CN111333365B - Porous concrete waterproof agent and preparation method thereof - Google Patents
Porous concrete waterproof agent and preparation method thereof Download PDFInfo
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- CN111333365B CN111333365B CN202010224576.1A CN202010224576A CN111333365B CN 111333365 B CN111333365 B CN 111333365B CN 202010224576 A CN202010224576 A CN 202010224576A CN 111333365 B CN111333365 B CN 111333365B
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/65—Water proofers or repellants
Abstract
The invention discloses a porous concrete waterproof agent and a preparation method thereof, wherein the waterproof agent comprises the following raw materials in parts by weight: 25-40 parts of modified gel, 4-6 parts of oxidant, 5-9 parts of cross-linking agent and 3-5 parts of photoinitiator by weight; the modified gel comprises the following raw materials in parts by weight: by weight, 30-40 parts of pretreated microspheres, 25-30 parts of 3, 4-dihydroxy phenylacetic acid, 15-20 parts of N-hydroxysuccinimide, 15-20 parts of 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride, 18-25 parts of sodium alginate and 10-14 parts of propyne. The invention discloses a porous concrete waterproof agent and a preparation method thereof, the process design is simple, the component proportion is reasonable, a compact double-gel network is formed by modifying chitosan and sodium alginate and utilizing Michael addition reaction and chemical click reaction, the waterproof and anti-seepage performance of concrete can be effectively improved when the porous concrete waterproof agent is used, and meanwhile, the porous concrete waterproof agent can be self-repaired, can be widely applied to concrete construction, and has higher practicability.
Description
Technical Field
The invention relates to the technical field of concrete, in particular to a porous concrete waterproof agent and a preparation method thereof.
Background
The water-proofing agent, a chemical additive, is added in the cement, when the cement is set and hardened, it can expand with its volume, and can compensate shrinkage and tension the reinforcing bar to produce prestress and fully fill the gap between cement.
For the problems of impermeability and waterproofness of concrete, the method is always the focus of research in the field of concrete materials and is also a hot topic of much attention of researchers; the concrete seepage is caused by the fact that concrete cracks appear and form a seepage channel, and the conventional waterproof material is short in service life, poor in waterproof durability, high in repair cost in engineering application and poor in practicability.
Aiming at the problem, a porous concrete waterproof agent and a preparation method thereof are disclosed, which are one of the technical problems to be solved urgently.
Disclosure of Invention
The invention aims to provide a porous concrete waterproof agent and a preparation method thereof, and aims to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
the porous concrete waterproof agent comprises the following raw materials in parts by weight: 25-40 parts of modified gel, 4-6 parts of oxidant, 5-9 parts of cross-linking agent and 3-5 parts of photoinitiator.
According to an optimized scheme, the modified gel comprises the following raw materials in parts by weight: by weight, 30-40 parts of pretreated microspheres, 25-30 parts of 3, 4-dihydroxy phenylacetic acid, 15-20 parts of N-hydroxysuccinimide, 15-20 parts of 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride, 18-25 parts of sodium alginate and 10-14 parts of propyne.
According to an optimized scheme, the pretreatment microspheres are prepared from modified microspheres, 2' - (1, 2-ethanediylbis oxo) bisethanethiol and absolute ethyl alcohol;
the modified microsphere comprises the following raw materials in parts by weight: 10-20 parts of modified silicon dioxide microspheres, 15-25 parts of chitosan, 5-12 parts of hydroxyl-terminated polydimethylsiloxane, 3-5 parts of dibutyltin dilaurate, 8-10 parts of ethyl orthosilicate, 3-5 parts of an emulsifier, 3-5 parts of liquid paraffin, 6-9 parts of vanillin and 10-14 parts of a waterproof auxiliary agent.
According to an optimized scheme, the modified silicon dioxide microspheres are prepared from absolute ethyl alcohol, hexadecyl trimethyl ammonium bromide, ammonia water, ethyl orthosilicate and a silane coupling agent.
According to an optimized scheme, the waterproof auxiliary agent comprises magnesium calcium carbonate, sodium sulfate and sodium silicate, and the mass ratio of the magnesium calcium carbonate to the sodium sulfate to the sodium silicate is (2): (8-9): 1.
in an optimized scheme, the silane coupling agent is 3- (trimethoxysilyl) propyl methacrylate, and the emulsifier is span-80.
In a more optimized scheme, the oxidizing agent is sodium periodate, and the crosslinking agent is four-arm polyethylene glycol thiol.
According to an optimized scheme, the preparation method of the porous concrete waterproof agent comprises the following steps:
1) preparing materials;
2) preparing modified silicon dioxide microspheres:
a) taking absolute ethyl alcohol and deionized water, stirring uniformly, adding hexadecyl trimethyl ammonium bromide and ammonia water, continuing stirring, slowly adding tetraethoxysilane, stirring and reacting in a water bath at 40 ℃, centrifuging, washing, and drying in vacuum to obtain silicon dioxide microspheres;
b) dissolving the silica microspheres in absolute ethyl alcohol, performing ultrasonic dispersion, adding a silane coupling agent, continuously stirring, washing and drying to obtain modified silica microspheres;
3) preparation of pretreated microspheres:
a) mixing and stirring chitosan, acetic acid and deionized water to obtain a chitosan solution; dissolving hydroxyl-terminated polydimethylsiloxane, dibutyltin dilaurate and ethyl orthosilicate in n-hexane, and stirring to obtain a solution A;
b) mixing and stirring an emulsifier and liquid paraffin, slowly dripping a chitosan solution, continuously stirring and emulsifying, adding sodium hydroxide, adjusting the pH value to 9, continuously stirring, adding vanillin and the solution A, reacting and crosslinking for 5-6h, adding a waterproof auxiliary agent, performing ultrasonic dispersion, stirring after dispersion, adding modified silicon dioxide microspheres, continuously stirring, washing, and performing vacuum drying to obtain modified microspheres;
c) taking the modified microspheres, 2' - (1, 2-ethanediylbis oxo) bisethanethiol and an absolute ethanol solution, stirring, placing in a vacuum box for low-pressure adsorption for 6-8h, washing after adsorption, performing centrifugal separation, and performing vacuum drying to obtain pretreated microspheres;
4) dissolving N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in a mixed solution of deionized water and absolute ethyl alcohol to obtain a solution B; dissolving sodium alginate and EMS buffer solution, and stirring to obtain solution C;
5) dissolving the pretreated microspheres with hydrochloric acid, adding sodium hydroxide, adjusting the pH value to 5, adding a 3, 4-dihydroxyphenylacetic acid solution, stirring, adding the solution C, continuously stirring, slowly dropwise adding the solution B, stirring for reaction, keeping the reaction pH value at 4.5-5, adding propyne, reacting at room temperature for 20-24h, dialyzing with hydrochloric acid, and freeze-drying to obtain modified gel;
6) and (3) taking the modified gel and an oxidant, fully reacting for 2-3h, adding a cross-linking agent and a photoinitiator, uniformly mixing, and irradiating for 10-15min under ultraviolet light to obtain the waterproof agent.
The optimized scheme comprises the following steps:
1) preparing materials;
a) weighing an oxidant, a cross-linking agent, a photoinitiator, 3, 4-dihydroxyphenylacetic acid, N-hydroxysuccinimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, sodium alginate and propyne according to a proportion for later use;
b) weighing 2, 2' - (1, 2-ethanediylbenzoxol) bisethanethiol, chitosan, hydroxyl-terminated polydimethylsiloxane, dibutyltin dilaurate, ethyl orthosilicate, an emulsifier, liquid paraffin and vanillin according to a proportion for later use;
c) weighing absolute ethyl alcohol, hexadecyl trimethyl ammonium bromide, ammonia water and a silane coupling agent according to a proportion for later use; mixing and stirring magnesium calcium carbonate, sodium sulfate and sodium silicate for 10-20min to obtain a waterproof auxiliary agent; preparing raw materials of each component in the step 1), so that an operator can conveniently perform subsequent steps;
2) preparing modified silicon dioxide microspheres:
a) taking absolute ethyl alcohol and deionized water, stirring uniformly, adding hexadecyl trimethyl ammonium bromide and ammonia water, continuously stirring for 10-20min, slowly adding tetraethoxysilane, stirring for 2-2.5h in water bath at 40 ℃, centrifuging, washing, and drying in vacuum at 40 ℃ to obtain silicon dioxide microspheres;
b) dissolving the silicon dioxide microspheres in absolute ethyl alcohol, performing ultrasonic dispersion for 5-10min, adding a silane coupling agent, continuously stirring for 25-35min, washing and drying to obtain modified silicon dioxide microspheres; the preparation of the modified silicon dioxide microspheres is carried out in the step 2), and the silicon dioxide surfaces are modified by the silane coupling agent, so that the silicon dioxide microspheres are uniform in size and excellent in dispersity;
3) preparation of pretreated microspheres:
a) mixing chitosan, acetic acid and deionized water, and stirring for 10-12h to obtain chitosan solution; dissolving hydroxyl-terminated polydimethylsiloxane, dibutyltin dilaurate and ethyl orthosilicate in n-hexane, and stirring for 40-50min to obtain a solution A;
b) mixing and stirring an emulsifier and liquid paraffin for 2-3h at the stirring speed of 1100r/min for 1000-25 min, slowly dropping a chitosan solution, continuously stirring and emulsifying for 20-25min at the stirring speed of 1050r/min for 950-950, adding sodium hydroxide, adjusting the pH value to 9, continuously stirring for 20-30min, adding vanillin and the solution A, reacting and crosslinking for 5-6h, adding a waterproof auxiliary agent, ultrasonically dispersing for 10-15min, stirring for 10-25min after dispersion, adding modified silica microspheres, continuously stirring for 10-15min, washing, and vacuum drying at 25-30 ℃ to obtain modified microspheres; in the step 3), firstly, components such as chitosan solution, emulsifier, liquid paraffin and the like are utilized, vanillin is taken as a cross-linking agent for cross-linking and forming a cross-linked network, meanwhile, in the solution A, hydroxyl-terminated polydimethylsiloxane and ethyl orthosilicate are subjected to dealcoholization reaction under the catalytic action of dibutyltin dilaurate and form a network cross-linked structure, the two network structures are cross-linked with each other, and then, a waterproof auxiliary agent and modified silica microspheres are added, so that a compact structure with components such as chitosan microspheres, chitosan cross-linked network and modified silica microspheres adsorbing the waterproof auxiliary agent, which are cross-linked with each other, is formed;
c) taking the modified microspheres, 2' - (1, 2-ethanediylbis oxo) bisethanethiol and an absolute ethanol solution, stirring for 20-30min, placing in a vacuum box for low-pressure adsorption for 6-8h, washing after adsorption, performing centrifugal separation, and performing vacuum drying to obtain pretreated microspheres; in the step c), 2 '- (1, 2-ethanediylbis oxo) bisethanethiol is loaded in the chitosan microspheres and the modified silica microspheres, when the concrete material is affected by external force to form cracks, the silica microspheres and the chitosan microspheres are cracked in the crack generating area, a loaded bismercapto cross-linking agent (2, 2' - (1, 2-ethanediylbis oxo) bisethanethiol) flows out, in the air, an oxidation reaction can be generated between mercapto molecules to generate a sulfur free radical, meanwhile, the chitosan and sodium alginate are modified in the subsequent steps, and when the cracks are generated, an exchange recombination reaction can be performed by using the sulfur free radical to perform self-repairing of the waterproof agent;
4) dissolving N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in a mixed solution of deionized water and absolute ethyl alcohol to obtain a solution B; dissolving sodium alginate in EMS buffer solution, and stirring for 10-15min to obtain solution C;
5) dissolving pretreated microspheres with hydrochloric acid, adding sodium hydroxide, adjusting pH to 5, adding a 3, 4-dihydroxyphenylacetic acid solution, stirring for 10-15min, adding a solution C, continuously stirring for 30-40min, slowly dropwise adding a solution B, stirring for reacting for 10-11h, keeping the reaction pH at 4.5-5, adding propyne, reacting for 20-24h at room temperature, dialyzing with hydrochloric acid, and freeze-drying to obtain a modified gel; modifying the pretreated microspheres in step 5), grafting catechol groups on chitosan microsphere structures by using coupling reaction, adding sodium alginate, modifying the sodium alginate while crosslinking the sodium alginate and the modified microspheres, and condensing propine and the sodium alginate to form sodium alginate with alkynyl;
6) and (3) taking the modified gel and an oxidant, fully reacting for 2-3h, adding a cross-linking agent and a photoinitiator, uniformly mixing, and irradiating for 10-15min under ultraviolet light to obtain the waterproof agent. In the step 6), under the action of an oxidant, the catechol group grafted on the surface of the chitosan and a sulfydryl group in a cross-linking agent (four-arm polyethylene glycol thiol) undergo a Michael addition reaction to form a gel network; meanwhile, the alkynyl of the sodium alginate and the sulfydryl in the cross-linking agent (four-arm polyethylene glycol thiol) are subjected to alkynyl-sulfydryl click reaction under the ultraviolet irradiation to form a gel network, and finally a compact double-network hydrogel structure is formed.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, a compact double-network structure is prepared through the steps, and the network structure contains a chitosan and sodium alginate cross-linked structure; a cross-linked structure of chitosan and a cross-linking agent; a cross-linked structure of sodium alginate and a cross-linking agent; chitosan microspheres and modified silica microspheres adsorbed with a waterproof auxiliary agent and a dimercapto cross-linking agent (2, 2' - (1, 2-ethanediylbiooxo) bisethanethiol); the gel prepared by the invention has a compact structure, can cover the surface of concrete and cover the surface pores of the concrete, and improves the waterproof performance of the concrete; meanwhile, when concrete cracks, the chitosan microspheres and the modified silica microspheres are cracked, the cross-linking agent (2, 2 '- (1, 2-ethanediylbis oxo) bisethanethiol) containing disulfide bonds inside flows out, the disulfide bonds can exchange with other disulfide bonds, and on the other hand, when the concrete cracks, the disulfide bonds of the cross-linking agent (2, 2' - (1, 2-ethanediylbis oxo) bisethanethiol) containing disulfide bonds can also be cracked to generate sulfur free radicals, and the sulfur free radicals can also rapidly exchange with other disulfide bonds, so that self-repairing of the waterproof agent is carried out by utilizing the reversible dynamic bisulphide bond exchange reaction, and self-healing can be rapidly realized under the stimulation of external ultraviolet light or an oxidizing agent.
The waterproof auxiliary agent comprises magnesium calcium carbonate, sodium sulfate and sodium silicate, wherein when the waterproof auxiliary agent is used, the magnesium calcium carbonate can permeate into concrete along with water and generates calcium carbonate crystals with calcium ions in the concrete. The cement hydration products such as calcium hydroxide, hydrated calcium aluminate and the like can react with sulfate ions in the waterproof auxiliary agent to form insoluble calcium sulfate and ettringite crystals, meanwhile, silicate ions in the sodium silicate can permeate into the matrix and react with calcium ions to form calcium silicate crystals, and the calcium sulfate, the calcium silicate crystals and the calcium silicate crystals interact with each other and can react with the cement to form crystals which permeate into pores, so that the structure of the cement is more compact, and the waterproof and anti-seepage performance of the cement is improved.
When the waterproof agent disclosed by the invention is used, when concrete cracks, the waterproof agent not only can play a self-repairing role, but also can repair the concrete cracks, so that the waterproof performance of the concrete is ensured.
The invention discloses a porous concrete waterproof agent and a preparation method thereof, the process design is simple, the component proportion is reasonable, a compact double-gel network is formed by modifying chitosan and sodium alginate and utilizing Michael addition reaction and chemical click reaction, the waterproof and anti-seepage performance of concrete can be effectively improved when the porous concrete waterproof agent is used, and meanwhile, the porous concrete waterproof agent can be self-repaired, can be widely applied to concrete construction, and has higher 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:
s1: preparing materials;
weighing an oxidant, a cross-linking agent, a photoinitiator, 3, 4-dihydroxyphenylacetic acid, N-hydroxysuccinimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, sodium alginate and propyne according to a proportion for later use;
weighing 2, 2' - (1, 2-ethanediylbenzoxol) bisethanethiol, chitosan, hydroxyl-terminated polydimethylsiloxane, dibutyltin dilaurate, ethyl orthosilicate, an emulsifier, liquid paraffin and vanillin according to a proportion for later use;
weighing absolute ethyl alcohol, hexadecyl trimethyl ammonium bromide, ammonia water and a silane coupling agent according to a proportion for later use; mixing and stirring magnesium calcium carbonate, sodium sulfate and sodium silicate for 10min to obtain a waterproof auxiliary agent;
s2: preparing modified silicon dioxide microspheres:
taking absolute ethyl alcohol and deionized water, stirring uniformly, adding hexadecyl trimethyl ammonium bromide and ammonia water, continuing stirring for 10min, slowly adding tetraethoxysilane, stirring for 2h in a water bath at 40 ℃, centrifugally washing, and drying in vacuum at 40 ℃ to obtain silicon dioxide microspheres;
dissolving the silica microspheres in absolute ethyl alcohol, performing ultrasonic dispersion for 5min, adding a silane coupling agent, continuously stirring for 25min, washing and drying to obtain modified silica microspheres;
s3: preparation of pretreated microspheres:
mixing and stirring chitosan, acetic acid and deionized water for 10 hours to obtain a chitosan solution; dissolving hydroxyl-terminated polydimethylsiloxane, dibutyltin dilaurate and ethyl orthosilicate in n-hexane, and stirring for 40min to obtain a solution A;
mixing and stirring an emulsifier and liquid paraffin for 2 hours at the stirring speed of 1000r/min, slowly dripping a chitosan solution, continuously stirring and emulsifying for 20 minutes at the stirring speed of 950r/min, adding sodium hydroxide, adjusting the pH value to 9, continuously stirring for 20 minutes, adding vanillin and the solution A, reacting and crosslinking for 5 hours, adding a waterproof auxiliary agent, ultrasonically dispersing for 10 minutes, stirring for 10 minutes after dispersion, adding modified silicon dioxide microspheres, continuously stirring for 10 minutes, washing, and vacuum drying at 25 ℃ to obtain modified microspheres;
taking the modified microspheres, 2' - (1, 2-ethanediylbis oxo) bisethanethiol and an absolute ethanol solution, stirring for 20min, placing in a vacuum box for low-pressure adsorption for 6h, washing after adsorption, performing centrifugal separation, and performing vacuum drying to obtain pretreated microspheres;
s4: dissolving N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in a mixed solution of deionized water and absolute ethyl alcohol to obtain a solution B; dissolving sodium alginate in EMS buffer solution, and stirring for 10min to obtain solution C;
s5: dissolving the pretreated microspheres with hydrochloric acid, adding sodium hydroxide, adjusting the pH value to 5, adding a 3, 4-dihydroxyphenylacetic acid solution, stirring for 10min, adding the solution C, continuously stirring for 3min, slowly dropwise adding the solution B, stirring for reaction for 10h, keeping the reaction pH value at 4.5, adding propyne, reacting for 20h at room temperature, dialyzing with hydrochloric acid, and freeze-drying to obtain modified gel;
s6: and (3) taking the modified gel and an oxidant, fully reacting for 2 hours, then adding a cross-linking agent and a photoinitiator, uniformly mixing, and then placing under ultraviolet light for irradiation for 10min to obtain the waterproof agent.
In the embodiment, the waterproof agent comprises the following raw materials: 25 parts of modified gel, 4 parts of oxidant, 5 parts of cross-linking agent and 3 parts of photoinitiator;
the modified gel comprises the following raw materials: by weight, 30 parts of pretreated microspheres, 25 parts of 3, 4-dihydroxy phenylacetic acid, 15 parts of N-hydroxysuccinimide, 15 parts of 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride, 18 parts of sodium alginate and 10 parts of propyne.
The modified microsphere comprises the following raw materials: by weight, 10 parts of modified silicon dioxide microspheres, 15 parts of chitosan, 5 parts of hydroxyl-terminated polydimethylsiloxane, 3 parts of dibutyltin dilaurate, 8 parts of ethyl orthosilicate, 3 parts of an emulsifier, 3 parts of liquid paraffin, 6 parts of vanillin and 10 parts of a waterproof auxiliary agent;
the mass ratio of the magnesium calcium carbonate to the sodium sulfate to the sodium silicate is (2): 8: 1; the silane coupling agent is 3- (trimethoxysilyl) propyl methacrylate, and the emulsifier is span-80; the oxidant is sodium periodate, and the cross-linking agent is four-arm polyethylene glycol mercaptan.
Example 2:
s1: preparing materials;
weighing an oxidant, a cross-linking agent, a photoinitiator, 3, 4-dihydroxyphenylacetic acid, N-hydroxysuccinimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, sodium alginate and propyne according to a proportion for later use;
weighing 2, 2' - (1, 2-ethanediylbenzoxol) bisethanethiol, chitosan, hydroxyl-terminated polydimethylsiloxane, dibutyltin dilaurate, ethyl orthosilicate, an emulsifier, liquid paraffin and vanillin according to a proportion for later use;
weighing absolute ethyl alcohol, hexadecyl trimethyl ammonium bromide, ammonia water and a silane coupling agent according to a proportion for later use; mixing and stirring magnesium calcium carbonate, sodium sulfate and sodium silicate for 15min to obtain a waterproof auxiliary agent;
s2: preparing modified silicon dioxide microspheres:
taking absolute ethyl alcohol and deionized water, stirring uniformly, adding hexadecyl trimethyl ammonium bromide and ammonia water, continuing stirring for 15min, slowly adding tetraethoxysilane, stirring for 2.2h in a water bath at 40 ℃, centrifuging, washing, and drying in vacuum at 40 ℃ to obtain silicon dioxide microspheres;
dissolving the silica microspheres in absolute ethyl alcohol, performing ultrasonic dispersion for 8min, adding a silane coupling agent, continuously stirring for 30min, washing and drying to obtain modified silica microspheres;
s3: preparation of pretreated microspheres:
mixing and stirring chitosan, acetic acid and deionized water for 11 hours to obtain a chitosan solution; dissolving hydroxyl-terminated polydimethylsiloxane, dibutyltin dilaurate and ethyl orthosilicate in n-hexane, and stirring for 45min to obtain a solution A;
mixing and stirring an emulsifier and liquid paraffin for 2.5 hours at the stirring speed of 1050r/min, slowly dripping a chitosan solution, continuously stirring and emulsifying for 22 minutes at the stirring speed of 1000r/min, adding sodium hydroxide, adjusting the pH value to 9, continuously stirring for 25 minutes, adding vanillin and the solution A, reacting and crosslinking for 5.5 hours, adding a waterproof auxiliary agent, ultrasonically dispersing for 12 minutes, stirring for 18 minutes after dispersion, adding modified silicon dioxide microspheres, continuously stirring for 12 minutes, washing, and vacuum drying at 28 ℃ to obtain modified microspheres;
taking the modified microspheres, 2' - (1, 2-ethanediylbis oxo) bisethanethiol and an absolute ethanol solution, stirring for 25min, placing in a vacuum box for low-pressure adsorption for 7h, washing after adsorption, performing centrifugal separation, and performing vacuum drying to obtain pretreated microspheres;
s4: dissolving N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in a mixed solution of deionized water and absolute ethyl alcohol to obtain a solution B; dissolving sodium alginate in EMS buffer solution, and stirring for 12min to obtain solution C;
s5: dissolving the pretreated microspheres with hydrochloric acid, adding sodium hydroxide, adjusting the pH value to 5, adding a 3, 4-dihydroxyphenylacetic acid solution, stirring for 12min, adding the solution C, continuously stirring for 35min, slowly dropwise adding the solution B, stirring for reacting for 10.5h, keeping the reaction pH value at 4.5, adding propyne, reacting for 22h at room temperature, dialyzing with hydrochloric acid, and freeze-drying to obtain modified gel;
s6: and (3) taking the modified gel and an oxidant, fully reacting for 2 hours, then adding a cross-linking agent and a photoinitiator, uniformly mixing, and then placing under ultraviolet light for irradiation for 12min to obtain the waterproof agent.
In the embodiment, the waterproof agent comprises the following raw materials: 35 parts of modified gel, 5 parts of oxidant, 8 parts of cross-linking agent and 4 parts of photoinitiator;
the modified gel comprises the following raw materials: by weight, 34 parts of pretreated microspheres, 28 parts of 3, 4-dihydroxy phenylacetic acid, 18 parts of N-hydroxysuccinimide, 18 parts of 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride, 20 parts of sodium alginate and 12 parts of propyne.
The modified microsphere comprises the following raw materials: by weight, 15 parts of modified silicon dioxide microspheres, 18 parts of chitosan, 10 parts of hydroxyl-terminated polydimethylsiloxane, 4 parts of dibutyltin dilaurate, 9 parts of ethyl orthosilicate, 4 parts of an emulsifier, 4 parts of liquid paraffin, 8 parts of vanillin and 12 parts of a waterproof auxiliary agent;
the mass ratio of the magnesium calcium carbonate to the sodium sulfate to the sodium silicate is (2): 8.5: 1; the silane coupling agent is 3- (trimethoxysilyl) propyl methacrylate, and the emulsifier is span-80; the oxidant is sodium periodate, and the cross-linking agent is four-arm polyethylene glycol mercaptan.
Example 3:
s1: preparing materials;
weighing an oxidant, a cross-linking agent, a photoinitiator, 3, 4-dihydroxyphenylacetic acid, N-hydroxysuccinimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, sodium alginate and propyne according to a proportion for later use;
weighing 2, 2' - (1, 2-ethanediylbenzoxol) bisethanethiol, chitosan, hydroxyl-terminated polydimethylsiloxane, dibutyltin dilaurate, ethyl orthosilicate, an emulsifier, liquid paraffin and vanillin according to a proportion for later use;
weighing absolute ethyl alcohol, hexadecyl trimethyl ammonium bromide, ammonia water and a silane coupling agent according to a proportion for later use; mixing and stirring magnesium calcium carbonate, sodium sulfate and sodium silicate for 20min to obtain a waterproof auxiliary agent;
s2: preparing modified silicon dioxide microspheres:
taking absolute ethyl alcohol and deionized water, stirring uniformly, adding hexadecyl trimethyl ammonium bromide and ammonia water, continuing stirring for 20min, slowly adding tetraethoxysilane, stirring for 2.5h in a water bath at 40 ℃, centrifuging, washing, and drying in vacuum at 40 ℃ to obtain silicon dioxide microspheres;
dissolving the silica microspheres in absolute ethyl alcohol, performing ultrasonic dispersion for 10min, adding a silane coupling agent, continuously stirring for 35min, washing and drying to obtain modified silica microspheres;
s3: preparation of pretreated microspheres:
mixing and stirring chitosan, acetic acid and deionized water for 12 hours to obtain a chitosan solution; dissolving hydroxyl-terminated polydimethylsiloxane, dibutyltin dilaurate and ethyl orthosilicate in n-hexane, and stirring for 50min to obtain a solution A;
mixing and stirring an emulsifier and liquid paraffin for 3 hours at the stirring speed of 1100r/min, slowly dripping a chitosan solution, continuously stirring and emulsifying for 25 minutes at the stirring speed of 1050r/min, then adding sodium hydroxide, adjusting the pH value to 9, continuously stirring for 30 minutes, adding vanillin and the solution A, reacting and crosslinking for 6 hours, adding a waterproof auxiliary agent, ultrasonically dispersing for 15 minutes, stirring for 25 minutes after dispersion, then adding modified silicon dioxide microspheres, continuously stirring for 15 minutes, washing, and performing vacuum drying at the temperature of 30 ℃ to obtain modified microspheres;
taking the modified microspheres, 2' - (1, 2-ethanediylbis oxo) bisethanethiol and an absolute ethanol solution, stirring for 30min, placing in a vacuum box for low-pressure adsorption for 8h, washing after adsorption, performing centrifugal separation, and performing vacuum drying to obtain pretreated microspheres;
s4: dissolving N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in a mixed solution of deionized water and absolute ethyl alcohol to obtain a solution B; dissolving sodium alginate in EMS buffer solution, and stirring for 15min to obtain solution C;
s5: dissolving the pretreated microspheres with hydrochloric acid, adding sodium hydroxide, adjusting the pH value to 5, adding a 3, 4-dihydroxyphenylacetic acid solution, stirring for 15min, adding a solution C, continuously stirring for 40min, slowly dropwise adding a solution B, stirring for reacting for 11h, keeping the reaction pH value at 5, adding propyne, reacting for 24h at room temperature, dialyzing with hydrochloric acid, and freeze-drying to obtain modified gel;
s6: and (3) taking the modified gel and an oxidant, fully reacting for 3 hours, then adding a cross-linking agent and a photoinitiator, uniformly mixing, and then placing under ultraviolet light for irradiating for 15min to obtain the waterproof agent.
In the embodiment, the waterproof agent comprises the following raw materials: 40 parts of modified gel, 6 parts of oxidant, 9 parts of cross-linking agent and 5 parts of photoinitiator;
the modified gel comprises the following raw materials: by weight, 40 parts of pretreated microspheres, 30 parts of 3, 4-dihydroxy phenylacetic acid, 20 parts of N-hydroxysuccinimide, 20 parts of 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride, 25 parts of sodium alginate and 14 parts of propyne.
The modified microsphere comprises the following raw materials: by weight, 20 parts of modified silicon dioxide microspheres, 25 parts of chitosan, 12 parts of hydroxyl-terminated polydimethylsiloxane, 5 parts of dibutyltin dilaurate, 10 parts of ethyl orthosilicate, 5 parts of an emulsifier, 3-5 parts of liquid paraffin, 9 parts of vanillin and 14 parts of a waterproof auxiliary agent;
the mass ratio of the magnesium calcium carbonate to the sodium sulfate to the sodium silicate is (2): 9: 1; the silane coupling agent is 3- (trimethoxysilyl) propyl methacrylate, and the emulsifier is span-80; the oxidant is sodium periodate, and the cross-linking agent is four-arm polyethylene glycol mercaptan.
Experiment:
1. a sample of the water repellent prepared in example 1-3 was taken, and the water absorption ratio of the water repellent for 48 hours was measured according to JC474-2008 "mortar and concrete water repellent"; according to the compressive strength of the JC476-2001 detector, specific detection data are as follows:
2. the sample prepared in example 2 was mixed into mortar at a cement mixing amount of 9%, a concrete sample was prepared, and a blank control was arranged.
Compared with a blank control group, the water permeability pressure ratio is 254 percent, and the compressive strength ratio is 124 percent; after the concrete sample is continuously maintained for 28 days, the compressive strength recovery rate of the concrete sample is 83 percent, and the water permeability pressure recovery rate is 81 percent.
And (4) conclusion: the invention has reasonable process design, can effectively improve the waterproof and anti-seepage performance of concrete by modifying chitosan and sodium alginate and forming a compact double-gel network by utilizing Michael addition reaction and chemical click reaction, can self-repair a waterproof agent, can be widely applied to concrete construction, and has higher practicability.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (5)
1. A porous concrete waterproofing agent is characterized in that: the waterproof agent comprises the following raw materials in parts by weight: 25-40 parts of modified gel, 4-6 parts of oxidant, 5-9 parts of cross-linking agent and 3-5 parts of photoinitiator by weight;
the modified gel comprises the following raw materials in parts by weight: by weight, 30-40 parts of pretreated microspheres, 25-30 parts of 3, 4-dihydroxy phenylacetic acid, 15-20 parts of N-hydroxysuccinimide, 15-20 parts of 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride, 18-25 parts of sodium alginate and 10-14 parts of propyne;
the pretreatment microsphere is prepared from a modified microsphere, 2' - (1, 2-ethanediylbis oxo) bisethanethiol and absolute ethyl alcohol;
the modified microsphere comprises the following raw materials in parts by weight: 10-20 parts of modified silicon dioxide microspheres, 15-25 parts of chitosan, 5-12 parts of hydroxyl-terminated polydimethylsiloxane, 3-5 parts of dibutyltin dilaurate, 8-10 parts of ethyl orthosilicate, 3-5 parts of an emulsifier, 3-5 parts of liquid paraffin, 6-9 parts of vanillin and 10-14 parts of a waterproof auxiliary agent by weight;
the modified silicon dioxide microspheres are prepared from absolute ethyl alcohol, hexadecyl trimethyl ammonium bromide, ammonia water, ethyl orthosilicate and a silane coupling agent;
the waterproof auxiliary agent comprises magnesium calcium carbonate, sodium sulfate and sodium silicate, wherein the mass ratio of the magnesium calcium carbonate to the sodium sulfate to the sodium silicate is (2): (8-9): 1.
2. a porous concrete waterproofing agent according to claim 1, wherein: the silane coupling agent is 3- (trimethoxysilyl) propyl methacrylate, and the emulsifier is span-80.
3. A porous concrete waterproofing agent according to claim 1, wherein: the oxidant is sodium periodate, and the cross-linking agent is four-arm polyethylene glycol thiol.
4. The method for producing a porous concrete waterproofing agent according to claim 1, wherein: the method comprises the following steps:
1) preparing materials;
2) preparing modified silicon dioxide microspheres:
a) taking absolute ethyl alcohol and deionized water, stirring uniformly, adding hexadecyl trimethyl ammonium bromide and ammonia water, continuing stirring, slowly adding tetraethoxysilane, stirring and reacting in a water bath at 40 ℃, centrifuging, washing, and drying in vacuum to obtain silicon dioxide microspheres;
b) dissolving the silica microspheres in absolute ethyl alcohol, performing ultrasonic dispersion, adding a silane coupling agent, continuously stirring, washing and drying to obtain modified silica microspheres;
3) preparation of pretreated microspheres:
a) mixing and stirring chitosan, acetic acid and deionized water to obtain a chitosan solution; dissolving hydroxyl-terminated polydimethylsiloxane, dibutyltin dilaurate and ethyl orthosilicate in n-hexane, and stirring to obtain a solution A;
b) mixing and stirring an emulsifier and liquid paraffin, slowly dripping a chitosan solution, continuously stirring and emulsifying, adding sodium hydroxide, adjusting the pH value to 9, continuously stirring, adding vanillin and the solution A, reacting and crosslinking for 5-6h, adding a waterproof auxiliary agent, performing ultrasonic dispersion, stirring after dispersion, adding modified silicon dioxide microspheres, continuously stirring, washing, and performing vacuum drying to obtain modified microspheres;
c) taking the modified microspheres, 2' - (1, 2-ethanediylbis oxo) bisethanethiol and an absolute ethanol solution, stirring, placing in a vacuum box for low-pressure adsorption for 6-8h, washing after adsorption, performing centrifugal separation, and performing vacuum drying to obtain pretreated microspheres;
4) dissolving N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in a mixed solution of deionized water and absolute ethyl alcohol to obtain a solution B; dissolving sodium alginate and EMS buffer solution, and stirring to obtain solution C;
5) dissolving the pretreated microspheres with hydrochloric acid, adding sodium hydroxide, adjusting the pH value to 5, adding a 3, 4-dihydroxyphenylacetic acid solution, stirring, adding the solution C, continuously stirring, slowly dropwise adding the solution B, stirring for reaction, keeping the reaction pH value at 4.5-5, adding propyne, reacting at room temperature for 20-24h, dialyzing with hydrochloric acid, and freeze-drying to obtain modified gel;
6) and (3) taking the modified gel and an oxidant, fully reacting for 2-3h, adding a cross-linking agent and a photoinitiator, uniformly mixing, and irradiating for 10-15min under ultraviolet light to obtain the waterproof agent.
5. The method for producing a porous concrete waterproofing agent according to claim 4, wherein: the method comprises the following steps:
1) preparing materials;
a) weighing an oxidant, a cross-linking agent, a photoinitiator, 3, 4-dihydroxyphenylacetic acid, N-hydroxysuccinimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, sodium alginate and propyne according to a proportion for later use;
b) weighing 2, 2' - (1, 2-ethanediylbenzoxol) bisethanethiol, chitosan, hydroxyl-terminated polydimethylsiloxane, dibutyltin dilaurate, ethyl orthosilicate, an emulsifier, liquid paraffin and vanillin according to a proportion for later use;
c) weighing absolute ethyl alcohol, hexadecyl trimethyl ammonium bromide, ammonia water and a silane coupling agent according to a proportion for later use; mixing and stirring magnesium calcium carbonate, sodium sulfate and sodium silicate for 10-20min to obtain a waterproof auxiliary agent;
2) preparing modified silicon dioxide microspheres:
a) taking absolute ethyl alcohol and deionized water, stirring uniformly, adding hexadecyl trimethyl ammonium bromide and ammonia water, continuously stirring for 10-20min, slowly adding tetraethoxysilane, stirring for 2-2.5h in water bath at 40 ℃, centrifuging, washing, and drying in vacuum at 40 ℃ to obtain silicon dioxide microspheres;
b) dissolving the silicon dioxide microspheres in absolute ethyl alcohol, performing ultrasonic dispersion for 5-10min, adding a silane coupling agent, continuously stirring for 25-35min, washing and drying to obtain modified silicon dioxide microspheres;
3) preparation of pretreated microspheres:
a) mixing chitosan, acetic acid and deionized water, and stirring for 10-12h to obtain chitosan solution; dissolving hydroxyl-terminated polydimethylsiloxane, dibutyltin dilaurate and ethyl orthosilicate in n-hexane, and stirring for 40-50min to obtain a solution A;
b) mixing and stirring an emulsifier and liquid paraffin for 2-3h at the stirring speed of 1100r/min for 1000-25 min, slowly dropping a chitosan solution, continuously stirring and emulsifying for 20-25min at the stirring speed of 1050r/min for 950-950, adding sodium hydroxide, adjusting the pH value to 9, continuously stirring for 20-30min, adding vanillin and the solution A, reacting and crosslinking for 5-6h, adding a waterproof auxiliary agent, ultrasonically dispersing for 10-15min, stirring for 10-25min after dispersion, adding modified silica microspheres, continuously stirring for 10-15min, washing, and vacuum drying at 25-30 ℃ to obtain modified microspheres;
c) taking the modified microspheres, 2' - (1, 2-ethanediylbis oxo) bisethanethiol and an absolute ethanol solution, stirring for 20-30min, placing in a vacuum box for low-pressure adsorption for 6-8h, washing after adsorption, performing centrifugal separation, and performing vacuum drying to obtain pretreated microspheres;
4) dissolving N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in a mixed solution of deionized water and absolute ethyl alcohol to obtain a solution B; dissolving sodium alginate in EMS buffer solution, and stirring for 10-15min to obtain solution C;
5) dissolving pretreated microspheres with hydrochloric acid, adding sodium hydroxide, adjusting pH to 5, adding a 3, 4-dihydroxyphenylacetic acid solution, stirring for 10-15min, adding a solution C, continuously stirring for 30-40min, slowly dropwise adding a solution B, stirring for reacting for 10-11h, keeping the reaction pH at 4.5-5, adding propyne, reacting for 20-24h at room temperature, dialyzing with hydrochloric acid, and freeze-drying to obtain a modified gel;
6) and (3) taking the modified gel and an oxidant, fully reacting for 2-3h, adding a cross-linking agent and a photoinitiator, uniformly mixing, and irradiating for 10-15min under ultraviolet light to obtain the waterproof agent.
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| CN111995307B (en) * | 2020-08-31 | 2022-04-29 | 湖北工业大学 | Preparation method of protective coating material for marine peripheral buildings |
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| CN115159926B (en) * | 2022-07-25 | 2023-08-22 | 南京佳彩恒环保材料有限公司 | Crack-resistant micro-cement with low shrinkage rate |
| CN115043612B (en) * | 2022-08-12 | 2022-11-01 | 甘肃省交通规划勘察设计院股份有限公司 | Breathable permeable concrete protective agent and preparation method thereof |
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