CN105693946A - Anti-crack high slump loss resistance concrete polycarboxylate superplasticizer - Google Patents

Anti-crack high slump loss resistance concrete polycarboxylate superplasticizer Download PDF

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CN105693946A
CN105693946A CN201610045092.4A CN201610045092A CN105693946A CN 105693946 A CN105693946 A CN 105693946A CN 201610045092 A CN201610045092 A CN 201610045092A CN 105693946 A CN105693946 A CN 105693946A
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water
concrete
reducer
cement
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肖燎
彭琳娜
陈维超
张鑫
刘维
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HUNAN CONSTRUCTION TECHNOLOGY INST
HUNAN CONSTRUCTION ENGINEERING GROUP Corp
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HUNAN CONSTRUCTION TECHNOLOGY INST
HUNAN CONSTRUCTION ENGINEERING GROUP Corp
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065Macromolecular 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688Copolymers containing at least three different monomers
    • C04B24/2694Copolymers containing at least three different monomers containing polyether side chains
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302Water reducers

Abstract

The invention discloses an anti-crack high slump loss resistance concrete polycarboxylate superplasticizer, being prepared from the following components in parts by weight: 25-35 parts of isopentenol polyethylene glycol monomethyl ether macromonomer, 40-50 parts of isopentenol polyethylene glycol monomethyl ether macromonomer, 3.5-4.5 parts of 2-propylene acyl amino-2-methyl-1-propane sulfonic acid, 4-5 parts of allyl polyoxyethylene ether, 3-5 parts of maleic anhydride, 2.5-3.5 parts of dimethyl fumarate, 3-5 parts of hydroxyalkyl acrylate, 4-8 parts of sodium hypophosphite, 0.5-1.5 parts of tartaric acid, 80-83 parts of water and 15-21 parts of sodium hydroxide. The anti-crack high slump loss resistance concrete polycarboxylate superplasticizer has good adaptability to cement, is less in amount of admixture and high in water-reducing rate, is capable of reducing water cement ratio and improving fluidity, is low in slump loss and remarkable in early strengthening effect, and is capable of improving the compactness of concrete, saving cement, improving the working performances of the concrete and improving the durability of the concrete.

Description

A kind of cracking resistance high-thin arch dam concrete polycarboxylate water-reducer
Technical field
The present invention relates to a kind of cracking resistance high-thin arch dam concrete polycarboxylate water-reducer。
Background technology
Water reducer is a kind of important concrete admixture, is one of the staple product of building material pillar industry。High efficiency water reducing agent not only substantially increases the mechanical property of high-strength concrete, and provides simple and easy to do construction technology。Up to the present, the development course of water reducer can be divided into the three below stage: the first generation (common) the water reducer stage being representative with wood calcium etc., with naphthalene system etc. be main representative the second filial generation (efficiently) the water reducer stage and be representative with polycarboxylic-acid up till now the third generation (high-performance) the water reducer stage。
Polycarboxylate high performance water-reducing agent be 20th century the mid-80 first developed the new concrete additive of application by Japan, belong to the third generation product of cement water reducing agent, the mid-90 is industrialized production formally, and has become the novel commercialization concrete admixture of the one being widely used in construction。Polycarboxylate high performance water-reducing agent is mainly by unsaturated monomer copolymerization under initiator effect, by on the side chain graft with active group to the main chain of polymer so that it is there is efficient diminishing, control slump loss and resisted shrinkage, do not affect the effects such as cement setting hardening simultaneously。Polycarboxylate high performance water-reducing agent is totally different from naphthalenesulfonate formaldehyde condensation compound NSF and melamine sulfonate and formaldehyde condensation substance MSF water reducer, in the water reducer of numerous series, poly carboxylic acid series water reducer has lot of advantages, the application of such additive quickly, will become one of important additive of 21 century concrete works use。
Such water reducer is broadly divided into alkene/maleic anhydride polymer and acrylic acid/methacrylate polymers etc.。After nineteen ninety-five, poly carboxylic acid series water reducer greatly exceed naphthalene water reducer and its kind, model and brand a multitude of names at the consumption that makes of Japan。To calendar year 2001, poly carboxylic acid series water reducer consumption has exceeded 80% in water reducer。Especially in recent years a large amount of high intensity, high-flowing concrete application driven extensive use and the technical development of polycarboxylate high performance water-reducing agent, utilize this type of water reducer to produce all kinds of concrete about 10,000,000 m every year3, and have the development trend of cumulative year after year。The development of U.S.'s high efficiency water reducing agent is more late than Japan, and the current U.S. just develops from naphthalene system, honey ammonia based water reducer to polycarboxylic acid series high efficiency water reducing agent。Record according to relevant document, polycarboxylate high performance water-reducing agent is now by first generation poly carboxylic acid series water reducer (methacrylic acid/e pioic acid methyl ester copolymer), second filial generation poly carboxylic acid series water reducer (propenyl ether copolymer) develops into third generation poly carboxylic acid series water reducer (amide rent imine), and is researching and developing the new jade-like gem high efficiency water reducing agent of forth generation polyamide one polyethylene glycol side chain。The exploitation polycarboxylate high performance water-reducing agent that water-reducing rate is higher, performance is more excellent, adaptability is higher is the Main way of Future Development。
Domestic during the nearly last ten years the research and development product of water reducer is mainly new and effective water reducer, and this series products mainly includes naphthalenesulfonate formaldehyde condensation compound, sulfonated melamine compound condensation substance and calcium lignosulfonate (wood sodium) sulfamate condensation substance etc.。No matter China's research to high-performance water reducing agent, be from raw-material selection, produce synthesis technique or improve aspect of performance also in the starting stage。But the progress of the development of China's concrete technology and additive synthesis technique and application technology, provides condition for preparing high-performance water reducing agent, and many research and development units and enterprise achieve some good scientific achievements。The research of China's polycarboxylate high performance water-reducing agent starts from the mid-90 in 20th century, and its industrialized production starts with being applied to the early 21st century。First Shanghai Construction Science Research Inst. is developed into polycarboxylate high performance water-reducing agent, is used successfully to the making of Shanghai Maglev railway high-precision orbital beam and Donghai Bridge maritime concrete and Yang Shan deep water port container road heap concrete。External much big chemical building material company, such as Degussa group, Grace building materials company, Ma Bei group, Sequa Corp, Fu Sile company and KAO. Corp. SA etc., the numerous and confused poly carboxylic acid series water reducer product by oneself production introduces Chinese market by import mode, serves very important effect to promoting poly carboxylic acid series water reducer application in engineering。The yield of current China poly carboxylic acid series water reducer accounts for the ratio of water reducer total output and has started to rise, according to statistics, 2003, China's polycarboxylate water-reducer make consumption less than 10,000 t, about 50,000 t in 2005, within 2006, rise to 150,000 t, within 2006, make uprushing of consumption have benefited from putting into operation of special line for passenger trains。Along with railway construction enters peak period, it is contemplated that within about 2010,300,000 t will be broken through。It is noted that in recent years, the domestic producer that a collection of oneself synthesis polycarboxylate water-reducer of having the ability has occurred。Ministry of Construction's industry standard JG/T223.2007 polycarboxylate high performance water-reducing agent is formally implemented in December in 2007 on the 1st, for promoting the further genralrlization application of poly carboxylic acid series water reducer to provide technical guarantee。
The aspects such as the synthesis of poly carboxylic acid series water reducer, mechanism of action discussion quickly, but are also only built upon the stage rationally speculated by the research and development of poly carboxylic acid series water reducer, there is much unpredictable factor, and many theories wait further investigation demonstration。But due to the advantage that polycarboxylic acid series water reducing agent is unique, two functional groups that diminishing and guarantor collapsed unite two into one, and overcome additive industry and rely on retarder and the shortcoming of slump retaining agent compounding coagulation soil pumping admixture for a long time。Raising along with Polymer Synthesizing, molecular structure characterization and modern detecting, pass through grafting method, by in direct for the side chain with active group grafting to the main chain of polymer so that it is have efficient diminishing, control slump loss and the several functions such as resisted shrinkage, the condensation hardening not affecting cement simultaneously。Although the new and effective water reducer of systematic study still suffers from a lot of difficulty, but countries in the world are all at actively research and application poly carboxylic acid series water reducer。In recent years, along with domestic construction industry is flourish, the demand of concrete high efficiency water reducing agent is increased year by year, but still there is the problem that supply exceed demand in high efficiency water reducing agent and various compound additive, on the low side, China's additive industry maintains the situation of low-grade product all the time, and aggregate level does not have big development。Limited industrial naphthalene raw material is well below the market demand producing concrete high efficiency water reducing agent, and main raw material(s) crude naphthalene lacks, rise in price, causes the added cost producing naphthalene water reducer, and its price raises year by year in fluctuation, no longer cheap。Owing to naphthalene water reducer water-reducing rate is less high, fresh concrete loss of slump is too fast, it is difficult to meet the construction requirement of Practical Project, joint product is also unstable with the adaptability of cement, even having influence on concrete condensation to harden and endurance quality, along with the consumption of construction market water reducer increases, problem is more aobvious prominent, therefore, in the urgent need to novel non-naphthalene water reducer。It practice, China's building trade is in the urgent need to adapting to the domestic poly carboxylic acid series water reducer product in domestic construction market and technology of high performance concrete。Technology of high performance concrete is decided by research and the application level of cement water reducing agent, and each special technical requirement of concrete all be unable to do without the technology innovation of chemical admixture。Therefore, proceed from the reality, the research topic selecting poly carboxylic acid series water reducer is very important, synthesizing new poly carboxylic acid series water reducer, discussion water reducer relation be-tween structure and properties, the mechanism of action and application performance etc., to improving the research level of China's additive, promoting the great-leap-forward development of China's concrete chemical admixture cause all to have positive effect。
Summary of the invention
It is contemplated that overcome the deficiencies in the prior art, it is provided that a kind of cracking resistance high-thin arch dam concrete polycarboxylate water-reducer。
In order to achieve the above object, technical scheme provided by the invention is:
Described cracking resistance high-thin arch dam concrete polycarboxylate water-reducer includes the component of following weight portion:
Prenol poly glycol monomethyl ether polymeric monomer 25 35 parts, prenol poly glycol monomethyl ether polymeric monomer 40 50 parts, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid 3.5 4.5 parts, allyl polyethenoxy ether 45 parts, maleic anhydride 35 parts, dimethyl fumarate 2.5 3.5 parts, acrylic acid hydroxy alkyl ester 35 parts, sodium hypophosphite 48 parts, 0.5 1.5 parts of tartaric acid, 80 83 parts of water, sodium hydroxide 15 21 parts。
Preferably, described water reducer includes the component of following weight portion:
Prenol poly glycol monomethyl ether polymeric monomer 25 parts, prenol poly glycol monomethyl ether polymeric monomer 40 parts, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid 3.5 parts, allyl polyethenoxy ether 4 parts, maleic anhydride 3 parts, dimethyl fumarate 2.5 parts, acrylic acid hydroxy alkyl ester 3 parts, sodium hypophosphite 4 parts, 0.5 part of tartaric acid, 81.5 parts of water, sodium hydroxide 15 parts。
Preferably, the described prenol poly glycol monomethyl ether polymeric monomer degree of polymerization is 27, and the described prenol poly glycol monomethyl ether polymeric monomer degree of polymerization is 113, and described sodium hydroxide is mass percent concentration is the sodium hydroxide of 30 32%。
The invention will be further described below:
In the present invention:
Allyl polyethenoxy ether: use as main raw material(s) in polycarboxylic acid series cement water reducer。
Maleic anhydride: also known as maleic anhydride (MAH), is called for short cis-butenedioic anhydride, is the anhydride of maleic acid, is sour colourless or white solid under room temperature, and molecular formula is C4H2O3。
Dimethyl fumarate: referred to as DMF, for white flakes shape crystalline solid。
Acrylic acid hydroxy alkyl ester: reacted in the presence of a catalyst by acrylic acid and epoxyalkane and prepare。
Sodium hypophosphite: be commonly called as sodium hypophosphite, chemical formula NaH2PO2 H2O, colourless monoclinic system crystal or have nacreous crystal or white crystalline powder。
Tartaric acid: i.e. 2,3 dihydroxybutanedioic acid, molecular formula C4H6O6, a kind of carboxylic acid。
Sodium hydroxide: chemical formula NaOH, white translucent crystalline solid。
Poly carboxylic acid series water reducer synthetic method generally has following several:
(1) the direct copolymerization method of polymerisable monomer。This synthetic method is usually first prepares the polymeric monomer (being generally methoxy polyethylene glycol methacrylate-styrene polymer) with polymerization activity, is then mixed by the monomer determining proportioning and directly adopts polymerisation in solution to obtain finished product。This synthesis technique seems very simple, but front summary synthesis polymeric monomer, and middle separation purge process is comparatively laborious, if industrialization purifies, relatively costly。As Li Chongzhi etc. 121 adopts radical polymerizations, and by monomer copolymerization polycarboxylic-acid PC23 high-performance water reducing agents under the initiation of persulfate such as (methyl) acrylic acid, (methyl) sodium allylsulfonate, polyoxyethylene chain base allyl esters。QianpingRan etc. adopt the method for radical polymerization, have synthesized the poly carboxylic acid series water reducer of a series of different side chain lengths and side chain density with methoxy polyethylene glycol acrylate and sodium acrylate for monomer。Reaction condition is: with water for reaction medium, and reaction temperature is 90 DEG C, and the response time is 8h, with sodium peroxydisulfate for initiator, and NaHSO3For catalyst, reaction atmosphere is N2。(41 with water for reaction medium for Sun Zhen equality; adopt radical polymerization; by homemade esterification polymeric monomer polyethylene glycol monomethyl ethermethacrylic acid esters (MPEGMA) and methacrylic acid (MAA), methacrylsulfonic acid sodium (SMAS) copolymerization poly carboxylic acid series water reducer, reaction density, feed way, the mol ratio of MAA and MPEGMA, the mol ratio of SMAS and MPEGMA, initiator amount (percentage ratios relative to all monomer mass sums), polymerization temperature and the response time impact on synthesized poly carboxylic acid series water reducer performance are inquired into。
(2) polymerization Post functionalization method。The method is modified mainly by existing polymer, is usually the polycarboxylic acid polymer adopting known molecular amount, carries out grafting by esterification at relatively high temperatures with polyethers, or adopt the unsaturated monomers such as acrylic acid under catalyst action。Carry out polymerisation in solution and form main polymer chain, then according to the side chain designing grafting different length on main polymer chain。Form the comb-shaped polymer of different structure。But this method there is also some problems: ready-made polycarboxylic acids product category and specification are limited, adjust its composition and molecular weight is relatively difficult;Polycarboxylic acids and the polyethers compatibility are bad, esterification practical operation difficulty;Along with constantly carrying out of esterification, moisture is constantly overflowed, it is easy to occur being separated。Certainly, if can select that a kind of polyethers good with the polycarboxylic acids compatibility, then the problem being separated can solve completely。How making tranquil etc. to ridicule first adopts styrene and maleic anhydride to obtain high polymer main chain SMA, then introduces specific function group on main chain, adopts S0, SMA is carried out sulfonation, introduces sulfonic group, remain carboxyl, then graft esterification polyether lateral chain on carboxyl, finally gives water reducer molecule。
(3) activity/controllable free-radical polymerisation method。The chain growth active center of radical polymerization is free radical, has strong double-basis termination and coupling or disproportionation termination tendency。Therefore, traditional radical polymerization is uncontrollable。Reversible addition one is ruptured chain tra nsfer (ReversibleAddition FragmentationTransfer, RAFT) radical polymerization: in the conventional free radical polymerization system that AIBN, BPO etc. cause, after adding the chain-transferring agent that chain transfer constant is very big, polyreaction from uncontrollable become controlled, adopt this method can control polymerization and obtain the polymer molecule that dispersion is less。HBouhamed etc. adopt RAFT by base polymerization, with 2 one acrylamido-2 monomethyl propane sulfonic acids and methoxy polyethylene glycol methacrylate-styrene polymer for raw material, are synthetically derived the water reducer molecule that the narrow each structure of molecular weight distribution is different。The method advantage is in that the water reducer molecular weight of synthesis is controlled, is beneficial to the interaction of research water reducer molecule and cement。
Synthesis monomer used by polycarboxylate water-reducer mainly has four kinds at present: (1) unsaturated acids: maleic anhydride, maleic acid and acrylic acid, methacrylic acid;(2) polyalkenyl material: polyalkenyl hydrocarbon and the derivant containing different functional groups thereof;(3) poly styrene sulfonate or ester;(4) (methyl) acrylates, ester or amide etc.。
Molecular structure determines performance, therefore to water reducer Molecular Design so that it possesses superior performance is significant。The molecular structure of poly carboxylic acid series water reducer mainly includes following aspect: backbone length, side chain lengths, side chain density, backbone charge density, molecular weight。The theoretical foundation of poly carboxylic acid series water reducer MOLECULE DESIGN mainly has dlvo theory, sterically hindered effect and the double ionic-layer theory of dispersed particle, macromolecules degradation theory。The above-mentioned five elements determining molecular structure is regulated thus designing the water reducer of superior performance according to these theories。NKazuoYamada etc. have studied the chemical constitution impact on poly carboxylic acid series water reducer performance, the poly carboxylic acid series water reducer impact on cement particle dispersibility is have studied from the purity of polymer, Suo Dai functional group carboxyl, sulfonic group and the aspect such as the chain length of polyoxyethylene base side chain, backbone polymerization degree, think the water reducer with long side chain, short main chain, high sulfonic group density structure, its good dispersion, can make cement slurry extend setting time containing highdensity anionic functional group in structure。The research of GFerran et al. finds。Macromonomer and the mol ratio of carboxylic acid small molecule monomer in polycarboxylate water-reducer are the key factors affecting polycarboxylate water-reducer water-reducing rate, and optimal proportion is l:3。Improving this mol ratio, polycarboxylate water-reducer molecule improves in the adsorbance of cement surface。FrankWinnefeld etc. have studied the impact of the poly carboxylic acid series water reducer of the different structure workability on cement mortar and early hydration situation。Result shows: the density reducing PEO side chain can improve workability, and water reducer molecular backbone length and molecular weight effects are less。
The sign of polycarboxylate water-reducer molecular structure generally includes the sign of molecular weight and distribution thereof and the sign of molecule micro structure。The molecular weight and molecualr weight distribution of polycarboxylate water-reducer generally can characterize with gel permeation chromatography (namely volume removing chromatogram)。
The micro structure of polycarboxylate water-reducer, namely in polycarboxylate water-reducer, the density of side chain and the mensuration of sequence distribution are of great interest in recent years。FPeurtas et al. infrared spectrum, proton magnetic resonance (PMR) and ultraviolet-visual spectrum method carry out structural analysis, determine that the main functional group in water reducer is ester, carboxylate and ether, measure the viscosity of water reducer solution with rotational rheometer, the viscosity higher obtained shows that water reducer molecule has a large amount of longer branched structure simultaneously。PascalBorget et al. " 21 grafting degree and the chain branches using proton magnetic resonance (PMR) characterized by techniques water reducer molecule; simultaneously with 13c nuclear magnetic resonance technique by ester bond in polycarboxylate water-reducer molecule and in carboxylic acid key the sign of carbonyl obtain side chain sequence distribution on main chain, experiments show that side chain is random in the molecule。
Liu is fine waits the technology adopting polymeric monomer with minor comonomer copolymerization, causes polymerisation in solution by free radical, has synthesized a series of polyacrylic acid grafted poly glycol monomethyl ether of water solublity comb-shaped polymer (PAA g mPEG)。Characterize the structure of copolymer with Fourier transform infrared spectroscopy (FT IR) and proton nmr spectra (1H NMR), and the crystallization behavior of its side chain has been studied。Adopt differential scanning calorimetery (DSC), characterize and analyze hot property and the crystallization situation thereof of the mPEG of different side chain lengths。Utilize phase contrast microscope and the crystallization shape of atomic force microscope (AFM) viewing film, show that the side chain mPEG of the comb-shaped polymer thin film crystallization pattern under confined condition is highly branched crystal, preliminary analysis and PEG chain length and the impact on crystal morphology of the weight percentage in the copolymer thereof。Wang Shuhui is reactant with the copolymer p (MMA CO MAh) of homemade methyl methacrylate and maleic anhydride, poly glycol monomethyl ether (PEGME) is grafted monomers, has synthesized pectination P (MMA CO MAh) copolymer multicondensed ethylene glycol ester (P (MMA CO MAh) g-MPEG)。He also adopts Fourier infrared spectrum (FTIR), nuclear magnetic resonance, NMR (NMR) 13c spectrum, 1H spectrum and H, C COSP spectrum that synthesized comb copolymer structure is characterized;By thermogravimetic analysis (TGA) (TGA) and differential scanning calorimetry (DSC), the physical property of synthesized copolymer is analyzed。
The mechanism of action of polycarboxylic acids dehydragent is not yet fully apparent from, and sums up and includes following several viewpoint:
(1) sterically hindered: poly carboxylic acid series water reducer forms the main matter of absorption shape on cement granules and is generally anion surfactant with dispersion water reducer, containing a lot of active groups in its molecular structure, can be adsorbed on cement granules and hydras thereof, formed and there is certain thickness adsorption layer and certain absorption shape, thus the active force significantly changed between the physico-chemical property of solid liquid interface and granule。The dispersion of cement particle is relevant with the form of its surface adsorption water reducer, kind and molecular structure etc.。Naphthalene system and melamine system water reducer belong to linear macromolecule condensation substance, are rigid chain accumbency absorption at cement particle surface, form very strong anionic surface's adsorption layer, make the dispersion phase of cement particle to stable by electrostatic repulsion effect。Polycarboxylate high performance water-reducing agent molecule belongs to highly branched chain structure, its main chain is connected with cement particle surface, side chain then extends into liquid phase and forms thicker polymer molecule adsorption layer, and the absorption in gear-like on cement particle surface, thus having bigger space to make resistance repulsion declines。So, just cement granules is had significant peptizaiton when volume is less。Meanwhile, the long side chain of polymer hydrophilicity still can trail in cement minerals hydrated product, and the hydration reaction impact that such polycarboxylate water-reducer is subject to cement is just little, it is possible to keeps its dispersion effect for a long time, makes loss of slump reduce。Therefore, it is main relevant with the body repulsive force of cement particle surface water reducer Adsorbed polymer layers that polycarboxylate water-reducer can keep cement mortar fluidity not lose, and is the steric repulsion power stability that maintains its disperse system。
(2) electrostatic repulsion: sulfonic group and carboxyl in polycarboxylate high performance water-reducing agent molecule provide adsorption site and electrostatic repulsion, water reducer molecular orientation is made to be adsorbed on cement particle surface, segment polarity group points to liquid phase, the ionization of hydrophilic group makes electric charge electrically identical on cement granules table filled band, forms electric double layer。When cement granules is close to each other, time overlapped between electric layer, just producing electrostatic repulsion between cement granules, cement granules flocculent structure is disintegrated, and granule disperses mutually, discharges the Free water being wrapped in floc sedimentation, thus effectively increasing the mobility of mixture。Document shows, sulfonate radical electrostatic repulsion effect is relatively strong, and carboxylic acid ion electrostatic repulsion effect is taken second place, and hydroxyl and ether electrostatic repulsion effect are minimum。
(3) adsorption layer: after cement particle surface absorption high performance water reducing agent of polyocarboxy acid molecule, its branch's conformation is different from naphthalene series high-efficiency water-reducing agent, forms additive adsorption layer one layer thicker at particle surface。After absorption high-performance water reducing agent molecule, cement particle surface current potential absolute value increases, and increases electrostatic repulsion forces, and macromolecule composition adsorption layer itself too increases the electrostatic dispersion ability of cement granules simultaneously。The slide surface of diffusion layer is actually outwards elapsed by the adsorption layer of high molecular polymer, makes the distance of counter ion and particle surface increase, and therefore, granule is close to each other is that the overlapping ranges of electric double layer increases, and the electrostatic repulsion forces of granule strengthens。
(4) hydration shell lubrication: containing substantial amounts of polar group in polycarboxylate water-reducer molecule, such as carboxyl, hydroxyl, sulfonic group, ehter bond and amino etc., these polar groups all have stronger hydrophilic interaction, hydrogen bond can be formed with associated water molecules, improve the wettability of cement particle surface, make water saturates in intergranular narrower and small pore。Water reducer Molecular Adsorption, after cement particle surface, forms one layer of solvent hydration shell with certain mechanical strength at cement particle surface, and the formation of hydration shell can destroy the flocculent structure of cement granules, makes cement granules fully dispersed, and produces to hinder the effect of cohesion。
(5) bleed isolation: polycarboxylate high performance water-reducing agent has the ability reducing liquid gas interface tension force, therefore has certain air-entraining effect。Water reducer mixes in concrete mix, is not only adsorbed in solid liquid interface, makes to be easily formed many micro-bubbles in concrete mix。Water reducer molecular orientation is arranged on the liquid interface of bubble, makes bubble top layer form one layer of hydration shell, simultaneously the upper electric charge identical with cement granules of band。Between bubble and bubble, between bubble and cement granules, all producing electrostatic repulsion, cement granules being produced buffer action, thus stoping cement granules to flocculate。And the ball of bubble and floating holder effect, also contribute to the relative sliding between cement granules in fresh concrete, aggregate。Therefore, the effect of the had bleed isolation ball of water reducer can improve the workability of concrete mix。
Compared to concrete polycarboxylate water-reducer of the prior art, the cracking resistance high-thin arch dam concrete polycarboxylate water-reducer of the present invention obtains innovation and is in that to be also added into allyl polyethenoxy ether, maleic anhydride, sodium hypophosphite and tartaric acid and sodium hydroxide etc., and the performance of the polycarboxylate water-reducer being is better。Allyl polyethenoxy ether uses as main raw material(s) in polycarboxylic acid series cement water reducer。The efficient based water reducer of polycarboxylic acids of synthesis has stronger cement granules dispersibility holding capacity, and volume is low, water-reducing rate is high, reinforced effects is good, durability, not Corrosion Reinforcement and the feature such as environmentally friendly to make product have。Sodium hypophosphite is chemical plating agent, also can be used as the catalyst of chemical reaction, stabilizer。Tartaric acid has the effects such as stronger emulsifying, dispersion, is good emulsifying agent and dispersant。Additionally, the addition of maleic anhydride, acrylic acid hydroxy alkyl ester and sodium hydroxide etc. also makes the performance of polycarboxylate water-reducer be improved。The preparation technology of the present invention is simple, without any discharge of poisonous waste in production process。The adaptability of cement is good, volume is little, water-reducing rate is high can reduce the ratio of mud, increase fluidity, and little loss of slump, early potent fruit are notable, can improve concrete compaction rate, save cement, improve concrete work performance, improve concrete durability。
Detailed description of the invention
Embodiment 1
The described cracking resistance each constituent content of high-thin arch dam concrete polycarboxylate water-reducer is: the degree of polymerization is the prenol poly glycol monomethyl ether polymeric monomer of 27: 25 parts, the degree of polymerization is the prenol poly glycol monomethyl ether polymeric monomer of 113: 40 parts, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid: 3.5 parts, allyl polyethenoxy ether: 4 parts, maleic anhydride: 3 parts, dimethyl fumarate: 2.5 parts, acrylic acid hydroxy alkyl ester: 3 parts, sodium hypophosphite: 4 parts, tartaric acid: 0.5 part, water: 81.5 parts, 30-32% mass concentration sodium hydroxide: 15 parts。Said components mixing is prepared cracking resistance high-thin arch dam concrete polycarboxylate water-reducer。
Show that to mix polycarboxylate water-reducer as follows on the impact of concrete batching system performance:
(1) additive homogeneity
The relevant regulations of GB8076 2001, to polycarboxylate water-reducer with how two kinds of additives of based water reducer have carried out homogeneity inspection。From homogeneity index it can be seen that
For naphthalene water reducer, the surface tension of polycarboxylate water-reducer is much lower, it is possible to the surface tension of concrete capillary tube is greatly lowered, thus reducing concrete dry shrinkage, improves concrete durability;The paste flowing degree adopting polycarboxylate water-reducer increases in time in 1h, and the loss rate after 2h only reaches 7.7%, and the loss of the paste flowing degree of naphthalene water reducer is very fast, is almost difficult to measure after 2h。
(2) mix performance
Fresh concrete mix performance mainly includes water-reducing rate, bleeding rate, setting time, air content, the slump and diffusance retention value etc., from comparative test result it can be seen that
A) with how based water reducer compares, when volume is only small, the water-reducing rate of polycarboxylate water-reducer is more than 20%。Having test to show: if properly increasing volume, the water-reducing rate of polycarboxylate water-reducer is up to 35%, and this is how based water reducer is too far behind to catch up。
B) from how based water reducer is different, polycarboxylate water-reducer has good slump retaining。With the concrete of this additive mixing, the slump of 1h and diffusance are substantially free of loss, the slump-loss of 2h only 12.6%;And under equal conditions, mix the 1h slump-loss nearly 37% of how based water reducer concrete batching system。2h slump-loss is then up to 67%。
C) compared with how based water reducer, the bleeding rate mixing polycarboxylate water-reducer concrete batching system is extremely low。Be conducive to suppressing the formation of inside concrete capillary channel, raising volume stability of concrete and durability is highly beneficial。
D) if it was found that carry out additive Quality Detection according to GB8076 1997 in the process of mixing and stirring, owing to concrete batching system is especially sensitive to water consumption, it is difficult to accurately measure the actual water-reducing rate of polycarboxylate water-reducer。
In a word, the feature that polycarboxylate water-reducer water-reducing rate is high, bleeding rate is low, slump retaining is good is highly beneficial to building important load-carrying members concrete, scour and abrasion resistant concrete。
(3) the acid water reducer impact on mechanical performance of concrete
The reinforced effects of polycarboxylate water-reducer and how based water reducer from maturing mechanical property Comparability test it can be seen that
A) each age compressive strength rate of polycarboxylate water-reducer concrete is mixed obviously higher than the concrete mixing naphthalene water reducer。
B) after mixing polycarboxylate water-reducer, concrete anti-compression, tensile strength are significantly increased, especially early strength, and the comprcssive strength increasing value of its 3d just reaches more than 200%, and the comprcssive strength of 7d has exceeded 180%, also have sustainable growth during to 90d age。After mixing polycarboxylate water-reducer, why concrete strength can significantly improve, mainly having following two reasons: 1) more how based water reducer has bigger water-reducing rate to polycarboxylate water-reducer, constant in glue material total amount, collapse (expansion) spends identical, the water-cement ratio of concrete batching system is less。2) more how based water reducer is much lower for polycarboxylate water-reducer interfacial tension, concrete batching system not bleeding substantially, thus being conducive to improving concrete internal pore structure, make Behavior of Hardened Cement Paste internal structure closely knit, bleeding is only small on the impact of the interfacial transition zone between Behavior of Hardened Cement Paste and aggregate such that it is able to improve concrete strength。
(4) polycarboxylate water-reducer impact on concrete durability
Polycarboxylate water-reducer and how based water reducer are the same with the mechanism affecting concrete crushing strength on the impact of concrete durability, cement granules is had extremely strong dispersibility by polycarboxylate water-reducer, the water-cement ratio of mix can be greatly lowered, and concrete batching system self not bleeding substantially, therefore the microstructure of inside concrete can be significantly improved, reduce the capillary channel of inside concrete, improve the interfacial structure between Behavior of Hardened Cement Paste and aggregate, thus improving concrete impervious, freeze proof and resistant abrasion performance。
(5) polycarboxylate water-reducer impact on concrete deformation performance
Polycarboxylate water-reducer the and how impact of concrete shrinkage performance is shown by based water reducer by result of the test: under identical conditions of mixture ratios, the contract with dry rate mixing polycarboxylate water-reducer concrete 28d is only the 82% of normal concrete, and the contract with dry rate mixing naphthalene water reducer concrete 28d has reached the 120% of normal concrete。Obviously, after mixing polycarboxylate water-reducer, the bleeding rate of concrete batching system reduces, and inside concrete pore quantity reduces, and this is the main cause that shrinkage deformation substantially reduces。
From the performance comparison analysis of experimental data to polycarboxylate water-reducer and how two kinds of additives of based water reducer, it is known that polycarboxylate water-reducer has been summed up with advantage:
1) volume is low, and water-reducing rate is high
By solid volume, general volume is Binder Materials weight about the 0.15%~0.25% of polycarboxylate high performance water-reducing agent, it is only about the 1/4 of the general volume of naphthalene system。Water-reducing rate is generally individually 25%~30%, and individual samples is higher than 30%;When close to limit doped amount about 0.5%, water-reducing rate is generally up to 40%, and individual samples is up to 45%~48%。Visible, compared with naphthalene system, while polycarboxylate high performance water-reducing agent volume is greatly lowered, water-reducing rate is but greatly improved。
2) retentivity is good, slump-loss is low for the mobility of concrete mix and flowing
Test result indicate that, the slump of polycarboxylate high performance water-reducing agent concrete mix keeps effect fine, and when adopting the good cement type of some qualities, the 2h slump is not lost substantially, and this is that naphthalene water reducer is extremely difficult to。Studies have reported that title, mix the concrete through special modified polycarboxylate high performance water-reducing agent, under the summer high temperature of more than 30 DEG C, its high workability can keep being basically unchanged of 6~8h, this technical performance height that naphthalene water reducer can not touch especially。Although concrete mix flowing maintenance performance is well one of distinguishing feature of polycarboxylate high performance water-reducing agent, but owing to kind and the quality of China's cement are complicated and changeable, so such water reducer yet suffers from the adaptability problem with cement。But many contrast tests and engineering practice prove, when same raw material, mobility and the flowing retentivity of mixing polycarboxylate high performance water-reducing agent concrete mix will significantly better than naphthalene systems。
3) concrete reinforced effects potentiality are big
Test result indicate that: compared with naphthalene system, the strength ratio of polycarboxylate high performance water-reducing agent concrete each age all has raising by a relatively large margin, and early anti pressured intension is more more notable than improving。For 3d, 7d days compressive strength rates: 3d, 7d compressive strength rate of naphthalene series high-efficiency water-reducing agent (is mixed the normal concrete comprcssive strength of Fresh Concrete with Admixtures comprcssive strength/do not mix additive) and is typically in about 130%, and the same age compressive strength rate of polycarboxylate high performance water-reducing agent is typically in more than 180%, some samples have reached more than 200%。Correlational study shows, for having filled the concrete of the mineral admixture such as flyash, slag, compared to naphthalene water reducer, the reinforced effects of polycarboxylate high performance water-reducing agent is more preferably。Certainly, due to the difference of cement type, the kind of mineral admixture and polycarboxylate high performance water-reducing agent kind, volume etc., the reinforced effects in Practical Project is different。
4) concrete lower shrinkage
Mix the concrete volume stability of polycarboxylate high performance water-reducing agent compared with the second filial generation water reducer concrete such as naphthalene system, improve a lot。" polycarboxylate high performance water-reducing agent JG/T223-2007 " establishment group is to domestic and international totally 11 kinds of samples, 28d shrinkage ratio is measured: mix polycarboxylate high performance water-reducing agent concrete contraction percentage than average out to 102% by GB8076 1997, minimum shrinkage ratio is only 91%, and the 28d shrinkage ratio of naphthalene series high-efficiency water-reducing agent is typically in more than 110%。This should be another remarkable advantage of polycarboxylate high performance water-reducing agent。If polycarboxylate high performance water-reducing agent selects to continue to be improved and improve to this performance with formula design aspect at raw material, then the popularization and application of this series products will significantly improve concrete volume stability, is substantially reduced the cracking probability of structural concrete。
5) certain amount of air entrainment
Measuring concrete 's air-containing by GB8076 1997, its meansigma methods is 3.58%, and peak is 6.3%, even higher。Compared with the second filial generation (efficiently) water reducers such as naphthalene system, its amount of air entrainment improves a lot。Polycarboxylate high performance water-reducing agent introduce these pores properties of hardened concrete is had what impact there is no final conclusion at present, we tackle this strengthen research, including air hole structure, spacing factor, bubble uniformity etc.。In general, suitable air content is conducive to improving concrete workability and frost resistance, is conducive to improving concrete endurance quality。
6) total alkali is extremely low
The meansigma methods of its total alkali is 1.35%, minimum in 11 kinds of samples is 0.19%, compared with the second filial generation (efficiently) water reducers such as naphthalene system, its total alkali content brought in concrete is only tens of grams, greatly reduce additive and introduce the alkali content in concrete, reduce the probability that alkali-aggregate reaction occurs, improve concrete durability。
7) chloride ion content is low
Polycarboxylate water-reducer chloride ion content is non-normally low, therefore affects less on the alkaline passivation film of rebar surface, it is appreciated that in concrete endurance quality。In experimental study, the poly carboxylic acid series water reducer chloride ion content of its use is only 0.03% mass ratio。

Claims (3)

1. a cracking resistance high-thin arch dam concrete polycarboxylate water-reducer, it is characterised in that described water reducer includes the component of following weight portion:
Prenol poly glycol monomethyl ether polymeric monomer 25 35 parts, prenol poly glycol monomethyl ether polymeric monomer 40 50 parts, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid 3.5 4.5 parts, allyl polyethenoxy ether 45 parts, maleic anhydride 35 parts, dimethyl fumarate 2.5 3.5 parts, acrylic acid hydroxy alkyl ester 35 parts, sodium hypophosphite 48 parts, 0.5 1.5 parts of tartaric acid, 80 83 parts of water, sodium hydroxide 15 21 parts。
2. water reducer as claimed in claim 1, it is characterised in that described water reducer includes the component of following weight portion:
Prenol poly glycol monomethyl ether polymeric monomer 25 parts, prenol poly glycol monomethyl ether polymeric monomer 40 parts, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid 3.5 parts, allyl polyethenoxy ether 4 parts, maleic anhydride 3 parts, dimethyl fumarate 2.5 parts, acrylic acid hydroxy alkyl ester 3 parts, sodium hypophosphite 4 parts, 0.5 part of tartaric acid, 81.5 parts of water, sodium hydroxide 15 parts。
3. water reducer as claimed in claim 1 or 2, it is characterized in that, the described prenol poly glycol monomethyl ether polymeric monomer degree of polymerization is 27, and the described prenol poly glycol monomethyl ether polymeric monomer degree of polymerization is 113, and described sodium hydroxide is mass percent concentration is the sodium hydroxide of 30 32%。
CN201610045092.4A 2016-01-25 2016-01-25 Anti-crack high slump loss resistance concrete polycarboxylate superplasticizer Pending CN105693946A (en)

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