CN113912340B - Low-temperature anti-freezing concrete and production process thereof - Google Patents
Low-temperature anti-freezing concrete and production process thereof Download PDFInfo
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- CN113912340B CN113912340B CN202111314489.6A CN202111314489A CN113912340B CN 113912340 B CN113912340 B CN 113912340B CN 202111314489 A CN202111314489 A CN 202111314489A CN 113912340 B CN113912340 B CN 113912340B
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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
- C04B28/02—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 containing hydraulic cements other than calcium sulfates
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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
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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
Abstract
The invention discloses a low-temperature antifreezing concrete and a production process thereof, wherein the low-temperature antifreezing concrete comprises the following raw materials in parts by weight: 350 parts of cement, 10-15 parts of a high-efficiency water reducing agent, 50-60 parts of a strengthening toughening agent, 10-15 parts of triethylene tetramine, 130 parts of fly ash, 400 parts of medium sand and 150 parts of water; this water-reducing agent can destroy the flocculation structure of cement granule when mixing with the concrete to release the moisture of wrapping up in the cement flocculating constituent and then promote the mobility of concrete, improve the workability of concrete, make concrete structure become closely knit, increased the intensity of concrete, should strengthen the synergist and use epoxy as the basement, can promote the frost resisting effect of concrete, contain a large amount of flexible group simultaneously on this molecular chain and promoted the toughness of strengthening the synergist, and then promoted the toughness of concrete.
Description
Technical Field
The invention relates to the technical field of concrete preparation, in particular to low-temperature antifreezing concrete and a production process thereof.
Background
The concrete is an engineering composite material formed by cementing aggregate into a whole by a cementing material, has the characteristics of rich raw materials, low price, simple production process and the like, is more and more used, and is widely applied to the fields of buildings, machinery, geothermal engineering and the like because the concrete also has the characteristics of high compressive strength, good durability and the like. With the continuous development of concrete composition materials, people not only can fill the compression resistance of heavy concrete, but also can fill the durability, frost resistance, fire and explosion resistance, water seepage resistance, corrosion resistance, heat preservation and other properties of the heavy concrete. High-strength concrete is currently a hot spot of domestic and foreign research as a construction application technology, and has become a mark for the development of the construction technology level. High-strength concrete is a kind of high-performance concrete, and refers to concrete with high or very high compressive strength, and the range is not strictly limited, and concrete with a strength grade greater than C50 is generally called high-strength concrete.
The existing concrete has poor anti-freezing effect in cold regions with cold temperature, so that the mechanical performance of the concrete is greatly reduced, and the normal use of buildings is influenced.
Disclosure of Invention
The invention aims to provide low-temperature antifreezing concrete and a production process thereof, and solves the problems of poor low-temperature antifreezing effect and low mechanical property of the existing stage concrete through a high-efficiency water reducing agent and a strengthening toughening agent.
The purpose of the invention can be realized by the following technical scheme:
the low-temperature antifreezing concrete comprises the following raw materials in parts by weight: 350 parts of cement, 10-15 parts of a high-efficiency water reducing agent, 50-60 parts of a strengthening toughening agent, 10-15 parts of triethylene tetramine, 130 parts of fly ash, 400 parts of medium sand and 150 parts of water;
the low-temperature anti-freezing concrete is prepared by the following steps:
weighing the raw materials, and uniformly mixing the raw materials to obtain the low-temperature anti-freezing concrete.
Further, the high-efficiency water reducing agent is prepared by the following steps:
step A1: uniformly mixing p-chloromethyl styrene, maleic anhydride, sodium methallyl sulfonate, dibenzoyl peroxide and toluene, reacting for 5-7h at the rotation speed of 150-200r/min and the temperature of 70-80 ℃, adding polyethylene glycol monomethyl ether and a sodium hydroxide solution, reacting for 1-1.5h at the temperature of 55-65 ℃, and adjusting the pH value of a reaction solution to 7 to prepare an intermediate 1;
The reaction process is as follows:
step A2: uniformly mixing concentrated sulfuric acid, p-aminobenzoic acid and deionized water, stirring and dropwise adding a sodium nitrite solution under the conditions that the rotation speed is 200-300r/min and the temperature is 1-3 ℃, stirring for 10-15min to prepare a diazo liquid, uniformly mixing concentrated sulfuric acid and deionized water, stirring and dropwise adding a diazo liquid under the conditions that the rotation speed is 150-200r/min and the temperature is 75-80 ℃, stirring for 5-10min, cooling to the temperature of 0-3 ℃, and continuously stirring for 10-15min to prepare an intermediate 2;
the reaction process is as follows:
step A3: adding naphthalene into a reaction kettle, stirring and adding concentrated sulfuric acid at the rotation speed of 150-fluid-reservoir temperature of 200r/min and the temperature of 135-fluid-reservoir temperature of 145 ℃, heating to the temperature of 150-fluid-reservoir temperature of 160 ℃, preserving heat for 2-4h to prepare an intermediate 3, uniformly mixing the intermediate 3 and the concentrated sulfuric acid, stirring and adding a formaldehyde saturated aqueous solution and the intermediate 2 at the rotation speed of 200-fluid-reservoir temperature of 300r/min and the temperature of 100-fluid-reservoir temperature of 110 ℃, preserving heat and reacting for 6-8h to prepare an intermediate 4;
the reaction process is as follows:
step A4: dissolving the intermediate 4 in N, N-dimethylformamide, stirring and adding ethylenediamine and 1-hydroxybenzotriazole under the conditions that the rotation speed is 150-200r/min and the temperature is 40-50 ℃, reacting for 3-5h, adding the intermediate 1, continuing to react for 5-7h, adding a sodium hydroxide solution, and adjusting the pH value of the reaction solution to 9-10 to prepare the high-efficiency water reducing agent.
The reaction process is as follows:
further, the molar ratio of the p-chloromethyl styrene to the maleic anhydride to the sodium methallyl sulfonate to the polyethylene glycol monomethyl ether in the step A1 is 1:2:0.36:1, the amount of the dibenzoyl peroxide is 3% of the sum of the p-chloromethyl styrene to the maleic anhydride to the sodium methallyl sulfonate to the polyethylene glycol monomethyl ether, the amount of the sodium hydroxide solution is 10% of the sum of the p-chloromethyl styrene to the maleic anhydride to the sodium methallyl sulfonate to the polyethylene glycol monomethyl ether, and the mass fraction of the sodium hydroxide solution is 25%.
Further, the use amount ratio of the concentrated sulfuric acid, the p-aminobenzoic acid, the deionized water and the sodium nitrite solution in the step A2 is 8mL:5g:16mL:10mL, the mass fraction of the concentrated sulfuric acid is 98%, the mass fraction of the sodium nitrite solution is 25%, and the use amount volume ratio of the concentrated sulfuric acid, the deionized water and the diazonium solution is 16:25: 35.
Further, the molar ratio of the naphthalene to the concentrated sulfuric acid in the step A3 is 1:1.3-1.5, and the molar ratio of the intermediate 3, the concentrated sulfuric acid, the formaldehyde and the intermediate 2 is 1:0.25-0.3:0.23-0.25: 0.4-0.5.
Further, the mass ratio of the intermediate 4, the ethylenediamine and the intermediate 1 in the step A4 is 2:5: 1.
Further, the strengthening and toughening agent is prepared by the following steps:
step B1: adding nitrobenzene, acetone and sulfuric acid solution into a reaction kettle, reacting for 6-8h at 35-45 ℃ to obtain an intermediate 5, uniformly mixing the intermediate 5, potassium permanganate and deionized water, performing reflux reaction for 3-4h at the rotation speed of 150-200r/min and the temperature of 110-120 ℃ to obtain an intermediate 6, uniformly mixing the intermediate 6, octadecylamine, 1-hydroxybenzotriazole and N, N-dimethylformamide, and reacting for 3-5h at the rotation speed of 200-300r/min and the temperature of 40-50 ℃ to obtain an intermediate 7;
the reaction process is as follows:
step B2: uniformly mixing the intermediate 7, tin powder and concentrated hydrochloric acid, reacting for 30-40min under the conditions that the rotation speed is 150-200r/min and the temperature is 100-110 ℃, adjusting the pH value of a reaction solution to be alkaline to obtain an intermediate 8, dissolving the intermediate 8 in dichloromethane, stirring and adding triphosgene solution under the conditions that the rotation speed is 300-500r/min and the temperature is 20-25 ℃, keeping the pH value of the reaction solution at 11-12, and reacting for 2-3h to obtain an intermediate 9;
the reaction process is as follows:
step B3: dissolving epoxy resin E-51 in xylene, adding intermediate 9 and dibutyltin dilaurate, reacting for 2-3h at the rotation speed of 200-300r/min and the temperature of 70-80 ℃, and distilling at the temperature of 140-150 ℃ to remove the solvent to obtain the reinforced toughening agent.
The reaction process is as follows:
further, the molar ratio of the nitrobenzene to the acetone to the sulfuric acid solution in the step B1 is 2:1:6, the mass fraction of the sulfuric acid solution is 40%, the molar ratio of the intermediate 5 to the potassium permanganate to the deionized water is 5g:8g:100mL, and the molar ratio of the intermediate 6 to the octadecylamine is 1: 2.
Furthermore, the dosage ratio of the intermediate 7, the tin powder and the concentrated hydrochloric acid in the step B2 is 3.6g to 5.3g to 20mL, the mass fraction of the concentrated hydrochloric acid is 36%, and the dosage molar ratio of the intermediate 8 to the triphosgene is 1: 3.
Further, the molar ratio of the hydroxyl groups on the epoxy resin E-51 to the isocyanate groups on the intermediate 9 in the step B3 was 1:1.1, and dibutyltin dilaurate was used in an amount of 5% by mass of the sum of the epoxy resin E-51 and the intermediate 8.
The invention has the beneficial effects that: the invention prepares a high-efficiency water reducing agent in the process of preparing low-temperature antifreeze concrete, the high-efficiency water reducing agent takes p-chloromethyl styrene, maleic anhydride and sodium methallylsulfonate as raw materials to polymerize, then the raw materials react with polyethylene glycol monomethyl ether to prepare an intermediate 1, p-aminobenzoic acid is processed to prepare diazo liquid, the diazo liquid is further processed by concentrated sulfuric acid to prepare an intermediate 2, naphthalene and concentrated sulfuric acid react through temperature control to prepare an intermediate 3, the intermediate 3 and the intermediate 2 react to prepare an intermediate 4, the intermediate 4 and one amino group of ethylenediamine are dehydrated and condensed, the intermediate 1 is added, the residual amino group of the ethylenediamine and carboxyl on the intermediate 1 are dehydrated and condensed to prepare the water reducing agent, the water reducing agent can destroy the flocculation structure of cement particles when being mixed with the concrete, thereby releasing the water wrapped in the cement floc to further improve the fluidity of the concrete, the workability of concrete is improved, a concrete structure becomes compact, the strength of the concrete is increased, a strengthening toughening agent is prepared, nitrobenzene reacts with acetone to prepare an intermediate 5, the intermediate 5 is oxidized to prepare an intermediate 6, the intermediate 6 and octadecylamine undergo dehydration condensation to prepare an intermediate 7, the intermediate 7 is reduced to prepare an intermediate 8, the intermediate 8 reacts with triphosgene to prepare an intermediate 9, the intermediate 9 reacts with epoxy resin E-51 to prepare a strengthening synergist, the strengthening synergist takes epoxy resin as a substrate, the anti-freezing effect of the concrete can be improved, and meanwhile, a large number of flexible groups are contained on a molecular chain to improve the toughness of the strengthening synergist and further improve the toughness of the concrete.
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 low-temperature antifreezing concrete comprises the following raw materials in parts by weight: 300 parts of cement, 10 parts of a strong water reducing agent, 50 parts of a strengthening toughening agent, 10 parts of triethylene tetramine, 120 parts of fly ash, 300 parts of medium sand and 100 parts of water;
the low-temperature anti-freezing concrete is prepared by the following steps:
weighing the raw materials, and uniformly mixing the raw materials to obtain the low-temperature anti-freezing concrete.
The high-efficiency water reducing agent is prepared by the following steps:
step A1: uniformly mixing p-chloromethyl styrene, maleic anhydride, sodium methallyl sulfonate, dibenzoyl peroxide and toluene, reacting for 5 hours at the rotation speed of 150r/min and the temperature of 70 ℃, adding polyethylene glycol monomethyl ether and a sodium hydroxide solution, reacting for 1 hour at the temperature of 55 ℃, and adjusting the pH value of a reaction solution to be 7 to prepare an intermediate 1;
Step A2: uniformly mixing concentrated sulfuric acid, p-aminobenzoic acid and deionized water, stirring and dropwise adding a sodium nitrite solution under the conditions of a rotation speed of 200r/min and a temperature of 1 ℃, stirring for 10min to prepare a diazo liquid, uniformly mixing concentrated sulfuric acid and deionized water, stirring and dropwise adding a diazo liquid under the conditions of a rotation speed of 150r/min and a temperature of 75 ℃, stirring for 5min, cooling to a temperature of 0 ℃, and continuously stirring for 10min to prepare an intermediate 2;
step A3: adding naphthalene into a reaction kettle, stirring and adding concentrated sulfuric acid at the rotation speed of 150r/min and the temperature of 135 ℃, heating to the temperature of 150 ℃, preserving heat for 2 hours to prepare an intermediate 3, uniformly mixing the intermediate 3 and the concentrated sulfuric acid, stirring and adding a formaldehyde saturated aqueous solution and the intermediate 2 at the rotation speed of 200r/min and the temperature of 100 ℃, preserving heat and reacting for 6 hours to prepare an intermediate 4;
step A4: dissolving the intermediate 4 in N, N-dimethylformamide, stirring and adding ethylenediamine and 1-hydroxybenzotriazole under the conditions that the rotating speed is 150r/min and the temperature is 40 ℃, reacting for 3 hours, adding the intermediate 1, continuing to react for 5 hours, adding a sodium hydroxide solution, and adjusting the pH value of a reaction solution to 9 to prepare the high-efficiency water reducing agent.
The reinforced toughening agent is prepared by the following steps:
step B1: adding nitrobenzene, acetone and sulfuric acid solution into a reaction kettle, reacting for 6 hours at the temperature of 35 ℃ to obtain an intermediate 5, uniformly mixing the intermediate 5, potassium permanganate and deionized water, performing reflux reaction for 3 hours at the rotation speed of 150r/min and the temperature of 110 ℃ to obtain an intermediate 6, uniformly mixing the intermediate 6, octadecylamine, 1-hydroxybenzotriazole and N, N-dimethylformamide, and reacting for 3 hours at the rotation speed of 200r/min and the temperature of 40 ℃ to obtain an intermediate 7;
step B2: uniformly mixing the intermediate 7, tin powder and concentrated hydrochloric acid, reacting for 30min at the rotation speed of 150r/min and the temperature of 100 ℃, adjusting the pH value of a reaction solution to be alkaline to obtain an intermediate 8, dissolving the intermediate 8 in dichloromethane, stirring and adding a triphosgene solution at the rotation speed of 300r/min and the temperature of 20 ℃, keeping the pH value of the reaction solution at 11, and reacting for 2h to obtain an intermediate 9;
step B3: dissolving epoxy resin E-51 in dimethylbenzene, adding an intermediate 9 and dibutyltin dilaurate, reacting for 2 hours at the rotation speed of 200r/min and the temperature of 70 ℃, and distilling to remove the solvent at the temperature of 140 ℃ to obtain the reinforced toughening agent.
Example 2
The low-temperature antifreezing concrete comprises the following raw materials in parts by weight: 330 parts of cement, 13 parts of a high-efficiency water reducing agent, 55 parts of a strengthening toughening agent, 13 parts of triethylene tetramine, 125 parts of fly ash, 350 parts of medium sand and 125 parts of water;
the low-temperature anti-freezing concrete is prepared by the following steps:
weighing the raw materials, and uniformly mixing the raw materials to obtain the low-temperature antifreeze concrete.
The high-efficiency water reducing agent is prepared by the following steps:
step A1: uniformly mixing p-chloromethyl styrene, maleic anhydride, sodium methallyl sulfonate, dibenzoyl peroxide and toluene, reacting for 6 hours at the rotation speed of 180r/min and the temperature of 75 ℃, adding polyethylene glycol monomethyl ether and a sodium hydroxide solution, reacting for 1.3 hours at the temperature of 60 ℃, and adjusting the pH value of a reaction solution to be 7 to prepare an intermediate 1;
step A2: uniformly mixing concentrated sulfuric acid, p-aminobenzoic acid and deionized water, stirring and dropwise adding a sodium nitrite solution under the conditions of a rotation speed of 200r/min and a temperature of 2 ℃, stirring for 13min to prepare a diazo liquid, uniformly mixing concentrated sulfuric acid and deionized water, stirring and dropwise adding a diazo liquid under the conditions of a rotation speed of 180r/min and a temperature of 78 ℃, stirring for 8min, cooling to a temperature of 1 ℃, and continuously stirring for 10-15min to prepare an intermediate 2;
Step A3: adding naphthalene into a reaction kettle, stirring and adding concentrated sulfuric acid at the rotation speed of 180r/min and the temperature of 140 ℃, heating to the temperature of 155 ℃, preserving heat for 3 hours to prepare an intermediate 3, uniformly mixing the intermediate 3 and the concentrated sulfuric acid, stirring and adding a formaldehyde saturated aqueous solution and the intermediate 2 at the rotation speed of 300r/min and the temperature of 105 ℃, preserving heat and reacting for 7 hours to prepare an intermediate 4;
step A4: dissolving the intermediate 4 in N, N-dimethylformamide, stirring and adding ethylenediamine and 1-hydroxybenzotriazole under the conditions that the rotating speed is 180r/min and the temperature is 45 ℃, reacting for 4 hours, adding the intermediate 1, continuing to react for 6 hours, adding a sodium hydroxide solution, and adjusting the pH value of a reaction solution to 10 to prepare the high-efficiency water reducing agent.
The reinforced toughening agent is prepared by the following steps:
step B1: adding nitrobenzene, acetone and sulfuric acid solution into a reaction kettle, reacting for 7 hours at the temperature of 40 ℃ to obtain an intermediate 5, uniformly mixing the intermediate 5, potassium permanganate and deionized water, performing reflux reaction for 3 hours at the rotation speed of 180r/min and the temperature of 115 ℃ to obtain an intermediate 6, uniformly mixing the intermediate 6, octadecylamine, 1-hydroxybenzotriazole and N, N-dimethylformamide, and reacting for 4 hours at the rotation speed of 300r/min and the temperature of 45 ℃ to obtain an intermediate 7;
Step B2: uniformly mixing the intermediate 7, tin powder and concentrated hydrochloric acid, reacting for 35min at the rotation speed of 180r/min and the temperature of 105 ℃, adjusting the pH value of a reaction solution to be alkaline to obtain an intermediate 8, dissolving the intermediate 8 in dichloromethane, stirring and adding a triphosgene solution at the rotation speed of 400r/min and the temperature of 23 ℃, keeping the pH value of the reaction solution at 12, and reacting for 2h to obtain an intermediate 9;
step B3: dissolving epoxy resin E-51 in dimethylbenzene, adding an intermediate 9 and dibutyltin dilaurate, reacting for 2 hours at the rotation speed of 300r/min and the temperature of 75 ℃, and distilling to remove the solvent at the temperature of 145 ℃ to obtain the reinforced toughening agent.
Example 3
The low-temperature antifreezing concrete comprises the following raw materials in parts by weight: 350 parts of cement, 15 parts of a strong water reducing agent, 60 parts of a strengthening toughening agent, 15 parts of triethylene tetramine, 130 parts of fly ash, 400 parts of medium sand and 150 parts of water;
the low-temperature anti-freezing concrete is prepared by the following steps:
weighing the raw materials, and uniformly mixing the raw materials to obtain the low-temperature anti-freezing concrete.
The high-efficiency water reducing agent is prepared by the following steps:
step A1: uniformly mixing p-chloromethyl styrene, maleic anhydride, sodium methallyl sulfonate, dibenzoyl peroxide and toluene, reacting for 7 hours at the rotation speed of 180r/min and the temperature of 80 ℃, adding polyethylene glycol monomethyl ether and a sodium hydroxide solution, reacting for 1.5 hours at the temperature of 65 ℃, and adjusting the pH value of a reaction solution to be 7 to prepare an intermediate 1;
Step A2: uniformly mixing concentrated sulfuric acid, p-aminobenzoic acid and deionized water, stirring and dripping a sodium nitrite solution under the conditions of a rotating speed of 300r/min and a temperature of 3 ℃, stirring for 15min to prepare a diazo liquid, uniformly mixing concentrated sulfuric acid and deionized water, stirring and dripping a diazo liquid under the conditions of a rotating speed of 200r/min and a temperature of 80 ℃, stirring for 10min, cooling to the temperature of 3 ℃, and continuously stirring for 15min to prepare an intermediate 2;
step A3: adding naphthalene into a reaction kettle, stirring and adding concentrated sulfuric acid at the rotation speed of 200r/min and the temperature of 145 ℃, heating to 160 ℃, preserving heat for 4 hours to prepare an intermediate 3, uniformly mixing the intermediate 3 and the concentrated sulfuric acid, stirring and adding a formaldehyde saturated aqueous solution and the intermediate 2 at the rotation speed of 300r/min and the temperature of 110 ℃, preserving heat and reacting for 8 hours to prepare an intermediate 4;
step A4: dissolving the intermediate 4 in N, N-dimethylformamide, stirring and adding ethylenediamine and 1-hydroxybenzotriazole under the conditions that the rotation speed is 200r/min and the temperature is 50 ℃, reacting for 5 hours, adding the intermediate 1, continuing to react for 7 hours, adding a sodium hydroxide solution, and adjusting the pH value of a reaction solution to 10 to prepare the high-efficiency water reducing agent.
The reinforced toughening agent is prepared by the following steps:
step B1: adding nitrobenzene, acetone and sulfuric acid solution into a reaction kettle, reacting for 8 hours at the temperature of 45 ℃ to obtain an intermediate 5, uniformly mixing the intermediate 5, potassium permanganate and deionized water, performing reflux reaction for 4 hours at the rotation speed of 200r/min and the temperature of 120 ℃ to obtain an intermediate 6, uniformly mixing the intermediate 6, octadecylamine, 1-hydroxybenzotriazole and N, N-dimethylformamide, and reacting for 5 hours at the rotation speed of 300r/min and the temperature of 50 ℃ to obtain an intermediate 7;
step B2: uniformly mixing the intermediate 7, tin powder and concentrated hydrochloric acid, reacting for 40min at the rotation speed of 200r/min and the temperature of 110 ℃, adjusting the pH value of a reaction solution to be alkaline to obtain an intermediate 8, dissolving the intermediate 8 in dichloromethane, stirring and adding a triphosgene solution at the rotation speed of 500r/min and the temperature of 25 ℃, keeping the pH value of the reaction solution at 12, and reacting for 3h to obtain an intermediate 9;
step B3: dissolving epoxy resin E-51 in xylene, adding an intermediate 9 and dibutyltin dilaurate, reacting for 3 hours at the rotation speed of 300r/min and the temperature of 80 ℃, and distilling to remove the solvent at the temperature of 150 ℃ to obtain the reinforced toughening agent.
Comparative example 1
This comparative example compared to example 1 using calcium lignosulfonate instead of the high efficiency water reducer.
Comparative example 2
This comparative example compared to example 1 using epoxy E-51 in place of the reinforcing toughener.
Comparative example 3
This comparative example is the frost resistant concrete disclosed in chinese patent CN 112125994A.
The freeze-thaw cycles of the samples of the freeze-thaw concretes prepared in examples 1 to 3 and comparative examples 1 to 3 were performed for 25 times, 50 times, 100 times, 200 times, 300 times and 400 times according to the surface of GB/T50082-2009, and the compressive strength and the flexural strength of the concrete after the freeze-thaw cycles were respectively measured, and the results are shown in the following table;
as can be seen from the above table, the frost-resistant concrete prepared in the embodiments 1 to 3 has a good frost-resistant effect, and simultaneously, the compressive strength and the breaking strength of the frost-resistant concrete are high, so that the service life of the concrete is greatly prolonged.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (2)
1. A low-temperature frost-resistant concrete is characterized in that: the feed comprises the following raw materials in parts by weight: 350 parts of cement, 10-15 parts of a high-efficiency water reducing agent, 50-60 parts of a strengthening toughening agent, 10-15 parts of triethylene tetramine, 130 parts of fly ash, 400 parts of medium sand and 150 parts of water;
The high-efficiency water reducing agent is prepared by the following steps:
step A1: uniformly mixing p-chloromethyl styrene, maleic anhydride, sodium methallyl sulfonate, dibenzoyl peroxide and toluene, reacting for 5-7h at the rotation speed of 150-200r/min and the temperature of 70-80 ℃, adding polyethylene glycol monomethyl ether and a sodium hydroxide solution, reacting for 1-1.5h at the temperature of 55-65 ℃, and adjusting the pH value of a reaction solution to 7 to prepare an intermediate 1;
step A2: uniformly mixing concentrated sulfuric acid, p-aminobenzoic acid and deionized water, stirring and dropwise adding a sodium nitrite solution under the conditions that the rotation speed is 200-300r/min and the temperature is 1-3 ℃, stirring for 10-15min to prepare a diazo liquid, uniformly mixing concentrated sulfuric acid and deionized water, stirring and dropwise adding a diazo liquid under the conditions that the rotation speed is 150-200r/min and the temperature is 75-80 ℃, stirring for 5-10min, cooling to the temperature of 0-3 ℃, and continuously stirring for 10-15min to prepare an intermediate 2;
step A3: adding naphthalene into a reaction kettle, stirring and adding concentrated sulfuric acid at the rotation speed of 150-fluid-reservoir temperature of 200r/min and the temperature of 135-fluid-reservoir temperature of 145 ℃, heating to the temperature of 150-fluid-reservoir temperature of 160 ℃, preserving heat for 2-4h to prepare an intermediate 3, uniformly mixing the intermediate 3 and the concentrated sulfuric acid, stirring and adding a formaldehyde saturated aqueous solution and the intermediate 2 at the rotation speed of 200-fluid-reservoir temperature of 300r/min and the temperature of 100-fluid-reservoir temperature of 110 ℃, preserving heat and reacting for 6-8h to prepare an intermediate 4;
Step A4: dissolving the intermediate 4 in N, N-dimethylformamide, stirring and adding ethylenediamine and 1-hydroxybenzotriazole under the conditions that the rotation speed is 150-200r/min and the temperature is 40-50 ℃, reacting for 3-5h, adding the intermediate 1, continuing to react for 5-7h, adding a sodium hydroxide solution, and adjusting the pH value of the reaction solution to 9-10 to prepare the strong-effect water reducer;
the molar ratio of the p-chloromethyl styrene to the maleic anhydride to the sodium methallyl sulfonate to the polyethylene glycol monomethyl ether in the step A1 is 1:2:0.36:1, the amount of the dibenzoyl peroxide is 3% of the mass sum of the p-chloromethyl styrene, the maleic anhydride, the sodium methallyl sulfonate and the polyethylene glycol monomethyl ether, the amount of the sodium hydroxide solution is 10% of the mass sum of the p-chloromethyl styrene, the maleic anhydride, the sodium methallyl sulfonate and the polyethylene glycol monomethyl ether, and the mass fraction of the sodium hydroxide solution is 25%; the using amount ratio of the concentrated sulfuric acid, the p-aminobenzoic acid, the deionized water and the sodium nitrite solution in the step A2 is 8mL:5g:16mL:10mL, the mass fraction of the concentrated sulfuric acid is 98%, the mass fraction of the sodium nitrite solution is 25%, and the using amount volume ratio of the concentrated sulfuric acid, the deionized water and the diazo liquid is 16:25: 35; the molar ratio of the naphthalene to the concentrated sulfuric acid in the step A3 is 1:1.3-1.5, and the molar ratio of the intermediate 3 to the concentrated sulfuric acid to the formaldehyde to the intermediate 2 is 1:0.25-0.3:0.23-0.25: 0.4-0.5; the mass ratio of the intermediate 4, the ethylenediamine and the intermediate 1 in the step A4 is 2:5: 1;
The strengthening toughening agent is prepared by the following steps:
step B1: adding nitrobenzene, acetone and sulfuric acid solution into a reaction kettle, reacting for 6-8h at the temperature of 35-45 ℃ to obtain an intermediate 5, uniformly mixing the intermediate 5, potassium permanganate and deionized water, performing reflux reaction for 3-4h at the rotation speed of 150-200r/min and the temperature of 110-120 ℃ to obtain an intermediate 6, uniformly mixing the intermediate 6, octadecylamine, 1-hydroxybenzotriazole and N, N-dimethylformamide, and reacting for 3-5h at the rotation speed of 200-300r/min and the temperature of 40-50 ℃ to obtain an intermediate 7;
step B2: uniformly mixing the intermediate 7, tin powder and concentrated hydrochloric acid, reacting for 30-40min under the conditions that the rotating speed is 150-200r/min and the temperature is 100-110 ℃, adjusting the pH value of a reaction solution to be alkaline to prepare an intermediate 8, dissolving the intermediate 8 in dichloromethane, stirring and adding triphosgene solution under the conditions that the rotating speed is 300-500r/min and the temperature is 20-25 ℃, keeping the pH value of the reaction solution at 11-12, and reacting for 2-3h to prepare an intermediate 9;
step B3: dissolving epoxy resin E-51 in xylene, adding an intermediate 9 and dibutyltin dilaurate, reacting for 2-3h at the rotation speed of 200-300r/min and the temperature of 70-80 ℃, and distilling at the temperature of 140-150 ℃ to remove the solvent to obtain the reinforced toughening agent;
In the step B1, the molar ratio of the nitrobenzene to the acetone to the sulfuric acid solution is 2:1:6, the mass fraction of the sulfuric acid solution is 40%, the molar ratio of the intermediate 5 to the potassium permanganate to the deionized water is 5g:8g:100mL, and the molar ratio of the intermediate 6 to the octadecylamine is 1: 2; the using amount ratio of the intermediate 7, the tin powder and the concentrated hydrochloric acid in the step B2 is 3.6g to 5.3g to 20mL, the mass fraction of the concentrated hydrochloric acid is 36%, and the using amount molar ratio of the intermediate 8 to the triphosgene is 1 to 3; the molar ratio of the hydroxyl groups on the epoxy resin E-51 to the isocyanate groups on the intermediate 9 described in step B3 was 1:1.1 and dibutyltin dilaurate was used in an amount of 5% of the sum of the masses of epoxy resin E-51 and intermediate 8.
2. The process for preparing low temperature frost-resistant concrete according to claim 1, wherein: the method specifically comprises the following steps:
weighing cement, a powerful water reducing agent, a strengthening toughening agent, triethylene tetramine, fly ash, medium sand and water, and uniformly mixing the raw materials to prepare the low-temperature antifreezing concrete.
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| CN112174589A (en) * | 2020-10-10 | 2021-01-05 | 杭州瑞鼎建材有限公司 | Anti-crack concrete and preparation method thereof |
| CN113480285A (en) * | 2021-08-16 | 2021-10-08 | 安徽列首新材料科技有限公司 | Concrete sealing curing agent and preparation method thereof |
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| CN109970920A (en) * | 2018-06-08 | 2019-07-05 | 科之杰新材料集团有限公司 | A kind of sulfonic acid modified polycarboxylate water-reducer and preparation method thereof |
| CN112174589A (en) * | 2020-10-10 | 2021-01-05 | 杭州瑞鼎建材有限公司 | Anti-crack concrete and preparation method thereof |
| CN113480285A (en) * | 2021-08-16 | 2021-10-08 | 安徽列首新材料科技有限公司 | Concrete sealing curing agent and preparation method thereof |
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