CN102910855B - Super plasticizer for precast concrete component - Google Patents

Super plasticizer for precast concrete component Download PDF

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Publication number
CN102910855B
CN102910855B CN201210396736.6A CN201210396736A CN102910855B CN 102910855 B CN102910855 B CN 102910855B CN 201210396736 A CN201210396736 A CN 201210396736A CN 102910855 B CN102910855 B CN 102910855B
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monomer
concrete
methyl
general formula
superplasticizer
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CN102910855A (en
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冉千平
刘金芝
刘加平
周栋梁
杨勇
张建纲
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Sobute New Materials Co Ltd
Taizhou Jiangyan Bote New Materials Co Ltd
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Sobute New Materials Co Ltd
Taizhou Jiangyan Bote New Materials Co Ltd
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Priority to CN201210396736.6A priority Critical patent/CN102910855B/en
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Priority to PCT/CN2013/073683 priority patent/WO2014059765A1/en
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    • 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
    • C04B24/2641Polyacrylates; Polymethacrylates
    • C04B24/2647Polyacrylates; Polymethacrylates 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
    • 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
    • C04B24/2652Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
    • 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
    • C04B2103/32Superplasticisers

Abstract

The invention relates to a super plasticizer for a precast concrete component, and the super plasticizer is prepared by carrying out free radical copolymerization reaction on monomer a, monomer b, monomer c and monomer d in an aqueous medium, and adding alkali compound into the reaction product for neutralization, wherein the molar ratio among the monomer a, the monomer b, the monomer c and the monomer d is 1.0:(5.0-16.0):(1.0-4.0):(2.0-6.0). Compared with the traditional high efficiency water reducing agent, the admixture has the characteristics that (1) the early hydration of the cement is obviously improved, the compression strength of the concrete is improved, and especially the early strength is improved; (2) the problem of slump loss caused by polyether long side chain belt can be greatly improved, so that the slump loss resistance of the concrete is improved, and the requirements of pumping pipe pile concrete can be met; and (3) under the condition of low amount of admixture, the super plasticizer for the precast concrete component has remarkable dispersing performance, slump-retaining capability and enhancement effect, is especially remarkable in early enhancement effect, is very remarkable in the early enhancement effect at the room temperature or low temperature, and is stable in later strength increment, thus being conductive to accelerating the turnover of templates, and accelerating the construction progress.

Description

Concrete prefabricated element superplasticizer
Technical field
The present invention relates to a kind of ultra early-strength superplasticizer that concrete prefabricated element is used that is applicable to, this superplasticizer is not delaying under the prerequisite of cement setting time, not only can significantly improve early age strength of concrete, and there is excellent slump hold facility, belong to technical field of concrete additives.
Background technology
Concrete prefabricated element is the major products of < < building materials industry " 12 " development program > > development.During 11th Five-Year, traditional prefabricated components output such as China's concrete precast pile, water shoot, penstock and electric pole have kept very fast growth.Meanwhile national large quantities of infrastructure construction engineering is more and more higher to concrete product state of the art and specification of quality, concrete and cement products industry new technology have been promoted, the fast development of product innovation, the key part concrete shield pipe-plate of for example building for city underground and river-crossing tunnel, diameter reaches the senior engineer of 4 meters and presses heavy caliber steel cylinder concrete water transmission pipe (PCCP), strength grade reaches high-strength prestressed (PHC) pile tube more than C80, high speed passenger dedicated railway replaces the concrete of sleeper without tiny fragments of stone, coal, etc. guidance tape, large scale prefabricated beams of concrete, embody architectural culture and ecological harmonious various decorative concretes and goods etc.Persistently overheating along with housing industrialization, precast concrete cast in place and precast construction operating technique, because its green, environmental protection construction mode are favored gradually, has been listed in one of 10 new technologies of construction industry by house and town and country construction portion.Can predict, concrete prefabricated element coming years field will welcome the development upsurge of a new round.Although precast concrete compares with onsite concrete the obvious advantage that demonstrated at aspects such as the stdn of producing, construction greenizations, is also faced with very large pressure at aspects such as energy-saving and emission-reduction, weather resistance.The common feature of concrete prefabricated element is concrete high-strength, early strong, in order to improve the early strength of precast concrete, Major Technology both domestic and external mainly contains and changes cement composition or fineness, additional morning strong admixture and the method such as thermal curing system, but these technology all more or less exist different defects at present.1) strong technology morning based on cement composition or fineness regulation and control: at present in order to improve early age strength of concrete, manufacturers has to adopt superfine cement and changes cement minerals and forms.The fineness of cement is thinner, and its early hydration speed is faster, and early strength is higher, but concrete construction poor performance, shrink large, easy to crack.Beijing-Tianjin Line for Passenger Transportation once adopted high grade superfine cement, and (specific surface area reaches 600m 2/ kg) Germany technology scheme is produced plate-type slag-free orbit plate, and this technology exists the defect that workability is poor, production efficiency is low, cost is high, is difficult to adapt to the needs that China Express Railway is built.In addition, also can improve early strength by adjusting the special cements such as cement minerals phase composite production quick hardening Portland cement, sulplo-aluminate super-early strength cement and fluoaluminate quick-setting and rapid-hardening cement, but high, the early stage contract with dry rate of early water heat-transmission is large, and later strength and performance present decline; 2) morning based on additional hardening accelerator strong technology: early strong admixture has had applicating history for many years at building materials field, and its utilisation technology is also more comprehensive, but still has some technical problems to be difficult to solve.Although early potent fruit is better for inorganic hardening accelerator, volume is higher, and late strength of concrete retraction is serious, concrete is dry to be shunk greatly, be unfavorable for concrete durability, alkaline metal salt hardening accelerator also can increase the risk of alkali-aggregate Reaction of Concrete, and its use is more and more restricted.Organic hardening accelerator uses more safe and reliablely comparatively speaking, but its addition content is difficult to control, and improper use easily causes the serious slow setting of concrete and concrete strength to decline, and its fancy price has affected its application at Concrete Industry; 3) strong technology morning based on maintaining process regulation and control: prefabricated components extensively adopt thermal curing technique to improve early strength in producing, accelerate form cycling rate.The prefabricated components such as subway segment more than C50, concrete prefabricated beam, concrete pipe mainly adopt the vapor cure at 40-60 ℃, and vapor cure is the main energy consumption link of these class prefabricated components.The above high-strength prestressed concrete pipe pile of C80 or section of jurisdiction (PHC, PCCP) two sections of maintaining process that mainly adopt normal pressure to be combined with autoclave curing, this technique mesohigh vapor cure occupies the more than 90% of total maintenance energy consumption, the standard coal that every production 1M3PHC pile tube consumes for maintenance reaches 40kg, discharges carbonic acid gas 30kg simultaneously.Steamed concrete member is later stage mechanical properties decrease not only, and the weather resistance of member reduces.4) super morning of the strong technology based on graft copolymer molecular structure.Current research confirms graft copolymer admixture except giving the high initial flow of fresh concrete and high workability maintenance, can also adopt modern molecule tailoring technique to give maturing super early strong, low contraction, even meet the several functions such as requirement that aquation is controlled, new approach has been opened up in the development of the super early strong technology of cement-based material.Patent of invention (EP1547986, US723287, EP2128110, ZL200710024394.4, ZL200710024392.5) adopt the technological approaches of overlength side chain polyethers, invented the ultra early-strength admixture that improves early age strength of concrete, although increased substantially early age strength of concrete, but the increase of polyether lateral chain length, accelerate cement early hydration, thereby aggravated the early stage slump-loss of fresh concrete.Along with the increase of labor cost, precast concrete not only has very high requirement to early strength, also requires concrete to carry out pumping simultaneously.
In sum, it is unsafty adopting traditional inorganic salt or organic hardening accelerator to improve early age strength of concrete, and its volume is high, has reduced late strength of concrete; Strong technology morning of tradition cement composition or fineness regulation and control is easily shunk, is ftractureed, and concrete durability is not high; Conventional high-temperature, autoclave curing are consumed energy high, are unfavorable for concrete durability.These tradition early strong technology can not effectively solve early strong and high durable contradiction, can not meet the growth requirement of construction industry " energy-conservation, low-carbon (LC), reduction of discharging ".And the morning of novel ultra early-strength admixture, potent fruit was satisfactory, but slump-loss is very large.And adopt composite collapse protection type admixture or retardant to improve its mobility retention, the deteriorated again development of early age strength of concrete.
Summary of the invention
Research purpose of the present invention is that development can overcome those shortcomings described in background technology, and production technology is relatively simple and have a concrete prefabricated element superplasticizer that high, the early stage reinforced effects of water-reducing rate is good, mobility hold facility is strong.
Applicant finds after deliberation, and graft copolymer side chain lengths is the major influence factors of hydrated cementitious speed.Side chain is longer, and hydrated cementitious is faster, and long-chain branch is because its strong space steric effect causes the dispersiveness of multipolymer excellence, has also accelerated the aquation of cement, is conducive to the raising of early age strength of concrete.
Applicant is surprised to find after deliberation, by introduce cation group on main chain, improves multipolymer absorption behavior, not only can accelerate cement early hydration, but also can significantly promote concrete flowability hold facility.
Applicant also finds after deliberation, by introduce hydroxy ester class comonomer cement strong basicity environment to response on main chain, can further promote fresh concrete mobility hold facility.
Based on above-mentioned research, carboxyl acid graft copolymer superplasticiser of the present invention adds basic cpd neutralization and is prepared from after free radicals copolymerization reaction occurs in aqueous medium for monomer a, monomer b, monomer c and monomer d, wherein monomer a: monomer b: monomer c: mol ratio=1.0:5.0 ~ 16.0:1.0 ~ 4.0:2.0 ~ 6.0 of monomer d;
Above-mentioned monomer is general formula (1) expression for a:
R in general formula (1) 1for H or methyl, R 2it is the alkyl of H or 1 ~ 4 carbon atom; AO is the oxyalkylene group of 2-4 carbon atom or the mixture of two or more this oxyalkylene group arbitrary proportion; N is the average addition mole number of AO, is 100~300 integer; (AO) n is homopolymerization, random copolymerization, diblock or multiblock structure;
Above-mentioned monomer is general formula (2) expression for b:
R in general formula (2) 3h or methyl, R 4be H or m is H, alkalimetal ion, alkaline-earth metal ions, ammonium ion or organic amine group;
Monomer c is cationic monomer, adopts by the represented material of general formula (3):
Wherein: R 5for H or methyl, R 6, R 7, R 8all independently represent H or C 1~ C 10alkyl;
X-is F, Cl, Br or I;
A is O or NH;
P is 1~3 positive integer;
Monomer d is hydroxyl esters monomer, adopts by the represented material of general formula (4):
R in general formula (4) 1same general formula (I), R 9be expressed as-(CH 2) xOH, the positive integer of x=2~10.
When the monomer a that formula of of the present invention (1) represents is polyalkylene glycol mono (methyl) acrylate monomer, be by alkoxyl group polyalkylene glycol and (methyl) vinylformic acid or with the esterification synthetics of (methyl) acrylic anhydride; Or be the affixture of at least one material in (methyl) acrylic acid hydroxy alkyl ester and oxyethane, propylene oxide, butylene oxide ring, these monomers are used separately or use with the form of mixtures of arbitrary proportion with two or more compositions.
The object lesson that can be used as polyalkylene glycol mono (methyl) acrylate monomer of large monomer a comprises: polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polytetramethylene glycol list (methyl) acrylate, polyoxyethylene glycol polypropylene glycol list (methyl) acrylate, polyoxyethylene glycol polytetramethylene glycol list (methyl) acrylate, polypropylene glycol polytetramethylene glycol list (methyl) acrylate, polyoxyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) list (methyl) acrylate, methoxyl group polypropylene glycol list (methyl) acrylate, methoxyl group polytetramethylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) polypropylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) polytetramethylene glycol list (methyl) acrylate, methoxyl group polypropylene glycol polytetramethylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) polypropylene glycol polytetramethylene glycol list (methyl) acrylate, oxyethyl group polyethyleneglycol (methyl) acrylate, oxyethyl group polypropylene glycol list (methyl) acrylate, oxyethyl group polytetramethylene glycol list (methyl) acrylate, oxyethyl group polyoxyethylene glycol polypropylene glycol list (methyl) acrylate, oxyethyl group polyoxyethylene glycol polytetramethylene glycol list (methyl) acrylate, oxyethyl group polypropylene glycol polytetramethylene glycol list (methyl) acrylate, oxyethyl group polyoxyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, propoxy-polyethyleneglycol (methyl) acrylate, propoxy-polypropylene glycol list (methyl) acrylate, propoxy-polytetramethylene glycol list (methyl) acrylate, propoxy-polyoxyethylene glycol polypropylene glycol list (methyl) acrylate, propoxy-polyoxyethylene glycol polytetramethylene glycol list (methyl) acrylate, propoxy-polypropylene glycol polytetramethylene glycol list (methyl) acrylate, propoxy-polyoxyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, butoxy polyethyleneglycol (methyl) acrylate, butoxy propoxy-polypropylene glycol list (methyl) acrylate, butoxy polytetramethylene glycol list (methyl) acrylate, butoxy polyoxyethylene glycol polypropylene glycol list (methyl) acrylate, butoxy polyoxyethylene glycol polytetramethylene glycol list (methyl) acrylate, butoxy polypropylene glycol polytetramethylene glycol list (methyl) acrylate, butoxy polyoxyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate.They are known, they or commercially available, or can be according to the method preparation described in disclosed document or patent.
The monomer b that formula of of the present invention (2) represents is unsaturated carboxylic acid, comprise vinylformic acid, methacrylic acid, toxilic acid, or the monovalent metal salt of these unsaturated carboxylic acids, divalent metal salt, ammonium salt or organic amine salt, these monomers are used separately or use with the form of mixtures of two or more compositions.
What the typical ion that can be used as cationic monomer c that formula of of the present invention (3) represents listed is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryloxyethyldimethyl benzyl ammonium chloride, methacryloxypropyl trimethyl ammonium chloride, methacryloxypropyl dimethyl benzyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, acrylyl oxy-ethyl dimethyl benzyl ammonium chloride, acrylamido oxypropyl trimethyl ammonium chloride, acrylamido propyl-dimethyl benzyl ammonium chloride, methacryloyl amido oxypropyl trimethyl ammonium chloride, methacryloyl amido propyl-dimethyl benzyl ammonium chloride, these monomers are used separately or use with the form of mixtures of two or more composition.
The monomer d that formula of of the present invention (4) represents is (methyl) acrylic acid hydroxy alkyl ester, comprise Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate or Rocryl 410, these monomers are used separately or use with the form of mixtures of two or more composition.
The monomer a that formula of of the present invention (1) represents is copolymerized in main chain, and its long-chain branch mainly provides space steric effect, thereby gives the dispersing property of graft copolymer excellence.If monomer a ratio is too low, the multipolymer early strength produced is lower.If ratio is too high, synthetic multipolymer dissemination a little less than.The average addition mole number that in general formula (1), n is AO, its integer that is 100~300, if n is too little, synthetic multipolymer early strength is low; If n is too large, its Copolymerization activity is poor, and monomer conversion is low, not only can not improve early strength, and synthetic multipolymer dispersing property is also poor.
Within the scope of the present invention, monomer b(general formula 2) be necessary, its hydroxy-acid group provides adsorption site and electric repulsion in multipolymer, and monomer b content is too low, and synthetic multipolymer can not fully be adsorbed onto on cement particle, therefore can not bring into play dissemination.If too high levels, the multipolymer early strength produced is lower.
Within the scope of the present invention, the represented cationic monomer c of general formula (3) is necessary, and its cation group not only improves adsorption site in multipolymer, has also improved the behavior of cement early hydration.Monomer c content is too low, and the amphoteric character of synthetic multipolymer is not obvious, can not fully be adsorbed onto on cement granules, can not obviously improve the early hydration of cement and promote mobility hold facility.If too high levels, the multipolymer dispersing property variation of producing.
Within the scope of the present invention, the represented hydroxyl esters monomer d of general formula (4) is necessary, is copolymerized to the absorption behavior of main dynamic regulation multipolymer in main chain, thereby promotes the mobility hold facility of multipolymer.Monomer d content is too low, does not have the effect of dynamic regulation multipolymer absorption behavior, and the mobility hold facility of multipolymer reduces.If too high levels, the early stage dispersing property of multipolymer and the early age strength of concrete produced also can variation.
Free radicals copolymerization reaction itself is unimportant, and it can, according to usual method, not carry out difficult in the situation that with known radical initiator.Being suitable for water soluble starter of the present invention is conventional free radical water soluble starter, the water-soluble ammonium persulphate of optional use, Potassium Persulphate, Sodium Persulfate or hydrogen peroxide or the wherein mixture of two or more arbitrary proportions.The whole initiators that join in reaction mixture account for 1.0~6.0% of added monomer (a+b+c+d) total mole number.The art those skilled in the art generally know that in copolyreaction, the actual add-on of initiator has certain relation with the initiator type adopting.
The molecular weight of multipolymer can utilize polymerizable chain transfer agents to select to control, as thiohydracrylic acid, and Thiovanic acid, mercaptoethanol and Dodecyl Mercaptan.The consumption of polymerizable chain transfer agents in polymerization process is 1.0~5.0% of total mole of monomer (a+b+c+d).
Copolyreaction monomer total mass concentration is advisable to be controlled at 25~50%, and the reaction times is controlled at 5~10 hours.Monomer and initiator solution take the mode separately simultaneously dripping to control the homogeneity of multipolymer chain link distribution and the stability of copolyreaction itself, and monomer mixed solution and initiator time for adding are advisable to be controlled at 2.0~6.0 hours.Interpolymerization temperature is carried out at 60~100 ℃ fortunately, and the decomposition temperature of the initiator that it is main and used is relevant.
After copolyreaction finishes, to adding in reaction product basic cpd to adjust pH value, be 6.0~10.0, oxyhydroxide or its carbonate of described basic cpd selection ammoniacal liquor, ammonium hydrogencarbonate, organic amine, monovalent metal or divalent metal.PH value is too low and too high, and the package stability of multipolymer is all bad.
In the present invention, using the weight-average molecular weight of the comb-shaped graft copolymer of Concrete superplastizer to be not particularly limited, generally at 20,000-100,000, if molecular weight is too little and too large, water-reducing property all can be deteriorated.
During use, the conventional volume of Concrete superplastizer of the present invention is in 0.1%~0.4% of total glue material amount, and optimum adding quantity of pulverized is 0.15~0.3%.If addition is less than 0.10%, its dispersing property and reinforced effects are unsafty so.If contrary addition surpasses 0.4%, excessive interpolation proof is only waste economically, because do not bring the corresponding growth in effect.
Certainly, Concrete superplastizer of the present invention also can be selected from aminosulfonic water-reducing agent known in the state of the art, Lignins ordinary water-reducing agent and existing poly carboxylic acid series super plasticizer with at least one and mixes mutually.
In addition, except known cement water reducing agent above-mentioned, from wherein also adding air entrapment agent, swelling agent, retardant, hardening accelerator, tackifier, economization agent and defoamer etc.
Prefabricated components superplasticizer of the present invention, compares with traditional high efficiency water reducing agent, and this admixture has following features:
(1) the present invention has introduced long side chain polyethers and cationic monomer, can obviously improve the early hydration of cement, improves concrete ultimate compression strength, especially early strength;
(2) the present invention has introduced hydroxyl esters monomer, can greatly improve the slump-loss problem that the long side chain of polyethers brings, and has improved the concrete guarantor ability of collapsing, and can meet the requirement of pumping line pile concrete, saves a large amount of human costs;
(3) in the present invention, prepared prefabricated components are compared with conventional Concrete superplastizer with superplasticizer, under low-dosage, show outstanding dispersing property, disperseed hold facility and reinforced effects, especially early stage reinforced effects is remarkable, and be all very remarkable at normal temperature or the early stage reinforced effects of low temperature, and middle and later periods intensity also increases stable, be conducive to accelerate template turnover, improve construction speed.
Embodiment
Following examples have described in more detail the process that the method according to this invention is prepared polymerisate, and these embodiment provide in the mode of explanation, its object is to allow person skilled in the art can understand content of the present invention and implement according to this, but these embodiment never limit the scope of the invention.All equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.If do not stipulated in addition, " umber " refers to " weight part ".Monomer used in following embodiment is as shown in table 1, and synthetic carboxylic-acid prefabricated components are PE with Concrete superplastizer brief note.
A), in the invention process, monomer a, monomer b, c and monomer d described in table 1 are commercially produced product, can on market, buy.
B), in the embodiment of the present invention, the weight-average molecular weight of polymkeric substance adopts Wyatt technology corporation gel permeation chromatograph to measure.(gel column: Shodex SB806+803 two root chromatogram column series connection; Eluant: 0.1M NaNO 3solution; Moving phase speed: 1.0ml/min; Injection: 20 μ l 0.5% aqueous solution; Detector: Shodex RI-71 type differential refraction detector; Standard substance: polyoxyethylene glycol GPC standard specimen (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,232).
C) in Application Example of the present invention, except special instruction, the cement adopting is little wild field 525R.P. II cement, and sand is the medium sand of fineness modulus Mx=2.6, and stone is that particle diameter is the rubble of 5~20mm continuous grading.
D) test of sand-cement slurry degree of mobilization is carried out with reference to GB/T8077-2000 standard, measures mortar divergence on sheet glass, and the mensuration of time of coagulation is carried out with reference to GB/T1346-2001 standard.
E) water-reducing rate, air content test method are carried out with reference to the relevant regulations of GB8076-2008 < < concrete admixture > >.The slump and slump-loss are carried out with reference to JC473-2001 < < concrete pump-feed agent > > relevant regulations.Concrete crushing strength is carried out with reference to the relevant regulations of GB/T50081-2002 < < standard for test methods of mechanical properties of ordinary concrete > >.
Monomer used in table 1 embodiment
Synthetic example 1
Thermometer is being housed, agitator, dropping funnel, in the glass reactor of nitrogen ingress pipe and reflux exchanger, add 300ml deionized water, use while stirring nitrogen purging reaction vessel, and be warming up to 95 ℃, then will contain 333.6g (a-1, 0.05mol), 28.8g (b-1, 0.4mol), 14.5g(c-1, 0.075mol), 16.25g (d-1, 0.125mol), 300 parts, water is mixed mutually with 3.4g thiohydracrylic acid, uniform monomer solution is made in stirring, be added dropwise to reactor, time for adding is 4h, and drip 100 parts of initiator solutions that contain 1.3g Potassium Persulphate simultaneously, the about 4h of time for adding, dropwise rear insulation reaction 2h, in reaction flask, add 30 parts of initiator solutions that contain 0.5g Potassium Persulphate again, and continuation insulation 1h, being cooled to room temperature adds alkaline solution to regulate pH value 8.2, solid content is 34.8% brown transparent liquid, molecular weight is 52, 600(PE-1).
Synthetic example 2
Thermometer is being housed, agitator, dropping funnel, in the glass reactor of nitrogen ingress pipe and reflux exchanger, add 300ml deionized water, use while stirring nitrogen purging reaction vessel, and be warming up to 75 ℃, then will contain 411.3g (a-2, 0.05mol), 51.6g (b-2, 0.6mol), 25.8g(c-2, 0.125mol), 23.2g (d-2, 0.2mol), 300 parts, water is mixed mutually with 2.0g Thiovanic acid, uniform monomer solution is made in stirring, be added dropwise to reactor, time for adding is 5h, and drip 120 parts of initiator solutions that contain 9.5g Sodium Persulfate simultaneously, the about 5h of time for adding, dropwise rear insulation reaction 2h, in reaction flask, add 40 parts of initiator solutions that contain 1.5g Sodium Persulfate again, and continuation insulation 1h, be cooled to room temperature and add alkali adjusting pH value 7.5, solid content is 39.5% brown transparent liquid, molecular weight is 68, 000(PE-2).
Synthetic example 3
Thermometer is being housed, agitator, dropping funnel, in the glass reactor of nitrogen ingress pipe and reflux exchanger, add 200ml deionized water, use while stirring nitrogen purging reaction vessel, and be warming up to 65 ℃, then will contain 445.7g (a-3, 0.04mol), 46.1g (b-1, 0.64mol), 24.9g c-2, 8.3g c-3(is 0.16mol altogether), 31.2g (d-3, 0.24mol), 200 parts, water is mixed mutually with 4.0g thiohydracrylic acid, uniform monomer solution is made in stirring, be added dropwise to reactor, time for adding is 6h, and drip 110 parts of initiator solutions that contain 11g ammonium persulphate simultaneously, the about 6h of time for adding, dropwise rear insulation reaction 2h, in reaction flask, add 40 parts of initiator solutions that contain 2.5g ammonium persulphate again, and continuation insulation 1h, be cooled to room temperature and add alkali adjusting pH value 9.0, solid content is 48.8% brown transparent liquid, molecular weight is 81, 400(PE-3).
Synthetic example 4
Thermometer is being housed, agitator, dropping funnel, in the glass reactor of nitrogen ingress pipe and reflux exchanger, add 400ml deionized water, use while stirring nitrogen purging reaction vessel, and be warming up to 80 ℃, then will contain 308.8g (a-4, 0.06mol), 34.8g (b-3, 0.3mol), 11.6g(c-1, 0.06mol), 11.6g d-2, 2.6g d-1 (0.12mol altogether), 400 parts, water is mixed mutually with 0.6g thiohydracrylic acid, uniform monomer solution is made in stirring, be added dropwise to reactor, time for adding is 2.5h, and drip 150 parts of initiator solutions that contain 2.0g Sodium Persulfate simultaneously, the about 2.5h of time for adding, dropwise rear insulation reaction 2h, in reaction flask, add 50 parts of initiator solutions that contain 0.6g Sodium Persulfate again, and continuation insulation 1h, be cooled to room temperature and add alkaline solution adjusting pH value 6.7, solid content is 27.6% brown transparent liquid, molecular weight is 43, 000(PE-4).
Synthetic example 5
Thermometer is being housed, agitator, dropping funnel, in the glass reactor of nitrogen ingress pipe and reflux exchanger, add 300ml deionized water, use while stirring nitrogen purging reaction vessel, and be warming up to 85 ℃, then will contain 267.4g a-1, 51.5g a-4 (0.05mol altogether), 28.8g b-1, 4.3g b-2 (0.45mol altogether), 20.6g(c-3, 0.1mol), 20.3g (d-2, 0.175mol), 300 parts, water is mixed mutually with 2.5g thiohydracrylic acid, uniform monomer solution is made in stirring, be added dropwise to reactor, time for adding is 4h, and drip 90 parts of initiator solutions that contain 4.5g Sodium Persulfate simultaneously, the about 4h of time for adding, dropwise rear insulation reaction 2h, in reaction flask, add 30 parts of initiator solutions that contain 1.0g Sodium Persulfate again, and continuation insulation 1h, be cooled to room temperature and add alkaline solution adjusting pH value 7.2, solid content is 34.5% brown transparent liquid, molecular weight is 35, 500(PE-5).
Comparative example 1
Thermometer is being housed, agitator, dropping funnel, in the glass reactor of nitrogen ingress pipe and reflux exchanger, add 300ml deionized water, use while stirring nitrogen purging reaction vessel, and be warming up to 95 ℃, then will contain 333.6g (a-1, 0.05mol), 28.8g (b-1, 0.4mol), 14.5g(c-1, 0.075mol), 300 parts, water is mixed mutually with 3.4g thiohydracrylic acid, uniform monomer solution is made in stirring, be added dropwise to reactor, time for adding is 4h, and drip 100 parts of initiator solutions that contain 1.3g Potassium Persulphate simultaneously, the about 4h of time for adding, dropwise rear insulation reaction 2h, in reaction flask, add 30 parts of initiator solutions that contain 0.5g Potassium Persulphate again, and continuation insulation 1h, being cooled to room temperature adds NaOH solution to regulate pH value 8.2, solid content is 32.5% brown transparent liquid, molecular weight is 45, 600 (CP-1).
Comparative example 2
Thermometer is being housed, agitator, dropping funnel, in the glass reactor of nitrogen ingress pipe and reflux exchanger, add 300ml deionized water, use while stirring nitrogen purging reaction vessel, and be warming up to 95 ℃, then will contain 333.6g (a-1, 0.05mol), 28.8g (b-1, 0.4mol), 16.25g (d-1, 0.125mol), 300 parts, water is mixed mutually with 3.4g thiohydracrylic acid, uniform monomer solution is made in stirring, be added dropwise to reactor, time for adding is 4h, and drip 100 parts of initiator solutions that contain 1.3g Potassium Persulphate simultaneously, the about 4h of time for adding, dropwise rear insulation reaction 2h, in reaction flask, add 30 parts of initiator solutions that contain 0.5g Potassium Persulphate again, and continuation insulation 1h, being cooled to room temperature adds alkaline solution to regulate pH value is 8.2, solid content is 33.2% brown transparent liquid, molecular weight is 48, 000 (CP-2).
Comparative example 3
Thermometer is being housed, agitator, dropping funnel, in the glass reactor of nitrogen ingress pipe and reflux exchanger, add 100ml deionized water, use while stirring nitrogen purging reaction vessel, and be warming up to 95 ℃, then will contain 104g (a-5, 0.05mol), 28.8g (b-1, 0.4mol), 14.5g(c-1, 0.075mol), 16.25g (d-1, 0.125mol), 200 parts, water is mixed mutually with 3.4g thiohydracrylic acid, uniform monomer solution is made in stirring, be added dropwise to reactor, time for adding is 4h, and drip 100 parts of initiator solutions that contain 1.3g Potassium Persulphate simultaneously, the about 4h of time for adding, dropwise rear insulation reaction 2h, in reaction flask, add 30 parts of initiator solutions that contain 0.5g Potassium Persulphate again, and continuation insulation 1h, being cooled to room temperature adds alkali to regulate pH value is 8.2, solid content is 27.5% brown transparent liquid, molecular weight is 31, 000 (CP-3).
Table 2
Application examples 1
Adopt little wild field 525R.P. II cement, sand is standard sand, proportioning cement 450g, standard sand 1350g, water 180g.In table 3, listed the impact of various multipolymers on degree of mobilization hold facility, time of coagulation and the cement mortar strength of sand-cement slurry, from table 3, the degree of mobilization hold facility that has not only improved mortar of polycarboxylic acid Concrete superplastizer of the present invention, promote cement early hydration simultaneously, improved the early mechanics characteristics of cement-based material.By contrast, short chain polymer is as CP-3 and not add the early strength of polymkeric substance CP-2 of cationic monomer on the low side, and does not use the guarantor of the CP-1 of the hydroxyl esters monomer ability of collapsing poor, is difficult to meet the requirement of concrete pumping.
Table 3
Application examples 2
Table 4 has been listed various multipolymers to concrete water-reducing ratio, the impact of air content and ultimate compression strength, test-results shows, polycarboxylic acid Concrete superplastizer of the present invention has excellent dispersing property, and can improve significantly concrete early strength, according to test-results, 3d ultimate compression strength relative datum improves 160~200%, the ultimate compression strength of 28d can increase by 50~65%, under low temperature environment, reinforced effects is remarkable simultaneously, under 5 ℃ of low temperature environments, 1d ultimate compression strength improves 270~350%, visible, the concrete ultimate compression strength of mixing polycarboxylic acid Concrete superplastizer of the present invention not only has quite high early strength, its later strength is also improved largely, and constantly steady growth.
Table 4
Application examples 3
The production process of prefabricated components has proposed the requirement of pumping, requires in the situation that existing pile tube proportioning is substantially constant, to realize the production of large chutable concrete, adopts the early strength of the vapor cure system raising member of comparative maturity simultaneously.Test proportioning cement: water: sand: stone=440:135:646:1100.Require concrete to go out the machine slump and be greater than 180mm, expansion ratio is greater than 450mm, and serviceability at least will keep 30min.Steam-cured intensity refers to the 80-90 ℃ of demoulding strength after maintenance 4h, and pressing steaming intensity is under 1MPa pressure, the ultimate compression strength of maintenance 4h.Test-results is in Table 5, polycarboxylic acid Concrete superplastizer of the present invention can significantly improve concrete slump hold facility, can meet the requirement of pumping, and can improve vapor cure and press the ultimate compression strength of steaming Under Concrete, in CP-1, there is no hydroxy ester class comonomer, make the concrete guarantor ability wretched insufficiency that collapses, in CP-2, do not introduce cation group, concrete ultimate compression strength obviously reduces, and CP-3 adopts shorter side chain copolyether, concrete steam-cured and press and steam intensity all far below the multipolymer that adopts long side chain.
Table 5

Claims (11)

1. a concrete prefabricated element superplasticizer, it is characterized in that adding basic cpd neutralization and be prepared from after free radicals copolymerization reaction occurs in aqueous medium for monomer a, monomer b, monomer c and monomer d, monomer a: monomer b: monomer c: the mol ratio of monomer d is 1.0:5.0~16.0:1.0~4.0:2.0~6.0;
Above-mentioned monomer is general formula (1) expression for a:
R in general formula (1) 1for H or methyl, R 2it is the alkyl of H or 1~4 carbon atom; AO is the oxyalkylene group of 2-4 carbon atom or the mixture of two or more this oxyalkylene group arbitrary proportion; N is the average addition mole number of AO, is 100~300 integer; (AO) n is homopolymerization, random copolymerization, diblock or multiblock structure;
Above-mentioned monomer is general formula (2) expression for b:
R in general formula (2) 3h or methyl, R 4be H hydrogen atom or m is H, alkalimetal ion, ammonium ion or organic amine group;
Monomer c is cationic monomer, adopts by the represented material of general formula (3):
Wherein: R 5for H or methyl, R 6, R 7, R 8all independently represent H or C 1~C 10alkyl;
X-is F, Cl, Br or I;
A is O or NH;
P is 1~3 positive integer;
Monomer d is hydroxyl esters monomer, adopts by the represented material of general formula (4):
R in general formula (4) 1same general formula (I), R 9be expressed as-(CH 2) xoH, the positive integer of x=2~10.
2. concrete prefabricated element superplasticizer as claimed in claim 1, while it is characterized in that monomer a that general formula (1) represents is polyalkylene glycol mono (methyl) acrylate monomer, be by alkoxyl group polyalkylene glycol and (methyl) vinylformic acid or with the esterification synthetics of (methyl) acrylic anhydride; Or be the affixture of (methyl) acrylic acid hydroxy alkyl ester and oxyethane, propylene oxide, at least one material of butylene oxide ring, these monomers are used separately or use with the form of mixtures of arbitrary proportion with two or more compositions.
3. concrete prefabricated element superplasticizer as claimed in claim 1, it is characterized in that the monomer b that general formula (2) represents is unsaturated carboxylic acid, be selected from vinylformic acid, methacrylic acid, toxilic acid, or the monovalent metal salt of these unsaturated carboxylic acids, divalent metal salt, ammonium salt or organic amine salt, these monomers are used separately or use with the form of mixtures of two or more arbitrary proportions.
4. concrete prefabricated element superplasticizer as claimed in claim 1, it is characterized in that the cationic monomer c that general formula (3) represents is selected from MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryloxyethyldimethyl benzyl ammonium chloride, methacryloxypropyl trimethyl ammonium chloride, methacryloxypropyl dimethyl benzyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, acrylyl oxy-ethyl dimethyl benzyl ammonium chloride, acrylamido oxypropyl trimethyl ammonium chloride, acrylamido propyl-dimethyl benzyl ammonium chloride, methacryloyl amido oxypropyl trimethyl ammonium chloride or methacryloyl amido propyl-dimethyl benzyl ammonium chloride, these monomers are used separately or use with the form of mixtures of two or more arbitrary proportions.
5. concrete prefabricated element superplasticizer as claimed in claim 1, it is characterized in that the hydroxyl esters monomer d that general formula (4) represents is (methyl) acrylic acid hydroxy alkyl ester, be selected from Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate or Rocryl 410, these monomers are used separately or use with the form of mixtures of two or more arbitrary proportions.
6. concrete prefabricated element superplasticizer as claimed in claim 1, it is characterized in that adopting free radical water soluble starter to cause free radicals copolymerization reaction, initiator is selected from water-soluble ammonium persulphate, Potassium Persulphate, Sodium Persulfate or hydrogen peroxide, or the mixture of two or more arbitrary proportions wherein, its consumption is 1.0~6.0% of a, b, c, tetra-kinds of total moles monomer of d.
7. concrete prefabricated element superplasticizer as claimed in claim 1, it is characterized in that utilizing polymerizable chain transfer agents to select to control the molecular weight of the multipolymer that copolyreaction forms, the consumption of polymerizable chain transfer agents in polymerization process is 1.0~5.0% of total mole of a, b, c, tetra-kinds of monomer of d.
8. concrete prefabricated element superplasticizer as claimed in claim 1, while it is characterized in that copolyreaction, monomer total mass concentration is controlled at 25~50%, and the reaction times is controlled at 5~10 hours.
9. concrete prefabricated element superplasticizer as claimed in claim 1, it is characterized in that monomer and initiator solution take the mode separately simultaneously dripping, monomer mixed solution and initiator time for adding are controlled at 2.0~6.0 hours, and copolyreaction is carried out at 60~100 ℃.
10. concrete prefabricated element superplasticizer as claimed in claim 1, after it is characterized in that copolyreaction finishes, to adding in reaction product basic cpd to adjust pH value, be 6.0~10.0, oxyhydroxide or its carbonate of described basic cpd selection ammoniacal liquor, ammonium hydrogencarbonate, organic amine, monovalent metal or divalent metal.
11. concrete prefabricated element superplasticizers as claimed in claim 1, is characterized in that its weight-average molecular weight is at 20,000-100,000.
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