CN108558259B - Application of high-water-reduction and mud-resistance water reducer in construction solid waste recycled aggregate concrete - Google Patents

Application of high-water-reduction and mud-resistance water reducer in construction solid waste recycled aggregate concrete Download PDF

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CN108558259B
CN108558259B CN201711499276.9A CN201711499276A CN108558259B CN 108558259 B CN108558259 B CN 108558259B CN 201711499276 A CN201711499276 A CN 201711499276A CN 108558259 B CN108558259 B CN 108558259B
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water
mud
reducing
reaction
reducing agent
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CN108558259A (en
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张小富
吴德龙
冯波
赵利华
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GUANGDONG REDWALL NEW MATERIALS CO Ltd
Shanghai Construction Building Materials Technology Group Co Ltd
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GUANGDONG REDWALL NEW MATERIALS CO Ltd
Shanghai Jiangong Construction Material Co Ltd
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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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
    • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/243—Phosphorus-containing polymers
    • C04B24/246—Phosphorus-containing polymers containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention discloses an application of a high water-reducing and mud-resistant water reducing agent in building solid waste recycled aggregate concrete, and also provides the building solid waste recycled aggregate concrete containing the high water-reducing and mud-resistant water reducing agent. The high water-reducing and mud-resisting water reducing agent is based on the principle of macromolecular structure design and is formed by polymerizing active monomers containing phosphorous acid functional groups and sulfonic acid functional groups, the molecular structure is in a group shape, and the molecular structure contains a large number of amino groups with positive charges, so that the high water-reducing and mud-resisting water reducing agent has the superior performances of high water reduction, high slump retention and high clay tolerance. The water reducer is used independently or in combination with other functional polycarboxylic acid water reducers, and has good water reducing and slump retaining performances on building solid waste recycled aggregate concrete.

Description

Application of high-water-reduction and mud-resistance water reducer in construction solid waste recycled aggregate concrete
Technical Field
The invention relates to an application of a water reducing agent in recycled concrete, in particular to an application of a high water-reducing and mud-resistant water reducing agent in building solid waste recycled aggregate concrete.
Background
Concrete is the second most expensive material to consume in addition to water on earth, the annual consumption of the world is over 200 hundred million tons, and the consumption of concrete is huge, and simultaneously, social and environmental problems of resource consumption and waste disposal are caused. China is the largest country in which new buildings are built in the world every year and is also the largest country in which old buildings are dismantled every year in the world, and according to preliminary estimation, the dismantling of buildings per square meter can generate about 1 ton of building solid waste. The rapid development of cities inevitably generates a large amount of building solid wastes, properly treats the building solid wastes, and becomes a problem needing attention and solution in the whole society. It is generally accepted in the industry that recycling of solid building waste is a key to solve this problem.
At present, the treatment modes of the waste concrete mainly comprise two types: one is simply used as a backfill material, and the other is simply stacked and buried when being transported to the suburb. The former has not reasonably utilized the resources, and the latter not only occupies a large amount of farmland, but also causes new environmental pollution. With the development of environmental protection and sustainable development strategies, people urgently require that the waste concrete is effectively and reasonably utilized, and the waste concrete is used for producing recycled aggregate, so that the engineering cost can be saved, the exploitation cost of natural aggregate and the treatment cost of waste concrete are saved, and the method has important economic and social benefits.
For recycling of waste concrete, a great deal of research work is being conducted in japan, the united states, germany, uk, denmark, the netherlands, and the like, wherein at the best of the japanese research they regard construction solid waste as a "construction by-product". The research of domestic recycled aggregate is late, and the produced recycled aggregate has poor performance (the particle shape and the gradation are poor, a large amount of mortar is attached to the surface, the water absorption is high, the compact volume is small, and the crushing index is low). In recent years, people have more and more researches on recycled concrete, and research work mainly focuses on the influence on the performance of prepared concrete after the recycled aggregate is used for partially or completely replacing natural aggregate, and on the improvement of various performances of the recycled concrete by adding mineral admixtures such as fly ash and the like during the preparation of the concrete, and satisfactory effects are not obtained.
The recycled aggregate produced by the construction solid waste mainly comprises two parts of crushing and screening. Compared with the foreign preparation process, the middle part lacks a strengthening treatment stage, so that the performance of the recycled aggregate obtained by the method is obviously inferior to that of the natural aggregate. The recycled coarse aggregate particles generally consist of three parts, namely clean stones on the surface, stones with part of cement mortar wrapped on the surface and cement mortar particles. The recycled fine aggregate mainly comprises sand grains without cement paste on the surface, sand grains with cement paste attached on the surface, cement stone grains and a small amount of broken stone blocks. The low-quality recycled aggregate which is the simply crushed recycled aggregate without strengthening treatment has more edges and corners and rough surface, the components also contain hardened cement mortar (the cement mortar has large porosity and high water absorption), and in addition, a large amount of micro cracks are accumulated in the concrete blocks due to damage in the process of disintegration and crushing, so that the porosity of the recycled aggregate is increased, and the water absorption rate are increased. The water absorption rate is related to factors such as the content of set cement in the aggregate, the adhesion rate of cement mortar on the surface of the aggregate, the strength of original concrete, the type of the aggregate used by the original concrete, the preparation method of the recycled aggregate and the like.
Because the surface of the recycled aggregate contains a large amount of cement mortar, compared with natural aggregate, the bulk density and the apparent density of the recycled aggregate are reduced; the mud content of the recycled aggregate is far higher than that of the natural aggregate; the porosity of the recycled aggregate concrete is higher than that of the natural aggregate concrete. The characteristics of the recycled aggregate determine that the recycled aggregate concrete has the following characteristics: (1) the water requirement is high, and the admixture mixing amount is high; (2) slump loss is large with time; (3) the shrinkage rate is large. Aiming at the problems of high mud content and complex components of recycled aggregate, high mud content of aggregate and absorption of a large amount of additives on the surface of soil particles, researches show that the PEO side chain of the polycarboxylate superplasticizer and the soil particles generate successive intercalation reaction, and the combined action of the PEO side chain and the soil particles results in rapid slump loss of concrete, so that the concrete completely loses fluidity and slump and loses workability, but no high-water-reducing superplasticizer with good mud resistance matched with the PEO side chain in the current market has good effect. The method solves the problem of quick slump loss caused by high mud content of recycled aggregate concrete, is one of the major problems of recycling of solid waste of buildings and realization of sustainable development of concrete.
Disclosure of Invention
Based on the above, the invention aims to overcome the defects of the prior art and provide the application of the high water-reducing and mud-resistant water reducing agent in the construction solid waste recycled aggregate concrete, and the invention also provides the construction solid waste recycled aggregate concrete containing the high water-reducing and mud-resistant water reducing agent. One characteristic of the polycarboxylate superplasticizer is that the designability is good, and different molecular structures can be designed according to different requirements. The invention relates to a high water-reducing and mud-resistant water reducing agent which is synthesized by performing end group modification on an active macromonomer PEO/PPO chain through a (Mannich) Mannich reaction, introducing a phosphorous acid functional group as a side chain end group, and synthesizing the high water-reducing and mud-resistant water reducing agent containing the phosphorous acid functional group and a sulfonic acid functional groupThe water reducing agent is a high-water-reducing and cement-resisting water reducing agent without a carboxylic acid group, and the sulfonic group functional group is an important leading functional group in the polycarboxylic acid water reducing agent, mainly shows strong electrostatic repulsion and has good dispersibility; the phosphorous acid functional group has two negative charges, has strong adsorbability, and can be quickly adsorbed to the surface of cement particles with positive charges to disperse the cement particles; the molecular structure of the water reducing agent is in a group shape, and amine cation and-PO in the molecular structure3 2-、Ca2+and-PO3 2-The physical crosslinking is formed to make the molecular structure be a group type, a complex adsorption layer is formed on the surface of cement particles to prevent the cement particles from contacting with each other and effectively disperse the cement particles, and meanwhile, the amine cations with positive charges in the molecular structure can be rapidly adsorbed on the surface of soil particles with negative charges to prevent the continuous intercalation reaction of PEO/PPO side chains to the clay particles, further, the end groups of the PEO/PPO side chains generate electrostatic repulsion with the clay particles with negative charges on the surface due to the introduction of the phosphorous acid functional groups with two negative charges, and the chain intercalation reaction of the PEO/PPO side chains to the clay particles is also avoided, so that the water reducer has high water reducing rate and good mud slump resistance. The water reducing agent has good dispersibility, high water reducing rate, large soil tolerance, certain slump retaining property and early strength performance.
In order to achieve the purpose, the invention adopts the technical scheme that: the building solid waste recycled aggregate concrete comprises a high water-reducing and mud-resisting water reducer, wherein the high water-reducing and mud-resisting water reducer is a compound shown in a formula (I), and the compound shown in the formula (I) has the following structural formula:
Figure BDA0001532174250000031
wherein x is an integer of 1 to 60, y is an integer of 1 to 150, j is an integer of 1 to 100, and k is an integer of 1 to 250;
a is
Figure BDA0001532174250000032
B is
Figure BDA0001532174250000041
C is
Figure BDA0001532174250000042
D is
Figure BDA0001532174250000043
Figure BDA0001532174250000044
Figure BDA0001532174250000051
Wherein m is an integer of 0 to 100, and n is an integer of 20 to 250.
Preferably, m is an integer of 1 to 100.
Preferably, the high water-reducing and mud-resistant water reducing agent is prepared by the following method:
(1) mixing water, 3-butene-1-amine and H3PO3Fully stirring and uniformly mixing, heating to 40-45 ℃, slowly dripping a formaldehyde water solution, controlling the dripping time to be 1.5-2 h, slowly heating to 75-85 ℃, and continuously reacting for 1.5-2.5 h to obtain a reaction monomer B;
(2) blocking water and amino group2CH2-NH2、HPEG-CH2CH2-NH2、TPEG-CH2CH2-NH2And VPEG-CH2CH2-NH2And H3PO3Fully stirring and uniformly mixing, heating to 40-45 ℃, slowly dripping a formaldehyde water solution, controlling the dripping time to be 2.0-3.0 h, then slowly heating to 80-90 ℃, and continuously reacting for 2.5-4.0 h to obtain an active macromonomer D;
(3) uniformly mixing deionized water, a molecular weight regulator, a reaction monomer A, a reaction monomer B, a reaction monomer C and an active macromonomer D, heating to 80-90 ℃, dropwise adding an aqueous solution of an initiator, controlling the dropwise adding time to be 2-3 h, then carrying out heat preservation reaction for 6-10 h, cooling to 40-45 ℃, and adjusting the pH to be 7-8 by using a NaOH solution to obtain the high water-reducing and mud-resistant water reducer.
Preferably, the 3-butene-1-amine, H in the step (1)3PO3And formaldehyde in a molar ratio of 3-buten-1-amine: h3PO3: formaldehyde 1.0:0.95: 0.95; the formaldehyde is an aqueous solution with the mass concentration of 37%.
Preferably, APEG-CH in step (2)2CH2-NH2、HPEG-CH2CH2-NH2、TPEG-CH2CH2-NH2And VPEG-CH2CH2-NH2One of (1), H3PO3The molar ratio of the formaldehyde to the APEG-CH is2CH2-NH2、HPEG-CH2CH2-NH2、TPEG-CH2CH2-NH2And VPEG-CH2CH2-NH2One of (1): h3PO3: formaldehyde 1.0: (0.90-0.95): (0.90-0.95); the formaldehyde is an aqueous solution with the mass concentration of 37%.
Preferably, the molar ratio of the reactive monomer A, the reactive monomer B, the reactive monomer C and the reactive macromonomer D in the step (3) is the molar ratio of the reactive monomer A: reaction of monomers B: reaction of monomers C: and (3-1.0) of active macromonomer D: (1.0-3.0): (0.5-4.0): (1.0-3.0); the molecular weight regulator is thioglycolic acid, and the using amount of the molecular weight regulator is 0.005-5 percent of the total mole number of the reaction monomer A, the reaction monomer B, the reaction monomer C and the active macromonomer D; the initiator is selected from at least one of ammonium persulfate, potassium persulfate and hydrogen peroxide, and the using amount of the initiator is 0.005-5 percent of the total mole number of the reaction monomer A, the reaction monomer B, the reaction monomer C and the active macromonomer D; the mass fraction of the NaOH solution is 30%.
Preferably, in the step (1), concentrated hydrochloric acid with the mass concentration of 37% is added into water, 3-butene-1-amine and H3PO3Fully stirring and uniformly mixing, heating to 40-45 ℃, wherein the volume of concentrated hydrochloric acid with the mass concentration of 37% accounts forThe proportion of the total volume of the reaction is 0.08-0.1%; in the step (2), concentrated hydrochloric acid with the mass concentration of 37% is added into water and amino-terminated APEG-CH2CH2-NH2、HPEG-CH2CH2-NH2、TPEG-CH2CH2-NH2And VPEG-CH2CH2-NH2And H3PO3Fully stirring and uniformly mixing, heating to 40-45 ℃, wherein the volume of concentrated hydrochloric acid with the mass concentration of 37% accounts for 0.08-0.1% of the total volume of the reaction.
APEG is
Figure BDA0001532174250000061
HPEG is
Figure BDA0001532174250000062
TPEG is
Figure BDA0001532174250000063
VPEG is
Figure BDA0001532174250000064
The reaction formula of the step (1) is as follows:
Figure BDA0001532174250000065
with APEG-CH2CH2NH2For example, the reaction formula of the step (2) is as follows:
Figure BDA0001532174250000071
preferably, the APEG-CH2CH2NH2、HPEG-CH2CH2NH2、TPEG-CH2CH2NH2And VPEG-CH2CH2NH2Number average molecular weight: 2000-5000.
Preferably, the recycled concrete further comprises water, cement, fly ash, mineral powder, river sand, natural pebbles and recycled pebbles, and the mass ratio of the water, the cement, the fly ash, the mineral powder, the river sand, the natural pebbles, the recycled pebbles and the high water-reducing and cement-resistant water reducing agent is water: cement: fly ash: mineral powder: river sand: natural stones: and (3) regenerating stones: the high water-reducing and mud-resistant water reducing agent is (170-190): (200-250): (50-80): (60-90): (770-870): (310-460): (550-700): (8-13).
Preferably, the water: cement: fly ash: mineral powder: river sand: natural stones: and (3) regenerating stones: high water-reducing and mud-resisting water reducing agent (175-188): (215-245): (55-70): (75-85): (800-850): (360-410): (560-690): (8.5-12.5); preferably, the water: cement: fly ash: mineral powder: river sand: natural stones: and (3) regenerating stones: high water-reducing and mud-resistant water reducing agent 180: 235: 65: 80: 842: 378: 630: 9.6.
the invention also provides an application of the high water-reducing and mud-resisting water reducing agent in building solid waste recycled aggregate concrete, wherein the high water-reducing and mud-resisting water reducing agent is a compound shown in a formula (I), and the structural formula of the compound shown in the formula (I) is as follows:
Figure BDA0001532174250000081
wherein x is an integer of 1 to 60, y is an integer of 1 to 150, j is an integer of 1 to 100, and k is an integer of 1 to 250;
a is
B is
Figure BDA0001532174250000083
C is
D is
Figure BDA0001532174250000085
Figure BDA0001532174250000091
Wherein m is an integer of 0 to 100, and n is an integer of 20 to 250.
Preferably, m is an integer of 1 to 100.
The mud-resistant water reducer is synthesized by modifying a PEO/PPO side chain end group through a Mannich reaction and introducing a phosphorous acid functional group as a side chain end group, and has the following advantages:
(1) the molecular structure contains a large amount of amine cations, and the amine cations are adsorbed on the surface of clay particles with negative charges, so that the chain intercalation reaction of common polycarboxylate superplasticizer PEO side chains to the clay particles is avoided, and the clay resistance is greatly improved;
(2) the sulfonate group contained in the molecular structure has good dispersibility on cement particles, and the phosphite group has good dispersibility and dispersibility retentivity on the cement particles, so that the cement has the characteristics of high water reducing rate and good slump retaining property;
(3) anion and cation balance, amine cation and-PO3 2--Ca and M in2+and-PO3 2-Form a physical micro-crosslinking structure;
(4) the molecules are in a cluster structure, the cluster structure is physical crosslinking, a complex adsorption layer is formed on the surface of cement particles, steric hindrance is formed, and excellent dispersion and slump retaining performance are endowed;
(5) the molecular structure contains a large amount of N+Electric charge, and N+The electric charge can accelerate the hydration reaction rate of cement, obviously improve the early strength of concrete, and can be used in precast components, tubular piles and segment concreteThe early strength of the concrete is obviously improved, and the form removal time and the turnover period of the mold are shortened.
Compared with the prior art, the invention has the beneficial effects that: the invention discloses application of a high water-reducing and mud-resistant water reducing agent in building solid waste recycled aggregate concrete, and also provides recycled concrete containing the high water-reducing and mud-resistant water reducing agent. The high water-reducing mud-resistant water reducing agent provided by the invention has the advantages of good dispersibility, high water reducing rate, large mud tolerance, certain slump retaining property and early strength property.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The embodiment of the preparation method of the high water-reducing and mud-resistant water reducing agent comprises the following steps:
(1) mixing water, 3-butene-1-amine and H3PO3Adding concentrated hydrochloric acid with the mass concentration of 37% into a 500ml four-mouth glass flask with a stirrer, a thermometer and a reflux condenser, fully stirring and uniformly mixing, heating to 40 ℃, slowly dropwise adding a formaldehyde water solution with the mass concentration of 37%, controlling the dropwise adding time to be 2h, slowly heating to 75 ℃, and continuously reacting for 2.5h to obtain a reaction monomer B;
(2) mixing water and APEG-CH2CH2NH2、H3PO3Adding concentrated hydrochloric acid with the mass concentration of 37% into a 500ml four-mouth glass flask with a stirrer, a thermometer and a reflux condenser, fully stirring and uniformly mixing, heating to 40 ℃, slowly dropwise adding a formaldehyde water solution with the mass concentration of 37%, controlling the dropwise adding time to be 3.0h, then slowly heating to 80 ℃, and continuously reacting for 4.0h to obtain an active macromonomer D shown in the following structural formula;
(3) adding deionized water, thioglycollic acid, a reaction monomer A, a reaction monomer B, a reaction monomer C and an active macromonomer D into a 1000ml four-neck glass flask with a stirrer, a thermometer and a reflux condenser, heating to 80 ℃, dropwise adding an aqueous solution of ammonium persulfate, controlling the dropwise adding time to be 3h, then carrying out heat preservation reaction for 6h, cooling to 40 ℃, and adjusting the pH to be 7.0 by using a NaOH solution with the mass fraction of 30% to obtain the high-water-reducing and mud-resistant water reducer.
The structural formula of the reaction monomer C is as follows:
Figure BDA0001532174250000111
3-butene-1-amine, H in the step (1)3PO3And formaldehyde in a molar ratio of 1.0:0.95: 0.95; the volume of the concentrated hydrochloric acid accounts for 0.08 percent of the total volume of the reaction.
APEG-CH in step (2)2CH2NH2、H3PO3And formaldehyde in a molar ratio of 1.0: 0.90: 0.90; the volume of the concentrated hydrochloric acid accounts for 0.08 percent of the total volume of the reaction.
The molar ratio of the reaction monomer A, the reaction monomer B, the reaction monomer C and the active macromonomer D in the step (3) is 0.3: 1.0: 0.5: 1.0; the using amount of the thioglycolic acid is 0.05 percent of the total mole number of the reaction monomer A, the reaction monomer B, the reaction monomer C and the active macromonomer D; the usage amount of the ammonium persulfate is 0.08 percent of the total mole number of the reaction monomer A, the reaction monomer B, the reaction monomer C and the active macromonomer D.
Example 2
The embodiment of the preparation method of the high water reducing mud-resistant water reducing agent comprises the following steps:
(1) mixing water, 3-butene-1-amine and H3PO3Adding concentrated hydrochloric acid with the mass concentration of 37% into a 500ml four-mouth glass flask with a stirrer, a thermometer and a reflux condenser, fully stirring and uniformly mixing, heating to 45 ℃, slowly dropwise adding a formaldehyde water solution with the mass concentration of 37%, controlling the dropwise adding time to be 1.5h, slowly heating to 85 ℃, and continuously reacting for 1.5h to obtain a reaction monomer B;
(2) mixing water and HPEG-CH2CH2NH2、H3PO3Adding concentrated hydrochloric acid with the mass concentration of 37% into a 500ml four-mouth glass flask with a stirrer, a thermometer and a reflux condenser, fully stirring and uniformly mixing, heating to 45 ℃, slowly dropwise adding a formaldehyde water solution with the mass concentration of 37%, controlling the dropwise adding time to be 3.0h, then slowly heating to 90 ℃, and continuously reacting for 2.5h to obtain an active macromonomer D shown in the following structural formula;
Figure BDA0001532174250000121
(3) adding deionized water, thioglycollic acid, a reaction monomer A, a reaction monomer B, a reaction monomer C and an active macromonomer D into a 1000ml four-neck glass flask with a stirrer, a thermometer and a reflux condenser, heating to 90 ℃, dropwise adding an aqueous solution of hydrogen peroxide, controlling the dropwise adding time to be 2h, then carrying out heat preservation reaction for 10h, cooling to 45 ℃, and adjusting the pH to be 8 by using a NaOH solution with the mass fraction of 30% to obtain the high-water-reducing and mud-resistant water reducer.
The structural formula of the reaction monomer C is as follows:
Figure BDA0001532174250000122
3-butene-1-amine, H in the step (1)3PO3And formaldehyde in a molar ratio of 1.0:0.95: 0.95; the volume of the concentrated hydrochloric acid accounts for 0.1 percent of the total volume of the reaction.
APEG and H in the step (2)3PO3And formaldehyde in a molar ratio of 1.0:0.95: 0.95; the volume of the concentrated hydrochloric acid accounts for 0.1 percent of the total volume of the reaction.
The molar ratio of the reaction monomer A, the reaction monomer B, the reaction monomer C and the active macromonomer D in the step (3) is 1.0: 3.0: 4.0: 3.0; the using amount of the thioglycolic acid is 4.0 percent of the total mole number of the reaction monomer A, the reaction monomer B, the reaction monomer C and the active macromonomer D; the usage amount of the hydrogen peroxide is 2.0 percent of the total mole number of the reaction monomer A, the reaction monomer B, the reaction monomer C and the active macromonomer D.
Example 3
One embodiment of the preparation method of the mud-resistant water reducer comprises the following steps:
(1) mixing water, 3-butene-1-amine and H3PO3Adding concentrated hydrochloric acid with the mass concentration of 37% into a 500ml four-neck glass flask with a stirrer, a thermometer and a reflux condenser, fully stirring and uniformly mixing, heating to 42 ℃, slowly dropwise adding a formaldehyde water solution with the mass concentration of 37%, controlling the dropwise adding time to be 2h, slowly heating to 80 ℃, and continuously reacting for 2h to obtain a reaction monomer B;
(2) mixing water and TPEG-CH2CH2NH2、H3PO3Adding concentrated hydrochloric acid with the mass concentration of 37% into a 500ml four-mouth glass flask with a stirrer, a thermometer and a reflux condenser, fully stirring and uniformly mixing, heating to 43 ℃, slowly dropwise adding a formaldehyde water solution with the mass concentration of 37%, controlling the dropwise adding time to be 2.5h, then slowly heating to 88 ℃, and continuously reacting for 3h to obtain an active macromonomer D shown in the following structural formula;
Figure BDA0001532174250000131
(3) adding deionized water, thioglycollic acid, a reaction monomer A, a reaction monomer B, a reaction monomer C and an active macromonomer D into a 1000ml four-neck glass flask with a stirrer, a thermometer and a reflux condenser, heating to 87 ℃, dropwise adding a potassium persulfate aqueous solution, controlling the dropwise adding time to be 3h, then carrying out heat preservation reaction for 7h, cooling to 43 ℃, and adjusting the pH to be 6.5 by using a NaOH solution with the mass fraction of 30% to obtain the high-water-reducing and mud-resistant water reducer.
The structural formula of the reaction monomer C is as follows:
Figure BDA0001532174250000132
3-butene-1-amine, H in the step (1)3PO3And formaldehyde in a molar ratio of: 1.0:0.95: 0.95; the volume of the concentrated hydrochloric acid accounts for 0.08 percent of the total volume of the reaction.
TPEG-CH in the step (2)2CH2NH2、H3PO3And the molar ratio of the formaldehyde to the water is 1.0: 0.93: 0.91; the volume of the concentrated hydrochloric acid accounts for 0.1 percent of the total volume of the reaction.
The molar ratio of the reaction monomer A, the reaction monomer B, the reaction monomer C and the active macromonomer D in the step (3) is 0.3: 2.0: 3.5: 1.8; the using amount of the thioglycolic acid is 1.5 percent of the total mole number of the reaction monomer A, the reaction monomer B, the reaction monomer C and the active macromonomer D; the usage amount of the potassium persulfate is 3 percent of the total mole number of the reaction monomer A, the reaction monomer B, the reaction monomer C and the active macromonomer D.
Example 4
One embodiment of the preparation method of the mud-resistant water reducer comprises the following steps:
(1) mixing water, 3-butene-1-amine and H3PO3Adding the mixture and concentrated hydrochloric acid with the mass concentration of 37% into a 500ml four-mouth glass flask with a stirrer, a thermometer and a reflux condenser, fully stirring and uniformly mixing, heating to 43 ℃, slowly dropwise adding a formaldehyde water solution with the mass concentration of 37%, controlling the dropwise adding time to be 1.8h, slowly heating to 82 ℃, and continuously reacting for 2.2h to obtain a reaction monomer B;
(2) mixing water and VPEG-CH2CH2NH2、H3PO3Adding the concentrated hydrochloric acid with the mass concentration of 37% into a 500ml four-mouth glass flask with a stirrer, a thermometer and a reflux condenser, fully stirring and uniformly mixing, heating to 44 ℃, slowly dropwise adding a formaldehyde water solution with the mass concentration of 37%, controlling the dropwise adding time to be 2.8h, then slowly heating to 83 ℃, and continuously reacting for 3.5h to obtain an active macromonomer D shown in the following structural formula;
Figure BDA0001532174250000141
(3) adding deionized water, thioglycollic acid, a reaction monomer A, a reaction monomer B, a reaction monomer C and an active macromonomer D into a 1000ml four-neck glass flask with a stirrer, a thermometer and a reflux condenser, heating to 82 ℃, dropwise adding an aqueous solution of ammonium persulfate, controlling the dropwise adding time to be 2.7h, then carrying out heat preservation reaction for 8.5h, cooling to 41 ℃, and adjusting the pH to 7 by using a NaOH solution with the mass fraction of 30% to obtain the high-water-reduction mud-resistant water reducer.
The structural formula of the reaction monomer C is as follows:
Figure BDA0001532174250000142
3-butene-1-amine, H in the step (1)3PO3And formaldehyde in a molar ratio of: 1.0:0.95: 0.95; the volume of the concentrated hydrochloric acid accounts for 0.1 percent of the total volume of the reaction.
VPEG-CH in the step (2)2CH2NH2、H3PO3And formaldehyde in a molar ratio of 1.0: 0.92: 0.90; the volume of the concentrated hydrochloric acid accounts for 0.1 percent of the total volume of the reaction.
The molar ratio of the reaction monomer A, the reaction monomer B, the reaction monomer C and the active macromonomer D in the step (3) is 1: 2.5: 3: 2; the using amount of the thioglycolic acid is 3 percent of the total mole number of the reaction monomer A, the reaction monomer B, the reaction monomer C and the active macromonomer D; the usage amount of the ammonium persulfate is 2.5 percent of the total mole number of the reaction monomer A, the reaction monomer B, the reaction monomer C and the active macromonomer D.
Example 5
One embodiment of the construction solid waste recycled aggregate concrete comprises water, cement, fly ash, mineral powder, river sand, natural pebbles, recycled pebbles and the high water-reducing and mud-resistant water reducing agent in the embodiment 1; the mass ratio of the water, the cement, the fly ash, the mineral powder, the river sand, the natural pebbles, the regenerated pebbles and the high water-reducing and mud-resistant water reducing agent is 185: 215: 80: 60: 770: 450: 630: 10.
example 6
One embodiment of the construction solid waste recycled aggregate concrete comprises water, cement, fly ash, mineral powder, river sand, natural pebbles, recycled pebbles and the high water-reducing and mud-resistant water reducing agent in the embodiment 1; the mass ratio of the water, the cement, the fly ash, the mineral powder, the river sand, the natural pebbles, the regenerated pebbles and the high water-reducing and mud-resistant water reducing agent is 170: 220: 50: 90: 870: 410: 570: 9.
example 7
One embodiment of the construction solid waste recycled aggregate concrete comprises water, cement, fly ash, mineral powder, river sand, natural pebbles, recycled pebbles and the high water-reducing and mud-resistant water reducing agent in the embodiment 1; the mass ratio of the water, the cement, the fly ash, the mineral powder, the river sand, the natural pebbles, the regenerated pebbles and the high water-reducing and mud-resistant water reducing agent is 170: 220: 70: 65: 835: 460: 555: 8.
example 8
One embodiment of the construction solid waste recycled aggregate concrete comprises water, cement, fly ash, mineral powder, river sand, natural pebbles, recycled pebbles and the high water-reducing and mud-resistant water reducing agent in the embodiment 2; the mass ratio of the water, the cement, the fly ash, the mineral powder, the river sand, the natural pebbles, the regenerated pebbles and the high water-reducing and mud-resistant water reducing agent is 190: 250: 50: 60: 815: 335: 700: 13.
example 9
One embodiment of the construction solid waste recycled aggregate concrete comprises water, cement, fly ash, mineral powder, river sand, natural pebbles, recycled pebbles and the high water-reducing and mud-resistant water reducing agent in embodiment 3; the mass ratio of the water, the cement, the fly ash, the mineral powder, the river sand, the natural pebbles, the regenerated pebbles and the high water-reducing and mud-resistant water reducing agent is 180: 200: 70: 85: 850: 340: 660: 10.2.
example 10
One embodiment of the construction solid waste recycled aggregate concrete comprises water, cement, fly ash, mineral powder, river sand, natural pebbles, recycled pebbles and the high water-reducing and mud-resistant water reducing agent in embodiment 4; the mass ratio of the water, the cement, the fly ash, the mineral powder, the river sand, the natural pebbles, the regenerated pebbles and the high water-reducing and mud-resistant water reducing agent is 190: 210: 65: 80: 842: 378: 630: 9.6.
example 11
One embodiment of the construction solid waste recycled aggregate concrete comprises water, cement, fly ash, mineral powder, river sand, natural pebbles, recycled pebbles and the high water-reducing and mud-resistant water reducing agent in embodiment 4; the mass ratio of the water, the cement, the fly ash, the mineral powder, the river sand, the natural pebbles, the regenerated pebbles and the high water-reducing and mud-resistant water reducing agent is 180: 235: 65: 80: 842: 378: 630: 9.6.
example 12 application of the high water-reducing and mud-resistant water reducing agent of the present invention to construction solid waste recycled aggregate concrete.
The structural formula of the high water-reducing and mud-resisting water reducing agent is shown as the formula (I):
Figure BDA0001532174250000161
the C may be selected from C1 or C2:
the D may be selected from D1, D2, D3, or D4:
Figure BDA0001532174250000172
Figure BDA0001532174250000181
in order to research the application effect of the high water-reducing and mud-resistant water reducer in the construction solid waste recycled aggregate concrete, experimental groups 1-8 and a control group 1 are arranged, wherein the construction solid waste recycled aggregate concrete in the experimental groups 1-8 contains the high water-reducing and mud-resistant water reducer, the construction solid waste recycled aggregate concrete in the control group 1 contains a common mud-resistant polycarboxylic acid water reducer, the component proportion of the control group 1 to the concrete of each experimental group is the same except that the use amount of the water reducer, and the initial state of the concrete is equivalent, which is specifically shown in table 1:
TABLE 1 design of the experiment
Figure BDA0001532174250000182
Figure BDA0001532174250000191
The performance of the concrete of the recycled aggregate of the construction solid waste prepared by each experimental group in table 1 is tested, and the results are shown in table 2.
TABLE 2 detection results of concrete performance of construction solid waste recycled aggregate
The data in table 2 show that the water reducing rate of the high water-reducing and mud-resistant water reducing agent with 8 structures (experimental group 1-8) is obviously higher than that of the common mud-resistant polycarboxylate water reducing agent (control group 1), the performance is superior to that of the common mud-resistant polycarboxylate water reducing agent, and the strength of hardened concrete develops faster, because the molecular structure of the high water-reducing and mud-resistant water reducing agent contains a large amount of amino groups with early strength, further, the amino groups have positive charges and can be adsorbed on the surface of mud particles with negative ions, so that the chain intercalation reaction of PEO side chains of the traditional polycarboxylate water reducing agent on the clay particles is inhibited, and the high water-reducing and mud-resistant water reducing agent has excellent clay resistance; meanwhile, the phosphorous acid functional group and the sulfonic acid functional group with two negative charges are introduced into the molecule, so that the phosphorous acid functional group and the sulfonic acid functional group can be quickly adsorbed on the surface of cement particles with positive charges, the cement particles are dispersed, the fluidity and the slump of concrete are kept, and the excellent slump retaining capability is realized.
Example 13 impact of the present invention on the performance of a construction solid waste recycled aggregate concrete formulation.
In this example, the performance of the recycled aggregate concrete for construction solid waste prepared in examples 7 to 11 was measured, and the results are shown in table 3.
TABLE 4 detection results of concrete performance of construction solid waste recycled aggregate
Figure BDA0001532174250000201
As can be seen from Table 3, the recycled concrete of the construction solid waste prepared in the embodiments 7 to 11 of the invention has good performance, which indicates that the mass ratio of water, cement, fly ash, mineral powder, river sand, natural pebbles, recycled pebbles and the high water-reducing and cement-resistant water reducing agent in the recycled concrete is (170-190): (200-250): (50-80): (60-90): (770-870): (310-460): (550-700): (8-13), the water reducing agent has good performance, wherein when the mass ratio of water, cement, fly ash, mineral powder, river sand, natural pebbles, regenerated pebbles to the high water reducing and cement resisting water reducing agent is 180: 235: 65: 80: 842: 378: 630: 9.6 (example 11) the recycled aggregate concrete prepared by the method has the best comprehensive performance.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (7)

1. The building solid waste recycled aggregate concrete is characterized by comprising a high water-reducing and mud-resisting water reducing agent, wherein the high water-reducing and mud-resisting water reducing agent is a compound shown in a formula (I), and the compound shown in the formula (I) has the following structural formula:
Figure FDA0002250323120000011
wherein x is an integer of 1 to 60, y is an integer of 1 to 150, j is an integer of 1 to 100, and k is an integer of 1 to 250;
a is
Figure FDA0002250323120000012
B is
Figure FDA0002250323120000013
C is
Figure FDA0002250323120000014
D is
Figure FDA0002250323120000015
Figure FDA0002250323120000021
Wherein m is an integer of 0 to 100, and n is an integer of 20 to 250;
the high water-reducing and mud-resistant water reducing agent is prepared by the following method:
(1) mixing water, 3-butene-1-amine and H3PO3Fully stirring and uniformly mixing, heating to 40-45 ℃, slowly dripping a formaldehyde water solution, controlling the dripping time to be 1.5-2 h, slowly heating to 75-85 ℃, and continuously reacting for 1.5-2.5 h to obtain a reaction monomer B;
(2) blocking water and amino group2CH2-NH2、HPEG-CH2CH2-NH2、TPEG-CH2CH2-NH2And VPEG-CH2CH2-NH2And H3PO3Fully stirring and uniformly mixing, heating to 40-45 ℃, slowly dripping a formaldehyde water solution, controlling the dripping time to be 2.0-3.0 h, then slowly heating to 80-90 ℃, and continuously reacting for 2.5-4.0 h to obtain an active macromonomer D;
(3) uniformly mixing deionized water, a molecular weight regulator, a reaction monomer A, a reaction monomer B, a reaction monomer C and an active macromonomer D, heating to 80-90 ℃, dropwise adding an aqueous solution of an initiator, controlling the dropwise adding time to be 2-3 h, then carrying out heat preservation reaction for 6-10 h, cooling to 40-45 ℃, and adjusting the pH to be 7-8 by using a NaOH solution to obtain the high water-reducing and mud-resistant water reducer;
wherein the content of the first and second substances,
APEG is
HPEG is
TPEG is
Figure FDA0002250323120000033
VPEG is
Figure FDA0002250323120000034
2. The building solid waste recycled aggregate concrete according to claim 1, wherein m is an integer of 1 to 100.
3. The building solid waste recycled aggregate concrete according to claim 1, wherein the molar ratio of the reaction monomer A to the reaction monomer B to the reaction monomer C to the active macromonomer D in the step (3) is: reaction of monomers B: reaction of monomers C: and (3-1.0) of active macromonomer D: (1.0-3.0): (0.5-4.0): (1.0-3.0); the molecular weight regulator is thioglycolic acid, and the using amount of the molecular weight regulator is 0.005-5 percent of the total mole number of the reaction monomer A, the reaction monomer B, the reaction monomer C and the active macromonomer D; the initiator is selected from at least one of ammonium persulfate, potassium persulfate and hydrogen peroxide, and the using amount of the initiator is 0.005-5 percent of the total mole number of the reaction monomer A, the reaction monomer B, the reaction monomer C and the active macromonomer D; the mass fraction of the NaOH solution is 30%.
4. The construction solid waste recycled aggregate concrete according to claim 1, wherein concentrated hydrochloric acid with the mass concentration of 37% is added into water, 3-butene-1-amine and H in the step (1)3PO3Fully stirring and uniformly mixing, heating to 40-45 ℃, wherein the volume of concentrated hydrochloric acid with the mass concentration of 37% accounts for 0.08-0.1% of the total volume of the reaction; the medium in the step (2)Adding concentrated hydrochloric acid with the concentration of 37% into water and amino-terminated APEG-CH2CH2-NH2、HPEG-CH2CH2-NH2、TPEG-CH2CH2-NH2And VPEG-CH2CH2-NH2And H3PO3Fully stirring and uniformly mixing, heating to 40-45 ℃, wherein the volume of concentrated hydrochloric acid with the mass concentration of 37% accounts for 0.08-0.1% of the total volume of the reaction.
5. The building solid waste recycled aggregate concrete according to claim 1, further comprising water, cement, fly ash, mineral powder, river sand, natural stones and recycled stones, wherein the mass ratio of the water, the cement, the fly ash, the mineral powder, the river sand, the natural stones, the recycled stones and the high water-reducing and cement-resistant water reducing agent is water: cement: fly ash: mineral powder: river sand: natural stones: and (3) regenerating stones: the high water-reducing and mud-resistant water reducing agent is (170-190): (200-250): (50-80): (60-90): (770-870): (310-460): (550-700): (8-13).
6. The building solid waste recycled aggregate concrete according to claim 5, wherein the water: cement: fly ash: mineral powder: river sand: natural stones: and (3) regenerating stones: high water-reducing and mud-resisting water reducing agent (175-188): (215-245): (55-70): (75-85): (800-850): (360-410): (560-690): (8.5-12.5);
7. the building solid waste recycled aggregate concrete according to claim 6, wherein the water: cement: fly ash: mineral powder: river sand: natural stones: and (3) regenerating stones: high water-reducing and mud-resistant water reducing agent 180: 235: 65: 80: 842: 378: 630: 9.6.
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