CN106365534A - Application of water-retaining reduced polycarboxylic acid water reducer to preparation of high-performance concrete - Google Patents

Application of water-retaining reduced polycarboxylic acid water reducer to preparation of high-performance concrete Download PDF

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CN106365534A
CN106365534A CN201610742495.4A CN201610742495A CN106365534A CN 106365534 A CN106365534 A CN 106365534A CN 201610742495 A CN201610742495 A CN 201610742495A CN 106365534 A CN106365534 A CN 106365534A
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water
performance concrete
high performance
reducer
integer
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CN106365534B (en
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张小富
赵利华
白淑英
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GUANGDONG REDWALL NEW MATERIALS CO Ltd
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GUANGDONG REDWALL NEW MATERIALS CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • 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
    • C04B24/166—Macromolecular compounds comprising sulfonate or sulfate groups obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers

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  • 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 an application of a water-retaining reduced polycarboxylic acid water reducer to preparation of high-performance concrete, and further provides the high-performance concrete containing the water-retaining reduced polycarboxylic acid water reducer. As polyhydroxy is introduced into molecular middle chains of the water-retaining reduced polycarboxylic acid water reducer, hydrogen bonds are formed between hydroxy and among the hydroxy and water molecules, a mico-crosslinking structure is formed, the viscosity of solution in cement paste capillary pores in the concrete is increased, the evaporation rate of the water molecules is delayed, and water-retaining property is remarkably improved, so that shrinkage of the high-performance concrete is reduced. High-performance concrete shrinkage test results indicate that the water-retaining reduced polycarboxylic acid water reducer has a good shrinkage effect, is high in cost performance has no influence on the workability and the strength of the high-performance concrete when being used for the high-performance concrete.

Description

Purposes in preparing high performance concrete for the water-retaining property shrinkage type polycarboxylate water-reducer
Technical field
The present invention relates to a kind of purposes in preparing high performance concrete for water reducer is and in particular to a kind of water-retaining property is reduced Purposes in preparing high performance concrete for the type polycarboxylate water-reducer.
Background technology
High performance concrete (high performance concrete, abbreviation hpc) is using durability as basic demand Concrete, development high performance concrete is conducive to improving the use function of building, extends the service life of building, and then Preserve the ecological environment, promote the sustainable development of economic society.High performance concrete is a kind of novel high-performance concrete, refers to Using conventional material and production technology, by what Mixed With Admixture and admixture were formulated, there is high workability, high intensity, height The concrete of the high comprehensive performance of durability, has obtained rapid development since its generation.But hpc is in application process, Also some problems are occurred in that, wherein particularly problematic with shrinkage cracking, the shrinkage cracking of hpc can affect its durability and use In the life-span, according to statistics, xoncrete structure cracking has 80% to cause because of deformation, and the deformation of concrete is mainly shown as receipts Contracting, the popularization and application of hpc must solve the problems, such as its early-age crack.
The microstructure of hpc has following features:
1. porosity is low, substantially without capability in the macropore more than 100 μm；
2. in hydras, ca (oh) 2 reduces, and c-s-h and entringite increase,
3. unhydrated gel material particle is more, each centroplasm hypotelorism, and favourable Core effect increases, centroplasm Network skeleton is strengthened；
4. interface transition layer thickness is little, and hydras crystalline particle size reduces, closer to Behavior of Hardened Cement Paste body hydras Distribution；
The microstructure feature of hpc determines that it is different from the deformation behaviour of normal concrete, brings early stage body therewith Long-pending stability is poor, easy problems of crack.
The microstructure feature of hpc determines that it is different from the deformation behaviour of normal concrete, brings early stage body therewith Long-pending stability is poor, easy problems of crack.
The early-age shrinkage of concrete includes plastic shrinkage, chemical shrinkage, dry shrinkage, temperature shrinkage, Carbonization contract, certainly receives Contracting.Compared with normal concrete, hpc has the features such as water-cement ratio is relatively low, cement consumption is larger, sand coarse aggregate ratio is higher, its plastic shrinkage The most prominent with self-constriction.
Dry shrinkage abbreviation drying shrinkage, after referring to that concrete stops maintenance, in undersaturated in the air, loses internal capillary hole Absorption water and the irreversible shrinkage that occurs, with the reduction of relative humidity in environment, the drying shrinkage of cement slurry increases, and is dried and receives Produce uneven contraction distortion in compression process, lead to inside concrete to produce stress, when it exceedes the tensile strength of concrete When, just produce crack.
After concreting molding, with the aquation of Binder Materials, in the case of there is no exchange of moisture with the external world, coagulation Native internal relative humidity relatively reduces so that pore is become unsaturated because moisture is absorbed, and creates inside concrete oneself It is dried, the water mudrock structure around pore bears and produces the inside tightening force of vacuum, the macroscopic view thus causing from vacuum action Volume reduces the self-constriction being concrete.When the ratio of mud is high, self-constriction is not the main aspect of concrete shrinkage, with coagulation The reduction of the native ratio of mud, self-constriction ratio in concrete shrinkage increases, and the ratio of mud of hpc is very low, the Free water of hydrated cementitious Divide few, early strength development is fast, and free water consumption is more.
The raw material of hpc and match ratio, determine its early hydration speed is fast, and self-desiccation degree is high, and self-constriction is big etc. The self-constriction of feature, therefore phc is more much bigger than normal concrete.
The root of self-constriction is the continuation aquation after cement setting hardening.
Polycarboxylate water-reducer has obtained extensive research in recent years and has paid close attention to, and polycarboxylate water-reducer molecule structure has well MOLECULE DESIGN, multiple changes can be assumed such that it is able to show different performances, adapt to different architectural engineerings to coagulation The requirement of native multiple performance, the functionalization of polycarboxylate water-reducer has become a kind of trend, and exploitation shrinkage type water reducer solves high property The problem of energy Shrinkage Cracking of Concrete, becomes the key point of hpc popularization and application.
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 freeze-thaw cycle, 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 extender, and main principle is in coagulation by extender Generate expansile hydrated product to compensate contraction in soil, decrease the probability of concrete cracking.But it is special using extender 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 vitriol 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 extender, 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, dry shrinkage and carbonization to receive Contract six big types, and wherein universal with dry shrinkage, mechanism is more complicated,
Existing theory mainly has capillary tube strain theory, surface adsorption theory, takes stress theory etc. apart, among these with hair Tubule strain theory is the most convincing, and this theory thinks, when ambient humidity is less than 100%, the water surface within capillary tube declines And form meniscus, and according to laplas formula, under the surface tension effects of water, the additonal pressure of generation in capillary tube: △ p =2 σ cos θ/r
In formula, △ p is 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 be capillary radius.
In the case that σ is constant, capillary tube 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 tube 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, the dry shrinkage of concrete, it 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, and 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 law 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 adsorption 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 glycerol, 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.
Hpc makes its problem of Cracking especially prominent because gel material content is big, water-cement ratio is low, always allows technology in the industry And big technological difficulties of research worker puzzlement, also there is no a kind of effective overcoming method both at home and abroad at present, using reducing Agent and polycarboxylic acids economization agent reach and reduce purpose, have research both at home and abroad, but effect is all undesirable.The purpose of the present invention is exactly out It is good with hpc adaptability to send out a kind of, shrinks/ftracture effective water-retaining property shrinkage type polycarboxylate water-reducer to reducing it, Reach minimizing hpc shrinkage cracking problem in use, be that hpc is able to promote rapidly in Practical Project.
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 high performance concrete for the carboxylic acid water reducer, present invention also offers a kind of contain this poly- carboxylic of water-retaining property shrinkage type The high performance concrete of sour water reducer, because this water-retaining property shrinkage type polycarboxylate water-reducer introduces substantial amounts of hydroxyl in side chain Group, these oh groups and hydrone form hydrogen bond, and itself is also due to forming hydrogen bond and forming similar micro- cross-linked structure simultaneously, Increased solution viscosity, improve water-retaining property, mainly play and reduce effect by its water-retaining property, be water conservation water-retaining property shrinkage type Polycarboxylate water-reducer.
For achieving the above object, the technical scheme taken: a kind of high performance concrete, described high performance concrete includes Cement, gather materials, 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 (), and the structural formula of the compound shown in described formula () is as follows:
Wherein a is 020 integer, b is 1080 integer, c is 030 integer；D is 10100 integer；
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 () and contain Have epoxy and hydroxyl bifunctional compound reaction and be obtained, the structural formula of the compound shown in described formula () 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 sodium allylsulfonate, 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, Deca contains the aqueous solution of 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 liquor 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, adopt Subtraction method Deca 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 sodium allylsulfonate 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 sodium allylsulfonate: 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 sodium allylsulfonate, 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 sodium allylsulfonate 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 sodium allylsulfonate: 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 sodium allylsulfonate, 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 regulator is at least one in sulfhydryl compound and isopropanol.
Preferably, the consumption of described step (3) middle-molecular-weihydroxyethyl regulator 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 () 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 (+)-2,3-Epoxy-1-propanol 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；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 of gained .... etc..
The structural formula of the compound shown in described formula () is as follows:
Corresponding reaction equation is as follows:
The structural formula of the compound shown in described formula () is as follows:
Corresponding reaction equation is as follows:
The structural formula of the compound shown in described formula () is as follows:
Corresponding reaction equation is as follows:
Preferably, described high performance concrete includes the component of following weight portion: 400 parts of cement, gather materials 1715 parts, additional Agent 12.5 (folding is solid) part and 140 parts of water.
Preferably, described high performance concrete also includes the flyash of 80 weight portions and the breeze of 100 weight portions.
Preferably, the described mixture gathering materials for sand and stone.Preferably, the weight of described sand and stone is than for 665: 1050.
The invention provides a kind of purposes in preparing high performance concrete for water-retaining property shrinkage type polycarboxylate water-reducer, institute Stating water-retaining property shrinkage type polycarboxylate water-reducer is the compound shown in formula (), and the structural formula of the compound shown in described formula () is such as Under:
Wherein a is 020 integer, b is 1080 integer, c is 030 integer；D is 10100 integer；
Described a is
Described b is
Described c isL is 0～30 integer；
r1For ch3Or h；
r2For h2C=ch-ch2-、Or h2C= ch-o-ch2ch2ch2ch2-；
Described d is polyhydroxy peg polymeric monomer, and described polyhydroxy peg polymeric monomer is compound shown in formula () and contain Have epoxy and hydroxyl bifunctional compound reaction and be obtained, the structural formula of the compound shown in described formula () 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 the property that 1, 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, hydrophilic 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.High performance concrete reduces result of the test and shows, it has preferable Reduce shrinkage effect, the common ethers with our company Polycarboxylate water-reducer is compared, and the shrinkage ratio of high performance concrete reduces notable, and the workability to high performance concrete and strong Degree does 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 contraction and the cracking of concrete by significantly improving water-retaining property.
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 Aqueouss, thus significantly reduce contraction and the cracking of 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 (+)-2,3-Epoxy-1-propanol 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 high in preparation Purposes in performance concrete, present invention also offers a kind of high-performance containing this water-retaining property shrinkage type polycarboxylate water-reducer is mixed Solidifying soil, the water-retaining property shrinkage type polycarboxylate water-reducer that the present invention provides is remarkably improved viscosity and the water-retaining property of cement slurry, high Performance concrete reduces result of the test and shows, it has preferable Reduce shrinkage effect, during for high performance concrete, high-performance is mixed The intensity of solidifying soil 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 Rapid:
(1) in the autoclave of closing, with the air in high pure nitrogen repeatedly replacement reaction kettle 2 times, inject 1mol propylene The catalyst naoh 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 amount of ethylene oxide needed for Deca 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 (+)-2,3-Epoxy-1-propanol of 1mol, Deca 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, and Deca contains the aqueous solution of 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 Rapid:
(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 0.5gmol, reactor is warming up to 110 DEG C, starts to be slowly added dropwise 40mol oxirane, makes reaction In the range of 115 DEG C, in kettle, Stress control, in 0.4mpa, controls the amount of ethylene oxide needed for Deca with Subtraction method to temperature control, 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 (+)-2,3-Epoxy-1-propanol of 2mol, Deca 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, and Deca contains the aqueous solution of 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 Rapid:
(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 amount of ethylene oxide needed for Deca 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 (+)-2,3-Epoxy-1-propanol of 3mol, Deca 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 sodium allylsulfonate, are warming up to 95 DEG C, and Deca contains the aqueous solution of 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 Rapid:
(1) in the autoclave of closing, with the air in high pure nitrogen repeatedly replacement reaction kettle 2 times, inject 1mol 4- 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 oxirane needed for Deca 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 (+)-2,3-Epoxy-1-propanol of 3mol, Deca 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 sodium allylsulfonate, are warming up to 95 DEG C, and Deca contains 0.04mo ammonium persulfate initiator 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, it is 6.5 that the naoh solution being 30% with mass fraction adjusts ph, obtains final product water-retaining property shrinkage type polycarboxylate water-reducer.
Embodiment 5: application in high performance 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 high performance concrete by the formula of table 1, its China and foreign countries Plus the consumption of agent is 12.5 weight portions, then test the performance of high performance concrete, result such as table 2.
Table 1 high performance concrete composition of raw materials
C (cement) Fa (flyash) K (breeze)) sFluvial sand(sand) g1-2(stone) W (water)
400 weight portions 80 weight portions 100 weight portions 665 weight portions 1050 weight portions 140 weight portions
The performance test results of table 2 high performance 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 Water preparation 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 hydrophilic 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 hpc, compared with common polyether polycarboxylate water-reducer pce, this Invention water conservation water-retaining property shrinkage type polycarboxylate water-reducer pce-s has more superior water conservation and Reduce shrinkage effect, when compounding use, With the increase of pce-s ratio, the contraction of concrete is remarkably decreased, and 28d shrinkage ratio reduces 76%.This is because in pce- In s, due to introducing polyhydroxy base side chain, increased the viscosity of capillary hole solution and cement slurry, moisture evaporation slows, fall The low contraction of 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 high performance concrete it is characterised in that described high performance concrete include cement, gather materials, additive and water, institute State additive and include water-retaining property shrinkage type polycarboxylate water-reducer, described water-retaining property shrinkage type polycarboxylate water-reducer is shown in formula () Compound, the structural formula of the compound shown in described formula () is as follows:
Wherein a isInteger, b isInteger, c isInteger；D is Integer；
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 () and contain ring Oxygen and hydroxyl bifunctional compound reaction and be obtained, the structural formula of the compound shown in described formula () is as follows:
Wherein m is 0～30 integer；
R is h2C=ch-ch2-、And h2C=ch-o- ch2ch2ch2ch2One of-.
2. high performance concrete according to claim 1 it is characterised in that described containing epoxy with hydroxyl difunctionality dough Compound isIn at least one.
3. high performance concrete according to claim 1 is it is characterised in that described water-retaining property shrinkage type polycarboxylate water-reducer It 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 sodium allylsulfonate, 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, Deca contains the aqueous solution of initiator, and time for adding is 2h, after completion of dropping, insulation reaction 3h, and fall To 45 DEG C, adjust ph with alkali liquor is 6.5 to temperature, obtains final product water-retaining property shrinkage type polycarboxylate water-reducer.
4. high performance concrete according to claim 3 is it is characterised in that enol and oxirane in described step (1) Mol ratio be 1:0～1:80.
5. high performance concrete according to claim 3 it is characterised in that in described step (1) enol be propenyl, different At least one in pentenol, isobutene alcohol and 4- ethyleneoxy butanol.
6. high performance concrete according to claim 3 it is characterised in that in described step (2) intermediate product with contain The mol ratio of epoxy and hydroxyl bifunctional compound is less than or equal to 1.
7. high performance concrete according to claim 3 is it is characterised in that maleic anhydride, itaconic acid in described step (3) One of with sodium allylsulfonate, one of apeg, hpeg, vpeg and tpeg, in acrylic acid and methacrylic acid Kind, the mol ratio of polyhydroxy peg polymeric monomer is one of maleic anhydride, itaconic acid and sodium allylsulfonate: apeg, hpeg, One of 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. high performance concrete according to claim 1 is it is characterised in that described high performance concrete includes following weight Part component: 400 parts of cement, gather materials 1715 parts, 12.5 parts of additive and 140 parts of water.
9. high performance concrete according to claim 8 is it is characterised in that described high performance concrete also includes 80 parts Flyash and the breeze of 100 weight portions.
10. purposes in preparing high performance concrete for the water-retaining property shrinkage type polycarboxylate water-reducer is it is characterised in that described water conservation Property shrinkage type polycarboxylate water-reducer be the compound shown in formula (), the structural formula of the compound shown in described formula () is as follows:
Wherein a isInteger, b isInteger, c isInteger；D is Integer；
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 () and contain ring Oxygen and hydroxyl bifunctional compound reaction and be obtained, the structural formula of the compound shown in described formula () is as follows:
Wherein m is 0～30 integer；
R is h2C=ch-ch2-、And h2C=ch-o- ch2ch2ch2ch2One of-.
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CN103408706A (en) * 2013-08-19 2013-11-27 科之杰新材料集团有限公司 High-performance polycarboxylic acid water reducing agent and preparation method thereof
CN104140503A (en) * 2014-07-30 2014-11-12 江西格雷斯科技股份有限公司 Method for synthesizing high-water-reduction high-slump-retaining high-performance polycarboxylate water reducer at normal temperature
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