CN112456870B - Waterproof and impervious concrete with self-repairing function and preparation method thereof - Google Patents
Waterproof and impervious concrete with self-repairing function and preparation method thereof Download PDFInfo
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
- C04B24/42—Organo-silicon compounds
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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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- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
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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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention discloses waterproof and impervious concrete with a self-repairing function and a preparation method thereof. S1, preparing water-soluble polyrotaxane; A. preparing modified cyclodextrin; B. synthesizing water-soluble polyrotaxane; s2, preparing a repairing material; A. preparing bioremediation microspheres; B. preparing a supplementary repair capsule; C. synthesizing a repairing material; s4, preparing modified adhesive resin; and S5, synthesizing concrete slurry. According to the invention, the filling material growth framework is formed in the crack, and then the filling material is generated in situ on the growth framework, so that the filling material in the crack can be effectively fixed, and the problems of poor mechanical property recovery degree of the concrete material and easy falling of the filling material caused by insufficient compatibility of the newly generated filling material and the concrete in the traditional self-repairing concrete are solved; the invention has good filling effect on concrete material cracks, high mechanical property recovery degree, good compatibility of the filling material and the concrete material, difficult loss, environmental protection, no pollution and very high practicability.
Description
Technical Field
The invention relates to the technical field of concrete, in particular to waterproof and impervious concrete with a self-repairing function and a preparation method thereof.
Background
The concrete is artificial stone which is formed by stirring and mixing a cementing material, aggregate, water, an additive and a blending material according to a certain proportion, has high compressive strength and good durability, and is one of the most widely applied engineering materials in the world at present; however, concrete is very brittle, cracks are easily generated under the action of environmental temperature or load, if the cracks are not repaired in time, the cracks of the concrete are very easily deepened, moisture and other harmful substances in the air can enter the concrete along with the cracks to cause erosion, the mechanical property of the concrete material is reduced, and if the cracks are serious, the wall collapse can be caused, so that personal safety threat and economic loss risk are caused.
At present, two types of concrete material repairing modes are mainly manual repairing and automatic repairing, the repairing effect of the traditional manual repairing method is good, but the method can only repair visible cracks, the damage inside the concrete is difficult to detect and repair in time, and meanwhile, the manual repairing method has no way for some cracks with special structures and cracks under dangerous environments and has certain limitation; in order to make up for the limitation of the manual repair technology, people research the automatic repair technology of the concrete on the basis; the method for pre-embedding the shape memory alloy in the automatic repair technology mainly adopts the method that the memory alloy metal is pre-embedded in the concrete, when the concrete cracks, the memory alloy is deformed by electrifying and heating so as to realize the self repair of the concrete, and the method has good repair effect, but has larger energy consumption and higher cost, and has certain limitation in market popularization; the bionic self-healing technology is mainly characterized in that a repair material is embedded in microspheres, when concrete cracks, the microspheres break, and the repair material flows out to fill the cracks, so that the self-healing effect of the concrete is realized; although the method can realize the self-repairing of the concrete to a certain extent, the repairing material has poor compatibility with the concrete, is easy to lose under the washing of wind or rain, and has poor repairing effect;
therefore, there is a need for a waterproof and impervious concrete having a self-repairing function to solve the problems suggested in the background.
Disclosure of Invention
In order to solve the technical problems, the invention provides the following technical scheme: a waterproof impervious concrete with self-repairing function and a preparation method thereof.
The waterproof and impervious concrete with the self-repairing function comprises the following raw material components, by weight, 300 parts of cement, 100 parts of sand, 150 parts of sand, 80-120 parts of polycarboxylic acid water reducing agent, 70-90 parts of pentahydrate copper sulfate powder, 100 parts of repairing material, 120 parts of modified adhesive resin and 200 parts of modified adhesive resin.
Furthermore, the modified adhesive resin comprises the following raw material components, by weight, 50-80 parts of aminopropyl terminated polydimethylsiloxane, 200 parts of rosin resin, 100 parts of polyurethane resin, 200 parts of isophorone diisocyanate, 80-120 parts of water-soluble polyrotaxane and 20-40 parts of dibutyltin dilaurate.
Furthermore, the repair material mainly comprises bioremediation microspheres and supplementary repair capsules; the mass ratio of the bioremediation microspheres to the supplementary remediation capsules is (1-3): 1; a layer of mixed solution of calcium lactate and cement is sprayed on the surface of the repairing material; the cement and the calcium lactate are in a mass ratio of (10-20): 1; the mass fraction of the cement is 15-25%.
Furthermore, the biological repair microsphere comprises the following raw material components, by weight, 50-100 parts of microorganisms, 100-200 parts of nutrient solution, 50-80 parts of urea, 30-50 parts of sodium chloride, 30-50 parts of sodium citrate and 200 parts of macroporous adsorption resin 120; the supplementary repairing capsule consists of a capsule core and a capsule wall, wherein the capsule core mainly comprises 40-60 parts of water-soluble polyrotaxane solution, 8-12 parts of emulsifier and 15-20 parts of assistant; the capsule wall is obtained by polymerizing formaldehyde and urea solution, wherein the mass ratio of the formaldehyde to the urea solution is (2-4): 3; the emulsifier is one or more of polyethylene glycol, sodium dodecyl benzene sulfonate and tween 80; the auxiliary agent is one or more of polyvinyl alcohol, propane diamine and ammonium chloride.
Further, the water-soluble polyrotaxane comprises the following raw material components: by weight, 100-200 parts of polyethylene glycol, 50-80 parts of triethylamine, 30-60 parts of tosyl chloride, 100-90 parts of modified cyclodextrin, 80-90 parts of 3, 5-dimethylphenol and 20-40 parts of sodium hydride.
Further, the raw material components of the modified cyclodextrin comprise, by weight, 200 parts of gamma-cyclodextrin 100, 80-130 parts of potassium hydroxide, 80-120 parts of L-cysteine and 50-70 parts of epichlorohydrin.
Further, the molecular weight of the polyethylene glycol is 3000-5000.
A preparation method of waterproof and impervious concrete with self-repairing function comprises the following steps:
s1, preparing water-soluble polyrotaxane;
A. preparing modified cyclodextrin;
B. synthesizing water-soluble polyrotaxane;
s2, preparing a repairing material;
A. preparing bioremediation microspheres;
B. preparing a supplementary repair capsule;
C. synthesizing a repairing material;
s4, preparing modified adhesive resin;
and S5, synthesizing concrete slurry.
The method specifically comprises the following steps:
s1, preparing water-soluble polyrotaxane:
A. preparing modified cyclodextrin: dissolving gamma-cyclodextrin in acetic acid under stirring, adding potassium hydroxide at constant temperature of 40-60 deg.C, reacting for 2-4min under stirring, sequentially adding L-cysteine and epichlorohydrin, reacting for 40-70min under stirring, cooling to room temperature, adjusting pH to 5-7, removing precipitate, and concentrating the filtrate to obtain modified cyclodextrin;
B. synthesizing water-soluble polyrotaxane:
a. placing polyethylene glycol and triethylamine in tetrahydrofuran, stirring and dissolving, adding tosyl chloride, stirring and reacting for 1-3h, carrying out suction filtration, removing solid precipitate, adding diethyl ether into filtrate, carrying out suction filtration, washing and drying to obtain a material A;
b. placing the material A in deionized water, stirring and dissolving, adding the modified cyclodextrin, and stirring and reacting for 3-5 hours at room temperature to obtain a material B;
c. putting 3, 5-dimethylphenol into N, N-dimethylphenol, stirring and dissolving, adding sodium hydride and a material B, stirring and reacting for 7-10h at the temperature of 32-38 ℃, adding methanol, centrifugally dispersing for 1-2h, and carrying out suction filtration and drying to obtain water-soluble polyrotaxane;
s2, preparing a repairing material:
A. preparing the bioremediation microsphere:
a. placing microorganisms, nutrient solution, sodium chloride and sodium citrate into deionized water, and uniformly stirring to obtain a mixed solution A;
b. adding macroporous adsorption resin into the mixed solution A, stirring at the rotating speed of 100-;
B. preparing a supplementary repair capsule: stirring and dissolving the formaldehyde solution and urea at 55-65 ℃, and adjusting the pH value to 8-9 to generate a prepolymer; cooling to room temperature, adding water-soluble polyrotaxane solution, emulsifier and adjuvant, stirring at 55-65 deg.C for 40-50min, adjusting pH to 2-4, reacting at 45-55 deg.C for 20-40min, washing, and oven drying to obtain supplementary repairing capsule;
C. synthesizing a repairing material:
a. adding calcium lactate into cement with the mass fraction of 15-25%, and uniformly mixing to obtain a mixed solution B;
b. uniformly mixing the bioremediation microspheres and the supplementary remediation capsules, spraying a mixed solution B on the surface layer of the bioremediation microspheres and the supplementary remediation capsules, and drying at the temperature of 18-24 ℃ to obtain a remediation material;
s4, preparing modified adhesive resin:
a. putting aminopropyl terminated polydimethylsiloxane into tetrahydrofuran, stirring and dissolving to obtain a solution A;
b. stirring and melting the rosin resin at the temperature of 60-70 ℃, adding the solution A, and stirring at the rotating speed of 200-400r/min for 10-15min to obtain the resin A;
c. stirring and melting the polyurethane resin at the temperature of 60-70 ℃, adding isophorone diisocyanate, and stirring at the rotating speed of 200-400r/min for 10-15min to obtain resin B;
d. adding the resin A into the resin B, raising the temperature to 65-85 ℃, stirring and reacting for 40-70min, sequentially adding the water-soluble polyrotaxane and the dibutyltin dilaurate, raising the rotating speed to 300-;
s5, synthesizing concrete slurry: and stirring and mixing the cement, the sand, the polycarboxylic acid water reducing agent and the water, sequentially adding the anhydrous copper sulfate powder, the repairing material and the modified adhesive resin, and continuously stirring and reacting for 30-50min to obtain the concrete slurry.
Furthermore, the thickness of the mixed liquid B on the surface layer of the repair material in the step S2 is 0.5-1.0 mm.
When the concrete material cracks, the shell materials of the bioremediation microsphere and the supplementary remediation capsule are cracked, and the core materials in the bioremediation microsphere flow out; reacting sodium citrate in the core material with copper sulfate pentahydrate to release heat, after the broken modified resin absorbs the heat, activating water-soluble polyrotaxane and aminopropyl-terminated polydimethylsiloxane molecular chains in the modified resin and starting to slide, displacing the modified cyclodextrin on the water-soluble polyrotaxane, and enabling a large number of hydrogen bonds in the molecular chains to interact with each other, wherein the synergistic effect of the hydrogen bonds and the polyrotaxane can promote the healing of the discontinuous broken parts of the modified resin and form new molecular chain entanglement; the newly generated molecular chains are mutually staggered to form a net-shaped framework with a stable structure so as to maintain the growth of the subsequent filling material; the problem that the wall material is cracked in the stirring process can be effectively solved by taking urea resin as a supplementary repair capsule wall material; when the concrete material is in a normal state, the supplementary repair capsule is in a stable state, when the concrete material cracks under the action of stress, the capsule wall of the supplementary repair capsule also cracks, the water-soluble polyrotaxane solution in the supplementary repair capsule flows out, under the action of the exothermic reaction of the blue vitriol and the sodium citrate, the water-soluble polyrotaxane molecular chain liquid displaces along with the water-soluble polyrotaxane solution, and is wound and connected with the molecular chain of the water-soluble polyrotaxane in the modified resin in the concrete material due to hydrogen bonding, so that the growth framework of the filling material is further consolidated; the addition of the auxiliary agent can increase the viscosity of the water-soluble polyrotaxane, and avoid the problem that the viscosity of the water-soluble polyrotaxane is too low and the water-soluble polyrotaxane is directly dispersed without having time to react with the modified resin.
Copper ions in the copper sulfate pentahydrate powder are dissociated under the action of moisture in the air, the copper ions with positive charges and calcium ions contained in concrete are complexed with functional groups such as sulfydryl, amino, hydroxyl and the like on the surface of modified cyclodextrin, the copper ions are attached to a modified resin molecular chain, copper is generated on the modified resin molecular chain by redox reaction of the copper sulfate pentahydrate and sodium citrate, and part of copper can be further oxidized to form copper oxide; calcium ions complexed by the molecular chain of the modified resin react with ammonia and carbonic acid generated by microorganisms to generate calcium carbonate in situ and the calcium carbonate is fixed on the molecular chain of the modified resin; because the shell layer of the microorganism has negative charges and has charge effect with the amino group on the modified cyclodextrin so as to be assembled on the surface of the modified cyclodextrin, the assembly can avoid the loss of the microorganism on one hand; on the other hand, the surfaces of the microorganisms also have negative charges and can also be used as complexing sites of calcium ions and copper ions, filling substances such as calcium carbonate, copper oxide and the like are generated on the surfaces of the microorganisms, the crosslinking density of the filling substances in cracks is increased, the moisture penetration is reduced, and the mechanical property of the concrete material is enhanced.
The water-soluble polyrotaxane is mainly quasi-polyethylene glycol polyrotaxane with a mechanical interlocking structure formed by assembling polyethylene glycol serving as a linear polymer and modified cyclodextrin; in order to ensure that the quasi-polyethylene glycol polyrotaxane can be fully mixed with the rosin resin and the polyurethane resin and react, acetyl groups are grafted on the quasi-polyethylene glycol polyrotaxane through tosyl chloride to obtain water-soluble polyrotaxane; further, the invention also mixes aminopropyl terminated polydimethylsiloxane with rosin to obtain resin A, and mixes isophorone diisocyanate with polyurethane resin to obtain resin B; fully mixing the resin A and the resin B, wherein the polydimethylsiloxane and the isophorone diisocyanate are subjected to prepolymerization reaction in the mixed resin, so that preparation is made for introducing water-soluble polyrotaxane on the molecular chain in the subsequent step; the method can ensure that the reaction of the pre-polymerization reactant in the mixed resin is more uniform and sufficient, the molecular chain of the pre-polymer is entangled with the molecular chain of the resin, and the compatibility of the mixed resin and the pre-polymer is increased; after the prepolymerization reaction is finished, adding water-soluble polyrotaxane and dibutyltin dilaurate into the mixed resin, and after full stirring reaction, successfully introducing the water-soluble polyrotaxane into aminopropyl terminated polydimethylsiloxane to obtain modified adhesive resin; the modified adhesive resin prepared by the invention has double cross-linking effects of hydrogen bonds and polyrotaxane macromolecules, has stronger bonding effect on concrete, and can effectively improve the slump problem of the concrete; the rosin resin used in the invention has excellent oxidation resistance, the polyurethane resin has good waterproof impermeability, and the modified resin using the rosin resin and the polyurethane resin as the matrix can combine the advantages of the rosin resin and the polyurethane resin and can be introduced into concrete slurry, so that the firmness and waterproof impermeability of the concrete can be obviously improved, the cracking risk of the concrete is reduced, and the service life of the concrete is prolonged.
According to the invention, epoxy chloropropane is used as a modifier to introduce L-cysteine containing sulfydryl onto cyclodextrin to obtain modified cyclodextrin, and the cyclodextrin modified by the L-cysteine contains more abundant active groups and can be connected with more molecular chains and metal ions, so that the crosslinking density in the concrete material is improved, and the mechanical property of the concrete material is enhanced; the surface of the concrete filling material contains sulfydryl and hydroxyl which can complex free calcium ions and copper ions in concrete, the calcium ions and the copper ions are subjected to a series of reactions to generate calcium carbonate, copper and copper oxide with stable properties in situ and are fixed in concrete cracks, the interface bonding force between the calcium carbonate, the copper and the copper oxide fixed by the modified cyclodextrin and the concrete is strong, the recovery rate of the mechanical property of the concrete is high, and filling materials such as the calcium carbonate, the copper and the copper oxide in the crack energy are not easy to fall off due to temperature change, rain wash and the like.
Further, the microorganism is one or more of bacillus subtilis and bacillus pasteurii; the nutrient solution is a conventional nutrient solution for microorganisms; the model of the macroporous adsorption resin is bleached a 510;
the bioremediation microsphere in the invention takes macroporous adsorption resin as a shell layer, and takes a mixed solution consisting of microorganisms, nutrient solution, urea, sodium chloride and sodium citrate as a core layer, and the specially added sodium citrate can maintain the pH value of the bioremediation microsphere on one hand and can be used as a reducing agent to reduce copper sulfate pentahydrate into copper with stable property on the other hand. The invention mainly hydrolyzes urea into ammonia and carbonic acid by using urease generated by microorganisms, and the carbonic acid is combined with free calcium ions in the concrete to generate calcium carbonate, thereby realizing the self-repairing process of the concrete.
Before the repairing material is added into the concrete slurry, a layer of mixed liquid of cement and calcium lactate is sprayed on the surface of the repairing material, so that the compressive strength of the repairing material can be increased, the breakage rate of the repairing material in the stirring process of the concrete slurry is reduced, the compatibility of the repairing material in the concrete slurry can be increased, and the repairing material is prevented from falling off due to poor compatibility with the repairing material after the concrete slurry is dried; the calcium lactate component added in the concrete repairing agent can be used as the supplement of calcium ions in the concrete repairing process, so that the influence of excessive consumption of the calcium ions of the concrete during self-repairing to the later-stage concrete performance is avoided.
Further, the molecular weight of the polyethylene glycol is 3000-5000.
A preparation method of waterproof and impervious concrete with self-repairing function comprises the following steps:
s1, preparing bioremediation microspheres:
s2, preparing modified adhesive resin:
a, preparing modified cyclodextrin;
b, preparing water-soluble polyrotaxane;
c, synthesizing modified adhesive resin;
and S3, synthesizing concrete slurry.
The method specifically comprises the following steps:
s1, preparing bioremediation microspheres:
A. placing microorganisms, nutrient solution, sodium chloride and sodium citrate into deionized water, and uniformly stirring to obtain a mixed solution A;
B. adding macroporous adsorption resin into the mixed solution A, stirring at the rotating speed of 100-;
C. adding calcium lactate into cement with the mass fraction of 15-25%, and uniformly mixing to obtain a mixed solution B;
D. spraying the mixed solution B on the surface layer of the bioremediation microsphere, and drying at the temperature of 18-24 ℃ to obtain the bioremediation microsphere;
s2, preparing modified adhesive resin:
a, preparing modified cyclodextrin: dissolving gamma-cyclodextrin in acetic acid under stirring, adding potassium hydroxide at constant temperature of 40-60 deg.C, reacting for 2-4min under stirring, sequentially adding L-cysteine and epichlorohydrin, reacting for 40-70min under stirring, cooling to room temperature, adjusting pH to 5-7, removing precipitate, and concentrating the filtrate to obtain modified cyclodextrin;
b, preparing water-soluble polyrotaxane:
a. placing polyethylene glycol and triethylamine in tetrahydrofuran, stirring and dissolving, adding tosyl chloride, stirring and reacting for 1-3h, carrying out suction filtration, removing solid precipitate, adding diethyl ether into filtrate, carrying out suction filtration, washing and drying to obtain a material A;
b. placing the material A in deionized water, stirring and dissolving, adding the modified cyclodextrin, and stirring and reacting for 3-5 hours at room temperature to obtain a material B;
c. putting 3, 5-dimethylphenol into N, N-dimethylphenol, stirring and dissolving, adding sodium hydride and a material B, stirring and reacting for 7-10h at the temperature of 32-38 ℃, adding methanol, centrifugally dispersing for 1-2h, and carrying out suction filtration and drying to obtain water-soluble polyrotaxane;
C. synthesis of modified adhesive resin:
a. putting aminopropyl terminated polydimethylsiloxane into tetrahydrofuran, stirring and dissolving to obtain a solution A;
b. stirring and melting the rosin resin at the temperature of 60-70 ℃, adding the solution A, and stirring at the rotating speed of 200-400r/min for 10-15min to obtain the resin A;
c. stirring and melting the polyurethane resin at the temperature of 60-70 ℃, adding isophorone diisocyanate, and stirring at the rotating speed of 200-400r/min for 10-15min to obtain resin B;
d. adding the resin A into the resin B, raising the temperature to 65-85 ℃, stirring and reacting for 40-70min, sequentially adding the water-soluble polyrotaxane and the dibutyltin dilaurate, raising the rotating speed to 300-;
s3, synthesizing concrete slurry: and stirring and mixing the cement, the sandstone, the polycarboxylic acid water reducing agent and the water, sequentially adding the anhydrous copper sulfate powder, the bioremediation microspheres and the modified adhesive resin, and continuously stirring and reacting for 30-50min to obtain the concrete slurry.
And in the step S1, the thickness of the mixed solution B on the surface layer of the bioremediation microsphere is 0.5-1.0 mm.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, the synergistic effect of water-soluble polyrotaxane and polydimethylsiloxane is utilized to form double cross-linking based on hydrogen bonds and polyrotaxane in the modified resin, so that the viscosity and the mechanical property of the modified resin are enhanced, and the mechanical property and the waterproof and anti-permeability performance of the concrete material are improved;
the molecular chain of the modified resin can slide after absorbing heat, new molecular chain entanglement is formed under the synergistic action of hydrogen bonds and water-soluble polyrotaxane, a large number of active groups such as sulfydryl, amino, hydroxyl and the like are contained on the newly generated molecular chain, and metal ions and microorganisms can be complexed, and substances with stable properties such as calcium carbonate, copper oxide and the like can be generated on the surface of the newly generated molecular chain in situ, so that the repair and filling of cracks are realized.
According to the invention, the filling material growth framework is formed in the crack, and then the filling material is generated in situ on the growth framework, so that the filling material in the crack can be effectively fixed, and the problems of poor mechanical property recovery degree of the concrete material and easy falling of the filling material caused by insufficient compatibility of the newly generated filling material and the concrete in the traditional self-repairing concrete are solved;
the invention has good filling effect on concrete material cracks, high mechanical property recovery degree, good compatibility of the filling material and the concrete material, difficult loss, environmental protection, no pollution and very high practicability.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The waterproof and impervious concrete with the self-repairing function comprises the following raw materials, by weight, 300 parts of cement, 100 parts of sandstone, 80 parts of a polycarboxylic acid water reducing agent, 70 parts of pentahydrate copper sulfate powder, 100 parts of a repairing material and 150 parts of modified adhesive resin.
The modified adhesive resin comprises the following raw material components, by weight, 50 parts of aminopropyl terminated polydimethylsiloxane, 100 parts of rosin resin, 100 parts of polyurethane resin, 30 parts of isophorone diisocyanate, 80 parts of water-soluble polyrotaxane and 20 parts of dibutyltin dilaurate.
The repair material mainly comprises bioremediation microspheres and supplementary repair capsules; the mass ratio of the bioremediation microspheres to the supplementary remediation capsules is 1: 1; a layer of mixed solution of calcium lactate and cement is sprayed on the surface of the repairing material; the mass ratio of the cement to the calcium lactate is 10: 1; the mass fraction of the cement is 15-25%.
The bioremediation microsphere comprises the following raw material components, by weight, 50 parts of microorganisms, 100 parts of nutrient solution, 50 parts of urea, 30 parts of sodium chloride, 30 parts of sodium citrate and 120 parts of macroporous adsorption resin; the supplementary repair capsule consists of a capsule core and a capsule wall, wherein the capsule core mainly comprises 40 parts of water-soluble polyrotaxane solution, 8 parts of emulsifier and 15 parts of auxiliary agent; the capsule wall is obtained by polymerizing formaldehyde and urea solution, wherein the mass ratio of the formaldehyde to the urea solution is 2: 3.
the water-soluble polyrotaxane comprises the following raw material components: the modified cyclodextrin compound comprises, by weight, 100 parts of polyethylene glycol, 50 parts of triethylamine, 30 parts of tosyl chloride, 100 parts of modified cyclodextrin, 80 parts of 3, 5-dimethylphenol and 20 parts of sodium hydride.
The raw material components of the modified cyclodextrin are as follows, by weight, 100 parts of gamma-cyclodextrin, 80 parts of potassium hydroxide, 80 parts of L-cysteine and 50 parts of epichlorohydrin; the molecular weight of the polyethylene glycol is 3000.
S1, preparing water-soluble polyrotaxane:
A. preparing modified cyclodextrin: dissolving gamma-cyclodextrin in acetic acid under stirring, adding potassium hydroxide at constant temperature of 40 deg.C, stirring for 2min, sequentially adding L-cysteine and epichlorohydrin, stirring for 40min, cooling to room temperature, adjusting pH to 5, removing precipitate, and concentrating the filtrate to obtain modified cyclodextrin;
B. synthesizing water-soluble polyrotaxane:
a. placing polyethylene glycol and triethylamine in tetrahydrofuran, stirring and dissolving, adding tosyl chloride, stirring and reacting for 1h, performing suction filtration, removing solid precipitate, adding diethyl ether into filtrate, performing suction filtration, washing and drying to obtain a material A;
b. placing the material A in deionized water, stirring and dissolving, adding the modified cyclodextrin, and stirring and reacting for 3 hours at room temperature to obtain a material B;
c. placing 3, 5-dimethylphenol in N, N-dimethylphenol, stirring for dissolving, adding sodium hydride and a material B, stirring for reacting for 7 hours at the temperature of 32 ℃, adding methanol for centrifugal dispersion for 1 hour, and performing suction filtration and drying to obtain water-soluble polyrotaxane;
s2, preparing a repairing material:
A. preparing the bioremediation microspheres:
a. placing microorganisms, nutrient solution, sodium chloride and sodium citrate into deionized water, and uniformly stirring to obtain a mixed solution A;
b. adding macroporous adsorption resin into the mixed solution A, stirring at the rotating speed of 100r/min for 30min, filtering and drying until the water content is 10 percent, and obtaining the bioremediation microsphere;
B. preparing a supplementary repair capsule: stirring and dissolving the formaldehyde solution and urea at 55 ℃, and adjusting the pH value to 8 to generate a prepolymer; cooling to room temperature, adding water-soluble polyrotaxane solution, emulsifier and auxiliary agent, stirring at 55 deg.C for 40min, adjusting pH to 2, reacting at 45 deg.C for 20min, washing, and oven drying to obtain capsule for repairing;
C. synthesizing a repairing material:
a. adding calcium lactate into cement with the mass fraction of 15%, and uniformly mixing to obtain a mixed solution B;
b. uniformly mixing the bioremediation microspheres and the supplementary remediation capsules, spraying a mixed solution B with the thickness of 0.5mm on the surface layer of the bioremediation microspheres and the supplementary remediation capsules, and drying at the temperature of 18 ℃ to obtain a remediation material;
s4, preparing modified adhesive resin:
a. putting aminopropyl terminated polydimethylsiloxane into tetrahydrofuran, stirring and dissolving to obtain a solution A;
b. stirring and melting the rosin resin at 60 ℃, adding the solution A, and stirring at the rotating speed of 200r/min for 10min to obtain resin A;
c. stirring and melting polyurethane resin at 60 ℃, adding isophorone diisocyanate, and stirring at the rotating speed of 200r/min for 10min to obtain resin B;
d. adding the resin A into the resin B, raising the temperature to 65 ℃, stirring for reacting for 40min, sequentially adding water-soluble polyrotaxane and dibutyltin dilaurate, raising the rotating speed to 300r/min, and stirring for reacting for 1h to obtain modified adhesive resin;
s5, synthesizing concrete slurry: and stirring and mixing the cement, the gravel, the polycarboxylic acid water reducing agent and the water, sequentially adding the anhydrous copper sulfate powder, the repairing material and the modified adhesive resin, and continuously stirring and reacting for 30min to obtain the concrete slurry.
Example 2
The waterproof and impervious concrete with the self-repairing function comprises, by weight, 400 parts of cement, 130 parts of sandstone, 100 parts of polycarboxylic acid water reducing agent, 80 parts of copper sulfate pentahydrate powder, 110 parts of repairing material and 170 parts of modified adhesive resin.
The modified adhesive resin comprises the following raw material components, by weight, 60 parts of aminopropyl terminated polydimethylsiloxane, 150 parts of rosin resin, 150 parts of polyurethane resin, 60 parts of isophorone diisocyanate, 100 parts of water-soluble polyrotaxane and 30 parts of dibutyltin dilaurate.
The repair material mainly comprises bioremediation microspheres and supplementary repair capsules; the mass ratio of the bioremediation microspheres to the supplementary remediation capsules is 2: 1; a layer of mixed solution of calcium lactate and cement is sprayed on the surface of the repairing material; the mass ratio of the cement to the calcium lactate is 15: 1; the mass fraction of the cement is 20%.
The bioremediation microsphere comprises the following raw materials, by weight, 80 parts of microorganisms, 150 parts of nutrient solution, 60 parts of urea, 40 parts of sodium chloride, 40 parts of sodium citrate and 160 parts of macroporous adsorption resin; the supplementary repair capsule consists of a capsule core and a capsule wall, wherein the capsule core mainly comprises 50 parts of water-soluble polyrotaxane solution, 10 parts of emulsifier and 18 parts of auxiliary agent; the capsule wall is obtained by polymerizing formaldehyde and urea solution, wherein the mass ratio of the formaldehyde to the urea solution is 1: 1.
the water-soluble polyrotaxane comprises the following raw material components: the modified polyethylene glycol modified cyclodextrin compound comprises, by weight, 150 parts of polyethylene glycol, 60 parts of triethylamine, 40 parts of tosyl chloride, 105 parts of modified cyclodextrin, 85 parts of 3, 5-dimethylphenol and 30 parts of sodium hydride.
The raw material components of the modified cyclodextrin comprise, by weight, 150 parts of gamma-cyclodextrin, 110 parts of potassium hydroxide, 100 parts of L-cysteine and 60 parts of epichlorohydrin; the molecular weight of the polyethylene glycol is 4000.
S1, preparing water-soluble polyrotaxane:
A. preparing modified cyclodextrin: dissolving gamma-cyclodextrin in acetic acid under stirring, adding potassium hydroxide at a constant temperature of 50 ℃, reacting for 3min under stirring, sequentially adding L-cysteine and epichlorohydrin, reacting for 55min under stirring, cooling to room temperature, adjusting pH to 6, removing precipitate, and concentrating the filtrate to obtain modified cyclodextrin;
B. synthesizing water-soluble polyrotaxane:
a. placing polyethylene glycol and triethylamine in tetrahydrofuran, stirring and dissolving, adding tosyl chloride, stirring and reacting for 2 hours, carrying out suction filtration, removing solid precipitate, adding diethyl ether into filtrate, carrying out suction filtration, washing and drying to obtain a material A;
b. placing the material A in deionized water, stirring and dissolving, adding the modified cyclodextrin, and stirring and reacting for 4 hours at room temperature to obtain a material B;
c. placing 3, 5-dimethylphenol in N, N-dimethylphenol, stirring for dissolving, adding sodium hydride and a material B, stirring for reacting for 8 hours at the temperature of 34 ℃, adding methanol for centrifugal dispersion for 1.5 hours, and performing suction filtration and drying to obtain water-soluble polyrotaxane;
s2, preparing a repairing material:
A. preparing the bioremediation microspheres:
a. placing microorganisms, nutrient solution, sodium chloride and sodium citrate into deionized water, and uniformly stirring to obtain a mixed solution A;
b. adding macroporous adsorption resin into the mixed solution A, stirring at the rotating speed of 150r/min for 40min, filtering and drying until the water content is 13 percent to obtain the bioremediation microsphere;
B. preparing a supplementary repair capsule: stirring and dissolving the formaldehyde solution and urea at 60 ℃, and adjusting the pH value to 8.5 to generate a prepolymer; cooling to room temperature, adding water-soluble polyrotaxane solution, emulsifier and auxiliary agent, stirring at 70 deg.C for 45min, adjusting pH to 3, reacting at 50 deg.C for 30min, washing, and oven drying to obtain capsule for repairing;
C. synthesizing a repairing material:
a. adding calcium lactate into cement with the mass fraction of 20%, and uniformly mixing to obtain a mixed solution B;
b. uniformly mixing the bioremediation microspheres and the supplementary remediation capsules, spraying a mixed solution B with the thickness of 0.7mm on the surface layer of the bioremediation microspheres and the supplementary remediation capsules, and drying at the temperature of 20 ℃ to obtain a remediation material;
s4, preparing modified adhesive resin:
a. putting aminopropyl terminated polydimethylsiloxane into tetrahydrofuran, stirring and dissolving to obtain a solution A;
b. stirring and melting the rosin resin at 65 ℃, adding the solution A, and stirring at the rotating speed of 300r/min for 13min to obtain resin A;
c. stirring and melting polyurethane resin at 65 ℃, adding isophorone diisocyanate, and stirring at the rotating speed of 300r/min for 13min to obtain resin B;
d. adding the resin A into the resin B, raising the temperature to 75 ℃, stirring and reacting for 60min, sequentially adding the water-soluble polyrotaxane and the dibutyltin dilaurate, raising the rotating speed to 450r/min, and stirring and reacting for 1.5h to obtain the modified adhesive resin;
s5, synthesizing concrete slurry: and stirring and mixing the cement, the gravel, the polycarboxylic acid water reducing agent and the water, sequentially adding the anhydrous copper sulfate powder, the repairing material and the modified adhesive resin, and continuously stirring and reacting for 40min to obtain the concrete slurry.
Example 3:
the waterproof and impervious concrete with the self-repairing function comprises the following raw materials, by weight, 500 parts of cement, 150 parts of sandstone, 120 parts of a polycarboxylic acid water reducing agent, 90 parts of pentahydrate copper sulfate powder, 120 parts of a repairing material and 200 parts of modified adhesive resin.
The modified adhesive resin comprises the following raw material components, by weight, 80 parts of aminopropyl terminated polydimethylsiloxane, 200 parts of rosin resin, 200 parts of polyurethane resin, 80 parts of isophorone diisocyanate, 120 parts of water-soluble polyrotaxane and 40 parts of dibutyltin dilaurate.
The repair material mainly comprises bioremediation microspheres and supplementary repair capsules; the mass ratio of the bioremediation microspheres to the supplementary remediation capsules is 3: 1; a layer of mixed solution of calcium lactate and cement is sprayed on the surface of the repairing material; the mass ratio of the cement to the calcium lactate is 20: 1; the mass fraction of the cement is 25%.
The bioremediation microsphere comprises the following raw materials, by weight, 100 parts of microorganisms, 200 parts of nutrient solution, 80 parts of urea, 50 parts of sodium chloride, 50 parts of sodium citrate and 200 parts of macroporous adsorption resin; the supplementary repairing capsule consists of a capsule core and a capsule wall, wherein the capsule core mainly comprises 60 parts of water-soluble polyrotaxane solution, 12 parts of emulsifier and 20 parts of auxiliary agent; the capsule wall is obtained by polymerizing formaldehyde and urea solution, wherein the mass ratio of the formaldehyde to the urea solution is 4: 3.
the water-soluble polyrotaxane comprises the following raw material components: the modified cyclodextrin compound comprises, by weight, 200 parts of polyethylene glycol, 80 parts of triethylamine, 60 parts of tosyl chloride, 110 parts of modified cyclodextrin, 90 parts of 3, 5-dimethylphenol and 40 parts of sodium hydride.
The raw material components of the modified cyclodextrin comprise, by weight, 200 parts of gamma-cyclodextrin, 130 parts of potassium hydroxide, 120 parts of L-cysteine and 70 parts of epichlorohydrin; the molecular weight of the polyethylene glycol is 5000.
S1, preparing water-soluble polyrotaxane:
A. preparing modified cyclodextrin: dissolving gamma-cyclodextrin in acetic acid under stirring, adding potassium hydroxide at a constant temperature of 60 ℃, reacting for 4min under stirring, sequentially adding L-cysteine and epichlorohydrin, reacting for 70min under stirring, cooling to room temperature, adjusting pH to 7, removing precipitate, and concentrating filtrate to obtain modified cyclodextrin;
B. synthesizing water-soluble polyrotaxane:
a. placing polyethylene glycol and triethylamine in tetrahydrofuran, stirring and dissolving, adding tosyl chloride, stirring and reacting for 3 hours, carrying out suction filtration, removing solid precipitate, adding diethyl ether into filtrate, carrying out suction filtration, washing and drying to obtain a material A;
b. placing the material A in deionized water, stirring and dissolving, adding the modified cyclodextrin, and stirring and reacting for 5 hours at room temperature to obtain a material B;
c. placing 3, 5-dimethylphenol in N, N-dimethylphenol, stirring for dissolving, adding sodium hydride and a material B, stirring for reacting for 10 hours at 38 ℃, adding methanol for centrifugal dispersion for 2 hours, and performing suction filtration and drying to obtain water-soluble polyrotaxane;
s2, preparing a repairing material:
A. preparing the bioremediation microspheres:
a. placing microorganisms, nutrient solution, sodium chloride and sodium citrate into deionized water, and uniformly stirring to obtain a mixed solution A;
b. adding macroporous adsorption resin into the mixed solution A, stirring at the rotating speed of 200r/min for 50min, filtering and drying until the water content is 15%, and obtaining the bioremediation microsphere;
B. preparing a supplementary repair capsule: stirring and dissolving the formaldehyde solution and urea at 65 ℃, and adjusting the pH value to 9 to generate a prepolymer; cooling to room temperature, adding water-soluble polyrotaxane solution, emulsifier and auxiliary agent, stirring at 65 deg.C for 50min, adjusting pH to 4, reacting at 55 deg.C for 40min, washing, and oven drying to obtain capsule for repairing;
C. synthesizing a repairing material:
a. adding calcium lactate into cement with the mass fraction of 25%, and uniformly mixing to obtain a mixed solution B;
b. uniformly mixing the bioremediation microspheres and the supplementary remediation capsules, spraying a mixed solution B with the thickness of 1.0mm on the surface layer of the bioremediation microspheres and the supplementary remediation capsules, and drying at the temperature of 24 ℃ to obtain a remediation material;
s4, preparing modified adhesive resin:
a. putting aminopropyl terminated polydimethylsiloxane into tetrahydrofuran, stirring and dissolving to obtain a solution A;
b. stirring and melting the rosin resin at 70 ℃, adding the solution A, and stirring at the rotating speed of 400r/min for 15min to obtain resin A;
c. stirring and melting polyurethane resin at 70 ℃, adding isophorone diisocyanate, and stirring at the rotating speed of 400r/min for 15min to obtain resin B;
d. adding the resin A into the resin B, raising the temperature to 85 ℃, stirring for reaction for 70min, sequentially adding water-soluble polyrotaxane and dibutyltin dilaurate, raising the rotating speed to 550r/min, and stirring for reaction for 2h to obtain modified adhesive resin;
s5, synthesizing concrete slurry: and stirring and mixing the cement, the gravel, the polycarboxylic acid water reducing agent and the water, sequentially adding the anhydrous copper sulfate powder, the repairing material and the modified adhesive resin, and continuously stirring and reacting for 50min to obtain the concrete slurry.
Experiment: pouring concrete slurry prepared in the examples 1-5 and the comparative example into a cube to obtain concrete blocks, wherein the sizes of the concrete blocks are 10cm multiplied by 10cm, and carrying out compression strength test on the concrete blocks respectively according to GB/T50081-2002 Standard of testing methods for mechanical properties of concrete; carrying out impermeability test on the concrete block according to GB 18445-2012 Standard of cementitious capillary crystalline waterproofing materials (waterproofing agents); after the test is finished, each concrete block passes through a splitting tensile test to enable the concrete to have a crack width of 0.2-0.4mm, after 28d of maintenance, the compressive strength of the concrete block is detected again, and the change condition of the crack width of the concrete block is observed, wherein the specific test data are shown in the following table:
as can be seen from the data in the table, the initial compressive strength of the concrete test block prepared in the examples 1-3 is greatly improved compared with that of the common concrete test block, and the concrete test block has stronger mechanical properties; the concrete test block prepared in the embodiment 1-3 has little change between the compressive strength and the initial compressive strength after being maintained again for 28 days through the splitting tensile test, and the crack recovery rate is more than 95%, which shows that the concrete test block prepared by the invention has stronger self-repairing performance; the concrete test block prepared by the invention has the advantages of seepage resistance pressure of more than 1.0MPa and excellent waterproof and anti-permeability performance.
Example 4
The difference from the embodiment 3 is that the common cyclodextrin is used, because the outer layer of the common cyclodextrin is hydrophilic hydroxyl, the common cyclodextrin has a certain complexing effect on metal ions, but cannot complex microorganisms with negative charges on the surface, the microorganisms are lost without generating enough carbonic acid after the shell layer is broken, the yield of calcium carbonate is low, the filling crosslinking density in cracks is insufficient, and the mechanical property recovery rate after the precast concrete block cracks is treated is larger than that in the embodiment 3.
Example 5
Compared with the embodiment 3, sodium citrate is not added into the bioremediation microspheres, and anhydrous copper sulfate powder is not added into the concrete slurry; because of lack of exothermic reaction of sodium citrate and blue vitriol, the modified resin can not absorb heat and generate molecular chain sliding, new molecular chain entanglement can not occur, the crosslinking density among the generated filling materials such as calcium carbonate, copper oxide and the like is poor, and the influence on the impermeability of the concrete test block is large; the fast interface binding force of the filling material and the concrete sample is insufficient, and the mechanical property recovery rate of the concrete sample is poor.
Comparative example: a common microorganism self-repairing concrete test block.
From the above data and experiments, we can conclude that: according to the invention, double cross-linking based on hydrogen bonds and polyrotaxane is formed in the modified resin by utilizing the synergistic effect of the water-soluble polyrotaxane and the polydimethylsiloxane, so that the viscosity and the mechanical property of the modified resin are enhanced, and further the mechanical property and the waterproof and anti-permeability performance of the concrete material are improved;
the molecular chain of the modified resin can slide after absorbing heat, new molecular chain entanglement is formed under the synergistic action of hydrogen bonds and water-soluble polyrotaxane, and the newly generated molecular chain contains a large number of active groups such as sulfydryl, amino, hydroxyl and the like, so that metal ions and microorganisms can be complexed, and substances with stable properties such as calcium carbonate, copper oxide and the like can be generated on the surface of the molecular chain in situ, and the repair and filling of cracks are realized.
According to the invention, the filling material growth framework is formed in the crack, and then the filling material is generated in situ on the growth framework, so that the filling material in the crack can be effectively fixed, and the problems of poor mechanical property recovery degree of the concrete material and easy falling of the filling material caused by insufficient compatibility of the newly generated filling material and the concrete in the traditional self-repairing concrete are solved;
the invention has good filling effect on concrete material cracks, high mechanical property recovery degree, good compatibility of the filling material and the concrete material, difficult loss, environmental protection, no pollution and very high practicability.
The invention will be finally explained in the following: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The utility model provides a waterproof impervious concrete with self-repairing function which characterized in that: the cement-modified cement comprises, by weight, 300-500 parts of cement, 100-150 parts of sand, 80-120 parts of polycarboxylic acid water reducing agent, 70-90 parts of pentahydrate copper sulfate powder, 100-120 parts of repair material and 150-200 parts of modified adhesive resin;
the modified adhesive resin comprises the following raw material components, by weight, 50-80 parts of aminopropyl terminated polydimethylsiloxane, 200 parts of rosin resin, 100 parts of polyurethane resin, 30-80 parts of isophorone diisocyanate, 80-120 parts of water-soluble polyrotaxane and 20-40 parts of dibutyltin dilaurate;
the repair material mainly comprises bioremediation microspheres and supplementary repair capsules; the mass ratio of the bioremediation microspheres to the supplementary remediation capsules is (1-3): 1; a layer of mixed solution of calcium lactate and cement is sprayed on the surface of the repairing material; the cement and the calcium lactate are in a mass ratio of (10-20): 1; the mass fraction of the cement is 15-25%;
the biological repair microsphere comprises the following raw material components, by weight, 50-100 parts of microorganisms, 100-200 parts of nutrient solution, 50-80 parts of urea, 30-50 parts of sodium chloride, 30-50 parts of sodium citrate and 120-200 parts of macroporous adsorption resin; the supplementary repair capsule consists of a capsule core and a capsule wall, wherein the capsule core mainly comprises 40-60 parts of water-soluble polyrotaxane solution, 8-12 parts of emulsifier and 15-20 parts of auxiliary agent; the capsule wall is obtained by polymerizing formaldehyde and urea solution, wherein the mass ratio of the formaldehyde to the urea solution is (2-4): 3;
the water-soluble polyrotaxane comprises the following raw material components: by weight, 100-200 parts of polyethylene glycol, 50-80 parts of triethylamine, 30-60 parts of toluene sulfonyl chloride, 100-90 parts of modified cyclodextrin, 80-90 parts of 3, 5-dimethylphenol and 20-40 parts of sodium hydride;
the raw material components of the modified cyclodextrin comprise, by weight, 200 parts of gamma-cyclodextrin 100, 80-130 parts of potassium hydroxide, 80-120 parts of L-cysteine and 50-70 parts of epichlorohydrin.
2. The self-repairing waterproof and impervious concrete as claimed in claim 1, wherein the molecular weight of said polyethylene glycol is 3000-5000.
3. The method for preparing waterproof and impervious concrete with self-repairing function according to claim 1 or 2, characterized by comprising the following steps:
s1, preparing water-soluble polyrotaxane;
A. preparing modified cyclodextrin;
B. synthesizing water-soluble polyrotaxane;
s2, preparing a repairing material;
A. preparing bioremediation microspheres;
B. preparing a supplementary repair capsule;
C. synthesizing a repairing material;
s4, preparing modified adhesive resin;
and S5, synthesizing concrete slurry.
4. The preparation method of the waterproof and impervious concrete with the self-repairing function as claimed in claim 3, which is characterized by comprising the following steps:
s1, preparing water-soluble polyrotaxane:
A. preparing modified cyclodextrin: dissolving gamma-cyclodextrin in acetic acid under stirring, adding potassium hydroxide at constant temperature of 40-60 ℃, reacting for 2-4min under stirring, sequentially adding L-cysteine and epichlorohydrin, reacting for 40-70min under stirring, cooling to room temperature, adjusting pH to 5-7, removing precipitate, and concentrating the filtrate to obtain modified cyclodextrin;
B. synthesizing water-soluble polyrotaxane:
a. placing polyethylene glycol and triethylamine in tetrahydrofuran, stirring and dissolving, adding tosyl chloride, stirring and reacting for 1-3h, carrying out suction filtration, removing solid precipitate, adding diethyl ether into filtrate, carrying out suction filtration, washing and drying to obtain a material A;
b. placing the material A in deionized water, stirring and dissolving, adding the modified cyclodextrin, and stirring and reacting for 3-5h at room temperature to obtain a material B;
c. putting 3, 5-dimethylphenol into N, N-dimethylphenol, stirring and dissolving, adding sodium hydride and a material B, stirring and reacting for 7-10h at the temperature of 32-38 ℃, adding methanol, centrifugally dispersing for 1-2h, and carrying out suction filtration and drying to obtain water-soluble polyrotaxane;
s2, preparing a repairing material:
A. preparing the bioremediation microspheres:
a. placing microorganisms, nutrient solution, sodium chloride and sodium citrate into deionized water, and uniformly stirring to obtain a mixed solution A;
b. adding macroporous adsorption resin into the mixed solution A, stirring at the rotating speed of 100-200r/min for 30-50min, filtering and drying until the water content is 10-15%, and obtaining the biological repair microspheres;
B. preparing a supplementary repairing capsule: stirring and dissolving the formaldehyde solution and urea at 55-65 ℃, and adjusting the pH value to 8-9 to generate a prepolymer; cooling to room temperature, adding water-soluble polyrotaxane solution, emulsifier and adjuvant, stirring at 55-65 deg.C for 40-50min, adjusting pH to 2-4, reacting at 45-55 deg.C for 20-40min, washing, and oven drying to obtain capsule for repairing;
C. synthesizing a repairing material:
a. adding calcium lactate into cement with the mass fraction of 15-25%, and uniformly mixing to obtain a mixed solution B;
b. uniformly mixing the bioremediation microspheres and the supplementary remediation capsules, spraying a mixed solution B on the surface layer of the bioremediation microspheres and the supplementary remediation capsules, and drying at the temperature of 18-24 ℃ to obtain a remediation material;
s4, preparing modified adhesive resin:
a. putting aminopropyl terminated polydimethylsiloxane into tetrahydrofuran, stirring and dissolving to obtain a solution A;
b. stirring and melting the rosin resin at 60-70 ℃, adding the solution A, and stirring at the rotating speed of 200-400r/min for 10-15min to obtain the resin A;
c. stirring and melting the polyurethane resin at 60-70 ℃, adding isophorone diisocyanate, and stirring at the rotating speed of 200-400r/min for 10-15min to obtain resin B;
d. adding the resin A into the resin B, raising the temperature to 65-85 ℃, stirring and reacting for 40-70min, sequentially adding the water-soluble polyrotaxane and the dibutyltin dilaurate, raising the rotating speed to 300-550r/min, and stirring and reacting for 1-2h to obtain the modified adhesive resin;
s5, synthesizing concrete slurry: and stirring and mixing the cement, the sandstone, the polycarboxylic acid water reducing agent and the water, sequentially adding the anhydrous copper sulfate powder, the repairing material and the modified adhesive resin, and continuously stirring and reacting for 30-50min to obtain the concrete slurry.
5. The method of claim 4, wherein the thickness of the mixed solution B on the surface of the repair material in the step C of the step S2 is 0.5-1.0 mm.
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| CN107963855A (en) * | 2017-11-27 | 2018-04-27 | 苏州混凝土水泥制品研究院有限公司 | A kind of super high strength high performance concrete and preparation method thereof |
| CN110240457A (en) * | 2019-06-24 | 2019-09-17 | 北京建工一建工程建设有限公司 | A kind of self-repair concrete and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114671642B (en) | 2023-05-05 |
| CN112456870A (en) | 2021-03-09 |
| CN114671642A (en) | 2022-06-28 |
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Effective date of registration: 20220620 Address after: 528042 Chaoyang Jidi Bund, Longjin village, Nanzhuang Town, Chancheng District, Foshan City, Guangdong Province Applicant after: Foshan Jianzhong Concrete Co.,Ltd. Address before: 212000 No.165 Huangshan Branch Road, Runzhou District, Zhenjiang City, Jiangsu Province Applicant before: LAN Gang |
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