CN106380548A - Application of water-retaining reduction type polycarboxyliy water reducer in preparing recycled aggregate concrete - Google Patents
Application of water-retaining reduction type polycarboxyliy water reducer in preparing recycled aggregate concrete Download PDFInfo
- Publication number
- CN106380548A CN106380548A CN201610742419.3A CN201610742419A CN106380548A CN 106380548 A CN106380548 A CN 106380548A CN 201610742419 A CN201610742419 A CN 201610742419A CN 106380548 A CN106380548 A CN 106380548A
- Authority
- CN
- China
- Prior art keywords
- water
- concrete
- aggregate concrete
- integer
- reducer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides the application of a water-retaining reduction type polycarboxyliy water reducer in preparing a recycled aggregate concrete. The invention also provides the recycled aggregate concrete containing the above water-retaining reduction type polycarboxyliy water reducer. Hydrogen bonds are slightly crosslinked to form the water-retaining reduction type polycarboxyliy water reducer, so that the viscosity of a capillary water solution and the viscosity of a cement paste are significantly improved. Meanwhile, the water-retaining property of the cement paste is significantly improved, and the shrinkage cracking of the concrete is reduced. The result of the reduction test on the recycled aggregate concrete shows that, the water-retaining reduction type polycarboxyliy water reducer is good in reduction effect. When the water-retaining reduction type polycarboxyliy water reducer is applied to the recycled aggregate concrete, the strength of the recycled aggregate concrete is not affected at all. Therefore, the cost performance is high.
Description
Technical field
The present invention relates to a kind of purposes in preparing regenerated aggregate concrete for water reducer is and in particular to a kind of water-retaining property subtracts
Purposes in preparing regenerated aggregate concrete for the miniature polycarboxylate water-reducer.
Background technology
With the continuous development of urban architecture industry, the consumption of concrete material more use bigger, annual remove waste and old mixed
The waste and old coagulation of solidifying soil, the discarded concrete that new building produces and the discharge such as concrete mixing plant and factory for prefabrication
Soil, enormous amount, according to statistics up-to-date at present, China is every year because abandoned building removes the discarded concrete producing
Nearly 200,000,000 tons.The processing mode of discarded concrete mainly has two kinds at present：One kind is simply to use as backfilling material, and two are
Transport countryside to and simply stack burial.The former is not yet rationally utilized to these resources, and the latter then not only occupies a large amount of farmlands,
Even new environmental pollution can be caused.With going deep into of environmental protection and the strategy of sustainable development, people's an urgent demand is to these
Discarded concrete is effectively and reasonably used, and using regeneration aggregate, can save engineering cost, save natural aggregate
Face cost and discarded concrete processing cost, have important economic benefit and social benefit.
First, domestic External building solid wastes recycling utilizes：
Japan and the United States, etc. developed country, the strategy carried out at present is " building solid waste source abatement ", refers in building solid waste
Before generation, scientific management and effective control is relied on to reach the purpose of decrement.Solid to building from scientific and reasonable processing mode
Give up and processed, form regenerated resources.
China's building solid waste discharge increases comparatively fast, and rubbish composition also becomes more diverse, and the up to several hundred million ton of total emission volumn is processed
Mode is mainly air storage or simple burial, and in recent years, the process side of some building solid wastes has been attempted in the city such as Shanghai, Beijing
Formula, such as backfill absolute altitude, reclaim land from the sea, Piled Mountain Landscape on Construction, make building materials etc..
2nd, the present Research of domestic and international regeneration concrete
Aggregate of recycled concrete (abbreviation regeneration aggregate), be by waste and old concrete block after broken, cleaning with classification, press
Certain ratio level joins the aggregate being mixed to form.Partly or entirely substitute what the natural aggregates such as sandstone were formulated with it
Novel concrete is referred to as regeneration concrete.For regeneration concrete, the waste and old concrete for producing regeneration aggregate is referred to as
Former concrete.
For the regeneration of waste and old concrete, produce regenerated aggregate concrete, Japan, the U.S., moral using regeneration aggregate
The countries such as state, Britain, Denmark, Holland have all carried out substantial amounts of research work, wherein best with Japanology, and they will build
Solid waste is considered as " building byproduct ".
The research of domestic regeneration aggregate is started late, the Performances of Recycled Aggregate of Existing produced poor (particle shape and level join all bad,
Surface has a large amount of mortars, and water absorption rate is big, closely knit small volume, and crush index is low).In recent years, people studied to regeneration concrete
More and more, research work is concentrated mainly on and is partly or entirely replaced after natural aggregate with regeneration aggregate, the concrete to preparation
Performance impact aspect, and add the mineral admixture such as flyash when preparing concrete and to improve the various of regeneration concrete
Performance.And there is no gratifying effect.
At present both at home and abroad the technology of preparing of regeneration aggregate mainly by cutting and crushing equipment, transmitting mechanical, screening plant and
Deimpurity clearly equipment is organically combined, and jointly completes to crush, sieve and remove the operations such as impurity, finally obtains and meet
The recycled fine aggregate of quality requirement and regenerated coarse aggregate.
3rd, low-quality regeneration aggregate：
Simple crushing regeneration aggregate without intensive treatment is low-quality concrete, the domestic research starting to regeneration aggregate
Later, mainly formed by crushing and sieve two parts.Compare with external preparation technology, centre lacks the intensive treatment stage,
Also thus obtained Performances of Recycled Aggregate of Existing is made substantially to be inferior to natural aggregate.
Regenerated coarse aggregate particle is typically wrapped in stone and the cement of part of cement mortar by the stone of clean surface, surface
Mortar particle three part forms.Recycled fine aggregate is mainly by the sand grains of surface no cement mortar, the sand grains of surface attachment cement mortar, water
Mudstone particle and a small amount of broken stone composition.The size range of natural fine aggregate is generally 0.16mm～5mm, due to regenerating thin bone
Tiny Behavior of Hardened Cement Paste particle is contained, the grain size scope of recycled fine aggregate can be relaxed and is set to 0.08mm～5mm in material.At present I
State there is no the relevant criterion of Aggregate of recycled concrete, should increase the research of Aggregate of recycled concrete, formulates related performance rating
Standard, makes regeneration concrete be widely used in Practical Project.
Low-quality regeneration aggregate grain corner is many, rough surface, also contains hardening cement mortar (cement mortar hole in component
Gap rate is big, water absorption rate is high), along with concrete block disintegrating, in shattering process because damage accumulation internally causes a large amount of fine fisssures
Line, leads to the porosity of regeneration aggregate to increase, so that water absorption rate and rate of water absorption increase.In the size of water absorption rate and aggregate
Behavior of Hardened Cement Paste content, aggregate species and the Regenerated Bone used by the former concrete of the former concrete strength of cement mortar adhesive rate of aggregate surface
The factors such as the preparation method of material are relevant.
Because substantial amounts of cement mortar is contained on low-quality regeneration aggregate surface, compared with natural aggregate, the heap of regeneration aggregate
Long-pending density and apparent density, all decrease.
The performance of low-quality regeneration aggregate
1st, water absorption rate
Simple crushing regeneration aggregate without intensive treatment is that low-quality regeneration aggregate grain corner is many, rough surface, group
Hardening cement mortar (cement mortar porosity is big, water absorption rate is high) is also contained, along with concrete block is disintegrating, crushing in point
Because damage accumulation internally causes a large amount of micro-cracks in journey, the porosity of regeneration aggregate is led to increase, so that water absorption rate and suction
Water speed rate increases.Behavior of Hardened Cement Paste content in the size of water absorption rate and aggregate, the former concrete of cement mortar adhesive rate of aggregate surface
Aggregate species used by the former concrete of intensity is relevant with factors such as the preparation methods of regeneration aggregate.
2nd, density：
Because substantial amounts of cement mortar is contained on regeneration aggregate surface, compared with natural aggregate, the bulk density of regeneration aggregate
And apparent density, all decrease.
3rd, clay content：
The clay content of regeneration aggregate is far above natural aggregate.
4. porosity：Porosity is higher than natural aggregate concrete.
4th, regenerated aggregate concrete：
The feature of regeneration aggregate, determine regenerated aggregate concrete have the characteristics that as follows：
1st, water requirement is high, and admixture dosage is high；
2nd, Slump Time losing of Large is big.
3rd, shrinkage factor is big：Because regeneration concrete uses the Regenerated Bone that water absorption rate is big, porosity is high, clay content is high
Material, so the drying shrinkage of regeneration concrete is bigger than natural aggregate concrete, and the degree of drying shrinkage and drying shrinkage duration
Increase with the increase of regeneration aggregate substitute proportion and lengthen.
The cracking of concrete is a big technical barrier of concrete application, mixes economization agent, reduces concrete shrinkage, is wherein
One of solution, with economization agent control and reduce the drying shrinkage of concrete, the plastic shrinkage of early stage and own vol shrink.1982
Year Japanese Nissan cement company and chemical company of Sanyo take the lead in developing economization agent, 1985, and U.S. Goto et al. achieves the
One economization agent patent.
Concrete shrinkage is the phenomenon that concrete produces volume-diminished after pouring and hardening.If shrinking excessive, produced
Raw shrinkage stress can make concrete produce cracking, not only can reduce structural strength, and crack is also air and water enters concrete
One passage is provided, makes concrete be susceptible to graphitic corrosion, steel bar corrosion, in cold district it also occur that Frozen-thawed cycled, this
A little durability all greatly reducing concrete, shorten the service life of building.Thus, shrinkage cracking is puzzlement concrete
One difficult problem of engineering.
The usual approach solving the problems, such as concrete shrinkage is to mix swelling agent, and main principle is in coagulation by swelling agent
Generate expansile hydrated product to compensate contraction in soil, decrease the possibility of concrete cracking.But it is special using swelling agent
Do not need concrete to have the maintenance of water in early stage, condition is harsh, and there is serious cement adaptability in itself and postpone calcium alum
The problems such as stone generates, in addition, having difficulties on adjusting its addition, if volume is very few, does not reach effect, if volume mistake
Greatly, excessive part may lead to expanded crack due to expansion, thus using swelling agent, final result is had certain
Uncertain.
Another is to mix fiber, but adding of fiber can only be the anti-crack ability improving concrete, can not reduce mixed
The contraction of solidifying soil, fiber price is high simultaneously, exists and concrete consistency problem.Also greatly limit its popularization.
Concrete shrinkage mechanism：
The contraction of concrete can be divided into chemical shrinkage, plastic shrinkage, temperature shrinkage, self-constriction, be dried and shrink and carbonization receipts
Contract six big types, is wherein shunk the most generally with being dried, mechanism is more complicated, and existing theory mainly has capillary tensiometry
Say, adsorption theory, take stress theory etc. apart, the most convincing with capillary tension theory among these, this theory thinks,
When ambient humidity is less than 100%, the water surface within capillary declines and forms meniscus, according to Laplas formula, in the table of water
Under the tension force effect of face, the additonal pressure of generation in capillary：In △ P=2 σ COS θ/R formula, △ P is additional under the bending page
Pressure, σ is the surface tension of water, and θ is the contact angle of water concave meniscus and capillary hole wall, and R is capillary radius.
In the case that σ is constant, capillary is thinner, and the radius of curvature of meniscus is less, and the capillary pressure of generation is bigger；
When R is constant, P is directly proportional to surface tension σ of water.
Scattering and disappearing with pore water, R diminishes, and △ P increases, and capillary tension acts on hole wall, produces pulling force, and then
Lead to concrete shrinkage macroscopically.
In formula, P is the additonal pressure under curved liquid surface, and σ is the surface tension of water, and R is water concave meniscus and capillary radius.
In the case that σ is constant, capillary is thinner, and the radius of curvature of meniscus is less, and the capillary pressure of generation is bigger,
When R is constant, P is directly proportional to the surface tension of water.With pore evaporation of water, R diminishes, and P increases, and capillary tension acts on
On hole wall, produce pulling force, and then lead to concrete shrinkage macroscopically.
Economization agent reduce principle：
According to contractile mechanism analysis above, being dried of concrete is shunk, and is the meniscus being formed due to water in pore
And the additonal pressure △ P producing causes, and determine △ P is three variables：σ, θ and R, R is by component materials of concrete
Composition and match ratio determine, the liquid in pore is relevant with infiltration for σ and θ, and the surface tension of pure water is 72N/m, very
Height, if 35N/m can be reduced to it, then corresponding stress is reduced by half, and economization agent is exactly therefore to be born.It is this
A kind of material of sample, can be greatly lowered the surface tension of water in the environment of highly basic, on the other hand, be made up of water and economization agent
Solution viscosity increases so that contact angle θ increases, thus also reducing the shrinkage stress of concrete further, reduces opening of concrete
Split.
Japan and the U.S. are more for the research of economization agent for concrete, from the point of view of its research and development distance, one-component before this
Micromolecular compound, due to readily volatilized, and then develop into macromolecular compound, also developed into by one-component multigroup simultaneously
The compound product of compound dividing, so can not only reduce the cracking shrinkage value of concrete, and single group before also overcoming
Divide many shortcomings of product, the long-term Reduce shrinkage effect of such as one-component economization agent is not ideal enough, relatively costly and concrete strength
Easily reduce etc., another rule of development is exactly gradually to be developed to multifunctional product from the product of simple function, for example, have simultaneously
Reduce and diminishing function.
The domestic research and development to economization agent are started late, and general economization agent price is again relatively higher, therefore not yet has more pushing away so far
Wide application.But constantly increase with economical, marine engineering concrete and infrastructure build durability and the quality appearance of thing
Requirement can step up, and the problem of concrete cracking also can incrementally increase, and solve this difficult problem and remain concrete research scholar
A challenge.
Economization agent can substantially reduce concrete early-age shrinkage, its Main Function mechanism be reduce pore water surface tension and
Reduce the shrinkage stress producing during pore dehydration, be on the other hand the viscosity increasing concrete pore water, strengthen water mixed
Coagulate the suction-operated in soil colloid and reduce the shrinkage value of concrete.The main component of economization agent is polyethers or polyalcohols and its derives
Thing, as glycerine, POLYPROPYLENE GLYCOL, contains polycarboxylic acids of ethylene glycol etc..
Drying shrinkage can make xoncrete structure or component produce cracking, and contraction is caused by many reasons, but moisture loss is main
Want reason：
First stage：Lose the water in pore；
Second stage：Lose C-H-S surface adsorption water；
Phase III：Lose the water in C-H-S structure；
When the water in these apertures loses, in hole, hole wall is furthered and so that volume is contracted by the surface tension of residual water.
Though the use of these economization agents reduces the contraction of concrete to a certain extent, engineering cost increases greatly, and
Synthesis technique is complicated.
In many use difficult points of regenerated aggregate concrete, the receipts that lead to because regeneration aggregate powder containing quantity containing mud is high
Shrinkage is big, especially allows big technological difficulties of technology and researcher's puzzlement in the industry, also do not have both at home and abroad at present a kind of row it
Effectively overcoming method.
Content of the invention
It is an object of the invention to overcoming the weak point of prior art presence and providing a kind of water-retaining property shrinkage type and gather
Purposes in preparing regenerated aggregate concrete for the carboxylic acid water reducer, present invention also offers a kind of gather containing this water-retaining property shrinkage type
The regenerated aggregate concrete of carboxylic acid water reducer, due to this water-retaining property shrinkage type polycarboxylate water-reducer introduce in side chain substantial amounts of
Oh group, these oh groups form hydrogen bond with hydrone, and itself is also due to forming hydrogen bond and forming similar micro- crosslinking simultaneously
Structure, increased solution viscosity, improves water-retaining property, is mainly played and is reduced effect by its water-retaining property, is water conservation water-retaining property
Shrinkage type polycarboxylate water-reducer.
For achieving the above object, the technical scheme taken：A kind of regenerated aggregate concrete, described regenerated aggregate concrete
Including cement, fine aggregate, regenerated coarse aggregate, natural coarse aggregate, additive and water, described additive includes water-retaining property shrinkage type and gathers
Carboxylic acid water reducer, described water-retaining property shrinkage type polycarboxylate water-reducer is the compound shown in formula (I), the change shown in described formula (I)
The structural formula of compound is as follows：
Wherein a isInteger, b isInteger, c isInteger；D is Whole
Number；
Described A is
Described B is
Described C isL is 0～30 integer；
R1For CH3Or H；
R2For H2C=CH-CH2-、Or H2C=
CHO-CH2CH2CH2CH2-；
Described D is polyhydroxy PEG polymeric monomer, and described polyhydroxy PEG polymeric monomer is compound shown in formula (II) and contain
Have epoxy and hydroxyl bifunctional compound reaction and be obtained, the structural formula of the compound shown in described formula (II) is as follows：
Wherein m is 0～30 integer；
R is H2C=CH-CH2-、And H2C=
CH-O-CH2CH2CH2CH2One of-.
Preferably, described containing epoxy and hydroxyl bifunctional compound it isWithIn
At least one.
Preferably, described water-retaining property shrinkage type polycarboxylate water-reducer is prepared from by following methods：
(1) in a nitrogen atmosphere enol and catalyst are mixed, be warming up to 70～115 DEG C, be then slowly added dropwise epoxy second
Alkane, reaction temperature is controlled in the range of 70～130 DEG C, and reaction pressure controls in 0.2～0.6MPa, when oxirane drips
Bi Hou, reaction temperature is controlled at 80～120 DEG C, continues reaction 0.5～5h, obtains intermediate product；
(2) temperature of the intermediate product obtaining step (1) is reduced to 80 DEG C, is then slowly added dropwise containing epoxy and hydroxyl
Bifunctional compound, time for adding controls after 1.5～2h, completion of dropping, continues reaction 4～6h, obtains polyhydroxy PEG big
Monomer；
(3) by one of maleic anhydride, itaconic acid and ALS, in APEG, HPEG, VPEG and TPEG
The big list of polyhydroxy PEG that kind, one of acrylic acid and methacrylic acid, molecular weight regulator, water and described step (2) are obtained
Body mixes, and is warming up to 95 DEG C, drips the aqueous solution containing initiator, and time for adding is 2h, after completion of dropping, insulation reaction 3h,
It is cooled to 45 DEG C, adjusting pH with alkali lye is 6.5, obtains final product water-retaining property shrinkage type polycarboxylate water-reducer.
Preferably, in described step (1), the mol ratio of enol and oxirane is 1:0～1:80.It is highly preferred that described step
Suddenly in (1), the mol ratio of enol and oxirane is 1:1～1:80.
Preferably, in described step (1), enol is in propenyl, prenol, isobutene alcohol and 4- ethyleneoxy butanol
At least one.
Preferably, in described step (1), the consumption of catalyst is the 0.1- of the weight sum of described enol and oxirane
0.5%.
Preferably, Subtraction method is adopted to drip oxirane in described step (1).
Preferably, in described step (2), intermediate product is little with the mol ratio containing epoxy and hydroxyl bifunctional compound
In equal to 1.
Preferably, one of maleic anhydride, itaconic acid and ALS in described step (3), APEG, HPEG,
One of VPEG and TPEG, one of acrylic acid and methacrylic acid, the mol ratio of polyhydroxy PEG polymeric monomer is maleic acid
One of acid anhydride, itaconic acid and ALS：One of APEG, HPEG, VPEG and TPEG：Acrylic acid and metering system
One of acid：Polyhydroxy PEG polymeric monomer=0～0.5：0.05～1.0：0～15：0.3-3.It is highly preferred that described step (3)
One of middle maleic anhydride, itaconic acid and ALS, one of APEG, HPEG, VPEG and TPEG, acrylic acid and
One of methacrylic acid, the mol ratio of polyhydroxy PEG polymeric monomer is in maleic anhydride, itaconic acid and ALS
A kind of：One of APEG, HPEG, VPEG and TPEG：One of acrylic acid and methacrylic acid：Polyhydroxy PEG polymeric monomer
=0.1～0.5：0.05～1.0：2～15：0.3-3.It is highly preferred that maleic anhydride, itaconic acid and allyl in described step (3)
One of base sodium sulfonate, one of APEG, HPEG, VPEG and TPEG, one of acrylic acid and methacrylic acid, polyhydroxy
The mol ratio of base PEG polymeric monomer is one of maleic anhydride, itaconic acid and ALS：APEG, HPEG, VPEG and
One of TPEG：One of acrylic acid and methacrylic acid：Polyhydroxy PEG polymeric monomer=0.1～0.5：0.5～1.0：5
～15：0.3-0.6.
Preferably, in described step (3), initiator is in potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide and benzoyl peroxide
One kind, the consumption of described initiator is one of described maleic anhydride, itaconic acid and ALS, APEG, HPEG,
One of VPEG and TPEG, one of acrylic acid and methacrylic acid, with the total mole number of polyhydroxy PEG polymeric monomer
0.5%～5%.
Preferably, described step (3) middle-molecular-weihydroxyethyl conditioning agent is at least one in sulfhydryl compound and isopropanol.
Preferably, the consumption of described step (3) middle-molecular-weihydroxyethyl conditioning agent is described maleic anhydride, itaconic acid and pi-allyl sulphur
One of sour sodium, one of APEG, HPEG, VPEG and TPEG, one of acrylic acid and methacrylic acid, with polyhydroxy
The 1%～5% of the total mole number of PEG polymeric monomer.
In above-mentioned steps (1) shown in the structural formula such as formula (II) of the intermediate product that reaction obtains,
Wherein m is 0～30 integer；
R is H2C=CH-CH2-、
And H2C=CH-O-CH2CH2CH2CH2One of-.
Reaction equation in above-mentioned steps (1) is as follows：
In above-mentioned steps (2), intermediate product and the mol ratio of glycidol are：1：(x-1), x is the end-blocking of surface-active macromonomer
Hydroxyl value, works as x=2, the product structure formula of reaction gained is as shown in formula III；Work as x=4, the product structure formula such as formula of reaction gained
Ⅳ；Work as x=8, react the product structure formula such as formula V of gained .... etc..
The structural formula of the compound shown in described formula (III) is as follows：
Corresponding reaction equation is as follows：
The structural formula of the compound shown in described formula (IV) is as follows：
Corresponding reaction equation is as follows：
The structural formula of the compound shown in described formula (V) is as follows：
Corresponding reaction equation is as follows：
Preferably, described regenerated aggregate concrete includes the component of following weight portion：235 parts of cement, 840 parts of fine aggregate,
620 parts of regenerated coarse aggregate, 376 parts of natural coarse aggregate, additive 7.6 (folding is solid) part and 165 parts of water.
Preferably, described regenerated aggregate concrete also includes the flyash of 65 weight portions and the breeze of 80 weight portions.
The invention provides a kind of purposes in preparing regenerated aggregate concrete for water-retaining property shrinkage type polycarboxylate water-reducer,
Described water-retaining property shrinkage type polycarboxylate water-reducer is the compound shown in formula (I), the structural formula of the compound shown in described formula (I)
As follows：
Wherein a isInteger, b isInteger, c isInteger；D is Whole
Number；
Described A is
Described B is
Described C isL is 0～30 integer；
R1For CH3Or H；
R2For H2C=CH-CH2-、Or H2C=
CHO-CH2CH2CH2CH2-；
Described D is polyhydroxy PEG polymeric monomer, and described polyhydroxy PEG polymeric monomer is compound shown in formula (II) and contain
Have epoxy and hydroxyl bifunctional compound reaction and be obtained, the structural formula of the compound shown in described formula (II) is as follows：
Wherein m is 0～30 integer；
R is H2C=CH-CH2-、
And H2C=CH-O-CH2CH2CH2CH2One of-.
Economization agent is a kind of nonionic surfactant, can reduce the surface tension of water, and the concrete mixing economization agent is received
Compression deformation reduces, and improves the anti-crack ability of concrete, underbead crack is relatively fewer, is beneficial to the raising of concrete durability.
Material as economization agent for concrete, should have following property：1st, liquid-vapor interface tension force is greatly reduced；2nd, increase solution
Viscosity, delay the volatilization 3 of hydrone, anomalous effects do not produced to hydrated cementitious process；4th, high temperature low volatility；5th, low bleed
Property.Polycarboxylate water-reducer can reduce the surface tension of liquid, therefore has the performance of certain reduction Shrinkage Cracking of Concrete,
But still engine request can not be met.The water-retaining property shrinkage type polycarboxylate water-reducer being synthesized by polyhydroxy PEG polymeric monomer of the present invention, by
In introduce in the molecule substantial amounts of reduce group hydroxy, form hydrogen bond between hydroxyl or between hydroxyl and hydrone, form hydrogen bond micro-
Cross-linked structure, compared with common polycarboxylate water-reducer, changes HLB value, hydrophily increases, lipophile slightly declines, incrementss
Solution viscosity, delays the evaporation rate of hydrone, significantly improves the water-retaining property of solution, receives thus reaching and significantly reducing concrete
The purpose of contracting.Regenerated aggregate concrete reduces result of the test and shows, it has preferable Reduce shrinkage effect, the common ether with our company
Class polycarboxylate water-reducer is compared, and the shrinkage ratio of regenerated aggregate concrete reduces 72%, and the sum to regenerated aggregate concrete
Easily property and intensity do not affect, and cost performance is higher.
The water conservation water-retaining property shrinkage type polycarboxylate water-reducer of present invention synthesis, introduces substantial amounts of hydroxyl in molecular side chain,
Hydroxyl hydrophilic is high, and forms hydrogen bond with hydrone, and itself forms micro- cross-linked structure due to forming hydrogen bond, improves hydrophilic
Property, significantly improve water-retaining property, Main Function mechanism is to reduce the receipts of regenerated aggregate concrete by significantly improving water-retaining property
Contracting and cracking.
The present invention synthesis water-retaining property shrinkage type polycarboxylate water-reducer with traditional surface-active macromonomer APEG, TPEG etc. be
The polycarboxylate water-reducer of primary raw material synthesis is compared, and has the advantage that：
1st, because polyhydroxy and water form hydrogen bond, increased the viscosity of cement slurry, improve the guarantor of concrete mix
Aqueous, thus significantly reducing contraction and the cracking of regenerated aggregate concrete；
2nd, hydrogen bond can be mutually formed between due to hydroxyl and form similar micro- cross-linked structure, thus having to clay higher
Tolerance, it is to avoid the chain intercalation of clay, improves resistance to mud performance.
Synthesize in preparation method step (2) of the present invention and there is the surface-active macromonomer that polyhydroxy reduces group, can basis
The needs of actual product performance, control the additional proportion of reactant glycidol and make surface-active macromonomer have 2,4,8,
16......n individual hydroxyl.
The beneficial effects of the present invention is：The invention provides a kind of water-retaining property shrinkage type polycarboxylate water-reducer is in preparation again
Purposes in raw aggregate concrete, present invention also offers a kind of Regenerated Bone containing this water-retaining property shrinkage type polycarboxylate water-reducer
Material concrete, the water-retaining property shrinkage type polycarboxylate water-reducer that the present invention provides can significantly decrease the surface tension of water, Regenerated Bone
Material concrete reducing result of the test shows, it has preferable Reduce shrinkage effect, during for regenerated aggregate concrete, to regeneration aggregate
The intensity of concrete does not affect, and cost performance is higher.
Specific embodiment
For better illustrating 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 preparation method of water-retaining property shrinkage type polycarboxylate water-reducer of the present invention, walks including following
Suddenly：
(1) in the autoclave of closing, with the air in high pure nitrogen repeatedly replacement reaction kettle 2 times, inject 1mol propylene
The catalyst n aOH of alcohol and 0.2g, reactor is warming up to 100-115 DEG C, starts to be slowly added dropwise 1mol oxirane, makes reaction
In the range of 70 DEG C, in kettle, Stress control, in 0.2MPa, controls the required amount of ethylene oxide of dropping with Subtraction method to temperature control, when
After oxirane completion of dropping, by temperature control at 80 DEG C, continue reaction 5h, obtain the intermediate products of molecular weight.
(2) keep the temperature at 80 DEG C, start to be slowly added dropwise the glycidol of 1mol, dropping controls in 1.5h, drips
Bi Hou, continues reaction 4h, cooling, blowing, obtains final product described polyhydroxy PEG polymeric monomer.
(3) in the glass four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, addition deionized water,
0.063mol isopropanol molecular weight regulator, 0.3mol step (2) be obtained polyhydroxy PEG polymeric monomer, 0.5mol APEG,
5mol acrylic acid, 0.5mol maleic anhydride, are warming up to 85 DEG C, drip the aqueous solution containing potassium peroxydisulfate initiator, described initiation
The mole of agent is 0.0315mol, and time for adding is 2h, after completion of dropping, insulation reaction 4h, and it is cooled to 45 DEG C, divided with quality
It is 7.0 that the NaOH solution for 30% for the number adjusts pH, obtains final product water-retaining property shrinkage type polycarboxylate water-reducer.
Embodiment 2
A kind of embodiment of the preparation method of water-retaining property shrinkage type polycarboxylate water-reducer of the present invention, walks including following
Suddenly：
(1) in the autoclave of closing, with the air in high pure nitrogen repeatedly replacement reaction kettle 3 times, inject 1mol isoamyl
The catalyst KOH of enol and 0.5g, reactor is warming up to 110 DEG C, starts to be slowly added dropwise 40mol oxirane, makes reaction temperature
Degree controls in the range of 115 DEG C, and in kettle, Stress control, in 0.4MPa, controls the required amount of ethylene oxide of dropping with Subtraction method, when
After oxirane completion of dropping, by temperature control at 110 DEG C, continue reaction 2h, obtain the intermediate products of molecular weight.
(2) temperature is reduced to 80 DEG C, starts to be slowly added dropwise the glycidol of 2mol, dropping controls in 2h, completion of dropping
Afterwards, continue reaction 5h, cooling, blowing, obtain final product described polyhydroxy PEG polymeric monomer.
(3) in the glass four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, addition deionized water,
The prepared polyhydroxy PEG polymeric monomer of 0.355mol isopropanol molecular weight regulator, 0.6mol step (2), 1mol HPEG, 5mol
Methacrylic acid, 0.5mol itaconic acid, are warming up to 90 DEG C, drip the aqueous solution containing 0.12mol ammonium persulfate initiator, described
The mole of initiator is 0.355mol, and time for adding is 3h, after completion of dropping, insulation reaction 2h, and it is cooled to 50 DEG C, use quality
Fraction be 30% NaOH solution adjust pH be 6.0, obtain final product water-retaining property shrinkage type polycarboxylate water-reducer.
Embodiment 3
A kind of embodiment of the preparation method of water-retaining property shrinkage type polycarboxylate water-reducer of the present invention, walks including following
Suddenly：
(1) in the autoclave of closing, with the air in high pure nitrogen repeatedly replacement reaction kettle 2 times, inject 1mol isobutyl
The catalyst potassium carbonate of enol and 2g, reactor is warming up to 115 DEG C, starts to be slowly added dropwise 80mol oxirane, makes reaction temperature
Degree controls in the range of 130 DEG C, and in kettle, Stress control, in 0.6MPa, controls the required amount of ethylene oxide of dropping with Subtraction method, when
After oxirane completion of dropping, by temperature control at 120 DEG C, continue reaction 0.5h, obtain the intermediate products of molecular weight.
(2) temperature is reduced to 80 DEG C, starts to be slowly added dropwise the glycidol of 3mol, dropping controls in 2h, completion of dropping
Afterwards, continue reaction 6h, cooling, blowing, obtain final product described polyhydroxy PEG polymeric monomer.
(3) in the glass four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, addition deionized water,
The prepared polyhydroxy PEG polymeric monomer of 0.342mol isopropanol molecular weight regulator, 0.3mol step (2), 1mol VPEG, 10mol
Acrylic acid, 0.1mol ALS, are warming up to 95 DEG C, drip the aqueous solution containing 0.05mol potassium peroxydisulfate initiator, institute
The mole stating initiator is 0.342mol, and time for adding is 2h, after completion of dropping, insulation reaction 3h, and it is cooled to 45 DEG C, use matter
Measuring the NaOH solution that fraction is 30% and adjusting pH is 6.5, obtains final product water-retaining property shrinkage type polycarboxylate water-reducer.
Embodiment 4
A kind of embodiment of the preparation method of water-retaining property shrinkage type polycarboxylate water-reducer of the present invention, walks including following
Suddenly：
(1) in the autoclave of closing, with the air in high pure nitrogen repeatedly replacement reaction kettle 2 times, inject 1mol4- second
Alkenyloxy group butanol and 2g catalyst potassium carbonate, reactor is warming up to 115 DEG C, starts to be slowly added dropwise 80mol oxirane, makes anti-
Answer temperature control in the range of 130 DEG C, in kettle, Stress control, in 0.6MPa, controls the required oxirane of dropping with Subtraction method
Amount, after oxirane completion of dropping, by temperature control at 120 DEG C, continues reaction 0.5h, obtains the middle product of molecular weight
Product.
(2) temperature is reduced to 80 DEG C, starts to be slowly added dropwise the glycidol of 3mol, dropping controls in 2h, completion of dropping
Afterwards, continue reaction 6h, cooling, blowing, obtain final product described polyhydroxy PEG polymeric monomer.
(3) in the glass four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, addition deionized water,
The prepared polyhydroxy PEG polymeric monomer of 0.328mol sulfhydryl compound molecular weight regulator, 0.6mol step (2), 0.5mol
TPEG, 15mol acrylic acid, 0.3mol ALS, are warming up to 95 DEG C, and dropping is containing 0.04mo ammonium persulfate initiator
The aqueous solution, the mole of described initiator is 0.4mol, and time for adding is 2h, after completion of dropping, insulation reaction 3h, it is cooled to 45
DEG C, adjusting pH with the NaOH solution that mass fraction is 30% is 6.5, obtains final product water-retaining property shrinkage type polycarboxylate water-reducer.
Embodiment 5：Application in regenerated aggregate concrete for the water-retaining property shrinkage type polycarboxylate water-reducer of the present invention
By the water-retaining property shrinkage type polycarboxylate water-reducer PCE-S of embodiment of the present invention 1-4 preparation and common polyether polycarboxylic acids
Water reducer PCE press in table 2 weight proportion mixing after as additive, prepare regenerated aggregate concrete by the formula of table 1, wherein
The consumption of additive is 4.5 weight portions, then tests the performance of regenerated aggregate concrete, result such as table 2.
Table 1 regenerated aggregate concrete composition of raw materials (weight portion)
The present invention using through simple screening, broken low-quality regeneration aggregate, because its water absorption rate is high, porosity is high,
The features such as clay content is high, water requirement is high, admixture dosage is high, Slump Time losing of Large is big, drying shrinkage to lead to regeneration concrete to have
Rate is high.The low-quality regenerated coarse aggregate that the present invention uses is as follows with the clay content of natural aggregate and water absorption rate contrast：
The performance test results of table 2 regenerated aggregate concrete
The water conservation water-retaining property shrinkage type polycarboxylate water-reducer of present invention synthesis, can be subtracted with common polyether or polyester polycarboxylic acids
Aqua compounding use or be used alone, compared with common polyether or polyester polycarboxylate water-reducer, has more superior Reduce shrinkage effect,
It reduces mechanism mainly due to introducing polyhydroxy base side chain in the molecular structure, and hydrophily increases, hydroxyl and water or hydroxyl it
Between formed hydrogen bond, increase the viscosity of concrete pore water, improve the water-retaining property of concrete mortar.
In table 2, result of the test shows：In the use preparing regenerated aggregate concrete, with common polyether polycarboxylate water-reducer
PCE compares, and water-retaining property shrinkage type polycarboxylate water-reducer PCE-S of the present invention has more superior water conservation and Reduce shrinkage effect, when compounding
During use, with the increase of PCE-S ratio, the contraction of regenerated aggregate concrete is remarkably decreased, with common polyether polycarboxylic acids diminishing
Agent PCE compares, and the 28d shrinkage ratio of concrete reduces 72%.This is because in PCE-S, due to introducing polyhydroxy side
Chain, hydroxyl hydrophilic is good, is formed between hydroxyl and between hydroxyl and hydrone and forms micro- cross-linked structure between hydrogen bond, and hydrogen bond, increased
The viscosity of the viscosity of capillary hole solution and cement slurry in concrete, so that water-retaining property significantly improves, slows down hydrone evaporation
Speed, thus reduce the shrinkage cracking of regenerated aggregate concrete.
Last should be noted that above example is only in order to illustrate technical scheme rather than to present invention guarantor
The restriction of shield scope, although being explained in detail to the present invention with reference to preferred embodiment, those of ordinary skill in the art should
Understand, technical scheme can be modified or equivalent, without deviating from the essence of technical solution of the present invention
And scope.
Claims (10)
1. a kind of regenerated aggregate concrete is it is characterised in that described regenerated aggregate concrete includes cement, fine aggregate, regeneration slightly
Aggregate, natural coarse aggregate, additive and water, described additive includes water-retaining property shrinkage type polycarboxylate water-reducer, described water-retaining property
Shrinkage type polycarboxylate water-reducer is the compound shown in formula (I), and the structural formula of the compound shown in described formula (I) is as follows：
Wherein a isInteger, b isInteger, c isInteger；D is Integer；
Described A is
Described B is
Described C isL isInteger；
R1For CH3Or H；
R2For H2C=CH-CH2-、Or H2C=CHO-
CH2CH2CH2CH2-；
Described D is polyhydroxy PEG polymeric monomer, and described polyhydroxy PEG polymeric monomer is compound shown in formula (II) and contain ring
Oxygen and hydroxyl bifunctional compound reaction and be obtained, the structural formula of the compound shown in described formula (II) is as follows：
Wherein m is 0～30 integer；
R is H2C=CH-CH2-、And H2C=CH-O-
CH2CH2CH2CH2One of-.
2. regenerated aggregate concrete according to claim 1 it is characterised in that described containing epoxy with hydroxyl difunctional
Compound isIn at least one.
3. regenerated aggregate concrete according to claim 1 and 2 is it is characterised in that described water-retaining property shrinkage type polycarboxylic acids
Water reducer is prepared from by following methods：
(1) in a nitrogen atmosphere enol and catalyst are mixed, be warming up to 70～115 DEG C, be then slowly added dropwise oxirane, will
Reaction temperature controls in the range of 70～130 DEG C, and reaction pressure controls in 0.2～0.6MPa, after oxirane completion of dropping,
Reaction temperature is controlled at 80～120 DEG C, continues reaction 0.5～5h, obtain intermediate product；
(2) temperature of the intermediate product obtaining step (1) is reduced to 80 DEG C, is then slowly added dropwise containing epoxy and the double official of hydroxyl
Energy dough compound, time for adding controls after 1.5～2h, completion of dropping, continues reaction 4～6h, obtains the big list of polyhydroxy PEG
Body；
(3) by one of maleic anhydride, itaconic acid and ALS, one of APEG, HPEG, VPEG and TPEG,
The polyhydroxy PEG polymeric monomer that one of acrylic acid and methacrylic acid, molecular weight regulator, water and described step (2) are obtained
Mixing, is warming up to 95 DEG C, drips the aqueous solution containing initiator, and time for adding is 2h, after completion of dropping, insulation reaction 3h, and fall
To 45 DEG C, adjust pH with alkali lye is 6.5 to temperature, obtains final product water-retaining property shrinkage type polycarboxylate water-reducer.
4. regenerated aggregate concrete according to claim 3 is it is characterised in that enol and epoxy second in described step (1)
The mol ratio of alkane is 1:0～1:80.
5. regenerated aggregate concrete according to claim 3 it is characterised in that in described step (1) enol be propenyl,
At least one in prenol, isobutene alcohol and 4- ethyleneoxy butanol.
6. regenerated aggregate concrete according to claim 3 it is characterised in that in described step (2) intermediate product with contain
Epoxy and the mol ratio of hydroxyl bifunctional compound is had to be less than or equal to 1.
7. regenerated aggregate concrete according to claim 3 is it is characterised in that maleic anhydride, clothing health in described step (3)
One of acid and ALS, one of APEG, HPEG, VPEG and TPEG, in acrylic acid and methacrylic acid
One kind, the mol ratio of polyhydroxy PEG polymeric monomer is one of maleic anhydride, itaconic acid and ALS：APEG、
One of HPEG, VPEG and TPEG：One of acrylic acid and methacrylic acid：Polyhydroxy PEG polymeric monomer=0～0.5：
0.05～1.0：0～15：0.3-3.
8. regenerated aggregate concrete according to claim 1 it is characterised in that described regenerated aggregate concrete include following
The component of weight portion：235 parts of cement, 840 parts of fine aggregate, 620 parts of regenerated coarse aggregate, 376 parts of natural coarse aggregate, additive 4.5
Part and 165 parts of water.
9. regenerated aggregate concrete according to claim 8 is it is characterised in that described regenerated aggregate concrete also includes 65
The flyash of weight portion and the breeze of 80 weight portions.
10. purposes in preparing regenerated aggregate concrete for the water-retaining property shrinkage type polycarboxylate water-reducer is it is characterised in that described guarantor
Aqueous shrinkage type polycarboxylate water-reducer is the compound shown in formula (I), and the structural formula of the compound shown in described formula (I) is as follows：
Wherein a isInteger, b isInteger, c isInteger；D is Integer；
Described A is
Described B is
Described C isL isInteger；
R1 is CH3 or H；
R2 is H2C=CH-CH2-、Or H2C=CHO-
CH2CH2CH2CH2-；
Described D is polyhydroxy PEG polymeric monomer, and described polyhydroxy PEG polymeric monomer is compound shown in formula (II) and contain ring
Oxygen and hydroxyl bifunctional compound reaction and be obtained, the structural formula of the compound shown in described formula (II) is as follows：
Wherein m is 0～30 integer；
R is H2C=CH-CH2-、And H2C=CH-O-
CH2CH2CH2CH2One of-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610742419.3A CN106380548B (en) | 2016-08-27 | 2016-08-27 | Application of water-retention-reduction-type polycarboxylate superplasticizer in preparation of recycled aggregate concrete |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610742419.3A CN106380548B (en) | 2016-08-27 | 2016-08-27 | Application of water-retention-reduction-type polycarboxylate superplasticizer in preparation of recycled aggregate concrete |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106380548A true CN106380548A (en) | 2017-02-08 |
| CN106380548B CN106380548B (en) | 2020-07-03 |
Family
ID=57917491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610742419.3A Active CN106380548B (en) | 2016-08-27 | 2016-08-27 | Application of water-retention-reduction-type polycarboxylate superplasticizer in preparation of recycled aggregate concrete |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106380548B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993432A (en) * | 2012-10-19 | 2013-03-27 | 江苏博特新材料有限公司 | Water reducer midbody, preparation method thereof and water reducer prepared by using preparation method |
| CN103936369A (en) * | 2014-04-18 | 2014-07-23 | 张家港江苏科技大学产业技术研究院 | Grade-C30 single-particle regenerated self-compaction concrete and preparation method thereof |
| CN104059199A (en) * | 2014-04-16 | 2014-09-24 | 广东红墙新材料股份有限公司 | Polycarboxylic acid super-retarding water reducer and preparation method and application thereof |
-
2016
- 2016-08-27 CN CN201610742419.3A patent/CN106380548B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993432A (en) * | 2012-10-19 | 2013-03-27 | 江苏博特新材料有限公司 | Water reducer midbody, preparation method thereof and water reducer prepared by using preparation method |
| CN104059199A (en) * | 2014-04-16 | 2014-09-24 | 广东红墙新材料股份有限公司 | Polycarboxylic acid super-retarding water reducer and preparation method and application thereof |
| CN103936369A (en) * | 2014-04-18 | 2014-07-23 | 张家港江苏科技大学产业技术研究院 | Grade-C30 single-particle regenerated self-compaction concrete and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106380548B (en) | 2020-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5091519B2 (en) | Geopolymer composition and method for producing the same | |
| CN101381217B (en) | Building material based on interaction of alkali and CO2 | |
| CN113429141B (en) | Cementing material and preparation method and application thereof | |
| CN102515673A (en) | Circulating fluidized bed boiler ash cement-based self-leveling material | |
| CN106279566B (en) | Water-retaining shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof | |
| CN111559899A (en) | Recycled material terrace brick and preparation method thereof | |
| CN112266193A (en) | Artificial steel slag aggregate and preparation method and application thereof | |
| CN107777981A (en) | A kind of regeneration concrete and preparation method thereof | |
| CN113213789B (en) | Paving brick prepared based on household garbage incineration fly ash and preparation method thereof | |
| CN103304262A (en) | Autoclaved fly ash aerated concrete building block containing sintering dry-process desulfurized ash and preparation method of autoclaved fly ash aerated concrete building block | |
| CN105198336A (en) | Seashore building cement resisting strong wind and big waves | |
| CN110078449A (en) | It is a kind of using rinsing the non-burning brick and preparation method thereof of mud preparation that rubble and Machine-made Sand generate | |
| KR101331057B1 (en) | Solidified agent to strengthen stratum | |
| CN102320801B (en) | Method for producing braking-free brick from red mud and magnesium slag used as main materials by press shaping | |
| CN109293313B (en) | Sludge brick and preparation process thereof | |
| CN110981271B (en) | Special composite anti-cracking agent for ultra-high performance concrete | |
| CN110845188A (en) | Sand-free macroporous concrete and preparation method thereof | |
| CN101045619A (en) | Blast-furnace slag powder and blast-furnace slag and coal cinder compound powder excitant | |
| CN105198337A (en) | Production method of marine engineering cement block | |
| CN106380548A (en) | Application of water-retaining reduction type polycarboxyliy water reducer in preparing recycled aggregate concrete | |
| CN106365534B (en) | Purposes of the water-retaining property shrinkage type polycarboxylate water-reducer in high performance concrete is prepared | |
| CN113620678A (en) | Grouting material and preparation method thereof | |
| CN113735545A (en) | Concrete product containing phosphogypsum fly ash cement and preparation method thereof | |
| CN106242412B (en) | Surface tension adjusts purposes of the shrinkage type polycarboxylate water-reducer in regenerated aggregate concrete is prepared | |
| CN106279666B (en) | A kind of polyhydroxy PEG polymeric monomer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |