CN101284717A - Preparation method of ultra-low hydration heat polycarboxylate-based water reducing agent - Google Patents

Preparation method of ultra-low hydration heat polycarboxylate-based water reducing agent Download PDF

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Publication number
CN101284717A
CN101284717A CNA2008100477922A CN200810047792A CN101284717A CN 101284717 A CN101284717 A CN 101284717A CN A2008100477922 A CNA2008100477922 A CN A2008100477922A CN 200810047792 A CN200810047792 A CN 200810047792A CN 101284717 A CN101284717 A CN 101284717A
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Prior art keywords
reducing agent
water reducing
polycarboxylate
ultra
preparation
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马保国
张慢
马玲
谭洪波
李亮
吕国玉
何向全
许红生
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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Priority to CNA2008100477922A priority Critical patent/CN101284717A/en
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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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention relates to a method for preparing an ultra-low hydration-heat polycarboxylate-based water reducing agent. Methacrylic acid and Monomer methylacrylic acid polyethylene glycol single armor ether ester (MAAMPEA) water solution, initiator and modifier solution are simultaneously and slowly added into the solvent water drop by drop within 6 to 7 hours at the temperature of 80 DEG C to 90 DEG C, then the solvent water is subjected to thermal insulation for 4 to 5 hours at 90 DEG C to 95 DEG C and is naturally cooled down to the room temperature, and finally NaOH is used to adjust the pH value to 7 to 8, thereby obtaining the ultra-low hydration-heat polycarboxylate-based water reducing agent. The reaction conditions are easily controlled, no organic solvent is used during the polymerization process, and the process is simple with no industrial pollution. The concrete prepared by adopting the ultra-low hydration-heat polycarboxylate-based water reducing agent has the advantages as follows: when the mixing amount of the water reducing agent with the concentration being 25 wt percent is 1.0% of the concrete weight, the water reducing ratio can reach 30 percent, the 3d compressive strength of the concrete can be improved by more than 60 percent, the 28d compressive strength can be improved by more than 50 percent, and the 90d compressive strength can be improved by 30 percent.

Description

A kind of preparation method of ultra-low hydration heat polycarboxylate-based water reducing agent
Technical field
The invention belongs to a kind of preparation method of ultra-low hydration heat polycarboxylate-based water reducing agent.
Background technology
High efficiency water reducing agent is core technology in the high performance concrete.High efficiency water reducing agent is since research and development, and through sulfonated lignin, naphthalene system and melamine series high-efficiency water-reducing agent stage, developing into gradually is the high efficiency water reducing agent of main representative at present with the poly carboxylic acid.Compare with traditional water reducer, high-efficiency water-reducing agent of poly-carboxylic acid is mainly by containing carboxyl (COOR) with polyoxyethylene groups grafted chain (OC 2H 4-) comb copolymer form, the strong polar group of these and water avidity is by absorption, electrostatic repulsion, surfactivity effect such as wetting, cement granules is provided dispersed and disperses retentivity, even under low water binder ratio, also can show good dispersive ability, concrete flowability and mobile hold facility have been improved greatly.
Polycarboxylate high performance water-reducing agent is by Japan's new concrete admixture of Application and Development at first, realizes industrialization and application to the mid-90 in 20th century, as wheat field 3000, the SP8 of SKW-MBT, the FP300 of Teng Ze of Japanese Kao.The research emphasis in North America and Europe also turns to polycarboxylic acid series, all has good performance as the Viscocrete 3010 of the Pheomix 700FC of the Adva series of Grace company, MBT company, the super early strength water-reducing agent of Rheobuild 300FC, Sika company etc.By contrast, the time of domestic research poly carboxylic acid series water reducer is shorter, and its product processes and technology control are ripe not as good as external.
Polyoxy alkene mono allyl ether/toxilic acid/other monomers=(70～90)/(30～50)/(0～10) wt% in the Japan catalyst company synthetic co-poly carboxylic acid, the ratio of unsaturated carboxylic acid monomer is necessary＞and 10%, otherwise do not reach suitable dispersiveness,＞30% causes slow setting and too high air bubble content.Public auspicious illuminates etc. propose in the co-poly carboxylic acid of allyl ethers type when one timing of polyether chain length, adjust a suitable chain density, it is dispersed and stable to help improving dispersion system, for reaching superelevation dispersiveness and high dispersion stability, introduce vinylbenzene (St) mol% and change polyether chain density, it is comparatively suitable that St% is controlled at 5～20 scopes.Wang Zhengxiang etc. have synthesized polyoxyethylene allyl ethers, toxilic acid and cinnamic multipolymer, think that molecular weight preferably is controlled between 8000～20000, and polyoxyethylated addition mole number generally is controlled between 15～40.
Introduce among the Te Kaiping 9-286648, taking by weighing polyoxyethylene (oxyethane) 33mol, monomethyl monoallyl ether 1mol, allyl sodium sulfonate 1mol and Maleic Acid, Anhydrous 3mol in the four-hole boiling flask that agitator, thermometer, prolong, nitrogen ingress pipe are housed is dissolved in the 1480g water, add ammonium persulphate 0.75mol as polymerization starter, 50 ± 2 ℃ were reacted 12 hours under nitrogen atmosphere, obtained interpolymer X.
Above-mentioned prior art shows, still exist than big-difference at present for the structure design of poly carboxylic acid series water reducer, and the performance of water reducer own is single.Ultra-low hydration heat polycarboxylate-based water reducing agent of the present invention is given this product diminishing and is reduced the hydration heat double properties by the control to carboxyl on the molecular chain and polyoxyethylene groups distribution density.For the complicated technology of domestic present production acrylic acid series water reducer, this production process is also fairly simple, is easy to control.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of ultra-low hydration heat polycarboxylate-based water reducing agent, this method technology is simple, easily-controlled reaction conditions, do not pollute, the low suitability for industrialized production that is easy to of cost.
Method difference of the present invention in the past, directly press certain mol proportion example carboxyl grafting side chain and polyoxyethylene side chain, as initiator, and add polyalcohol modified dose, the mol ratio of grafted carboxyl and polyoxyethylene groups on the control poly carboxylic acid series water reducer side chain with Diisopropyl azodicarboxylate and ferrous sulfate.
The present invention realizes by the following technical solutions:
A kind of preparation method of ultra-low hydration heat polycarboxylate-based water reducing agent, it is characterized in that: under 80～90 ℃ of conditions, simultaneously slowly be added drop-wise in the aqueous solvent methacrylic acid and the monomer Methylacrylic acid polyethylene glycol single armor ether ester aqueous solution and initiator and modifier aqueous solution, in 6～7h, drip off, 90～95 ℃ of insulation 4～5h, naturally cool to room temperature, transfer pH to 7～8, obtain the following ultra-low hydration heat polycarboxylate-based water reducing agent of structural formula with NaOH:
Figure A20081004779200051
In the formula: R represents CH 3M represents Na; A=4～9, m=3～20, n=10～45, and the mol ratio of grafted carboxyl and polyoxyethylene groups is 1～7: 1 on the main chain.
The consumption weight percent of reactant composition is in the above-mentioned building-up process:
Methacrylic acid: 22～53%
Methylacrylic acid polyethylene glycol single armor ether ester: 41～70%
Initiator: 4～5%
Properties-correcting agent: 1～5%.
The concentration of the above-mentioned methacrylic acid and the Methylacrylic acid polyethylene glycol single armor ether ester aqueous solution is 40～60wt%, and the concentration of initiator and modifier aqueous solution is 3～4wt%.
The molecular weight ranges of above-mentioned Methylacrylic acid polyethylene glycol single armor ether ester is 300～500.
Above-mentioned properties-correcting agent is polyvalent alcohol, and hydroxy radical content is 30～50%, and its general formula of molecular structure is as follows:
Figure A20081004779200061
In the formula: q=1～10.
Above-mentioned initiator is the mixture of Diisopropyl azodicarboxylate and ferrous sulfate, and its mass ratio is 10～20: 1.
The present invention is controlled at 1～7 with grafted carboxyl on the water reducer main chain in the mol ratio of polyoxyethylene groups: in 1 scope by the molar weight of conditioned reaction thing.Temperature of reaction substantially constant, reaction conditions are easy to control, do not use any organic solvent in the polymerization process, and technology is simple, no industrial pollution.The concrete that the ultra-low hydration heat polycarboxylate-based water reducing agent that adopts the present invention to make is prepared, when this water reducer volume with 20wt% concentration be cement weight 1.0% the time, water-reducing rate can reach 30%, concrete 3d ultimate compression strength improves more than 60%, 28d ultimate compression strength improves more than 50%, and 90d ultimate compression strength improves more than 30%; Concrete surface does not have bleeding line, no air pocket, aberration is little, Surface Quality of Concrete good; Alkali content is low; Chloride ion-containing not is to the reinforcing bar non-corrosiveness; Freeze-thaw-ability and anti-carbonization ability significantly improve than normal concrete; Concrete 28d shrinking percentage is that analog high efficiency water reducing agent reduces more than 20% than naphthalene; The adaptation of product is strong, be adapted to the cement of plurality of specifications, model, especially suitable and high-quality fly ash, slag isoreactivity adulterant compatibility prepare high performance concrete, can be widely used in high-strength concrete, self-leveling concrete, in the field that pump concrete, sprayed concrete etc. have higher requirements to workability of concrete, intensity, weather resistance etc.; Product performance are stable, and long storage is not stratified, the nothing precipitation, does not have crystallization winter; Advantages such as the product nontoxic pollution-free does not contain formaldehyde, and is environmentally safe.
Embodiment
Embodiment 1:
The water that in reactor, adds 16.67g, heat up, under 80～90 ℃ of temperature, drip on one side by the 10.3g methacrylic acid, 8.0g the solution that Methylacrylic acid polyethylene glycol single armor ether ester (molecular weight 500) and 20.95g water are formed (takes by weighing methacrylic acid and Methylacrylic acid polyethylene glycol single armor ether ester, be dissolved in then in the water and can obtain), the other side drips initiator and modifier solution (0.73g Diisopropyl azodicarboxylate, 0.05g ferrous sulfate, 0.45g mixing with 38.01g water, polyvalent alcohol (q=1) obtains), the control rate of addition, drip off at 6～7h, at 90～95 ℃ of insulation 4～5h.Be cooled to room temperature, regulate pH=7～8, obtain the ultra-low hydration heat polycarboxylate-based water reducing agent (mol ratio of grafted carboxyl and polyoxyethylene groups is about 7: 1 on the main chain) of 20wt% concentration of the present invention with sodium hydroxide.
Embodiment 2:
The water that in reactor, adds 16.67g, heat up, under 80 ± 5 ℃ of temperature, drip the solution of forming by 10.8g methacrylic acid, 15.5g Methylacrylic acid polyethylene glycol single armor ether ester (molecular weight 400) and 33.75g water on one side, the other side drips initiator and modifier solution (1.05g Diisopropyl azodicarboxylate, 0.107g ferrous sulfate, 0.85g polyvalent alcohol (q=4) and 57.92g water), the control rate of addition, drip off 90～95 ℃ of insulation 4～5h at 6～7h.Be cooled to room temperature, regulate pH=7～8, obtain the ultra-low hydration heat polycarboxylate-based water reducing agent (mol ratio of grafted carboxyl and polyoxyethylene groups is about 3: 1 on the main chain) of 20wt% concentration of the present invention with sodium hydroxide.
Embodiment 3:
The water that in reactor, adds 16.67g, heat up, under 80 ± 5 ℃ of temperature, drip the solution of forming by 8.2g methacrylic acid, 26.1g Methylacrylic acid polyethylene glycol single armor ether ester (molecular weight 300) and 46.55g water on one side, the other side drips initiator and modifier solution (1.37g Diisopropyl azodicarboxylate, 0.152g ferrous sulfate, 1.35g polyvalent alcohol (q=10) and 77.95g water), the control rate of addition, drip off 90～95 ℃ of insulation 4～5h at 6～7h.Be cooled to room temperature, regulate pH=7～8, obtain the ultra-low hydration heat polycarboxylate-based water reducing agent (mol ratio of grafted carboxyl and polyoxyethylene groups is about 1: 1 on the main chain) of 20wt% concentration of the present invention with sodium hydroxide.
The hydration heat performance test results of product:
Figure A20081004779200071
t Max---time corresponding when the cement slurry hydration heat reaches top temperature;
T Max---the temperature of correspondence when the cement slurry hydration heat reaches top temperature;
Q (1d)---1 day thermal discharge of cement slurry aquation;
Q (3d)---3 days thermal discharge of cement slurry aquation.

Claims (5)

1. the preparation method of a ultra-low hydration heat polycarboxylate-based water reducing agent, it is characterized in that: under 80～90 ℃ of conditions, simultaneously slowly be added drop-wise in the aqueous solvent methacrylic acid and the monomer Methylacrylic acid polyethylene glycol single armor ether ester aqueous solution and initiator and modifier aqueous solution, in 6～7h, drip off, 90～95 ℃ of insulation 4～5h, naturally cool to room temperature, transfer pH to 7～8, obtain the following ultra-low hydration heat polycarboxylate-based water reducing agent of structural formula with NaOH:
Figure A20081004779200021
In the formula: R represents CH 3M represents Na; A=4～9, m=3～20, n=10～45, and the mol ratio of grafted carboxyl and polyoxyethylene groups is 1～7: 1 on the main chain;
The consumption weight percent of reactant composition is in the building-up process:
Methacrylic acid: 22～53%
Methylacrylic acid polyethylene glycol single armor ether ester: 41～70%
Initiator: 4～5%
Properties-correcting agent: 1～5%.
2. preparation method according to claim 1 is characterized in that: the concentration of the methacrylic acid and the Methylacrylic acid polyethylene glycol single armor ether ester aqueous solution is 40～60wt%, and the concentration of initiator and modifier aqueous solution is 3～4wt%.
3. preparation method according to claim 1 and 2 is characterized in that: the molecular weight ranges of Methylacrylic acid polyethylene glycol single armor ether ester is 300～500.
4. preparation method according to claim 1 and 2 is characterized in that: properties-correcting agent is polyvalent alcohol, and hydroxy radical content is 30～50%, and its general formula of molecular structure is as follows:
Figure A20081004779200031
In the formula: q=1～10.
5. claim 1 or 2 described preparation methods, it is characterized in that: initiator is the mixture of Diisopropyl azodicarboxylate and ferrous sulfate, its mass ratio is 10～20: 1.
CNA2008100477922A 2008-05-20 2008-05-20 Preparation method of ultra-low hydration heat polycarboxylate-based water reducing agent Pending CN101284717A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102936112A (en) * 2012-11-13 2013-02-20 中建商品混凝土有限公司 Polycarboxylic acid water reducing agent suitable for high-strength self-compacting concrete and preparation method of polycarboxylic acid water reducing agent
CN103880988A (en) * 2014-03-18 2014-06-25 武汉理工大学 Functionalized azo initiator for free radical polymerization as well as preparation and application methods thereof
CN111620609A (en) * 2020-06-24 2020-09-04 广西南宁嘉泰水泥制品有限公司 Ultra-low electric flux concrete and preparation method thereof
CN111961148A (en) * 2020-08-31 2020-11-20 武汉理工大学 Reaction air-entraining type polycarboxylate superplasticizer and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102936112A (en) * 2012-11-13 2013-02-20 中建商品混凝土有限公司 Polycarboxylic acid water reducing agent suitable for high-strength self-compacting concrete and preparation method of polycarboxylic acid water reducing agent
CN102936112B (en) * 2012-11-13 2014-06-25 中建商品混凝土有限公司 Polycarboxylic acid water reducing agent suitable for high-strength self-compacting concrete and preparation method of polycarboxylic acid water reducing agent
CN103880988A (en) * 2014-03-18 2014-06-25 武汉理工大学 Functionalized azo initiator for free radical polymerization as well as preparation and application methods thereof
CN111620609A (en) * 2020-06-24 2020-09-04 广西南宁嘉泰水泥制品有限公司 Ultra-low electric flux concrete and preparation method thereof
CN111961148A (en) * 2020-08-31 2020-11-20 武汉理工大学 Reaction air-entraining type polycarboxylate superplasticizer and preparation method thereof

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