CN108276575A - A kind of resistance to mud collapse protection type water-reducing agent and preparation method thereof - Google Patents
A kind of resistance to mud collapse protection type water-reducing agent and preparation method thereof Download PDFInfo
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- CN108276575A CN108276575A CN201711499684.4A CN201711499684A CN108276575A CN 108276575 A CN108276575 A CN 108276575A CN 201711499684 A CN201711499684 A CN 201711499684A CN 108276575 A CN108276575 A CN 108276575A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
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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
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
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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
- 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 kind of resistance to mud collapse protection type water-reducing agents and preparation method thereof, present invention application macromolecular structure design principle, pass through Manny strange (Mannich) reaction, it is modified to water-soluble polymer polyethyleneimine (PEI), phosphorous acid functional group is introduced, the collapse protection type water-reducing agent that there is special tolerance to soil and recycled aggregate powder is synthesized.Contain a large amount of amido for carrying positive charge in the products molecule structure, molecular structure is in group's type, this type structure is physical crosslinking, Absorptive complex wave layer is formed in cement particle surface, it collapses ability with good dispersion and guarantor, overcome that collapse protective poly-carboxylic acid water reducing agent bad dispersibility, water-reducing rate in the market be low, disadvantage of clay tolerance difference, the collapse protection type of the resistance to mud water-reducing agent is independent or is used in compounding with other functional polycarboxylate water reducing agents, has good dispersion and function of slump protection to clay and building solid waste regenerated aggregate concrete.
Description
Technical field
The present invention relates to technical field of concrete additives, specifically a kind of collapse protection type of resistance to mud water-reducing agent and its preparation side
Method.
Background technology
Concrete refers to by water, cement, sand and stone mix and through hardenite made of pouring, conserve, hardening, extensive use
It is one of the present age most important civil engineering material, concrete has abundant raw materials, cheap, production in civil engineering
Feature simple for process is a kind of material full of vitality.
Concrete admixture is the component mixed in concrete, it be in concrete raw material except cement, water, sand and stone with
The 5th kind of outer component has been acknowledged as raising concrete strength using additive in concrete, has improved concrete strength, expands
Its various performance is opened up, saves energy consumption, an important measures of environmental protection etc., cement water reducing agent is coagulation
A kind of most widely used in native additive, the maximum additive of usage amount, major function be in the case of not reducing cement consumption,
Improve the performance of fresh concrete, improves mobility and workability, or keeping identical fluidity, reduce cement and use
Amount saves cement, reduces mix water consumption, improves concrete strength.
In recent years, the rapid development with building construction technology is greatly improved in concrete material performance, depends on
The raising and application of the raising of chemical admixture performance, especially high efficiency water reducing agent performance are popularized, and are used at present more
It is polycarboxylate water-reducer.
Polycarboxylate water-reducer has many advantages, such as that volume is low, water-reducing rate is high, concrete contraction percentage is low, environmentally protective, is got over
To be more widely applied.But it being found in practical application, traditional polycarboxylate water-reducer is very sensitive to the clay content in aggregate, with
The raising of clay content in aggregate, the dispersibility and slump retaining of polycarboxylate water-reducer are substantially reduced, or even lose dispersibility, excellent
Matter sand and stone resources are increasingly deficient, almost under exhausted overall situation, and under the background of environmental protection and concrete sustainable development, building
The application of solid waste recycled aggregate and the practice and extension application for building solid waste regenerated aggregate concrete, it is imperative.
The present situation that the current concrete in China and raw material face is：
1, cement type is more, and performance difference is big；
2, the use of low-quality coal ash；
3, concrete slump gradual loss is big；
4, water requirement is high, and admixture dosage is high；
5, shrinking percentage is big, is also easy to produce crack and cracking；
6, the use of Machine-made Sand and building solid waste recycled aggregate, and lack matched high-quality additive.
Cope with the Machine-made Sand or building solid waste recycled aggregate of clay powder content height and complicated component, coagulation caused by solving thus
Native Slump Time losing of Large is big, pumping and construction technological difficulties, is a problem in the urgent need to address, the present invention exactly according to
This is starting point, by high score clamp mechanism design principle, and is based on the basis of polycarboxylate water-reducer and the clay mechanism of action, if
Meter research and development.
Invention content
A kind of resistance to mud collapse protection type diminishing is provided it is an object of the invention to overcome the shortcomings of the prior art place
Agent, the present invention also provides the preparation methods of the collapse protection type of the resistance to mud water-reducing agent to be passed through using macromolecular structure design principle
Mannich mannich reactions, it is modified to high molecular weight water soluble polymer polyethyleneimine (PEI), phosphate functional group is introduced, is closed
Pairs of soil and building solid waste recycled aggregate powder have the collapse protection type water-reducing agent of special tolerance.
To achieve the above object, the technical solution taken：A kind of resistance to mud collapse protection type water-reducing agent, the collapse protection type of resistance to mud subtract
Aqua is formula (I) or formula (II) compound represented, and the formula (I) and formula (II) compound represented structural formula are as follows：
Wherein, the integer that x is 0~50；The integer that y is 10~300；The integer that n is 10~300.
Present invention application macromolecular structure design theory, research and development have synthesized a kind of novel collapse protection type of resistance to mud water-reducing agent, by
Polyethyleneimine contains a large amount of amidos for carrying positive charge in molecular structure, can be adsorbed on the mud particles with anion
Surface inhibits traditional polycarboxylate water-reducer PEO side chains to have superior anti-Property of Clay to the chain intercalation of clay particle；
A large amount of bands are introduced in the molecule simultaneously there are two the orthophosphite of negative electrical charge, are adsorbed on the cement granules with positive charge rapidly
And cement-hydrate particle surface, disperse cement particles and hydrated cementitious composition granule, make concrete that there is good mobility, separately
On the one hand, due to anion-cation balance, amine cation and-PO3 2-Between, Ca2+With-PO3 2-Between formed the micro- crosslinking of physics, molecule
Structure forms Absorptive complex wave layer in cement particle surface, forms certain space in group's shape, group's shape structure of this physical crosslinking
Steric hindrance, meanwhile, group's shape structure of this physical crosslinking gradually and is slowly decomposed and is beaten with the progress of cement hydration process
It opens, releases-PO3 2-, continue disperse cement particles and hydrated cementitious composition granule, keep the mobility and the slump of concrete, have
Have excellent dispersibility and guarantor's degree of collapsing retentivity, overcome collapse protective poly-carboxylic acid water reducing agent bad dispersibility, water-reducing rate in the market it is low,
The low disadvantage of clay patience, the collapse protection type of the resistance to mud water-reducing agent is independent or is used in compounding with other functional polycarboxylate water reducing agents,
There is good diminishing and function of slump protection to machine-made sand concrete and building solid waste regenerated aggregate concrete, and largely have early
The presence of powerful amine cation, while also giving the collapse protection type of resistance to mud water-reducing agent of the invention there is good early powerful,
Make it that can be efficiently used in the preparation of prefabricated components.
Preferably, the integer that the x is 1~50.Its effect of the water-reducing agent of branching type is more than linear water-reducing agent effect
It is good, this is because branched polyethylene imine sodium phosphite than L-PEI sodium phosphite there is the steric hindrance of bigger to imitate
It answers, having more bands, there are two the orthophosphites of negative electrical charge to be adsorbed on cement particle surface, disperse cement particles, to have
Better water-reducing effect and resistance to mud protect effect of collapsing；
Preferably, the collapse protection type of the resistance to mud water-reducing agent is prepared by following methods：
By 50wt% aq. polyethyleneimines and phosphorous acid, 0.3 milliliter of 37wt% concentrated hydrochloric acid, fully stirred at 40~45 DEG C
It mixes, formalin is slowly added dropwise, be added dropwise within 2-3 hours, slow heating is warming up to 80-90 DEG C, and the reaction was continued 2-4 hours,
To solution be yellowish-brown, reduce temperature to 40 DEG C hereinafter, plus 40%NaOH adjust pH=8-9, obtain formula I) or formula II) polyethyleneimine
Amine sodium phosphite.
Preferably, shown in the polyethyleneimine amine structure formula such as formula (III) and formula (IV)：
The integer that wherein x is 0~50；The integer that y is 10~300；The integer that n is 10~300.
Preferably, the integer that the x is 1~50.
Preferably, the polyethyleneimine:Phosphorous acid:The molar ratio of formaldehyde is 1.0:(0.2~3.0):(0.2~3.0).
Preferably, the polyethyleneimine:Phosphorous acid:The molar ratio of formaldehyde is 1.0:2.2:2.1.It has been found that should
Under the conditions of ratio, best results are since amido reacts the most reason of the phosphorous acid radical to be formed by Mannich.
Preferably, described will further include 37wt% concentrated hydrochloric acids, institute in aq. polyethyleneimine and phosphorous acid mixed solution
It is 0.08%~0.1% to state concentrated hydrochloric acid and account for the percent by volume of overall reaction system, and the aq. polyethyleneimine is a concentration of
50wt%, the naoh concentration are 40wt%.
Such as application of the collapse protection type of the resistance to mud water-reducing agent in building solid waste regenerated aggregate concrete.
If the collapse protection type of the resistance to mud water-reducing agent is in the application of machine-made sand concrete prefabricated components.
Beneficial effects of the present invention：
(1) it is adsorbed on rapidly with negative electrical charge containing a large amount of amine cation for carrying positive charge in PEI molecular structures
Mud particles surface prevents common polycarboxylate water-reducer PEO side chains from substantially increasing anti-mud to the chain intercalation of clay particle.
(2) anion-cation balance, amine cation and-PO3 2-Between, Ca2+With-PO3 2-Between formed the micro- cross-linked structure of physics；
(3) molecule is physical crosslinking in group's shape structure, this shape structure, and Absorptive complex wave is formed in cement particle surface
Layer, group's shape structure gradually and slowly decompose opening, release-PO with the progress of hydrated cementitious3 2-, disperse cement again
Grain and hydrated cementitious composition granule have excellent dispersibility and guarantor's degree of collapsing retentivity, assign its superior function of slump protection；
(4) orthophosphite of a large amount of negative electrical charges with there are two is introduced in the collapse protection type of resistance to mud water-reducing agent molecular structure, it is fast
Speed is adsorbed on cement granules and cement-hydrate particle surface, disperse cement particles and cement-hydrate with positive charge
Grain makes concrete have good mobility.
(5) since the amido of PEI and water form hydrogen bond, the viscosity of cement slurry is increased, concrete mix is improved
Mobility and cohesiveness.
(6) contain a large amount of N in molecular structure+Charge, and N+Charge can accelerate hydrated reaction of cement rate, have early
Powerful significantly improves the early strength of concrete, uses, can significantly improve in prefabricated components and pile pile, section of jurisdiction concrete
The early strength of concrete shortens striking time and mold turn around time.
(7) product uses in the high Machine-made Sand prefabricated components of clay powder content, while keeping concrete slump,
It can accelerate hydrated cementitious, significantly improve early strength of concrete, be conserved under the non-evaporating natural conditions supported, exempt from pressure steaming, 8-12
Reach strength of mould stripping in hour, be not spiked with any mineral reinforcement and glass fibre, substantially reduces production cost and mold week
The turn-week phase saves place, meets the fundamental requirement for the assembled construction for reducing energy consumption, environmental protection, is that realization is prefabricated assembled
The key technology node of construction, fills the domestic gaps, economy and social effect with bigger.
Specific implementation mode
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
Embodiment 1
A kind of embodiment of the collapse protection type water-reducing agent of the present invention, collapse protection type water-reducing agent described in the present embodiment is by following methods system
It is standby to form：
With blender, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 500ml in, be added 50wt%PEI it is water-soluble
Liquid, phosphorous acid H3PO3With 0.3 milliliter of 37wt% concentrated hydrochloric acid (volume accounts for the 0.1% of overall reaction system), it is sufficiently stirred, is warming up to 40
DEG C, 37% formalin is slowly added dropwise, is added dropwise within 2 hours, slow heating is warming up to 80 DEG C, and the reaction was continued 3 hours, and solution is
Yellowish-brown, reduce temperature to 40 DEG C hereinafter, plus 40% sodium hydroxide solution, adjust pH=8-9, obtain product polyethyleneimine phosphorous
Sour sodium.
Wherein, PEI：H3PO3：The molar ratio of HCHO is 1.0:0.2:0.9.
The PEI structures of the present embodiment areFor linear structure, wherein n is 10~300
Integer.
The structural formula of the polyethyleneimine phosphite ester of the present embodiment is:
The integer that wherein n is 10~300.
Embodiment 2
A kind of embodiment of the collapse protection type water-reducing agent of the present invention, collapse protection type water-reducing agent described in the present embodiment is by following methods system
It is standby to form：
With blender, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 500ml in, be added 50wt%PEI it is water-soluble
Liquid, phosphorous acid H3PO3With 0.3 milliliter of 37wt% concentrated hydrochloric acid (volume accounts for the 0.1% of overall reaction system), it is sufficiently stirred, is warming up to 40
DEG C, 37% formalin is slowly added dropwise, is added dropwise within 2 hours, slow heating is warming up to 80 DEG C, and the reaction was continued 3 hours, and solution is
Yellowish-brown, reduce temperature to 40 DEG C hereinafter, plus 40% sodium hydroxide solution, adjust pH=8-9, obtain product polyethyleneimine phosphorous
Sour sodium.
Wherein, PEI：H3PO3：The molar ratio of HCHO is 1.0:0.95:0.9.
The PEI structures of the present embodiment areFor linear structure, wherein n is 10~300
Integer.
The structural formula of the polyethyleneimine phosphite ester of the present embodiment is:
The integer that wherein n is 10~300.
Embodiment 3
A kind of embodiment of the collapse protection type water-reducing agent of the present invention, collapse protection type water-reducing agent described in the present embodiment is by following methods system
It is standby to form：
With blender, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 500ml in, the 50wt%PEI water of addition
Solution and phosphorous acid H3PO3, 0.25 milliliter of 37wt% concentrated hydrochloric acid (volume accounts for the 0.08% of overall reaction system), be sufficiently stirred, heat up
To 45 DEG C, 37% formalin is slowly added dropwise, is added dropwise within 2.5 hours, slow heating is warming up to 85 DEG C, and the reaction was continued 2 hours,
Solution is yellowish-brown, reduce temperature to 40 DEG C hereinafter, plus 40% sodium hydroxide solution, adjust pH=8-9, obtain product polyethyleneimine
Amine sodium phosphite.
Wherein, PEI：H3PO3：The molar ratio of HCHO is 1.0:1.5:1.3.
As different from Example 1, PEI structures of the invention are the PEI structures of the present embodiment：
Wherein x is 1, is branching type PEI.
The structural formula of the polyethyleneimine sodium phosphite of the present embodiment is:
Wherein x is the integer that 1, y is 10~300.
Embodiment 4
A kind of embodiment of the collapse protection type water-reducing agent of the present invention, collapse protection type water-reducing agent described in the present embodiment is by following methods system
It is standby to form：
With blender, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 500ml in, the 50wt%PEI water of addition
Solution and phosphorous acid H3PO3, 0.25 milliliter of 37wt% concentrated hydrochloric acid (volume accounts for the 0.08% of overall reaction system), be sufficiently stirred, heat up
To 45 DEG C, 37% formalin is slowly added dropwise, is added dropwise within 2.5 hours, slow heating is warming up to 85 DEG C, and the reaction was continued 2 hours,
Solution is yellowish-brown, reduce temperature to 40 DEG C hereinafter, plus 40% sodium hydroxide solution, adjust pH=8-9, obtain product polyethyleneimine
Amine sodium phosphite.
Wherein, PEI：H3PO3：The molar ratio of HCHO is 1.0:1.5:0.2.
As different from Example 1, PEI structures of the invention are the PEI structures of the present embodiment：
Wherein x is 1, is branching type PEI.
The structural formula of the polyethyleneimine sodium phosphite of the present embodiment is:
Wherein x is the integer that 1, y is 10~300.
Embodiment 5
A kind of embodiment of the collapse protection type of the resistance to mud water-reducing agent of the present invention, the collapse protection type of resistance to mud water-reducing agent described in the present embodiment by with
Lower section method is prepared：
With blender, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 500ml in, be added 50wt%PEI it is water-soluble
Liquid, phosphorous acid H3PO3, 0.3 milliliter of 37wt% concentrated hydrochloric acid (volume accounts for the 0.1% of overall reaction system), be sufficiently stirred, be warming up to 43
DEG C, 37% formalin is slowly added dropwise, is added dropwise within 3 hours, slow heating is warming up to 90 DEG C, and the reaction was continued 3 hours, and solution is
Yellowish-brown, reduce temperature to 40 DEG C hereinafter, plus 40% sodium hydroxide solution, adjust pH=8-9, obtain product polyethyleneimine phosphorous
Sour sodium.
Wherein, PEI：H3PO3：The molar ratio of HCHO is 1.0:2.2:2.1.
The PEI structures of the present embodiment are branching type PEI, and structural formula is：
The integer that wherein x is 1~50, the integer that y is 10~300.
The structural formula of the polyethyleneimine sodium phosphite being prepared of the present embodiment is：
The integer that wherein x is 1~50, the integer that y is 10~300.
Embodiment 6
A kind of embodiment of the collapse protection type water-reducing agent of the present invention, collapse protection type water-reducing agent described in the present embodiment is by following methods system
It is standby to form：
With blender, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 500ml in, the 50wt% of metering is added
PEI aqueous solutions, phosphorous acid H3PO3And 0.3 milliliter of 37wt% concentrated hydrochloric acid (volume accounts for the 0.1% of overall reaction system), it is sufficiently stirred,
40 DEG C are warming up to, 37% acetaldehyde solution of metering is slowly added dropwise, is added dropwise within 3 hours, slow heating is warming up to 90 DEG C, continues anti-
Answer 4 hours, solution is yellowish-brown, reduce temperature to 40 DEG C hereinafter, plus 40% sodium hydroxide solution, adjust pH=8-9, obtain product
Polyethyleneimine sodium phosphite.
Wherein, PEI：H3PO3：The molar ratio of HCHO is 1.0:1.8:3.
The PEI structures of the present embodiment are branching type PEI, and structural formula is：
The integer that wherein x is 1~50, the integer that y is 10~300.
The structural formula of the polyethyleneimine sodium phosphite being prepared of the present embodiment is：
The integer that wherein x is 1~50, the integer that y is 10~300.
Embodiment 7
A kind of embodiment of the collapse protection type water-reducing agent of the present invention, collapse protection type water-reducing agent described in the present embodiment is by following methods system
It is standby to form：
With blender, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 500ml in, the 50wt% of metering is added
PEI aqueous solutions, phosphorous acid H3PO3And 0.3 milliliter of 37wt% concentrated hydrochloric acid (volume accounts for the 0.1% of overall reaction system), it is sufficiently stirred,
40 DEG C are warming up to, 37% acetaldehyde solution of metering is slowly added dropwise, is added dropwise within 3 hours, slow heating is warming up to 90 DEG C, continues anti-
Answer 4 hours, solution is yellowish-brown, reduce temperature to 40 DEG C hereinafter, plus 40% sodium hydroxide solution, adjust pH=8-9, obtain product
Polyethyleneimine sodium phosphite.
Wherein, PEI：H3PO3：The molar ratio of HCHO is 1.0:1.8:1.5.
The PEI structures of the present embodiment are branching type PEI, and structural formula is：
The integer that wherein x is 1~50, the integer that y is 10~300.
The structural formula of the polyethyleneimine sodium phosphite being prepared of the present embodiment is：
The integer that wherein x is 1~50, the integer that y is 10~300.
Embodiment 8
A kind of embodiment of the collapse protection type of the resistance to mud water-reducing agent of the present invention, the collapse protection type of resistance to mud water-reducing agent described in the present embodiment by with
Lower section method is prepared：
With blender, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 500ml in, the 50wt% of metering is added
PEI aqueous solutions and phosphorous acid H3PO3And 0.3 milliliter of 37wt% concentrated hydrochloric acid (volume accounts for the 0.1% of overall reaction system), it is sufficiently stirred,
45 DEG C are warming up to, 37% formalin of metering is slowly added dropwise, is added dropwise within 3 hours, slow heating is warming up to 90 DEG C, continues anti-
Answer 3.5 hours, solution is yellowish-brown, reduce temperature to 40 DEG C hereinafter, plus 40% sodium hydroxide solution, adjust pH=8-9, must produce
Product polyethyleneimine sodium phosphite.
Wherein, PEI：H3PO3：The molar ratio of HCHO is 1.0:3:2.1.
The PEI structures of the present embodiment are branching type PEI, and structural formula is：
The integer that wherein x is 1~50, the integer that y is 10~300.
The structural formula of the polyethyleneimine sodium phosphite being prepared of the present embodiment is：
The integer that wherein x is 1~50, the integer that y is 10~300.
Embodiment 9
A kind of embodiment of the collapse protection type of the resistance to mud water-reducing agent of the present invention, the collapse protection type of resistance to mud water-reducing agent described in the present embodiment by with
Lower section method is prepared：
With blender, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 500ml in, the 50wt% of metering is added
PEI aqueous solutions and phosphorous acid H3PO3And 0.3 milliliter of 37wt% concentrated hydrochloric acid (volume accounts for the 0.1% of overall reaction system), it is sufficiently stirred,
45 DEG C are warming up to, 37% formalin of metering is slowly added dropwise, is added dropwise within 3 hours, slow heating is warming up to 90 DEG C, continues anti-
Answer 3.5 hours, solution is yellowish-brown, reduce temperature to 40 DEG C hereinafter, plus 40% sodium hydroxide solution, adjust pH=8-9, must produce
Product polyethyleneimine sodium phosphite.
Wherein, PEI：H3PO3：The molar ratio of HCHO is 1.0:1.0:1.0.
The PEI structures of the present embodiment are branching type PEI, and structural formula is：
The integer that wherein x is 1~50, the integer that y is 10~300.
The structural formula of the polyethyleneimine sodium phosphite being prepared of the present embodiment is：
The integer that wherein x is 1~50, the integer that y is 10~300.
Embodiment 10
The collapse protection type of the resistance to mud water-reducing agent of the present invention is used to prepare building solid waste regenerated aggregate concrete, the present invention is implemented
The collapse protection type of resistance to mud water-reducing agent prepared by example 1~9 is with common polyether polycarboxylate water-reducer according to 50:Make after 50 weight proportion mixing
For additive, regeneration concrete is prepared by the formula of table 1, water-reducing agent volume with the concrete prepared have it is identical go out the machine slump
And subject to divergence, volume is 9.5~13.3 parts, and the results are shown in Table 2；
Table 1 is that application examples 1 builds solid waste regenerated aggregate concrete parts by weight of raw materials formula：
| Group | Water | Cement | Flyash | Miberal powder | River sand | Regenerate stone | Water-reducing agent |
| 180 | 235 | 65 | 80 | 842 | 630 | 10.5 |
The water-reducing agent that water-reducing agent in above-mentioned table 1 is prepared with Examples 1 to 9 respectively.
Table 2 builds the performance test results of solid waste regenerated aggregate concrete
In the application example, in the case of remaining ingredient is identical with content, the collapse protection type of resistance to mud water-reducing agent (this of the present invention is selected
Invent the water-reducing agent that different structure is prepared in different embodiments) and common polycarboxylic acid slump retaining agent and common polyether polycarboxylic acids diminishing
Agent is used in compounding, and effect is as shown in table 2, table 2 the result shows that, with producing building solid waste regenerated aggregate concrete in use,
Compared with common polycarboxylic acid slump retaining agent, the slump retaining agent of resistance to chamotte mould of the invention has superior water-reducing rate, and its concrete expands
The latitude of emulsion and the slump are smaller with the change of time, and significant difference occurs in effect, and by experiment it is found that embodiment 3~9 is made
The water-reducing agent of standby branching type be used for regeneration concrete in, effect than Examples 1 to 2 linear water-reducing agent effect more
It is good, this is because branched polyethylene imine sodium phosphite than L-PEI sodium phosphite there is the steric hindrance of bigger to imitate
It answers, having more bands, there are two the orthophosphites of negative electrical charge to be adsorbed on cement particle surface, disperse cement particles, to have
Better water-reducing effect and resistance to mud protect effect of collapsing；Wherein with 5 best results of embodiment, this is the result is that due to amido in embodiment 5
The most reason of the phosphorous acid radical to be formed is reacted by Mannich.The slump of the present invention is being less than 20mm from 2h losses, and general
Logical polycarboxylic acid slump retaining agent is down to 90 from 200, loses as 110mm.The slump of the present invention is after 120min, Slump Time losing of Large
It is small, and common polycarboxylic acid slump retaining agent collapses substantially, and the maturing intensity of the present invention is bigger than common polycarboxylic acid slump retaining agent；This
Invention a large amount of amidos since polyethyleneimine contains, and amido carries positive charge, can be adsorbed on the soil with anion
Grain surface inhibits traditional polycarboxylate water-reducer PEO side chains to have superior anti-stick soil nature to the chain intercalation of clay particle
Can, and clay is the main reason for leading to regeneration concrete Slump Time losing of Large.
Embodiment 7
The collapse protection type of the resistance to mud water-reducing agent of the present invention is applied in machine-made sand concrete prefabricated components, by Examples 1 to 9 system
Standby water-reducing agent is added as concrete admixture into concrete, which includes the original of following parts by weight
Material, 156 parts of water, 405 parts of cement, 60 parts of flyash, 685 parts of Machine-made Sand, 1130 parts of stone (10-20mm rubbles), water-reducing agent is
11 parts.
The preparation method of the prefabricated components is：Extremely by body natural curing at the beginning of the prefabricated components formed after the completion of concreting
It is demoulded after demoulding strength, continues nature watering maintenance later to get to the machine-made sand concrete prefabricated components；Wherein water-reducing agent
For the collapse protection type of the resistance to mud water-reducing agent for being respectively prepared by embodiment 1 to 9.Its demoulding time is 10~12h.
It prepares the prefabricated components of product to adding Examples 1 to 9 the age same period does not carry out strength test, test result is as follows table
1；
| Age | 10~12h | 7d | 28d |
| Intensity (MPa) | 35~39 | 50~55 | 60~66 |
| Curing condition | It is natural | It is natural | It is natural |
Comparative example
Concrete prefabricated element is prepared using existing common polycarboxylate water-reducer as water-reducing agent, specific prefabricated components
Preparation method：To be demoulded after body natural curing to demoulding strength at the beginning of the prefabricated components formed after the completion of concreting, it is subsequent
Continuous nature watering maintenance is to get to the concrete prefabricated element.Wherein demoulding strength is more than 25MPa.
In addition to water-reducing agent is using the concrete prefabricated element that other than common polycarboxylate water-reducer, comparative example is used with the present invention
Raw material is the same, and demoulding time is 36~40h.
The age same period does not carry out strength test, test result is as follows table 2 to prefabricated components prepared by comparative example；
| Age | 36~40h | 7d | 28d |
| Intensity (MPa) | 31 | 43 | 55 |
| Curing condition | It is natural | It is natural | It is natural |
It can be seen that, prepared in machine-made sand concrete prefabricated components from table 1 and table 2, collapsed using the resistance to mud guarantor of the present invention
Type water-reducing agent, under using common water-reducing agent to compare, under identical curing time, obtained prefabricated component intensity higher, and
The water-reducing agent prepared using Examples 1 to 9 in table 1, is told on and is had any different, the diminishing of branching type prepared by embodiment 3~9
Agent is used in concrete prefabricated element, and effect is more better than the linear water-reducing agent of Examples 1 to 2, wherein to implement
3 best results of example, and the concrete of the present invention can accelerate hydrated cementitious, significantly carry while keeping concrete slump
High concrete early strength conserves under non-evaporating foster natural conditions, reaches strength of mould stripping in 9-12 hours, is not spiked with any mine
Object reinforcing material and glass fibre substantially reduce production cost and mold turn around time, save place, and meeting reduces energy consumption, protects
The fundamental requirement that the assembled in retaining ring border is built, is the key technology node for realizing prefabricated assembled construction, fills the domestic gaps,
Economy with bigger and social effect.
Meanwhile to water-reducing agent using 5 water-reducing agent of invention embodiment and comparative example preparation it is concrete prefabricated
Component carries out slump test, obtains table 3；
As can be seen from Table 3, using the collapse protection type of the resistance to mud water-reducing agent of the present invention, the prefabricated components prepared have good
Function of slump protection.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent substitution, improvement and etc. done should be included within the scope of protection of the invention god.
Claims (10)
1. a kind of resistance to mud collapse protection type water-reducing agent, which is characterized in that the collapse protection type of the resistance to mud water-reducing agent is shown in formula (I) or formula (II)
Compound, the formula (I) and formula (II) compound represented structural formula are as follows：
Wherein, the integer that x is 0~50；The integer that y is 10~300；The integer that n is 10~300.
2. the collapse protection type of resistance to mud water-reducing agent according to claim 1, which is characterized in that the integer that the x is 1~50.
3. a kind of preparation method of resistance to mud collapse protection type water-reducing agent as claimed in claim 1 or 2, which is characterized in that the resistance to mud
Collapse protection type water-reducing agent is prepared by following methods：
It by aq. polyethyleneimine and phosphorous acid, is sufficiently stirred at 40~45 DEG C, slowly drips formalin, dripped within 2-3 hours
Add it is complete, slow heating be warming up to 80-90 DEG C, the reaction was continued 2-4 hour, until solution be yellowish-brown, reduction temperature to 40 DEG C with
Under, add NaOH to adjust pH=8-9, obtain formula I) or formula II) polyethyleneimine sodium phosphite.
4. the preparation method of the collapse protection type of resistance to mud water-reducing agent according to claim 3, which is characterized in that the polyethyleneimine
Shown in structural formula such as (III) and formula (IV)：
Wherein, the integer that x is 0~50；The integer that y is 10~300；The integer that n is 10~300.
5. the preparation method of the collapse protection type of resistance to mud water-reducing agent according to claim 4, which is characterized in that the x is 1~50
Integer.
6. the preparation method of the collapse protection type of resistance to mud water-reducing agent according to claim 3, which is characterized in that the polyethyleneimine
Amine:Phosphorous acid:The molar ratio of formaldehyde is 1.0:(0.2~3.0):(0.2~3.0).
7. the preparation method of the collapse protection type of resistance to mud water-reducing agent according to claim 3, which is characterized in that the polyethyleneimine
Amine:Phosphorous acid:The molar ratio of formaldehyde is 1.0:2.2:2.1.
8. the preparation method of the collapse protection type of resistance to mud water-reducing agent according to claim 3, which is characterized in that described by polyethyleneimine
Further include 37wt% concentrated hydrochloric acids in amine aqueous solution and phosphorous acid mixed solution, the concentrated hydrochloric acid accounts for the volume basis of overall reaction system
Than being 0.08%~0.1%, a concentration of 50wt% of the aq. polyethyleneimine, the naoh concentration are 40wt%.
9. application of the collapse protection type of the resistance to mud water-reducing agent in building solid waste regenerated aggregate concrete as described in claim 1~2.
10. application of the collapse protection type of the resistance to mud water-reducing agent in machine-made sand concrete prefabricated components as described in claim 1~2.
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| CN113912348A (en) * | 2021-10-18 | 2022-01-11 | 佛山市顺德区和乐商品混凝土有限公司 | High-performance recycled concrete and preparation method thereof |
| CN116023062A (en) * | 2022-12-28 | 2023-04-28 | 四川金江建材科技有限公司 | Water-based synergist for concrete and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912348A (en) * | 2021-10-18 | 2022-01-11 | 佛山市顺德区和乐商品混凝土有限公司 | High-performance recycled concrete and preparation method thereof |
| CN116023062A (en) * | 2022-12-28 | 2023-04-28 | 四川金江建材科技有限公司 | Water-based synergist for concrete and preparation method thereof |
| CN116023062B (en) * | 2022-12-28 | 2024-05-03 | 四川金江建材科技有限公司 | Water-based synergist for concrete and preparation method thereof |
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