CN103965416A - Early-strength polycarboxylate water reducing agent for component and preparation method for early-strength polycarboxylate water reducing agent - Google Patents
Early-strength polycarboxylate water reducing agent for component and preparation method for early-strength polycarboxylate water reducing agent Download PDFInfo
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Abstract
The invention discloses an early-strength polycarboxylate water reducing agent for a component and a preparation method for the early-strength polycarboxylate water reducing agent, and belongs to the field of water reducing agent preparation. The water reducing agent is formed by polymerization of the following ingredients in percentage by weight: 80-85% of methyl alkene butyl polyoxyethylene polypropylene oxide monomer with the molecular weight more than 2400, 10-15% of unsaturated monocarboxylic acid and derivative monomer thereof and 0.5-5% of unsaturated alkenyl sulfoacid and sodium salt thereof; the preparation method comprises the following steps: under the temperature condition of 20-40 DEG C, all ingredients are enabled to be subjected to polymerization reaction in an aqueous solution by adopting a redox initiation system, after polymerization reaction is performed, neutralization is performed through a neutralizing agent, so that the polymer with low air entraining amount and good dispersibility is obtained; the early-strength performance of the polycarboxylate water reducing agent is reinforced with the increasing of the macromonomer molecular weight; the using requirements of early strength or super early strength of the component are met.
Description
Technical field
The present invention relates to the preparation field of cement water reducing agent, relate in particular to a kind of prefabricated components high-early strength type polycarboxylic acids dehydragent and preparation method thereof.
Background technology
The advantages such as precast concrete technology has good product quality, and construction is fast, and place is clean, are applicable to overhead large-span prestressed U-shaped bridge and prestressed high-strength concrete pile.Along with the development of construction industry, 21 century is constantly advocated resources conservation and environmental friendliness, and the precast concrete of C40～C100 is often mixed with a large amount of mineral admixtures, and the building engineering field of having stable political situation in city application is more and more wider, development is more and more faster.It is naphthalene water reducer that general early strength concrete adopts traditional additive product, aliphatic water reducing agent, aminosulfonic water-reducing agent and melamine system water reducer, be applied to the production of high-performance prefabricated concrete members and have great number of issues, wherein most importantly there is delayed coagulation in various degree and the problem of bad adaptability, as 1 day ultimate compression strength under at normal temperature condition can only reach 20% left and right of design strength, within 3 days, can reach 40～50%, early strength is lower for large volume mineral admixture concrete, within 7 days, intensity just can reach 50% left and right, and lower than 5 DEG C in the situation that, early age strength of concrete may be lower.
Adopt early-strength type or the ultra high early strength poly-carboxylic based water reducer technology of superelevation water-reducing rate, can improve finely-powdered minerals Additive consumption, reduce ordinary Portland cement, realize ultralow water-binder ratio, also can make concrete obtain in early days high strength, stable long-term strength increases, the super early strength concrete of C60～C80 that can prepare under normal temperature condition, 1 day intensity can reach 50% left and right of design strength grade, even under the cold condition of 0 DEG C of left and right and ensureing that concrete has under good serviceability precondition, also can shorten the quiet of member stops and curing time, meet the requirement of the rapid demoulding time of coagulation, concrete member there will not be honeycomb, pitted skin phenomenon, can meet specification of quality completely.Therefore, can meet concrete slump retaining, fast solidifying, the special early-strength type water reducer of strong and fast demoulding early in the urgent need to a kind of, the gordian technique that the special ultra early-strength poly carboxylic acid series water reducer of concrete members is precast concrete technology is also the developing direction of member concrete admixture.
As everyone knows, poly carboxylic acid series water reducer has that water-reducing rate is high, concrete workability good and little loss of slump, chlorion and alkali content are low, concrete shrinkage is little and production and application process environmentally friendly, to human body, without harm, but at present early-strength type or ultra early-strength poly carboxylic acid series water reducer member are actually rare on market at home with admixture.Composite can the reaching of domestic common employing inorganic salt or organic hardening accelerator and poly carboxylic acid series water reducer improved concrete effect, but 28 days intensity often increases seldom even retraction, within 1 day, does not substantially exist with the i.e. super early strength function of interior intensity and improve.Chinese invention patent CN102786248A discloses a kind of " synthetic method of high-performance prefabricated member polycarboxylic acid series high efficiency water reducing agent ", use the minor comonomers such as the large monomer of methacrylic polyoxyethylene polyoxypropylene and vinylformic acid, 2-acrylamide-2-methylpro panesulfonic acid temperature in 60～65 DEG C of water solution systems synthetic, strong DeGrain morning of product; CN101205128A discloses " a kind of high-early strength type polycarboxylic acids dehydragent formula and manufacture method " and has adopted the minor comonomers such as the large monomer of allyl polyethenoxy of the polymerization degree 37 and the polymerization degree 54 and vinylformic acid, acrylamide, methylpropene sodium sulfonate above synthetic at 55 DEG C, large monomer polymerization degree is low, slow setting is serious, without super early potent fruit; CN101085701A discloses a kind of ultra early-strength poly carboxylic acid series water reducer preparation method, owing to adopting vinylformic acid and methoxy poly (ethylene glycol) 4000 esterifications to obtain the large monomer of macro molecules amount, esterification reaction temperature high (more than 120 DEG C), molecular weight makes too greatly by product many, the lower effective constituent that makes of esterification yield reduces, and 60～100 DEG C of excess Temperature quality of second step synthesis reaction temperature are wayward; CN101066853A has announced " a kind of polyethers ultra early and strong type concrete superplasticizer ", also adopted molecular weight to exceed 4000 the large monomer of methacrylic polyoxyethylene polyoxypropylene, synthesize a kind of poly carboxylic acid series water reducer with the high diminishing ultra early-strength of low bubble with vinylformic acid and maleic anhydride polyoxyethylene polyoxypropylene ester etc., the synthesis technique complexity of maleic anhydride polyoxyethylene polyoxypropylene ester self, this material adds and causes water-reducing rate reduction, though product has super early potent fruit, need to improve volume because water-reducing rate is too low.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of member high-early strength type polycarboxylic acids dehydragent and preparation method thereof, its amount of air entrainment is low, good dispersity, can be used for having the strong concrete member requiring 1 day morning strong with interior super morning or 1～3 day, environmentally friendly, harmless to the person, thus the early strong and bad problem of minimizing property of existing poly carboxylic acid series water reducer solved.
For solving the problems of the technologies described above, the invention provides a kind of member high-early strength type polycarboxylic acids dehydragent, this water reducer is polymerized by following each component by weight percentage, and each component comprises:
Molecular weight is not less than 2400 methyl alkene butyl polyoxyethylene polyoxypropylene monomer 80～85%;
Unsaturated monocarboxylic acid and derivatives monomer 10～15% thereof;
Unsaturated thiazolinyl sulfonic acid and sodium salt 0.5～5% thereof.
The embodiment of the present invention also provides the preparation method of a kind of member high-early strength type polycarboxylic acids dehydragent, comprising:
Get each component by formula of the present invention;
Under 20～40 DEG C of temperature condition, adopt redox initiation system to make each component in the aqueous solution, carry out polyreaction each component, after polyreaction through in neutralizing agent and after the polymkeric substance that obtains be member early-strength type or ultra early-strength poly carboxylic acid series water reducer.
Beneficial effect of the present invention is: by molecular weight being not less than to 2400 methyl alkene butyl polyoxyethylene polyoxypropylene monomer, unsaturated monocarboxylic acid and derivatives monomer thereof and unsaturated thiazolinyl sulfonic acid and sodium salt polymerization under redox initiator system thereof form a kind of member early-strength type or ultra early-strength poly carboxylic acid series water reducer, this water reducer molecule is due to the long side chain of the polyoxyalkylenes with intensive, be conducive to the dispersion of cement granules, increase hydrated cementitious speed in concrete, and with 10～15% carboxylic acid group, amide group, sulfonic group works, stablized in early days the absorption of cement and admixture at hydrated cementitious, can control the concrete slump loss at initial stage, after cement starts to condense, hydrated cementitious speed is strengthened.This water reducer early epistasis can be enhanced with the molecular weight increase of methyl alkene butyl polyoxyethylene polyoxypropylene, adopt the methyl alkene butyl polyoxyethylene polyoxypropylene monomer of molecular weight 2400 to make concrete there is potent fruit morning of 1～3 day, and adopt the more than 4000 methyl alkene butyl polyoxyethylene polyoxypropylene monomer of molecular weight to make concrete there is 1 day with interior super morning of potent fruit, this products production and environment for use close friend, have that amount of air entrainment is low, good dispersity, to the harmless advantage of the person.
Embodiment
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on embodiments of the invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to protection scope of the present invention.
The embodiment of the present invention provides a kind of member high-early strength type polycarboxylic acids dehydragent, and this water reducer is polymerized by following each component by weight percentage, and each component comprises:
Molecular weight is not less than 2400 methyl alkene butyl polyoxyethylene polyoxypropylene monomer 80～85%;
Unsaturated monocarboxylic acid and derivatives monomer 10～15% thereof;
Unsaturated thiazolinyl sulfonic acid and sodium salt 0.5～5% thereof.
In above-mentioned water reducer, molecular weight is not less than 2400 methyl alkene butyl polyoxyethylene polyoxypropylene monomer by following general formula one expression:
General formula one
The average addition mole number of group that in described general formula one, m is oxyethylene group, arbitrary number that m is 50～200; N is the average addition mole number of the group of oxypropylene group, arbitrary number that n is 1～5.
Preferably, methyl alkene butyl polyoxyethylene polyoxypropylene monomer adopts the methyl alkene butyl polyoxyethylene polyoxypropylene monomer of molecular weight more than 2400～4000, can obtain high-early strength type polycarboxylic acids dehydragent.
If methyl alkene butyl polyoxyethylene polyoxypropylene monomer adopts the methyl alkene butyl polyoxyethylene polyoxypropylene monomer that molecular weight is 4000～9000, can obtain ultra early-strength poly carboxylic acid series water reducer.
In reality, can adopt as required the methyl alkene butyl polyoxyethylene polyoxypropylene monomer of different molecular weight, thereby obtain early-strength type or ultra early-strength poly carboxylic acid series water reducer.
In above-mentioned water reducer, unsaturated monocarboxylic acid and derivatives monomer thereof are represented by general formula two:
General formula two
R in described general formula two
2represent hydrogen, methyl; R
3represent OM
1, wherein M
1represent hydrogen, monovalence metal, divalent metal, ammonium or organic amine; In multipolymer, unsaturated monocarboxylic acid and derivatives monomer thereof are for wherein a kind of use separately or multiple mixing are used.
Above-mentioned water reducer also comprises: unsaturated thiazolinyl sulfonic acid and sodium salt thereof, its consumption is 0.5～5% by mass percentage.
In above-mentioned water reducer, unsaturated sulfonic acid or its sodium salt are selected from: any in allyl sulphonic acid or its salt, methallylsulfonic acid or its salt, styrene sulfonic acid or its salt, 2-Methacrylamide-3-propene sulfonic acid or its salt or any two kinds.
The embodiment of the present invention also provides the preparation method of a kind of member high-early strength type polycarboxylic acids dehydragent, comprising:
Get each component by the formula of the embodiment of the present invention;
Under 20～40 DEG C of temperature condition, adopt redox initiation system to make each component in the aqueous solution, carry out polyreaction each component, after polyreaction through in neutralizing agent and after the polymkeric substance that obtains be member high-early strength type polycarboxylic acids dehydragent.
In above-mentioned preparation method, the oxygenant in the redox initiation system of employing is a kind of in hydroperoxide, persulphate or their mixture, the consumption of described oxygenant be in each component total monomer weight 0.2%～2.0%;
A kind of in reductive agent in the redox initiation system the adopting sub-compound that is sulphur, L-AA or their mixture, the consumption of described reductive agent is in feed composition all 0.1～1.0% of total monomer weights.
In above-mentioned preparation method, control in the following manner polymerization rate, oxygenant in the redox initiation system of employing is mixed with to solution, or reductive agent is mixed with to solution, or oxygenant and reductive agent are mixed with respectively solution, can directly add in reactor and do not need to be mixed with another component of solution, by dropping mode by the solution of preparation to dripping and control polymerization rate in reaction system, time for adding is controlled at 1～5 hour.
In above-mentioned preparation method, after polyreaction, after any in available hydrogen sodium oxide, trolamine or quadrol, diethylenetriamine etc. neutralizes, obtain mass concentration and be 40～60% described member high-early strength type polycarboxylic acids dehydragent.
This above-mentioned high-early strength type polycarboxylic acids dehydragent can be used as mother liquor, when use, generally need be mixed with 10～20% admixture to first adding water in this mother liquor, and then use according to actual the optimum mix amount.
The present invention is by adopting simple production process at normal atmosphere temperature, when selecting to exceed the large monomer of methyl alkene butyl polyoxyethylene polyoxypropylene of 4000 molecular weight and vinylformic acid, acrylamide, methylpropene sodium sulfonate or during simultaneously with raw materials such as amide group and sulfonic minor comonomer 2-acrylamide-2-methylpro panesulfonic acids, can synthetic concrete members ultra early-strength poly carboxylic acid series water reducer, its amount of air entrainment is low, good dispersity, have 1 day with interior super early strength function, environmental friendliness, harmless to the person.
Below in conjunction with specific embodiment, water reducer of the present invention is described further.
The embodiment of the present invention provides a kind of member early-strength type or ultra early-strength poly carboxylic acid series water reducer, and this water reducer is polymerized by following each component by weight percentage, and each component comprises:
Molecular weight is not less than 2400 methyl alkene butyl polyoxyethylene polyoxypropylene monomer 80～85%;
Unsaturated monocarboxylic acid and derivatives monomer 10～15% thereof;
Unsaturated thiazolinyl sulfonic acid and sodium salt 0.5～5% thereof.
Further, the methyl alkene butyl polyoxyethylene polyoxypropylene monomer in above-mentioned water reducer is represented by following general formula one:
General formula one
The average addition mole number of group that in above-mentioned general formula one, m is oxyethylene group, arbitrary number that m is 50～200; N is the average addition mole number of the group of oxypropylene group, arbitrary number that n is 1～5.
In above-mentioned water reducer, unsaturated monocarboxylic acid and derivatives monomer thereof are represented by general formula three:
General formula two
R in general formula two
2represent hydrogen, methyl; R
3represent OM
1, wherein M
1represent hydrogen, monovalence metal, divalent metal, ammonium or organic amine; In multipolymer, unsaturated monocarboxylic acid and derivatives monomer thereof are for wherein a kind of use separately or multiple mixing are used.
Unsaturated sulfonic acid in above-mentioned water reducer or its salt are selected from: the mixture of any in allyl sulphonic acid or its salt, methallylsulfonic acid or its salt, styrene sulfonic acid or its salt, 2-Methacrylamide-3-propene sulfonic acid or its salt or any two kinds.
The embodiment of the present invention also provides a kind of preparation method who prepares above-mentioned member high-early strength type polycarboxylic acids dehydragent, comprising:
Get each component by above-mentioned formula, by each component under 20～40 DEG C of temperature condition, adopt redox initiation system to make each component in the aqueous solution, carry out polyreaction, after polyreaction through in neutralizing agent and after obtain the polymkeric substance of concentration 40～60%, be this member high-early strength type polycarboxylic acids dehydragent mother liquor.
In aforesaid method, the oxygenant in the redox initiation system adopting is a kind of in hydroperoxide, persulphate or their mixture, the consumption of described oxygenant be in each component total monomer weight 0.2%～2.0%;
Reductive agent in the redox initiation system of described employing is a kind of in the sub-compound, L-AA of sulphur or their mixture, and the consumption of described reductive agent is in feed composition all 0.1～1.0% of total monomer weights.
Further, in aforesaid method, control in the following manner the speed of polyreaction, oxygenant in the redox initiation system of employing is mixed with to solution, or reductive agent is mixed with to solution, or oxygenant and reductive agent are mixed with respectively solution, by dropping mode by the solution of preparation to dripping and control polymerization rate in reaction system, time for adding is controlled at 1～5 hour.
The present embodiment provides a kind of member as follows with the raw material of the actual employing of each component in high-early strength type polycarboxylic acids dehydragent:
The molecular weight 2400～9000 of methyl alkene butyl polyoxyethylene glycol polypropylene glycol ether;
Unsaturated monocarboxylic acid and derivatives monomer thereof can be: (methyl) vinylformic acid, (methyl) acrylamide, (methyl) vinylformic acid first (second or third or fourth) ester, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate etc.;
Olefin sulfonic acid and sodium salt monomer thereof are: (methyl) allyl sulphonic acid or its salt, styrene sulfonic acid or its salt, 2-Methacrylamide-3-propene sulfonic acid or its salt etc.
This water reducer adopts redox initiation system to make each component in the aqueous solution, carry out polyreaction and forms, and in the redox initiation system of employing, oxygenant comprises: ammonium persulphate, hydrogen peroxide, tertbutyl peroxide etc.;
Reductive agent comprises: Sulfothiorine, sodium bisulfite, S-WAT, methylol sodium bisulfite, stannous sulfate, ferrous sulfate, L-AA etc.
The molecular weight regulator adopting can be: Thiovanic acid, thiohydracrylic acid.
Neutralizing agent can be: wherein one or more such as sodium hydroxide, quadrol, diethylenetriamine, triethylene tetramine, trolamine.
In preparation process, large monomer all adds before reaction starts, and other monomer can add a part before reaction, also can after reaction starts, add in batches or continuously, or add method to combine use these.
In the preparation, deionization electrical conductivity of water used is preferably 5～10us/cm of 1～20us/cm(); In redox initiation system, oxygenant consumption is 0.2%～2.0% of total monomer weight used, reductive agent consumption is 0.1～1.0% of total monomer weight used, the consumption of molecular weight regulator is 0.1～2.0% of total monomer weight used, the mass concentration of polymerization single polymerization monomer mixing solutions is 50～60%, and the reaction times is controlled at 1～5 hour.Neutralization with alkali or with alkaline organic amine, consumption be in each component total monomer weight 0.5～2.0%.The member high-early strength type polycarboxylic acids dehydragent of preparation is light brown transparent liquid, and the final quality concentration of thin up mother liquor is 40%～60%.
Doing the present invention below in conjunction with embodiment illustrates further.
Embodiment mono-
The present embodiment provides a kind of member high-early strength type polycarboxylic acids dehydragent, preparation method is as follows: the add-on of this water reducer each component used all by weight, disposing agitator, thermometer, Dropping feeder, reflux exchanger, in the four-hole glass flask of nitrogen protection device, add the methyl butene base polyoxyethylene glycol propylene glycol (m=55 of 450 weight part weight-average molecular weight 2500, n=1), the mass concentration of the deionized water of 400 weight parts and 4.0 weight parts is 27% hydrogen peroxide, stir and control temperature after 25 ± 3 DEG C, in 2～3 hours, in reaction vessel, drip the vinylformic acid that has mixed 37.5 weight parts respectively simultaneously, the acrylamide of 7.5 weight parts, the monomer solution of the deionized water of the methylpropene sodium sulfonate of 2.5 weight parts and 100 weight parts, dropping has mixed the reaction promotor solution of the L-AA that the thiohydracrylic acid of 2.5 weight parts and the mass concentration of 60 weight parts are 2%, after dropwising, reaction finishes, temperature is controlled at 50 DEG C of following continuation and is incubated 60 minutes, polyreaction is completed, after insulation finishes, the sodium hydroxide solution neutralization that the mass concentration that adds 26 weight parts is 30%, and add water that to be adjusted to mass concentration be 45%, obtain the member high-early strength type polycarboxylic acids dehydragent of the present embodiment.In follow-up contrast experiment by this water reducer called after PE-ER1.
Embodiment bis-
The present embodiment provides a kind of member high-early strength type polycarboxylic acids dehydragent, preparation method is as follows: the add-on of this water reducer each component used all by weight, disposing agitator, thermometer, Dropping feeder, reflux exchanger, in the four-hole glass flask of nitrogen protection device, add the methyl butene base polyoxyethylene glycol dipropylene glycol (m=87 of 450 weight part weight-average molecular weight 4000, n=2), the mass concentration of the deionized water of 400 weight parts and 4.0 weight parts is 27% hydrogen peroxide, stir and control temperature after 25 ± 3 DEG C, in 2～3 hours, in reaction vessel, drip and mixed 40.0 parts by weight of acrylic acid simultaneously respectively, the monomer solution of 2-Methacrylamide-3-propene sulfonic acid of 7.5 weight parts and the deionized water of 100 weight parts, dropping has mixed the reaction promotor solution of the L-AA that the thiohydracrylic acid of 2.5 weight parts and the mass concentration of 60 weight parts are 2%, after dropwising, reaction finishes, temperature is controlled at 50 DEG C of following continuation and is incubated 60 minutes, polyreaction is completed, after insulation finishes, the quadrol neutralization that the mass concentration that adds 20 weight parts is 30%, and add water that to be adjusted to mass concentration be 45%, obtain the member high-early strength type polycarboxylic acids dehydragent of the present embodiment.In follow-up contrast experiment by this water reducer called after PE-ER2.
Embodiment tri-
The present embodiment provides a kind of member high-early strength type polycarboxylic acids dehydragent, preparation method is as follows: the add-on of this water reducer each component used all by weight, disposing agitator, thermometer, Dropping feeder, reflux exchanger, in the four-hole glass flask of nitrogen protection device, add 450 weight part weight-average molecular weight 6000 methyl butene base polyoxyethylene glycol tripropylene glycol ether (m=132, n=3), the mass concentration of the deionized water of 400 weight parts and 4.0 weight parts is 27% hydrogen peroxide, stir and control temperature after 25 ± 3 DEG C, in 2～3 hours, in reaction vessel, drip and mixed 35 parts of vinylformic acid simultaneously respectively, the monomer solution of 2-Methacrylamide-3-propene sulfonic acid of 10.5 weight parts and the deionized water of 100 weight parts, dropping has mixed the reaction promotor solution of the L-AA that the thiohydracrylic acid of 2.5 weight parts and the mass concentration of 60 weight parts are 2%, after dropwising, reaction finishes, temperature is controlled at 50 DEG C of following continuation and is incubated 60 minutes, polyreaction is completed, after insulation finishes, the trolamine neutralization that the mass concentration that adds 10 weight parts is 85%, and add water that to be adjusted to mass concentration be 45%, obtain the member high-early strength type polycarboxylic acids dehydragent of the present embodiment.In follow-up contrast experiment by this water reducer called after PE-ER3.
Comparative example 1
This comparative example provides a kind of conventional standard type poly carboxylic acid series water reducer, its preparation method is: the add-on of this water reducer each component used all by weight, disposing agitator, thermometer, Dropping feeder, reflux exchanger, in the four-hole glass flask of nitrogen protection device, add the methacrylic polyoxyethylene glycol that 450 weight part molecular weight are 2400, the mass concentration of the deionized water of 400 weight parts and 4.0 weight parts is 27.5% hydrogen peroxide, be warmed up to after 60 DEG C, in 1～3 hour to the reaction promotor solution that drips the thiohydracrylic acid that has mixed the vinylformic acid of 50.5 weight parts and the aqueous solution of 49.5 deionized waters and 2.0 weight parts in reaction vessel simultaneously, temperature of reaction is controlled at 50～65 DEG C, after dropwising, at 65 DEG C, continue insulation 60 minutes, polyreaction is completed, after finishing, insulation is cooled to 40 DEG C, the Na0H neutralization that the mass concentration that adds 30 weight parts is 30%, and add water that to be adjusted to mass concentration be 40%, obtain the standard type poly carboxylic acid series water reducer of this comparing embodiment, in follow-up contrast experiment by this water reducer called after PE-C1.
In the performance comparison experiment of the water reducer of preparing in the embodiment of the present invention, early-strength type water reducer and contrast sample admixture for member, comprise that PE-ER1, PE-ER2, PE-ER3, PE-C1 water reducer sample are all mixed with 15% mass concentration and use, below this is further elaborated.
The inspection of Application Example 1(cement paste):
Select Jinyu P.O.42.5 cement, (GB/T1346-2001) carry out consumptive use of water normal consistence and alcohol coagulation test according to specification " cement normal consistency water consumption, time of coagulation, stability detection method ", water reducer volume is 2%, and test-results is as shown in table 1
Table 1 normal consistency of cement paste water consumption and time of coagulation
Application Example (cement mortar test) 2:
With reference to Test method for strength of hydraulic cement mortar (ISO), cement consumption increases 50g, gets 500g, standard sand 1350g, and blank sample water-cement ratio 0.5, water reducer concentration 15%, water-cement ratio is identical, gets 0.22, controls mortar divergence at 130 ± 20mm, and result is as table 2.
Table 2 cement mortar ultimate compression strength
Application Example (concrete test) 3:
The test of concrete application performance is carried out with reference to " GB50081-2002 normal concrete mechanical test method ", prefabricated components are controlled at 180～200mm by the slump of high performance concrete, admixture is mixed by solid active principle, moisture is deducted in total water amount, and concrete folk prescription material usage is as table 3.(1) concrete 1 day, 2 days, 3 days, 28 days mean compressive strengths of different intensity grades under examination criteria curing condition; (2) owing to conventionally adopting vapor cure after prefabricated components moulding, therefore with C50 group carry out 4 hours quiet stop after 55～60 DEG C of vapor cures, the demoulding after naturally cooling, the mean compressive strength that detects test block pressure resistance intensity and later stage normal curing to 28 day contrasts with not steam-cured test block pressure resistance intensity; (3) for C80 super high strength concrete, detect under winter 0～5 DEG C of condition and summer 30～35 DEG C of conditions under the mean compressive strength of test block 1 day and natural curing in 3 days and later stage normal curing to 28 day.Result is as table 4, table 5, table 6.
Table 3 prefabricated components high performance concrete folk prescription material usage (kg)
Table 4 precast concrete is supported difference ultimate compression strength in the length of time under condition at mark
The C50 strength grade precast concrete intensity of the different curing conditions of table 5
Table 6 precast concrete is moisture-keeping maintaining ultimate compression strength in the different length of time under 10 DEG C of highest temperature conditions
From table 4, table 5, table 6 result can be found out, the ultra early-strength poly carboxylic acid series water reducer PE-ER1 that the embodiment of the present invention is synthetic, PE-ER2, the water-reducing rate of PE-ER3 is except PE-ER1 approaches contrast sample PE-C1, increase obviously and reduce with the molecular weight of large monomer, PE-ER1 has obvious early strength function, PE-ER2, PE-ER3 has super early potent fruit, early-strength type polycarboxylate water-reducer is applied to preparation C40～C80 precast concrete, no matter adopt which kind of maintenance method, the more common contrast sample PE-C1 of its 1 day～3 days early strengths is obviously higher, especially PE-ER2, PE-ER31 days more obvious with interior concrete morning of potent fruit, under winter temperature condition, concrete 1 day intensity of C80 can reach the more than 30% of design strength, the 28 day length of time, mean compressive strength remained basically stable.
The above; only for preferably embodiment of the present invention, but protection scope of the present invention is not limited to this, is anyly familiar with in technical scope that those skilled in the art disclose in the present invention; the variation that can expect easily or replacement, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (9)
1. a member high-early strength type polycarboxylic acids dehydragent, is characterized in that, this water reducer is polymerized by following each component by weight percentage, and each component comprises:
Molecular weight is not less than 2400 methyl alkene butyl polyoxyethylene polyoxypropylene monomer 80～85%;
Unsaturated monocarboxylic acid and derivatives monomer 10～15% thereof;
Unsaturated thiazolinyl sulfonic acid and sodium salt 0.5～5% thereof.
2. water reducer as claimed in claim 1, is characterized in that, described molecular weight is not less than 2400 methyl alkene butyl polyoxyethylene polyoxypropylene monomer by following general formula one expression:
General formula one
The average addition mole number of group that in described general formula one, m is oxyethylene group, arbitrary number that m is 50～200; N is the average addition mole number of the group of oxypropylene group, arbitrary number that n is 1～5.
3. water reducer as claimed in claim 1 or 2, is characterized in that, described methyl alkene butyl polyoxyethylene polyoxypropylene monomer adopts the methyl alkene butyl polyoxyethylene polyoxypropylene monomer that molecular weight is 4000～9000.
4. water reducer as claimed in claim 1, is characterized in that, described unsaturated monocarboxylic acid and derivatives monomer thereof are represented by general formula two:
General formula two
R in described general formula two
2represent hydrogen, methyl; R
3represent OM
1, wherein M
1represent hydrogen, monovalence metal, divalent metal, ammonium or organic amine; In multipolymer, unsaturated monocarboxylic acid and derivatives monomer thereof are for wherein a kind of use separately or multiple mixing are used.
5. the water reducer as described in claim 1,2 or 4, it is characterized in that, described unsaturated sulfonic acid or its sodium salt are selected from: any in allyl sulphonic acid or its salt, methallylsulfonic acid or its salt, styrene sulfonic acid or its salt, 2-Methacrylamide-3-propene sulfonic acid or its salt or any two kinds.
6. a preparation method for high-early strength type polycarboxylic acids dehydragent for member, is characterized in that, comprising:
Get each component by formula described in claim 1 to 5 any one;
Under 20～40 DEG C of temperature condition, adopt redox initiation system to make each component in the aqueous solution, carry out polyreaction each component, after polyreaction through in neutralizing agent and after the polymkeric substance that obtains be member high-early strength type polycarboxylic acids dehydragent.
7. method as claimed in claim 6, it is characterized in that, oxygenant in the redox initiation system of described employing is a kind of in hydroperoxide, persulphate or their mixture, the consumption of described oxygenant be in each component total monomer weight 0.2%～2.0%;
Reductive agent in the redox initiation system of described employing is a kind of in the sub-compound, L-AA of sulphur or their mixture, and the consumption of described reductive agent is in feed composition all 0.1～1.0% of total monomer weights.
8. method as claimed in claim 7, it is characterized in that, in described method, control in the following manner polymerization rate, oxygenant in the redox initiation system of employing is mixed with to solution, or reductive agent is mixed with to solution, or oxygenant and reductive agent are mixed with respectively solution, can directly add in reactor and do not need to be mixed with another component of solution, by dropping mode by the solution of preparation to dripping and control polymerization rate in reaction system, time for adding is controlled at 1～5 hour.
9. method as claimed in claim 6, it is characterized in that, in described method, after polyreaction, after neutralizing with any in sodium hydroxide, trolamine, quadrol, diethylenetriamine, obtain mass concentration and be 40～60% member high-early strength type polycarboxylic acids dehydragent.
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| CN104292397A (en) * | 2014-09-23 | 2015-01-21 | 江苏奥莱特新材料有限公司 | Method for preparing special functional polycarboxylate water reducer for PHC pipe pile |
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| CN105731863A (en) * | 2014-12-09 | 2016-07-06 | 上海东大化学有限公司 | Viscosity-lowering type polycarboxylic acid water reducing agent and preparation and use methods therefor |
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| CN108623756A (en) * | 2018-05-28 | 2018-10-09 | 中交二航武汉港湾新材料有限公司 | Special polycarboxylate water-reducer of ultra-high performance concrete and preparation method thereof |
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| CN109608594A (en) * | 2018-12-13 | 2019-04-12 | 广东奥克化学有限公司 | A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN109796565A (en) * | 2018-12-24 | 2019-05-24 | 联泓(江苏)新材料研究院有限公司 | A kind of Early-strength polycarboxylate superplasticizer and its preparation method and application |
| CN109796565B (en) * | 2018-12-24 | 2021-09-28 | 联泓(江苏)新材料研究院有限公司 | Early-strength polycarboxylate superplasticizer and preparation method and application thereof |
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