CN107952404A - Inside repair outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule and preparation method thereof - Google Patents
Inside repair outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule and preparation method thereof Download PDFInfo
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- CN107952404A CN107952404A CN201711237991.5A CN201711237991A CN107952404A CN 107952404 A CN107952404 A CN 107952404A CN 201711237991 A CN201711237991 A CN 201711237991A CN 107952404 A CN107952404 A CN 107952404A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/16—Interfacial polymerisation
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/20—After-treatment of capsule walls, e.g. hardening
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
Abstract
For the problems of self-healing system in the prior art, outer curable type porous boron nitride (BN) polyureas base double-walled self-repairing microcapsule and preparation method thereof is repaiied the present invention provides interior.Inside repair outer curable type porous boron nitride polyureas base double-walled self-repairing microcapsule, including internal layer cyst wall and outer layer cyst wall.The internal layer cyst wall coats pre-polymer emulsion, and the outer layer cyst wall coats amido chain extender BN lotions；The internal layer cyst wall polyureas is reacted to obtain by the pre-polymer emulsion that internal layer cyst wall coats and water, and the amido chain extender emulsion that the outer layer cyst wall polyureas is coated by a small amount of pre-polymer emulsion with outer layer cyst wall reacts to obtain, and BN is disperseed in the outer layer cyst wall polyureas.Double-walled microcapsule systems of the present invention introduce boron nitride, as packing material and dispersion, not only solve the problems, such as that renovation agent and curing agent contact rate are relatively low, and realize to the more preferable quick response of crackle, have a vast market application prospect.
Description
Technical field
The invention belongs to organic composite material field, is related to a kind of self-repair material, and in particular to repaiies outer curable type in one kind
Porous boron nitride (BN) -- polyureas base double-walled self-repairing microcapsule and preparation method thereof, prevents applied to building disaster prevention mitigation, coating
The engineering fields such as shield reparation.
Background technology
With the continuous development of society, building trade is also quickly grown, various high buildings and large mansions, bridge road pick up successively and
Rise.Concrete the excellent properties such as it derives from a wealth of sources, compression strength is high, easily construction and durability be higher because being widely used in
Building field.But crackle easily occurs during service life for concrete structure.With load change and the time passage,
Crackle can gradually be extended to crack, or even extending into surface causes concrete material to crack.After through crack is formed, concrete
The erosion and destruction of external environment and various adverse factors are subject to, such as steel bar corrosion, carbonization, Chloride Attack and sulfate
Corrode etc., ultimately result in the cracking of concrete material, destroy, seriously affect the durability of concrete material, in some instances it may even be possible to cause
Sudden building is destroyed the people's wealth for causing to retrieve and is lost.Similarly, coating is wide as most common protective materials
General is applied to the fields such as infrastructure, aerospace, automobile making.However, coating is easily subject to outside during military service
The influence of boundary's factor causes its internal chemical structure to produce change, causes different size micro-cracks and local damage and makes coating
Mechanical property declines to a great extent, and coat inside micro-crack is constantly be generated and collects and ultimately results in disbonding and it can not be realized pair
Base material is effectively protected.Since these micro-cracks damages are difficult to by naked eyes, therefore common repair methods are often difficult to reach
Preferable effect.Therefore, influence of the micro crack to material military service performance is more and more widely paid close attention to and is paid attention to.Tradition
Recovery technique method mainly include surface mending method, sectional repair method and grouting method, these methods be to face crack and
Localized cracks are repaired, and can not realize the reparation to intrinsic silicon micro-crack, and palliative, repair materials can not resist sea
The erosion of foreign environment, and the regeneration of more difficult effectively control crackle.
2001, White et al. delivered one on polymer self-repair technology on natural science magazine first
Article so that self-repair technology is widely used.Under this technical background, researchers begin through the original of bionical selfreparing
Manage the research that selfreparing is carried out to realize aggressive mode to concrete structure.When concrete structure is cracked, in micro-crack
Under the action of by capillary force force additive rupture release renovation agent and to enter crack, repair and prevent the further of crack
Growth, so as to form active reparation network system in inside concrete.Micro-capsule self-repair technology reviews one's lessons by oneself compound as one kind
Solidifying soil material structure important component, before many aspects such as civil engineering construction from now on and reparation have very big application
Scape.High cost of this method needed for without extra artificial monitoring and maintenance surface, extends the concrete structure service life
The operation spending of part construction material is also saved at the same time.
At present, microcapsules self-healing system mainly includes single wall microcapsules reparation system, the double microcapsules of single wall repair systems
With double-walled microcapsule systems.The research of early stage is concentrated mainly on single wall microcapsule systems, and renovation agent is coated on micro- by this system
In capsule, catalyst is contained in matrix is repaired.Single wall microcapsule systems are mainly comprising DCPD-Grubbs systems, ureaformaldehyde tree
Fat (UF) system, interior cover dicyclopentadiene (DCPD) system and epoxy curing agent system.But there are following for above-mentioned system
Problem：(1) microcapsules thermo-chemical stability is poor；(2) it is slow to react film-forming speed, it is impossible to effective filling cracks；(3) catalyst
Expensive, easy inactivation；(4) self-healing system application range is relatively narrow, can only be confined in certain base material.Patent of invention
ZL200710044358.4 is disclosed " polyurea microcapsule and preparation method thereof ".The invention provides a kind of polyurea microcapsule and its
Preparation method, preparation method include the following steps：(1) organic containing methyl diphenylene diisocyanate is added to containing table
The water phase of face activating agent, stirring and emulsifying, obtains latex A；(2) diethylenetriamine is added into the aqueous solution containing surfactant,
Obtain continuous phase solution B；(3) continuous phase solution B is added into latex A, triggers interface polymerization reaction on oil-water interfaces, contained
There is the suspension of polyurea microcapsule.The polyureas wall material of microcapsule systems is direct with amino-compound by isocyanates in the invention
Generated by interface polymerization reaction, solve the problems, such as that film-forming is slow-footed；But what the system obtained is linear polyureas
Cyst wall structure, the poor performance of this wall material, can not realize the protective effect to core.Secondly, the invention is in isocyanates breast
Employ emulsion oil-in-water in liquid preparation process, cause isocyanates due to its sensitiveness to water premature failure so that
It is unfavorable for subsequent reactions generation polyurea microcapsule.In addition, the polyurea microcapsule is single-wall structure, however it remains single wall microcapsules
It is the problems such as remediation efficiency is relatively low.
Occur the double microcapsule systems of single wall in subsequent research, this system includes two kinds of microcapsules, and one kind cladding is repaiied
Multiple agent, one kind cladding curing agent.The double microcapsule systems of single wall solve the problems with of single wall microcapsule systems to a certain extent：
(1) need to add catalyst in the substrate to realize selfreparing；(2) repairing effect that the easy premature inactivation of catalyst is brought is not
It is good；(3) production cost is excessive.But the double microcapsule systems of single wall still have renovation agent can not be contacted at the same time with curing agent, cannot
It is quick to be repaired and the problems such as complicated is managed to crackle answering machine.Under these technical backgrounds, some researchers have reported that double-walled
Microcapsule systems.Compared with single wall microcapsule systems, the microcapsule systems of double-walled cladding have more preferable stability, therefore reduce
The probability of renovation agent and curing agent inactivation；It also greatly increases the contact probability of renovation agent and catalyst at the same time, avoid and add
Add the adverse effect of excessive renovation agent and catalyst to concrete performance.
Patent of invention ZL200510014698.3 is disclosed " preparation method of bilayered microcapsule of polyurea-urea formaldehyde resin ".Should
Invention uses interfacial polymerization, and interface is carried out as monomer using glutaraldehyde modified multicomponent aminated compounds and diisocyanate cpd
Polymerization, prepares polyurea microcapsule；Using situ aggregation method, using this polyurea microcapsule as kernel, using urea and formaldehyde as monomer,
Lauxite shell is generated under acid condition, obtains polyureas-ureaformaldehyde bilayered microcapsule.The invention divides in preparation process twice
Two kinds of different systems of interfacial polymerization and in-situ polymerization have not been selected, and situ aggregation method is to core material and generation cyst wall material
The dissolubility of material has certain requirement, not only limits the species of reagent, and make it that flow is increasingly complex, adds operation
Difficulty.Secondly, which employs emulsion oil-in-water in isocyanate emulsion preparation process, cause isocyanates due to
Its sensitiveness to water and premature failure, so as to be unfavorable for subsequent reactions generation polyurea microcapsule.In addition, the invention employs tool
There are very high toxicity and volatile toluene di-isocyanate(TDI), larger pollution is easily caused to environment；And in preparation process,
Need constantly to realize the synthesis of microcapsules by adjusting pH value, show the dependence excessive to different pH value, further increase
The complexity of operation.
Except the research of double-walled microcapsule systems, added stratified materials such as carbon nanotubes or graphenes as functional stuffing
Report in self-healing system is commonplace.Patent of invention ZL201110147435.5 discloses a kind of " carbon nanotubes enhancing ring
The preparation method of oxygen tree fat self-repairing microcapsule ".The invention, as core, selects three using epoxy resin-carbon nanotubes lotion
Cyst wall prepolymer is made in poly cyanamid, formaldehyde, and epoxy resin-carbon nanotubes lotion and cyst wall prepolymer are further blended in necessarily
Under the conditions of microcapsules are made, the repairing effects of microcapsules can be further improved, improve mechanical property.Patent of invention
201510395245.3 disclose " a kind of self-healing coatings of graphene-containing and preparation method thereof ".This report invented it is a kind of by
The organic renovation agent of graphene coated and form for metal surface self-repairability organic anti-corrosive lose coating.The self-healing system selects
It is basis material with water-base resin, graphene is effectively prevented from coating after breakage to gold as the shell of self-repairing microcapsule
Belong to matrix and lose corrosion resistance protection.
Application for a patent for invention 201510153922.0 discloses " a kind of epoxy resin micro-capsule and preparation method thereof ".The hair
It is bright using epoxy resin as capsule-core raw material, using the inorganic particulate of absorption solidification agent as cyst wall raw material, by by capsule-core and cyst material
Disperse in aqueous, under proper condition, utilize absorption of the core materials to inorganic particulate and curing agent to trigger capsule-core surface
Generation polymerisation, forms the epoxy microcapsule using epoxy resin film and inorganic particulate as cyst wall component.This application is by mesoporous silicon
It is introduced into nm-class boron nitride in the design of cyst wall, but the purpose that the invention introduces nm-class boron nitride is to improve cyst material heat resistance
The problem of relatively low and improve adaptability of the cyst wall in high-temperature process.In addition, nm-class boron nitride, mesoporous silicon are with consolidating in this application
Combination between agent is the suction-operated by physics, therefore is easily spread out in high-speed agitating process, it is difficult to realization pair
The modification of cyst material.
The content of the invention
For the problems of self-healing system in the prior art, outer curable type porous boron nitride is repaiied the present invention provides interior
(BN)-polyureas base double-walled self-repairing microcapsule and preparation method thereof.Double-walled microcapsule systems of the present invention introduce boron nitride,
As packing material and dispersion, not only solve the problems, such as that renovation agent and curing agent contact rate are relatively low, and realize
To the more preferable quick response of crackle, application prospect is had a vast market.
Technical scheme：
Inside repair outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule, including internal layer cyst wall and outer layer cyst wall.Institute
Internal layer cyst wall cladding pre-polymer emulsion is stated, the outer layer cyst wall coats amido chain extender-BN lotions；The internal layer cyst wall polyureas by
The pre-polymer emulsion of internal layer cyst wall cladding reacts to obtain with water, and the outer layer cyst wall polyureas is by a small amount of pre-polymer emulsion and outer layer capsule
The amido chain extender emulsion of wall cladding reacts to obtain, and BN is disperseed in the outer layer cyst wall polyureas.Boron nitride not only has stability
Height, intensity is high, the series of advantages such as corrosion resistance, and due to its porous effect, is dispersed in when producing micro-crack in cyst wall
Boron nitride will increase micro-crack to the capillary siphonages of microcapsules, increase the machine that renovation agent curing agent enters micro-crack
Rate.In addition, boron nitride also has excellent cutting ability, make it that there is the sensitiveness of height to crackle, can quickly be split
The response of line causes repairing effect to greatly improve.
The preparation method of outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule is inside repaiied, is comprised the following steps：
(1) pre-polymer emulsion is prepared：By appropriate aliphatic category isocyanates renovation agent, amine terminated polyether, emulsifying agent and molten
Agent is uniformly mixed under high velocity agitation, prepares pre-polymer emulsion；Specially：By aliphatic category isocyanates renovation agent and Amino End Group
Polyethers is according to 1:1-1:5 mass ratio is uniformly mixed, and obtains prepolymer；Stir evenly, add under the rotating speed of 1000-2500rpm
Enter emulsifying agent and solvent, under the rotating speed of 1000-2500rpm, 60 DEG C of -70 DEG C of insulation 2-3h, obtain pre-polymer emulsion；The breast
The amount of agent is the 3%-6% of pre-polymerization amount of substance, and the mass ratio of the emulsifying agent and solvent is 1:140-1:150.
The NCO group content of the aliphatic category isocyanates renovation agent is 3%-12%, and average functionality is 1.5
To 5；The aliphatic category isocyanates renovation agent is isophorone diisocyanate (IPDI), hexamethylene diisocyanate
(HDI), 1,4- cyclohexane diisocyanates, cyclohexyl-methane -4,4- diisocyanate, 1,6- hexamethylene diisocyanates
Allophanate or HDI trimer system；The amine terminated polyether for polyetheramine D400, polyetheramine D230, polyetheramine D2000,
3,5- dimethyl sulphur-based Toluene-2,4-diisocyanates, 6- diamines, 3,5- diethyltoluene -2,4- diamines, 3,5- dimethyl sulphur-based Toluene-2,4-diisocyanates, 4- diamines,
1,4 butanediamine or 1,6 hexamethylene diamines.
(2) amido chain extender-BN lotions are prepared：Amido chain extender, BN dispersion liquids, solvent and emulsifying agent are under high velocity agitation
It is uniformly mixed, prepares amido chain extender-BN lotions；Specially：Suitable emulsifying agent and solvent are taken, in turning for 2000-3500rpm
Speed is lower to be stirred to uniformly mixed；The mass ratio of the emulsifying agent and solvent is 1:40-1:50；Amido chain extender is added, in 2000-
Stirred under the rotating speed of 3500rpm to uniformly mixed；BN dispersion liquids are added, are stirred with the rotating speed of 2000-3500rpm equal to mixing
Even, ultrasonic disperse, is made amido chain extender-BN lotions；The amount of the emulsifying agent is the 10%-20% of amido chain extender quality.
The preparation method of the BN dispersion liquids is：Hydroxylating is carried out to BN powder surface using Piranha washing lotions first
Processing, then by itself and emulsifying agent high speed dispersion, is ultrasonically treated, is centrifuged with 4000r/min rotating speeds, take supernatant, to obtain the final product
To BN dispersion liquids.Hydroxyl modification is carried out to boron nitride using the method for chemistry, makes boron nitride and chain extender emulsion and solvent all
It can produce and combine power well, so as to fulfill modification of the boron nitride to wall material is added in wall material.
The amido chain extender is diethyl toluene diamine, dimethythiotoluene diamine, N, N'- dialkyl methyl hexichol
Amine, cyclohexane diamine, chlorination MDH, ethylenediamine, 1,3- diaminopropanes, 1,4- diaminobutanes, diethylenetriamines, five Asias
Hexamine, six ethylene diamines, tetren, penten, polyetheramine D400, polyetheramine D230, ethylenediamine
Or 3,3'-4,4'- diaminourea-diphenyl-methane MOCA.
(3) polyureas encapsulating double-walled microcapsules are prepared：Water is added dropwise in the pre-polymer emulsion of step (1) preparation, synthesis
Microcapsules inner wall wall material, forms single wall microcapsule emulsion；The amine that emulsifying agent, solvent and excess are added in lotion is stated then up
Base chain extender-BN lotions, instill pre-polymer emulsion after the completion of emulsification, synthesize microcapsules outer wall wall material, form double-walled microcapsules breast
Liquid.Specially：
1. water droplet is added in pre-polymer emulsion, in mass ratio 1:1-1:3 ratio is uniformly mixed, in 1000-2500rpm
Rotating speed under, 60 DEG C -70 DEG C insulation 2-3h, formed single wall microcapsule emulsion；Principle is：Copolymer emulsion droplet surface absorption go from
Sub- water drop, by the polymerisation of prepolymer and water, completes the synthesis of microcapsules inner wall wall material, forms single wall microcapsules breast
Liquid.2. the amido chain extender-BN lotions that suitable emulsifying agent, solvent and excess are added in the system 1. obtained to step carry out breast
Change, form single wall microcapsules-amido chain extender-BN composite emulsifying drop systems；The emulsifying agent expands in single wall microcapsules-amido
Mass fraction in chain agent-BN composite emulsifying drop systems is 4%-6%；The mass ratio of the emulsifying agent and solvent is 1:150-
1:160；Instill pre-polymer emulsion after the completion of emulsification, the mass ratio of the pre-polymer emulsion and amido chain extender-BN lotions is 1:
1-1:3；Under the rotating speed of 1000-2500rpm, 60 DEG C of -70 DEG C of insulation 2-3h, form double-walled microcapsule emulsion；Principle is：Amido
Chain extender-BN emulsion droplets adsorptions remove pre-polymer emulsion drop, anti-by prepolymer and polymerizeing for amido chain extender-BN lotions
Should, the synthesis of microcapsules outer wall wall material is completed, forms double-walled microcapsule emulsion.3. double-walled microcapsule emulsion is centrifuged, is done
Dry, drying and carrying out washing treatment, that is, obtain the interior of polyureas encapsulating and repair outer curable type porous boron nitride-micro- glue of polyureas base double-walled selfreparing
Capsule, its size distribution are 10 μm -200 μm.The present invention introduces boron nitride in cyst wall wall material, will be improved using its porous performance
The siphonage of micro-crack is to improve self-repair efficiency.The pre-polymer emulsion that the application uses and amido chain extender emulsion, not only
Respectively as renovation agent and curing agent, and react with each other and generate outer layer cyst wall, utilization rate is high, so as to enormously simplify technique
Flow.
It is described when 2. preparing double-walled microcapsule emulsion, 1-5 drops can also be added while adding pre-polymer emulsion and are defoamed
Agent；The defoamer is n-butanol, 1,4- butanediols, polyoxyethylene polyoxypropylene glycerin ether or dimethyl silicone polymer.
Emulsifying agent described in above-mentioned steps is neopelex, OP-10, octadecane alcohol radical APEO,
Arabic gum, polyoxyethylene ether, fatty amine polyoxyethylene ether or polyvinyl alcohol；The solvent is ethyl acetate, acetone, hexamethylene
Alkane, pentamethylene, toluene or chlorobenzene.
Using the self-repair concrete system of the porous boron nitride-polyureas base double-walled microcapsules, the nitride porous
Boron-mass fraction of the polyureas base double-walled microcapsules in compound system is reviewed one's lessons by oneself is 5%-18%；The self-healing system is to review one's lessons by oneself
Multiple concrete or coatings.
Beneficial effects of the present invention：
(1) porous boron nitride double-walled construction microcapsules of the present invention can make renovation agent with chain extender with stable state
Inside base material, curing reaction is released at the same time under crack tip effect, simplifies crackle response mechanism.
(2) aliphatic category isocyanates-amine terminated polyether prepolymer directly reacts with water and generates polyureas in the present invention
Cyst wall, without catalyst and adhesive, significantly simplifies the process of microcapsules repair crack, expands the model that selfreparing is applied
Enclose, broken the limitation of base material, possess wide application prospect.
(3) can be when aliphatic category isocyanates-amine terminated polyether polymer for using of the present invention runs into amido chain extender
Reaction is quickly cured under room temperature, it is simple to operate in the application without heating, and solve film-forming speed
Slowly, it is impossible to the problem of effectively preventing crack from extending；
(4) compared with the self-healing system based on epoxy resin base material, the present invention utilizes the double-walled of interfacial polymerization generation
Self-repairing microcapsule has broken the limitation of base material, has and is more widely applied value.
Brief description of the drawings
Attached drawing 1 is the structure diagram of double-walled microcapsules.
Embodiment
With reference to embodiment, the present invention is described further.
Embodiment 1：
Inside repair outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule, including internal layer cyst wall and outer layer cyst wall.Institute
Internal layer cyst wall cladding pre-polymer emulsion is stated, the outer layer cyst wall coats amido chain extender-BN lotions；The internal layer cyst wall is pre-polymerization
Thing and water are prepared by interface polymerization reaction；The outer layer cyst wall is obtained for amido chain extender with prepolymer by interface polymerization reaction
Arrive, BN is disperseed in the outer layer cyst wall.Boron nitride not only has stability height, and intensity is high, the series of advantages such as corrosion resistance, and
And due to its porous effect, the boron nitride being dispersed in when producing micro-crack in cyst wall will increase capillary of the micro-crack to microcapsules
Siphonage, big renovation agent curing agent enter the probability of micro-crack.In addition, boron nitride also has excellent cutting ability, make
It has crackle the sensitiveness of height, quickly can carry out the response of crackle so that repairing effect greatly improves.
The preparation method of outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule is inside repaiied, is comprised the following steps：
(1) pre-polymer emulsion is prepared：By aliphatic category isocyanates renovation agent isophorone diisocyanate (IPDI)
With amine terminated polyether polyetheramine D400 according to 1:1 mass ratio is uniformly mixed, and obtains prepolymer；Stirred under the rotating speed of 1200rpm
Mix uniformly, add emulsifying agent and solvent, under the rotating speed of 1000rpm, 65 DEG C of insulation 2-3h, obtain pre-polymer emulsion；The breast
The amount of agent is the 6% of pre-polymerization amount of substance, and the mass ratio of the emulsifying agent and solvent is 1:150.
(2) amido chain extender-BN lotions are prepared：Take suitable emulsifying agent and solvent, stirred under the rotating speed of 2200rpm to
It is uniformly mixed；The mass ratio of the emulsifying agent and solvent is 1:44；Amido chain extender diethyl toluene diamine is added,
Stirred under the rotating speed of 2600rpm to uniformly mixed；BN dispersion liquids are added, are stirred with the rotating speed of 2000rpm to uniformly mixed, ultrasound
It is scattered, amido chain extender-BN lotions are made；The amount of the emulsifying agent is the 18% of amido chain extender quality.
The preparation method of the BN dispersion liquids is：Hydroxylating is carried out to BN powder surface using Piranha washing lotions first
Processing, then by itself and emulsifying agent high speed dispersion, is ultrasonically treated, is centrifuged with 4000r/min rotating speeds, take supernatant, to obtain the final product
To BN dispersion liquids.Hydroxyl modification is carried out to boron nitride using the method for chemistry, makes boron nitride and chain extender emulsion and solvent all
It can produce and combine power well, so as to fulfill modification of the boron nitride to wall material is added in wall material.
(3) polyureas encapsulating double-walled microcapsules are prepared：
1. water droplet is added in pre-polymer emulsion, in mass ratio 1:3 ratio is uniformly mixed, under the rotating speed of 1000rpm,
62 DEG C of insulation 2-3h, form single wall microcapsule emulsion；Principle is：Copolymer emulsion droplet surface adsorption deionizing water drop, passes through
The polymerisation of prepolymer and water, completes the synthesis of microcapsules inner wall wall material, forms single wall microcapsule emulsion.
2. the amido chain extender-BN lotions of suitable emulsifying agent, solvent and excess are added in the system 1. obtained to step
Emulsified, form single wall microcapsules-amido chain extender-BN composite emulsifying drop systems；The emulsifying agent single wall microcapsules-
Mass fraction in amido chain extender-BN composite emulsifying drop systems is 5%；The mass ratio of the emulsifying agent and solvent is 1:
160；Instill pre-polymer emulsion after the completion of emulsification, the mass ratio of the pre-polymer emulsion and amido chain extender-BN lotions is 1:1；
Under the rotating speed of 1800rpm, 62 DEG C of insulation 2-3h, form double-walled microcapsule emulsion；Principle is：Amido chain extender-BN emulsion droplets
Adsorption removes pre-polymer emulsion drop, by prepolymer and the polymerisation of amido chain extender-BN lotions, completes outside microcapsules
The synthesis of wall wall material, forms double-walled microcapsule emulsion.
3. double-walled microcapsule emulsion is centrifuged, is dried, is dried and carrying out washing treatment, that is, obtain polyureas encapsulating in repair it is outer
Curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule.The present invention introduces boron nitride in cyst wall wall material, porous using its
Performance will improve the siphonage of micro-crack to improve self-repair efficiency.The pre-polymer emulsion that the application uses and amido chain extension
Agent emulsion, not only respectively as renovation agent and curing agent, and reacts with each other and generates outer layer cyst wall, and utilization rate is high, so that greatly
Simplify technological process greatly.
Emulsifying agent described in above-mentioned steps is neopelex；The solvent is ethyl acetate.
Using the self-repair concrete of the polyureas base double-walled microcapsules, the polyureas base double-walled microcapsules are in selfreparing
Mass fraction in concrete is 5%.
Embodiment 2：
As different from Example 1,
The preparation method of outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule is inside repaiied, is comprised the following steps：
(1) pre-polymer emulsion is prepared：By aliphatic category isocyanates renovation agent 1,4- cyclohexane diisocyanates and end
Amino-polyether 3,5- dimethyl sulphur-based Toluene-2,4-diisocyanates, 6- diamines is according to 1:2 mass ratio is uniformly mixed, and obtains prepolymer；In 1000rpm
Rotating speed under stir evenly, add emulsifying agent and solvent, under the rotating speed of 1300rpm, 68 DEG C of insulation 2-3h, obtain prepolymer breast
Liquid；The amount of the emulsifying agent is the 5.5% of pre-polymerization amount of substance, and the mass ratio of the emulsifying agent and solvent is 1:154.
(2) amido chain extender-BN lotions are prepared：Take suitable emulsifying agent and solvent, stirred under the rotating speed of 2000rpm to
It is uniformly mixed；The mass ratio of the emulsifying agent and solvent is 1:42；Amido chain extender cyclohexane diamine is added, 2800rpm's
Stirred under rotating speed to uniformly mixed；BN dispersion liquids are added, are stirred with the rotating speed of 3000rpm to being uniformly mixed, ultrasonic disperse, is made
Amido chain extender-BN lotions；The amount of the emulsifying agent is the 20% of amido chain extender quality.
(3) polyureas encapsulating double-walled microcapsules are prepared：
1. water droplet is added in pre-polymer emulsion, in mass ratio 1:1 ratio is uniformly mixed, under the rotating speed of 1200rpm,
65 DEG C of insulation 2-3h, form single wall microcapsule emulsion.
2. the amido chain extender-BN lotions of suitable emulsifying agent, solvent and excess are added in the system 1. obtained to step
Emulsified, form single wall microcapsules-amido chain extender-BN composite emulsifying drop systems；The emulsifying agent single wall microcapsules-
Mass fraction in amido chain extender-BN composite emulsifying drop systems is 5.5%；The mass ratio of the emulsifying agent and solvent is 1:
150；Instill pre-polymer emulsion and 1-5 drop defoamers after the completion of emulsification, the defoamer is dimethyl silicone polymer, the pre-polymerization
The mass ratio of thing lotion and amido chain extender-BN lotions is 1:1.5；Under the rotating speed of 2500rpm, 65 DEG C of insulation 2-3h, form
Double-walled microcapsule emulsion.
3. double-walled microcapsule emulsion is centrifuged, is dried, is dried and carrying out washing treatment, that is, obtain polyureas encapsulating in repair it is outer
Curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule.
Emulsifying agent described in above-mentioned steps is neopelex；The solvent is ethyl acetate.
Using the coatings of the polyureas base double-walled microcapsules, the polyureas base double-walled microcapsules are in selfreparing ring
Mass fraction in oxygen coating is 8%.
Embodiment 3：
As different from Example 1,
The preparation method of outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule is inside repaiied, is comprised the following steps：
(1) pre-polymer emulsion is prepared：By aliphatic category isocyanates renovation agent 1,6- hexamethylene diisocyanates
Allophanate is with 1,4 butanediamine of amine terminated polyether according to 1:3 mass ratio is uniformly mixed, and obtains prepolymer；1600rpm's
Stirred evenly under rotating speed, add emulsifying agent and solvent, under the rotating speed of 1500rpm, 70 DEG C of insulation 2-3h, obtain prepolymer breast
Liquid；The amount of the emulsifying agent is the 5% of pre-polymerization amount of substance, and the mass ratio of the emulsifying agent and solvent is 1:158.
(2) amido chain extender-BN lotions are prepared：Take suitable emulsifying agent and solvent, stirred under the rotating speed of 2600rpm to
It is uniformly mixed；The mass ratio of the emulsifying agent and solvent is 1:48；Amido chain extender ethylenediamine is added, in the rotating speed of 2200rpm
It is lower to stir to uniformly mixed；BN dispersion liquids are added, are stirred with the rotating speed of 2500rpm to being uniformly mixed, ultrasonic disperse, is made amido
Chain extender-BN lotions；The amount of the emulsifying agent is the 15% of amido chain extender quality.
(3) polyureas encapsulating double-walled microcapsules are prepared：
1. water droplet is added in pre-polymer emulsion, in mass ratio 1:1.2 ratio is uniformly mixed, in the rotating speed of 1400rpm
Under, 68 DEG C of insulation 2-3h, form single wall microcapsule emulsion.
2. the amido chain extender-BN lotions of suitable emulsifying agent, solvent and excess are added in the system 1. obtained to step
Emulsified, form single wall microcapsules-amido chain extender-BN composite emulsifying drop systems；The emulsifying agent single wall microcapsules-
Mass fraction in amido chain extender-BN composite emulsifying drop systems is 6%；The mass ratio of the emulsifying agent and solvent is 1:
160；Instill pre-polymer emulsion and 1-5 drop defoamers after the completion of emulsification, the defoamer is n-butanol, the pre-polymer emulsion and
The mass ratio of amido chain extender-BN lotions is 1:2；Under the rotating speed of 1400rpm, 68 DEG C of insulation 2-3h, form double-walled microcapsules
Lotion.
3. double-walled microcapsule emulsion is centrifuged, is dried, is dried and carrying out washing treatment, that is, obtain polyureas encapsulating in repair it is outer
Curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule.
Emulsifying agent described in above-mentioned steps is neopelex；The solvent is ethyl acetate.
Using the self-repair concrete of the polyureas base double-walled microcapsules, the polyureas base double-walled microcapsules are in selfreparing
Mass fraction in concrete is 18%.
Embodiment 4：
As different from Example 1,
The preparation method of outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule is inside repaiied, is comprised the following steps：
(1) by aliphatic category isocyanates renovation agent hexamethylene diisocyanate (HDI) and amine terminated polyether polyethers
Amine D230 is according to 1:4 mass ratio is uniformly mixed, and obtains prepolymer；Stirred evenly under the rotating speed of 1800rpm, add emulsifying agent
And solvent, under the rotating speed of 1800rpm, 60 DEG C of insulation 2-3h, obtain pre-polymer emulsion；The amount of the emulsifying agent is pre-polymerization material
The 3% of amount, the mass ratio of the emulsifying agent and solvent is 1:156.
(2) amido chain extender-BN lotions are prepared：Take suitable emulsifying agent and solvent, stirred under the rotating speed of 2800rpm to
It is uniformly mixed；The mass ratio of the emulsifying agent and solvent is 1:50；Amido chain extender 1,4-Diaminobutane is added,
Stirred under the rotating speed of 3500rpm to uniformly mixed；BN dispersion liquids are added, are stirred with the rotating speed of 2800rpm to uniformly mixed, ultrasound
It is scattered, amido chain extender-BN lotions are made；The amount of the emulsifying agent is the 12% of amido chain extender quality.
(3) polyureas encapsulating double-walled microcapsules are prepared：
1. water droplet is added in pre-polymer emulsion, in mass ratio 1:1.5 ratio is uniformly mixed, in the rotating speed of 2500rpm
Under, 70 DEG C of insulation 2-3h, form single wall microcapsule emulsion.
2. the amido chain extender-BN lotions of suitable emulsifying agent, solvent and excess are added in the system 1. obtained to step
Emulsified, form single wall microcapsules-amido chain extender-BN composite emulsifying drop systems；The emulsifying agent single wall microcapsules-
Mass fraction in amido chain extender-BN composite emulsifying drop systems is 4%；The mass ratio of the emulsifying agent and solvent is 1:
154；Instill pre-polymer emulsion after the completion of emulsification, the mass ratio of the pre-polymer emulsion and amido chain extender-BN lotions is 1:
2.5；Under the rotating speed of 2000rpm, 70 DEG C of insulation 2-3h, form double-walled microcapsule emulsion.
3. double-walled microcapsule emulsion is centrifuged, is dried, is dried and carrying out washing treatment, that is, obtain polyureas encapsulating in repair it is outer
Curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule.
Emulsifying agent described in above-mentioned steps is neopelex；The solvent is ethyl acetate.
Using the coatings of the polyureas base double-walled microcapsules, the polyureas base double-walled microcapsules are in selfreparing ring
Mass fraction in oxygen coating is 12%.
Embodiment 5：
As different from Example 1,
The preparation method of outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule is inside repaiied, is comprised the following steps：
(1) by aliphatic category isocyanates renovation agent cyclohexyl-methane -4,4- diisocyanate and amine terminated polyether 3,
5- diethyltoluene -2,4- diamines is according to 1:5 mass ratio is uniformly mixed, and obtains prepolymer；Stirred under the rotating speed of 2000rpm
Uniformly, emulsifying agent and solvent are added, under the rotating speed of 2000rpm, 62 DEG C of insulation 2-3h, obtain pre-polymer emulsion；The emulsification
The amount of agent is the 4% of pre-polymerization amount of substance, and the mass ratio of the emulsifying agent and solvent is 1:152.
(2) amido chain extender-BN lotions are prepared：Take suitable emulsifying agent and solvent, stirred under the rotating speed of 3000rpm to
It is uniformly mixed；The mass ratio of the emulsifying agent and solvent is 1:40；Amido chain extender tetren is added, in 3000rpm
Rotating speed under stirring to be uniformly mixed；BN dispersion liquids are added, are stirred with the rotating speed of 2200rpm to being uniformly mixed, ultrasonic disperse, makes
Obtain amido chain extender-BN lotions；The amount of the emulsifying agent is the 10% of amido chain extender quality.
(3) polyureas encapsulating double-walled microcapsules are prepared：
1. water droplet is added in pre-polymer emulsion, in mass ratio 1:2.5 ratio is uniformly mixed, in the rotating speed of 1800rpm
Under, 60 DEG C of insulation 2-3h, form single wall microcapsule emulsion.
2. the amido chain extender-BN lotions of suitable emulsifying agent, solvent and excess are added in the system 1. obtained to step
Emulsified, form single wall microcapsules-amido chain extender-BN composite emulsifying drop systems；The emulsifying agent single wall microcapsules-
Mass fraction in amido chain extender-BN composite emulsifying drop systems is 4.5%；The mass ratio of the emulsifying agent and solvent is 1:
156；It is 1,4-butanediol that pre-polymer emulsion and 1-5 drop defoamers, the defoamer are instilled after the completion of emulsification, the prepolymer breast
Liquid and the mass ratio of amido chain extender-BN lotions are 1:3；Under the rotating speed of 1000rpm, 60 DEG C of insulation 2-3h, it is micro- to form double-walled
Capsule lotion.
3. double-walled microcapsule emulsion is centrifuged, is dried, is dried and carrying out washing treatment, that is, obtain polyureas encapsulating in repair it is outer
Curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule.
Emulsifying agent described in above-mentioned steps is neopelex；The solvent is ethyl acetate.
Using the coatings of the polyureas base double-walled microcapsules, the polyureas base double-walled microcapsules are in selfreparing ring
Mass fraction in oxygen coating is 15%.
Embodiment 6：
As different from Example 1,
The preparation method of outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule is inside repaiied, is comprised the following steps：
(1) by aliphatic category isocyanates renovation agent HDI trimer system and 1,6 hexamethylene diamine of amine terminated polyether according to 1:
2.5 mass ratio is uniformly mixed, and obtains prepolymer；Stirred evenly under the rotating speed of 2500rpm, add emulsifying agent and solvent,
Under the rotating speed of 2500rpm, 65 DEG C of insulation 2-3h, obtain pre-polymer emulsion；The amount of the emulsifying agent is pre-polymerization amount of substance
4.5%, the mass ratio of the emulsifying agent and solvent is 1:160.
(2) amido chain extender-BN lotions are prepared：Take suitable emulsifying agent and solvent, stirred under the rotating speed of 3500rpm to
It is uniformly mixed；The mass ratio of the emulsifying agent and solvent is 1:46；Amido chain extender polyetheramine D400 is added, 2400rpm's
Stirred under rotating speed to uniformly mixed；BN dispersion liquids are added, are stirred with the rotating speed of 2500rpm to being uniformly mixed, ultrasonic disperse, is made
Amido chain extender-BN lotions；The amount of the emulsifying agent is the 16% of amido chain extender quality.
(3) polyureas encapsulating double-walled microcapsules are prepared：
1. water droplet is added in pre-polymer emulsion, in mass ratio 1:3 ratio is uniformly mixed, under the rotating speed of 2000rpm,
65 DEG C of insulation 2-3h, form single wall microcapsule emulsion.
2. the amido chain extender-BN lotions of suitable emulsifying agent, solvent and excess are added in the system 1. obtained to step
Emulsified, form single wall microcapsules-amido chain extender-BN composite emulsifying drop systems；The emulsifying agent single wall microcapsules-
Mass fraction in amido chain extender-BN composite emulsifying drop systems is 5%；The mass ratio of the emulsifying agent and solvent is 1:
158；Instill pre-polymer emulsion after the completion of emulsification, the mass ratio of the pre-polymer emulsion and amido chain extender-BN lotions is 1:2；
Under the rotating speed of 1200rpm, 65 DEG C of insulation 2-3h, form double-walled microcapsule emulsion.
3. double-walled microcapsule emulsion is centrifuged, is dried, is dried and carrying out washing treatment, that is, obtain polyureas encapsulating in repair it is outer
Curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule.
Emulsifying agent described in above-mentioned steps is neopelex；The solvent is ethyl acetate.
Using the self-repair concrete of the polyureas base double-walled microcapsules, the polyureas base double-walled microcapsules are in selfreparing
Mass fraction in concrete is 10%.
1 embodiment 1-6 of table prepares the microscopic pattern characterization of microcapsules
The mechanical property characterization of microcapsules prepared by 2 embodiment 1-6 of table
The particle diameter of the microcapsules prepared from Tables 1 and 2 characterization result, embodiment 1-6 is 10-200 μm, tensile strength
For 11.89-15.07MPa, elongation at break 250-355%, microcapsules shore (A) hardness for 50-55 with it is of the prior art
Microcapsules are compared, and the present invention can realize the control to Microcapsules Size by different preparation process preparation conditions, to meet
Different substrate materials demand；Simultaneously as the addition of boron nitride makes obtained double-walled microcapsules show excellent mechanical property, effectively
Avoid microcapsules to fail in the whipping process for adding base material, the performance repair for stablizing microcapsules.
Microcapsules prepared by embodiment 1,3 and 6 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) with pressure testing machine gently press the self-repair concrete to be cracked by inside it, 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 5 are incorporated into epoxy coating and carry out coatings
Preparation.Take one group of (every group contains 3 pieces of coatings) selfreparing epoxy coating to carry out the test of initial tensile strength, take another group (often
Group contains 3 pieces of coatings) the selfreparing epoxy coating is stretched using tensile testing machine make to crack inside it, after two weeks, to this
Group selfreparing epoxy coating tensile strength carries out test and obtains data as shown in table 3.
Strength detection after self-healing system prepared by 3 embodiment 1-6 of table is repaired
In conclusion repair outer curable type porous boron nitride-micro- glue of polyureas base double-walled selfreparing in as made from interfacial polymerization
Capsule form in terms of microscopic pattern is good, and particle diameter is mainly distributed between 10-200 μm；Mechanical test shows the polyureas after curing
Microcapsules are the elastic materials for having certain intensity (tensile strength is in 11.89-15.07MPa) and hardness (shore A50-55)
(elongation at break 250-350%)；By the way that polyurea microcapsule is mixed concrete and epoxy coating progress precompressed crackle experiment table
Bright, polyurea microcapsule has certain repair to crackle, and concrete crushing strength increase rate is 8.90% after reparation, is repaired
The tensile strength increase rate of epoxy coating is 13.50% afterwards.
Claims (10)
- Outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule, including internal layer cyst wall and outer layer cyst wall are repaiied in 1.；It is special Sign is：The internal layer cyst wall coats pre-polymer emulsion, and the outer layer cyst wall coats amido chain extender-BN lotions；The internal layer Cyst wall polyureas is reacted to obtain by the pre-polymer emulsion that internal layer cyst wall coats and water, and the outer layer cyst wall polyureas is by a small amount of prepolymer breast The amido chain extender emulsion that liquid is coated with outer layer cyst wall reacts to obtain, and BN is disperseed in the outer layer cyst wall polyureas.
- 2. the preparation method of outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule is repaiied in, it is characterised in that：Including with Lower step：(1) pre-polymer emulsion is prepared：By appropriate aliphatic category isocyanates renovation agent, amine terminated polyether, emulsifying agent and solvent It is uniformly mixed under high velocity agitation, prepares pre-polymer emulsion；(2) amido chain extender-BN lotions are prepared：Amido chain extender, BN point Dispersion liquid, solvent and emulsifying agent are uniformly mixed under high velocity agitation, prepare amido chain extender-BN lotions；(3) it is double to prepare polyureas encapsulating Wall microcapsules：Water is added dropwise in the pre-polymer emulsion of step (1) preparation, synthesizes microcapsules inner wall wall material, it is micro- to form single wall Capsule lotion；Amido chain extender-BN the lotions that emulsifying agent, solvent and excess are added in lotion are stated then up, and emulsification is completed After instill pre-polymer emulsion, synthesize microcapsules outer wall wall material, form double-walled microcapsule emulsion.
- 3. outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule preparation method is repaiied according to claim 2, It is characterized in that：Described in step (3) prepare polyureas encapsulating double-walled microcapsules be specially：1. water droplet is added to pre-polymer emulsion In, in mass ratio 1:1-1:3 ratio is uniformly mixed, under the rotating speed of 1000-2500rpm, 60 DEG C of -70 DEG C of insulation 2-3h, and shape Into single wall microcapsule emulsion；2. the amido chain extension of suitable emulsifying agent, solvent and excess is added in the system 1. obtained to step Agent-BN lotions are emulsified, and form single wall microcapsules-amido chain extender-BN composite emulsifying drop systems；The emulsifying agent is in list Mass fraction in wall microcapsules-amido chain extender-BN composite emulsifying drop systems is 4%-6%；The emulsifying agent and solvent Mass ratio be1:150-1:160；Pre-polymer emulsion, the pre-polymer emulsion and amido chain extender-BN are instilled after the completion of emulsification The mass ratio of lotion is1:1-1:3；Under the rotating speed of 1000-2500rpm, 60 DEG C of -70 DEG C of insulation 2-3h, form double-walled microcapsules Lotion；3. carrying out centrifugal treating to double-walled microcapsule emulsion, that is, obtain the interior of polyureas encapsulating and repair outer curable type porous boron nitride-polyureas Base double-walled self-repairing microcapsule.
- 4. the preparation side of outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule is repaiied according to claim 2 Method, it is characterised in that：The pre-polymer emulsion for preparing described in step (1) is specially：By aliphatic category isocyanates renovation agent with Amine terminated polyether is according to 1:1-1:5 mass ratio is uniformly mixed, and obtains prepolymer；Stirred under the rotating speed of 1000-2500rpm equal It is even, emulsifying agent and solvent are added, under the rotating speed of 1000-2500rpm, 60 DEG C of -70 DEG C of insulation 2-3h, obtain pre-polymer emulsion； The amount of the emulsifying agent is the 3-6% of pre-polymerization amount of substance, and the mass ratio of the emulsifying agent and solvent is 1:40-1:50.
- 5. the preparation side of outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule is repaiied according to claim 2 Method, it is characterised in that：Amido chain extender-BN the lotions that prepare described in step (2) are specially：Suitable emulsifying agent and solvent are taken, Stirred under the rotating speed of 2000-3500rpm to uniformly mixed；The mass ratio of the emulsifying agent and solvent is 1:40-1:50；Add Amido chain extender, is stirred under the rotating speed of 2000-3500rpm to uniformly mixed；BN dispersion liquids are added, with the rotating speed of 3000rpm Amido chain extender-BN lotions are made to being uniformly mixed in stirring；The amount of the emulsifying agent is the 10-20% of amido chain extender quality.
- It is micro- that 6. outer curable type porous boron nitride-polyureas base double-walled selfreparing is repaiied according to any one in claim 3-5 The preparation method of capsule, it is characterised in that：The NCO group content of aliphatic category isocyanates renovation agent described in step (1) For 3%-12%, and average functionality is 1.5 to 5.0；The aliphatic category isocyanates renovation agent is two isocyanide of isophorone Acid esters (IPDI), hexamethylene diisocyanate (HDI), 1,4- cyclohexane diisocyanates, two isocyanides of cyclohexyl-methane -4,4- Acid esters, the allophanate of 1,6- hexamethylene diisocyanates or HDI trimer system；The amine terminated polyether is polyetheramine D400, polyetheramine D230, polyetheramine D2000,3,5- dimethyl sulphur-based Toluene-2,4-diisocyanate, 6- diamines, 3,5- diethyltoluenes -2,4- two Amine, 3,5- dimethyl sulphur-based Toluene-2,4-diisocyanates, 4- diamines, 1,4 butanediamine or 1,6 hexamethylene diamines.
- It is micro- that 7. outer curable type porous boron nitride-polyureas base double-walled selfreparing is repaiied according to any one in claim 3-5 The preparation method of capsule, it is characterised in that：Amido chain extender described in step (2) is diethyl toluene diamine, dimethyl sulphur-based Toluenediamine, N, N'- dialkyl methyls diphenylamines, cyclohexane diamine, chlorination MDH, ethylenediamine, 1,3- diaminopropanes, 1,4- Diaminobutane, diethylenetriamines, penten, six ethylene diamines, tetren, penten, Polyetheramine D400, polyetheramine D230, ethylenediamine or 3,3'-4,4'- diaminourea-diphenyl-methane MOCA.
- It is micro- that 8. outer curable type porous boron nitride-polyureas base double-walled selfreparing is repaiied according to any one in claim 3-5 The preparation method of capsule, it is characterised in that：Emulsifying agent described in step (1)-(3) is neopelex, OP-10, Octadecane alcohol radical APEO, Arabic gum, polyoxyethylene ether, fatty amine polyoxyethylene ether or polyvinyl alcohol；The solvent For ethyl acetate, acetone, hexamethylene, pentamethylene, toluene or chlorobenzene.
- It is micro- that 9. outer curable type porous boron nitride-polyureas base double-walled selfreparing is repaiied according to any one in claim 3-5 The preparation method of capsule, it is characterised in that：Described in step (3) when 2. preparing double-walled microcapsule emulsion, add pre-polymer emulsion While add 1-5 drop defoamers；The defoamer for n-butanol, 1,4- butanediols, polyoxyethylene polyoxypropylene glycerin ether or Dimethyl silicone polymer；The preparation method of BN dispersion liquids described in step (2) is：First using Piranha washing lotions to BN powder Surface carries out hydroxylating processing, then by itself and emulsifying agent high speed dispersion, is ultrasonically treated, centrifuging and taking supernatant, that is, obtains BN points Dispersion liquid.
- That 10. outer curable type porous boron nitride-polyureas base double-walled self-repairing microcapsule is repaiied in described in use claim 1 reviews one's lessons by oneself complex System, it is characterised in that：The porous boron nitride-mass fraction of the polyureas base double-walled microcapsules in self-healing system is 5%- 18%；The self-healing system is self-repair concrete or coatings.
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| CN110862670A (en) * | 2019-12-12 | 2020-03-06 | 罗更荣 | Heat-conducting boron nitride-modified polyurea insulating composite material and preparation method thereof |
| 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 |
| WO2023111068A3 (en) * | 2021-12-15 | 2023-08-17 | Université de Franche-Comté | Material functionalised by an aliphatic polyamine |
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