanical property of cyst wall to a certain extent
The adhesive force of energy, responding ability and microcapsules and concrete substrate.
(4) of the present invention with repairing outer curable type graphene functionalized self-repairing microcapsule in cell structure, and it is existing
Some double-walled microcapsules are compared, and curing agent and renovation agent react more rapidly, therefore, are accelerated repairing effect, are realized counterincision
The timely reparation of line avoids more serious consequence and higher rehabilitation cost.
Detailed description of the invention
Attached drawing 1 is with the structural schematic diagram for repairing outer curable type graphene functionalized self-repairing microcapsule in cell structure；
Wherein A is curing agent microcapsules, and B is renovation agent microcapsules.
Attached drawing 2 for prepared by embodiment 6 there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule
Light microscopic figure.
Specific embodiment
The present invention will be further explained with reference to the examples below.
Embodiment 1:
With the preparation method for repairing outer curable type graphene functionalized self-repairing microcapsule in cell structure, including following step
It is rapid:
(1) oil-in-water type silane emulsion 1 is prepared:
(1a) weighs appropriate silane, emulsifier and dispersing agent, the weight ratio 80:1:1 of silane, emulsifier and dispersing agent, often
Temperature stirs 30min under the revolving speed of 2000rpm, obtains finely dispersed oily phase；The silane is vinyl triethoxyl silicon
Alkane, the emulsifier are Op-10, and the dispersing agent is polyethylene glycol.
(1b) weighs appropriate Emulsifier O p-10 and water, and the weight ratio of emulsifier and water is 1:110, and room temperature is at 1400rpm
Stirring 26min obtains compound water phase；
(1c) is mutually gradually dripped to oily in water phase, and oil is mutually and the weight ratio of water phase is 1:1.2, and 7000rpm is stirred at 44 DEG C
4h obtains uniform and stable oil-in-water type multiple emulsion, i.e. silane emulsion 1.
(2) micro/nano level microcapsule emulsion is prepared:
(2a) weighs appropriate isocyanates renovation agent, solvent and emulsifier, and room temperature stirs 80min at 5400rpm, obtains
Agent emulsion 2a1 is repaired to isocyanates；The weight ratio of the isocyanates renovation agent, solvent and emulsifier is 1:15:0.08.
The isocyanates renovation agent is '-diphenylmethane diisocyanate, and the solvent is ethyl acetate, and the emulsifier is Op-
10。
(2b) weighs appropriate curing agent, solvent and emulsifier, and room temperature stirs 80min at 6600rpm, obtains curing agent cream
Liquid 2b1；The weight ratio of curing agent, solvent and emulsifier is 1:10:0.12.The curing agent is hydroxy compounds, the hydroxyl
Compound is 1,4-butanediol；The solvent is ethyl acetate；The emulsifier is Op-10.
Curing agent emulsion 2b1 is added dropwise isocyanates and repaired in agent emulsion 2a1 by (2c), and room temperature is stirred at 6000rpm
1h is mixed, isocyanates repairs the curing agent in agent emulsion 2a1 and curing agent emulsion 2b1 and interfacial reaction occurs, cyst wall is generated, thus
Obtain the micro/nano level microcapsule emulsion 2 of cladding renovation agent；The isocyanates repairs agent emulsion 2a1 and curing agent emulsion
The weight ratio 1:2 of 2b1.This step must use high speed rotation, can just obtain micro/nano level microcapsule emulsion；And isocyanates
The opposite drop than curing agent emulsion of drop more greatly.
(3) preparation of the modifies graphene emulsion of oxygen plasma: appropriate graphene powder is taken to be placed in oxygen plasma instrument
In device, it is vacuum-treated 3-5min under conditions of 200mTorr-400Torr, is then introduced into the oxygen 3-5min of 3-5ml/min,
Make to connect carbonyl, hydroxy or carboxy functional group on graphene surface, obtains modified graphene powder；Modified graphene powder is molten
It in appropriate solvent, stirs evenly at 1600 rpm, obtains modified graphene lotion 3.
(4) there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule for preparation:
(4a) weighs appropriate isocyanates reagent, emulsifier and solvent, room temperature uniform stirring at 3,000 rpm
100min obtains isocyanate emulsion 4a2；The weight ratio of isocyanates reagent, solvent and emulsifier is 1:15:0.06.Institute
Stating isocyanates renovation agent is '-diphenylmethane diisocyanate；The emulsifier is Op-10；The solvent is ethyl acetate.
(4b) weighs appropriate curing agent, modified graphene lotion 3, dispersing agent and solvent, and room temperature is stirred at 2200rpm
60min obtains curing agent-graphene dispersing solution 4b2；Curing agent, modified graphene lotion 3, the weight ratio of solvent and dispersing agent
For 1:0.4:10:0.06.The curing agent is hydroxy compounds, and the hydroxy compounds is 1,4-butanediol；The dispersing agent
For polyethylene glycol；The solvent is ethyl acetate.
A certain amount of silane emulsion 1, micro/nano level microcapsules is added in (4c) into curing agent-graphene dispersing solution 4b2 first
Lotion 2 and emulsifier are formed then in the emulsified 1.5h of revolving speed of room temperature, 2200rpm comprising multiple micro/nano level microcapsules
The composite solution of emulsion droplet；The outer layer of the emulsion droplet is curing agent.The emulsifier is Op-10.Then to compound molten
Appropriate amount of acid is added dropwise in liquid, makes the pH value 5 of system；Then isocyanate emulsion 4a2 is added dropwise, in 65 DEG C of temperature conditions and
2h, isocyanate emulsion 4a2 and the curing agent emulsion drop comprising multiple micro/nano level microcapsules are stirred under the revolving speed of 2000rpm
Interfacial reaction occurs, generates cyst wall.Obtain that there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule cream
Liquid；The curing agent-graphene dispersing solution 4b2, silane emulsion 1, nanometer-sized microcapsules lotion 2, emulsifier and isocyanates cream
The weight ratio of liquid 4a2 is 1:0.5:0.5:0.15:1.The committed step of the application is: micro-nano microcapsules are added dropwise first, then
Emulsification curing agent obtains compound system, could form the emulsion droplet comprising multiple micro-nano microcapsules in this way.To composite solution
The middle purpose that acid is added dropwise is to accelerate silane emulsion hydrolysis to generate silica, to participate in the preparation of wall material.Modified graphene and
SiO2Nanoparticle participates in the synthesis process of cyst wall, improve to a certain extent mechanical property, the responding ability of cyst wall with
And the adhesive force of microcapsules and concrete substrate.
The lotion that (4d) obtains (4c) is centrifuged, washs, is dry, obtains that there is the interior of cell structure to repair outer curable type graphene
Functionalization self-repairing microcapsule.Self-repairing microcapsule of the present invention is completed to crack forming mechanism when the micro capsules are broken
Hydrophobic film can be formed in concrete pore again simultaneously, effectively prevent the further infiltration of moisture.
Compound is reviewed one's lessons by oneself with repair outer curable type graphene functionalized self-repairing microcapsule in cell structure using described
Solidifying soil, mass fraction of the self-repairing microcapsule in self-repair concrete are 10%.
Embodiment 2:
Unlike the first embodiment, there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule
Preparation method, comprising the following steps:
(1) oil-in-water type silane emulsion 1 is prepared:
(1a) weighs appropriate silane, emulsifier and dispersing agent, the weight ratio 100:2:1 of silane, emulsifier and dispersing agent, often
Temperature stirs 26min under the revolving speed of 2400rpm, obtains finely dispersed oily phase；The silane is vinyl trimethoxy silicon
Alkane, the emulsifier are polyvinyl alcohol, and the dispersing agent is potassium citrate.
(1b) weighs appropriate emulsifier polyethylene alcohol and water, and the weight ratio of emulsifier and water is 1:120, and room temperature exists
22min is stirred under 1800rpm obtains compound water phase；
(1c) is mutually gradually dripped to oily in water phase, and oil is mutually and the weight ratio of water phase is 1:1.4, and 8000rpm is stirred at 48 DEG C
4h obtains uniform and stable oil-in-water type multiple emulsion, i.e. silane emulsion 1.
(2) micro/nano level microcapsule emulsion is prepared:
(2a) weighs appropriate isocyanates renovation agent, solvent and emulsifier, and room temperature stirs 90min at 6200rpm, obtains
Agent emulsion 2a1 is repaired to isocyanates；The weight ratio of the isocyanates renovation agent, solvent and emulsifier is 1:16:0.08.
The isocyanates renovation agent is toluene di-isocyanate(TDI), and the solvent is glycol dimethyl ether, and the emulsifier is poly- second
Enol.
(2b) weighs appropriate curing agent, solvent and emulsifier, and room temperature stirs 85min at 9000rpm, obtains curing agent cream
Liquid 2b1；The weight ratio of curing agent, solvent and emulsifier is 1:10:0.15.The curing agent is hydroxy compounds, the hydroxyl
Compound is the mixture of n-butanol and pentanediol；The solvent is glycol dimethyl ether, and the emulsifier is Span 80.
Curing agent emulsion 2b1 is added dropwise isocyanates and repaired in agent emulsion 2a1 by (2c), and room temperature is stirred at 2000rpm
2h is mixed, isocyanates repairs the curing agent in agent emulsion 2a1 and curing agent emulsion 2b1 and interfacial reaction occurs, cyst wall is generated, thus
Obtain the micro/nano level microcapsule emulsion 2 of cladding renovation agent；The isocyanates repairs agent emulsion 2a1 and curing agent emulsion
The weight ratio 1:3 of 2b1.
(3) preparation of the modifies graphene emulsion of oxygen plasma: modified graphene powder is dissolved in appropriate solvent,
It is stirred evenly under 1800rpm, obtains modified graphene lotion 3.
(4) there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule for preparation:
(4a) weighs appropriate isocyanates reagent, emulsifier and solvent, room temperature uniform stirring 95min at 3600rpm,
Obtain isocyanate emulsion 4a2；The weight ratio of isocyanates reagent, solvent and emulsifier is 1:18:0.06.The isocyanic acid
Esters renovation agent is isofoer diisocyanate, and the emulsifier is polyvinyl alcohol, and the solvent is hexamethylene.
(4b) weighs appropriate curing agent, modified graphene lotion 3, dispersing agent and solvent, and room temperature is stirred at 2800rpm
65min obtains curing agent-graphene dispersing solution 4b2；Curing agent, modified graphene lotion 3, the weight ratio of solvent and dispersing agent
For 1:0.5:10:0.09.The curing agent is hydroxy compounds, and the hydroxy compounds is n-butanol；The dispersing agent is silicon
Sour sodium, the solvent are hexamethylene, pentamethylene.
A certain amount of silane emulsion 1, micro/nano level microcapsules is added in (4c) into curing agent-graphene dispersing solution 4b2 first
Lotion 2 and emulsifier are formed then in the emulsified 1.5h of revolving speed of room temperature, 2600rpm comprising multiple micro/nano level microcapsules
The composite solution of emulsion droplet；The outer layer of the emulsion droplet is curing agent.The emulsifier is Span 80.Then to compound molten
Appropriate amount of acid is added dropwise in liquid, makes the pH value 5.5 of system；Isocyanate emulsion 4a2 is added dropwise, in 70 DEG C of temperature conditions and
2.5h, isocyanate emulsion 4a2 and the curing agent emulsion liquid comprising multiple micro/nano level microcapsules are stirred under the revolving speed of 2300rpm
Interfacial reaction occurs for drop, generates cyst wall.Obtain that there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule
Lotion；The curing agent-graphene dispersing solution 4b2, silane emulsion 1, nanometer-sized microcapsules lotion 2, emulsifier and isocyanates
The weight ratio of lotion 4a2 is 1:0.65:0.5:0.18:1.
The lotion that (4d) obtains (4c) is centrifuged, washs, is dry, obtains that there is the interior of cell structure to repair outer curable type graphene
Functionalization self-repairing microcapsule.
Overcoating is reviewed one's lessons by oneself with repair outer curable type graphene functionalized self-repairing microcapsule in cell structure using described
Layer, mass fraction of the self-repairing microcapsule in coatings are 15%.
Embodiment 3:
Unlike the first embodiment, there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule
Preparation method, comprising the following steps:
(1) oil-in-water type silane emulsion 1 is prepared:
(1a) weighs appropriate silane, emulsifier and dispersing agent, the weight ratio 120:2.5:1 of silane, emulsifier and dispersing agent,
Room temperature stirs 22min under the revolving speed of 2800rpm, obtains finely dispersed oily phase；The silane is isobutyl group triethoxy
Silane, the emulsifier are neopelex, and the dispersing agent is linoleic acid sodium.
(1b) weighs appropriate emulsifier neopelex and water, and the weight ratio of emulsifier and water is 1:105, room temperature
20min is stirred at 2200rpm obtains compound water phase；
(1c) is mutually gradually dripped to oily in water phase, and oil is mutually and the weight ratio of water phase is 1:1.5, and 9000rpm is stirred at 52 DEG C
4.5h obtains uniform and stable oil-in-water type multiple emulsion, i.e. silane emulsion 1.
(2) micro/nano level microcapsule emulsion is prepared:
(2a) weighs appropriate isocyanates renovation agent, solvent and emulsifier, and room temperature stirs 100min at 7000rpm,
It obtains isocyanates and repairs agent emulsion 2a1；The weight ratio of the isocyanates renovation agent, solvent and emulsifier is 1:18:
0.08.The isocyanates renovation agent is 1,6- hexamethylene diisocyanate, and the solvent is cyclohexanol, the emulsifier
For neopelex.
(2b) weighs appropriate curing agent, solvent and emulsifier, and room temperature stirs 120min at 8500rpm, obtains curing agent
Lotion 2b1；The weight ratio of curing agent, solvent and emulsifier is 1:15:0.18.The curing agent is hydroxy compounds, the hydroxyl
Based compound is pentaerythrite；The amine compound be cyclohexane diamine, the solvent be pentamethylene, the emulsifier be Ah
Draw primary glue.
Curing agent emulsion 2b1 is added dropwise isocyanates and repaired in agent emulsion 2a1 by (2c), and room temperature is stirred at 2800rpm
2h is mixed, isocyanates repairs the curing agent in agent emulsion 2a1 and curing agent emulsion 2b1 and interfacial reaction occurs, cyst wall is generated, thus
Obtain the micro/nano level microcapsule emulsion 2 of cladding renovation agent；The isocyanates repairs agent emulsion 2a1 and curing agent emulsion
The weight ratio 1:4 of 2b1.
(3) preparation of the modifies graphene emulsion of oxygen plasma: modified graphene powder is dissolved in appropriate solvent,
It is stirred evenly under 2000rpm, obtains modified graphene lotion 3.
(4) there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule for preparation:
(4a) weighs appropriate isocyanates reagent, emulsifier and solvent, room temperature uniform stirring 90min at 4200rpm,
Obtain isocyanate emulsion 4a2；The weight ratio of isocyanates reagent, solvent and emulsifier is 1:20:0.06.The isocyanic acid
Esters renovation agent is 1,6- hexamethylene diisocyanate, and the emulsifier is Arabic gum, and the solvent is hexamethylene.
(4b) weighs appropriate curing agent, modified graphene lotion 3, dispersing agent and solvent, and room temperature is stirred at 3400rpm
70min obtains curing agent-graphene dispersing solution 4b2；Curing agent, modified graphene lotion 3, the weight ratio of solvent and dispersing agent
For 1:0.6:10:0.12.The curing agent amine group compound, the amine compound are diethyl toluene diamine；The dispersion
Agent is linoleic acid sodium, and the solvent is hexamethylene.
A certain amount of silane emulsion 1, micro/nano level microcapsules is added in (4c) into curing agent-graphene dispersing solution 4b2 first
Lotion 2 and emulsifier form the cream comprising multiple micro/nano level microcapsules then in the emulsified 1h of revolving speed of room temperature, 3000rpm
Change the composite solution of drop；The outer layer of the emulsion droplet is curing agent.The emulsifier is neopelex.Then
Appropriate amount of acid is added dropwise into composite solution, makes the pH value 6 of system；Then isocyanate emulsion 4a2 is added dropwise, in 50 DEG C of temperature strip
2.5h, isocyanate emulsion 4a2 and the curing agent cream comprising multiple micro/nano level microcapsules are stirred under the revolving speed of part and 2500rpm
Interfacial reaction occurs for liquid drop, generates cyst wall.Obtain having cell structure in repair outer curable type graphene functionalized selfreparing micro-
Capsule lotion；The curing agent-graphene dispersing solution 4b2, silane emulsion 1, nanometer-sized microcapsules lotion 2, emulsifier and isocyanide
The weight ratio of acid esters lotion 4a2 is 1:0.8:0.5:0.18:1.
The lotion that (4d) obtains (4c) is centrifuged, washs, is dry, obtains that there is the interior of cell structure to repair outer curable type graphene
Functionalization self-repairing microcapsule.
Compound is reviewed one's lessons by oneself with repair outer curable type graphene functionalized self-repairing microcapsule in cell structure using described
Solidifying soil, mass fraction of the self-repairing microcapsule in self-repair concrete are 18%.
Embodiment 4:
Unlike the first embodiment, there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule
Preparation method, comprising the following steps:
(1) oil-in-water type silane emulsion 1 is prepared:
(1a) weighs appropriate silane, emulsifier and dispersing agent, the weight ratio 90:3:1 of silane, emulsifier and dispersing agent, often
Temperature stirs 20min under the revolving speed of 3200rpm, obtains finely dispersed oily phase；The silane is trimethylsiloxy silane,
The emulsifier is octadecane alcohol radical APEO, and the dispersing agent is sodium metasilicate.
(1b) weighs appropriate emulsifier octadecane alcohol radical APEO and water, and the weight ratio of emulsifier and water is 1:80,
Room temperature stirs 18min at 2600rpm and obtains compound water phase；
(1c) is mutually gradually dripped to oily in water phase, and oil is mutually and the weight ratio of water phase is 1:1.1, and 10000rpm is stirred at 56 DEG C
4.5h obtains uniform and stable oil-in-water type multiple emulsion, i.e. silane emulsion 1.
(2) micro/nano level microcapsule emulsion is prepared:
(2a) weighs appropriate isocyanates renovation agent, solvent and emulsifier, room temperature and stirs 60min at 3,000 rpm, obtains
Agent emulsion 2a1 is repaired to isocyanates；The weight ratio of the isocyanates renovation agent, solvent and emulsifier is 1:20:0.15.
The isocyanates renovation agent is 1,6- hexamethylene diisocyanate, and the solvent is toluene, and the emulsifier is 18
Silane alcohol base polyoxyethylene ether.
(2b) weighs appropriate curing agent, solvent and emulsifier, and room temperature stirs 110min at 5800rpm, obtains curing agent
Lotion 2b1；The weight ratio of curing agent, solvent and emulsifier is 1:10:0.08.The curing agent is amine compound, the amine
Based compound is ethylenediamine；The solvent is dimethylbenzene, and the emulsifier is octadecane alcohol radical APEO.
Curing agent emulsion 2b1 is added dropwise isocyanates and repaired in agent emulsion 2a1 by (2c), and room temperature is stirred at 3600rpm
1.5h is mixed, isocyanates repairs the curing agent in agent emulsion 2a1 and curing agent emulsion 2b1 and interfacial reaction occurs, cyst wall is generated, from
And obtain the micro/nano level microcapsule emulsion 2 of cladding renovation agent；The isocyanates repairs agent emulsion 2a1 and curing agent emulsion
The weight ratio 1:5 of 2b1.
(3) preparation of the modifies graphene emulsion of oxygen plasma: modified graphene powder is dissolved in appropriate solvent,
It is stirred evenly under 1000rpm, obtains modified graphene lotion 3.
(4) there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule for preparation:
(4a) weighs appropriate isocyanates reagent, emulsifier and solvent, room temperature uniform stirring 85min at 4800rpm,
Obtain isocyanate emulsion 4a2；The weight ratio of isocyanates reagent, solvent and emulsifier is 1:15:0.08.The isocyanic acid
Esters renovation agent is 1,6- hexamethylene diisocyanate, and the emulsifier is Arabic gum, and the solvent is cyclohexanol.
(4b) weighs appropriate curing agent, modified graphene lotion 3, dispersing agent and solvent, and room temperature is stirred at 4000rpm
60min obtains curing agent-graphene dispersing solution 4b2；Curing agent, modified graphene lotion 3, the weight ratio of solvent and dispersing agent
For 1:0.7:10:0.15.The curing agent is amine compound, and the amine compound is cyclohexane diamine, the dispersing agent
For sodium metasilicate, the solvent is chlorobenzene.
A certain amount of silane emulsion 1, micro/nano level microcapsules is added in (4c) into curing agent-graphene dispersing solution 4b2 first
Lotion 2 and emulsifier form the cream comprising multiple micro/nano level microcapsules then in the emulsified 1h of revolving speed of room temperature, 3500rpm
Change the composite solution of drop；The outer layer of the emulsion droplet is curing agent.The emulsifier is Span 80.Then to composite solution
Middle dropwise addition appropriate amount of acid makes the pH value 4 of system；Then isocyanate emulsion 4a2 is added dropwise, in 55 DEG C of temperature conditions and
3h, isocyanate emulsion 4a2 and the curing agent emulsion drop comprising multiple micro/nano level microcapsules are stirred under the revolving speed of 1000rpm
Interfacial reaction occurs, generates cyst wall.Obtain that there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule cream
Liquid；The curing agent-graphene dispersing solution 4b2, silane emulsion 1, nanometer-sized microcapsules lotion 2, emulsifier and isocyanates cream
The weight ratio of liquid 4a2 is 1:0.5:0.65:0.25:2.
The lotion that (4d) obtains (4c) is centrifuged, washs, is dry, obtains that there is the interior of cell structure to repair outer curable type graphene
Functionalization self-repairing microcapsule.
Overcoating is reviewed one's lessons by oneself with repair outer curable type graphene functionalized self-repairing microcapsule in cell structure using described
Layer, mass fraction of the self-repairing microcapsule in coatings are 10%.
Embodiment 5:
Unlike the first embodiment, there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule
Preparation method, comprising the following steps:
(1) oil-in-water type silane emulsion 1 is prepared:
(1a) weighs appropriate silane, emulsifier and dispersing agent, the weight ratio 110:4:1 of silane, emulsifier and dispersing agent, often
Temperature stirs 18min under the revolving speed of 3600rpm, obtains finely dispersed oily phase；The silane is trimethylsiloxy silane,
The emulsifier is octadecane alcohol radical APEO, and the dispersing agent is sodium metasilicate.
(1b) weighs appropriate emulsifier octadecane alcohol radical APEO and water, and the weight ratio of emulsifier and water is 1:90,
Room temperature stirs 15min at 3,000 rpm and obtains compound water phase；
(1c) is mutually gradually dripped to oily in water phase, and oil is mutually and the weight ratio of water phase is 1:0.8, and 5000rpm is stirred at 60 DEG C
5h obtains uniform and stable oil-in-water type multiple emulsion, i.e. silane emulsion 1.
(2) micro/nano level microcapsule emulsion is prepared:
(2a) weighs appropriate isocyanates renovation agent, solvent and emulsifier, and room temperature stirs 70min at 3800rpm, obtains
Agent emulsion 2a1 is repaired to isocyanates；The weight ratio of the isocyanates renovation agent, solvent and emulsifier is 1:20:0.12.
The isocyanates renovation agent is tetramethyl for m-xylylene diisocyanate, and the solvent is chlorobenzene, the emulsifier
For octadecane alcohol radical APEO.
(2b) weighs appropriate curing agent, solvent and emulsifier, and room temperature stirs 100min at 5000rpm, obtains curing agent
Lotion 2b1；The weight ratio of curing agent, solvent and emulsifier is 1:12:0.18.The curing agent is amine compound, the amine
Based compound is tetren, and the solvent is hexamethylene, and the emulsifier is Arabic gum.
Curing agent emulsion 2b1 is added dropwise isocyanates and repaired in agent emulsion 2a1 by (2c), and room temperature is stirred at 4200rpm
1.5h is mixed, isocyanates repairs the curing agent in agent emulsion 2a1 and curing agent emulsion 2b1 and interfacial reaction occurs, cyst wall is generated, from
And obtain the micro/nano level microcapsule emulsion 2 of cladding renovation agent；The isocyanates repairs agent emulsion 2a1 and curing agent emulsion
The weight ratio 1:1 of 2b1.
(3) preparation of the modifies graphene emulsion of oxygen plasma: modified graphene powder is dissolved in appropriate solvent,
It is stirred evenly under 1200rpm, obtains modified graphene lotion 3.
(4) there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule for preparation:
(4a) weighs appropriate isocyanates reagent, emulsifier and solvent, room temperature uniform stirring 80min at 5400rpm,
Obtain isocyanate emulsion 4a2；The weight ratio of isocyanates reagent, solvent and emulsifier is 1:15:0.10.The isocyanic acid
Esters renovation agent is isofoer diisocyanate, and the emulsifier is neopelex, and the solvent is hexamethylene.
(4b) weighs appropriate curing agent, modified graphene lotion 3, dispersing agent and solvent, and room temperature is stirred at 5000rpm
50min obtains curing agent-graphene dispersing solution 4b2；Curing agent, modified graphene lotion 3, the weight ratio of solvent and dispersing agent
For 1:0.8:12:0.10.The curing agent is amine compound, and the amine compound is diethylidene amine, the dispersing agent
For sodium metasilicate, the solvent is cyclohexanol.
A certain amount of silane emulsion 1, the micro- glue of micro/nano level is added in (4c) into curing agent-graphene dispersing solution 4b2 first
Capsule lotion 2 and emulsifier are formed then in the emulsified 2h of revolving speed of room temperature, 1500rpm comprising multiple micro/nano level microcapsules
The composite solution of emulsion droplet；The outer layer of the emulsion droplet is curing agent.The emulsifier is neopelex.So
Appropriate amount of acid is added dropwise in backward composite solution, makes the pH value 4.5 of system；Then isocyanate emulsion 4a2 is added dropwise, in 60 DEG C of temperature
3h, isocyanate emulsion 4a2 and the curing agent comprising multiple micro/nano level microcapsules are stirred under the revolving speed of degree condition and 1300rpm
Interfacial reaction occurs for emulsion droplet, generates cyst wall.Obtain that there is the interior of cell structure to repair outer curable type graphene functionalized selfreparing
Microcapsule emulsion；The curing agent-graphene dispersing solution 4b2, silane emulsion 1, nanometer-sized microcapsules lotion 2, emulsifier and different
The weight ratio of cyanate lotion 4a2 is 1:0.5:0.8:0.15:1.
The lotion that (4d) obtains (4c) is centrifuged, washs, is dry, obtains that there is the interior of cell structure to repair outer curable type graphene
Functionalization self-repairing microcapsule.
Compound is reviewed one's lessons by oneself with repair outer curable type graphene functionalized self-repairing microcapsule in cell structure using described
Solidifying soil, mass fraction of the self-repairing microcapsule in self-repair concrete are 15%.
Embodiment 6:
Unlike the first embodiment, there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule
Preparation method, comprising the following steps:
(1) oil-in-water type silane emulsion 1 is prepared:
(1a) weighs appropriate silane, emulsifier and dispersing agent, the weight ratio 100:5:1 of silane, emulsifier and dispersing agent, often
Temperature stirs 15min under the revolving speed of 4000rpm, obtains finely dispersed oily phase；The silane is octyltri-ethoxysilane,
The emulsifier is octadecane alcohol radical APEO, and the dispersing agent is positive phosphoric acid sodium ethylene oxide ether.
(1b) weighs appropriate emulsifier octadecane alcohol radical APEO and water, and the weight ratio of emulsifier and water is 1:100,
Room temperature stirs 30min at 1000rpm and obtains compound water phase；
(1c) is mutually gradually dripped to oily in water phase, and oil is mutually and the weight ratio of water phase is 1:0.8, and 6000rpm is stirred at 50 DEG C
5h obtains uniform and stable oil-in-water type multiple emulsion, i.e. silane emulsion 1.
(2) micro/nano level microcapsule emulsion is prepared:
(2a) weighs appropriate isocyanates renovation agent, solvent and emulsifier, and room temperature stirs 75min at 4600rpm, obtains
Agent emulsion 2a1 is repaired to isocyanates；The weight ratio of the isocyanates renovation agent, solvent and emulsifier is 1:15:0.10.
The isocyanates renovation agent is 2,2,5- trimethylhexane diisocyanates, and the solvent is dimethylbenzene, the emulsifier
For neopelex.
(2b) weighs appropriate curing agent, solvent and emulsifier, and room temperature stirs 90min at 7200rpm, obtains curing agent cream
Liquid 2b1；The weight ratio of curing agent, solvent and emulsifier is 1:15:0.08.The curing agent is hydroxy compounds, the hydroxyl
Compound is polyoxypropylene polyol, the solvent toluene, and the emulsifier is Arabic gum.
Curing agent emulsion 2b1 is added dropwise isocyanates and repaired in agent emulsion 2a1 by (2c), and room temperature is stirred at 5000rpm
1h is mixed, isocyanates repairs the curing agent in agent emulsion 2a1 and curing agent emulsion 2b1 and interfacial reaction occurs, cyst wall is generated, thus
Obtain the micro/nano level microcapsule emulsion 2 of cladding renovation agent；The isocyanates repairs agent emulsion 2a1 and curing agent emulsion
The weight ratio 1:2.5 of 2b1.This step must use high speed rotation, can just obtain micro/nano level microcapsule emulsion；And isocyanic acid
The opposite drop than curing agent emulsion of the drop of ester is more greatly.
(3) preparation of the modifies graphene emulsion of oxygen plasma: modified graphene powder is dissolved in appropriate solvent,
It is stirred evenly under 1400rpm, obtains modified graphene lotion 3.
(4) there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule for preparation:
(4a) weighs appropriate isocyanates reagent, emulsifier and solvent, room temperature uniform stirring 70min at 6000rpm,
Obtain isocyanate emulsion 4a2；The weight ratio of isocyanates reagent, solvent and emulsifier is 1:20:0.12.The isocyanic acid
Esters renovation agent is toluene di-isocyanate(TDI), and the emulsifier is Arabic gum, and the solvent is cyclohexanol.
(4b) weighs appropriate curing agent, modified graphene lotion 3, dispersing agent and solvent, and room temperature is stirred at 2000rpm
55min obtains curing agent-graphene dispersing solution 4b2；Curing agent, modified graphene lotion 3, the weight ratio of solvent and dispersing agent
For 1:0.8:15:0.15.The curing agent is hydroxy compounds, and the hydroxy compounds is polyoxypropylene polyol, described
Dispersing agent is sodium metasilicate, and the solvent is hexamethylene.
A certain amount of silane emulsion 1, micro/nano level microcapsules is added in (4c) into curing agent-graphene dispersing solution 4b2 first
Lotion 2 and emulsifier form the cream comprising multiple micro/nano level microcapsules then in the emulsified 2h of revolving speed of room temperature, 1800rpm
Change the composite solution of drop；The outer layer of the emulsion droplet is curing agent.The emulsifier is neopelex.Then
Appropriate amount of acid is added dropwise into composite solution, makes the pH value 5 of system；Then isocyanate emulsion 4a2 is added dropwise, in 65 DEG C of temperature strip
2h, isocyanate emulsion 4a2 and the curing agent emulsion comprising multiple micro/nano level microcapsules are stirred under the revolving speed of part and 1600rpm
Interfacial reaction occurs for drop, generates cyst wall.Obtain that there is the interior of cell structure to repair the outer micro- glue of curable type graphene functionalized selfreparing
Capsule lotion；The curing agent-graphene dispersing solution 4b2, silane emulsion 1, nanometer-sized microcapsules lotion 2, emulsifier and isocyanic acid
The weight ratio of ester lotion 4a2 is 1:0.8:0.8:0.25:3.
The lotion that (4d) obtains (4c) is centrifuged, washs, is dry, obtains that there is the interior of cell structure to repair outer curable type graphene
Functionalization self-repairing microcapsule.
Overcoating is reviewed one's lessons by oneself with repair outer curable type graphene functionalized self-repairing microcapsule in cell structure using described
Layer, mass fraction of the self-repairing microcapsule in coatings are 18%.
The micromorphology characterization of the microcapsules of 1 embodiment 1-6 of table preparation
2 embodiment 1-6 of table prepares the mechanical property characterization of microcapsules
By Tables 1 and 2 characterization result it is found that the partial size of the microcapsules of embodiment 1-6 preparation is 10-180 μm, tensile strength
For 9.24-10.93MPa, elongation at break 217.75-231.62%, microcapsules shore hardness (A) is 54-62.
As shown in Figure 2, microcapsules of the present invention are cell structure, i.e., it is micro- to be dispersed with series in the curing agent of cyst wall cladding
Nanometer-sized microcapsules greatly improve so as to which the probability that microcapsules rupture during concrete for making is greatly reduced
Self-repair efficiency.
Embodiment 7: the strength character after self-healing system is repaired detects
Microcapsules prepared by embodiment 1,3 and 5 are incorporated into the preparation that self-repair concrete is carried out in cement.Maintenance 28 days
After, take one group of (every group contains 3 pieces of test blocks) self-repair concrete to carry out the test of initial compression strength；Taking another group, (every group contains 3
Block test block) gently press the self-repair concrete to crack by inside it with pressure testing machine, after two weeks, compound is reviewed one's lessons by oneself to the group
Solidifying soil compression strength is tested.Microcapsules prepared by embodiment 2,4 and 6 are incorporated into the system that coatings are carried out in coating
It is standby.One group of (every group contains 3 pieces of coatings) coatings is taken to carry out the test of initial tensile strength, taking another group, (every group containing 3 pieces of paintings
Layer) it stretches the selfreparing soil layer using tensile testing machine and makes to crack inside it, it is anti-to this group of coatings after two weeks
Tensile strength is tested, and data as shown in table 3 are obtained.
3 embodiment 1-6 of table prepares the strength detection after microcapsules self-healing system is repaired
As shown in Table 3, the compression strength of concrete is 45.97-46.73Mpa, average value 46.38MPa after reparation；With
It is compared before reparation, remediation efficiency improves 10.48%.The compression strength of epoxy coating is 16.78-18.66Mpa after reparation, is put down
Mean value is 17.76MPa；Compared with before reparation, remediation efficiency improves 13.72%.
Embodiment 8: the water imbibition after self-healing system is repaired measures
The embodiment 1-6 microcapsules prepared are incorporated into the preparation (microcapsule content that self-repair concrete is carried out in cement
For 8%), while preparing one group of blank control concrete test block.After maintenance 28 days, gently this is pressed to review one's lessons by oneself compound with pressure testing machine
Solidifying soil allows inside it and cracks, and after two weeks, after baking oven dries to constant weight, surveys to the water imbibition of this group of self-repair concrete
Examination.Using weightening finish method test sample 2,4,8,12, for 24 hours when water suction increment.
4 embodiment 1-6 of table prepares the water imbibition test after microcapsules self-healing system is repaired
As shown in Table 4, the water absorption of concrete for 24 hours is 577.3-592.2g/m after reparation3, compared with blank sample, drop
Low 5.3-7.7%.
In conclusion described there is the interior of cell structure to repair outer curable type self-repairing microcapsule form in terms of micromorphology
Well, partial size is mainly distributed between 30-200 μm；Mechanical test shows that the microcapsules after solidifying are that have certain intensity (anti-
Tensile strength 9.24-10.93MPa) and hardness (shore A 54-62) elastic material (elongation at break 217.75-231.62%).
This is because, the SiO that silane emulsion hydrolysis generates2Nanoparticle participates in the synthesis process of cyst wall, improves to a certain extent
The mechanical property of cyst wall.In addition, being dispersed with plasma modification graphene in the cyst wall, the property of cyst wall is also further enhanced
Energy.
Outer curable type self-repairing microcapsule incorporation concrete and epoxy coating are repaired by that will have in cell structure, and is carried out
The experiment of precompressed crackle shows that the microcapsules have certain repair to crackle, and the compression strength of concrete mentions after reparation
High rate is 10.48%, and the tensile strength increase rate of epoxy coating is 13.72% after reparation.This is because its multicore microcapsules ruler
Very little is nanoscale, and the probability that microcapsules rupture during concrete for making is greatly reduced, greatly improves self-repair efficiency.
Outer curable type self-repairing microcapsule incorporation concrete is repaired by that will have in cell structure, and carries out water imbibition test
Show that microcapsules fracture has certain repair, the water absorption reduced rate of concrete is 5.3-7.7% after reparation.This
When being due to microcapsules rupture, while completing to crack forming mechanism, unhydrolysed silane emulsion can be in concrete pore
Interior formation hydrophobic film effectively prevents the further infiltration of moisture.
Claims (10)
1. repairing outer curable type graphene functionalized self-repairing microcapsule in cell structure, the self-repairing microcapsule includes capsule
The curing agent of wall and cyst wall cladding, it is characterised in that: be dispersed with graphene in the cyst wall；Series is dispersed in the curing agent
Micro/nano level microcapsules, to constitute cell structure；Renovation agent is coated in the micro/nano level microcapsules.
It is 2. according to claim 1 that there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule,
Be characterized in that: the curing agent for being dispersed with graphene that the cyst wall of the self-repairing microcapsule is coated by self-repairing microcapsule with review one's lessons by oneself
The silane-modified cyst wall that isocyanate emulsion, silane emulsion outside multiple microcapsules react；The curing agent is hydroxyl
Compound emulsion or amine compound lotion, the renovation agent are isocyanate emulsion.
It is 3. according to claim 2 that there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule,
Be characterized in that: the cyst wall of the micro/nano level microcapsules by micro/nano level microcapsule coated renovation agent and micro/nano level microcapsules
The cyst wall that external curing agent reacts, the graphene are plasma modification graphene.
4. repairing the preparation method of outer curable type graphene functionalized self-repairing microcapsule in cell structure, it is characterised in that:
The following steps are included:
(1) oil-in-water type silane emulsion 1 is prepared；
(2) prepare micro/nano level microcapsule emulsion: (2a) weighs appropriate isocyanates renovation agent, solvent and emulsifier, room temperature
60-100min is stirred at 3000-7000rpm, isocyanates is obtained and repairs agent emulsion 2a1；(2b) weighs appropriate curing agent, molten
Agent and emulsifier, room temperature stir 80-120min at 5000-9000rpm, obtain curing agent emulsion 2b1；(2c) is newborn by curing agent
Liquid 2b1 is added dropwise isocyanates and repairs in agent emulsion 2a1, and room temperature stirs 1-2h at 2000-6000rpm, obtains cladding and repairs
The micro/nano level microcapsule emulsion 2 of multiple agent.
(3) preparation of the modifies graphene emulsion of oxygen plasma: taking appropriate graphene powder to be placed in oxygen plasma instrument,
It is vacuum-treated, is then introduced into oxygen, makes linkage function group on graphene surface, obtain modified graphene powder；By modified graphite
Alkene powder is dissolved in appropriate solvent, is stirred evenly at 1000-2000rpm, and modified graphene lotion 3 is obtained；
(4) there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule for preparation: (4a) weighs appropriate isocyanide
Esters of gallic acid reagent, emulsifier and solvent, room temperature uniform stirring 70-100min at 3000-6000rpm obtain isocyanates cream
Liquid 4a2；(4b) weighs appropriate curing agent, modified graphene lotion 3, dispersing agent and solvent, and room temperature is stirred at 2000-5000rpm
50-70min is mixed, obtains being curing agent-graphene dispersing solution 4b2；(4c) is added one into curing agent-graphene dispersing solution 4b2
Quantitative silane emulsion 1, micro/nano level microcapsule emulsion 2 and emulsifier, room temperature 1500-3500rpm the emulsified 1-2h of revolving speed,
Obtain multiple emulsion；Then isocyanate emulsion 4a2 is added dropwise into multiple emulsion, in 50-70 DEG C of temperature condition and 1000-
2-3h is stirred under the revolving speed of 2500rpm, obtains that there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule
Lotion；The lotion that (4d) obtains (4c) is centrifuged, washs, is dry, obtains that there is the interior of cell structure to repair outer curable type graphene function
Self-repairing microcapsule can be changed.
5. the interior system for repairing outer curable type graphene functionalized self-repairing microcapsule according to claim 4 with cell structure
Preparation Method, it is characterised in that: isocyanates repairs the weight ratio 1 of agent emulsion 2a1 and curing agent emulsion 2b1 in step (2c):
1-1:5；In step (3), the vacuum condition of vacuum processing is 200mTorr-400Torr, and the processing time is 3-5min；Import oxygen
The flow of gas is 3-5ml/min, and the time for importing oxygen is 3-5min；The functional group is carbonyl, hydroxy or carboxy；Step
Curing agent-graphene dispersing solution 4b2, silane emulsion 1, nanometer-sized microcapsules lotion 2, emulsifier and isocyanate emulsion in (4c)
The weight ratio of 4a2 is 1:(0.5-0.8): (0.5-0.8): (0.15-0.25): (1-3).
6. the interior system for repairing outer curable type graphene functionalized self-repairing microcapsule according to claim 5 with cell structure
Preparation Method, it is characterised in that: the weight ratio of isocyanates renovation agent, solvent and emulsifier described in step (2a) is 1:(15-
20):(0.08-0.15)；The weight ratio of curing agent, solvent and emulsifier is 1:(10-15 in step (2b)): (0.08-0.18)；
The weight ratio of isocyanates reagent, solvent and emulsifier is 1:(15-20 in step (4a)): (0.06-0.12)；Step (4b)
Middle curing agent, graphene emulsion 3, the weight ratio of solvent and dispersing agent are 1:(0.4-0.8): (10-15): (0.06-0.15).
7. having in cell structure according to claim 4-6 any one and repairing outer curable type graphene functionalized selfreparing
The preparation method of microcapsules, it is characterised in that: in the step (4c), when to mixed solution and dripping isocyanate emulsion 4a2,
Appropriate amount of acid is added dropwise simultaneously, makes the pH value 4-6 of system.
8. the interior system for repairing outer curable type graphene functionalized self-repairing microcapsule according to claim 7 with cell structure
Preparation Method, it is characterised in that: step (1) specifically: step (1) specifically: (1a) weighs appropriate silane, emulsifier and dispersion
Agent, the weight ratio 80:1:1-120:5:1 of silane, emulsifier and dispersing agent, room temperature stir under the revolving speed of 2000-4000rpm
15-30min obtains finely dispersed oily phase；(1b) weighs appropriate emulsifier and water, and the weight ratio of emulsifier and water is 1:80-1:
120, room temperature stirs 15-30min at 1000-3000rpm and obtains compound water phase；(1c) is mutually gradually dripped to oily in water phase, oil
Mutually and the weight ratio of water phase is 1:0.8-1:1.5, and 5000-10000rpm stirs 4-5h at 40-60 DEG C, obtains uniform and stable water
Oil-in multiple emulsion, i.e. silane emulsion 1.
9. the interior system for repairing outer curable type graphene functionalized self-repairing microcapsule according to claim 8 with cell structure
Preparation Method, it is characterised in that: the silane is vinyltriethoxysilane, vinyltrimethoxysilane, positive silicic acid second
One or more of ester, isobutyl triethoxy silane, trimethylsiloxy silane and octyltri-ethoxysilane；
The emulsifier is that Op-10, polyvinyl alcohol, Span 80, Arabic gum, neopelex and octadecane alcohol radical are poly-
One or more of ethylene oxide ether；
The dispersing agent is one of polyethylene glycol, potassium citrate, sodium metasilicate, linoleic acid sodium and orthophosphoric acid acid sodium ethylene oxide ether
Or it is several；
The isocyanates renovation agent is '-diphenylmethane diisocyanate, toluene di-isocyanate(TDI), different Fu Er ketone diisocyanate
Ester, 1,6- hexamethylene diisocyanate, 2,2,5- trimethylhexane diisocyanates and tetramethyl are different for m-phenylenedimethylim- two
One or more of cyanate；
The solvent is in ethyl acetate, glycol dimethyl ether, hexamethylene, pentamethylene, cyclohexanol, toluene, dimethylbenzene and chlorobenzene
One or more；
The curing agent is hydroxy compounds or amine compound；The hydroxy compounds be 1,4-butanediol, n-butanol, penta
Glycol, 1,6- hexylene glycol, cyclohexanedimethanol, pentaerythrite, in polyoxypropylene polyol and polytetrahydrofuran polyol
It is one or more of；The amine compound is diethyl toluene diamine, dimethythiotoluene diamine, N, N'- dialkyl methyl two
Aniline, cyclohexane diamine, chlorination MDH, ethylenediamine, 1,3- diaminopropanes, 1,4- diaminobutane, diethylidene amine, five Asias
Hexamine, six ethylene diamines, tetren, penten, polyetheramine D400, polyetheramine D230, ethylenediamine
Or 3,3'-4,4'- diamino-diphenyl-methane MOCA.
10. using described in claim 1 with cell structure in repair outer curable type graphene functionalized self-repairing microcapsule from
Reparation system, it is characterised in that: described that there is the interior of cell structure to repair outer curable type graphene functionalized self-repairing microcapsule certainly
Mass fraction in reparation system is 5%-18%；The self-healing system is self-repair concrete or coatings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810838460.XA CN108975759B (en) | 2018-07-27 | 2018-07-27 | Internal-modification external-fixation graphene functional self-repairing microcapsule with cellular structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810838460.XA CN108975759B (en) | 2018-07-27 | 2018-07-27 | Internal-modification external-fixation graphene functional self-repairing microcapsule with cellular structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108975759A true CN108975759A (en) | 2018-12-11 |
| CN108975759B CN108975759B (en) | 2021-01-15 |
Family
ID=64551222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810838460.XA Active CN108975759B (en) | 2018-07-27 | 2018-07-27 | Internal-modification external-fixation graphene functional self-repairing microcapsule with cellular structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108975759B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111146429A (en) * | 2020-01-10 | 2020-05-12 | 安徽师范大学 | Preparation method of graphene oxide/sulfur microcapsule composite material, lithium-sulfur battery positive electrode and lithium-sulfur battery |
| CN111233366A (en) * | 2020-01-13 | 2020-06-05 | 沈阳大学 | Preparation of corrosion-resistant self-repairing reinforced concrete member with built-in microcapsules |
| CN111334176A (en) * | 2020-03-09 | 2020-06-26 | 沪宝新材料科技（上海）股份有限公司 | Solvent-free double-component finish paint for plastic track |
| CN111875320A (en) * | 2020-08-19 | 2020-11-03 | 济南大学 | Super-hydrophobic microcapsule polymer cement-based anticorrosive paint and preparation method and application thereof |
| CN112897916A (en) * | 2021-01-21 | 2021-06-04 | 深圳大学 | Silicon dioxide wall material microcapsule and preparation method and application thereof |
| CN115230193B (en) * | 2022-07-01 | 2024-04-26 | 浙江大学 | Preparation method of interlayer graphene toughened CFRPs composite material laminated plate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702947A (en) * | 2012-06-18 | 2012-10-03 | 中国石油大学(华东) | Organosilicone-nano compound modified polyurea corrosion-resisting coating for mechanical recovery well environment and preparation method for organosilicone-nano compound modified polyurea corrosion-resisting coating |
| CN104688714A (en) * | 2015-03-20 | 2015-06-10 | 武汉理工大学 | Graphene/ chitosan compound micro-capsule and preparation method thereof |
| KR20170037399A (en) * | 2015-09-25 | 2017-04-04 | 삼중씨엠텍(주) | Coating agents compositions having self-healing function for concrete structure and coating agents construction method using that |
| CN106753151A (en) * | 2016-11-30 | 2017-05-31 | 青岛爱尔家佳新材料股份有限公司 | A kind of preventing explosion impact polyurea coating and preparation method thereof |
| CN107961747A (en) * | 2017-11-30 | 2018-04-27 | 青岛理工大学 | Inside repair outer curable type polyureas base double-walled self-repairing microcapsule and preparation method thereof |
| CN108218273A (en) * | 2018-03-09 | 2018-06-29 | 湖北工业大学 | Micro-nano latent heat storage capsule suitable for cement-based material and preparation method thereof |
-
2018
- 2018-07-27 CN CN201810838460.XA patent/CN108975759B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702947A (en) * | 2012-06-18 | 2012-10-03 | 中国石油大学(华东) | Organosilicone-nano compound modified polyurea corrosion-resisting coating for mechanical recovery well environment and preparation method for organosilicone-nano compound modified polyurea corrosion-resisting coating |
| CN104688714A (en) * | 2015-03-20 | 2015-06-10 | 武汉理工大学 | Graphene/ chitosan compound micro-capsule and preparation method thereof |
| KR20170037399A (en) * | 2015-09-25 | 2017-04-04 | 삼중씨엠텍(주) | Coating agents compositions having self-healing function for concrete structure and coating agents construction method using that |
| CN106753151A (en) * | 2016-11-30 | 2017-05-31 | 青岛爱尔家佳新材料股份有限公司 | A kind of preventing explosion impact polyurea coating and preparation method thereof |
| CN107961747A (en) * | 2017-11-30 | 2018-04-27 | 青岛理工大学 | Inside repair outer curable type polyureas base double-walled self-repairing microcapsule and preparation method thereof |
| CN108218273A (en) * | 2018-03-09 | 2018-06-29 | 湖北工业大学 | Micro-nano latent heat storage capsule suitable for cement-based material and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111146429A (en) * | 2020-01-10 | 2020-05-12 | 安徽师范大学 | Preparation method of graphene oxide/sulfur microcapsule composite material, lithium-sulfur battery positive electrode and lithium-sulfur battery |
| CN111233366A (en) * | 2020-01-13 | 2020-06-05 | 沈阳大学 | Preparation of corrosion-resistant self-repairing reinforced concrete member with built-in microcapsules |
| CN111334176A (en) * | 2020-03-09 | 2020-06-26 | 沪宝新材料科技（上海）股份有限公司 | Solvent-free double-component finish paint for plastic track |
| CN111875320A (en) * | 2020-08-19 | 2020-11-03 | 济南大学 | Super-hydrophobic microcapsule polymer cement-based anticorrosive paint and preparation method and application thereof |
| CN112897916A (en) * | 2021-01-21 | 2021-06-04 | 深圳大学 | Silicon dioxide wall material microcapsule and preparation method and application thereof |
| CN115230193B (en) * | 2022-07-01 | 2024-04-26 | 浙江大学 | Preparation method of interlayer graphene toughened CFRPs composite material laminated plate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108975759B (en) | 2021-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108975759A (en) | With repairing outer curable type graphene functionalized self-repairing microcapsule and preparation method thereof in cell structure | |
| CN108993330A (en) | Interior curable type graphene functionalized self-repairing microcapsule and preparation method thereof of dispatching workers to do on-site repairs with cell structure | |
| CN108993331A (en) | With repairing outer curable type self-repairing microcapsule and preparation method thereof in cell structure | |
| Ullah et al. | The potential of microencapsulated self-healing materials for microcracks recovery in self-healing composite systems: A review | |
| Tan et al. | Silica‐based self‐healing microcapsules for self‐repair in concrete | |
| CN103331133B (en) | Epoxy microcapsule with polyurea as wall material and preparation method thereof | |
| CN103467791B (en) | Double-wall sandwich structural microcapsule selfreparing rubber and preparation method thereof | |
| CN101314706B (en) | Preparation of solidification type steel adhesion structure glue in low-temperature and humidity surroundings | |
| CN106118367B (en) | The microcapsules for implying repair function with damage and its application in epoxy coating | |
| CN107961747A (en) | Inside repair outer curable type polyureas base double-walled self-repairing microcapsule and preparation method thereof | |
| CN106007553B (en) | A kind of carbon nanotube/polyvinyl alcohol high tenacity intelligent cement mortar and its preparation | |
| CN108219641A (en) | A kind of lignosulfonates dispersion self-healing carbamide paint and preparation method thereof and coating and application | |
| CN101289299A (en) | Self-repair concrete using polyurea resin high molecule microcapsule and method of manufacture | |
| CN107970868A (en) | Dispatch workers to do on-site repairs interior curable type polyureas base double-walled self-repairing microcapsule and preparation method thereof | |
| CN101289300A (en) | Self-repair concrete using polyurethane high molecule microcapsule and method of manufacture | |
| CN105964194B (en) | A kind of self-repairing microcapsule and the preparation method and application thereof | |
| CN103316617A (en) | Preparation method of surface-modified self-healing type microcapsule | |
| Adibzadeh et al. | A novel two-component self-healing coating comprising vinyl ester resin-filled microcapsules with prolonged anticorrosion performance | |
| CN1884422A (en) | Modified ethenyl resin grouting material and its preparation method and construction method | |
| CN107382180A (en) | A kind of high ductility enhanced water resistance cement-base composite material of high intensity and preparation method thereof | |
| CN106496428B (en) | Embed nanometer polymerization composite capsule and its preparation and application of aerobic quick fluorescence indicator | |
| CN107961748A (en) | Dispatch workers to do on-site repairs interior curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule and preparation method thereof | |
| CN107952404A (en) | Inside repair outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule and preparation method thereof | |
| CN112409924A (en) | Self-repairing epoxy resin coating and preparation method thereof | |
| CN108947319A (en) | Interior curable type self-repairing microcapsule and preparation method thereof of dispatching workers to do on-site repairs with cell structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |