CN103979824B - Situ aggregation method preparation is for the microcapsule preparation method of cement-based material selfreparing - Google Patents
Situ aggregation method preparation is for the microcapsule preparation method of cement-based material selfreparing Download PDFInfo
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- CN103979824B CN103979824B CN201410172949.XA CN201410172949A CN103979824B CN 103979824 B CN103979824 B CN 103979824B CN 201410172949 A CN201410172949 A CN 201410172949A CN 103979824 B CN103979824 B CN 103979824B
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Abstract
The present invention relates to bionical self-repairing cement-base material field.The preparation of a kind of situ aggregation method is used for the microcapsule preparation method of cement-based material selfreparing, including: step 1, dilution epoxy resin；Step 2, another extracting container, add deionized water, highly active emulsifying agent, surfactant, dispersed with stirring, it is thus achieved that emulsion dispersion aqueous solution；Step 3, the emulsion dispersion aqueous solution obtained is joined in step 1 in container used, stirring and emulsifying；Step 4, in the product of step 3 add styrene, add styrene amount be 1:8～1:12 relative to the mass ratio range originally putting into epoxy resin；Step 5, evacuation, inert atmosphere, heat up, oil bath polyreaction；Step 6, addition potassium peroxydisulfate continue catalytic reaction, i.e. obtain final microcapsule emulsion.Synthetic method of the present invention is simple, and solves the adverse effect of noxious substance in building-up process well.
Description
Technical field
The present invention relates to bionical self-repairing cement-base material field, main study subject is for having with situ aggregation method preparation
The microcapsule of self-repair function, the crack that can be widely applied to cement-based material is repaired.
Background technology
Using the widest, that consumption is maximum material as current building field, the service life of concrete material is at very great Cheng
Its destructiveness is depended on degree.Crackle is as a kind of typical failure mode of concrete material, the safety to xoncrete structure
Property with suitability important.Currently for the repairing of distress in concrete, though existing substantial amounts of traditional method, but, this
The most traditional mode mainly carries out correction maintenance and periodic maintenance to xoncrete structure, and not only repairing effect is inconspicuous, also can
Produce substantial amounts of expense.
In recent years, along with research and the application of intellectual material, there is the intelligence from functions such as perception, self diagnosis, selfreparings
Concrete obtains extensive concern and research.Compared with traditional method for repairing and mending, self-repair technology not only saved periodic maintenance and
The expense of later period maintenance, moreover it is possible to reduce the indirect cost of engineering.Self-repair concrete has become the important composition portion of Fiber in Smart Structure
Point, can solve can not solve with conventional fracture method for repairing and mending or insoluble technical problem, to guaranteeing body of groundwater tying
The durability of the great civil engineering facilities such as structure, skyscraper, dam and safety important in inhibiting, additionally, alleviating ground
The weather impact failures such as shake, typhoon, tsunami and other destructive factors also have the biggest application prospect.Therefore, to reviewing one's lessons by oneself compound
Solidifying soil is studied so that it is automatically can detect in fracture district, automatically repair, recover or improve concrete material
Serviceability, it has also become the development trend of concrete technology.
Present stage, domestic and international self-repairing of concrete cracks technology can be divided into crystallization patching, built-in support methods, shape memory
Alloy selfreparing and composite sensor selfreparing etc..Wherein, the studied utilization of built-in support methods is more.In recent years, with
Research application and the development of microcapsule technology so that it is the technology application in material crack self-healing field is gradually weighed
Depending on, and become a hot issue of field of new research.
At present, a lot of Chinese scholars have done the most many research for microcapsule self-repair material, and have obtained one
Fixed achievement.But still suffer from many problems to be solved.In existing achievement in research, prepared microcapsule is mostly with urine
Element yuban is cyst wall, this kind of building-up process first urea synthesis formaldehyde pre-polymerization under the conditions of high-temperature pressure
Body, due to the effumability of formalin, in course of reaction, is inevitably generated toxic gas or harmful substance, and this
Class method raw materials is easily long placed in inefficacy.The synthesis technique of urea aldehydes microcapsule is complex, relatively costly.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, the present invention is with styrene as cyst wall, and epoxy resin is for repairing
Multiple agent, uses situ aggregation method preparation to have the microcapsule of selfreparing effect, and synthetic method is simple, and solves synthesis well
During the adverse effect of noxious substance.
To this end, the method and technology scheme that the present invention is given is:
Use epoxy resin-styrene situ aggregation method to prepare microcapsule, choose epoxy resin good as adhesive property
Material, polystyrene is as cyst wall, and concrete process of preparing is:
Step 1, being diluted by epoxy resin with diluent, the mass ratio range of epoxy resin and diluent is 5:1～8:
1, join in container；
Step 2, size according to the solid content of set microcapsule, the emulsion dispersion aqueous solution that preparation mass concentration is different:
Another extracting container, adds deionized water, highly active emulsifying agent, surfactant, and the quality of described emulsifying agent accounts for three
The 2%～10% of person's gross mass, the quality of surfactant accounts for the 2%～8% of three's gross mass, and surplus is deionized water, stirs
Mix dispersion 5～10 minutes, it is thus achieved that emulsion dispersion aqueous solution；
Step 3, emulsion dispersion aqueous solution step 2 obtained join in step 1 in container used, stirring and emulsifying 8～
15 minutes；
Step 4, in the product of step 3 add styrene, add styrene amount relative to originally putting into epoxy resin
Mass ratio range is 1:8～1:12；
Step 5, the air pumped in container, keep inert gas atmosphere, be warming up to 60 DEG C～80 DEG C, oil bath polyreaction
5h～6h；
Step 6, add higher active catalyst (such as potassium peroxydisulfate) and continue catalytic reaction 3h～4h, i.e. obtain final
Microcapsule emulsion.
Major ingredient cyst material in technique scheme selects styrene analytical pure, and needs before use to carry out pre-place
Reason.Pre-treatment step is: pour appropriate styrene in separatory funnel into, adds the sodium hydroxide that appropriate concentration is 1mol/L molten
Liquid, after repeatedly vibrating for several times, stands until layering, takes the styrene being in upper strata.Repeatedly clean three to four times by this step,
After once clean with deionized water.Add appropriate anhydrous magnesium sulfate at cleaned styrene, stand 8h～12h, cross and filter
Remove magnesium sulfate solid.
Major ingredient epoxy resin can select bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin,
Bisphenol-A epoxy resin, linear phenolic epoxy resin, multiple functional radical glycidyl ether resin, multiple functional radical (+)-2,3-Epoxy-1-propanol
Polyimide resin or halogenated epoxy resin.
The preferred E of described bisphenol A epoxide resin 55, E 51, E 44, E 42, E 33, E 20.Described bisphenol-A
Epoxy molecule structure is as follows:
The preferred F of described linear phenolic epoxy resin 44, F 51, F 48, F 46, JF 45, JF 43,
Epiclon N-740, EPN-1139, DEN-431, Epikote-154 etc..
The epoxy resin of described halogenation mainly has tetrabormated bisphenol A epoxide resin or four chlorination bisphenol A epoxide resins.
In step 1, described diluent is in order to increase the balling ratio of microcapsule, and after microcapsule breakage, by increasing capacitance it is possible to increase
The mobility of epoxy resin, diluent selects benzyl alcohol, acetone, butanone, Ketohexamethylene, benzene,toluene,xylene or positive fourth
Alcohol.
In step 2, described emulsifying agent in order to promote the formation of thin film and electric double layer, thus contribute to cyst wall formation and
Described microcapsule emulsion system uniform and stable.Described emulsifying agent includes: sodium alkyl benzene sulfonate, polyoxyethylene, and bunching water is sweet
One or more of oil or polyol etc..
When described microcapsule join cement-based material carry out selfreparing time, firming agent need to be added so that epoxy resin occur
Curing reaction, thus improve the serviceability of cement-based material each side.Described firming agent includes straight-chain aliphatic polyamines, polyamides
Amine, aliphatic polyamine, aromatic amine, modified polyamine, polymercaptan, urinate analog derivative and have the one in household which owns machines for production's analog derivative or many
Kind.Described aniline molecule structure is as follows:
Microcapsule of the present invention is stable in the presence of emulsion system, and solid content is 20% 40%.Microcapsule is in emulsion
Favorable dispersibility, system is uniformly dispersed not stratified.
Microcapsule prepared by the present invention is further used for the selfreparing of cement-based material, is calculating its mix with water-cement ratio
During water consumption, the water contained by microcapsule emulsion system should contribute in mixing water, to keep water-cement ratio to immobilize.
Based on technique scheme, technique effect and the innovative point of the present invention are embodied in:
(1) present invention uses epoxy resin styrene situ aggregation method can prepare the microcapsule with repairing effect,
Avoid the harm of noxious substance in building-up process, improve with Lauxite simultaneously, phenolic resin, micro-for cyst wall such as polyureas
The volatile rotten adverse effect of raw material in capsule preparation, has green environmental protection；
(2) present invention is by the change to raw material ratio and synthesis technique, can change microcapsule to a certain extent
Performance, such as sphere diameter, solid content, surface nature etc., be conducive to preparation to be more suitable for repairing the microcapsule of concrete material；
(3) xoncrete structure under microcapsule prepared by the present invention is applicable not only to generic condition carries out selfreparing, additionally,
For the initial damage of xoncrete structure and the constructional deficiency of groundwater environment, described microcapsule is changed by certain technique
Enter, can design and prepare the self-repairing microcapsule being applicable to groundwater environment.
Accompanying drawing explanation
Microcapsule distribution--the amplification 200 of Fig. 1 embodiment 1
Microcapsule distribution--the amplification 200 of Fig. 2 embodiment 2
Fig. 3 verifies the assay device schematic diagram of example 5
During Fig. 4 microcapsule volume 1%, test specimen linear water absorption rate change when precompressed 0% and precompressed 30%
Detailed description of the invention
Embodiment 1-2
Preparation has the microcapsule of self-healing properties.Microcapsule granule quality and microcapsule finished product, i.e. microcapsule emulsion body
It it is the solid content that ratio is microcapsule of gross mass.Embodiment 1 each provides two kinds of micro-glue of different solid contents of preparation with embodiment 2
The preferred raw material proportioning of capsule, in embodiment 1, the solid content of microcapsule is 20%, and in embodiment 2, the solid content of microcapsule is
40%.Raw material ratio is following, and (the present embodiment raw materials is direct producer and buys, and wherein, styrene need to be by the present invention
Described preprocess method processes):
Table 1 embodiment 1-2 proportioning
| Raw material | Embodiment 1 | Embodiment 2 |
| Epoxy resin/part | 9 | 14 |
| Styrene/part | 1 | 1.5 |
| Benzyl alcohol/part | 1.5 | 2 |
| Dodecylbenzene sodium sulfonate/part | 0.75 | 1.25 |
| Octyl phenyl polyethylene glycol oxide/part | 0.75 | 1.25 |
| Benzoyl peroxide/part | 0.2 | 0.3 |
| Divinylbenzene/part | 0.05 | 0.08 |
| Potassium peroxydisulfate/part | 0.2 | 0.3 |
| Deionized water/part | 24 | 22 |
Preparation process is as follows:
(1) each component materials is weighed by proportioning；
(2) after diluting with benzyl alcohol for diluent, epoxy resin joins in bottle bucket class container, agitation and dilution；
(3) dodecylbenzene sodium sulfonate is as emulsifying agent, and octyl phenyl polyethylene glycol oxide, as surfactant, incite somebody to action both
Mixing with deionized water, dispersed with stirring, after 8 minutes, joins in reaction unit, mixes with epoxy resin, stirring and emulsifying 10 points
Clock；
(4) using as the mixed liquor of the benzoyl peroxide of catalyst and divinylbenzene and styrene mix and blend, drip
It is added in reaction unit.Capping device, pumps the air in device, is passed through argon.Keep, under argon gas atmosphere, being warming up to 70
DEG C, mixing speed 400rmp, successive reaction 5h；
(5) dripping mass concentration in reaction unit is the potassium persulfate solution of 1%, continues reaction 3h.
Testing according to the proportioning of embodiment 1-2, prepared microcapsule is regular spherical, and center is capsule-core, around
Substantially being wrapped in heavy wall, the seal of microcapsule is good.Microcapsule sphere diameter is distributed between tens microns to 200 microns.With
Time, along with the reduction of solid content, microcapsule sphere diameter increases, and distribution density is decreased obviously.
Wherein, the microcapsule distribution density obtained by embodiment 1 is less than the microcapsule obtained by embodiment 2；Embodiment 1 institute
The microcapsule sphere diameter obtained is more than the microcapsule obtained by embodiment 2.When the solid content of microcapsule is relatively low, high with solid content
Microcapsule finished product is compared, and its distribution density declines, but, the sphere diameter of microcapsule increased.By the observation of optical microscope
Result is shown in Fig. 1-2.
Checking example 3-4
The present invention uses 40mm × 40mm × 160mm cement paste test block, tests cement based after the selfreparing of microcapsule
The performance recovery situation of test specimen.
The water-cement ratio of sample used by the present invention is fixed as 0.3, and microcapsule volume is 0%, 1% and 2%.
In checking raw material used by example 3-4, microcapsule is the microcapsule prepared by the technical scheme according to embodiment 2,
Solid content is 40%；Cement uses P O42.5 level Portland cement；Firming agent uses aqueous epoxy curing agent, and volume is
1.3 times of microcapsule solid content.Test material mixture ratio is shown in Table 2.
Example 3-4 microcapsule self-repairing cement-base material mechanical test material mixture ratio verified by table 2
| Microcapsule volume | Cement/g | Water/g | Microcapsule/g | Firming agent/g |
| 0% | 600 | 180 | 0 | 0 |
| 1% | 600 | 171 | 15 | 7.8 |
| 2% | 600 | 162 | 30 | 15.6 |
The raw material ratio that checking example 3 uses with checking example 4 is consistent, and after molding, checking example 3 is put into concrete standard and supported
Protecting room maintenance 28d, checking example 4 puts into saturated calcium hydroxide aqueous solution maintenance 28 days.
Checking example 3 is consistent with the test method of checking example 4, specifically comprises the following steps that
(1) sample is prepared according to Sample Prep Protocol of the present invention；
(2) after test specimen arrives age, in crack, side in the way of cutting；
(3) carry out 3 bending tests with omnipotent servo hydraulic machine, measure sample under different addition quantity difference curing condition
Constitutive behavior, mechanical property, the data such as dynamic modulus of elasticity；
(4) checking example 3 is carried out prestrain in various degree with checking example 4 test specimen, measure the test number of preloading phase
After play, reloading and destroy completely to test specimen after standing 1d of indoor, second time measures its constitutive behavior, mechanical property, dynamic bullet
The test datas such as data such as property modulus.
By the test of checking example 3 with checking example 4, result of the test is analyzed, available following preliminary concluding remarks:
(1) in prefabricated localized cracks is tested, after destroying in advance and repairing, the rigidity of test specimen, fracture property, mechanical property
Energy and degree of compaction situation have improvement in various degree, illustrate that at microcapsule, cement-based material being had good reparation imitates
Really；
(2) in terms of intensity reply, in the result of prefabricated localized cracks and dispersion crackle, the rupture strength of test specimen and resistance to compression
Intensity response rate all improves along with the raising of precompressed degree.When microcapsule volume is 1%, comprcssive strength and the anti-folding of test specimen are strong
It is test specimen when 2% that the response rate of degree is all higher than volume.
(3) microcapsule in checking example 3 is more than the reparation of test specimen in checking example 4 to the remediation efficiency of test specimen various aspects of performance
Efficiency, the self-repair efficiency under description standard curing condition is better than the remediation efficiency under the conditions of water is supported.
Checking example 5
The present embodiment uses the cement paste cylinder test block of high 25 ± 2mm, base diameter 100 ± 2mm, tests test specimen
The change of its capillary water absorption rate before and after reparation, and then characterize the self-repair function of microcapsule.
The water-cement ratio of sample used by the present invention is fixed as 0.3, and microcapsule volume is 0%, 1% and 2%.
In checking raw material used by example 5, microcapsule is the microcapsule prepared by the technical scheme according to embodiment 2, Gu
Content is 40%；Cement uses P O42.5 level Portland cement；Firming agent uses aqueous epoxy curing agent, and volume is micro-
1.3 times of capsule solid content.Test material mixture ratio is shown in Table 3.
Table 3 embodiment 5 microcapsule self-repairing cement-base material capillary water absorption rate test material proportioning
| Microcapsule volume | Cement/g | Water/g | Microcapsule/g | Firming agent/g |
| 0% | 500 | 150 | 0 | 0 |
| 1% | 500 | 130 | 25 | 6.5 |
| 2% | 500 | 110 | 50 | 13.0 |
It is as follows that the present invention carries out capillary water absorption rate testing procedure to test specimen:
(1) sample is prepared according to Sample Prep Protocol of the present invention, standard curing room maintenance 7 days after molding；
(2) quality of sample under different addition quantity is measured, the test data such as comprcssive strength；
(3) crackle to the specimen prefabricated different range verifying example 5；
(4) the one-dimensional water absorption rate of test specimen is played in measurement the most in the same time.
Fig. 3 is shown in by assay device schematic diagram.Material mixture ratio and method of testing according to checking example 5 are tested.Numerous studies
Showing, the one-dimensional water absorption rate of material becomes logarithmic relationship with 0.5 power of time.When mixing without microcapsule or add microcapsule but
The test specimen in time without precompressed, its linear water absorption rate becomes logarithmic relationship with 0.5 power of time.When adding microcapsule and carry out precompressed,
Its linear water absorption rate has decline in various degree in the later stage, declines degree maximum when volume is 1%.When volume is 2%, precompressed
Degree is bigger, and it is the biggest that the linear water absorption rate in its test later stage declines degree.Partial results is as shown in Figure 4.
This result illustrates under water environment, and prepared microcapsule remains to play the reparation to cement-based material well and makees
With, it is possible to it is effectively improved the degree of compaction of material internal, therefore, can be suitable for well according to the microcapsule prepared by the technical program
Initial damage and constructional deficiency in underground environment water environment xoncrete structure.
Claims (1)
1. a situ aggregation method prepares the microcapsule preparation method for cement-based material selfreparing, it is characterised in that use
Epoxy resin-styrene situ aggregation method prepares microcapsule, chooses epoxy resin as the good material of adhesive property, polyphenyl second
Alkene is as cyst wall, and concrete process of preparing is:
Step 1, being diluted by epoxy resin with diluent, the mass ratio range of epoxy resin and diluent is 5:1～8:1, adds
Enter in container；
Step 2, another extracting container, add deionized water, highly active emulsifying agent, surfactant, and described emulsifying agent includes alkane
One or more in base benzene sulfonic acid sodium salt, polyoxyethylene and poly epihydric alcohol, the quality of described emulsifying agent accounts for three's gross mass
2%～10%, the quality of surfactant accounts for the 2%～8% of three's gross mass, and surplus is deionized water, dispersed with stirring 5～10
Minute, it is thus achieved that emulsion dispersion aqueous solution；
Step 3, emulsion dispersion aqueous solution step 2 obtained join in step 1 in container used, stirring and emulsifying 8～15 points
Clock；
Step 4, in the product of step 3 add styrene, add styrene amount relative to the quality originally putting into epoxy resin
Proportion is 1:8～1:12；
Step 5, the air pumped in container, keep inert gas atmosphere, be warming up to 60 DEG C～80 DEG C, oil bath polyreaction 5h～
6h；
Step 6, addition potassium peroxydisulfate continue catalytic reaction 3h～4h, i.e. obtain final microcapsule emulsion.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410172949.XA CN103979824B (en) | 2014-04-28 | 2014-04-28 | Situ aggregation method preparation is for the microcapsule preparation method of cement-based material selfreparing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410172949.XA CN103979824B (en) | 2014-04-28 | 2014-04-28 | Situ aggregation method preparation is for the microcapsule preparation method of cement-based material selfreparing |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788039B (en) * | 2015-03-16 | 2016-08-24 | 山西省交通科学研究院 | A kind of interior reinforcement and repair agent of cement based structural cracks under wet environment |
| CN105645802B (en) * | 2016-01-05 | 2018-06-26 | 同济大学 | Concrete self-dissolving type microcapsules self-repairing system under a kind of water environment |
| CN105565690B (en) * | 2016-01-05 | 2017-07-28 | 同济大学 | A kind of distress in concrete self-dissolving type self-repairing system and preparation method thereof |
| CN110382437A (en) * | 2017-03-07 | 2019-10-25 | 沙特***石油公司 | Pit shaft cement with polymer latex softgel shell |
| CA3054429C (en) * | 2017-03-07 | 2021-08-31 | Saudi Arabian Oil Company | Method of encapsulating signaling agents for use downhole |
| CN110922087B (en) * | 2019-11-20 | 2021-09-28 | 天津大学 | Efficient self-healing agent for ultrahigh-temperature oil well cement based on crack response and application |
| CN111517703A (en) * | 2020-04-29 | 2020-08-11 | 澳门大学 | High-fracture-resistance cement-based material and preparation method thereof |
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| CN102049230B (en) * | 2010-10-29 | 2013-10-30 | 济南大学 | Preparation and application of cement material self-repairing molecular self-assembled microspheres |
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