CN115286282B - Composite concrete foaming agent based on animal protein modification - Google Patents
Composite concrete foaming agent based on animal protein modification Download PDFInfo
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- CN115286282B CN115286282B CN202210629065.7A CN202210629065A CN115286282B CN 115286282 B CN115286282 B CN 115286282B CN 202210629065 A CN202210629065 A CN 202210629065A CN 115286282 B CN115286282 B CN 115286282B
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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
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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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to the technical field of foaming agents, and discloses a composite concrete foaming agent based on animal protein modification, which consists of a basic component, a modified protein-based foaming agent, a foam stabilizing component, an early strength component and water, wherein the foaming agent comprises the following components in parts by weight: 15-25 parts of basic components, 5-15 parts of modified protein-based foaming agents, 3-7 parts of foam stabilizing components, 10-15 parts of early strength components and 40-70 parts of water; the basic components are alpha-sodium alkenyl sulfonate, sodium dodecyl sulfate and fatty alcohol polyoxyethylene ether sodium sulfate according to the mass ratio of 1 (1-2) (1.5-3.0); the foam stabilizing component is at least one of dodecanol and cellulose ether; the early strength component is composed of sodium sulfate and starch-based graft copolymer according to the mass ratio of (1-5): 1. The composite concrete foaming agent has excellent foaming capacity, and can be applied to foam concrete, so that the formed foam concrete has no die collapse phenomenon, high strength, good stability and wide application prospect.
Description
Technical Field
The invention relates to the technical field of foaming agents, in particular to a composite concrete foaming agent based on animal protein modification.
Background
The foam concrete is prepared by adding foam prepared by a foaming agent into cement paste or cement mortar in a physical and mechanical foaming mode, uniformly stirring, pouring into various specifications, and curing to form the light concrete with a large number of closed air holes, and has the characteristics of light weight, good heat preservation and heat insulation performance, good sound insulation and fire resistance, good shock resistance, environmental protection and the like, and is widely used at present. In the preparation process of foam concrete, the quality of the foaming agent plays a crucial role. The foaming agent is a substance which can lead the water solution to generate a large amount of foam under the condition of introducing air by mechanical force, and the substance is actually the surface active action of the foaming agent, and cannot be foamed without the surface active action, namely cannot become the foaming agent, and the surface active is the core of foaming.
At present, the foaming agent used in foam concrete has a plurality of types, mainly including rosin soaps, synthetic surfactants and proteins, but the existing foaming agent has certain disadvantages, for example, chinese patent CN2010101413836 discloses a nonionic concrete foaming agent and a preparation method thereof, the foaming agent prepared by the method has the characteristics of large foaming multiple under strong stirring, long foam stability time, adjustable concentration of the concrete foaming agent according to the actual construction requirement, simple synthesis process, difficult deterioration, high stability and the like, but the foaming agent has higher requirements on raw materials, complex preparation process, and needs to input a special reaction generator, so that the production cost is too high, and the prepared foaming agent has the disadvantages of incomplete performance, single components and functions and cannot completely meet the actual foam concrete production requirement; for example, chinese patent CN2012104160231 discloses a compound animal and plant protein foaming agent, and the performance of the compound protein foaming agent prepared by using animal and plant protein is better than that of the single animal or plant protein foaming agent, so as to solve the problem that the comprehensive performance of the single protein component foaming agent is not high, but the foaming agent is easy to shrink, sink, collapse and deform when preparing foam concrete, especially lower density foam concrete, and the fluidity of the foam concrete is poor, resulting in insufficient compactness of the concrete, so that the strength of the concrete cannot meet the requirements.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a composite concrete foaming agent based on animal protein modification.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the composite concrete foaming agent based on animal protein modification consists of a basic component, a modified protein-based foaming agent, a foam stabilizing component, an early strength component and water, wherein the foaming agent comprises the following components in parts by weight: 15-25 parts of basic components, 5-15 parts of modified protein-based foaming agents, 3-7 parts of foam stabilizing components, 10-15 parts of early strength components and 40-70 parts of water; the basic components are alpha-sodium alkenyl sulfonate, sodium dodecyl sulfate and fatty alcohol polyoxyethylene ether sodium sulfate according to the mass ratio of 1 (1-2) (1.5-3.0); the foam stabilizing component is at least one of dodecanol and cellulose ether; the early strength component is composed of sodium sulfate and starch-based graft copolymer according to the mass ratio of (1-5): 1.
As a further technical scheme, the preparation method of the modified protein-based foaming agent comprises the following steps:
1) Sequentially adding animal cutin protein, calcium hydroxide and sodium bisulphite into deionized water, hydrolyzing at 95-100deg.C for 3-7 hr, cooling to room temperature, filtering, removing residue, adding diluted hydrochloric acid to neutralize the filtrate, filtering again to remove precipitate, and concentrating the filtrate to obtain foaming agent mother liquor;
2) Magnetically stirring the foaming agent mother liquor for 20-50min, regulating the pH value to 11-12 by using a sodium hydroxide solution, then filling the foaming agent mother liquor into a plastic bag, suspending the plastic bag in an ultrasonic reaction kettle for ultrasonic treatment, and controlling the total time to be 50-70min by adopting an intermittent working mode, wherein the ultrasonic working time is 5-15s and the intermittent time is 1-3s, and regulating the pH value to be neutral by using a hydrochloric acid solution after the treatment is finished to obtain a pretreated foaming agent mother liquor;
3) Adding dodecyl amine and 1-ethyl- (3-dimethylaminopropyl) carbodiimide into the pretreated foaming agent mother solution, reacting for 2-3 hours at 45-65 ℃, stopping adding after the reaction is finished, cooling to room temperature, diluting the obtained solution with deionized water according to the mass ratio of 1:40-50 to obtain a diluted solution, respectively weighing secondary alkyl sodium sulfate and sodium dodecyl benzene sulfonate, sequentially adding into the diluted solution, and stirring uniformly to obtain the modified protein-based foaming agent.
As a further technical scheme, in the step 1), the animal keratin is at least one selected from bovine keratin and caprine keratin;
the dosage proportion of the animal cutin protein, the calcium hydroxide, the sodium bisulphite and the deionized water is (20-50) g (1.5-7.5) g (0.5-4.3) g (250-420) mL;
the density of the foaming agent mother liquor is 1.05-1.08g/cm 3 。
As a further technical scheme, in the step 2), the concentration of the sodium hydroxide solution is 2.0-2.5mol/L;
the concentration of the hydrochloric acid solution is 1.0-1.5mol/L;
in the ultrasonic treatment process, the temperature is kept at 30-50 ℃ and the power density is 82-98W/L.
As a further technical scheme, in the step 3), the dosage proportion of the pretreatment foaming agent mother liquor, the dodecyl amine, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide, the secondary sodium alkyl sulfate and the sodium dodecyl benzene sulfonate is (100-160) mL (3.0-4.8) g (2.0-3.2) g (0.8-1.5) g (0.1-0.3) g.
As a further technical scheme, the preparation method of the starch-based graft copolymer comprises the following steps:
1) Adding urea into deionized water, stirring and dissolving to obtain urea solution, adding starch into a three-neck flask, pouring the prepared urea solution into the three-neck flask, connecting a condensation reflux device, reacting for 3-5 hours at the speed of 20-50r/min under the oil bath condition of 80-90 ℃, cooling to room temperature, adding lactic acid into a reaction system, adding hydrochloric acid, controlling the concentration of hydrochloric acid in the whole reaction system to be 0.4-0.6mol/L, heating the temperature of the reaction system to 90-96 ℃, reacting for 3-5 hours, and finely purifying a product by adopting a Soxhlet extraction method by taking acetone as an extraction solvent to obtain pretreated starch;
2) Adding chitosan into acetic acid solution, stirring uniformly to prepare chitosan solution, adding nano aluminum oxide into sodium hexametaphosphate solution, performing ultrasonic dispersion to obtain suspension, adding chitosan solution into the suspension, mixing uniformly, adding pretreated starch, and stirring at constant temperature of 50-120r/min and 85-95 ℃ for 40-70min to obtain modified starch gelatinized liquid;
3) Adding ammonium persulfate into the modified starch pasting liquid, stirring uniformly, standing at room temperature for initiating for 1-3h, adding monomer acrylic acid, adjusting the reaction temperature to 50-80 ℃ at 230-380r/min, reacting for 2-5h, taking out the product, adjusting the absolute ethanol solution of the product to be neutral by using sodium hydroxide solution, filtering, and drying at 50-55 ℃ to obtain the starch-based graft copolymer.
As a further technical scheme, in the step 1), the dosage proportion of the urea, the deionized water, the starch and the lactic acid is (4.2-10.5) g (80-130) mL (5-15) g (10-30) g.
As a further technical scheme, in the step 2), the dosage proportion of the chitosan, the acetic acid solution, the nano aluminum oxide, the sodium hexametaphosphate solution and the pretreated starch is (1-5) g (30-60) mL (0.01-0.06) g (20-40) mL (3-8) g;
the concentration of the acetic acid solution is 1-3wt%;
the concentration of the sodium hexametaphosphate solution is 1-5wt%.
As a further technical scheme, in the step 3), the dosage of the ammonium persulfate accounts for 2-6% of the mass of the modified starch gelatinization liquid;
the dosage of the monomer acrylic acid accounts for 10-18% of the mass of the modified starch gelatinization liquid.
As a further technical scheme, the preparation method of the composite concrete foaming agent comprises the following steps:
according to the proportion, firstly weighing the basic component, the modified protein-based foaming agent, the early strength component and water, heating to 60-90 ℃ in water bath heating, slowly stirring for 2-10min at 50-180r/min, then weighing the foam stabilizing component, continuously stirring for 2-10min after adding, standing, and cooling to room temperature to obtain the required composite concrete foaming agent.
Compared with the prior art, the invention has the following beneficial effects:
in the invention, animal protein is hydrolyzed, long chains are dissolved into a short chain mixture, hydrophilic groups such as carboxyl and hydroxyl and hydrophobic groups such as long-carbon chain hydrocarbon are used for reducing the surface tension of liquid, and a surface active substance with a double-electron layer after hydrolysis wraps air to form a bubble protection film, so that bubbles formed subsequently are not easy to collapse, thereby being beneficial to improving the foaming capacity of a foaming agent and improving the stability of foam; however, as the amount of the foaming agent increases, the amount of the foaming agent increases sharply, the attractive force between foam molecules increases, the foam fuses to form larger-volume bubbles, the fused foam can collapse, in order to avoid collapse of the foam, the animal protein is pretreated, the ultrasonic treatment is applied while the pH shift modification is carried out on the animal protein, the ultrasonic shearing force and the shock wave generated by the acoustic cavitation are beneficial to breaking the non-covalent bond of the protein, changing the microstructure of the animal protein, further increasing the solubility of the animal protein, thereby being beneficial to improving the solubility of the foaming agent, and the secondary structure of the animal protein changes after the treatment, so that the beta-folding structure in the animal protein increases, thereby enabling the foaming agent to form a tighter film and a more stable foam, and effectively solving the collapse problem of the foam; meanwhile, animal protein is subjected to secondary modification treatment by adopting the dodecyl amine, amino bonds in the dodecyl amine are crosslinked to carboxyl bonds of the animal protein, so that the regularity and crystallinity of molecular chain segments of the animal protein are increased, the repulsive force among molecules is increased, the particle size of particles formed by multi-molecule aggregation is reduced, the dispersion coefficient is reduced, the foamability of the foaming agent is further improved, the foam pore size can be improved by compounding and penetrating secondary alkyl sodium sulfate and sodium dodecyl benzene sulfonate, the pore structure compactness is optimized, and the foam is not easy to collapse, so that the foaming agent has excellent foaming capability.
According to the invention, hydrochloric acid is used as a catalyst to carry out graft copolymerization reaction on starch and lactic acid, the surface roughness of the starch is increased through copolymerization reaction, and the surface is in a loose cluster-like lamellar structure, so that on one hand, the starch is used as a bonding node, the bonding strength among components in the concrete is increased, the strength of the concrete is enhanced, and on the other hand, strong interaction between subsequent nano particles and the starch is formed; simultaneously, chitosan and nano aluminum oxide are introduced into starch, and amino groups in a chitosan molecular chain are easily protonated into NH under an acidic condition 3 + The crystallinity of the starch is destroyed during the gelling process to form-OH groups, NH during the blending gelatinization process 3 + and-OH to form hydrogen bond, and the charged amino group promotes polarization of other chains and increases attraction between chains, so as to help to enhance compactness of subsequent concrete, improve strength of the concrete, and promote the polarization of other chains due to nano aluminum oxide and starchThe hydrogen bond and the covalent bond exist between the powder-chitosan aggregate, so that the intermolecular interface adhesion and the molecular chain rigidity of the starch and the chitosan are enhanced, and a firm stable structure is formed between the chitosan and the starch, so that the strength of the concrete can be further enhanced; meanwhile, the starch is modified again by adopting an acrylic acid graft polymerization mode, a plurality of polar groups such as carboxyl, hydroxyl and the like are introduced to the surface of starch molecules, and can be associated with water molecules through hydrogen bonds, so that the starch is adsorbed on the surface of concrete particles to form a layer of hydration film, the concrete particles are wetted, the concrete particles are prevented from being aggregated, the flowability of concrete slurry is further enhanced, the uniform mixing of concrete is facilitated, the compactness of the concrete is enhanced, and the strength of the concrete can be further enhanced.
The composite concrete foaming agent has excellent foaming capacity, high foaming multiple, excellent foam stability, difficult foam collapse, good water solubility and excellent compatibility with concrete slurry, and the foam concrete formed by the composite concrete foaming agent is free from mould collapse phenomenon, high in strength, good in stability and wide in application prospect when the composite concrete foaming agent is applied to foam concrete.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The following are specific examples:
example 1
The composite concrete foaming agent based on animal protein modification consists of a basic component, a modified protein-based foaming agent, a foam stabilizing component, an early strength component and water, wherein the foaming agent comprises the following components in parts by weight: 15 parts of basic component, 5 parts of modified protein-based foaming agent, 3 parts of foam stabilizing component, 10 parts of early strength component and 40 parts of water; the basic components comprise alpha-sodium alkenyl sulfonate, sodium dodecyl sulfate and fatty alcohol polyoxyethylene ether sodium sulfate according to the mass ratio of 1:1:1.5; the foam stabilizing component is dodecanol; the early strength component is composed of sodium sulfate and starch-based graft copolymer according to the mass ratio of 1:1.
The preparation method of the modified protein-based foaming agent comprises the following steps:
1) Weighing 20g of animal cutin protein, 1.5g of calcium hydroxide and 0.5g of sodium bisulphite, sequentially adding into 250mL of deionized water, hydrolyzing at 95 ℃ for 7h, cooling to room temperature, filtering, removing residues, adding dilute hydrochloric acid to neutralize the filtrate, removing precipitate after secondary filtering, concentrating the obtained filtrate to a density of 1.05g/cm 3 Obtaining a foaming agent mother solution;
2) Magnetically stirring the foaming agent mother liquor for 20min, regulating the pH value to 11 by using 2.0mol/L sodium hydroxide solution, then filling the foaming agent mother liquor into a plastic bag, suspending the plastic bag in an ultrasonic reaction kettle, keeping the temperature at 30 ℃ in the ultrasonic process and the power density at 82W/L, adopting an intermittent working mode, controlling the ultrasonic working time to be 5s and the intermittent time to be 1s, controlling the total time to be 50min, and regulating the pH value to be neutral by using 1.0mol/L hydrochloric acid solution after the treatment is finished to obtain the pretreated foaming agent mother liquor;
3) 3.0g of dodecyl amine and 2.0g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide are added into 100mL of pretreatment foaming agent mother solution, the reaction is carried out for 3 hours at 45 ℃, after the reaction is finished, the addition is stopped, the reaction is cooled to room temperature, the obtained solution and deionized water are diluted according to the mass ratio of 1:40 to obtain a diluted solution, then 0.8g of secondary alkyl sodium sulfate and 0.1g of sodium dodecyl benzene sulfonate are respectively weighed and sequentially added into the diluted solution, and the modified protein-based foaming agent is obtained after uniform stirring.
The preparation method of the starch-based graft copolymer comprises the following steps:
1) Weighing 4.2g of urea, adding into a container, adding 80mL of deionized water, stirring and dissolving to obtain urea solution, weighing 5g of starch in a three-neck flask, pouring the prepared urea solution into the three-neck flask, connecting a condensation reflux device, reacting for 5 hours at the rotating speed of 20r/min under the oil bath condition of 80 ℃, cooling to room temperature, adding 10g of lactic acid into a reaction system, adding hydrochloric acid, controlling the concentration of hydrochloric acid in the whole reaction system to be 0.4mol/L, heating the reaction system to 90 ℃, reacting for 5 hours, and finely purifying a product by using acetone as an extraction solvent by adopting a Soxhlet extraction method to obtain pretreated starch;
2) 1g of chitosan is weighed and added into 30mL of acetic acid solution with the concentration of 1wt percent, the mixture is stirred uniformly to prepare chitosan solution, and 0.01g of nano aluminum oxide is weighed and added into 20mL of sodium hexametaphosphate with the concentration of 1wt percent, 200W ultrasonic dispersion is carried out for 30min to obtain suspension, the chitosan solution is added into the suspension, 3g of pretreated starch is added after uniform mixing, and the mixture is stirred at the constant temperature of 50r/min and the constant temperature of 85 ℃ for 70min to obtain modified starch pasting liquid;
3) Adding a proper amount of ammonium persulfate into the modified starch pasting liquid, controlling the ammonium persulfate to account for 2% of the mass of the modified starch pasting liquid, standing at room temperature for initiating for 1h after uniformly stirring, adding monomer acrylic acid, controlling the monomer acrylic acid to account for 10% of the mass of the modified starch pasting liquid, adjusting the reaction temperature to 50 ℃ at 230r/min, reacting for 5h, taking out a product, adjusting the absolute ethanol solution of the product to be neutral by using a sodium hydroxide solution, and drying at 50 ℃ after filtering to obtain the starch-based graft copolymer.
A preparation method of the composite concrete foaming agent based on animal protein modification comprises the following steps:
according to the proportion, firstly weighing a basic component, a modified protein-based foaming agent, an early strength component and water, heating to 60 ℃ in water bath heating, slowly stirring for 10min at 50r/min, then weighing a foam stabilizing component, continuously stirring for 10min after adding, standing, and cooling to room temperature to obtain the required composite concrete foaming agent.
Example 2
The composite concrete foaming agent based on animal protein modification consists of a basic component, a modified protein-based foaming agent, a foam stabilizing component, an early strength component and water, wherein the foaming agent comprises the following components in parts by weight: 20 parts of basic component, 10 parts of modified protein-based foaming agent, 5 parts of foam stabilizing component, 12 parts of early strength component and 55 parts of water; the basic components comprise alpha-sodium alkenyl sulfonate, sodium dodecyl sulfate and fatty alcohol polyoxyethylene ether sodium sulfate according to the mass ratio of 1:1.5:2.5; the foam stabilizing component is methyl cellulose; the early strength component is composed of sodium sulfate and starch-based graft copolymer according to the mass ratio of 3:1.
The preparation method of the modified protein-based foaming agent comprises the following steps:
1) Weighing 35g of animal cutin protein, 4.5g of calcium hydroxide and 2.4g of sodium bisulphite, sequentially adding into 350mL of deionized water, hydrolyzing at 98 ℃ for 5h, cooling to room temperature, filtering, removing residues, adding dilute hydrochloric acid to neutralize the filtrate, removing precipitate after secondary filtering, concentrating the obtained filtrate to a density of 1.06g/cm 3 Obtaining a foaming agent mother solution;
2) Magnetically stirring the foaming agent mother liquor for 30min, regulating the pH value to 11.5 by using 2.3mol/L sodium hydroxide, then filling the foaming agent mother liquor into a plastic bag, suspending the plastic bag in an ultrasonic reaction kettle, keeping the temperature at 40 ℃ in the ultrasonic process and the power density at 90W/L, adopting an intermittent working mode, controlling the ultrasonic working time to be 10s and the intermittent time to be 2s, controlling the total time to be 60min, and regulating the pH value to be neutral by using 1.2mol/L hydrochloric acid solution after the treatment is finished to obtain the pretreated foaming agent mother liquor;
3) Adding 3.9g of dodecyl amine and 2.6g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide into 130mL of pretreatment foaming agent mother solution, reacting for 2.5h at 55 ℃, stopping adding after the reaction is finished, cooling to room temperature, diluting the obtained solution with deionized water according to a mass ratio of 1:45 to obtain a diluted solution, then respectively weighing 1.2g of secondary alkyl sodium sulfate and 0.2g of sodium dodecyl benzene sulfonate, sequentially adding into the diluted solution, and stirring uniformly to obtain the modified protein-based foaming agent.
The preparation method of the starch-based graft copolymer comprises the following steps:
1) Weighing 7.4g of urea, adding into a container, adding 110mL of deionized water, stirring and dissolving to obtain urea solution, weighing 10g of starch in a three-neck flask, pouring the prepared urea solution into the three-neck flask, connecting a condensation reflux device, reacting for 4 hours at the speed of 35r/min under the condition of oil bath at the temperature of 85 ℃, cooling to room temperature, adding 20g of lactic acid into a reaction system, adding hydrochloric acid, controlling the concentration of hydrochloric acid in the whole reaction system to be 0.5mol/L, heating the reaction system to 93 ℃, reacting for 4 hours, and finely purifying a product by adopting a Soxhlet extraction method by taking acetone as an extraction solvent to obtain pretreated starch;
2) 3g of chitosan is weighed and added into 50mL of acetic acid solution with the concentration of 2wt percent, the mixture is stirred uniformly to prepare chitosan solution, and 0.04g of nano aluminum oxide is additionally weighed and added into 30mL of sodium hexametaphosphate solution with the concentration of 3wt percent, the ultrasonic dispersion is carried out for 25min at 250W to obtain suspension, the chitosan solution is added into the suspension, 5g of pretreated starch is added after the uniform mixing, and the mixture is stirred at the constant temperature of 80r/min and the constant temperature of 90 ℃ for 55min to obtain modified starch pasting liquid;
3) Adding a proper amount of ammonium persulfate into the modified starch pasting liquid, controlling the ammonium persulfate to account for 4% of the mass of the modified starch pasting liquid, standing at room temperature for initiation for 2 hours after uniformly stirring, adding monomer acrylic acid, controlling the monomer acrylic acid to account for 14% of the mass of the modified starch pasting liquid, adjusting the reaction temperature to 65 ℃ at 300r/min, reacting for 3 hours, taking out a product, adjusting the absolute ethanol solution of the product to be neutral by using a sodium hydroxide solution, and drying at 52 ℃ after filtering to obtain the starch-based graft copolymer.
A preparation method of the composite concrete foaming agent based on animal protein modification comprises the following steps:
according to the proportion, firstly weighing a basic component, a modified protein-based foaming agent, an early strength component and water, heating to 75 ℃ in water bath heating, slowly stirring for 6min at 120r/min, then weighing a foam stabilizing component, continuously stirring for 6min after adding, standing, and cooling to room temperature to obtain the required composite concrete foaming agent.
Example 3
The composite concrete foaming agent based on animal protein modification consists of a basic component, a modified protein-based foaming agent, a foam stabilizing component, an early strength component and water, wherein the foaming agent comprises the following components in parts by weight: 25 parts of basic component, 15 parts of modified protein-based foaming agent, 7 parts of foam stabilizing component, 15 parts of early strength component and 70 parts of water; the basic component comprises alpha-sodium alkenyl sulfonate, sodium dodecyl sulfate and fatty alcohol polyoxyethylene ether sodium sulfate according to the mass ratio of 1:2:3.0; the foam stabilizing component is dodecanol; the early strength component is composed of sodium sulfate and starch-based graft copolymer according to the mass ratio of 5:1.
The preparation method of the modified protein-based foaming agent comprises the following steps:
1) Weighing 50g of animal cutin protein, 7.5g of calcium hydroxide and 4.3g of sodium bisulphite, sequentially adding 420mL of deionized water, hydrolyzing at 100 ℃ for 3h, cooling to room temperature, filtering, removing residues, adding dilute hydrochloric acid to neutralize the filtrate, removing precipitate after secondary filtering, concentrating the obtained filtrate to a density of 1.08g/cm 3 Obtaining a foaming agent mother solution;
2) Magnetically stirring the foaming agent mother liquor for 50min, regulating the pH value to 12 by using 2.5mol/L sodium hydroxide, then filling the foaming agent mother liquor into a plastic bag, suspending the plastic bag in an ultrasonic reaction kettle, keeping the temperature at 50 ℃ in the ultrasonic process, and controlling the power density at 98W/L, wherein the ultrasonic operation time is 15s, the intermittent time is 3s, the total time is controlled to be 70min, and regulating the pH value to be neutral by using 1.5mol/L hydrochloric acid solution after the treatment is finished, so as to obtain the pretreated foaming agent mother liquor;
3) Adding 4.8g of dodecyl amine and 3.2g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide into 160mL of pretreatment foaming agent mother solution, reacting for 2 hours at 65 ℃, stopping adding after the reaction is finished, cooling to room temperature, diluting the obtained solution with deionized water according to a mass ratio of 1:50 to obtain a diluted solution, then respectively weighing 1.5g of secondary alkyl sodium sulfate and 0.3g of sodium dodecyl benzene sulfonate, sequentially adding into the diluted solution, and uniformly stirring to obtain the modified protein-based foaming agent.
The preparation method of the starch-based graft copolymer comprises the following steps:
1) Weighing 10.5g of urea, adding 130mL of deionized water into a container, stirring and dissolving to obtain urea solution, weighing 15g of starch into a three-neck flask, pouring the prepared urea solution into the three-neck flask, connecting a condensation reflux device, reacting for 3 hours at the speed of 50r/min under the condition of 90 ℃ oil bath, cooling to room temperature, adding 30g of lactic acid into a reaction system, adding hydrochloric acid, controlling the concentration of hydrochloric acid in the whole reaction system to be 0.6mol/L, heating the reaction system to 96 ℃, reacting for 3 hours, and finely purifying a product by adopting a Soxhlet extraction method by taking acetone as an extraction solvent to obtain pretreated starch;
2) Weighing 5g of chitosan, adding the chitosan into 60mL of acetic acid solution with the concentration of 3wt%, uniformly stirring to prepare a chitosan solution, weighing 0.06g of nano aluminum oxide, adding the nano aluminum oxide into 40mL of sodium hexametaphosphate with the concentration of 5wt%, performing ultrasonic dispersion for 20min at 300W to obtain a suspension, adding the chitosan solution into the suspension, uniformly mixing, adding 8g of pretreated starch, and stirring at the constant temperature of 120r/min and 95 ℃ for 40min to obtain a modified starch gelatinized liquid;
3) Adding a proper amount of ammonium persulfate into the modified starch pasting liquid, controlling the ammonium persulfate to account for 6% of the mass of the modified starch pasting liquid, standing at room temperature for 3 hours after uniformly stirring, adding monomer acrylic acid, controlling the monomer acrylic acid to account for 18% of the mass of the modified starch pasting liquid, adjusting the reaction temperature to 80 ℃ at 380r/min, reacting for 2 hours, taking out a product, adjusting the absolute ethanol solution of the product to be neutral by using a sodium hydroxide solution, and drying at 55 ℃ after filtering to obtain the starch-based graft copolymer.
A preparation method of the composite concrete foaming agent based on animal protein modification comprises the following steps:
according to the proportion, firstly weighing a basic component, a modified protein-based foaming agent, an early strength component and water, heating to 90 ℃ in water bath heating, slowly stirring for 2min at 180r/min, then weighing a foam stabilizing component, continuously stirring for 2min after adding, standing, and cooling to room temperature to obtain the required composite concrete foaming agent.
Comparative example 1: the present comparative example is substantially the same as the raw material composition of the animal protein-modified composite concrete foaming agent of example 1, except that step 1) is omitted in the preparation method of the modified protein-based foaming agent.
Comparative example 2: the present comparative example is substantially the same as the raw material composition of the animal protein-modified composite concrete foaming agent of example 1, except that step 2) is omitted in the preparation method of the modified protein-based foaming agent.
Comparative example 3: the present comparative example is substantially the same as the raw material composition of the animal protein-modified composite concrete foaming agent of example 1, except that step 3) is omitted in the preparation method of the modified protein-based foaming agent.
Comparative example 4: the comparative example is substantially identical to the raw material composition of the animal protein-modified composite concrete foaming agent of example 1, except that step 1) is omitted in the preparation method of the starch-based graft copolymer.
Comparative example 5: the comparative example is substantially identical to the raw material composition of the animal protein-modified composite concrete foaming agent of example 1, except that step 2) is omitted in the preparation method of the starch-based graft copolymer.
Comparative example 6: the present comparative example is substantially the same as the raw material composition of the animal protein-modified composite concrete foaming agent of example 1, except that step 3) is omitted in the preparation method of the starch-based graft copolymer.
Test experiment 1
The foaming agent foam performance detection (foaming multiple and sedimentation distance) is carried out according to the test method specified in the standard JG/T266-2011 foam concrete.
The foam concrete strength test method comprises the following steps: the foam concrete test block has the dimensions of 100mm multiplied by 100mm, the temperature of a curing chamber is 20 ℃ and 1 ℃, the relative humidity is not more than 90%, the foam concrete test block is cured for more than 48 hours with a mold after molding, and a pressure tester is adopted for compression test after demolding and curing until the test age.
The foaming agents provided in examples 1 to 3 and comparative examples 1 to 6 were subjected to foam performance test, the results are shown in Table 1, and the foaming agents were applied to foam concrete respectively, and the test results of the strength of the foam concrete are shown in Table 1:
TABLE 1
As can be seen from the table, the foaming agent has excellent foaming capacity, high foaming multiple and excellent foam stability, and foam is not easy to collapse, and the foaming agent is applied to foam concrete, so that the formed foam concrete has no collapse phenomenon, and has high strength and good stability.
Test experiment 2
The fluidity of the purified slurry was measured according to national standard GB 8077-2000 "concrete admixture homogeneity test method", and the test results are shown in Table 2:
TABLE 2
As can be seen from the table, the foaming agent provided by the invention is applied to concrete, and is beneficial to enhancing the flow property of concrete slurry, so that the compactness of the concrete is enhanced, and the strength of the concrete can be enhanced.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The composite concrete foaming agent based on animal protein modification is characterized by comprising a basic component, a modified protein-based foaming agent, a foam stabilizing component, an early strength component and water, wherein the foaming agent comprises the following components in parts by weight: 15-25 parts of basic components, 5-15 parts of modified protein-based foaming agents, 3-7 parts of foam stabilizing components, 10-15 parts of early strength components and 40-70 parts of water; the basic components are alpha-sodium alkenyl sulfonate, sodium dodecyl sulfate and fatty alcohol polyoxyethylene ether sodium sulfate according to the mass ratio of 1 (1-2) (1.5-3.0); the foam stabilizing component is at least one of dodecanol and cellulose ether; the early strength component is composed of sodium sulfate and starch-based graft copolymer according to the mass ratio of (1-5): 1;
the preparation method of the modified protein-based foaming agent comprises the following steps:
1) Sequentially adding animal cutin protein, calcium hydroxide and sodium bisulphite into deionized water, hydrolyzing at 95-100deg.C for 3-7 hr, cooling to room temperature, filtering, removing residue, adding diluted hydrochloric acid to neutralize the filtrate, filtering again to remove precipitate, and concentrating the filtrate to obtain foaming agent mother liquor;
2) Magnetically stirring the foaming agent mother liquor for 20-50min, regulating the pH value to 11-12 by using a sodium hydroxide solution, then filling the foaming agent mother liquor into a plastic bag, suspending the plastic bag in an ultrasonic reaction kettle for ultrasonic treatment, and controlling the total time to be 50-70min by adopting an intermittent working mode, wherein the ultrasonic working time is 5-15s and the intermittent time is 1-3s, and regulating the pH value to be neutral by using a hydrochloric acid solution after the treatment is finished to obtain a pretreated foaming agent mother liquor;
3) Adding dodecyl amine and 1-ethyl- (3-dimethylaminopropyl) carbodiimide into the pretreated foaming agent mother solution, reacting for 2-3 hours at 45-65 ℃, stopping adding after the reaction is finished, cooling to room temperature, diluting the obtained solution with deionized water according to a mass ratio of 1:40-50 to obtain a diluted solution, respectively weighing secondary alkyl sodium sulfate and sodium dodecyl benzene sulfonate, sequentially adding into the diluted solution, and uniformly stirring to obtain a modified protein-based foaming agent;
the preparation method of the starch-based graft copolymer comprises the following steps:
1) Adding urea into deionized water, stirring and dissolving to obtain urea solution, adding starch into a three-neck flask, pouring the prepared urea solution into the three-neck flask, connecting a condensation reflux device, reacting for 3-5 hours at the speed of 20-50r/min under the oil bath condition of 80-90 ℃, cooling to room temperature, adding lactic acid into a reaction system, adding hydrochloric acid, controlling the concentration of hydrochloric acid in the whole reaction system to be 0.4-0.6mol/L, heating the temperature of the reaction system to 90-96 ℃, reacting for 3-5 hours, and finely purifying a product by adopting a Soxhlet extraction method by taking acetone as an extraction solvent to obtain pretreated starch;
2) Adding chitosan into acetic acid solution, stirring uniformly to prepare chitosan solution, adding nano aluminum oxide into sodium hexametaphosphate solution, performing ultrasonic dispersion to obtain suspension, adding chitosan solution into the suspension, mixing uniformly, adding pretreated starch, and stirring at constant temperature of 50-120r/min and 85-95 ℃ for 40-70min to obtain modified starch gelatinized liquid;
3) Adding ammonium persulfate into the modified starch pasting liquid, stirring uniformly, standing at room temperature for initiating for 1-3h, adding monomer acrylic acid, adjusting the reaction temperature to 50-80 ℃ at 230-380r/min, reacting for 2-5h, taking out the product, adjusting the absolute ethanol solution of the product to be neutral by using sodium hydroxide solution, filtering, and drying at 50-55 ℃ to obtain the starch-based graft copolymer.
2. The modified-composition concrete foaming agent based on animal proteins according to claim 1, wherein in the step 1) of the preparation method of the modified-protein-based foaming agent, the animal keratin is at least one selected from bovine keratin and caprine keratin;
the dosage proportion of the animal cutin protein, the calcium hydroxide, the sodium bisulphite and the deionized water is (20-50) g (1.5-7.5) g (0.5-4.3) g (250-420) mL;
the density of the foaming agent mother liquor is 1.05-1.08g/cm 3 。
3. The animal protein-modified composite concrete foaming agent according to claim 1, wherein in the step 2) of the preparation method of the modified protein-based foaming agent, the concentration of the sodium hydroxide solution is 2.0-2.5mol/L;
the concentration of the hydrochloric acid solution is 1.0-1.5mol/L;
in the ultrasonic treatment process, the temperature is kept at 30-50 ℃ and the power density is 82-98W/L.
4. The animal protein-modified composite concrete foaming agent according to claim 1, wherein in the step 3) of the preparation method of the modified protein-based foaming agent, the pretreated foaming agent mother liquor, the dodecyl amine, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide, the secondary sodium alkyl sulfate and the sodium dodecyl benzene sulfonate are used in the proportion of (100-160) mL, (3.0-4.8) g, (2.0-3.2) g, (0.8-1.5) g and (0.1-0.3) g.
5. The animal protein-modified composite concrete foaming agent according to claim 1, wherein in the step 1) of the preparation method of the starch-based graft copolymer, the urea, deionized water, starch and lactic acid are used in the proportion of (4.2-10.5) g (80-130) mL (5-15) g (10-30) g.
6. The animal protein-modified composite concrete foaming agent according to claim 1, wherein in the step 2) of the preparation method of the starch-based graft copolymer, the dosage ratio of the chitosan, the acetic acid solution, the nano aluminum oxide, the sodium hexametaphosphate solution and the pretreated starch is (1-5) g, (30-60) mL, (0.01-0.06) g, (20-40) mL, (3-8) g;
the concentration of the acetic acid solution is 1-3wt%;
the concentration of the sodium hexametaphosphate solution is 1-5wt%.
7. The animal protein modified composite concrete foaming agent according to claim 1, wherein in the step 3) of the preparation method of the starch-based graft copolymer, the ammonium persulfate is used in an amount of 2-6% of the mass of the modified starch gelatinization liquid;
the dosage of the monomer acrylic acid accounts for 10-18% of the mass of the modified starch gelatinization liquid.
8. The animal protein modified composite concrete foaming agent according to claim 1, wherein the preparation method of the composite concrete foaming agent is as follows:
according to the proportion, firstly weighing the basic component, the modified protein-based foaming agent, the early strength component and water, heating to 60-90 ℃ in water bath heating, slowly stirring for 2-10min at 50-180r/min, then weighing the foam stabilizing component, continuously stirring for 2-10min after adding, standing, and cooling to room temperature to obtain the required composite concrete foaming agent.
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