CN108947319A - Interior curable type self-repairing microcapsule and preparation method thereof of dispatching workers to do on-site repairs with cell structure - Google Patents
Interior curable type self-repairing microcapsule and preparation method thereof of dispatching workers to do on-site repairs with cell structure Download PDFInfo
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- CN108947319A CN108947319A CN201810838496.8A CN201810838496A CN108947319A CN 108947319 A CN108947319 A CN 108947319A CN 201810838496 A CN201810838496 A CN 201810838496A CN 108947319 A CN108947319 A CN 108947319A
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- 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 silane-functionalized self-repairing microcapsules and preparation method thereof with cell structure.Interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure is dispersed with serial micro/nano level microcapsules in the renovation agent, to constitute cell structure including the renovation agent that cyst wall and cyst wall coat;Curing agent is coated in the micro/nano level microcapsules.The interior solid self-repairing microcapsule system of dispatching workers to do on-site repairs 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
Silane-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 201711236097.6 disclose " dispatch workers to do on-site repairs interior curable type polyureas base double-walled self-repairing microcapsule and its
Preparation method ".The interior curable type polyureas base double-walled self-repairing microcapsule of dispatching workers to do on-site repairs, 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 outer layer capsule-core and internal 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.
Summary of the invention
For the problems of self-healing system in the prior art, the present invention provides the silane function with cell structure
Self-repairing microcapsule and preparation method thereof can be changed.The interior solid self-repairing microcapsule system of dispatching workers to do on-site repairs has the multicore packet of micro/nano level
Structure is covered, the stability of microcapsules is not only increased, while increasing the probability that renovation agent is contacted with curing agent, improves reparation
Efficiency.In addition, the cyst wall of the self-repairing microcapsule system uses silane-modified, unhydrolysed silane emulsion after microcapsules rupture
Hydrophobic film can be formed in concrete capillary hole, prevent the further diffusion of moisture, and the silane emulsion hydrolyzed
The synthesis that can participate in wall material improves the performance of microcapsules.
Technical solution of the present invention:
Interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure, the self-repairing microcapsule includes cyst wall and cyst wall packet
The renovation agent covered is dispersed with serial micro/nano level microcapsules in the renovation agent, to constitute cell structure;The micro/nano level
Curing agent is coated in microcapsules.The renovation agent is isocyanate emulsion, and the curing agent is hydroxy compounds lotion or amido
Compound emulsion.Wherein, renovation agent and the micro- glue of selfreparing that the cyst wall of the self-repairing microcapsule is coated by self-repairing microcapsule
The silane-modified cyst wall that curing agent, silane emulsion outside capsule react.The cyst wall of the micro/nano level microcapsules is by micro-
The cyst wall that the curing agent of nanometer-sized microcapsules cladding is reacted with the renovation agent outside micro/nano level microcapsules.
The preparation method of interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure, 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 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 80- at 6000-9000rpm
120min obtains isocyanates and repairs agent emulsion 2a1;The weight ratio of the isocyanates renovation agent, solvent and emulsifier is
1:(10-15):(0.10-0.18).(2b) weighs appropriate curing agent, solvent and emulsifier, and room temperature is stirred at 4000-7000rpm
60-100min is mixed, curing agent emulsion 2b1 is obtained;The weight ratio of the curing agent, solvent and emulsifier is 1:(15-20):
(0.08-0.15).(2c) isocyanates reparation agent emulsion 2a1 is added dropwise in curing agent emulsion 2b1, and room temperature is in 2000-
1-2h is stirred under 6000rpm, obtains the micro/nano level microcapsule emulsion 2 of cladding curing agent.Curing agent emulsion 2b1 and isocyanates
Interfacial reaction occurs for the renovation agent repaired in agent emulsion 2a1, generates cyst wall, to obtain the micro- glue of micro/nano level of cladding curing agent
Capsule lotion 2;The isocyanates repairs the weight ratio 1:1-5:1 of agent emulsion 2a1 and curing agent emulsion 2b1.It, must in this step
High speed rotation must be used, micro/nano level microcapsule emulsion can be just obtained;And the drop of isocyanates is opposite than curing agent cream
The drop of liquid is big, to make curing agent emulsion droplet distribution on the surface of isocyanate emulsion drop, interfacial reaction occurs, generates
Cyst wall.
(3) preparation has the interior curable type silane-functionalized self-repairing microcapsule of dispatching workers to do on-site repairs of cell structure:
(3a) weighs appropriate curing agent, emulsifier and solvent, room temperature uniform stirring 70- at 4000-6000rpm
100min obtains curing agent emulsion 3a2;The weight ratio of the curing agent, solvent and emulsifier is 1:(10-15): (0.06-
0.15)。
(3b) weighs appropriate isocyanates renovation agent, dispersing agent and solvent, and room temperature stirs 50- at 3000-5000rpm
70min obtains isocyanates dispersion liquid 3b2;The weight ratio of the isocyanates renovation agent, solvent and dispersing agent is 1:(15-
20):(0.06-0.12)。
(3c) a certain amount of silane emulsion 1, micro/nano level microcapsule emulsion 2 and cream are added into isocyanates dispersion liquid 3b2
Agent, room temperature obtain the emulsion droplet comprising multiple micro/nano level microcapsules in the emulsified 1-2h of revolving speed of 1500-3500rpm
Multiple emulsion;Then curing agent emulsion 3a2 is added dropwise into multiple emulsion, in 50-70 DEG C of temperature condition and 1000-
2-3h, curing agent emulsion 3a2 and the renovation agent emulsion droplet comprising multiple micro/nano level microcapsules are stirred under the revolving speed of 2500rpm
Interfacial reaction occurs, generates cyst wall;Obtain the interior curable type silane-functionalized self-repairing microcapsule lotion of dispatching workers to do on-site repairs with cell structure.
The isocyanates dispersion liquid 3b2, silane emulsion 1, nanometer-sized microcapsules lotion 2, emulsifier and curing agent ester lotion 3a2 weight
Amount is than being 1:(0.5-0.8): (0.5-0.8): (0.06-0.15): (1-3).
The lotion that (3d) obtains (3c) is centrifuged, washs, is dry, obtains the interior curable type silane function of dispatching workers to do on-site repairs with cell structure
Self-repairing microcapsule can be changed.Silane-functionalized self-repairing microcapsule of the present invention completes counterincision when the micro capsules are broken
Line can form hydrophobic film while reparation in concrete pore again, effectively prevent the further infiltration of moisture.
Preferably, it in the step (3c), when to mixed solution and dripping curing agent emulsion 3a2, while being added dropwise appropriate
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.SiO2
Nanoparticle participates in the synthesis process of cyst wall, improves the mechanical property of cyst wall, responding ability and micro- to a certain extent
The adhesive force of capsule 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.
It is described that there is born of the same parents' shape using the self-healing system of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure
Mass fraction of the interior curable type silane-functionalized self-repairing microcapsule in self-healing system of dispatching workers to do on-site repairs of structure is 5%-18%;It is described
Self-healing system is self-repair concrete or coatings.
Beneficial effects of the present invention:
(1) the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs of the present invention with cell structure, the renovation agent of cyst wall cladding
In be dispersed with serial micro/nano level microcapsules --- i.e. multicore capsule size be nanoscale, so as to which microcapsules are greatly reduced
The probability ruptured during concrete for making, greatly improves self-repair efficiency.
(2) interior curable type self-repairing microcapsule of the present invention of dispatching workers to do on-site repairs is silane-modified microcapsules;Therefore, when microcapsules are broken
When splitting, while completing to crack forming mechanism, unhydrolysed silane emulsion can form hydrophobic film in concrete pore, have
Effect prevents the further infiltration of moisture, adds during military service since steam is invaded and harassed to efficiently solve maritime concrete
The problem of fast concrete erosion.
(3) in the preparation process of interior curable type self-repairing microcapsule of the present invention of dispatching workers to do on-site repairs, silane emulsion hydrolysis is generated
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.
(4) the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs of the present invention with cell structure, with the micro- glue of existing double-walled
Capsule is compared, and renovation agent and curing agent react more rapidly;In addition to this, renovation agent can also be reacted with the steam of outside and be repaired
Mend crack;Therefore, it greatly accelerates repairing effect, realizes the timely reparation to crackle, avoid more serious consequence and higher
Rehabilitation cost.
Detailed description of the invention
Attached drawing 1 is the structural schematic diagram of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure;Wherein A is renovation agent
Microcapsules, B are curing agent microcapsules.
Attached drawing 2 is the light microscopic figure of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure prepared by embodiment 6.
Specific embodiment
The present invention will be further explained with reference to the examples below.
Embodiment 1:
The preparation method of interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure, 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 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 100min at 7800rpm,
It obtains isocyanates and repairs agent emulsion 2a1;The weight ratio of the isocyanates renovation agent, solvent and emulsifier is 1:10:
0.10.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 60min at 5200rpm, obtains curing agent cream
Liquid 2b1;The weight ratio of the curing agent, solvent and emulsifier is 1:15:0.12.The curing agent is hydroxy compounds, described
Hydroxy compounds is 1,4-butanediol;The solvent is ethyl acetate;The emulsifier is Op-10.
(2c) isocyanates reparation agent emulsion 2a1 is added dropwise in curing agent emulsion 2b1, and room temperature is stirred at 6000rpm
1h is mixed, curing agent emulsion 2b1 and isocyanates repair the renovation agent in agent emulsion 2a1 and interfacial reaction occur, cyst wall is generated, thus
Obtain the micro/nano level microcapsule emulsion 2 of cladding curing agent.The isocyanates repairs agent emulsion 2a1 and curing agent emulsion
The weight ratio 2:1 of 2b1.
(3) preparation has the interior curable type silane-functionalized self-repairing microcapsule of dispatching workers to do on-site repairs of cell structure:
(3a) weighs appropriate curing agent, emulsifier and solvent, room temperature uniform stirring 100min at 4000rpm, consolidate
Agent lotion 3a2;The weight ratio of the curing agent, solvent and emulsifier is 1:10:0.06.The isocyanates renovation agent is
'-diphenylmethane diisocyanate;The emulsifier is Op-10;The solvent is ethyl acetate.
(3b) weighs appropriate isocyanates renovation agent, dispersing agent and solvent, and room temperature stirs 60min at 3400rpm, obtains
To isocyanates dispersion liquid 3b2;The weight ratio of the isocyanates renovation agent, solvent and dispersing agent is 1:15:0.06.It is described
Curing agent is hydroxy compounds, and the hydroxy compounds is 1,4-butanediol;The dispersing agent is polyethylene glycol;The solvent is
Ethyl acetate.
(3c) a certain amount of silane emulsion 1, micro/nano level microcapsule emulsion 2 and cream are added into isocyanates dispersion liquid 3b2
Agent, room temperature obtain the compound of the emulsion droplet comprising multiple micro/nano level microcapsules in the emulsified 1.5h of revolving speed of 2200rpm
Lotion;The emulsifier is Op-10.Then appropriate amount of acid is added dropwise, makes the pH value 5 of system;Solidification is added dropwise into multiple emulsion again
Agent emulsion 3a2, stirs 2h under 65 DEG C of temperature condition and the revolving speed of 2000rpm, curing agent emulsion 3a2 and includes multiple micro-nanos
Interfacial reaction occurs for the renovation agent emulsion droplet of meter level microcapsules, generates cyst wall;Obtain the interior curable type of dispatching workers to do on-site repairs with cell structure
Silane-functionalized self-repairing microcapsule lotion.The isocyanates dispersion liquid 3b2, silane emulsion 1, nanometer-sized microcapsules lotion 2,
The weight ratio of emulsifier and curing agent ester lotion 3a2 are 1:0.5:0.5:0.06:1.The committed step of the application is: dripping first
Add micro-nano microcapsules, then emulsify curing agent and obtain compound system, the cream comprising multiple micro-nano microcapsules could be formed in this way
Change drop.The purpose that acid is added dropwise into composite solution is to accelerate silane emulsion hydrolysis to generate silica, to participate in the system of wall material
It is standby.SiO2Nanoparticle participates in the synthesis process of cyst wall, improves mechanical property, the responding ability of cyst wall to a certain extent
And the adhesive force of microcapsules and concrete substrate.
The lotion that (3d) obtains (3c) is centrifuged, washs, is dry, obtains the interior curable type silane function of dispatching workers to do on-site repairs with cell structure
Self-repairing microcapsule can be changed.Silane-functionalized self-repairing microcapsule of the present invention completes counterincision when the micro capsules are broken
Line can form hydrophobic film while reparation in concrete pore again, effectively prevent the further infiltration of moisture.
It is described to review one's lessons by oneself using the self-repair concrete of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure
Multiple mass fraction of the microcapsules in self-repair concrete is 10%.
Embodiment 2:
Unlike the first embodiment, the preparation method of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure, including
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 110min at 8400rpm,
It obtains isocyanates and repairs agent emulsion 2a1;The weight ratio of the isocyanates renovation agent, solvent and emulsifier is 1:12:
0.10.The isocyanates renovation agent is toluene di-isocyanate(TDI), and the solvent is glycol dimethyl ether, and the emulsifier is
Polyvinyl alcohol.
(2b) weighs appropriate curing agent, solvent and emulsifier, and room temperature stirs 70min at 7000rpm, obtains curing agent cream
Liquid 2b1;The weight ratio of the curing agent, solvent and emulsifier is 1:15:0.15.The curing agent is hydroxy compounds, described
Hydroxy compounds is the mixture of n-butanol and pentanediol;The solvent is glycol dimethyl ether, and the emulsifier is Span 80.
(2c) isocyanates reparation agent emulsion 2a1 is added dropwise in curing agent emulsion 2b1, and room temperature is stirred at 2000rpm
2h is mixed, curing agent emulsion 2b1 and isocyanates repair the renovation agent in agent emulsion 2a1 and interfacial reaction occur, cyst wall is generated, thus
Obtain the micro/nano level microcapsule emulsion 2 of cladding curing agent.The isocyanates repairs agent emulsion 2a1 and curing agent emulsion
The weight ratio 3:1 of 2b1.
(3) preparation has the interior curable type silane-functionalized self-repairing microcapsule of dispatching workers to do on-site repairs of cell structure:
(3a) weighs appropriate curing agent, emulsifier and solvent, and room temperature uniform stirring 95min at 4400rpm is solidified
Agent emulsion 3a2;The weight ratio of the curing agent, solvent and emulsifier is 1:12:0.06.The isocyanates renovation agent is different
Fu Er ketone diisocyanate, the emulsifier are polyvinyl alcohol, and the solvent is hexamethylene.
(3b) weighs appropriate isocyanates renovation agent, dispersing agent and solvent, and room temperature stirs 65min at 3800rpm, obtains
To isocyanates dispersion liquid 3b2;The weight ratio of the isocyanates renovation agent, solvent and dispersing agent is 1:15:0.08.It is described
Curing agent is hydroxy compounds, and the hydroxy compounds is n-butanol;The dispersing agent is sodium metasilicate, and the solvent is hexamethylene
Alkane, pentamethylene.
(3c) a certain amount of silane emulsion 1, micro/nano level microcapsule emulsion 2 and cream are added into isocyanates dispersion liquid 3b2
Agent, room temperature obtain the compound of the emulsion droplet comprising multiple micro/nano level microcapsules in the emulsified 1.5h of revolving speed of 2600rpm
Lotion;The emulsifier is Span 80.Then appropriate amount of acid is added dropwise, makes the pH value 6 of system;Solidification is added dropwise into multiple emulsion again
Agent emulsion 3a2, stirs 2.5h under 70 DEG C of temperature condition and the revolving speed of 2300rpm, curing agent emulsion 3a2 with comprising multiple micro-
Interfacial reaction occurs for the renovation agent emulsion droplet of nanometer-sized microcapsules, generates cyst wall;Obtain having dispatching workers to do on-site repairs for cell structure interior solid
Type silane-functionalized self-repairing microcapsule lotion.The isocyanates dispersion liquid 3b2, silane emulsion 1, nanometer-sized microcapsules lotion
2, the weight ratio of emulsifier and curing agent ester lotion 3a2 are 1:0.65:0.5:0.09:1.
The lotion that (3d) obtains (3c) is centrifuged, washs, is dry, obtains the interior curable type silane function of dispatching workers to do on-site repairs with cell structure
Self-repairing microcapsule can be changed.
Using the coatings of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure, the selfreparing
Mass fraction of the microcapsules in coatings is 15%.
Embodiment 3:
Unlike the first embodiment, the preparation method of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure, including
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 120min at 9000rpm,
It obtains isocyanates and repairs agent emulsion 2a1;The weight ratio of the isocyanates renovation agent, solvent and emulsifier is 1:15:
0.10.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 100min at 6400rpm, obtains curing agent
Lotion 2b1;The weight ratio of the curing agent, solvent and emulsifier is 1:20:0.15.The curing agent is hydroxy compounds, institute
Stating hydroxy compounds is pentaerythrite;The amine compound is cyclohexane diamine, and the solvent is pentamethylene, the emulsifier
For Arabic gum.
(2c) isocyanates reparation agent emulsion 2a1 is added dropwise in curing agent emulsion 2b1, and room temperature is stirred at 2800rpm
2h is mixed, curing agent emulsion 2b1 and isocyanates repair the renovation agent in agent emulsion 2a1 and interfacial reaction occur, cyst wall is generated, thus
Obtain the micro/nano level microcapsule emulsion 2 of cladding curing agent.The isocyanates repairs agent emulsion 2a1 and curing agent emulsion
The weight ratio 4:1 of 2b1.
(3) preparation has the interior curable type silane-functionalized self-repairing microcapsule of dispatching workers to do on-site repairs of cell structure:
(3a) weighs appropriate curing agent, emulsifier and solvent, and room temperature uniform stirring 90min at 4800rpm is solidified
Agent emulsion 3a2;The weight ratio of the curing agent, solvent and emulsifier is 1:15:0.06.The isocyanates renovation agent is 1,
6- hexamethylene diisocyanate, the emulsifier are Arabic gum, and the solvent is hexamethylene.
(3b) weighs appropriate isocyanates renovation agent, dispersing agent and solvent, and room temperature stirs 70min at 4200rpm, obtains
To isocyanates dispersion liquid 3b2;The weight ratio of the isocyanates renovation agent, solvent and dispersing agent is 1:15:0.10.It is described
Curing agent amine group compound, the amine compound are diethyl toluene diamine;The dispersing agent is linoleic acid sodium, the solvent
For hexamethylene.
(3c) a certain amount of silane emulsion 1, micro/nano level microcapsule emulsion 2 and cream are added into isocyanates dispersion liquid 3b2
Agent, room temperature obtain the compound of the emulsion droplet comprising multiple micro/nano level microcapsules in the emulsified 1.0h of revolving speed of 3000rpm
Lotion;The emulsifier is neopelex.Then appropriate amount of acid is added dropwise, makes the pH value 6 of system;Again to multiple emulsion
Middle dropwise addition curing agent emulsion 3a2, stirs 2.5h under 50 DEG C of temperature condition and the revolving speed of 2500rpm, curing agent emulsion 3a2 with
Interfacial reaction occurs for the renovation agent emulsion droplet comprising multiple micro/nano level microcapsules, generates cyst wall;It obtains with cell structure
Interior curable type silane-functionalized self-repairing microcapsule lotion of dispatching workers to do on-site repairs.The isocyanates dispersion liquid 3b2, silane emulsion 1, nanoscale
The weight ratio of microcapsule emulsion 2, emulsifier and curing agent ester lotion 3a2 is 1:0.8:0.5:0.12:1.
The lotion that (3d) obtains (3c) is centrifuged, washs, is dry, obtains the interior curable type silane function of dispatching workers to do on-site repairs with cell structure
Self-repairing microcapsule can be changed.
It is described to review one's lessons by oneself using the self-repair concrete of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure
Multiple mass fraction of the microcapsules in self-repair concrete is 18%.
Embodiment 4:
Unlike the first embodiment, the preparation method of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure, including
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, and room temperature stirs 80min at 6000rpm, obtains
Agent emulsion 2a1 is repaired to isocyanates;The weight ratio of the isocyanates renovation agent, solvent and emulsifier is 1:15:0.18.
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 90min at 4600rpm, obtains curing agent cream
Liquid 2b1;The weight ratio of the curing agent, solvent and emulsifier is 1:15:0.08.The curing agent is amine compound, described
Amine compound is ethylenediamine;The solvent is dimethylbenzene, and the emulsifier is octadecane alcohol radical APEO.
(2c) isocyanates reparation agent emulsion 2a1 is added dropwise in curing agent emulsion 2b1, and room temperature is stirred at 3600rpm
1.5h is mixed, curing agent emulsion 2b1 and isocyanates repair the renovation agent in agent emulsion 2a1 and interfacial reaction occur, cyst wall is generated, from
And obtain the micro/nano level microcapsule emulsion 2 of cladding curing agent.The isocyanates repairs agent emulsion 2a1 and curing agent emulsion
The weight ratio 5:1 of 2b1.
(3) preparation has the interior curable type silane-functionalized self-repairing microcapsule of dispatching workers to do on-site repairs of cell structure:
(3a) weighs appropriate curing agent, emulsifier and solvent, and room temperature uniform stirring 85min at 5200rpm is solidified
Agent emulsion 3a2;The weight ratio of the curing agent, solvent and emulsifier is 1:10:0.09.The isocyanates renovation agent is 1,
6- hexamethylene diisocyanate, the emulsifier are Arabic gum, and the solvent is cyclohexanol.
(3b) weighs appropriate isocyanates renovation agent, dispersing agent and solvent, and room temperature stirs 60min at 4600rpm, obtains
To isocyanates dispersion liquid 3b2;The weight ratio of the isocyanates renovation agent, solvent and dispersing agent is 1:15:0.12.It is described
Curing agent is amine compound, and the amine compound is cyclohexane diamine, and the dispersing agent is sodium metasilicate, and the solvent is chlorine
Benzene.
(3c) a certain amount of silane emulsion 1, micro/nano level microcapsule emulsion 2 and cream are added into isocyanates dispersion liquid 3b2
Agent, room temperature obtain the compound of the emulsion droplet comprising multiple micro/nano level microcapsules in the emulsified 1.0h of revolving speed of 3500rpm
Lotion;The emulsifier is Span 80.Then appropriate amount of acid is added dropwise, makes the pH value 4 of system;Solidification is added dropwise into multiple emulsion again
Agent emulsion 3a2, stirs 3h under 55 DEG C of temperature condition and the revolving speed of 1000rpm, curing agent emulsion 3a2 and includes multiple micro-nanos
Interfacial reaction occurs for the renovation agent emulsion droplet of meter level microcapsules, generates cyst wall;Obtain the interior curable type of dispatching workers to do on-site repairs with cell structure
Silane-functionalized self-repairing microcapsule lotion.The isocyanates dispersion liquid 3b2, silane emulsion 1, nanometer-sized microcapsules lotion 2,
The weight ratio of emulsifier and curing agent ester lotion 3a2 are 1:0.5:0.65:0.15:2.
The lotion that (3d) obtains (3c) is centrifuged, washs, is dry, obtains the interior curable type silane function of dispatching workers to do on-site repairs with cell structure
Self-repairing microcapsule can be changed.
Using the coatings of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure, the selfreparing
Mass fraction of the microcapsules in coatings is 10%.
Embodiment 5:
Unlike the first embodiment, the preparation method of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure, including
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 90min at 6600rpm, 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 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 80min at 4000rpm, obtains curing agent cream
Liquid 2b1;The weight ratio of the curing agent, solvent and emulsifier is 1:18:0.08.The curing agent is amine compound, described
Amine compound is tetren, and the solvent is hexamethylene, and the emulsifier is Arabic gum.
(2c) isocyanates reparation agent emulsion 2a1 is added dropwise in curing agent emulsion 2b1, and room temperature is stirred at 4600rpm
1.5h is mixed, curing agent emulsion 2b1 and isocyanates repair the renovation agent in agent emulsion 2a1 and interfacial reaction occur, cyst wall is generated, from
And obtain the micro/nano level microcapsule emulsion 2 of cladding curing agent.The isocyanates repairs agent emulsion 2a1 and curing agent emulsion
The weight ratio 1:1 of 2b1.
(3) preparation has the interior curable type silane-functionalized self-repairing microcapsule of dispatching workers to do on-site repairs of cell structure:
(3a) weighs appropriate curing agent, emulsifier and solvent, and room temperature uniform stirring 80min at 5600rpm is solidified
Agent emulsion 3a2;The weight ratio of the curing agent, solvent and emulsifier is 1:10:0.12.The isocyanates renovation agent is different
Fu Er ketone diisocyanate, the emulsifier are neopelex, and the solvent is hexamethylene.
(3b) weighs appropriate isocyanates renovation agent, dispersing agent and solvent, and room temperature stirs 50min at 5000rpm, obtains
To isocyanates dispersion liquid 3b2;The weight ratio of the isocyanates renovation agent, solvent and dispersing agent is 1:18:0.10.It is described
Curing agent is amine compound, and the amine compound is diethylidene amine, and the dispersing agent is sodium metasilicate, and the solvent is ring
Hexanol.
(3c) a certain amount of silane emulsion 1, micro/nano level microcapsule emulsion 2 and cream are added into isocyanates dispersion liquid 3b2
Agent, room temperature obtain the Composite Milk of the emulsion droplet comprising multiple micro/nano level microcapsules in the emulsified 2h of revolving speed of 1500rpm
Liquid;The emulsifier is neopelex.Then appropriate amount of acid is added dropwise, makes the pH value 4.5 of system;Again to multiple emulsion
Middle dropwise addition curing agent emulsion 3a2 stirs 3h, curing agent emulsion 3a2 and packet under 60 DEG C of temperature condition and the revolving speed of 1300rpm
Interfacial reaction occurs for the renovation agent emulsion droplet containing multiple micro/nano level microcapsules, generates cyst wall;Obtain that there is cell structure
It dispatches workers to do on-site repairs interior curable type silane-functionalized self-repairing microcapsule lotion.The isocyanates dispersion liquid 3b2, silane emulsion 1, nanoscale are micro-
The weight ratio of capsule lotion 2, emulsifier and curing agent ester lotion 3a2 is 1:0.5:0.8:0.06:1.
The lotion that (3d) obtains (3c) is centrifuged, washs, is dry, obtains the interior curable type silane function of dispatching workers to do on-site repairs with cell structure
Self-repairing microcapsule can be changed.
It is described to review one's lessons by oneself using the self-repair concrete of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure
Multiple mass fraction of the microcapsules in self-repair concrete is 15%.
Embodiment 6:
Unlike the first embodiment, the preparation method of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure, including
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 95min at 7200rpm, obtains
Agent emulsion 2a1 is repaired to isocyanates;The weight ratio of the isocyanates renovation agent, solvent and emulsifier is 1:15:0.12.
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 75min at 5800rpm, obtains curing agent cream
Liquid 2b1;The weight ratio of the curing agent, solvent and emulsifier is 1:20:0.08.The curing agent is hydroxy compounds, described
Hydroxy compounds is polyoxypropylene polyol, the solvent toluene, and the emulsifier is Arabic gum.
(2c) isocyanates reparation agent emulsion 2a1 is added dropwise in curing agent emulsion 2b1, and room temperature is stirred at 5000rpm
1h is mixed, curing agent emulsion 2b1 and isocyanates repair the renovation agent in agent emulsion 2a1 and interfacial reaction occur, cyst wall is generated, thus
Obtain the micro/nano level microcapsule emulsion 2 of cladding curing agent.The isocyanates repairs agent emulsion 2a1 and curing agent emulsion
The weight ratio 2.5:1 of 2b1.
(3) preparation has the interior curable type silane-functionalized self-repairing microcapsule of dispatching workers to do on-site repairs of cell structure:
(3a) weighs appropriate curing agent, emulsifier and solvent, and room temperature uniform stirring 70min at 6000rpm is solidified
Agent emulsion 3a2;The weight ratio of the curing agent, solvent and emulsifier is 1:15:0.15.The isocyanates renovation agent is first
Phenylene diisocyanate, the emulsifier are Arabic gum, and the solvent is cyclohexanol.
(3b) weighs appropriate isocyanates renovation agent, dispersing agent and solvent, room temperature and stirs 55min at 3,000 rpm, obtains
To isocyanates dispersion liquid 3b2;The weight ratio of the isocyanates renovation agent, solvent and dispersing agent is 1:20:0.12.It is described
Curing agent is hydroxy compounds, and the hydroxy compounds is polyoxypropylene polyol, and the dispersing agent is sodium metasilicate, described molten
Agent is hexamethylene.
(3c) a certain amount of silane emulsion 1, micro/nano level microcapsule emulsion 2 and cream are added into isocyanates dispersion liquid 3b2
Agent, room temperature obtain the Composite Milk of the emulsion droplet comprising multiple micro/nano level microcapsules in the emulsified 2h of revolving speed of 1800rpm
Liquid;The emulsifier is neopelex.Then appropriate amount of acid is added dropwise, makes the pH value 5 of system;Again into multiple emulsion
Curing agent emulsion 3a2 is added dropwise, stirs 2h under 65 DEG C of temperature condition and the revolving speed of 1600rpm, curing agent emulsion 3a2 with comprising
Interfacial reaction occurs for the renovation agent emulsion droplet of multiple micro/nano level microcapsules, generates cyst wall;Obtain that there is the outer of cell structure
Repair interior curable type silane-functionalized self-repairing microcapsule lotion.The isocyanates dispersion liquid 3b2, silane emulsion 1, the micro- glue of nanoscale
The weight ratio of capsule lotion 2, emulsifier and curing agent ester lotion 3a2 is 1:0.8:0.8:0.15:3.
The lotion that (3d) obtains (3c) is centrifuged, washs, is dry, obtains the interior curable type silane function of dispatching workers to do on-site repairs with cell structure
Self-repairing microcapsule can be changed.
Using the coatings of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure, the selfreparing
Mass fraction of the microcapsules in coatings is 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 the characterization result of Tables 1 and 2 it is found that the partial size of the microcapsules of embodiment 1-6 preparation is 10-200 μm, stretch strong
Degree is 9.27-11.64MPa, and elongation at break is 218.28-233.85%, and microcapsules shore hardness (A) is 52-63.
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 detection after self-healing system reparation
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, concrete crushing strength is 46.34-46.92Mpa, average value 46.71MPa after reparation;With repair
It is compared before multiple, remediation efficiency improves 9.88%.Epoxy coating is 17.47-17.74Mpa after reparation, and average value is
17.57MPa;Compared with before reparation, remediation efficiency improves 13.33%.
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 583.4-596.4g/m after reparation3, compared with blank sample, drop
Low 5.1-7.1%.
In conclusion interior curable type self-repairing microcapsule form in terms of micromorphology of dispatching workers to do on-site repairs with cell structure
Well, partial size is mainly distributed between 10-200 μm.Mechanical test shows that the microcapsules after solidification are that have certain intensity
Elastic material (the elongation at break 218.28- of (tensile strength 9.27-11.64MPa) and hardness (shore A 52-63)
233.85%).This is because, the SiO that silane emulsion hydrolysis generates2Nanoparticle participates in the synthesis process of cyst wall, centainly
The mechanical property of cyst wall is improved in degree.
By that there will be the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs of cell structure to mix concrete and epoxy coating, and carry out
The experiment of precompressed crackle shows that the microcapsules have certain repair to crackle, and concrete crushing strength improves after reparation
Rate is 9.88%, and the tensile strength increase rate of epoxy coating is 13.33% after reparation.This is because, its multicore capsule size
For nanoscale, the probability that microcapsules rupture during concrete for making is greatly reduced, greatly improves self-repair efficiency.It removes
Except this, renovation agent can also be reacted with the steam of outside to mend a split;Repairing effect has been further speeded up, has been realized to crackle
It repairs in time.
By that there will be the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs of cell structure to mix concrete, and carry out water imbibition test
Show that microcapsules fracture has certain repair, the water absorption reduced rate of concrete is 5.1-7.1% 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. the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure, the self-repairing microcapsule includes cyst wall and cyst wall cladding
Renovation agent, it is characterised in that: serial micro/nano level microcapsules are dispersed in the renovation agent, to constitute cell structure;Institute
It states in micro/nano level microcapsules and coats curing agent.
2. the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs according to claim 1 with cell structure, it is characterised in that: described
The curing agent outside renovation agent and self-repairing microcapsule that the cyst wall of self-repairing microcapsule is coated by self-repairing microcapsule, silane cream
The silane-modified cyst wall that liquid reacts;The curing agent be hydroxy compounds lotion or amine compound lotion, it is described to repair
Multiple agent is isocyanate emulsion.
3. the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs according to claim 2 with cell structure, it is characterised in that: described
The cyst wall of micro/nano level microcapsules is by the renovation agent outside the curing agent and micro/nano level microcapsules of micro/nano level microcapsule coated
React obtained cyst wall.
4. the preparation method of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs with 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
80-120min is stirred at 6000-9000rpm, isocyanates is obtained and repairs agent emulsion 2a1;(2b) weighs appropriate curing agent, molten
Agent and emulsifier, room temperature stir 60-100min at 4000-7000rpm, obtain curing agent emulsion 2b1;(2c) is by isocyanates
It repairs agent emulsion 2a1 to be added dropwise in curing agent emulsion 2b1, room temperature stirs 1-2h at 2000-6000rpm, and it is solid to obtain cladding
The micro/nano level microcapsule emulsion 2 of agent.
(3) preparation have cell structure interior curable type silane-functionalized self-repairing microcapsule of dispatching workers to do on-site repairs: (3a) weigh appropriate curing agent,
Emulsifier and solvent, room temperature uniform stirring 70-100min at 4000-6000rpm, obtain curing agent emulsion 3a2;(3b) is weighed
Appropriate isocyanates renovation agent, dispersing agent and solvent, room temperature stir 50-70min at 3000-5000rpm, obtain isocyanic acid
Ester dispersion liquid 3b2;(3c) a certain amount of silane emulsion 1, micro/nano level microcapsule emulsion 2 are added into isocyanates dispersion liquid 3b2
And emulsifier, room temperature obtain multiple emulsion in the emulsified 1-2h of revolving speed of 1500-3500rpm;Then it is added dropwise into multiple emulsion
Curing agent emulsion 3a2 stirs 2-3h under 50-70 DEG C of temperature condition and the revolving speed of 1000-2500rpm, obtains with born of the same parents' shape
The interior curable type silane-functionalized self-repairing microcapsule lotion of dispatching workers to do on-site repairs of structure;The lotion that (3d) obtains (3c) is centrifuged, washing, does
It is dry, obtain the interior curable type silane-functionalized self-repairing microcapsule of dispatching workers to do on-site repairs with cell structure.
5. the preparation method of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs according to claim 4 with cell structure, special
Sign is: isocyanates repairs the weight ratio 1:1-5:1 of agent emulsion 2a1 and curing agent emulsion 2b1 in step (2c);Step
Isocyanates dispersion liquid 3b2 in (3c), silane emulsion 1, nanometer-sized microcapsules lotion 2, emulsifier and curing agent ester lotion 3a2
Weight ratio is 1:(0.5-0.8): (0.5-0.8): (0.06-0.15): (1-3).
6. the preparation method of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs according to claim 5 with cell structure, special
Sign is: the weight ratio of isocyanates renovation agent, solvent and emulsifier described in step (2a) is 1:(10-15): (0.10-
0.18);The weight ratio of curing agent, solvent and emulsifier is 1:(15-20 in step (2b)): (0.08-0.15);In step (3a)
The weight ratio of curing agent, solvent and emulsifier is 1:(10-15): (0.06-0.15);Isocyanates reparation in step (3b)
The weight ratio of agent, solvent and dispersing agent is 1:(15-20): (0.06-0.12).
7. the preparation of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs according to claim 4-6 any one with cell structure
Method, it is characterised in that: in the step (3c), when to mixed solution and dripping curing agent emulsion 3a2, while being added dropwise appropriate
Acid makes the pH value 4-6 of system.
8. the preparation method of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs according to claim 7 with cell structure, special
Sign is: step (1) specifically: (1a) weighs appropriate silane, emulsifier and dispersing agent, the weight of silane, emulsifier and dispersing agent
Than 80:1:1-120:5:1, room temperature stirs 15-30min under the revolving speed of 2000-4000rpm and obtains finely dispersed oily phase amount;
(1b) weighs appropriate emulsifier and water, and the weight ratio of emulsifier and water is 1:80-1:120, and room temperature is stirred at 1000-3000rpm
It mixes 15-30min 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 1:0.8-1:
5000-10000rpm stirs 4-5h at 1.5,40-60 DEG C, obtains uniform and stable oil-in-water type multiple emulsion, i.e. silane emulsion
1。
9. the preparation method of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs according to claim 8 with cell structure, special
Sign is: the silane is vinyltriethoxysilane, vinyltrimethoxysilane, ethyl orthosilicate, isobutyl group three
One or more of Ethoxysilane, 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. special using the self-healing system of the interior curable type self-repairing microcapsule of dispatching workers to do on-site repairs described in claim 1 with cell structure
Sign is: the quality of the interior curable type silane-functionalized self-repairing microcapsule in self-healing system of dispatching workers to do on-site repairs with cell structure
Score is 5%-18%;The self-healing system is self-repair concrete or coatings.
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