CN109134784B - Coagulation-accelerating early-strength polycarboxylic acid superplasticizer and preparation method thereof - Google Patents
Coagulation-accelerating early-strength polycarboxylic acid superplasticizer and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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Abstract
A coagulation-accelerating early-strength polycarboxylic acid superplasticizer and a preparation method thereof are disclosed, wherein the polycarboxylic acid superplasticizer is prepared from the following raw materials in parts by weight: 70-80 parts of polyoxyethylene ether macromonomer, 1-1.5 parts of reducing agent and water-based initiator, 40-50 parts of deionized water, feed liquid A and feed liquid B; the material liquid A is formed by mixing 7-9 parts of acrylic acid, 0.1-2 parts of coagulation accelerating early strength monomer, namely unsaturated alcohol amine ester, 0.1-1 part of unsaturated amide and 15-25 parts of deionized water; the material liquid B is prepared by mixing 0.08-0.15 part of reducing agent Y, 0.3-0.5 part of chain transfer agent and 18-28 parts of deionized water. The preparation method comprises the following steps: putting polyoxyethylene ether macromonomer, reducing agent and deionized water into a reaction kettle, heating and stirring; and adding a water-based initiator into the reaction kettle, dropwise adding the material liquid A and the material liquid B, after dropwise adding, preserving the temperature for reaction, cooling to room temperature, and adding liquid alkali to adjust the pH value to 7. The invention effectively improves the early strength of the concrete and shortens the setting time of the concrete.
Description
Technical Field
The invention relates to a concrete admixture, in particular to a polycarboxylic acid superplasticizer, specifically a set-accelerating early-strength polycarboxylic acid superplasticizer, and belongs to the technical field of building materials. The invention also relates to a preparation method of the polycarboxylic acid superplasticizer, in particular to a preparation method of the coagulation-accelerating early-strength polycarboxylic acid superplasticizer.
Background
The prefabricated member is gradually widely applied to the market due to the characteristics of high construction speed, labor saving, construction site environment improvement and good economic benefit. In the production of prefabricated parts, rapid formwork turnover is often required, which often requires high early strength of the concrete. The common method is as follows: the cement consumption is increased, the early strength inorganic salt is doped, and the steam curing temperature is increased. The increase of the cement dosage brings about the increase of the production cost, the inorganic salt is usually required to be doped in a high dosage and causes the reduction of the later strength, and the higher energy consumption is required for increasing the temperature. Attention has been paid to improving the early strength of concrete from the viewpoint of dispersants.
The invention can effectively promote the early hydration of cement by adopting high-component long side chain synthesis, and generates more compact and fine hydration products. Unsaturated alcohol amine is introduced into the main chain, and the unsaturated alcohol amine can be hydrolyzed due to the alkaline environment of cement to release the alcohol amine, so that the hydration is further accelerated to play a role of a condensation catalyst, and meanwhile, part of carboxyl can be protected to play a role of maintaining slump loss. The backbone is grafted with a portion of amide groups, and because of the presence of N, early hydration can be promoted to provide early strength. Because organic functional groups are not introduced, the mineral phase change of the hydration product is not influenced, and the later strength is not reduced.
The inventors searched the following related patent documents: CN101066853 discloses a polyether super early strength concrete superplasticizer, which is prepared by the following steps: 1) aqueous radical copolymerization: carrying out free radical copolymerization on 84-94% of monomer a, 5-15% of monomer b and 1-3% of monomer c in an aqueous medium; 2) and (3) neutralization reaction: after the copolymerization reaction is finished, adding alkoxy organic amine d shown by a general formula (5) or a general formula (6) into the copolymer for neutralization reaction, and adjusting the pH value of the copolymer to 6.0-7.5. CN101085701 discloses a method for pumping prefabricated part concreteThe superplasticizer is prepared by the free radical copolymerization reaction of a monomer a, a monomer b, a monomer c and a modified monomer d, wherein the modified monomer d is prepared from a monomer d and nano SiO2The reaction is carried out to obtain; the viscosity-average molecular weight of the superplasticizer is controlled to be 30000-80000. CN101357834 discloses an early strength type polycarboxylic acid superplasticizer, which is obtained by copolymerizing four monomers in an aqueous solution at a temperature of between 60 and 95 ℃ in the presence of a free radical initiator and a chain transfer agent. New polymeric monomers are introduced into a polymer molecular chain to form a new polymer molecular structure, so that the water reducing rate and the early strengthening capability of the polycarboxylic acid superplasticizer are improved. CN107602773A discloses a polycarboxylic acid dispersant for oil well cement and a preparation method thereof, wherein the polycarboxylic acid dispersant is a copolymer taking acrylic acid, N-vinyl pyrrolidone, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid, sodium vinylsulfonate, sodium vinylbenzenesulfonate and allyl polyethylene glycol as monomers; the weight average molecular weight of the allyl polyethylene glycol is 300-2400; based on the total mass of the monomers being 100%, the mass percent of acrylic acid is 0.5-20%, the mass percent of N-vinyl pyrrolidone is 0.5-15%, the mass percent of itaconic acid is 0.5-10%, the mass percent of 2-acrylamide-2-methyl propane sulfonic acid is 5-60%, the mass percent of sodium vinyl sulfonate is 0.5-30%, the mass percent of sodium vinyl benzene sulfonate is 0.5-30%, and the mass percent of allyl polyethylene glycol is 20-70%; the weight average molecular weight of the polycarboxylic acid dispersant is 5000-250000. CN103406067A discloses a polycarboxylic acid dispersant, a preparation method and application thereof. The polycarboxylic acid dispersant is obtained by performing free radical polymerization reaction on 1.0-3.0 parts by weight of unsaturated monomer containing carboxyl, 1.1-2.2 parts by weight of sulfonic acid group unsaturated monomer and 0.6-1.2 parts by weight of other free radical polymerization unsaturated base monomer in the presence of 25-35 parts by weight of water, 0.11-0.22 part by weight of initiator, 0.03-0.06 part by weight of chain transfer agent and 1.5-4.0 parts by weight of alkaline compound. CN106519151A discloses an amphiphilic polycarboxylic acid cement dispersant and a preparation method thereof. The amphiphilic polycarboxylic acid cement dispersant is a dispersion liquid of polycarboxylic acid particles with a worm-like microscopic morphology; which comprises the following componentsAmphiphilic polycarboxylic acid nanoparticles and water; the weight average molecular weight of the amphiphilic polycarboxylic acid particles is 15000-40000, the RAFT polymerization method is adopted, the RAFT polymerization cost is high, and the chain transfer agent is difficult to purchase. There are difficulties in industrial practical use. United States Patent 4792360 discloses the preparation of amphiphilic polycarboxylic acid dispersants by the incorporation of styrene sulfonic acid. However, the price of the styrene sulfonic acid is very high, and the styrene sulfonic acid also has the problem of difficult popularization. US Patent 5158996 discloses the synthesis of amphoteric dispersants by using acetone as a solvent, but the use of a solvent causes environmental pollution and must be removed by distillation in subsequent use, increasing costs.
The above techniques do not provide specific guidance for how to enable the polycarboxylic acid superplasticizer to effectively improve the early strength of concrete and shorten the setting time of concrete.
Disclosure of Invention
The invention aims to solve the technical problem of providing a coagulation-accelerating early-strength polycarboxylic acid superplasticizer which can effectively improve the early strength of concrete and shorten the setting time of the concrete.
Therefore, the invention also aims to solve the technical problem of providing a preparation method of the coagulation-accelerating early-strength polycarboxylic acid superplasticizer.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the technical scheme of the solidification-accelerating early-strength polycarboxylic acid superplasticizer is that the plasticizer is prepared from the following raw materials in parts by weight: 70-80 parts of (unsaturated) polyoxyethylene ether macromonomer, 1-1.5 parts of reducing agent X, water-based initiator, 40-50 parts of deionized water, feed liquid A and feed liquid B. The material liquid A is prepared by mixing 7-9 parts of acrylic acid, 0.1-2 parts of a coagulation accelerating early strength monomer, namely unsaturated alcohol amine ester, 0.1-1 part of unsaturated amide and 15-25 parts of deionized water; the material liquid B is prepared by mixing 0.08-0.15 part of reducing agent Y, 0.3-0.5 part of chain transfer agent and 18-28 parts of deionized water.
Wherein, the polyoxyethylene ether macromonomer (the molecular weight can be 4000-10000) improves the steric hindrance. The polyoxyethylene ether macromonomer is one of methyl allyl polyoxyethylene ether, prenol polyoxyethylene ether (TPEG) and isobutenol polyoxyethylene ether; the unsaturated alcohol amine ester is at least one of triethanolamine diester maleate, diethanol amine maleate, ethanol amine maleate, triethanol amine trimethacrylate, diethanol amine methacrylate, monoethanol amine methacrylate, diethanol amine acrylate, monoethanol amine acrylate, triethanol amine fumarate, diethanol amine fumarate, and monoethanol amine fumarate (or a combination of two or more thereof, when combined, according to any mass ratio); the unsaturated amide is at least one of acrylamide, methacrylamide, N-isopropyl acrylamide, methylene bisacrylamide, N-dimethylacrylamide, N-diethylacrylamide (N, N-diethyl-2-acrylamide) and 2-acrylamide (or a combination of two or more of acrylamide and 2-acrylamide, and the combination of two or more of acrylamide and N, N-diethyl-2-acrylamide can be combined according to any mass ratio); the water-based initiator is one or the combination of any two of hydrogen peroxide, persulfate and azodiisobutyramidine hydrochloride according to any mass ratio; the mass ratio of the reducing agent Y to the reducing agent X is 10-11: 1.
The preparation method of the coagulation-accelerating early-strength polycarboxylic acid superplasticizer comprises the following process steps: 70-80 parts of polyoxyethylene ether macromonomer, a reducing agent X and 40-50 parts of deionized water are put into a reaction kettle (a 500ml three-neck flask with magnetic stirring) according to the mass ratio, heated to 40-50 ℃, and stirred until the polyoxyethylene ether macromonomer is completely dissolved; secondly, adding a water-based initiator into the reaction kettle, then beginning to simultaneously dropwise add the material liquid A and the material liquid B by using a constant flow pump, completing dropwise adding the material liquid A within 2.5-3 hours, completing dropwise adding the material liquid B within 3-3.5 hours, after completing dropwise adding all the material liquids, performing heat preservation reaction for 1.5-2 hours, finally cooling the obtained product to room temperature, adding liquid alkali to adjust the pH value to 7, and obtaining the coagulation-accelerating early-strength type polycarboxylic acid superplasticizer.
In the above technical solution, a preferable technical solution of the present invention may be that the reducing agent X is ferrous sulfate, the reducing agent Y is L-ascorbic acid, and a mass ratio of the reducing agent Y to the reducing agent X is 10: 1. The chain transfer agent is mercaptopropionic acid.
In the above technical solution, the preferable technical solution of the present invention may also be that the coagulation accelerating early strength type polycarboxylic acid superplasticizer is prepared from the following raw materials in parts by mass: 72 parts of polyoxyethylene ether macromonomer namely prenol polyoxyethylene ether, 0.009 parts of reducing agent ferrous sulfate, 1.2 parts of aqueous initiator namely hydrogen peroxide, 45 parts of deionized water, feed liquid A and feed liquid B; the material liquid A is prepared by mixing 8.6 parts of acrylic acid, 0.4 part of unsaturated alcohol amine ester namely triethanolamine trimethacrylate, 0.5 part of unsaturated amide namely acrylamide and 20 parts of deionized water; the feed liquid B is prepared by mixing 0.09 part of reducing agent L-ascorbic acid, 0.3 part of chain transfer agent namely mercaptopropionic acid and 20 parts of deionized water. The preparation method of the coagulation-accelerating early-strength polycarboxylic acid superplasticizer comprises the following process steps: putting 72 parts of polyoxyethylene ether macromonomer, 0.009 parts of ferrous sulfate and 45 parts of deionized water into a reaction kettle according to the mass ratio, heating to 40 ℃, and stirring until the polyoxyethylene ether macromonomer is completely dissolved; adding 1.2 parts of water-based initiator into a reaction kettle, then respectively starting to simultaneously dropwise add the material liquid A and the material liquid B by using a constant flow pump, finishing dropwise adding the material liquid A within 3 hours, finishing dropwise adding the material liquid B within 3.5 hours, after finishing dropwise adding all the material liquids, carrying out heat preservation reaction for 1.5 hours, finally cooling the obtained product to room temperature, adding liquid alkali to adjust the pH value to 7, and obtaining the coagulation-promoting early-strength type polycarboxylic acid superplasticizer.
In the above technical solution, the preferable technical solution of the present invention may also be that the coagulation accelerating early strength type polycarboxylic acid superplasticizer is prepared from the following raw materials in parts by mass: 76 parts of polyoxyethylene ether macromonomer namely prenol polyoxyethylene ether, 0.012 part of reducing agent ferrous sulfate, 1.5 parts of aqueous initiator namely hydrogen peroxide, 48 parts of deionized water, feed liquid A and feed liquid B; the material liquid A is prepared by mixing 9 parts of acrylic acid, 1 part of triethanolamine trimethacrylate, 0.2 part of methacrylamide and 22 parts of deionized water; the feed liquid B is prepared by mixing 0.12 part of reducing agent L-ascorbic acid, 0.32 part of chain transfer agent namely mercaptopropionic acid and 25 parts of deionized water. The preparation method of the coagulation-accelerating early-strength polycarboxylic acid superplasticizer comprises the following process steps: putting 76 parts of polyoxyethylene ether macromonomer, 0.012 part of ferrous sulfate and 48 parts of deionized water into a reaction kettle according to the mass ratio, heating to 42 ℃, and stirring until the polyoxyethylene ether macromonomer is completely dissolved; adding 1.5 parts of water-based initiator into a reaction kettle, then respectively starting to simultaneously dropwise add the material liquid A and the material liquid B by using a constant flow pump, finishing dropwise adding the material liquid A within 3 hours, finishing dropwise adding the material liquid B within 3.5 hours, after finishing dropwise adding all the material liquids, carrying out heat preservation reaction for 1.5 hours, finally cooling the obtained product to room temperature, adding liquid alkali to adjust the pH value to 7, and obtaining the coagulation-promoting early-strength type polycarboxylic acid superplasticizer.
The preferable technical scheme of the invention can also be seen in the following embodiments 3-5.
The invention can effectively promote the early hydration of cement by adopting high-component long side chain synthesis, and generates more compact and fine hydration products. Unsaturated alcohol amine is introduced into the main chain, and the unsaturated alcohol amine can be hydrolyzed due to the alkaline environment of cement to release the alcohol amine, so that the hydration is further accelerated to play a role of a condensation catalyst, and meanwhile, part of carboxyl can be protected to play a role of maintaining slump loss. The backbone is grafted with a portion of amide groups, and because of the presence of N, early hydration can be promoted to provide early strength. Because organic functional groups are not introduced, the mineral phase change of the hydration product is not influenced, and the later strength is not reduced.
The invention discloses a polycarboxylic acid superplasticizer, relates to a polycarboxylic acid dispersant, and is prepared by carrying out free radical polymerization by taking (methyl) acrylic acid, unsaturated alcohol amine ester, unsaturated amide and polyoxyethylene ether as monomers. The water reducer has high water reducing capacity and high retention capacity, and can effectively shorten the concrete setting time, thereby reducing the static stop time of a prefabricated part, accelerating the turnover of a template and saving the cost. Meanwhile, the early strength of the concrete in 1 day can be effectively improved, the strength of the concrete in 28 days is not reduced, the steam curing temperature can be reduced, the demolding speed is accelerated, the steam curing energy consumption is saved, the template turnover is improved, and the construction cost is reduced.
Drawings
FIG. 1 is a graph of the initial setting time of concrete of different samples in the test of the present invention.
Detailed Description
Example 1: the coagulation-accelerating early-strength polycarboxylic acid superplasticizer is prepared from the following raw materials in parts by weight: 72 parts of polyoxyethylene ether macromonomer namely prenyl polyoxyethylene ether (TPEG4000), 0.009 parts of reducing agent ferrous sulfate, 1.2 parts of aqueous initiator namely hydrogen peroxide (30 percent of mass percentage concentration and 30 percent of hydrogen peroxide), 45 parts of deionized water, feed liquid A and feed liquid B. The material liquid A is prepared by mixing 8.6 parts of acrylic acid, 0.4 part of unsaturated alcohol amine ester namely triethanolamine trimethacrylate, 0.5 part of unsaturated amide namely acrylamide and 20 parts of deionized water; the feed liquid B is prepared by mixing 0.09 part of reducing agent L-ascorbic acid, 0.3 part of chain transfer agent namely mercaptopropionic acid and 20 parts of deionized water.
The preparation method of the coagulation-accelerating early-strength polycarboxylic acid superplasticizer comprises the following process steps: putting 72 parts of polyoxyethylene ether macromonomer, 0.009 parts of ferrous sulfate and 45 parts of deionized water into a reaction kettle (500ml three-neck flask with magnetic stirring) according to the mass ratio, heating to 40 ℃, and stirring until the polyoxyethylene ether macromonomer is completely dissolved; adding 1.2 parts of water-based initiator into a reaction kettle, then respectively starting to simultaneously dropwise add the material liquid A and the material liquid B by using a constant flow pump, finishing dropwise adding the material liquid A within 3 hours, finishing dropwise adding the material liquid B within 3.5 hours, after finishing dropwise adding all the material liquids, carrying out heat preservation reaction for 1.5 hours, finally cooling the obtained product to room temperature, adding liquid alkali (which can be sodium hydroxide aqueous solution with the mass percentage concentration of 30%) to adjust the pH value to 7, and thus obtaining the coagulation-promoting early-strength type polycarboxylic acid superplasticizer.
Example 2: the coagulation-accelerating early-strength polycarboxylic acid superplasticizer is prepared from the following raw materials in parts by weight: 76 parts of polyoxyethylene ether macromonomer namely prenyl polyoxyethylene ether (TPEG4000), 0.012 part of reducing agent ferrous sulfate, 1.5 parts of aqueous initiator namely hydrogen peroxide (30 percent of hydrogen peroxide), 48 parts of deionized water, feed liquid A and feed liquid B. The material liquid A is prepared by mixing 9 parts of acrylic acid, 1 part of triethanolamine trimethacrylate, 0.2 part of methacrylamide and 22 parts of deionized water; the feed liquid B is prepared by mixing 0.12 part of reducing agent L-ascorbic acid, 0.32 part of chain transfer agent namely mercaptopropionic acid and 25 parts of deionized water.
The preparation method of the coagulation-accelerating early-strength polycarboxylic acid superplasticizer comprises the following process steps: putting 76 parts of polyoxyethylene ether macromonomer, 0.012 part of ferrous sulfate and 48 parts of deionized water into a reaction kettle (500ml three-neck flask with magnetic stirring) according to the mass ratio, heating to 42 ℃, and stirring until the polyoxyethylene ether macromonomer is completely dissolved; adding 1.5 parts of water-based initiator into a reaction kettle, then respectively starting to simultaneously dropwise add the material liquid A and the material liquid B by using a constant flow pump, finishing dropwise adding the material liquid A within 3 hours, finishing dropwise adding the material liquid B within 3.5 hours, after finishing dropwise adding all the material liquids, carrying out heat preservation reaction for 1.5 hours, finally cooling the obtained product to room temperature, adding liquid alkali to adjust the pH value to 7, and obtaining the coagulation-promoting early-strength type polycarboxylic acid superplasticizer.
Example 3: the coagulation-accelerating early-strength polycarboxylic acid superplasticizer is prepared from the following raw materials in parts by weight: 72 parts of polyoxyethylene ether macromonomer namely prenyl polyoxyethylene ether (TPEG6000), 0.015 part of reducing agent ferrous sulfate, 1.5 parts of aqueous initiator namely hydrogen peroxide (30 percent of hydrogen peroxide), 46 parts of deionized water, feed liquid A and feed liquid B. The material liquid A is prepared by mixing 8 parts of acrylic acid, 1 part of triethanolamine maleate diester, 0.5 part of acrylamide and 21 parts of deionized water; the feed liquid B is prepared by mixing 0.15 part of reducing agent L-ascorbic acid, 0.32 part of chain transfer agent namely mercaptopropionic acid and 22 parts of deionized water.
The preparation method of the coagulation-accelerating early-strength polycarboxylic acid superplasticizer comprises the following process steps: adding 72 parts of polyoxyethylene ether macromonomer, 0.015 part of ferrous sulfate and 46 parts of deionized water into a reaction kettle (a 500ml three-neck flask with magnetic stirring) according to the mass ratio, heating to 45 ℃, and stirring until the polyoxyethylene ether macromonomer is completely dissolved; adding 1.5 parts of water-based initiator into a reaction kettle, then respectively starting to simultaneously dropwise add the material liquid A and the material liquid B by using a constant flow pump, finishing dropwise adding the material liquid A within 3 hours, finishing dropwise adding the material liquid B within 3.5 hours, after finishing dropwise adding all the material liquids, carrying out heat preservation reaction for 1.5 hours, finally cooling the obtained product to room temperature, adding liquid alkali to adjust the pH value to 7, and obtaining the coagulation-promoting early-strength type polycarboxylic acid superplasticizer.
Example 4: the coagulation-accelerating early-strength polycarboxylic acid superplasticizer is prepared from the following raw materials in parts by weight: 72 parts of polyoxyethylene ether macromonomer namely methyl allyl polyoxyethylene ether, 0.015 part of reducing agent ferrous sulfate, 1.5 parts of aqueous initiator namely hydrogen peroxide (30 percent of hydrogen peroxide), 44 parts of deionized water, feed liquid A and feed liquid B. The feed liquid A is prepared by mixing 9 parts of acrylic acid, 2 parts of triethanolamine maleate diester, 1 part of acrylamide and 23 parts of deionized water; the feed liquid B is prepared by mixing 0.15 part of reducing agent L-ascorbic acid, 0.45 part of chain transfer agent namely mercaptopropionic acid and 26 parts of deionized water.
The preparation method of the coagulation-accelerating early-strength polycarboxylic acid superplasticizer comprises the following process steps: adding 72 parts of polyoxyethylene ether macromonomer, 0.015 part of ferrous sulfate and 44 parts of deionized water into a reaction kettle (a 500ml three-neck flask with magnetic stirring) according to the mass ratio, heating to 40 ℃, and stirring until the polyoxyethylene ether macromonomer is completely dissolved; adding 1.5 parts of water-based initiator into a reaction kettle, then respectively starting to simultaneously dropwise add the material liquid A and the material liquid B by using a constant flow pump, finishing dropwise adding the material liquid A within 3 hours, finishing dropwise adding the material liquid B within 3.5 hours, after finishing dropwise adding all the material liquids, carrying out heat preservation reaction for 1.5 hours, finally cooling the obtained product to room temperature, adding liquid alkali to adjust the pH value to 7, and obtaining the coagulation-promoting early-strength type polycarboxylic acid superplasticizer.
Example 5: the coagulation-accelerating early-strength polycarboxylic acid superplasticizer is prepared from the following raw materials in parts by weight: 75 parts of polyoxyethylene ether macromonomer namely prenyl polyoxyethylene ether (TPEG, molecular weight is 4000), 0.012 part of reducing agent ferrous sulfate, 1 part of aqueous initiator namely azodiisobutyl amidine hydrochloride, 42 parts of deionized water, feed liquid A and feed liquid B. The material liquid A is prepared by mixing 8 parts of acrylic acid, 0.6 part of unsaturated alcohol amine ester, 0.8 part of unsaturated amide, namely N, N-dimethylacrylamide and 20 parts of deionized water; the feed liquid B is formed by mixing 0.12 part of reducing agent L-ascorbic acid, 0.4 part of chain transfer agent namely mercaptopropionic acid and 23 parts of deionized water; the unsaturated alcohol amine ester is the combination of two raw materials of triethanolamine diester maleate and triethanolamine trimethacrylate, and the mass ratio of the triethanolamine diester maleate to the triethanolamine trimethacrylate is 2: 1.
The preparation method of the coagulation-accelerating early-strength polycarboxylic acid superplasticizer comprises the following process steps: firstly, 75 parts of polyoxyethylene ether macromonomer, 0.012 part of ferrous sulfate and 42 parts of deionized water are put into a reaction kettle (500ml three-neck flask with magnetic stirring) according to the mass ratio, heated to 40 ℃, and stirred until the polyoxyethylene ether macromonomer is completely dissolved; secondly, adding 1 part of water-based initiator into the reaction kettle, then respectively adopting a constant flow pump to start to simultaneously dropwise add the material liquid A and the material liquid B, completing dropwise adding the material liquid A in 3 hours, completing dropwise adding the material liquid B in 3.5 hours, after completing dropwise adding all the material liquids, preserving heat for reacting for 1.5 hours, finally cooling the obtained product to room temperature, adding liquid alkali to adjust the pH value to 7, and obtaining the coagulation-promoting early-strength type polycarboxylic acid superplasticizer.
The following are the experimental part of the invention:
testing materials:
cement: omei cement P.O 42.5.5, density 3.11g/cm3, specific surface 362m2And/kg, the compressive strength 3d is 24.9MPa, and the compressive strength 28d is 49.7 MPa.
TABLE 1 Cement Components, expressed in mass percent
Sand: the artificial machine-made sand has the water absorption rate of 1.2 percent, the stone powder content of 16 percent and the apparent density of 2720kg/m3。
Stone: artificial macadam 5-20 mm, water absorption 0.3%, needle sheet content 6%, apparent density 2720kg/m3。
Performance evaluation: the cement paste fluidity test is carried out according to the regulation of GB8077-2012 'concrete admixture homogeneity test method', and the water-to-gel ratio is 0.29. The admixture mixing amount is cement mass percent, and the concrete test data is as follows:
TABLE 2 static slurry test data
As can be seen from the net slurry test data, the commercial PCE has good dispersion and retention performance on cement slurry, but the dispersion and retention performance of the commercial early-strength PCE is weaker than that of the conventional PCE, particularly, the expansion loss is very large, the expansion loss from the initial 200mm to 1 hour is only 140mm, and the loss rate reaches 30%. The set-accelerating early-strength PCE has similar dispersing capacity and holding capacity to the conventional PCE, and particularly, the product of the example 5 has better holding capacity than the conventional PCE, and the 1h loss rate is only 2.3 percent.
The concrete tests are shown in the following concrete mixing ratio table 3, and the concrete slump and the concrete expansion tests are carried out according to the regulations of GB/T50080-2002 Standard for Performance test methods of ordinary concrete mixtures (description of attached items), the test temperature is 20 ℃, and the humidity is 52%.
TABLE 3 concrete mix proportions
Under the condition of ensuring that the water consumption is not changed, the PCE doping amount (by mass percentage of the cement) is adjusted so as to achieve the effect that the concrete output machine has the same slump (the error is plus or minus 10 mm). The concrete slump out of the machine and the loss with time are as follows:
TABLE 4 concrete slump test results
As can be seen from the table above, the concrete test results are consistent with the net slurry results. The commercially available early strength PCE has the highest doping amount required for reaching the same slump, and simultaneously loses the slump for half an hour to only 20mm, and the loss rate is as high as 76%. The mixing amount and slump loss condition of the set-accelerating early-strength PCE in the invention are similar to those of the conventional PCE, and the performance of example 5 is better than that of the conventional PCE sold in the market.
FIG. 1 is a graph of the initial setting time of concrete of different samples in the test of the present invention. As can be seen from FIG. 1, with the commercial PCE, the initial setting time of the commercial early strength PCE is close to that of the concrete of example 1, and is about 250 min. The initial setting time was significantly advanced using the concrete from example 2 to example 5, and in particular the initial setting time of example 5 was 60% shorter than that of the commercial PCE.
The concrete is filled into a mold, the mold is stood still for 4 hours in a laboratory with moderate temperature of 20 ℃ and 52 percent, then the mold is put into a quick curing box, the steam curing is carried out for 6 hours at the temperature of 40 ℃, then a test piece is taken out and placed in a laboratory with the temperature of 20 ℃ and 52 percent for 14 hours, and then the one-day strength of the concrete is tested. The intensity data are as follows:
TABLE 5 concrete Strength data
As can be seen from the above table, the commercial early strength PCE has a significantly improved strength in 1 day compared with the conventional PCE, and the strength in 28 days is slightly higher than that of the conventional PCE. In the present example, both the 1-day and 28-day strengths were higher than the commercial early strength PCE. In particular, in example 5, the strength of 1 day is higher than that of commercially available PCE by 21 percent and higher than that of commercially available early strength PCE by 11 percent, and the early strength effect is more obvious. The 28-day strength is higher than that of commercial PCE 7%, higher than that of commercial early strength PCE 6%, and the later strength of the concrete is also improved.
Examples 1 to 5 described above are examples 1 to 5. The invention mainly improves the early strength of the concrete and has no adverse effect on the later strength. Meanwhile, the invention can shorten the initial setting time of the concrete, thereby accelerating the turnover of the precast concrete template and improving the economic benefit. The amphiphilic polycarboxylic acid dispersant in the related literature can improve the fluidity of concrete, particularly the capacity of self-compacting concrete under the condition of reinforcing steel bar density, and improve the workability and the wrapping property of the concrete by mainly adjusting the hydrophilic and lipophilic values of the dispersant. Compared with the prior art, the invention has different proportions and components and solves different technical problems.
In conclusion, the invention effectively improves the early strength of the concrete and shortens the setting time of the concrete.
Claims (5)
1. The coagulation-accelerating early-strength polycarboxylic acid superplasticizer is characterized by being prepared from the following raw materials in parts by weight: 72 parts of polyoxyethylene ether macromonomer namely prenol polyoxyethylene ether, 0.009 parts of reducing agent ferrous sulfate, 1.2 parts of aqueous initiator namely hydrogen peroxide, 45 parts of deionized water, feed liquid A and feed liquid B; the material liquid A is prepared by mixing 8.6 parts of acrylic acid, 0.4 part of unsaturated alcohol amine ester namely triethanolamine trimethacrylate, 0.5 part of unsaturated amide namely acrylamide and 20 parts of deionized water; the feed liquid B is formed by mixing 0.09 part of reducing agent L-ascorbic acid, 0.3 part of chain transfer agent namely mercaptopropionic acid and 20 parts of deionized water;
the preparation method of the coagulation-accelerating early-strength polycarboxylic acid superplasticizer comprises the following process steps: putting 72 parts of polyoxyethylene ether macromonomer, 0.009 parts of ferrous sulfate and 45 parts of deionized water into a reaction kettle according to the mass ratio, heating to 40 ℃, and stirring until the polyoxyethylene ether macromonomer is completely dissolved; adding 1.2 parts of water-based initiator into a reaction kettle, then respectively starting to simultaneously dropwise add the material liquid A and the material liquid B by using a constant flow pump, finishing dropwise adding the material liquid A within 3 hours, finishing dropwise adding the material liquid B within 3.5 hours, after finishing dropwise adding all the material liquids, carrying out heat preservation reaction for 1.5 hours, finally cooling the obtained product to room temperature, adding liquid alkali to adjust the pH value to 7, and obtaining the coagulation-promoting early-strength type polycarboxylic acid superplasticizer.
2. The coagulation-accelerating early-strength polycarboxylic acid superplasticizer is characterized by being prepared from the following raw materials in parts by weight: 76 parts of polyoxyethylene ether macromonomer namely prenol polyoxyethylene ether, 0.012 part of reducing agent ferrous sulfate, 1.5 parts of aqueous initiator namely hydrogen peroxide, 48 parts of deionized water, feed liquid A and feed liquid B; the material liquid A is prepared by mixing 9 parts of acrylic acid, 1 part of triethanolamine trimethacrylate, 0.2 part of methacrylamide and 22 parts of deionized water; the feed liquid B is formed by mixing 0.12 part of reducing agent L-ascorbic acid, 0.32 part of chain transfer agent namely mercaptopropionic acid and 25 parts of deionized water;
the preparation method of the coagulation-accelerating early-strength polycarboxylic acid superplasticizer comprises the following process steps: putting 76 parts of polyoxyethylene ether macromonomer, 0.012 part of ferrous sulfate and 48 parts of deionized water into a reaction kettle according to the mass ratio, heating to 42 ℃, and stirring until the polyoxyethylene ether macromonomer is completely dissolved; adding 1.5 parts of water-based initiator into a reaction kettle, then respectively starting to simultaneously dropwise add the material liquid A and the material liquid B by using a constant flow pump, finishing dropwise adding the material liquid A within 3 hours, finishing dropwise adding the material liquid B within 3.5 hours, after finishing dropwise adding all the material liquids, carrying out heat preservation reaction for 1.5 hours, finally cooling the obtained product to room temperature, adding liquid alkali to adjust the pH value to 7, and obtaining the coagulation-promoting early-strength type polycarboxylic acid superplasticizer.
3. The coagulation-accelerating early-strength polycarboxylic acid superplasticizer is characterized by being prepared from the following raw materials in parts by weight: 72 parts of polyoxyethylene ether macromonomer namely prenol polyoxyethylene ether, 0.015 part of reducing agent ferrous sulfate, 1.5 parts of aqueous initiator namely hydrogen peroxide, 46 parts of deionized water, feed liquid A and feed liquid B; the material liquid A is prepared by mixing 8 parts of acrylic acid, 1 part of triethanolamine maleate diester, 0.5 part of acrylamide and 21 parts of deionized water; the feed liquid B is formed by mixing 0.15 part of reducing agent L-ascorbic acid, 0.32 part of chain transfer agent namely mercaptopropionic acid and 22 parts of deionized water;
the preparation method of the coagulation-accelerating early-strength polycarboxylic acid superplasticizer comprises the following process steps: putting 72 parts of polyoxyethylene ether macromonomer, 0.015 part of ferrous sulfate and 46 parts of deionized water into a reaction kettle according to the mass ratio, heating to 45 ℃, and stirring until the polyoxyethylene ether macromonomer is completely dissolved; adding 1.5 parts of water-based initiator into a reaction kettle, then respectively starting to simultaneously dropwise add the material liquid A and the material liquid B by using a constant flow pump, finishing dropwise adding the material liquid A within 3 hours, finishing dropwise adding the material liquid B within 3.5 hours, after finishing dropwise adding all the material liquids, carrying out heat preservation reaction for 1.5 hours, finally cooling the obtained product to room temperature, adding liquid alkali to adjust the pH value to 7, and obtaining the coagulation-promoting early-strength type polycarboxylic acid superplasticizer.
4. The coagulation-accelerating early-strength polycarboxylic acid superplasticizer is characterized by being prepared from the following raw materials in parts by weight: 72 parts of polyoxyethylene ether macromonomer namely methyl allyl polyoxyethylene ether, 0.015 part of reducing agent ferrous sulfate, 1.5 parts of aqueous initiator namely hydrogen peroxide, 44 parts of deionized water, feed liquid A and feed liquid B; the feed liquid A is prepared by mixing 9 parts of acrylic acid, 2 parts of triethanolamine maleate diester, 1 part of acrylamide and 23 parts of deionized water; the feed liquid B is formed by mixing 0.15 part of reducing agent L-ascorbic acid, 0.45 part of chain transfer agent namely mercaptopropionic acid and 26 parts of deionized water;
the preparation method of the coagulation-accelerating early-strength polycarboxylic acid superplasticizer comprises the following process steps: putting 72 parts of polyoxyethylene ether macromonomer, 0.015 part of ferrous sulfate and 44 parts of deionized water into a reaction kettle according to the mass ratio, heating to 40 ℃, and stirring until the polyoxyethylene ether macromonomer is completely dissolved; adding 1.5 parts of water-based initiator into a reaction kettle, then respectively starting to simultaneously dropwise add the material liquid A and the material liquid B by using a constant flow pump, finishing dropwise adding the material liquid A within 3 hours, finishing dropwise adding the material liquid B within 3.5 hours, after finishing dropwise adding all the material liquids, carrying out heat preservation reaction for 1.5 hours, finally cooling the obtained product to room temperature, adding liquid alkali to adjust the pH value to 7, and obtaining the coagulation-promoting early-strength type polycarboxylic acid superplasticizer.
5. The coagulation-accelerating early-strength polycarboxylic acid superplasticizer is characterized by being prepared from the following raw materials in parts by weight: 75 parts of polyoxyethylene ether macromonomer namely prenyl polyoxyethylene ether, 0.012 part of reducing agent ferrous sulfate, 1 part of aqueous initiator namely azobisisobutyramidine hydrochloride, 42 parts of deionized water, feed liquid A and feed liquid B; the material liquid A is prepared by mixing 8 parts of acrylic acid, 0.6 part of unsaturated alcohol amine ester, 0.8 part of unsaturated amide, namely N, N-dimethylacrylamide and 20 parts of deionized water; the feed liquid B is formed by mixing 0.12 part of reducing agent L-ascorbic acid, 0.4 part of chain transfer agent namely mercaptopropionic acid and 23 parts of deionized water; the unsaturated alcohol amine ester is the combination of two raw materials, namely triethanolamine diester maleate and triethanolamine trimethacrylate, wherein the mass ratio of the triethanolamine diester maleate to the triethanolamine trimethacrylate is 2: 1;
the preparation method of the coagulation-accelerating early-strength polycarboxylic acid superplasticizer comprises the following process steps: firstly, putting 75 parts of polyoxyethylene ether macromonomer, 0.012 part of ferrous sulfate and 42 parts of deionized water into a reaction kettle according to the mass ratio, heating to 40 ℃, and stirring until the polyoxyethylene ether macromonomer is completely dissolved; secondly, adding 1 part of water-based initiator into the reaction kettle, then respectively adopting a constant flow pump to start to simultaneously dropwise add the material liquid A and the material liquid B, completing dropwise adding the material liquid A in 3 hours, completing dropwise adding the material liquid B in 3.5 hours, after completing dropwise adding all the material liquids, preserving heat for reacting for 1.5 hours, finally cooling the obtained product to room temperature, adding liquid alkali to adjust the pH value to 7, and obtaining the coagulation-promoting early-strength type polycarboxylic acid superplasticizer.
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| CN113321438B (en) * | 2021-05-29 | 2023-04-07 | 石家庄市长安育才建材有限公司 | Slurry-rich concrete additive and preparation method thereof |
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