CN106242412B - Surface tension adjusts purposes of the shrinkage type polycarboxylate water-reducer in regenerated aggregate concrete is prepared - Google Patents
Surface tension adjusts purposes of the shrinkage type polycarboxylate water-reducer in regenerated aggregate concrete is prepared Download PDFInfo
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- CN106242412B CN106242412B CN201610744359.9A CN201610744359A CN106242412B CN 106242412 B CN106242412 B CN 106242412B CN 201610744359 A CN201610744359 A CN 201610744359A CN 106242412 B CN106242412 B CN 106242412B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- 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
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Abstract
The invention provides a kind of purposes of surface tension adjustment shrinkage type polycarboxylate water-reducer in regenerated aggregate concrete is prepared, present invention also offers a kind of regenerated aggregate concrete that miniature polycarboxylate water-reducer is adjusted and reduced containing the surface tension, surface tension provided by the invention, which adjusts and reduce miniature polycarboxylate water-reducer, can significantly decrease the surface tension of pore water in concrete water slurry body, regenerated aggregate concrete decrement result of the test shows, it has preferable Reduce shrinkage effect, during for regenerated aggregate concrete, workability and intensity on regenerated aggregate concrete do not influence, cost performance is higher.
Description
Technical field
The present invention relates to a kind of purposes of water reducer, and in particular to a kind of surface tension adjusts shrinkage type polycarboxylate water-reducer
Purposes in regenerated aggregate concrete is prepared.
Background technology
With the continuous development of urban architecture industry, more with bigger, that removes every year is waste and old mixed for the consumption of concrete material
The waste and old coagulation of the discharge such as discarded concrete and concrete mixing plant and factory for prefabrication caused by solidifying soil, new building
Soil, enormous amount, according to statistical result newest at present, China is every year due to discarded concrete caused by abandoned building dismounting
Nearly 200,000,000 tons.The processing mode of discarded concrete mainly has two kinds at present：One kind is simply used as backfilling material, second,
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,
New environmental pollution even can be caused.With going deep into for 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 be saved engineering cost, be saved natural aggregate
Face cost and discarded concrete processing cost, there are important economic benefit and social benefit.
First, domestic External building solid wastes recycling utilizes：
The developed countries such as Japan and the United States, DS, the strategy carried out at present are " building solid waste source abatements ", are referred in building solid waste
Before generation, reach the purpose of decrement by scientific management and effectively control.It is solid to building from scientific and reasonable processing mode
It is useless to be handled, form regenerated resources.
China's building solid waste discharge increases comparatively fast, and rubbish composition also becomes more diverse, the up to several hundred million tons of total emission volumn, processing
Mode is mainly air storage or simple burial, and in recent years, processing sides of some building solid wastes have 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, making building materials.
2nd, the present Research of domestic and international regeneration concrete
Aggregate of recycled concrete (abbreviation regeneration aggregate), it is with after classification, pressing by waste and old concrete block by broken, cleaning
The aggregate that certain ratio grading is 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, it is referred to as producing the waste and old concrete of regeneration aggregate
Former concrete.
Regeneration for waste and old concrete, regenerated aggregate concrete, Japan, the U.S., moral are produced using regeneration aggregate
The country such as state, Britain, Denmark, Holland has all carried out substantial amounts of research work, wherein with the best of Japanology, 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 it is poor (particle shape and grading are 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 were studied regeneration concrete
It is more and more, research work be concentrated mainly on regeneration aggregate partly or entirely replace natural aggregate after, to the concrete of preparation
Performance impact in terms of, and add the mineral admixture such as flyash when preparing concrete to improve the various of regeneration concrete
Performance.And there is no gratifying effect.
At present both at home and abroad regeneration aggregate technology of preparing mainly by cutting and crushing equipment, transmitting mechanical, screening plant and
Clear deimpurity equipment is organically combined, common to complete broken, screening and remove the processes such as impurity, is finally obtained and is met
The recycled fine aggregate and regenerated coarse aggregate of quality requirement.
3rd, low-quality regeneration aggregate
Simple crushing regeneration aggregate without intensive treatment is low-quality concrete, the domestic research starting to regeneration aggregate
It is later, mainly formed by crushing and sieving two parts.To compare with the preparation technology of foreign countries, centre lacks the intensive treatment stage,
Also so that thus obtained Performances of Recycled Aggregate of Existing is substantially inferior to natural aggregate.
Regenerated coarse aggregate particle is typically wrapped in the stone and cement of part of cement mortar by the stone of clean surface, surface
Mortar particle three parts form.Recycled fine aggregate is mainly by sand grains of the surface without 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
Contain tiny Behavior of Hardened Cement Paste particle in material, the grain size scope of recycled fine aggregate, which can relax, is set to 0.08mm~5mm.At present I
State there is no the relevant criterion of Aggregate of recycled concrete, should increase the research of Aggregate of recycled concrete, formulate the performance rating of correlation
Standard, regeneration concrete is set to be widely used in Practical Project.
Low-quality regeneration aggregate grain corner is more, rough surface, and hardening cement mortar (cement mortar hole is also contained in component
Gap rate is big, water absorption rate is high), along with concrete block disintegrate, in shattering process because of damage accumulation a large amount of fine fisssures caused by internally
Line, the porosity of regeneration aggregate is caused to increase, so that water absorption rate and rate of water absorption increase.In the size and aggregate of water absorption rate
Behavior of Hardened Cement Paste content, the cement mortar attachment Shuai ﹑ originals Hun of aggregate surface coagulate aggregate species and Regenerated Bone used in Tu Qiang Du ﹑ original concrete
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
Product 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 more, rough surface, group
Also contain hardening cement mortar (cement mortar porosity is big, water absorption rate is high) in point, along with concrete block is disintegrating, crushed
Because of damage accumulation a large amount of micro-cracks caused by internally in journey, the porosity of regeneration aggregate is caused to increase, so that water absorption rate and suction
Water speed rate increases.The cement mortar attachment Shuai ﹑ original concrete of Behavior of Hardened Cement Paste content, aggregate surface in the size and aggregate of water absorption rate
The factors such as aggregate species used in Qiang Du ﹑ original concrete and the preparation method of regeneration aggregate are relevant.
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, the characteristics of regenerated aggregate concrete：
The characteristics of regeneration aggregate, determine that regenerated aggregate concrete has the characteristics of following：
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 and lengthen with the increase of regeneration aggregate substitute proportion.
The cracking of concrete is a big technical barrier of concrete application, mixes economization agent, reduces concrete shrinkage, is wherein
One of solution, controlled with economization agent 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 contraction is excessive, produced
Raw shrinkage stress can make concrete produce cracking, can not only reduce structural strength, and crack also enters concrete for air and water
One passage is provided, makes concrete that graphitic corrosion, steel bar corrosion easily occur, in cold district it also occur that Frozen-thawed cycled, this
A little durability for all greatly reducing concrete, shorten the service life of building.Thus, shrinkage cracking is puzzlement concrete
One problem of engineering.
The approach for generally solving the problems, such as concrete shrinkage is incorporation swelling agent, and main principle is in coagulation by swelling agent
Expansile hydrated product is generated in soil and is shunk to compensate, reduces the possibility of concrete cracking.But use swelling agent special
Concrete is not needed in the maintenance for having water in early days, condition harshness, and serious cement adaptability and delay calcium alum in itself be present
The problems such as stone generates, in addition, being had difficulties on its addition is adjusted, if volume is very few, effect is not reached, if volume mistake
Greatly, excessive part may cause expanded crack due to expansion, thus be had to final result using swelling agent certain
It is uncertain.
Another is to mix fiber, but adding of fiber can only be the anti-crack ability for improving concrete, can not reduce mixed
The contraction of soil is coagulated, while fiber price is high, exists and concrete consistency problem.Also it greatly limit its popularization.
Concrete shrinkage mechanism：
The contraction of concrete can be divided into chemical shrinkage, plastic shrinkage, temperature shrinkage, self-constriction, dry contraction and carbonization and receive
Contract six big types, wherein the most universal to dry contraction, mechanism is more complicated, and existing theory mainly has capillary tensiometry
Say, adsorption theory, take stress theory etc. apart, most convincing with capillary tension theory among these, the theory thinks,
When ambient humidity is less than 100%, the water surface inside capillary declines and forms meniscus, according to Laplas formula, in the table of water
Under the tension force effect of face, the caused additonal pressure in capillary：△ P=2 σ COS θ/R
In formula, △ P are the additonal pressure under the bending page, and σ is the surface tension of water, and θ is water concave meniscus and capillary hole wall
Contact angle, R is capillary radius.
In the case where σ is constant, capillary is thinner, and the radius of curvature of meniscus is smaller, and caused capillary pressure is bigger；
When R is constant, P is directly proportional to the surface tension σ of water.
With scattering and disappearing for pore water, R diminishes, and △ P increases, capillary tension is acted on hole wall, produces pulling force, and then
Cause 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 where σ is constant, capillary is thinner, and the radius of curvature of meniscus is smaller, and caused capillary pressure is bigger,
When R is constant, P is directly proportional to the surface tension of water.With the evaporation of pore water, R diminishes, P increases, capillary tension effect
On hole wall, pulling force is produced, and then cause concrete shrinkage macroscopically.
The decrement principle of economization agent：
Analyzed according to contractile mechanism above, the meniscus dried contraction, be due to pore reclaimed water is formed of concrete
And caused by caused additonal pressure △ P, and determine △ P is three variables：σ, θ and R, R are by component materials of concrete
What composition and match ratio determined, the liquid of σ and θ with infiltration in pore is relevant, and the surface tension of pure water is 72N/m, very
Height, if it can be reduced to 35N/m, 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, the surface tension of water can be greatly lowered in the environment of highly basic, on the other hand, be made up of water and economization agent
Solution viscosity increase so that contact angle θ increases, and so as to also further reduce the shrinkage stress of concrete, reduces opening for concrete
Split.
Japan and research of the U.S. for economization agent for concrete are more, 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, while also developed into by one-component multigroup
The compound product of compound divided, can not only so reduce the cracking shrinkage value of concrete, and also overcome single group in the past
Many shortcomings of point product, the long-term Reduce shrinkage effect such as one-component economization agent is not ideal enough, and cost is higher and concrete strength
Easily reduce etc., another rule of development is exactly gradually to be developed from the product of simple function to multifunctional product, such as is had simultaneously
Decrement and diminishing function.
The domestic research and development to economization agent are started late, and general economization agent price is again higher, therefore is pushed away so far there has been no more
Wide application.But constantly increase with economical, the durability and quality appearance of marine engineering concrete and infrastructure building thing
It can also be incrementally increased it is required that can step up, the problem of concrete cracking, it is still concrete research scholar to solve this problem
A challenge.
Economization agent can substantially reduce concrete early-age shrinkage, its main function mechanism be reduce pore water surface tension and
Shrinkage stress caused by pore dehydration is reduced, is on the other hand the viscosity for increasing concrete pore water, enhancing water is mixed
Coagulate the suction-operated in native colloid and reduce the shrinkage value of concrete.The main component of economization agent is polyethers or polyalcohols and its derivative
Thing, such as glycerine, POLYPROPYLENE GLYCOL, the polycarboxylic acids containing ethylene glycol.
Drying shrinkage can make concrete structure or component produce cracking, shrink as 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 waters；
Phase III：Lose the water in C-H-S structures；
When the water in these apertures loses, hole wall is furthered and makes volume contraction by the surface tension of residual water in hole.
Though the use of these economization agents reduces the contraction of concrete to a certain extent, engineering cost increase is big, and
Synthesis technique is complicated.
In many use difficult points of regenerated aggregate concrete, received caused by the height of powder containing quantity containing mud of regeneration aggregate
Shrinkage is big, the big technological difficulties for especially allowing technology in the industry and researcher to perplex, at present both at home and abroad also without a kind of row it
Effective overcoming method.
The content of the invention
Provide a kind of shrinkage type polycarboxylic acids it is an object of the invention to overcome the shortcomings of the prior art part and subtract
Purposes of the aqua in regenerated aggregate concrete is prepared, present invention also offers a kind of containing the shrinkage type polycarboxylate water-reducer
Regenerated aggregate concrete, the shrinkage type polycarboxylate water-reducer is by diminishing agent molecule, introducing hydrophobic group benzyl, first
At least one of base benzyl, phenethyl, phenylpropyl, benzene butyl, methylphenethyl, methyl phenylpropyl and methylbenzene butyl and dredge
The water-based PPO more than PEO reduces the convergent force of surface tension, reduction water evaporation process to reach, and reduces regeneration so as to reach
The purpose that aggregate concrete shrinks.The hydrophobicity introduced in surface tension adjustment shrinkage type polycarboxylate water-reducer molecule structure subtracts
Contracting group benzyl, methyl-benzyl, phenethyl, phenylpropyl, benzene butyl, methylphenethyl, methyl phenylpropyl, methylbenzene butyl etc.,
And the PPO that hydrophobicity is strong, it is intended to by putting forward high molecular hydrophobicity, break HLB balance, water is significantly reduced so as to reach
Surface tension, moisture evaporation is reduced, that reduces regenerated aggregate concrete dries contraction.
To achieve the above object, the technical scheme taken：A kind of regenerated aggregate concrete, the regenerated aggregate concrete
Including cement, fine aggregate, regenerated coarse aggregate, natural coarse aggregate, additive and water, the additive includes surface tension adjustment and subtracted
Miniature polycarboxylate water-reducer, the surface tension adjust shrinkage type polycarboxylate water-reducer as the compound shown in formula (I), the formula
(I) structural formula of the compound shown in is as follows：
Wherein a isInteger, b isInteger, c isInteger；D is It is whole
Number, e are 1-100 integer；
The A is
The B isM1 isInteger, m2 is 0~15
Integer；
The C isL is 1~30 integer；
The D is
The E isN is 1~4 integer；
R1For H or CH3；
R2For H or CH3；
R3For H2C=CH-CH2-、Or H2C=
CHO-CH2CH2CH2CH2-；
R4For H2C=CH-CH2-、Or H2C=
CHO-CH2CH2CH2CH2-。
Preferably, the surface tension adjustment shrinkage type polycarboxylate water-reducer is prepared by following methods：
(1) by least one of acrylic acid and methacrylic acid and benzyl alcohol, methyl-benzyl alcohol, benzyl carbinol, phenylpropanol,
At least one of benzene butanol, methyl benzyl carbinol, methyl phenylpropanol and methylbenzene butanol mix, and add catalyst and polymerization inhibitor,
Stirring, 80~90 DEG C, 5~6h of insulation reaction are warming up to, cooling, obtains reaction product；
(2) by water, one kind in methacrylic acid and acrylic acid, one kind in APEG, HPEG, VPEG and TPEG, APPG,
The reaction product mixing that one kind in HPPG, VPPG and TPPG, ALS, chain-transferring agent and step (1) obtain, while stirring
Mix side and be warming up to 60~70 DEG C, initiator solution is added dropwise, and be added dropwise in 2.0h, continue 4~6h of insulation reaction, cool,
PH=6~7 are neutralized to alkali lye, produce surface tension adjustment shrinkage type polycarboxylate water-reducer.
The structural formula of reaction product is as follows in above-mentioned steps (1)：
Wherein R1For CH3Or H, R2For CH3Or the integer that H, n are 1~4.
Reaction equation in above-mentioned steps (1) is as follows：
Preferably, at least one of acrylic acid and methacrylic acid and benzyl alcohol, methyl-benzyl in the step (1)
The mol ratio of at least one of alcohol, benzyl carbinol, phenylpropanol, benzene butanol, methyl benzyl carbinol, methyl phenylpropanol and methylbenzene butanol
For at least one of acrylic acid and methacrylic acid：Benzyl alcohol, methyl-benzyl alcohol, benzyl carbinol, phenylpropanol, benzene butanol, methyl
At least one of benzyl carbinol, methyl phenylpropanol and methylbenzene butanol=1:1~1.2:1.
Preferably, catalyst is toluene sulfonic acide in the step (1), the dosage of the catalyst be the acrylic acid and
At least one of methacrylic acid and benzyl alcohol, methyl-benzyl alcohol, benzyl carbinol, phenylpropanol, benzene butanol, methyl benzyl carbinol, first
The 2%~2.5% of the gross weight of at least one of base phenylpropanol and methylbenzene butanol.
Preferably, polymerization inhibitor is at least one of 4- metoxyphenols and methoxyhydroquinon in the step (1), described
The dosage of polymerization inhibitor is at least one of described acrylic acid and methacrylic acid and benzyl alcohol, methyl-benzyl alcohol, benzyl carbinol, benzene
The 0.2% of the gross weight of at least one of propyl alcohol, benzene butanol, methyl benzyl carbinol, methyl phenylpropanol and methylbenzene butanol~
0.3%.
Preferably, one kind in the step (2) in methacrylic acid and acrylic acid, in APEG, HPEG, VPEG and TPEG
One kind, one kind in APPG, HPPG, VPPG and TPPG, mole for the reaction product that ALS and step (1) obtain
Than for one kind in methacrylic acid and acrylic acid：One kind in APEG, HPEG, VPEG and TPEG：APPG, HPPG, VPPG and
One kind in TPPG：ALS：Reaction product=4~5 that step (1) obtains:0.15~0.3:0.015~0.06:1
~1.5:1.
Preferably, one kind in described APPG, HPPG, VPPG and TPPG is pi-allyl polyethenoxy ether.
Preferably, step (2) Chain transfer agent is in mercaptoethanol, TGA, mercaprol, mercaptopropionic acid
It is at least one.Preferably, the mole dosage of step (2) Chain transfer agent is one in the acrylic acid and methacrylic acid
Plant, one kind in APEG, HPEG, VPEG and TPEG, one kind in APPG, HPPG, VPPG and TPPG, ALS and step
Suddenly the 0.5%~5% of the molal quantity sum for the reaction product that (1) obtains.
Preferably, initiator solution is at least one in potassium persulfate solution and ammonium persulfate solution in the step (2)
Kind.Preferably, the initiator solution is at least one of potassium peroxydisulfate and ammonium persulfate that mass fraction is 10--20%
The aqueous solution.
Preferably, the mole dosage of initiator is one kind in the acrylic acid and methacrylic acid in the step (2),
One kind in APEG, HPEG, VPEG and TPEG, one kind in APPG, HPPG, VPPG and TPPG, ALS and step
(1) 1%-5% of the molal quantity sum of the reaction product obtained.
Preferably, alkali lye is the sodium hydroxide solution that mass fraction is 30% in the step (2).
Preferably, the regenerated aggregate concrete includes the component of following parts by weight：235 parts of cement, 840 parts of fine aggregate,
165 parts of 620 parts of regenerated coarse aggregate, 376 parts of natural coarse aggregate, 7.6 parts of additive and water.
Preferably, the miberal powder of flyash and 80 parts by weight of the concrete also including 65 parts by weight.
A kind of use of the surface tension adjustment shrinkage type polycarboxylate water-reducer of the present invention in regenerated aggregate concrete is prepared
On the way, the surface tension adjustment shrinkage type polycarboxylate water-reducer is the compound shown in formula (I), the chemical combination shown in the formula (I)
The structural formula of thing is as follows：
Wherein a isInteger, b isInteger, c isInteger；D is It is whole
Number, e are 1-100 integer；
The A is
The B isM1 isInteger, m2 is 0~15
Integer；
The C isL is 1~30 integer；
The D is
The E isN is 1~4 integer；
R1For H or CH3；
R2For H or CH3；
R3For H2C=CH-CH2-、Or H2C=
CHO-CH2CH2CH2CH2-；
R4For H2C=CH-CH2-、Or H2C=
CHO-CH2CH2CH2CH2-。
The present invention utilizes molecular design theory, introduces decrement group benzyl, methyl-benzyl, phenethyl, phenylpropyl alcohol in the molecule
At least one of base, benzene butyl, methylphenethyl, methyl phenylpropyl and methylbenzene butyl, and with certain hydrophobic effect
PPO, the ability for making sintetics that there is excellent reduction surface tension, the convergent force of moisture evaporation is reduced, is regenerated so as to reduce
The shrinkage cracking of aggregate concrete.
In surface tension adjustment shrinkage type polycarboxylate water-reducer molecule structure of the present invention, hydrophobic group benzyl is anti-by being esterified
Answer and introduce, ester group hydrolyzes under cement strong alkali environment, and-COO- the groups of formation form second adsorption to cement granules and divided
Dissipate, therefore surface tension of the present invention adjustment shrinkage type polycarboxylate water-reducer has certain function of slump protection concurrently.
Surface tension adjustment shrinkage type polycarboxylate water-reducer of the present invention introduces double decrement groups, and there is good decrement to make
With being excellent hydrophobic type economization agent for concrete.
The beneficial effects of the present invention are：Miniature polycarboxylate water-reducer is adjusted and reduced the invention provides a kind of surface tension making
Purposes in standby regenerated aggregate concrete, miniature polycarboxylate water-reducer is adjusted and reduced containing the surface tension present invention also offers one kind
Regenerated aggregate concrete, surface tension provided by the invention, which adjusts and reduce miniature polycarboxylate water-reducer, can significantly decrease concrete water
The surface tension of pore water in slurry body, regenerated aggregate concrete decrement result of the test show that there is preferably decrement to imitate for it
Fruit, during for regenerated aggregate concrete, workability and intensity on regenerated aggregate concrete do not influence, and cost performance is higher.
Embodiment
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 surface tension adjustment shrinkage type polycarboxylate water-reducer of the present invention, the surface tension adjustment
The preparation method of shrinkage type polycarboxylate water-reducer is as follows：
(1) equipped with agitator, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 500ml in, add 0.5mol methyl
Acrylic acid, 0.5mol benzyl alcohols, toluene sulfonic acide (dosage is the 2% of methacrylic acid and benzyl alcohol gross weight), 4- methoxyl groups
Phenol (dosage is the 0.2% of methacrylic acid and benzyl alcohol gross weight), stirring, is warming up to 80 DEG C, insulation reaction 6h, cools,
Obtain reaction product benzyl methacrylate.
(2) equipped with agitator, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 2000ml in add 1200ml water,
The metering system that methacrylic acid, APEG, pi-allyl polyethenoxy ether, ALS, mercaptoethanol, step (1) obtain
Sour benzyl ester, the methacrylic acid, APEG, pi-allyl pi-allyl polyethenoxy ether, benzene sulfonic acid sodium salt and step (1) obtain anti-
The mol ratio for answering product is methacrylic acid：Allyl polyethenoxy ether：Pi-allyl polyethenoxy ether：ALS：Step
Suddenly reaction product=4 that (1) obtains:0.15:0.015:1:1, the mole dosage of the mercaptoethanol be the methacrylic acid,
The 0.5% of the molal quantity sum for the reaction product that APEG, pi-allyl polyethenoxy ether, ALS and step (1) obtain,
Potassium persulfate solution is added dropwise to 60 DEG C in warming while stirring, the mole dosage of the potassium peroxydisulfate be methacrylic acid, APEG,
The 1% of the molal quantity sum for the reaction product that pi-allyl polyethenoxy ether, ALS and step (1) obtain, and
It is added dropwise in 2.0h, continues insulation reaction 6h, cooling, pH=6 is neutralized to 30Wt% sodium hydroxide solutions, produce surface
Power adjustment shrinkage type polycarboxylate water-reducer PCE-S-P.
Embodiment 2
A kind of embodiment of surface tension adjustment shrinkage type polycarboxylate water-reducer of the present invention, the surface tension adjustment
The preparation method of shrinkage type polycarboxylate water-reducer is as follows：
(1) equipped with agitator, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 500ml in, add 0.6mol propylene
Acid, 0.5mol methyl-benzyl alcohols, toluene sulfonic acide (dosage is the 2.5% of methacrylic acid and benzyl alcohol gross weight), methoxyl group
Quinhydrones (dosage is the 0.3% of methacrylic acid and benzyl alcohol gross weight), stirring, is warming up to 90 DEG C, insulation reaction 5h, cools,
Obtain reaction product acrylic acid methyl-benzyl ester.
(2) equipped with agitator, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 2000ml in add 1200ml water,
The propylene acid methyl benzyl that acrylic acid, HPEG, pi-allyl polyethenoxy ether, ALS, TGA, step (1) obtain
Base ester, the reaction product that the acrylic acid, HPEG, pi-allyl polyethenoxy ether, ALS and step (1) obtain are rubbed
Your ratio is acrylic acid：Allyl polyethenoxy ether：Pi-allyl polyethenoxy ether：ALS：The reaction that step (1) obtains
Product=5:0.3:0.06:1.5:1, the mole dosage of the TGA is the acrylic acid, HPEG, pi-allyl polyoxypropylene
The 5% of the molal quantity sum for the reaction product that ether, ALS and step (1) obtain, warming while stirring is to 70 DEG C, drop
Add potassium persulfate solution, the mole dosage of potassium peroxydisulfate is the acrylic acid, HPEG, pi-allyl polyoxy third in the step (2)
The 5% of the molal quantity sum for the reaction product that alkene ether, ALS and step (1) obtain, and be added dropwise in 2.0h,
Continue insulation reaction 4h, cooling, pH=7 is neutralized to 30Wt% sodium hydroxide solutions, produce surface tension adjustment shrinkage type and gather
Carboxylic acid water reducer PCE-S-P.
Embodiment 3
A kind of embodiment of surface tension adjustment shrinkage type polycarboxylate water-reducer of the present invention, the surface tension adjustment
The preparation method of shrinkage type polycarboxylate water-reducer is as follows：
(1) equipped with agitator, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 500ml in, add 0.6mol methyl
Acrylic acid, 0.5mol benzyl carbinols, toluene sulfonic acide (dosage is the 2% of methacrylic acid and benzyl alcohol gross weight), 4- methoxyl groups
Phenol (dosage is the 0.2% of methacrylic acid and benzyl alcohol gross weight), stirring, is warming up to 85 DEG C, insulation reaction 6h, cools,
Obtain reaction product methacrylic acid phenethyl ester.
(2) equipped with agitator, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 2000ml in add 1200ml water,
The metering system that methacrylic acid, VPEG, pi-allyl polyethenoxy ether, ALS, mercaprol, step (1) obtain
Sour phenethyl ester, the reaction that the methacrylic acid, VPEG, pi-allyl polyethenoxy ether, ALS and step (1) obtain
The mol ratio of product is methacrylic acid：Allyl polyethenoxy ether：Pi-allyl polyethenoxy ether：ALS：Step
(1) reaction product=4.5 obtained:0.2:0.03:1.2:1, the mole dosage of the mercaprol be the methacrylic acid,
The 2% of the molal quantity sum for the reaction product that VPEG, pi-allyl polyethenoxy ether, ALS and step (1) obtain, side
Stirring side is warming up to 60 DEG C, is added dropwise potassium persulfate solution, the mole dosage of the potassium peroxydisulfate be the methacrylic acid,
The 2% of the molal quantity sum for the reaction product that VPEG, pi-allyl polyethenoxy ether, ALS and step (1) obtain, and
It is added dropwise in 2.0h, continues insulation reaction 5h, cooling, be neutralized to pH=7 with 30Wt% sodium hydroxide solutions, produce surface
Tension adjustment shrinkage type polycarboxylate water-reducer PCE-S-P.
Embodiment 4
A kind of embodiment of surface tension adjustment shrinkage type polycarboxylate water-reducer of the present invention, the surface tension adjustment
The preparation method of shrinkage type polycarboxylate water-reducer is as follows：
(1) equipped with agitator, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 500ml in, add 0.5mol methyl
Acrylic acid, 0.5mol phenylpropanols, toluene sulfonic acide (dosage is the 2% of methacrylic acid and benzyl alcohol gross weight), 4- methoxyl groups
Phenol (dosage is the 0.2% of methacrylic acid and benzyl alcohol gross weight), stirring, is warming up to 80 DEG C, insulation reaction 6h, cools,
Obtain reaction product methacrylic acid phenylpropyl alcohol ester.
(2) equipped with agitator, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 2000ml in add 1200ml water,
The metering system that methacrylic acid, TPEG, pi-allyl polyethenoxy ether, ALS, mercaptoethanol, step (1) obtain
Sour phenylpropyl alcohol ester, the reaction that the methacrylic acid, TPEG, pi-allyl polyethenoxy ether, ALS and step (1) obtain
The mol ratio of product is methacrylic acid：Allyl polyethenoxy ether：Pi-allyl polyethenoxy ether：ALS：Step
(1) reaction product=4 obtained:0.15:0.015:1:1, the mole dosage of mercaptoethanol is the methyl in the step (2)
The molal quantity sum for the reaction product that acrylic acid, TPEG, pi-allyl polyethenoxy ether, ALS and step (1) obtain
3%, warming while stirring to 60 DEG C, be added dropwise potassium persulfate solution, the mole dosage of the potassium peroxydisulfate is the methyl-prop
The molal quantity sum for the reaction product that olefin(e) acid, TPEG, pi-allyl polyethenoxy ether, ALS and step (1) obtain
3%, and be added dropwise in 2.0h, continue insulation reaction 6h, cooling, be neutralized to pH=6 with 30Wt% sodium hydroxide solutions, i.e.,
Obtain surface tension adjustment shrinkage type polycarboxylate water-reducer PCE-S-P.
Embodiment 5
A kind of embodiment of surface tension adjustment shrinkage type polycarboxylate water-reducer of the present invention, the surface tension adjustment
The preparation method of shrinkage type polycarboxylate water-reducer is as follows：
(1) equipped with agitator, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 500ml in, add 0.6mol propylene
Acid, 0.5mol methylbenzene butanol, toluene sulfonic acide (dosage is the 2.5% of methacrylic acid and benzyl alcohol gross weight), methoxyl group
Quinhydrones (dosage is the 0.3% of methacrylic acid and benzyl alcohol gross weight), stirring, is warming up to 90 DEG C, insulation reaction 5h, cools,
Obtain reaction product acrylic acid methyl butyl benzenesulfonamide.
(2) equipped with agitator, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 2000ml in add 1200ml water,
The acrylic acid methylbenzene that acrylic acid, APEG, pi-allyl polyethenoxy ether, ALS, mercaptoethanol, step (1) obtain
Butyl ester, the reaction product that the acrylic acid, APEG, pi-allyl polyethenoxy ether, ALS and step (1) obtain are rubbed
Your ratio is acrylic acid：Allyl polyethenoxy ether：Pi-allyl polyethenoxy ether：ALS：The reaction that step (1) obtains
Product=5:0.3:0.06:1.5:1, the mole dosage of the mercaptoethanol is the acrylic acid, APEG, pi-allyl polyoxypropylene
The 1% of the molal quantity sum for the reaction product that ether, ALS and step (1) obtain, warming while stirring is to 70 DEG C, drop
Add potassium persulfate solution, the mole dosage of the potassium peroxydisulfate is the acrylic acid, APEG, pi-allyl polyethenoxy ether, allyl
The 2% of the molal quantity sum for the reaction product that base sodium sulfonate and step (1) obtain, and be added dropwise in 2.0h, continue to be incubated
4h is reacted, cooling, pH=7 is neutralized to 30Wt% sodium hydroxide solutions, produces surface tension adjustment shrinkage type polycarboxylic acids diminishing
Agent PCE-S-P.
Embodiment 6
A kind of embodiment of surface tension adjustment shrinkage type polycarboxylate water-reducer of the present invention, the surface tension adjustment
The preparation method of shrinkage type polycarboxylate water-reducer is as follows：
(1) equipped with agitator, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 500ml in, add 0.6mol methyl
Acrylic acid, 0.5mol benzene butanol, toluene sulfonic acide (dosage is the 2% of methacrylic acid and benzyl alcohol gross weight), 4- methoxyl groups
Phenol (dosage is the 0.2% of methacrylic acid and benzyl alcohol gross weight), stirring, is warming up to 85 DEG C, insulation reaction 6h, cools,
Obtain reaction product methacrylic acid butyl benzenesulfonamide.
(2) equipped with agitator, thermometer, reflux condensing tube tetra- mouthfuls of glass flasks of 2000ml in add 1200ml water,
The metering system that methacrylic acid, APEG, pi-allyl polyethenoxy ether, ALS, mercaprol, step (1) obtain
Sour butyl benzenesulfonamide, the reaction that the methacrylic acid, APEG, pi-allyl polyethenoxy ether, ALS and step (1) obtain
The mol ratio of product is methacrylic acid：Allyl polyethenoxy ether：Pi-allyl polyethenoxy ether：ALS：Step
(1) reaction product=4.5 obtained:0.2:0.03:1.2:1, the mole dosage of the mercaprol be the methacrylic acid,
The 0.5% of the molal quantity sum for the reaction product that APEG, pi-allyl polyethenoxy ether, ALS and step (1) obtain,
Potassium persulfate solution is added dropwise to 60 DEG C in warming while stirring, the mole dosage of the potassium peroxydisulfate be the methacrylic acid,
The 5% of the molal quantity sum for the reaction product that APEG, pi-allyl polyethenoxy ether, ALS and step (1) obtain, and
It is added dropwise in 2.0h, continues insulation reaction 5h, cooling, be neutralized to pH=7 with 30Wt% sodium hydroxide solutions, produce surface
Tension adjustment shrinkage type polycarboxylate water-reducer PCE-S-P.
Embodiment 7：Application of the surface tension adjustment shrinkage type polycarboxylate water-reducer of the present invention in regenerated aggregate concrete
Surface tension adjustment shrinkage type polycarboxylate water-reducer PCE-S-P prepared by 1-6 of the embodiment of the present invention gathers with common
Ether polycarboxylate water-reducer PCE is used as additive after pressing the weight proportion mixing in table 2, and preparing regeneration aggregate by the formula of table 1 mixes
Solidifying soil, the wherein dosage of additive are 7.6 (folding is solid) parts by weight, then test the performance of regenerated aggregate concrete.
The regenerated aggregate concrete composition of raw materials (parts by weight) of table 1
The present invention using by simple screening, broken low-quality regeneration aggregate, due to its water absorption rate is high, porosity is high,
The features such as clay content is high, causing regeneration concrete to have, water requirement is high, admixture dosage is high, Slump Time losing of Large is big, drying shrinkage
Rate is high.Clay content and the water absorption rate contrast of low-quality regenerated coarse aggregate and natural aggregate that the present invention uses are as follows：
Clay content (%) water absorption rate (%)
Natural aggregate 0.1 0.75
Low-quality regenerated coarse aggregate 8.5 7.0
The performance test results of the regenerated aggregate concrete of table 2
The surface tension adjustment shrinkage type polycarboxylate water-reducer that the present invention synthesizes, can be with common polyether or polyester polycarboxylic acids
Water reducer compounding use or exclusive use, compared with common polyether or polyester polycarboxylate water-reducer, there is more superior decrement to imitate
Fruit, it reduces mechanism mainly due to introducing decrement group benzyl, methyl-benzyl, phenethyl, phenylpropyl, benzene fourth in the molecule
At least one of base, methylphenethyl, methyl phenylpropyl and methylbenzene butyl, and the PPO with certain hydrophobic effect, make conjunction
There is the ability of excellent reduction surface tension into product, reduce the convergent force of moisture evaporation, so as to reduce the contraction of concrete
Cracking.
Result of the test shows in table 2：In preparation regenerated aggregate concrete in use, and common polyether polycarboxylate water-reducer
PCE is compared, and there is surface tension adjustment shrinkage type polycarboxylate water-reducer PCE-S-P of the present invention more superior water conservation and decrement to imitate
Fruit, when compounding use, with the increase of PCE-S-P ratios, the slump and fluidity retentivity of regenerated aggregate concrete are bright
Aobvious to improve, 28d shrinkage ratios significantly reduce.Because in PCE-S-P, due to introducing hydrophobic grouping, water surface is reduced
Tension force, the convergent force of moisture evaporation is reduced, so as to reduce the shrinkage cracking of regenerated aggregate concrete.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of scope is protected, although being explained in detail with reference to preferred embodiment to the present invention, one of ordinary skill in the art should
Understand, technical scheme can be modified or equivalent substitution, without departing from the essence of technical solution of the present invention
And scope.
Claims (10)
1. a kind of regenerated aggregate concrete, it is characterised in that the regenerated aggregate concrete includes cement, fine aggregate, regeneration slightly
Aggregate, natural coarse aggregate, additive and water, the additive includes surface tension adjustment shrinkage type polycarboxylate water-reducer, described
Surface tension adjusts shrinkage type polycarboxylate water-reducer as the compound shown in formula (I), the structure of the compound shown in the formula (I)
Formula is as follows：
Wherein a isInteger, b isInteger, c isInteger；D is Integer, e is
1-100 integer；
The A is
The B isM1 isInteger, m2 be 0~15 integer；
The C isL is 1~30 integer；
The D is
The E isN is 1~4 integer；
R1For H or CH3；
R2For H or CH3；
R3For H2C=CH-CH2-、Or H2C=CHO-
CH2CH2CH2CH2-；
R4For H2C=CH-CH2-、Or H2C=CHO-
CH2CH2CH2CH2-。
2. regenerated aggregate concrete according to claim 1, it is characterised in that the surface tension adjusts the poly- carboxylic of shrinkage type
Sour water reducer is prepared by following methods：
(1) by least one of acrylic acid and methacrylic acid and benzyl alcohol, methyl-benzyl alcohol, benzyl carbinol, phenylpropanol, benzene fourth
At least one of alcohol, methyl benzyl carbinol, methyl phenylpropanol and methylbenzene butanol mix, and add catalyst and polymerization inhibitor, stir,
80~90 DEG C, 5~6h of insulation reaction are warming up to, cooling, obtains reaction product；
(2) by water, one kind in methacrylic acid and acrylic acid, one kind in APEG, HPEG, VPEG and TPEG, APPG,
The reaction product mixing that one kind in HPPG, VPPG and TPPG, ALS, chain-transferring agent and step (1) obtain, while stirring
Mix side and be warming up to 60~70 DEG C, initiator solution is added dropwise, and be added dropwise in 2.0h, continue 4~6h of insulation reaction, cool,
PH=6~7 are neutralized to alkali lye, produce surface tension adjustment shrinkage type polycarboxylate water-reducer.
3. regenerated aggregate concrete according to claim 2, it is characterised in that acrylic acid and methyl in the step (1)
At least one of acrylic acid and benzyl alcohol, methyl-benzyl alcohol, benzyl carbinol, phenylpropanol, benzene butanol, methyl benzyl carbinol, methylbenzene
The mol ratio of at least one of propyl alcohol and methylbenzene butanol is at least one of acrylic acid and methacrylic acid：Benzyl alcohol,
At least one of methyl-benzyl alcohol, benzyl carbinol, phenylpropanol, benzene butanol, methyl benzyl carbinol, methyl phenylpropanol and methylbenzene butanol
=1:1~1.2:1.
4. regenerated aggregate concrete according to claim 2, it is characterised in that catalyst is methyl in the step (1)
Benzene sulfonic acid, the dosage of the catalyst is at least one of described acrylic acid and methacrylic acid and benzyl alcohol, methyl-benzyl
The gross weight of at least one of alcohol, benzyl carbinol, phenylpropanol, benzene butanol, methyl benzyl carbinol, methyl phenylpropanol and methylbenzene butanol
2%~2.5%.
5. regenerated aggregate concrete according to claim 2, it is characterised in that polymerization inhibitor is 4- first in the step (1)
At least one of epoxide phenol and methoxyhydroquinon, the dosage of the polymerization inhibitor is in the acrylic acid and methacrylic acid
At least one and benzyl alcohol, methyl-benzyl alcohol, benzyl carbinol, phenylpropanol, benzene butanol, methyl benzyl carbinol, methyl phenylpropanol and methyl
The 0.2%~0.3% of the gross weight of at least one of benzene butanol.
6. regenerated aggregate concrete according to claim 2, it is characterised in that in the step (2) methacrylic acid and
One kind in acrylic acid, one kind in APEG, HPEG, VPEG and TPEG, one kind in APPG, HPPG, VPPG and TPPG, allyl
The mol ratio for the reaction product that base sodium sulfonate and step (1) obtain is one kind in methacrylic acid and acrylic acid：APEG、
One kind in HPEG, VPEG and TPEG：One kind in APPG, HPPG, VPPG and TPPG：ALS：Step (1) obtains
Reaction product=4~5:0.15~0.3:0.015~0.06:1~1.5:1.
7. regenerated aggregate concrete according to claim 2, it is characterised in that step (2) Chain transfer agent is mercapto
At least one of base ethanol, TGA, mercaprol, mercaptopropionic acid.
8. regenerated aggregate concrete according to claim 1, it is characterised in that the regenerated aggregate concrete includes following
The component of parts by weight：235 parts of cement, 840 parts of fine aggregate, 620 parts of regenerated coarse aggregate, 376 parts of natural coarse aggregate, additive 7.6
165 parts of part and water.
9. regenerated aggregate concrete according to claim 8, it is characterised in that the concrete also includes 65 parts by weight
The miberal powder of flyash and 80 parts by weight.
10. surface tension adjusts purposes of the shrinkage type polycarboxylate water-reducer in regenerated aggregate concrete is prepared, it is characterised in that
The surface tension adjustment shrinkage type polycarboxylate water-reducer is the compound shown in formula (I), the compound shown in the formula (I)
Structural formula is as follows：
Wherein a isInteger, b isInteger, c isInteger；D is Integer, e is
1-100 integer；
The A is
The B isM1 isInteger, m2 be 0~15 integer；
The C isL is 1~30 integer；
The D is
The E isN is 1~4 integer；
R1For H or CH3；
R2For H or CH3；
R3For H2C=CH-CH2-、Or H2C=CHO-
CH2CH2CH2CH2-；
R4For H2C=CH-CH2-、Or H2C=CHO-
CH2CH2CH2CH2-。
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| CN105199060A (en) * | 2015-10-14 | 2015-12-30 | 广东红墙新材料股份有限公司 | Super-early-strength PCE (polycarboxylate ether) superplasticizer and preparation method thereof |
| CN105294950A (en) * | 2015-10-14 | 2016-02-03 | 广东红墙新材料股份有限公司 | Tubular pile and preparation method thereof |
| CN105294949A (en) * | 2015-10-14 | 2016-02-03 | 广东红墙新材料股份有限公司 | Super-early-strength polycarboxylate superplasticizer and preparation method thereof |
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| CN105199060A (en) * | 2015-10-14 | 2015-12-30 | 广东红墙新材料股份有限公司 | Super-early-strength PCE (polycarboxylate ether) superplasticizer and preparation method thereof |
| CN105294950A (en) * | 2015-10-14 | 2016-02-03 | 广东红墙新材料股份有限公司 | Tubular pile and preparation method thereof |
| CN105294949A (en) * | 2015-10-14 | 2016-02-03 | 广东红墙新材料股份有限公司 | Super-early-strength polycarboxylate superplasticizer and preparation method thereof |
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