CN102211909A - Cement-based grouting material containing polyether carboxylic acid type water reducing agent and preparation method of cement-based grouting material - Google Patents

Cement-based grouting material containing polyether carboxylic acid type water reducing agent and preparation method of cement-based grouting material Download PDF

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CN102211909A
CN102211909A CN2011100875052A CN201110087505A CN102211909A CN 102211909 A CN102211909 A CN 102211909A CN 2011100875052 A CN2011100875052 A CN 2011100875052A CN 201110087505 A CN201110087505 A CN 201110087505A CN 102211909 A CN102211909 A CN 102211909A
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cement
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grouting material
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water
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CN102211909B (en
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马清浩
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Foshan Huili Concrete Co Ltd
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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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention provides a cement-based grouting material containing polyether carboxylic acid type water reducing agent and a preparation method of the cement-based grouting material. The cement-based grouting material containing the polyether carboxylic acid type water reducing agent comprises the following components in part by weight: 350 to 500 parts of cement clinker, 80 to 130 parts of fly ash, 20 to 30 parts of expanding agent, 80 to 120 parts of gypsum, 1 to 2 parts of pH regulator, 8 to 15 parts of water reducing agent and 300 to 500 parts of quartz sand, wherein the water reducing agent is the polyether carboxylic acid type water reducing agent prepared from the following components: polypropylene alcohol ether, maleic anhydride, methyl sodium allylsulfonate, acrylamide, acrylic-2-hydroxyethyl ester, initiator and water. The grouting material has high strength and low bleeding rate.

Description

Contain cement-based grouting material of polyether-type carboxylic-acid water reducer and preparation method thereof
Technical field
The present invention relates to a kind of material of construction and preparation method thereof, relate in particular to a kind of cement-based grouting material that contains particular variety polyether-type carboxylic-acid water reducer and preparation method thereof.
Background technology
Concrete structure is big because of its fragility, tends to take place cracking phenomena in engineering is used, and the concrete structure watertightness descends, seepage and concrete cracking can cause, and then influences the work-ing life of engineering.Thereby in construction and operational phase, many engineerings such as water conservancy, railway, highway, bridge etc. need injection material that the crack is repaired and reinforced inevitably.And the installation of many large-scale instruments also needs the combining site on usefulness high performance grouting material perfusion wall screw and machinery bed or steel construction and basis etc.
Distress in concrete commonly used is repaired with the injection material of reinforcing a lot, divides from material type, mainly contains chemical grouting material and cement-based grouting material two big classes.Chemical grouting material has that particle is thin, intensity is high, viscosity is low, and flowability, stability and concrete castability are good, gelling or set time can advantage such as regulate by requirement of engineering, but its cost height, transportation and storage inconvenience, construction technology complexity, has toxicity in various degree mostly, comprise pungency, corrodibility, sensitization and shortcoming such as inflammable and explosive, simultaneously, because of test, constructing operation and discharging dead meal etc. cause environmental pollution and to phreatic pollution, the application of chemical grouting material also more and more is restricted.That the cement based cement grouting material has is easy to use, intensity is high, good endurance, pollution-free, characteristics such as cost is low, the source is wide, thereby, more and more obtained using widely.But Portland cement base grouting material particle is thicker, the poor stability of slurries, easily precipitates bleed, and volumetric shrinkage is arranged during sclerosis.In addition, after the strengthening of foundation grouting, slurry has certain contraction, ftractures once more easily.Therefore, those skilled in the art are devoted to overcome by approach such as interpolation admixtures the above-mentioned defective of cement-based grouting material in recent years.Wherein, cement additive commonly used, also be concrete admixture for example the adding of water reducer help to improve above-mentioned defective, but, the raising that cement-based grouting material intensity under necessity, especially the winter severe cold condition that improves is again still arranged is the problem that those skilled in the art want to solve and be difficult to solution always.
Water reducer is called dispersion agent or fluidizer again, during owing to use the water consumption of fresh concrete is reduced, and therefore gains the name.In the modern concrete technical field, water reducer is one of admixture that improves rheological property of concrete, has been taken as five component of concrete except that cement, sand, stone and water.
Common water reducer mainly contains xylogen ring phosphate-gallate series, naphthalene system, trimeric cyanamide system, sulfamate system and polycarboxylic acid etc.Be the application and the developing period of ordinary water-reducing agent the thirties to the sixties in 20 century, the early stage water reducer that uses is mainly organic compound such as sodium abietate, sodium lignosulfonate, stearate, it mainly is to be used to improve Concrete Construction, solves the endurance issues such as freeze-thaw-of concrete road surface.But along with improving constantly of construction requirement, the water-reducing effect of the water reducer that these are early stage can not satisfy the needs that modern project is built.
Since at first developing naphthalene sulfonic acidformaldehyde condensation product high efficiency water reducing agent and West Germany's exploitation trimeric cyanamide series high-efficiency water-reducing agent in 1964 from Japan in 1962, the exploitation and the application period of high efficiency water reducing agent have been entered, advantageously promoted the development of concrete technology, the outstanding feature of these two series of high efficiency water reducers is water-reducing rate height, the cement dispersion effect is good, it mainly acts on is to reduce unit consumption of water or unit cement consumption significantly, be used to prepare high-strength, superelevation is strong, high durability concrete, but its fatal shortcoming is that slump-loss is big, and formaldehyde volatilization environmental pollution is serious in the preparation process.And polycarboxylic acid high efficiency water reducing agent blending amount is low, but to the good dispersity of concrete (cement), slump retaining is good, and easily modification, so its high performance potentiality are big, is considered to the regeneration product of high efficiency water reducing agent.
External polycarboxylic acid high efficiency water reducing agent is extensive use of in the concrete preparation, and product type is main with maleic anhydride mainly.With Japan is example, and the product synthetic method is mainly: the first step, under the nitrogen protection condition, methyl alcohol and oxyethane react under certain temperature and pressure, add NaOH, elevated temperature decompression dehydration again in reaction vessel.Subsequently, in mixture, add a certain amount of chlorallylene, when mixture basicity is reduced to a stationary value, use the HCl neutralise mixt, separate obtaining allyl ethers.Second step: as solvent, under nitrogen protection, the allyl ethers and the maleic anhydride that obtain with the first step reaction carry out polyreaction, steam and remove toluene solvant, obtain maleic anhydride series high performance concrete water reducer with toluene.
The domestic relevant report that the polycarboxylic acid high efficiency water reducing agent is also arranged in recent years.Its use raw material generally by unsaturated carboxylic acid class (vinylformic acid, methacrylic acid, maleic anhydride), polyoxy alkene (polyoxyethylene, polyoxyethylene glycol etc.), unsaturated carboxylate type, contain the unsaturated monomer of sulfonic acid group etc.; Its synthesis step generally be divided into two the step carry out.As the polycarboxylic acid water reducing agents for efficient aerocrote reported among the CN1316398A tosic acid do catalyzer, Resorcinol do stopper, dibenzoyl peroxide do the initiator condition little with the methacrylic acid polymerization reaction take place, obtain bleed type high efficiency water reducing agent except that desolvating question response is finished substantially after.The water reducer that this method obtains is only soluble in alkali lye and is insoluble in water, brings very big inconvenience to use.CN1800076A also discloses a kind of acrylic acid or the like multiple copolymer analog high efficiency water reducing agent, the shared umber of its each raw material is: 100 parts of vinylformic acid or derivatives thereofs, 150～450 parts of polyoxy alkenes, sulfonic acid are 10～80 parts in derivative, 450～800 parts of deionized water solvents, 0.5～6 part of catalyzer, 0.1～5 part of stopper, 5～30 parts of Virahol chain-transfer agents, 0.5～5 part of initiator, and the add-on of NaOH solution is to make the pH value of product reach 6～8.But the method reaction process that this patent provided is difficult to control, and water-reducing rate and slump retention value still are not very desirable yet.
Summary of the invention
The present invention provides a kind of novel water reducer in order to overcome above-mentioned deficiency of the prior art, and this water reducer environmental protection, slump-loss is little, water-reducing rate is high, and preparation technology is simple, and is with low cost.Further, the invention provides a kind of cement-based grouting material that contains this water reducer and preparation method thereof, this injection material intensity height, bleeding rate is low.
Cement-based grouting material of the present invention comprises by weight: cement clinker 350～500, flyash 80～130, swelling agent 20～30, gypsum 80～120, pH value conditioning agent 1～2, polyether-type carboxylic-acid water reducer 8～15, quartz sand 300～500, the carboxylic-acid water reducer of wherein said polyether-type carboxylic-acid water reducer for being prepared from: polypropylene alcohol ether, MALEIC ANHYDRIDE, methylpropene sodium sulfonate, acrylamide, 2-Hydroxy ethyl acrylate, initiator and water by following component.Preferably, the weight ratio of each component is in the described polyether-type carboxylic-acid water reducer: polypropylene alcohol ether: MALEIC ANHYDRIDE: methylpropene sodium sulfonate: acrylamide: 2-Hydroxy ethyl acrylate: initiator: water=25-40: 3-6: 1-6: 0.5-4: 1-5: 0.5-4: 100.
Further preferably, the weight ratio of each component is in the described polyether-type carboxylic-acid water reducer: polypropylene alcohol ether: MALEIC ANHYDRIDE: methylpropene sodium sulfonate: acrylamide: 2-Hydroxy ethyl acrylate: initiator: water=30-35: 3.5-4: 2-3: 1-2: 2-3: 1-2: 100.
Preferably, the parts by weight of described cement clinker are 380～420, and the parts by weight of described water reducer are 9～11.Preferably, described cement clinker is a Portland clinker.Preferably, described swelling agent comprises sulplo-aluminate, and further preferably, described swelling agent is sulplo-aluminate, more preferably calcium sulphoaluminate.Preferably, the described pH value conditioning agent mixed thing that to be boric acid and tripoly phosphate sodium STPP obtain according to 1: 2 ratio.
Preferably, described quartz sand comprises thick quartz sand, middle quartz sand and three kinds of fractions of fine quartz sand, the amount ratio of three kinds of fractions is 45～60: 35～50: 10～20, wherein the particle size range of thick quartz sand is＞3mm～5mm, the particle size range of middle quartz sand is 2～3mm, and the particle size range of fine quartz sand is＞0mm～2mm.The inventor finds unexpectedly, is used according to three kinds of quartz sands that will satisfy above-mentioned qualification and can further improves concrete intensity, reduces bleeding rate.
Preferred described polypropylene alcohol ether is CH 2=CHCH 2O (CH 2CH 2O) nH, wherein n=10-60.Preferred described initiator is ammonium persulphate, Potassium Persulphate or Sodium Persulfate.
The present invention provides a kind of preparation method of cement-based grouting material in addition, comprising the step that following raw material is mixed according to following parts by weight: cement clinker 350～500, flyash 80～130, swelling agent 20～30, gypsum 80～120, pH value conditioning agent 1～2, polyether-type carboxylic-acid water reducer 8～15, quartz sand 300～400, wherein said polyether-type carboxylic-acid water reducer is prepared from by following component: polypropylene alcohol ether, MALEIC ANHYDRIDE, methylpropene sodium sulfonate, acrylamide, 2-Hydroxy ethyl acrylate, initiator and water.Preferably, the weight ratio of each component is in the described polyether-type carboxylic-acid water reducer: polypropylene alcohol ether: MALEIC ANHYDRIDE: methylpropene sodium sulfonate: acrylamide: 2-Hydroxy ethyl acrylate: initiator: water=25-40: 3-6: 1-6: 0.5-4: 1-5: 0.5-4: 100.
The preparation method of described polyether-type carboxylic-acid water reducer comprises:
Step 1: propylene alcohol ether, MALEIC ANHYDRIDE and methylpropene sodium sulfonate are mixed with the aqueous solution, join in the reactor, stir, be warming up to 80～100 ℃;
Step 2: drip acrylamide and the aqueous solution of 2-Hydroxy ethyl acrylate formation and the aqueous solution of initiator in the mixture that obtains in step 1, maintain the temperature at 80～100 ℃ in the dropping process, the dropping time is 2～5 hours;
Step 3: after dropwising, 80～100 ℃ following isothermal reaction 2-8 hour;
Step 4: filter.
Preferably, in the described aqueous solution of step 1, with respect to the water of 100 weight parts, the parts by weight of propylene alcohol ether, MALEIC ANHYDRIDE and methylpropene sodium sulfonate are respectively: 100-150 weight part, 15-25 weight part, 1-15 weight part.
Preferably, in the aqueous solution that described acrylamide of step 2 and 2-Hydroxy ethyl acrylate form, with respect to the water of 100 weight parts, the parts by weight of acrylamide and 2-Hydroxy ethyl acrylate are respectively 12-18 weight part and 15-25 weight part.In the step 2 in the initiator solution initiator concentration be 2-5 weight %.Preferably, the time of dropping described in the step 2 is 3-4 hour, and constant temperature time described in the step 3 is 4-5 hour.
Embodiment
The testing method explanation:
The testing method of the slump: with a 100mm suitable for reading, end opening 200mm, the trumpet-shaped slump bucket of high 300mm, tamping behind the penetration concrete, pull up bucket then, concrete produces the slump phenomenon because of deadweight, deduct the height of concrete vertex after the slump with bucket high (300mm), be called slump, unit is mm.
Water-reducing rate is according to the method test of stipulating among the GB8076-2008.
Ultimate compression strength is tested according to GB/T 50448-2008; Bleeding rate is according to the regulation test of GB/T 50080 the 5.1st joint.
Preparation embodiment 1
Step 1: with 320Kg propylene alcohol ether CH 2=CHCH 2O (CH 2CH 2O) nH (wherein n=10-60), 420Kg MALEIC ANHYDRIDE and 50Kg methylpropene sodium sulfonate join in the 300Kg water and are mixed with the aqueous solution, join in the reactor, stir, and are warming up to 90 ℃;
Step 2: the aqueous solution that drips the aqueous solution of 13Kg acrylamide and 26Kg 2-Hydroxy ethyl acrylate and the formation of 140Kg water and 860Kg concentration in the mixture that in step 1, obtains and be 3% Potassium Persulphate initiator, maintain the temperature at 90 ℃ in the dropping process, the dropping time is 3-3.5 hour;
Step 3: after dropwising, about 5 hours of 80～100 ℃ of following isothermal reactions;
Step 4: filter.
Productive rate is 94%.The slump retention value and the water-reducing rate value of products obtained therefrom see Table 1.
Preparation embodiment 2
Other step is identical with preparation embodiment 1, and difference is that replacing the n value with 320Kg propylene alcohol ether is the CH of 200-300 2=CHCH 2O (CH 2CH 2O) nH replaces the CH of n=10-60 among the preparation embodiment 1 2=CHCH 2O (CH 2CH 2O) nH.Productive rate is 90%.The slump retention value and the water-reducing rate value of products obtained therefrom see Table 1.
Preparation embodiment 3
Other step is identical with preparation embodiment 1, and difference is the consumption of acrylamide is reduced to 8Kg.Productive rate is 80%.The slump retention value and the water-reducing rate value of products obtained therefrom see Table 1.
Preparation embodiment 4
Other step is identical with preparation embodiment 1, and difference is in the step 2 temperature to be remained on 80 ℃, rather than 90 ℃.Productive rate is 93%.The slump retention value and the water-reducing rate value of products obtained therefrom see Table 1.
Preparation Comparative Examples 1
Other step is identical with preparation embodiment 1, and difference is to replace 420Kg MALEIC ANHYDRIDE described in the step 1 with the 420Kg terephthalic anhydride.Productive rate is 95%.The slump retention value and the water-reducing rate value of products obtained therefrom see Table 1.
Preparation Comparative Examples 2
Other step is identical with preparation embodiment 1, and difference is not add MALEIC ANHYDRIDE.Productive rate is 95%.The slump retention value and the water-reducing rate value of products obtained therefrom see Table 1.
Preparation Comparative Examples 3
Other step is identical with preparation embodiment 1, and difference is not add acrylamide.Productive rate is 90%.The slump retention value and the water-reducing rate value of products obtained therefrom see Table 1.
Preparation Comparative Examples 4
Other step is identical with preparation embodiment 1, and difference is to replace 2-Hydroxy ethyl acrylate with Virahol.
Table 1:
Performance after adding to water reducer of the present invention and the described water reducer of Comparative Examples in the Lafarge cement respectively relatively
Figure BSA00000469050800081
Illustrate: " * " representative reaction is carried out smoothly
On behalf of reaction process, "-" be difficult to control
Embodiment 1
A kind of preparation method of cement-based grouting material is provided, and this method makes by following component is mixed according to following weight part, wherein:
Cement clinker 380, flyash 90, calcium sulphoaluminate 25, gypsum 80, boric acid 0.5, tripoly phosphate sodium STPP 1, the water reducer 8 of preparation embodiment 1, average particle size particle size is the middle quartz sand 450 about 2.5mm.
Embodiment 2
Other is identical with embodiment 1, and difference is that the water reducer with preparation embodiment 2 replaces the water reducer of preparation embodiment 1.
Embodiment 3
Other is identical with embodiment 1, and difference is that the water reducer with preparation embodiment 3 replaces the water reducer of preparation embodiment 1.
Embodiment 4
Other is identical with embodiment 1, and difference is that the water reducer with preparation embodiment 4 replaces the water reducer of preparation embodiment 1.
Embodiment 5
Other is identical with embodiment 1, and it is that to replace average particle size particle size among the embodiment 1 be quartz sand in 450 weight parts about 2.5mm for fine quartz sand 70 weight parts, middle quartz sand 200 weight parts about 2.5mm and thick quartz sand 180 weight parts about 4mm about 1mm that difference is with average particle size particle size.
Comparative Examples 1
Other is identical with embodiment 1, and difference is that the water reducer with preparation Comparative Examples 1 replaces the water reducer of preparation embodiment 1.
Comparative Examples 2
Other is identical with embodiment 1, and difference is that the water reducer with preparation Comparative Examples 2 replaces the water reducer of preparation embodiment 1.
Comparative Examples 3
Other is identical with embodiment 1, and difference is that the water reducer with preparation Comparative Examples 3 replaces the water reducer of preparation embodiment 1.
Comparative Examples 4
In the Lafarge cement of 1026 commercially available weight parts, add the water reducer that makes among the preparation embodiment 1 of 8 weight parts.
Table 2:
The performance of embodiment 1-5 and the described cement-based grouting material of Comparative Examples 1-4 relatively
Figure BSA00000469050800091
Figure BSA00000469050800101
Annotate 1:R -7The ratio of expression 7 days test specimen compression strength value of negative temperature conservation and 28 days test specimen compression strength value of normal curing.

Claims (10)

1. cement-based grouting material that contains polyether-type carboxylic-acid water reducer, it contains by weight: cement clinker 350～500, flyash 80～130, swelling agent 20～30, gypsum 80～120, pH value conditioning agent 1～2, water reducer 6～15, quartz sand 300～500, the polyether-type carboxylic-acid water reducer of wherein said water reducer for being prepared from: polypropylene alcohol ether, MALEIC ANHYDRIDE, methylpropene sodium sulfonate, acrylamide, 2-Hydroxy ethyl acrylate, initiator and water by following component.
2. the described cement-based grouting material of claim 1, wherein said cement clinker is a Portland clinker, preferably, described swelling agent comprises sulplo-aluminate, further preferably, described swelling agent is sulplo-aluminate, more preferably calcium sulphoaluminate, perhaps preferably, the described pH value conditioning agent mixed thing that to be boric acid and tripoly phosphate sodium STPP obtain according to 1: 2 ratio; Perhaps preferably, the parts by weight of described cement clinker are 380～420, and the parts by weight of described water reducer are 9～11.
3. claim 1 or 2 described cement-based grouting materials, the weight ratio of wherein said each component of water reducer is: polypropylene alcohol ether: MALEIC ANHYDRIDE: methylpropene sodium sulfonate: acrylamide: 2-Hydroxy ethyl acrylate: initiator: water=25-40: 3-6: 1-6: 0.5-4: 1-5: 0.5-4: 100.
4. the described cement-based grouting material of claim 3, the weight ratio of wherein said each component of water reducer is: polypropylene alcohol ether: MALEIC ANHYDRIDE: methylpropene sodium sulfonate: acrylamide: 2-Hydroxy ethyl acrylate: initiator: water=30-35: 3.5-4: 2-3: 1-2: 2-3: 1-2: 100.
5. each described cement-based grouting material of claim 1-4, wherein said polypropylene alcohol ether is CH 2=CHCH 2O (CH 2CH 2O) nH, wherein n=10-60.
6. the preparation method of each described cement-based grouting material of claim 1-5 is comprising with each component blended step.
7. the described method of claim 6, the preparation process of wherein said water reducer comprises:
Step 1: propylene alcohol ether, MALEIC ANHYDRIDE and methylpropene sodium sulfonate are mixed with the aqueous solution, join in the reactor, stir, be warming up to 80～100 ℃;
Step 2: drip acrylamide and the aqueous solution of 2-Hydroxy ethyl acrylate formation and the aqueous solution of initiator in the mixture that obtains in step 1, maintain the temperature at 80～100 ℃ in the dropping process, the dropping time is 2～5 hours;
Step 3: after dropwising, 80～100 ℃ following isothermal reaction 2-8 hour;
Step 4: filter.
8. the described method of claim 7, wherein in the described aqueous solution of step 1, with respect to the water of 100 weight parts, the parts by weight of propylene alcohol ether, MALEIC ANHYDRIDE and methylpropene sodium sulfonate are respectively: 100-150 weight part, 15-25 weight part, 1-15 weight part.。
9. each described method of claim 7-8, wherein the preparation process of B material is: in the aqueous solution that described acrylamide of step 2 and 2-Hydroxy ethyl acrylate form, with respect to the water of 100 weight parts, the parts by weight of acrylamide and 2-Hydroxy ethyl acrylate are respectively 12-18 weight part and 15-25 weight part.
10. each described method of claim 7-9, wherein in the step 2 in the initiator solution initiator concentration be 2-5 weight %, preferably, the time of dropping described in the step 2 is 3-4 hour, constant temperature time described in the step 3 is 4-5 hour.
CN2011100875052A 2011-04-08 2011-04-08 Cement-based grouting material containing polyether carboxylic acid type water reducing agent and preparation method of cement-based grouting material Expired - Fee Related CN102211909B (en)

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