CN109250940A - A kind of calcium alginate microcapsule of high core material content - Google Patents
A kind of calcium alginate microcapsule of high core material content Download PDFInfo
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- CN109250940A CN109250940A CN201811172180.6A CN201811172180A CN109250940A CN 109250940 A CN109250940 A CN 109250940A CN 201811172180 A CN201811172180 A CN 201811172180A CN 109250940 A CN109250940 A CN 109250940A
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- calcium alginate
- core material
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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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1018—Coating or impregnating with organic materials
- C04B20/1029—Macromolecular compounds
- C04B20/1037—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
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Abstract
The present invention relates to a kind of calcium alginate microcapsules of high core material content.The high core material content calcium alginate microcapsule structure includes polymeric outer layer, calcium alginate bracket and core material renovation agent.Wherein, curable fluoropolymer resin is core material renovation agent, is filled in the interconnected duct of calcium alginate bracket；Outermost layer is cured polymer resins layers.Preparation method is: preparing the first calcium alginate microcapsule processed of high core material content using orifice-coagulating bath method first；The fluoropolymer resin of outer layer is solidified again, to obtain the high core material content calcium alginate microcapsule of above structure.Microcapsules of the invention have water imbibition, and volume sweell(ing) rate is controllable, and polymer core material content 65%-95% can be used for cement matrix crack autogenous healing.
Description
Technical field
The present invention relates to a kind of calcium alginate microcapsules of high core material content, belong to distress in concrete recovery technique field.
Background technique
Cement be it is a kind of use extensive construction material, but it is also easy to produce micro-crack in material internal, and traditional inspection
Maintaining method, the period is long, low efficiency and costly.Therefore, people have researched and developed cement-based material certainly according to bionic principle
Reparation system extends the service life of cement-based material for being automatically repaired crackle.
Micro-capsule self-repair technology has strong applicability, at low cost, synthesis technology convenient for control and in cement-based material
It is easy to the advantages that evenly dispersed.Wherein, calcium alginate microcapsule is using the calcium alginate with water absorption and swelling characteristic as bracket, gathers
Polymer resin is the three-dimensional net structure microballoon of core material.The microcapsules are applied to cement-based material selfreparing with unique excellent
Gesture: when cement matrix generates crack, calcium alginate microcapsule rupture discharges capsule-core renovation agent, rapid link crack；When there is water
When penetrating into cement matrix, volume expansion occurs for calcium alginate water suction, blocks crack, and barrier carries the liquid water enchroachment (invasion) of harmful ion
Enter；The calcium alginate of water suction additionally aids the secondary hydration of surrounding cement granules, promotes the spontaneous reparation of cement matrix.So
And there is also some problems in practical applications for the high water absorption swelling character of calcium alginate microcapsule, such as: in cement mix process
Middle water absorption and swelling causes the reduction of available moisture, influences cement workability；Volume contraction can occur when microcapsules dehydration, hard
Change in cement matrix and causes gap, damaging substrate mechanical strength and anti-permeability performance.
By rationally controlling the water absorption and swelling rate of calcium alginate microcapsule, the unfavorable shadow of above problem bring can be reduced
It rings.The accounting for reducing calcium alginate wall material in calcium alginate microcapsule, can reduce the water absorption and swelling rate of microcapsules；And Gao Xin
The microcapsules of material content are also beneficial to improve the remediation efficiency of matrix crack.But with the raising of core material content, part core material
It can be exuded to surface of microcapsule, cause the bonding of microcapsules, it is difficult to disperse.
For this problem, the present invention prepares a kind of high core material content calcium alginate microcapsule with three-decker, benefit
Solidified with the fluoropolymer resin thin layer that curing agent oozes out calcium alginate microcapsule surface.On the one hand cured polymeric outer layer solves
The problem of high core material calcium alginate microcapsule surface bonding of having determined；On the other hand it can also further be controlled by adjusting outer layer thickness
The water absorption and swelling rate of calcium alginate microcapsule processed makes it not only keep water absorption character but also can be reduced the sky of interface caused by dehydration shrinkage
Gap.
Summary of the invention
It is an object of the invention to overcome defect of the existing technology, the calcium alginate for providing a kind of high core material content is micro-
Capsule can not only improve Crack Self efficiency, additionally it is possible to which it is right to reduce its for the water absorption and swelling rate for reducing calcium alginate microcapsule
The adverse effect of cement workability reduces interface void, improves cement matrix intensity.
To achieve the above object, as follows using technical solution:
A kind of calcium alginate microcapsule of high core material content, microcapsule structure include core material renovation agent, calcium alginate bracket
And polymeric outer layer.Wherein, core material renovation agent is curable fluoropolymer resin, is filled in calcium alginate support aperture；Outside
Layer is cured fluoropolymer resin；There is the duct of connection in the calcium alginate bracket.
The partial size of the microcapsules is 0.3-3mm.
The microcapsule polymer outer layer (3) with a thickness of 20-300 μm.
The curable fluoropolymer resin is epoxy resin, fluorocarbon resin, organic siliconresin, Lauxite, phenolic aldehyde tree
Rouge, one of or several, the preferred epoxy in unsaturated polyester resin.
The preparation method of the calcium alginate microcapsule of above-mentioned high core material content, comprising the following steps:
(1) just the fluoropolymer resin and curing agent on calcium alginate microcapsule surface processed crosslink curing reaction, carry out one
Secondary solidification, cured fluoropolymer resin form microcapsules outer layer；Solidification temperature is 0-60 DEG C, curing time 5-40min；
(2) baking step (1) resulting microcapsules, to obtain the calcium alginate microcapsule of high core material content；
(3) if you need to obtain more fine and close or thicker polymeric outer layer, secondary curing can be carried out, i.e., is dried step (2)
Microcapsules and curing agent (curing agent in curing agent used herein and step (1) may be the same or different) afterwards are again
It is secondary to crosslink curing reaction, secondary curing is completed, solidification temperature is 0-60 DEG C, curing time 5-40min, to obtain outer
The more fine and close or bigger thickness high core material content calcium alginate microcapsule of layer.
First calcium alginate microcapsule processed in the step (1), fluoropolymer resin core material are stored in calcium alginate duct.
Curing agent in the step (2) (3) be ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine,
Benzene dimethylamine, B- hydroxyethyl ethylenediamine, ammonium chloride, modified amine curing agent, polyisocyanates, p-methyl benzenesulfonic acid, phenolsulfonic acid,
The one or more of methyl ethyl ketone peroxide, ethyl orthosilicate.
It can choose one-step solidification or secondary curing in the microcapsules preparation process, wherein outside the polymer of one-step solidification
Layer is with a thickness of 20-250 μm, and the polymeric outer layer of secondary curing is with a thickness of 50-300 μm.
It is described as follows:
(1) sodium alginate soln is prepared first, and emulsifier is added in concentration 0.015g/mL-0.035g/mL, stirs, so
It is added fluoropolymer resin thereto afterwards, the mixed emulsion of stirring to obtain fluoropolymer resin and sodium alginate, wherein fluoropolymer resin
Mass ratio with sodium alginate is 10:1~20:1, and emulsifier additional amount is the 0.5wt%-2.5wt% of fluoropolymer resin.It will system
Standby mixed emulsion is added drop-wise in the calcium chloride solution that concentration is 0.01g/mL-0.03g/mL by orifice, and 3h is reacted, and is filtered,
Obtain just calcium alginate microcapsule processed.
(2) first calcium alginate microcapsule processed is contacted with curing agent, the polymer and curing agent of microcapsule exterior surface occur
Cross-linking reaction, completes one-step solidification, and cured fluoropolymer resin forms microcapsules outer layer；Solidification temperature is 0-60 DEG C, when solidification
Between be 5-40min；
(3) baking step (2) resulting microcapsules obtain the calcium alginate microcapsule of high core material content；
(4) if you need to obtain more fine and close or thicker polymeric outer layer, secondary curing can be carried out, i.e., is dried step (2)
Microcapsules and curing agent (curing agent in curing agent used herein and step (1) may be the same or different) afterwards are again
Secondary carry out cross-linking and curing reaction completes secondary curing, and solidification temperature is 0-60 DEG C, and curing time 5-40min obtains outer layer more
For fine and close or bigger thickness high core material content calcium alginate microcapsule.
First calcium alginate microcapsule processed in the method step (2), it is total that the quality of polymer accounts for calcium alginate microcapsule
The percentage of quality is 65% -95%.
The invention has the benefit that
The fluoropolymer resin thin layer for oozing out calcium alginate microcapsule surface is solidified using curing agent, outer layer is formed, solves
The dispersion of high core material content calcium alginate microcapsule, to obtain a kind of calcium alginate microcapsule of high core material content.
(1) microcapsules water absorption rate of the invention is 1.3%-10.7%, with pure calcium alginate microsphere (water absorption rate 998%) phase
Than water absorption rate significantly reduces, and can weaken the influence to cement workability, reduces interface void caused by the dry contraction of microcapsules.
(2) for microcapsules of the invention using calcium alginate as bracket, single microcapsules rupture load is 7.24N-2.51N, power
The polymer microcapsule that intensity is higher than core-shell structure is learned, remaining intact property during cement mix is conducive to.
(3) microcapsules of the invention have cured polymeric outer layer, solve high core material content calcium alginate microcapsule
Adhesion problem, core material content is up to 65%-95%, polymer core material can be improved to the repairing effect in cement base crack.
(4) the selfreparing mechanism of microcapsules of the invention to cement-based material are as follows: (1) when cement-based material is in load and ring
When generating microcrack under the coupling of border, crack tip stress will lead to the rupture of microcapsules outer layer, fluoropolymer resin outflow filling
Microcrack meets with curing agent, solidification bonding crack；(2) when there is water infiltration in cement matrix, volume occurs for microcapsules water suction
Swelling blocks crack, and can promote the continuation aquation of cement granules around, promotes spontaneous reparation.
Detailed description of the invention
Fig. 1: the preparation technology flow chart for reviewing one's lessons by oneself multiplexing calcium alginate microcapsule of high core material content of the invention
Fig. 2: the structural schematic diagram for reviewing one's lessons by oneself multiplexing calcium alginate microcapsule of high core material content of the invention
Specific embodiment
Below with reference to example, the present invention will be further described, but not as limiting the scope of the invention.
Embodiment 1
(1) 17.5g sodium alginate solid is weighed, is added in 500mL deionized water, is stirred, it is complete to sodium alginate solid
After fully dissolved, the sodium alginate soln of 0.035g/mL is obtained；
55 DEG C of water-baths, are added above-mentioned sodium alginate soln and 1.875g neopelex into four-hole boiling flask respectively
Stirring；75.0gE-51 bisphenol A type epoxy resin is added, low whipping speed is that 1.5h is stirred under 600r/min, is obtained after cooling
Epoxy resin-sodium alginate mixed liquor.
(2) 9.0g calcium chloride solid is weighed, is added in 300mL deionized water, after calcium to be chlorinated is completely dissolved, is obtained
The calcium chloride solution of 0.03g/mL；The mixed liquor that step (1) obtains is added drop-wise in above-mentioned calcium chloride solution by syringe, is dripped
After the completion of adding, the reaction was continued 3h obtains just calcium alginate microcapsule processed.
(3) just calcium alginate microcapsule processed is taken out, is immersed in epoxy hardener triethylene tetramine, solidification temperature 25
DEG C, curing time 10min, triethylene tetramine and the epoxy resin for being exuded to calcium alginate microcapsule surface are cured instead
It answers, forms transparent lamina, obtain the microcapsules of one-step solidification.
(4) it is taken out after the microcapsules after one-step solidification being put into 60 DEG C of air dry ovens dry 6h, obtains high core material and contain
Amount reviews one's lessons by oneself multiplexing calcium alginate microcapsule.
Gained microcapsules average grain diameter is 0.3mm, and outer layer thickness is 20 μm；Microcapsules core material content is 65.14%.
A certain amount of dry microcapsules are weighed, is fitted into the nylon net bag of aperture 0.076mm and weighs；It is soaked in pure water
In no longer change to quality, drain the moisture in mesh bag, weigh, measure microcapsules water absorption rate be 10.7%.
Embodiment 2
(1) 7.5g sodium alginate solid is weighed, is added in 500mL deionized water, is stirred, it is complete to sodium alginate solid
After dissolution, the sodium alginate soln of 0.015g/mL is obtained；
55 DEG C of water-baths, are added above-mentioned sodium alginate soln and 0.375g neopelex into four-hole boiling flask respectively
Stirring；150.0gE-51 bisphenol A type epoxy resin is added, low whipping speed is that 1.5h is stirred under 600r/min, is obtained after cooling
To epoxy resin-sodium alginate mixed liquor.
(2) 3.0g calcium chloride solid is weighed, is added in 300mL deionized water, after calcium solid to be chlorinated is completely dissolved, is obtained
To the calcium chloride solution of 0.01g/mL；The mixed liquor that step (1) obtains is added drop-wise in above-mentioned calcium chloride solution by syringe,
After being added dropwise to complete, the reaction was continued 3h obtains just calcium alginate microcapsule processed.
(3) just calcium alginate microcapsule processed to be taken out, is immersed in T-31 phenolic aldehyde amine epoxy curing agent, solidification temperature is 0 DEG C,
Curing time is 40min, and T-31 phenolic aldehyde amine is cured with the epoxy resin for being exuded to calcium alginate microcapsule surface reacts, shape
At transparent lamina, the microcapsules of one-step solidification are obtained.
(4) it is taken out after the microcapsules after one-step solidification being put into 60 DEG C of air dry ovens dry 6h, is again dipped into T-31
Secondary curing is carried out in phenolic aldehyde amine, solidification temperature is 0 DEG C, curing time 40min, and obtain high core material content reviews one's lessons by oneself multiplexing sea
Calcium alginate microcapsules.
Gained microcapsules average grain diameter is 3.0mm, and outer layer thickness is 300 μm；Microcapsules core material content is 94.92%.
A certain amount of dry microcapsules are weighed, is fitted into the nylon net bag of aperture 0.076mm and weighs；It is soaked in pure water
In no longer change to quality, drain the moisture in mesh bag, weigh, measure microcapsules water absorption rate be 1.3%.
Embodiment 3
(1) 7.5g sodium alginate solid is weighed, is added in 500mL deionized water, is stirred, it is complete to sodium alginate solid
After dissolution, the sodium alginate soln of 0.015g/mL is obtained；
55 DEG C of water-baths, are added above-mentioned sodium alginate soln and 2.00g emulsifier for mixing into four-hole boiling flask respectively；It adds
85.0g531 urea-formaldehyde resin adhesive, low whipping speed are that 1.5h is stirred under 600r/min, obtain Lauxite-sodium alginate after cooling
Mixed liquor.
(2) 7.5g calcium chloride solid is weighed, is added in 300mL deionized water, after calcium solid to be chlorinated is completely dissolved, is obtained
To the calcium chloride solution of 0.025g/mL；The mixed liquor that step (1) obtains is added drop-wise to above-mentioned calcium chloride solution by syringe
In, after being added dropwise to complete, the reaction was continued 3h obtains just calcium alginate microcapsule processed.
(3) just calcium alginate microcapsule processed is taken out, is immersed in curing agent ammonium chloride, solidification temperature is 60 DEG C, when solidification
Between be 5min, ammonium chloride is cured with the Lauxite for being exuded to calcium alginate microcapsule surface to react, formation translucent thin
Layer, obtains the microcapsules of one-step solidification.
(4) it is taken out after the microcapsules after one-step solidification being put into 60 DEG C of air dry ovens dry 6h, obtains high core material and contain
Amount reviews one's lessons by oneself multiplexing calcium alginate microcapsule.
Gained microcapsules average grain diameter is 2.0mm, and outer layer thickness is 180 μm；Microcapsules core material content is 83.85%.
A certain amount of dry microcapsules are weighed, is fitted into the nylon net bag of aperture 0.076mm and weighs；It is soaked in pure water
In no longer change to quality, drain the moisture in mesh bag, weigh, measure microcapsules water absorption rate be 5.2%.
Embodiment 4
(1) 7.5g sodium alginate solid is weighed, is added in 500mL deionized water, is stirred, it is complete to sodium alginate solid
After dissolution, the sodium alginate soln of 0.015g/mL is obtained；
55 DEG C of water-baths, are added above-mentioned sodium alginate soln into four-hole boiling flask respectively and 2.00gSPan-10 emulsifier stirs
It mixes；90.0g phenolic resin is added, low whipping speed is that 1.5h is stirred under 600r/min, obtains phenolic resin-seaweed after cooling
Sour sodium mixed liquor.
(2) 7.5g calcium chloride solid is weighed, is added in 300mL deionized water, after calcium solid to be chlorinated is completely dissolved, is obtained
To the calcium chloride solution of 0.025g/mL；The mixed liquor that step (1) obtains is added drop-wise to above-mentioned calcium chloride solution by syringe
In, after being added dropwise to complete, the reaction was continued 3h obtains just calcium alginate microcapsule processed.
(3) just calcium alginate microcapsule processed to be taken out, is immersed in curing agent p-methyl benzenesulfonic acid, solidification temperature is 25 DEG C, Gu
The change time is 20min, and p-methyl benzenesulfonic acid is cured with the phenolic resin for being exuded to calcium alginate microcapsule surface to react, and is formed
Semi-transparent coating obtains the microcapsules of one-step solidification.
(4) it takes out, is again dipped into first after the microcapsules after one-step solidification being put into 60 DEG C of air dry ovens dry 6h
Secondary curing is carried out in benzene sulfonic acid, solidification temperature is 25 DEG C, curing time 20min, and obtain high core material content reviews one's lessons by oneself multiplexing
Calcium alginate microcapsule.
Gained microcapsules average grain diameter is 1.5mm, and outer layer thickness is 300 μm；Microcapsules core material content is 86.94%.
A certain amount of dry microcapsules are weighed, is fitted into the nylon net bag of aperture 0.076mm and weighs；It is soaked in pure water
In no longer change to quality, drain the moisture in mesh bag, weigh, measure microcapsules water absorption rate be 3.3%.
Embodiment 5
(1) 7.5g sodium alginate solid is weighed, is added in 500mL deionized water, is stirred, it is complete to sodium alginate solid
After dissolution, the sodium alginate soln of 0.015g/mL is obtained；
Above-mentioned sodium alginate soln and 2.50g octyl phenyl polyethylene glycol is added in 55 DEG C of water-baths into four-hole boiling flask respectively
Ether emulsifier for mixing；120.0gDC191 unsaturated polyester resin is added, low whipping speed is to stir 1.5h under 600r/min,
Unsaturated polyester resin-sodium alginate mixed liquor is obtained after cooling.
(2) 7.5g calcium chloride solid is weighed, is added in 300mL deionized water, after calcium solid to be chlorinated is completely dissolved, is obtained
To the calcium chloride solution of 0.025g/mL；The mixed liquor that step (1) obtains is added drop-wise to above-mentioned calcium chloride solution by syringe
In, after being added dropwise to complete, the reaction was continued 3h obtains just calcium alginate microcapsule processed.
(3) just calcium alginate microcapsule processed is taken out, is immersed in curing agent styrene, solidification temperature is 25 DEG C, when solidification
Between be 40min, styrene is cured with the unsaturated polyester resin for being exuded to calcium alginate microcapsule surface react, formation partly
Transparent lamina obtains the microcapsules of one-step solidification.
(4) it is taken out after the microcapsules after one-step solidification being put into 60 DEG C of air dry ovens dry 6h, is again dipped into benzene second
Secondary curing is carried out in alkene, solidification temperature is 25 DEG C, curing time 40min, and obtain high core material content reviews one's lessons by oneself multiplexing seaweed
Sour calcium microcapsules.
Gained microcapsules average grain diameter is 1.0mm, and outer layer thickness is 60 μm；Microcapsules core material content is 89.31%.
A certain amount of dry microcapsules are weighed, is fitted into the nylon net bag of aperture 0.076mm and weighs；It is soaked in pure water
In no longer change to quality, drain the moisture in mesh bag, weigh, measure microcapsules water absorption rate be 2.7%.
Embodiment 6
(1) 7.5g sodium alginate solid is weighed, is added in 500mL deionized water, is stirred, it is complete to sodium alginate solid
After dissolution, the sodium alginate soln of 0.015g/mL is obtained；
55 DEG C of water-baths, are added above-mentioned sodium alginate soln and 2.50g neopelex into four-hole boiling flask respectively
Emulsifier, stirring；120.0g fluorocarbon resin is added, low whipping speed is that 1.5h is stirred under 600r/min, obtains fluorine after cooling
Carbon resin-sodium alginate mixed liquor.
(2) 7.5g calcium chloride solid is weighed, is added in 300mL deionized water, after calcium solid to be chlorinated is completely dissolved, is obtained
To the calcium chloride solution of 0.025g/mL；The mixed liquor that step (1) obtains is added drop-wise to above-mentioned calcium chloride solution by syringe
In, after being added dropwise to complete, the reaction was continued 3h obtains just calcium alginate microcapsule processed.
(3) just calcium alginate microcapsule processed is taken out, is immersed in isocyanate curing agent, solidification temperature is 25 DEG C, solidification
Time is 40min, and isocyanate curing agent is cured with the fluorocarbon resin for being exuded to calcium alginate microcapsule surface to react, shape
At semi-transparent coating, the microcapsules of one-step solidification are obtained.
(4) it is taken out after the microcapsules after one-step solidification being put into 60 DEG C of air dry ovens dry 6h, is again dipped into benzene second
Secondary curing is carried out in alkene, solidification temperature is 25 DEG C, curing time 40min, and obtain high core material content reviews one's lessons by oneself multiplexing seaweed
Sour calcium microcapsules.
Gained microcapsules average grain diameter is 1.0mm, and outer layer thickness is 60 μm；Microcapsules core material content is 91.31%.
A certain amount of dry microcapsules are weighed, is fitted into the nylon net bag of aperture 0.076mm and weighs；It is soaked in pure water
In no longer change to quality, drain the moisture in mesh bag, weigh, measure microcapsules water absorption rate be 2.61%.
Embodiment 7
(1) 7.5g sodium alginate solid is weighed, is added in 500mL deionized water, is stirred, it is complete to sodium alginate solid
After dissolution, the sodium alginate soln of 0.015g/mL is obtained；
Above-mentioned sodium alginate soln and 1.50g octyl phenyl polyethylene glycol is added in 55 DEG C of water-baths into four-hole boiling flask respectively
Ether emulsifier for mixing；70.0g organic siliconresin is added, low whipping speed is that 1.5h is stirred under 600r/min, is obtained after cooling
Organic siliconresin-sodium alginate mixed liquor.
(2) 7.5g calcium chloride solid is weighed, is added in 300mL deionized water, after calcium solid to be chlorinated is completely dissolved, is obtained
To the calcium chloride solution of 0.025g/mL；The mixed liquor that step (1) obtains is added drop-wise to above-mentioned calcium chloride solution by syringe
In, after being added dropwise to complete, the reaction was continued 3h obtains just calcium alginate microcapsule processed.
(3) just calcium alginate microcapsule processed to be taken out, is immersed in ethyl orthosilicate curing agent, solidification temperature is 25 DEG C, Gu
The change time is 40min, and ethyl orthosilicate is cured with the organic siliconresin for being exuded to calcium alginate microcapsule surface to react, shape
At semi-transparent coating, the microcapsules of one-step solidification are obtained.
(4) it is taken out after the microcapsules after one-step solidification being put into 60 DEG C of air dry ovens dry 6h, is again dipped into benzene second
Secondary curing is carried out in alkene, solidification temperature is 25 DEG C, curing time 40min, and obtain high core material content reviews one's lessons by oneself multiplexing seaweed
Sour calcium microcapsules.
Gained microcapsules average grain diameter is 1.0mm, and outer layer thickness is 180 μm；Microcapsules core material content is 65.21%.
A certain amount of dry microcapsules are weighed, is fitted into the nylon net bag of aperture 0.076mm and weighs；It is soaked in pure water
In no longer change to quality, drain the moisture in mesh bag, weigh, measure microcapsules water absorption rate be 9.9%.
The microcapsules that above-described embodiment 1,2,3,4,5,6,7 is prepared are added in the ratio of the 1%-10% of cement quality
Into cement-based material, it is prepared into self-repairing cement-base material.There are two kinds of reparation behaviors in cement matrix for microcapsules: (1)
When cement-based material generates microcrack under load and environment coupled action, crack tip stress causes microcapsules outer layer broken
It splits, fluoropolymer resin flows out at the microcrack of cement matrix, is bonded crack, and (2) when there is water infiltration in matrix, microcapsules are sent out
Raw water absorption and swelling, blocks crack, or even promotes the aquation of cement granules continuation around, promotes autogenous repairing.
Claims (9)
1. a kind of high core material content reviews one's lessons by oneself multiplexing calcium alginate microcapsule, which is characterized in that microcapsule structure includes (1) core material
Renovation agent, (2) calcium alginate bracket and (3) polymeric outer layer；Wherein, core material renovation agent (1) is curable fluoropolymer resin,
It is filled in calcium alginate bracket (2) duct；Outer layer (3) is cured polymer resins layers；The calcium alginate bracket (2)
There are the ducts of connection.
2. microcapsules according to claim 1, which is characterized in that the partial size of microcapsules is 0.3-3mm.
3. microcapsules according to claim 1, which is characterized in that the polymeric outer layer (3) with a thickness of 20-300 μm.
4. microcapsules according to claim 1, which is characterized in that the curable fluoropolymer resin is epoxy resin, fluorine
Carbon resin, organic siliconresin, Lauxite, phenolic resin are one of or several in unsaturated polyester resin.
5. preparing the calcium alginate microcapsule of high core material content described in claim 1, it is characterised in that the following steps are included:
(1) just the fluoropolymer resin and curing agent on calcium alginate microcapsule surface processed crosslink curing reaction, carry out once solid
Change, cured fluoropolymer resin forms microcapsules outer layer；Solidification temperature is 0-60 DEG C, curing time 5-40min；
(2) baking step (1) resulting microcapsules, to obtain the calcium alginate microcapsule of high core material content；Wherein polymer
Core material content 65wt%-95wt%.
6. according to method for claim 5, which is characterized in that first calcium alginate microcapsule processed, polymer tree described in step (1)
Rouge core material is stored in calcium alginate duct.
7. according to method for claim 5, which is characterized in that the curing agent is ethylenediamine, diethylenetriamine, triethylene four
Amine, tetraethylenepentamine, m-xylene diamine, B- hydroxyethyl ethylenediamine, ammonium chloride, modified amine curing agent, polyisocyanates, to first
The one or more of benzene sulfonic acid, phenolsulfonic acid, methyl ethyl ketone peroxide, ethyl orthosilicate.
8. according to method for claim 5, which is characterized in that one-step solidification or secondary curing are selected in preparation process, wherein one
Secondary cured polymeric outer layer is with a thickness of 20-250 μm, and the polymeric outer layer after secondary curing is with a thickness of 50-300 μm.
9. according to method for claim 5, which is characterized in that when more fine and close or bigger thickness polymeric outer layer need to be obtained,
Carry out secondary curing, i.e., by the microcapsules and curing agent after step (2) drying, the curing agent used and the solidification in step (1)
Agent is same or different；It crosslinks curing reaction again, completes secondary curing, solidification temperature is 0-60 DEG C, and curing time is
5-40min；To obtain the high core material content calcium alginate microcapsule that outer layer is more fine and close or thickness is bigger.
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