CN113563541B - Preparation method of polycarboxylate superplasticizer - Google Patents
Preparation method of polycarboxylate superplasticizer Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- 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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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The invention discloses a preparation method of a polycarboxylate water reducer, which comprises the steps of preparing a modifier, preparing an annular matrix, preparing a primary polycarboxylate water reducer, and carrying out aftertreatment; wherein the modifier is prepared by uniformly mixing allyl polyethylene glycol, acrylic acid, azobisisobutyronitrile and diallyldimethylammonium chloride, then preserving heat at 60-70 ℃ for 45-60min, cooling to-10 ℃ to-5 ℃, and freezing at-10 ℃ to-5 ℃ for 30-40min to obtain the modifier; the preparation method of the polycarboxylic acid can improve the adaptability of the polycarboxylic acid water reducing agent, reduce the addition of the slump retaining agent, reduce the sensitivity to the mud content and the temperature of the sandstone aggregate and improve the durability.
Description
Technical Field
The invention relates to a preparation method of a polycarboxylate water reducer, belonging to the technical field of water reducers for cement concrete.
Background
The polycarboxylate water reducer is a high-performance water reducer, is a cement dispersant in cement concrete application, and is widely applied to projects such as highways, bridges, dams, tunnels, high-rise buildings and the like.
Nowadays, in many concrete projects, traditional high-efficiency concrete such as naphthalene series cannot meet engineering requirements more and more due to the limitation of technical performance. The novel generation water reducing agent which is concerned at home and abroad, namely the polycarboxylic acid high-performance water reducing agent, really designs an effective molecular structure according to the action mechanism of dispersed cement, has a super-dispersion type, can prevent the slump loss of concrete without causing obvious retardation, exerts a higher plasticizing effect under low doping amount, has the technical performance characteristics of good fluidity retentivity, wide cement adaptability, large freedom degree on the molecular structure, multiple synthesis technologies, very large scope of high performance, obvious concrete reinforcing effect, capability of reducing the concrete shrinkage, extremely low content of harmful substances and the like, gives the concrete excellent construction workability, good strength development and excellent durability, has good comprehensive technical performance advantages and environmental protection characteristics, and meets the requirements of modern concrete engineering.
The mineral components of cement in China are relatively complex, and in addition, the large application of admixtures, especially the instability of the performance of fly ash, and the adaptability problem of the polycarboxylic acid water reducing agent to the cement and the admixtures still exist, and the problem is mostly reflected in that: the polycarboxylic acid water reducing agent has the advantages of different saturation points of different cements, reduced water reducing rate, increased concrete slump loss, beancurd residue phenomenon, bleeding, sedimentation and segregation and difficult pumping when the concrete is lack of slurry, and the problem of the concrete not being opened or excessively released when the polycarboxylic acid water reducing agent is sensitive to the mixing amount.
In terms of the adaptability of the current polycarboxylic acid water reducing agent, the following solutions are mainly adopted:
on the premise of ensuring the strength of concrete, the sand rate and the size proportion of coarse aggregate are adjusted, the amount of concrete system slurry is increased, the using amount of fly ash is increased, or the mother liquor is compounded by ether and ester and the mixing amount is properly increased, but the method easily causes that the sensitivity of the polycarboxylic acid water reducing agent to the mud content of the sandstone aggregate is strong;
the components of the polycarboxylic acid water reducer are properly added or changed, air entraining agents such as SJ, Degussa DY, foam stabilizer AR and K12 are used, the proportion of the slump retaining agent is increased, composite retarders such as sodium gluconate, white sugar, phosphate, ATMP, citric acid and modified starch are used, soluble cellulose, xanthan gum, dextrin and modified soluble thickener are used, but the method can cause the polycarboxylic acid water reducer to have strong temperature sensitivity and can not meet the requirement of high durability;
the composite polycarboxylate superplasticizer is used for coating the polycarboxylate superplasticizer, but the method can cause the viscosity to be increased, and particularly in the preparation of concrete with high admixture and low cement ratio, the concrete has high viscosity, thus being not beneficial to construction.
Moreover, excessive addition of the slump retaining agent also leads to increased costs. Therefore, the development of a polycarboxylate superplasticizer which can improve the adaptability of the polycarboxylate superplasticizer, reduce the addition of a slump retaining agent, reduce the sensitivity to the mud content and the temperature of the sandstone aggregate and improve the durability is a problem to be solved urgently at present.
The patent CN105130248B discloses that the compound polycarboxylate water reducer comprises a polycarboxylate water reducer and a protective colloid coated outside the polycarboxylate water reducer, wherein the protective colloid coated outside the polycarboxylate water reducer can improve the thermal decomposition temperature of the polycarboxylate water reducer, so that the thermal decomposition temperature of the compound polycarboxylate water reducer is high, the water reducing rate of the compound polycarboxylate water reducer can be greatly improved, and the compound polycarboxylate water reducer has good construction property, high strength and good adaptability; the patent has the following defects: the prepared composite polycarboxylic acid water reducing agent has high viscosity.
Patent CN107298541B discloses a viscosity-reducing type composite polycarboxylic acid water reducer and a preparation method thereof, comprising a polycarboxylic acid water reducer A, a polycarboxylic acid water reducer B, a polycarboxylic acid water reducer C, a beta-cyclodextrin derivative, methyl-beta-cyclodextrin and deionized water; the preparation raw materials of the polycarboxylate superplasticizer A comprise isopentenyl polyoxyethylene ether, acrylic acid, an initiator 1, a chain transfer agent 1 and deionized water; the preparation raw materials of the polycarboxylate superplasticizer B comprise methyl allyl polyglycol ether, acrylic acid, sodium methallyl sulfonate, an initiator 2, a chain transfer agent 2 and deionized water; the preparation raw materials of the polycarboxylate superplasticizer C comprise diallyl-terminated polyether, acrylic acid, methallyl polyglycol ether, an initiator 3, a chain transfer agent 3 and deionized water; the patent has the following defects: the prepared composite polycarboxylic acid water reducing agent is sensitive to temperature and has insufficient slump retaining property at high temperature and low temperature.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a polycarboxylic acid water reducing agent, which realizes the following purposes: the adaptability of the polycarboxylate superplasticizer can be improved, the addition of the slump retaining agent can be reduced, the sensitivity to the mud content and the temperature of the sandstone aggregate is reduced, and the durability can be improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a polycarboxylate water reducer comprises the steps of preparing a modifier, preparing an annular matrix, preparing a primary polycarboxylate water reducer and carrying out aftertreatment.
The preparation method comprises the steps of uniformly mixing allyl polyethylene glycol, acrylic acid, azobisisobutyronitrile and diallyldimethylammonium chloride, then preserving heat at the temperature of 60-70 ℃ for 45-60min, cooling to the temperature of-10 ℃ to-5 ℃, and freezing at the temperature of-10 ℃ to-5 ℃ for 30-40min to obtain the modifier.
The content of the diallyl dimethyl ammonium chloride is 65%.
Wherein the weight ratio of allyl polyethylene glycol, acrylic acid, azobisisobutyronitrile and diallyldimethylammonium chloride is 30-35: 1-1.1: 0.2-0.5: 0.1-0.2.
The preparation method comprises the steps of uniformly mixing sodium methallyl sulfonate, maleic anhydride and lauroyl peroxide, then preserving heat for 30-40min at the temperature of 50-55 ℃, then adding 1, 3-butadiene, vinylamine and nano titanium dioxide, uniformly mixing, then increasing the temperature to 65-70 ℃, preserving heat for 25-30min at the temperature of 65-70 ℃, then carrying out microwave radiation in vacuum, and finishing the microwave radiation to obtain the annular matrix.
The raw materials for preparing the annular matrix comprise the following components in parts by weight: 30-33 parts of sodium methyl propylene sulfonate, 18-20 parts of maleic anhydride, 0.1-0.2 part of lauroyl peroxide, 1-2 parts of 1, 3-butadiene, 0.05-0.1 part of vinylamine and 2-3 parts of nano titanium dioxide.
The vacuum degree during microwave radiation is 120-130Pa, the frequency of microwave radiation is 2400-2500MHz, and the time of microwave radiation is 20-25 min.
Uniformly mixing a modifier, an annular matrix, isopropanol and 25-30% by mass of a methanol solution of sodium methoxide, performing ultraviolet irradiation at 45-50 ℃, controlling the wavelength of the ultraviolet irradiation to be 160-170nm, and keeping the ultraviolet irradiation time to be 25-30min, stopping the ultraviolet irradiation, adding glyoxal, activated carbon and sodium dodecyl benzene sulfonate, and keeping the temperature at 45-50 ℃ for 20-25min to obtain the primary polycarboxylic acid water reducer.
The raw materials for preparing the primary polycarboxylic acid water reducing agent comprise the following components in parts by weight: 5-6 parts of modifier, 60-70 parts of annular matrix, 0.5-1 part of isopropanol, 2-3 parts of 25-30% by mass of sodium methoxide methanol solution, 0.2-0.5 part of glyoxal, 3-4 parts of activated carbon and 1-2 parts of sodium dodecyl benzene sulfonate.
And the post-treatment comprises the steps of carrying out spray drying on the primary polycarboxylic acid water reducing agent, carrying out ball milling in a liquid nitrogen ball mill after the spray drying is finished, controlling the temperature of the liquid nitrogen ball mill to be-155-160 ℃, introducing liquid nitrogen for cold quenching for 10-12min before the ball milling, and then carrying out the ball milling, wherein the ball-to-material ratio in the ball milling process is controlled to be 5-6:1, the rotating speed is 120 plus 130rpm, and the polycarboxylic acid water reducing agent is obtained after the ball milling is carried out for 45-50 min.
The temperature of the spray drying is 110-120 ℃, and the pressure of the spray drying is 0.4-0.5 MPa.
Compared with the prior art, the invention has the beneficial effects that:
(1) the concrete prepared by the polycarboxylic acid water reducing agent has the gas content of 4.5-4.8 percent, the water content of 0.18-0.25 percent, the initial expansion degree of 540-560mm, the expansion degree of 535-555mm after 2h, the compressive strength of 20.9-22.7MPa after 24h, the compressive strength of 56.9-59.2MPa after 28h, the flexural strength of 6.69-7.02MPa after 24h and the flexural strength of 7.85-8.03MPa after 28 h;
(2) according to the polycarboxylic acid water reducing agent prepared by the invention, vinylamine and nano titanium dioxide are added in the preparation of the annular matrix, and liquid nitrogen ball milling is carried out in the post-treatment process, so that the high temperature resistance can be improved, the concrete prepared from the polycarboxylic acid water reducing agent is subjected to high temperature treatment at 1000 ℃ for 5 hours, then is cooled at room temperature for 2 hours, the expansion rate is 100.8-101.5%, the residual temperature is 50-52 ℃, and the decomposed chlorine is 0.4-0.8%;
(3) according to the polycarboxylate superplasticizer prepared by the invention, vinylamine and nano titanium dioxide are added in the preparation of the annular matrix, and liquid nitrogen ball milling is carried out in the post-treatment process, so that the low temperature resistance can be improved, after the concrete prepared by the polycarboxylate superplasticizer is subjected to low-temperature treatment for 48 hours at the humidity of 90% and the temperature of-50 ℃, the compressive strength is 20.6-22.1MPa, and the breaking strength is 6.62-7.01 MPa;
(4) according to the polycarboxylic acid water reducing agent prepared by the invention, vinylamine and nano titanium dioxide are added in the preparation of the annular matrix, and liquid nitrogen ball milling is carried out in the post-treatment process, so that the viscosity of the prepared concrete can be reduced, and the collapse time of the prepared concrete can be shortened to 6s07-6s 24;
(5) according to the polycarboxylic acid water reducing agent prepared by the invention, vinylamine and nano titanium dioxide are added in the preparation of the annular matrix, and liquid nitrogen ball milling is carried out in the post-treatment process, so that the sensitivity to the mud content of the sandstone aggregate can be reduced, and the water, cement, slag, fly ash, montmorillonite and the water reducing agent are mixed according to the mass ratio of 40: 60: 10: 10: 15: 1.8 obtaining the mortar after mixing, wherein the net slurry fluidity after 5 minutes is 281-294mm, the net slurry fluidity after 30 minutes is 274-291mm, and the net slurry fluidity after 60 minutes is 262-285 mm;
(6) the polycarboxylic acid water reducing agent prepared by the invention can improve the water reducing rate of the water reducing agent by carrying out liquid nitrogen ball milling in the post-treatment process, and the water reducing rate is improved to 31.8-33.7%;
(7) according to the polycarboxylic acid water reducing agent prepared by the invention, the modifier branched chain is introduced to the annular matrix during preparation, the durability of the prepared concrete is improved under the condition that a preservative and a bactericide are not required to be added, and the mildew-proof bactericidal performance test shows that mildew, hypha or peculiar smell still can not appear after mould is inoculated and the constant-temperature culture is carried out for 24 months;
(8) the polycarboxylate superplasticizer prepared by the invention can reduce the addition of the slump retaining agent, and after the water reducer is used, the slump reduction rate after 6 hours can be controlled to be 4% only by controlling the mixing amount of the slump retaining agent to be 0.1%.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
A preparation method of a polycarboxylic acid water reducing agent comprises the following steps:
1. preparing a modifier: mixing allyl polyethylene glycol, acrylic acid, azobisisobutyronitrile and diallyldimethylammonium chloride according to a weight ratio of 30: 1: 0.2: 0.1, uniformly mixing, then preserving heat for 45min at the temperature of 60 ℃, cooling to-10 ℃, and carrying out freezing treatment for 30min at the temperature of-10 ℃ to obtain the modifier.
The content of the diallyl dimethyl ammonium chloride is 65%.
2. Preparing an annular matrix: uniformly mixing sodium methallyl sulfonate, maleic anhydride and lauroyl peroxide, then preserving heat for 30min at the temperature of 50 ℃, then adding 1, 3-butadiene, vinylamine and nano titanium dioxide, uniformly mixing, then increasing the temperature to 65 ℃, preserving heat for 25min at the temperature of 65 ℃, then performing microwave radiation under vacuum, controlling the vacuum degree to be 120Pa, the frequency of the microwave radiation to be 2400MHz, and the time of the microwave radiation to be 20min, and finishing the microwave radiation to obtain an annular matrix;
the raw materials for preparing the annular matrix comprise the following components in parts by weight: 30 parts of sodium methyl propylene sulfonate, 18 parts of maleic anhydride, 0.1 part of lauroyl peroxide, 1 part of 1, 3-butadiene, 0.05 part of vinylamine and 2 parts of nano titanium dioxide.
3. Preparing a primary polycarboxylic acid water reducing agent: uniformly mixing a modifier, an annular matrix, isopropanol and 25-30% by mass of a methanol solution of sodium methoxide, performing ultraviolet irradiation at the temperature of 45 ℃, controlling the wavelength of the ultraviolet irradiation to be 160nm, keeping the ultraviolet irradiation time for 25min, stopping the ultraviolet irradiation, adding glyoxal, activated carbon and sodium dodecyl benzene sulfonate, and continuously keeping the temperature at the temperature of 45 ℃ for 20min to obtain a primary polycarboxylic acid water reducer;
the raw materials for preparing the primary polycarboxylic acid water reducing agent comprise the following components in parts by weight: 5 parts of modifier, 60 parts of annular matrix, 0.5 part of isopropanol, 2 parts of methanol solution of sodium methoxide with the mass fraction of 25%, 0.2 part of glyoxal, 3 parts of activated carbon and 1 part of sodium dodecyl benzene sulfonate.
4. And (3) post-treatment: spray drying the primary polycarboxylic acid water reducing agent, controlling the temperature of spray drying to be 110 ℃, the pressure of spray drying to be 0.4MPa, placing the spray drying into a liquid nitrogen ball mill for ball milling after the spray drying is finished, controlling the temperature of the liquid nitrogen ball mill to be-155 ℃, filling liquid nitrogen for cold quenching for 10min before ball milling, then performing ball milling, controlling the ball-to-material ratio in the ball milling process to be 5:1, the rotating speed to be 120rpm, and performing ball milling for 45min to obtain the polycarboxylic acid water reducing agent.
Example 2
A preparation method of a polycarboxylic acid water reducing agent comprises the following steps:
1. preparing a modifier: mixing allyl polyethylene glycol, acrylic acid, azobisisobutyronitrile and diallyldimethylammonium chloride according to a weight ratio of 32: 1: 0.3: 0.1, uniformly mixing, then preserving heat at 65 ℃ for 50min, cooling to-8 ℃, and carrying out freezing treatment at-8 ℃ for 35min to obtain the modifier.
The content of the diallyl dimethyl ammonium chloride is 65%.
2. Preparing an annular matrix: uniformly mixing sodium methallyl sulfonate, maleic anhydride and lauroyl peroxide, then preserving heat for 35min at the temperature of 52 ℃, then adding 1, 3-butadiene, vinylamine and nano titanium dioxide, uniformly mixing, then increasing the temperature to 68 ℃, preserving heat for 28min at the temperature of 68 ℃, then performing microwave radiation under vacuum, controlling the vacuum degree to be 125Pa, the frequency of the microwave radiation to be 2450MHz, controlling the time of the microwave radiation to be 22min, and finishing the microwave radiation to obtain an annular matrix;
the raw materials for preparing the annular matrix comprise the following components in parts by weight: 32 parts of sodium methyl propylene sulfonate, 19 parts of maleic anhydride, 0.1 part of lauroyl peroxide, 1 part of 1, 3-butadiene, 0.08 part of vinylamine and 2.5 parts of nano titanium dioxide.
3. Preparing a primary polycarboxylic acid water reducing agent: uniformly mixing a modifier, an annular matrix, isopropanol and a methanol solution of 28% by mass of sodium methoxide, performing ultraviolet irradiation at the temperature of 48 ℃, controlling the wavelength of the ultraviolet irradiation to be 165nm, and the time of the ultraviolet irradiation to be 28min, stopping the ultraviolet irradiation, adding glyoxal, activated carbon and sodium dodecyl benzene sulfonate, and continuously keeping the temperature at the temperature of 48 ℃ for 23min to obtain a primary polycarboxylic acid water reducer;
the raw materials for preparing the primary polycarboxylic acid water reducing agent comprise the following components in parts by weight: 5.5 parts of modifier, 65 parts of annular matrix, 0.7 part of isopropanol, 2.5 parts of 28 mass percent methanol solution of sodium methoxide, 0.4 part of glyoxal, 3.5 parts of activated carbon and 1.5 parts of sodium dodecyl benzene sulfonate.
4. And (3) post-treatment: spray drying the primary polycarboxylic acid water reducing agent, controlling the temperature of spray drying to be 115 ℃, controlling the pressure of spray drying to be 0.45MPa, placing the spray drying into a liquid nitrogen ball mill for ball milling after the spray drying is finished, controlling the temperature of the liquid nitrogen ball mill to be-158 ℃, filling liquid nitrogen for cold quenching for 11min before ball milling, and then carrying out ball milling, wherein the ball-to-material ratio in the ball milling process is controlled to be 5:1, the rotating speed is 125rpm, and the polycarboxylic acid water reducing agent is obtained after ball milling for 48 min.
Example 3
A preparation method of a polycarboxylic acid water reducing agent comprises the following steps:
1. preparing a modifier: mixing allyl polyethylene glycol, acrylic acid, azobisisobutyronitrile and diallyldimethylammonium chloride according to the weight ratio of 35: 1.1: 0.5: 0.2, uniformly mixing, then preserving heat at the temperature of 70 ℃ for 60min, cooling to-5 ℃, and carrying out freezing treatment at the temperature of-5 ℃ for 40min to obtain the modifier.
The content of the diallyl dimethyl ammonium chloride is 65%.
2. Preparing an annular matrix: uniformly mixing sodium methallyl sulfonate, maleic anhydride and lauroyl peroxide, then preserving heat for 40min at the temperature of 55 ℃, then adding 1, 3-butadiene, vinylamine and nano titanium dioxide, uniformly mixing, then increasing the temperature to 70 ℃, preserving heat for 30min at the temperature of 70 ℃, then performing microwave radiation under vacuum, controlling the vacuum degree to be 130Pa, the frequency of the microwave radiation to be 2500MHz, and the time of the microwave radiation to be 25min, and finishing the microwave radiation to obtain an annular matrix;
the raw materials for preparing the annular matrix comprise the following components in parts by weight: 33 parts of sodium methyl propylene sulfonate, 20 parts of maleic anhydride, 0.2 part of lauroyl peroxide, 2 parts of 1, 3-butadiene, 0.1 part of vinylamine and 3 parts of nano titanium dioxide.
3. Preparing a primary polycarboxylic acid water reducing agent: uniformly mixing a modifier, an annular matrix, isopropanol and 25-30% by mass of a methanol solution of sodium methoxide, performing ultraviolet irradiation at the temperature of 50 ℃, controlling the wavelength of the ultraviolet irradiation to be 170nm, and the time of the ultraviolet irradiation to be 30min, stopping the ultraviolet irradiation, adding glyoxal, activated carbon and sodium dodecyl benzene sulfonate, and continuously preserving the temperature at the temperature of 50 ℃ for 25min to obtain a primary polycarboxylic acid water reducer;
the raw materials for preparing the primary polycarboxylic acid water reducing agent comprise the following components in parts by weight: 6 parts of modifier, 70 parts of annular matrix, 1 part of isopropanol, 3 parts of 30 mass percent methanol solution of sodium methoxide, 0.5 part of glyoxal, 4 parts of activated carbon and 2 parts of sodium dodecyl benzene sulfonate.
4. And (3) post-treatment: spray drying the primary polycarboxylic acid water reducing agent, controlling the temperature of spray drying to be 120 ℃, controlling the pressure of spray drying to be 0.5MPa, placing the spray drying into a liquid nitrogen ball mill for ball milling after the spray drying is finished, controlling the temperature of the liquid nitrogen ball mill to be-160 ℃, filling liquid nitrogen for cold quenching for 12min before ball milling, then performing ball milling, controlling the ball-to-material ratio in the ball milling process to be 6:1, controlling the rotation speed to be 130rpm, and performing ball milling for 50min to obtain the polycarboxylic acid water reducing agent.
Comparative example 1
The preparation method of the polycarboxylate superplasticizer in the embodiment 1 is adopted, and the difference is that: no diallyldimethylammonium chloride was added during the step of preparing the modifier.
Comparative example 2
The preparation method of the polycarboxylate superplasticizer in the embodiment 1 is adopted, and the difference is that: in the step of preparing the annular matrix, vinylamine and nano titanium dioxide are not added.
Comparative example 3
The preparation method of the polycarboxylate superplasticizer in the embodiment 1 is adopted, and the difference is that: liquid nitrogen ball milling is not performed in the post-treatment step.
And (3) performance testing:
water, cement, slag, fly ash and the water reducing agents of the examples 1 to 3 and the comparative examples 1 to 3 were mixed in a mass ratio of 40: 60: 10: 10: 1.8, obtaining mortar after mixing, and then detecting the performance parameters of gas content, water content, expansion degree, air flowing time, compressive strength and flexural strength according to the regulation of JC/T985-2017 cement-based self-leveling mortar for the ground.
And (3) high temperature resistance test:
water, cement, slag, fly ash and the water reducing agents of the examples 1 to 3 and the comparative examples 1 to 3 were mixed in a mass ratio of 40: 60: 10: 10: 1.8 obtaining mortar after mixing, building a three-dimensional model with the length, width and height of one meter by using the mortar, then heating the three-dimensional model, wherein the heating temperature is 1000 ℃, the heating time is 5h, placing the three-dimensional model at room temperature after heating is finished, cooling the three-dimensional model for 2h, and measuring the expansion rate, residual temperature and decomposition rate of the three-dimensional model, wherein the results are as follows:
and (3) low temperature resistance test:
water, cement, slag, fly ash and the water reducing agents of the examples 1 to 3 and the comparative examples 1 to 3 were mixed in a mass ratio of 40: 60: 10: 10: 1.8 obtaining mortar after mixing, then preparing a sample block according to the specification of JC/T985-2017 cement-based self-leveling mortar for ground, treating the cured sample block for 24 hours at the temperature of 100 ℃ and under the humidity of 90 percent, and then respectively testing the compression strength and the bending strength of the sample block before low-temperature treatment;
then respectively processing the sample blocks at the humidity of 90% and the temperature of-50 ℃ for 48h, and then respectively testing the compression strength and the bending strength of the sample blocks after low-temperature processing;
the test results are shown below:
and (3) viscosity testing:
water, cement, slag, fly ash and the water reducing agents of the examples 1 to 3 and the comparative examples 1 to 3 were mixed in a mass ratio of 40: 60: 10: 10: 1.8, obtaining mortar after mixing, and testing the viscosity of the concrete by an inverted slump cone method test according to GB/T50080-2016 standard for testing the performance of common concrete mixtures, wherein the test results are as follows:
sensitivity testing for the mud content of the sandstone aggregates:
water, cement, slag, fly ash, montmorillonite and the water reducing agents of the examples 1-3 and the comparative examples 1-3 are mixed according to the mass ratio of 40: 60: 10: 10: 15: 1.8, obtaining the mortar after mixing, and referring to GB/T8077-2012 concrete admixture homogeneity test method, carrying out the test of net slurry fluidity on examples 1-3 and comparative examples 1-3, and testing the net slurry fluidity after 5 minutes, 30 minutes and 60 minutes.
And (3) testing the water reducing rate:
the water reducing rates of the water reducing agents of examples 1 to 3 and comparative examples 1 to 3 were tested with reference to GB8076-2016 concrete admixture Specification, and the test results were as follows:
and (3) durability test:
water, cement, slag, fly ash and the water reducing agents of the examples 1 to 3 and the comparative examples 1 to 3 were mixed in a mass ratio of 40: 60: 10: 10: 1.8, mixing to obtain mortar, placing the mortar in a constant-temperature incubator, controlling the temperature to be 30 ℃, introducing mould into a sample, controlling the inoculation amount of the mould to be 10cfu/g of the mortar, and testing the mould-proof and bactericidal performance after 6 months, 12 months and 24 months according to the standard of JC/T2552-2019 Fungicide for concrete admixtures, wherein the test results are as follows:
reduction of slump loss test:
water, cement, slag, fly ash and the water reducing agents of the examples 1 to 3 and the comparative examples 1 to 3 were mixed in a mass ratio of 40: 60: 10: 10: 1.8, obtaining the mortar after mixing, and testing the change of slump with time when the mixing amount of the polycarboxylic acid slump retaining agent is 0.1%, 0.2% and 0.3% according to GB8076-2016 concrete admixture specification, wherein the test results are as follows:
all percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the polycarboxylate superplasticizer is characterized by comprising the steps of preparing a modifier, preparing a matrix, preparing a primary polycarboxylate superplasticizer, and carrying out aftertreatment;
the preparation method comprises the steps of uniformly mixing allyl polyethylene glycol, acrylic acid, azobisisobutyronitrile and diallyldimethylammonium chloride, then preserving heat at the temperature of 60-70 ℃ for 45-60min, cooling to the temperature of-10 ℃ to-5 ℃, and freezing at the temperature of-10 ℃ to-5 ℃ for 30-40min to obtain the modifier;
uniformly mixing sodium methallyl sulfonate, maleic anhydride and lauroyl peroxide, then preserving heat for 30-40min at the temperature of 50-55 ℃, then adding 1, 3-butadiene, vinylamine and nano titanium dioxide, uniformly mixing, then increasing the temperature to 65-70 ℃, preserving heat for 25-30min at the temperature of 65-70 ℃, then carrying out microwave radiation in vacuum, and finishing the microwave radiation to obtain a substrate;
uniformly mixing a modifier, a matrix, isopropanol and 25-30% by mass of a methanol solution of sodium methoxide, performing ultraviolet irradiation at 45-50 ℃, controlling the wavelength of the ultraviolet irradiation to be 160-170nm, and keeping the ultraviolet irradiation time to be 25-30min, stopping the ultraviolet irradiation, adding glyoxal, activated carbon and sodium dodecyl benzene sulfonate, and keeping the temperature at 45-50 ℃ for 20-25min to obtain a primary polycarboxylic acid water reducer;
and the post-treatment comprises the steps of carrying out spray drying on the primary polycarboxylic acid water reducing agent, carrying out ball milling in a liquid nitrogen ball mill after the spray drying is finished, controlling the temperature of the liquid nitrogen ball mill to be-155-160 ℃, introducing liquid nitrogen for cold quenching for 10-12min before the ball milling, and then carrying out the ball milling, wherein the ball-to-material ratio in the ball milling process is controlled to be 5-6:1, the rotating speed is 120 plus 130rpm, and the polycarboxylic acid water reducing agent is obtained after the ball milling is carried out for 45-50 min.
2. The preparation method of the polycarboxylate water reducer according to claim 1, wherein the weight ratio of allyl polyethylene glycol, acrylic acid, azobisisobutyronitrile and diallyldimethylammonium chloride in the preparation modifier is 30-35: 1-1.1: 0.2-0.5: 0.1-0.2.
3. The preparation method of the polycarboxylate water reducer as claimed in claim 1, wherein the raw materials in the preparation matrix comprise, in parts by weight: 30-33 parts of sodium methyl propylene sulfonate, 18-20 parts of maleic anhydride, 0.1-0.2 part of lauroyl peroxide, 1-2 parts of 1, 3-butadiene, 0.05-0.1 part of vinylamine and 2-3 parts of nano titanium dioxide.
4. The preparation method of the polycarboxylate water reducer as claimed in claim 1, wherein the degree of vacuum in the preparation matrix during microwave irradiation is 120-130Pa, the frequency of microwave irradiation is 2400-2500MHz, and the time of microwave irradiation is 20-25 min.
5. The preparation method of the polycarboxylate water reducer as claimed in claim 1, wherein the raw materials for preparing the primary polycarboxylate water reducer comprise, by weight: 5-6 parts of modifier, 60-70 parts of matrix, 0.5-1 part of isopropanol, 2-3 parts of methanol solution of sodium methoxide with the mass fraction of 25% -30%, 0.2-0.5 part of glyoxal, 3-4 parts of activated carbon and 1-2 parts of sodium dodecyl benzene sulfonate.
6. The method for preparing a polycarboxylic acid water reducer as claimed in claim 1, wherein the temperature of spray drying in the post-treatment is 110-120 ℃, and the pressure of spray drying is 0.4-0.5 MPa.
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