CN106365534B - Purposes of the water-retaining property shrinkage type polycarboxylate water-reducer in high performance concrete is prepared - Google Patents

Purposes of the water-retaining property shrinkage type polycarboxylate water-reducer in high performance concrete is prepared Download PDF

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CN106365534B
CN106365534B CN201610742495.4A CN201610742495A CN106365534B CN 106365534 B CN106365534 B CN 106365534B CN 201610742495 A CN201610742495 A CN 201610742495A CN 106365534 B CN106365534 B CN 106365534B
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water
high performance
performance concrete
reducer
integer
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CN106365534A (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 a kind of purposes of water-retaining property shrinkage type polycarboxylate water-reducer in high performance concrete is prepared, present invention also offers a kind of high performance concrete containing the water-retaining property shrinkage type polycarboxylate water-reducer, water-retaining property shrinkage type polycarboxylate water-reducer provided by the invention in side chain in the molecule due to introducing polyhydroxy, between hydroxyl and form hydrogen bond between hydroxyl and hydrone and form micro- cross-linked structure, add the viscosity of solution in cement slurry pore in concrete, the evaporation rate of hydrone is delayed, considerably improve water-retaining property, so as to reduce the contraction of high performance concrete.High performance concrete decrement result of the test shows that it has preferable Reduce shrinkage effect, and during for high performance concrete, workability and intensity on high performance concrete do not influence, and cost performance is higher.

Description

Purposes of the water-retaining property shrinkage type polycarboxylate water-reducer in high performance concrete is prepared
Technical field
The present invention relates to a kind of purposes of water reducer in high performance concrete is prepared, and in particular to a kind of water-retaining property decrement Purposes of the type polycarboxylate water-reducer in high performance concrete is prepared.
Background technology
High performance concrete (High performance concrete, abbreviation HPC) is to be used as basic demand using durability Concrete, development high performance concrete is advantageous to improve 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, is referred to Using conventional material and production technology, there is high workability, high intensity, height by what Mixed With Admixture and admixture were formulated The concrete of the high comprehensive performance of durability, rapid development is obtained since its generation.But HPC is in application process, Also there are some problems, wherein particularly problematic with shrinkage cracking, HPC shrinkage cracking can influence its durability and use In the life-span, according to statistics, it is because of caused by deformation that concrete structure cracking, which has 80%, and the deformation of concrete is mainly shown as receipts Contracting, HPC popularization and application must solve the problems, such as its early-age crack.
HPC microstructure has following features：
1. porosity is low, the substantially without capability macropore more than 100 μm；
2. Ca (OH) 2 is reduced in hyrate, C-S-H and entringite increase,
3. unhydrated gel material particle is more, each centroplasm hypotelorism, favourable Core effect increases, centroplasm Network skeleton is strengthened；
4. interface transition layer thickness is small, hyrate crystalline particle size reduces, closer to Behavior of Hardened Cement Paste body hyrate Distribution；
HPC microstructure feature determines that it is different from the deformation behaviour of normal concrete, brings early stage body therewith Product stability is poor, easy problems of crack.
HPC microstructure feature determines that it is different from the deformation behaviour of normal concrete, brings early stage body therewith Product stability is poor, easy problems of crack.
The early-age shrinkage of concrete includes plastic shrinkage, chemical shrinkage, dries contraction, temperature shrinkage, certainly Carbonization contract, receipts Contracting.Compared with normal concrete, HPC has the characteristics that water-cement ratio is relatively low, cement consumption is larger, sand coarse aggregate ratio is higher, its plastic shrinkage It is the most prominent with self-constriction.
Dry and shrink abbreviation drying shrinkage, after referring to that concrete stops maintenance, in undersaturated air, lose internal capillary hole Absorption water and the irreversible contraction that occurs, with the reduction of relative humidity in environment, the drying shrinkage of cement slurry increases, and dries and receives Uneven contraction distortion is produced in compression process, causes inside concrete to produce stress, when it exceedes the tensile strength of concrete When, just produce crack.
After concreting shaping, with the aquation of binder materials, in the case where there is no exchange of moisture with the external world, coagulation Native internal relative humidity relatively reduces so that pore becomes unsaturated because moisture is absorbed, and generates inside concrete oneself Dry, the water mudrock structure around pore bears to produce the inside tightening force of vacuum from vacuum action, thus caused macroscopic view Volume reduces the self-constriction of as 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 increase, and the HPC ratio of mud is very low, the Free water of hydrated cementitious Divide less, early strength development is fast, and free water consumption is more.
HPC raw material and match ratio, determine that its early hydration speed is fast, self-desiccation degree is high, and self-constriction is big etc. Feature, therefore PHC self-constriction 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 and concern in recent years, and polycarboxylate water-reducer molecule structure has good MOLECULE DESIGN, a variety of changes can be presented, so as to show different performances, adapt to different architectural engineerings to coagulation The requirement of native multiple performance, the functionalization of polycarboxylate water-reducer turn into a kind of trend, and exploitation shrinkage type water reducer solves high property The problem of energy Shrinkage Cracking of Concrete, turn into 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, 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,
Existing theory mainly has capillary strain theory, adsorption theory, takes stress theory etc. apart, among these with hair Tubule strain theory is most convincing, and the theory thinks, when ambient humidity is less than 100%, the water surface inside capillary declines And meniscus is formed, according to Laplas formula, under the surface tension effects of water, 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.
HPC makes its problem of Cracking especially prominent because gel material content is big, water-cement ratio is low, is always the technology in the industry that allows And a big technological difficulties of researcher's puzzlement, use decrement also without a kind of effective overcoming method both at home and abroad at present Agent and polycarboxylic acids economization agent reach decrement 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 and reduce the shrinkage cracking problems of HPC in use, be that HPC is able to promote rapidly in Practical Project.
The content of the invention
Provide a kind of water-retaining property shrinkage type it is an object of the invention to overcome the shortcomings of the prior art part and gather Purposes of the carboxylic acid water reducer in high performance concrete is prepared, present invention also offers one kind to contain the poly- carboxylic of water-retaining property shrinkage type The high performance concrete of sour water reducer, because the 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, while itself is also due to form hydrogen bond and form similar micro- cross-linked structure, Solution viscosity is added, improves water-retaining property, is mainly acted on by its water-retaining property to play decrement, is water conservation water-retaining property shrinkage type Polycarboxylate water-reducer.
To achieve the above object, the technical scheme taken：A kind of high performance concrete, the high performance concrete include Cement, gather materials, additive and water, the additive include water-retaining property shrinkage type polycarboxylate water-reducer, the water-retaining property shrinkage type Polycarboxylate water-reducer is the compound shown in formula (I), and the structural formula of the compound shown in the formula (I) is as follows：
Wherein a is 020 integer, b 1080 integer, c 030 integer；D is 10100 integer；
The A is
The B is
The C isL is 0~30 integer；
R1For CH3Or H；
R2For H2C=CH-CH2-、Or H2C= CHO-CH2CH2CH2CH2-；
The D is polyhydroxy PEG polymeric monomers, and the polyhydroxy PEG polymeric monomers are with containing as the compound shown in formula (II) There is prepared by epoxy and hydroxyl bifunctional compound react, the structural formula of the compound shown in the formula (II) is as follows：
Wherein m is 0~30 integer；
R is H2C=CH-CH2-、And H2C= CH-O-CH2CH2CH2CH2- in one kind.
Preferably, it is described to be containing epoxy and hydroxyl bifunctional compoundWithIn It is at least one.
Preferably, the water-retaining property shrinkage type polycarboxylate water-reducer is prepared by following methods：
(1) enol and catalyst are mixed in a nitrogen atmosphere, is warming up to 70~115 DEG C, epoxy second is then slowly added dropwise Alkane, by reaction temperature control in the range of 70~130 DEG C, reaction pressure control is in 0.2~0.6MPa, when oxirane drips Bi Hou, reaction temperature is controlled at 80~120 DEG C, continues 0.5~5h of reaction, obtains intermediate product；
(2) temperature for the intermediate product for obtaining step (1) is reduced to 80 DEG C, is then slowly added dropwise containing epoxy and hydroxyl Bifunctional compound, time for adding control in 1.5~2h, after being added dropwise, continue 4~6h of reaction, it is big to obtain polyhydroxy PEG Monomer；
(3) by one kind in maleic anhydride, itaconic acid and ALS, one in APEG, HPEG, VPEG and TPEG Kind, one kind in acrylic acid and methacrylic acid, molecular weight regulator, the big lists of polyhydroxy PEG made from water and the step (2) Body mixes, and is warming up to 95 DEG C, is added dropwise the aqueous solution containing initiator, time for adding 2h, after being added dropwise, insulation reaction 3h, 45 DEG C are cooled to, is 6.5 with alkali lye regulation pH, produces water-retaining property shrinkage type polycarboxylate water-reducer.
Preferably, the mol ratio of enol and oxirane is 1 in the step (1):0~1:80.It is highly preferred that the step Suddenly the mol ratio of enol and oxirane is 1 in (1):1~1:80.
Preferably, enol is in propenyl, prenol, isobutene alcohol and 4- ethyleneoxy butanol in the step (1) At least one.
Preferably, the dosage of catalyst is the enol and the 0.1- of the weight sum of oxirane in the step (1) 0.5%.
Preferably, oxirane is added dropwise using Subtraction method in the step (1).
Preferably, intermediate product and the mol ratio containing epoxy and hydroxyl bifunctional compound are small in the step (2) In equal to 1.
Preferably, one kind in the step (3) in maleic anhydride, itaconic acid and ALS, APEG, HPEG, One kind in VPEG and TPEG, one kind in acrylic acid and methacrylic acid, the mol ratio of polyhydroxy PEG polymeric monomers is maleic acid One kind in acid anhydride, itaconic acid and ALS：One kind in APEG, HPEG, VPEG and TPEG：Acrylic acid and metering system One kind in acid：Polyhydroxy PEG polymeric monomer=0~0.5：0.05~1.0：0~15：0.3-3.It is highly preferred that the step (3) One kind in middle maleic anhydride, itaconic acid and ALS, one kind in APEG, HPEG, VPEG and TPEG, acrylic acid and One kind in methacrylic acid, the mol ratio of polyhydroxy PEG polymeric monomers is in maleic anhydride, itaconic acid and ALS It is a kind of：One kind in APEG, HPEG, VPEG and TPEG：One kind in acrylic acid and methacrylic acid：Polyhydroxy PEG polymeric monomers =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 the step (3) One kind in base sodium sulfonate, one kind in APEG, HPEG, VPEG and TPEG, one kind in acrylic acid and methacrylic acid, polyhydroxy The mol ratio of base PEG polymeric monomers is one kind in maleic anhydride, itaconic acid and ALS：APEG, HPEG, VPEG and One kind in TPEG：One kind in acrylic acid and methacrylic acid：Polyhydroxy PEG polymeric monomer=0.1~0.5：0.5~1.0：5 ~15：0.3-0.6.
Preferably, initiator is in potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide and benzoyl peroxide in the step (3) One kind, the dosage of the initiator is one kind in the maleic anhydride, itaconic acid and ALS, APEG, HPEG, One kind in VPEG and TPEG, one kind in acrylic acid and methacrylic acid, with the total mole number of polyhydroxy PEG polymeric monomers 0.5%~5%.
Preferably, step (3) the middle-molecular-weihydroxyethyl conditioning agent is at least one of sulfhydryl compound and isopropanol.
Preferably, the dosage of step (3) the middle-molecular-weihydroxyethyl conditioning agent is the maleic anhydride, itaconic acid and pi-allyl sulphur One kind in sour sodium, one kind in APEG, HPEG, VPEG and TPEG, one kind in acrylic acid and methacrylic acid, with polyhydroxy The 1%~5% of the total mole number of PEG polymeric monomers.
In above-mentioned steps (1) shown in the structural formula such as formula (II) for the intermediate product that reaction obtains,
Wherein m is 0~30 integer；
R is H2C=CH-CH2-、And H2C= CH-O-CH2CH2CH2CH2- in one kind.
Reaction equation in above-mentioned steps (1) is as follows：
The mol ratio of intermediate product and glycidol is in above-mentioned steps (2)：1：(x-1), x is the end-blocking of surface-active macromonomer Hydroxyl value, work as x=2, react the product structure formula of gained as shown in formula III；Work as x=4, react the product structure formula such as formula of gained Ⅳ；Work as x=8, react the product structure formula such as formula V of gained ... etc..
The structural formula of compound shown in the formula (III) is as follows：
Corresponding reaction equation is as follows：
The structural formula of compound shown in the formula (IV) is as follows：
Corresponding reaction equation is as follows：
The structural formula of compound shown in the formula (V) is as follows：
Corresponding reaction equation is as follows：
Preferably, the high performance concrete includes the component of following parts by weight：400 parts of cement, gather materials 1715 parts, it is additional 140 parts of (folding the is solid) part of agent 12.5 and water.
Preferably, the miberal powder of flyash and 100 parts by weight of the high performance concrete also including 80 parts by weight.
Preferably, the mixture to gather materials for sand and stone.Preferably, the weight ratio of the sand and stone is 665： 1050。
The invention provides a kind of purposes of water-retaining property shrinkage type polycarboxylate water-reducer in high performance concrete is prepared, institute Water-retaining property shrinkage type polycarboxylate water-reducer is stated as the compound shown in formula (I), the structural formula of the compound shown in the formula (I) is such as Under：
Wherein a is 020 integer, b 1080 integer, c 030 integer；D is 10100 integer；
The A is
The B is
The C isL is 0~30 integer；
R1For CH3Or H；
R2For H2C=CH-CH2-、Or H2C= CH-O-CH2CH2CH2CH2-；
The D is polyhydroxy PEG polymeric monomers, and the polyhydroxy PEG polymeric monomers are with containing as the compound shown in formula (II) There is prepared by epoxy and hydroxyl bifunctional compound react, the structural formula of the compound shown in the formula (II) is as follows：
Wherein m is 0~30 integer；
R is H2C=CH-CH2-、And H2C= CH-O-CH2CH2CH2CH2- in one kind.
Economization agent is a kind of nonionic surfactant, can reduce the surface tension of water, and the concrete for mixing economization agent is received Compression deformation is reduced, 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, there should be following property：1st, liquid-vapor interface tension force is greatly reduced；2nd, solution is increased Viscosity, delay the volatilization 3 of hydrone, anomalous effects do not produced to hydrated cementitious process；4th, high temperature low volatility；5th, low entraining Property.Polycarboxylate water-reducer can reduce the surface tension of liquid, therefore have 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 synthesized by polyhydroxy PEG polymeric monomers of the present invention, by Largely reduce group hydroxy in introducing in the molecule, form hydrogen bond between hydroxyl or between hydroxyl and hydrone, it is micro- to form hydrogen bond Cross-linked structure, compared with common polycarboxylate water-reducer, HLB value, hydrophily increase are changed, lipophile slightly declines, incrementss Solution viscosity, delay the evaporation rate of hydrone, significantly improve the water-retaining property of solution, concrete receipts are significantly reduced so as to reach The purpose of contracting.High performance concrete decrement result of the test shows that 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 workability to high performance concrete and strong Degree does not influence, and cost performance is higher.
The water conservation water-retaining property shrinkage type polycarboxylate water-reducer that the present invention synthesizes, 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, improved hydrophilic Property, water-retaining property is significantly improved, main function mechanism is to reduce the contraction of concrete and cracking by significantly improving water-retaining property.
The water-retaining property shrinkage type polycarboxylate water-reducer that the present invention synthesizes with being with traditional surface-active macromonomer APEG, TPEG etc. The polycarboxylate water-reducer of primary raw material synthesis is compared, and is had the following advantages that：
1st, because polyhydroxy and water form hydrogen bond, the viscosity of cement slurry is added, improves the guarantor of concrete mix It is water-based, so as to significantly reduce the contraction of concrete and cracking；
2nd, similar micro- cross-linked structure is formed due between hydroxyl hydrogen bond can be mutually formed, it is higher so as to have to clay Tolerance, the chain intercalation of clay is avoided, improve resistance to mud performance.
The surface-active macromonomer with polyhydroxy decrement group has been synthesized in preparation method step (2) of the present invention, can basis The needs of actual product performance, control reactant glycidol additional proportion and make surface-active macromonomer have 2,4,8., 16.....n individual hydroxyl.
The beneficial effects of the present invention are：The invention provides a kind of water-retaining property shrinkage type polycarboxylate water-reducer to prepare height Purposes in performance concrete, present invention also offers a kind of high-performance containing the water-retaining property shrinkage type polycarboxylate water-reducer to mix Solidifying soil, water-retaining property shrinkage type polycarboxylate water-reducer provided by the invention are remarkably improved the viscosity and water-retaining property of cement slurry, high Performance concrete decrement result of the test shows that it has preferable Reduce shrinkage effect, and during for high performance concrete, high-performance is mixed Coagulating the intensity of soil does 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 the preparation method of water-retaining property shrinkage type polycarboxylate water-reducer of the present invention, including following step Suddenly：
(1) in the autoclave of closing, with the air 2 times in high pure nitrogen repeatedly replacement reaction kettle, 1mol propylene is injected The catalyst n aOH of alcohol and 0.2g, 100-115 DEG C is warming up to by reactor, is started that 1mol oxirane is slowly added dropwise, is made reaction Temperature control in the range of 70 DEG C, in kettle Stress control in 0.2MPa, be added dropwise with Subtraction method control needed for amount of ethylene oxide, when After oxirane is added dropwise, by temperature control at 80 DEG C, continues to react 5h, obtain the intermediate products of required molecular weight.
(2) 80 DEG C are kept the temperature at, starts that 1mol glycidol is slowly added dropwise, is added dropwise and controls in 1.5h, drip Bi Hou, continue to react 4h, cooling, blowing, produce the polyhydroxy PEG polymeric monomers.
(3) in the glass four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, addition deionized water, Polyhydroxy PEG polymeric monomers made from 0.063mol isopropanols molecular weight regulator, 0.3mol steps (2), 0.5mol APEG, 5mol acrylic acid, 0.5mol maleic anhydrides, are warming up to 85 DEG C, and the aqueous solution containing potassium peroxydisulfate initiator, the initiation is added dropwise The mole of agent is 0.0315mol, time for adding 2h, after being added dropwise, insulation reaction 4h, is cooled to 45 DEG C, with quality point Number is 7.0 for 30% NaOH solution regulation pH, produces 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, including following step Suddenly：
(1) in the autoclave of closing, with the air 3 times in high pure nitrogen repeatedly replacement reaction kettle, 1mol isoamyls are injected The catalyst KOH of enol and 0.5gmol, reactor is warming up to 110 DEG C, starts that 40mol oxirane is slowly added dropwise, make reaction Temperature control in the range of 115 DEG C, in kettle Stress control in 0.4MPa, be added dropwise with Subtraction method control needed for amount of ethylene oxide, After oxirane is added dropwise, by temperature control at 110 DEG C, continues to react 2h, obtain the intermediate products of required molecular weight.
(2) temperature is reduced to 80 DEG C, starts that 2mol glycidol is slowly added dropwise, be added dropwise and control in 2h, be added dropwise Afterwards, continue to react 5h, cooling, blowing, produce the polyhydroxy PEG polymeric monomers.
(3) in the glass four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, addition deionized water, Polyhydroxy PEG polymeric monomers, 1mol HPEG, 5mol made from 0.355mol isopropanols molecular weight regulator, 0.6mol steps (2) Methacrylic acid, 0.5mol itaconic acids, are warming up to 90 DEG C, and the aqueous solution containing 0.12mol ammonium persulfate initiators is added dropwise, described The mole of initiator is 0.355mol, time for adding 3h, after being added dropwise, insulation reaction 2h, is cooled to 50 DEG C, uses quality The NaOH solution regulation pH that fraction is 30% is 6.0, produces 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, including following step Suddenly：
(1) in the autoclave of closing, with the air 2 times in high pure nitrogen repeatedly replacement reaction kettle, 1mol isobutyls are injected The catalyst potassium carbonate of enol and 2g, reactor is warming up to 115 DEG C, starts that 80mol oxirane is slowly added dropwise, make reaction temperature Degree control in the range of 130 DEG C, in kettle Stress control in 0.6MPa, be added dropwise with Subtraction method control needed for amount of ethylene oxide, when After oxirane is added dropwise, by temperature control at 120 DEG C, continues to react 0.5h, obtain the intermediate products of required molecular weight.
(2) temperature is reduced to 80 DEG C, starts that 3mol glycidol is slowly added dropwise, be added dropwise and control in 2h, be added dropwise Afterwards, continue to react 6h, cooling, blowing, produce the polyhydroxy PEG polymeric monomers.
(3) in the glass four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, addition deionized water, Polyhydroxy PEG polymeric monomers, 1mol VPEG, 10mol made from 0.342mol isopropanols molecular weight regulator, 0.3mol steps (2) Acrylic acid, 0.1mol ALSs, are warming up to 95 DEG C, and the aqueous solution containing 0.05mol potassium peroxydisulfate initiators, institute is added dropwise The mole for stating initiator is 0.342mol, time for adding 2h, after being added dropwise, insulation reaction 3h, is cooled to 45 DEG C, uses matter It is 6.5 to measure the NaOH solution regulation pH that fraction is 30%, produces 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, including following step Suddenly：
(1) in the autoclave of closing, with the air 2 times in high pure nitrogen repeatedly replacement reaction kettle, 1mol 4- second is injected Alkenyloxy group butanol and 2g catalyst potassium carbonate, 115 DEG C are warming up to by reactor, start that 80mol oxirane is slowly added dropwise, and are made anti- Temperature control is answered in the range of 130 DEG C, in kettle Stress control in 0.6MPa, be added dropwise with Subtraction method control needed for oxirane Amount, after oxirane is added dropwise, by temperature control at 120 DEG C, continue to react 0.5h, obtain the middle production of required molecular weight Product.
(2) temperature is reduced to 80 DEG C, starts that 3mol glycidol is slowly added dropwise, be added dropwise and control in 2h, be added dropwise Afterwards, continue to react 6h, cooling, blowing, produce the polyhydroxy PEG polymeric monomers.
(3) in the glass four-hole boiling flask equipped with agitator, thermometer and reflux condensing tube, addition deionized water, Polyhydroxy PEG polymeric monomers, 0.5mol made from 0.328mol sulfhydryl compounds molecular weight regulator, 0.6mol steps (2) TPEG, 15mol acrylic acid, 0.3mol ALSs, are warming up to 95 DEG C, are added dropwise containing 0.04mo ammonium persulfate initiators The aqueous solution, the mole of the initiator is 0.4mol, time for adding 2h, after being added dropwise, insulation reaction 3h, is cooled to 45 DEG C, the NaOH solution for being 30% with mass fraction regulation pH is 6.5, produces water-retaining property shrinkage type polycarboxylate water-reducer.
Embodiment 5：Application of the water-retaining property shrinkage type polycarboxylate water-reducer of the present invention in high performance concrete
Water-retaining property shrinkage type polycarboxylate water-reducer PCE-S prepared by 1-4 of the embodiment of the present invention and common polyether polycarboxylic acids Water reducer PCE is used as additive after pressing the weight proportion mixing in table 2, prepares high performance concrete by the formula of table 1, its China and foreign countries The dosage for adding agent is 12.5 parts by weight, then tests the performance of high performance concrete, as a result such as table 2.
The high performance concrete composition of raw materials of table 1
C (cement) FA (flyash) K (miberal powder)) SRiver sand(sand) G1-2(stone) W (water)
400 parts by weight 80 parts by weight 100 parts by weight 665 parts by weight 1050 parts by weight 140 parts by weight
The performance test results of the high performance concrete of table 2
The water conservation water-retaining property shrinkage type polycarboxylate water-reducer that the present invention synthesizes, can subtract with common polyether or polyester polycarboxylic acids Aqua compounding use or exclusive use, compared with common polyether or polyester polycarboxylate water-reducer, there is more superior Reduce shrinkage effect, It reduces mechanism mainly due to introducing polyhydroxy base side chain in the molecular structure, hydrophily increase, hydroxyl and water or hydroxyl it Between form hydrogen bond, increase the viscosity of concrete pore water, improve the water-retaining property of concrete mortar.
Result of the test shows in table 2：HPC's in use, compared with common polyether polycarboxylate water-reducer PCE is being prepared, 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 ratios, the contraction of concrete is remarkably decreased, and 28d shrinkage ratios reduce 76%.Because in PCE- In S, due to introducing polyhydroxy base side chain, the viscosity of capillary hole solution and cement slurry is added, water evaporation rate is slack-off, drop The low contraction of 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 high performance concrete, it is characterised in that the high performance concrete includes cement, gathered materials, additive and water, institute Stating additive includes water-retaining property shrinkage type polycarboxylate water-reducer, and the water-retaining property shrinkage type polycarboxylate water-reducer is shown in formula (I) Compound, the structural formula of the compound shown in the formula (I) is as follows：
Wherein a isInteger, b isInteger, c isInteger；D is Integer；
The A is
The B is
The C isL is 0~30 integer；
R1For CH3Or H；
R2For H2C=CH-CH2-、Or H2C=CHO- CH2CH2CH2CH2-；
The D is polyhydroxy PEG polymeric monomers, and the polyhydroxy PEG polymeric monomers are as the compound shown in formula (II) and contain ring Prepared by oxygen and hydroxyl bifunctional compound react, the structural formula of the compound shown in the formula (II) is as follows：
Wherein m is 0~30 integer；
R is H2C=CH-CH2-、And H2C=CH-O- CH2CH2CH2CH2- in one kind.
2. high performance concrete according to claim 1, it is characterised in that described to contain epoxy and hydroxyl difunctionality dough Compound isAt least one of.
3. high performance concrete according to claim 1, it is characterised in that the water-retaining property shrinkage type polycarboxylate water-reducer It is prepared by following methods：
(1) enol and catalyst are mixed in a nitrogen atmosphere, is warming up to 70~115 DEG C, oxirane is then slowly added dropwise, will Reaction temperature is controlled in the range of 70~130 DEG C, and reaction pressure control is in 0.2~0.6MPa, after oxirane is added dropwise, Reaction temperature is controlled at 80~120 DEG C, continues 0.5~5h of reaction, obtains intermediate product；
(2) temperature for the intermediate product for obtaining step (1) is reduced to 80 DEG C, is then slowly added dropwise containing epoxy and the double officials of hydroxyl Energy dough compound, time for adding control in 1.5~2h, after being added dropwise, continue 4~6h of reaction, obtain the big lists of polyhydroxy PEG Body；
(3) by one kind in maleic anhydride, itaconic acid and ALS, one kind in APEG, HPEG, VPEG and TPEG, Polyhydroxy PEG polymeric monomers made from one kind in acrylic acid and methacrylic acid, molecular weight regulator, water and the step (2) Mixing, is warming up to 95 DEG C, and the aqueous solution containing initiator is added dropwise, time for adding 2h, after being added dropwise, insulation reaction 3h, drops Temperature is 6.5 with alkali lye regulation pH, produces water-retaining property shrinkage type polycarboxylate water-reducer to 45 DEG C.
4. high performance concrete according to claim 3, it is characterised in that enol and oxirane in the step (1) Mol ratio be 1:0~1:80.
5. high performance concrete according to claim 3, it is characterised in that enol is propenyl, different in the step (1) At least one of pentenol, isobutene alcohol and 4- ethyleneoxy butanol.
6. high performance concrete according to claim 3, it is characterised in that intermediate product is with containing in the step (2) The mol ratio of epoxy and hydroxyl bifunctional compound is less than or equal to 1.
7. high performance concrete according to claim 3, it is characterised in that maleic anhydride, itaconic acid in the step (3) With one kind in ALS, one kind in APEG, HPEG, VPEG and TPEG, one in acrylic acid and methacrylic acid Kind, the mol ratio of polyhydroxy PEG polymeric monomers is one kind in maleic anhydride, itaconic acid and ALS：APEG、HPEG、 One kind in VPEG and TPEG：One kind in acrylic acid and methacrylic acid：Polyhydroxy PEG polymeric monomer=0~0.5：0.05~ 1.0：2~15：0.3-3.
8. high performance concrete according to claim 1, it is characterised in that the high performance concrete includes following weight The component of part：400 parts of cement, gather materials 1715 parts, 140 parts of 12.5 parts of additive and water.
9. high performance concrete according to claim 8, it is characterised in that the high performance concrete is also including 80 parts The miberal powder of flyash and 100 parts by weight.
10. purposes of the water-retaining property shrinkage type polycarboxylate water-reducer in high performance concrete is prepared, it is characterised in that the water conservation Property shrinkage type polycarboxylate water-reducer be compound shown in formula (I), the structural formula of the compound shown in the formula (I) is as follows：
Wherein a isInteger, b isInteger, c isInteger；D is Integer；
The A is
The B is
The C isL is 0~30 integer；
R1For CH3Or H；
R2For H2C=CH-CH2-、Or H2C=CHO- CH2CH2CH2CH2-；
The D is polyhydroxy PEG polymeric monomers, and the polyhydroxy PEG polymeric monomers are as the compound shown in formula (II) and contain ring Prepared by oxygen and hydroxyl bifunctional compound react, the structural formula of the compound shown in the formula (II) is as follows：
Wherein m is 0~30 integer；
R is H2C=CH-CH2-、And H2C=CH-O- CH2CH2CH2CH2- in one kind.
CN201610742495.4A 2016-08-27 2016-08-27 Purposes of the water-retaining property shrinkage type polycarboxylate water-reducer in high performance concrete is prepared Active CN106365534B (en)

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