CN102910855A - Super plasticizer for precast concrete component - Google Patents
Super plasticizer for precast concrete component Download PDFInfo
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- CN102910855A CN102910855A CN2012103967366A CN201210396736A CN102910855A CN 102910855 A CN102910855 A CN 102910855A CN 2012103967366 A CN2012103967366 A CN 2012103967366A CN 201210396736 A CN201210396736 A CN 201210396736A CN 102910855 A CN102910855 A CN 102910855A
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- superplasticizer
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/32—Superplasticisers
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
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 under the prerequisite that does not delay cement setting time, not only can significantly improve early age strength of concrete, and have 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 the 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, for example be used for the key part concrete shield pipe-plate that city underground and river-crossing tunnel are built, diameter reaches 4 meters senior engineer and presses heavy caliber steel cylinder concrete water transmission pipe (PCCP), strength grade reaches above high-strength prestressed (PHC) pile tube of 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 embodies 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 has been listed in one of 10 new technologies of construction industry by house and town and country construction section because its green, environmental protection construction mode favor gradually.Can predict, the coming years, the concrete prefabricated element field will welcome the development upsurge of a new round.Although precast concrete is compared the obvious advantage that demonstrated at aspects such as the stdn of producing, construction greenizations with onsite concrete, also is 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 change cement composition or fineness, adds the methods such as early strong admixture and thermal curing system, but these technology all more or less exist different defectives at present.1) based on strong technology morning of cement composition or fineness regulation and control: in order to improve early age strength of concrete, manufacturers has to adopt superfine cement and changes cement minerals and forms at present.The fineness of cement is thinner, and its early hydration speed is faster, and early strength is higher, but the concrete construction poor performance, shrink large, easy to crack.The Beijing-Tianjin Line for Passenger Transportation once adopted the high grade superfine cement, and (specific surface area reaches 600m
2/ kg) Germany technology scheme is produced the plate-type slag-free orbit plate, and there is the defective that workability is poor, production efficiency is low, cost is high in this technology, 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 the early water heat-transmission is high, early stage contract with dry rate is large, and later strength and performance present decline; 2) based on the strong technology morning that adds hardening accelerator: early strong admixture has had for many years applicating history 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 the 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 causes the serious slow setting of concrete and concrete strength to descend easily, and its fancy price has affected its application at Concrete Industry; 3) strong technology morning of regulating and control based on maintaining process: extensively adopt thermal curing technique to improve early strength, the quickening form cycling rate during prefabricated components are produced.The prefabricated components such as the subway segment more than the C50, concrete prefabricated beam, concrete pipe mainly adopt the vapor cure under 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 maintaining process that mainly adopt normal pressure to be combined with autoclave curing, this technique mesohigh vapor cure occupies more than 90% of total maintenance energy consumption, every production 1M3PHC pile tube reaches 40kg for the standard coal that maintenance consumes, and discharges simultaneously carbonic acid gas 30kg.The steamed concrete member is the later stage mechanical properties decrease not only, and the weather resistance of member reduces.4) based on super morning of the strong technology of graft copolymer molecular structure.Current research confirms the graft copolymer admixture except can giving the maintenance of the high initial flow of fresh concrete and high workability, can also adopt modern molecule tailoring technique to give maturing super early strong, the low contraction, even satisfying 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) technological approaches of employing 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 the 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 power consumption height are unfavorable for concrete durability.These tradition early strong technology can not effectively solve early strong and high durable contradiction, can not satisfy 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 mobile 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 described those shortcomings of background technology, and production technology is relatively simple and have water-reducing rate height, an early stage strong concrete prefabricated element superplasticizer of good, the mobile hold facility of reinforced effects.
The applicant finds that after deliberation the 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 also accelerated the aquation of cement because its strong space steric effect causes the dispersiveness of multipolymer excellence, is conducive to the raising of early age strength of concrete.
The applicant is surprised to find after deliberation, by introducing cation group at main chain, improves the multipolymer absorption behavior, not only can accelerate the cement early hydration, but also can significantly promote the concrete flowability hold facility.
The applicant also finds after deliberation, by introducing the hydroxy ester class comonomer that cement strong basicity environment is had response at main chain, can further promote the mobile hold facility of fresh concrete.
Based on above-mentioned research, the basic cpd neutralization occurs to add behind the free radicals copolymerization reaction by monomer a, monomer b, monomer c and monomer d and is prepared from carboxyl acid graft copolymer superplasticiser of the present invention in aqueous medium, wherein monomer a: monomer b: monomer c: mol ratio=1.0:5.0 of monomer d ~ 16.0:1.0 ~ 4.0:2.0 ~ 6.0;
Above-mentioned monomer a represents with general formula (1):
R in the general formula (1)
1Be 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 b represents with general formula (2):
R in the 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
5Be 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 the hydroxyl esters monomer, adopts by the represented material of general formula (4):
R in the 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 of formula of of the present invention (1) expression 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 a material in (methyl) acrylic acid hydroxy alkyl ester and oxyethane, propylene oxide, the butylene oxide ring, these monomers use 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, perhaps can prepare according to the method described in disclosed document or the patent.
The monomer b of formula of of the present invention (2) expression 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 use 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 of formula of of the present invention (3) expression listed is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryloxyethyldimethyl benzyl ammonium chloride, the methacryloxypropyl trimethyl ammonium chloride, the methacryloxypropyl dimethyl benzyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, the 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 use separately or use with the form of mixtures of two or more composition.
The monomer d of formula of of the present invention (4) expression is (methyl) acrylic acid hydroxy alkyl ester, comprise Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate or Rocryl 410, these monomers use separately or use with the form of mixtures of two or more composition.
The monomer a of formula of of the present invention (1) expression is copolymerized in the 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 excessively low, the multipolymer early strength of then producing is lower.If ratio is too high, then synthetic multipolymer dissemination a little less than.N is the average addition mole number of AO in the general formula (1), and it is 100～300 integer, if n is too little, then synthetic multipolymer early strength is low; If n is too large, then 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 excessively low, and synthetic multipolymer can not fully be adsorbed onto on the cement particle, therefore can not bring into play dissemination.If too high levels, the multipolymer early strength of then producing 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, also improved the behavior of cement early hydration.Monomer c content is excessively low, and then the amphoteric character of synthetic multipolymer is not obvious, can not fully be adsorbed onto on the cement granules, can not obviously improve the early hydration of cement and promote mobile hold facility.If too high levels, the multipolymer dispersing property variation of then 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 the main chain, thereby promotes the mobile hold facility of multipolymer.Monomer d content is excessively low, does not then have the effect of dynamic regulation multipolymer absorption behavior, and the mobile hold facility of multipolymer reduces.If too high levels, the early stage dispersing property of multipolymer and the early age strength of concrete then produced also can variation.
Free radicals copolymerization reaction itself is unimportant, and it can according to usual method, carry out in not difficult situation with known radical initiator.Be suitable for water soluble starter of the present invention and be conventional free radical water soluble starter, the water-soluble ammonium persulphate of optional usefulness, Potassium Persulphate, Sodium Persulfate or hydrogen peroxide or the mixture of two or more arbitrary proportions wherein.Join whole initiators in the reaction mixture account for add 1.0～6.0% of monomer (a+b+c+d) total mole number.The art those skilled in the art know that generally the actual add-on of initiator has certain relation with the initiator type that adopts in the copolyreaction.
The molecular weight of multipolymer can utilize polymerizable chain transfer agents to select control, such 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 the 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.The mode that monomer and initiator solution are taked separately to drip is simultaneously controlled 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.The interpolymerization temperature is carried out under 60～100 ℃ fortunately, and the decomposition temperature of the initiator that it is main and used is relevant.
After copolyreaction finished, adding basic cpd in the reaction product, 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.The pH value is crossed low and too high, and then 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 opposite addition surpasses 0.4%, then excessive interpolation proof only is waste economically, because do not bring the corresponding growth on the effect.
Certainly, Concrete superplastizer of the present invention also can mix mutually with at least a aminosulfonic water-reducing agent known in the state of the art, Lignins ordinary water-reducing agent and the existing poly carboxylic acid series super plasticizer of being selected from.
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 is compared 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 the 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 satisfy the requirement of pumping line pile concrete, saves a large amount of human costs;
(3) prepared prefabricated components are compared with conventional Concrete superplastizer with superplasticizer among the present invention, 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 the template turnover, improve construction speed.
Embodiment
Following examples more detailed description the method according to this invention prepare the process of polymerisate, and these embodiment provide in the mode of explanation, its purpose is to allow the personage who is familiar with technique can understand content of the present invention and according to this enforcement, but these embodiment never limit the scope of the invention.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.If do not stipulate in addition that " 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 the Concrete superplastizer brief note.
A) in the invention process, the described monomer a of table 1, monomer b, c and monomer d are commercially produced product, can buy on the market.
B) in the embodiment of the 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 columns 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 the Application Example of the present invention, except specifying that the cement that adopts is little wild field 525R.P. II cement, 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 the GB/T8077-2000 standard, measures the mortar divergence at sheet glass, and the mensuration of time of coagulation is carried out with reference to the 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 ".
Used monomer among 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 the 300ml deionized water, use while stirring the 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 in water is mixed mutually with the 3.4g thiohydracrylic acid, stirs and makes uniform monomer solution, and it is added dropwise to reactor, time for adding is 4h, and dripping simultaneously 100 parts of initiator solutions that contain the 1.3g Potassium Persulphate, the about 4h of time for adding dropwises rear insulation reaction 2h, in reaction flask, add 30 parts of initiator solutions that contain the 0.5g Potassium Persulphate again, and continue insulation 1h, and being cooled to room temperature and adding alkaline solution adjusting 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 the 300ml deionized water, use while stirring the 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 in water is mixed mutually with the 2.0g Thiovanic acid, stirs and makes uniform monomer solution, and it is added dropwise to reactor, time for adding is 5h, and dripping simultaneously 120 parts of initiator solutions that contain the 9.5g Sodium Persulfate, the about 5h of time for adding dropwises rear insulation reaction 2h, in reaction flask, add 40 parts of initiator solutions that contain the 1.5g Sodium Persulfate again, and continue insulation 1h, and being cooled to room temperature and adding 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 the 200ml deionized water, use while stirring the 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 in water is mixed mutually with the 4.0g thiohydracrylic acid, uniform monomer solution is made in stirring, it is added dropwise to reactor, and time for adding is 6h, and drips simultaneously 110 parts of initiator solutions that contain the 11g ammonium persulphate, the about 6h of time for adding, dropwise rear insulation reaction 2h, in reaction flask, add 40 parts of initiator solutions that contain the 2.5g ammonium persulphate again, and continue insulation 1h, be cooled to room temperature and add alkali adjusting pH value 9.0, solid content is 48.8% brown transparent liquid, and 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 the 400ml deionized water, use while stirring the 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 (altogether 0.12mol), 400 parts in water is mixed mutually with the 0.6g thiohydracrylic acid, uniform monomer solution is made in stirring, it is added dropwise to reactor, and time for adding is 2.5h, and drips simultaneously 150 parts of initiator solutions that contain the 2.0g Sodium Persulfate, the about 2.5h of time for adding, dropwise rear insulation reaction 2h, in reaction flask, add 50 parts of initiator solutions that contain the 0.6g Sodium Persulfate again, and continue insulation 1h, be cooled to room temperature and add alkaline solution adjusting pH value 6.7, solid content is 27.6% brown transparent liquid, and 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 the 300ml deionized water, use while stirring the nitrogen purging reaction vessel, and be warming up to 85 ℃, then will contain 267.4g a-1,51.5g a-4 (altogether 0.05mol), 28.8g b-1,4.3g b-2 (altogether 0.45mol), 20.6g(c-3,0.1mol), 20.3g (d-2,0.175mol), 300 parts in water is mixed mutually with the 2.5g thiohydracrylic acid, stirs and makes uniform monomer solution, and it is added dropwise to reactor, time for adding is 4h, and dripping simultaneously 90 parts of initiator solutions that contain the 4.5g Sodium Persulfate, the about 4h of time for adding dropwises rear insulation reaction 2h, in reaction flask, add 30 parts of initiator solutions that contain the 1.0g Sodium Persulfate again, and continue insulation 1h, and being cooled to room temperature and adding 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 the 300ml deionized water, use while stirring the 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 in water is mixed mutually with the 3.4g thiohydracrylic acid, uniform monomer solution is made in stirring, it is added dropwise to reactor, and time for adding is 4h, and drips simultaneously 100 parts of initiator solutions that contain the 1.3g Potassium Persulphate, the about 4h of time for adding, dropwise rear insulation reaction 2h, in reaction flask, add 30 parts of initiator solutions that contain the 0.5g Potassium Persulphate again, and continue insulation 1h, be cooled to room temperature and add NaOH solution adjusting pH value 8.2, solid content is 32.5% brown transparent liquid, and 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 the 300ml deionized water, use while stirring the 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 in water is mixed mutually with the 3.4g thiohydracrylic acid, uniform monomer solution is made in stirring, it is added dropwise to reactor, and time for adding is 4h, and drips simultaneously 100 parts of initiator solutions that contain the 1.3g Potassium Persulphate, the about 4h of time for adding, dropwise rear insulation reaction 2h, in reaction flask, add 30 parts of initiator solutions that contain the 0.5g Potassium Persulphate again, and continue insulation 1h, being cooled to room temperature adds alkaline solution to regulate the pH value is 8.2, solid content is 33.2% brown transparent liquid, and 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 the 100ml deionized water, use while stirring the 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 in water is mixed mutually with the 3.4g thiohydracrylic acid, stirs and makes uniform monomer solution, and it is added dropwise to reactor, time for adding is 4h, and dripping simultaneously 100 parts of initiator solutions that contain the 1.3g Potassium Persulphate, the about 4h of time for adding dropwises rear insulation reaction 2h, in reaction flask, add 30 parts of initiator solutions that contain the 0.5g Potassium Persulphate again, and continue insulation 1h, and being cooled to room temperature and adding alkali to regulate the pH value be 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.Various multipolymers have been listed in the table 3 to the impact of degree of mobilization hold facility, time of coagulation and the cement mortar strength of sand-cement slurry, by as seen 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 simultaneously the cement early hydration, improved the early mechanics characteristics of cement-based material.By contrast, short chain polymer such as CP-3 and not add the early strength of polymkeric substance CP-2 of cationic monomer on the low side, and do not use the guarantor of the CP-1 of the hydroxyl esters monomer ability of collapsing poor, be difficult to satisfy 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%, reinforced effects is remarkable under low temperature environment simultaneously, under 5 ℃ of low temperature environments, 1d ultimate compression strength improves 270～350%, as seen, the concrete ultimate compression strength of mixing polycarboxylic acid Concrete superplastizer of the present invention not only has quite high early strength, and its later strength also is 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 production that has the large chutable concrete of realization in the substantially constant situation of pile tube proportioning now, adopts simultaneously the early strength of the vapor cure system raising member of comparative maturity.Test proportioning cement: water: sand: stone=440:135:646:1100.Require concrete to go out the machine slump greater than 180mm, expansion ratio is greater than 450mm, and serviceability will keep 30min at least.Steam-cured intensity refers to the 80-90 ℃ of demoulding strength behind the maintenance 4h, and pressing steaming intensity is under the 1MPa pressure, the ultimate compression strength of maintenance 4h.Test-results sees Table 5, polycarboxylic acid Concrete superplastizer of the present invention can significantly improve concrete slump hold facility, can satisfy the requirement of pumping, and can improve vapor cure and press the ultimate compression strength of steaming Under Concrete, there is not hydroxy ester class comonomer among the CP-1, the ability wretched insufficiency so that concrete guarantor is collapsed, do not introduce cation group among the CP-2, concrete ultimate compression strength obviously reduces, and CP-3 adopts shorter side chain copolyether, and is concrete steam-cured and press and steam intensity all far below the multipolymer that adopts long side chain.
Table 5
Claims (11)
1. concrete prefabricated element superplasticizer, it is characterized in that by monomer a, monomer b, monomer c and monomer d the basic cpd neutralization occuring in aqueous medium to add behind the free radicals copolymerization reaction is prepared from 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 a represents with general formula (1):
R in the general formula (1)
1Be 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 b represents with general formula (2):
R in the general formula (2)
3H or methyl, R
4Be the H hydrogen atom 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
5Be 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 the hydroxyl esters monomer, adopts by the represented material of general formula (4):
R in the 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, when the monomer a that it is characterized in that general formula (1) expression 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 a material of butylene oxide ring, these monomers use 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, the monomer b that it is characterized in that general formula (2) expression 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 use separately or use with the form of mixtures of two or more arbitrary proportions.
4. concrete prefabricated element superplasticizer as claimed in claim 1, the cationic monomer c that it is characterized in that general formula (3) expression is selected from MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryloxyethyldimethyl benzyl ammonium chloride, the methacryloxypropyl trimethyl ammonium chloride, the methacryloxypropyl dimethyl benzyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, the 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 use separately or use with the form of mixtures of two or more arbitrary proportions.
5. concrete prefabricated element superplasticizer as claimed in claim 1, the hydroxyl esters monomer d that it is characterized in that general formula (4) expression is (methyl) acrylic acid hydroxy alkyl ester, be selected from Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate or Rocryl 410, these monomers use 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 the 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, four 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 the molecular weight of the multipolymer of control copolyreaction formation, the consumption of polymerizable chain transfer agents in polymerization process is 1.0～5.0% of a, b, the total mole of four kinds of monomers of c, d.
8. concrete prefabricated element superplasticizer as claimed in claim 1, the monomer total mass concentration is controlled at 25～50% when it is characterized in that copolyreaction, 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 that separately drips simultaneously, monomer mixed solution and initiator time for adding are controlled at 2.0～6.0 hours, and copolyreaction is carried out under 60～100 ℃.
10. concrete prefabricated element superplasticizer as claimed in claim 1, after it is characterized in that copolyreaction finishes, adding basic cpd in the reaction product, 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 superplasticizer as claimed in claim 1 is characterized in that its weight-average molecular weight at 20,000-100,000.
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| PCT/CN2013/073683 WO2014059765A1 (en) | 2012-10-18 | 2013-04-03 | Super plasticizer for precast concrete component |
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| WO2014059765A1 (en) * | 2012-10-18 | 2014-04-24 | 江苏博特新材料有限公司 | Super plasticizer for precast concrete component |
| CN103772623A (en) * | 2013-12-30 | 2014-05-07 | 大连市铭源全科技开发有限公司 | Anti-sludge concrete water reducer and preparation method thereof |
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Address after: No.6 shuiyougang, Gulou District, Nanjing City, Jiangsu Province 210013 Patentee after: JIANGSU SUBOTE NEW MATERIALS Co.,Ltd. Patentee after: TAIZHOU JIANGYAN BOTE NEW MATERIAL Co.,Ltd. Address before: 211103 No. 69 Liquan Road, Jiangning District, Nanjing City, Jiangsu Province Patentee before: JIANGSU SUBOTE NEW MATERIALS Co.,Ltd. Patentee before: TAIZHOU JIANGYAN BOTE NEW MATERIAL Co.,Ltd. |
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