Background technology
In recent years, along with the sustained and rapid development of China's economic society, the infrastructure construction dynamics of China and scale are also continuing to increase, and the application of concrete prefabricated element also gets more and more.Realizing the high-level efficiency of residential housing, high-quality, low consumption of resources and low environmental impact by concrete prefabricated technology, have significant economic and social benefit, is the development trend of Current Housing building.In concrete member is produced, for accelerating template turn around time, pedestal utilization ratio, and accelerate engineering construction progress, realize maximum economic benefit, just need to adopt concrete early strength agent to promote hydrated cementitious, to shorten the tempo of concrete time of coagulation and quickening early age strength of concrete.Along with the development of architectural engineering technology, hardening accelerator by increasing in concrete works.
At present, the method preparing Early-strength polycarboxylate superplasticizer mainly contains two kinds, be respectively synthesis and composite, composite method mainly water reducer and hardening accelerator component composite; Synthetic method, mainly through poly carboxylic acid Molecular Structure Design, molecular chain is introduced the functional group with early epistasis energy.
Patent CN100595173C provides a kind of early strength polycarboxylic acid high performance dehydragent and preparation method thereof, and this invention is with based on ester class poly carboxylic acid series water reducer, and composite accelerating component, reaches the object improving early age strength of concrete.Use composite method to improve early age strength of concrete, the volume of water reducer is general larger, and composite after the stability adaptability that is relatively poor, product of water reducer product also can be affected.
Patent CN101475664B reports the preparation method of the polycarboxylate water-reducer for prefabricated components, this water reducer is under the effect of initiator persulphate, by methoxy polyethylene glycol acrylate, vinylformic acid, unsaturated sulfonic acid or its salt monomer, unsaturated amides or its salt monomer in aqueous copolymerization obtain.The method in two steps, needs first to utilize high molecular polyoxy base polyoxyethylene glycol (molecular weight 2000-5000) and vinylformic acid generation esterification, prepares methoxy polyethylene glycol acrylate.For improving esterifying efficiency, in preparation process, employ a large amount of organic solvent cyclohexane gives is water entrainer.Preparation technology is loaded down with trivial details, and production unit requires higher, and processing safety is poor.
Patent application CN103450408A provides a kind of ethers Early-strength polycarboxylate superplasticizer and preparation method thereof, this invention is by unsaturated ester, di-alcohol monoisopropanolamine, 2-acrylamido-methyl propanesulfonic acid and methacrylic polyoxyethylene poly-oxygen propylene aether etc. are as primary chemical synthesis material, under the effect of catalyzer, initiator, chain-transfer agent etc., in certain condition through amidation and polymerization process, obtain a kind of high molecular polymer with both sexes structure.This reactions steps is loaded down with trivial details, needs to obtain through amidation and copolymerization two-step reaction, and copolyreaction also needs to be heated to 50-70 DEG C and just can react, and fails to reach energy-conservation object.
Patent application CN102432776A provides a kind of preparation method of high-early strength type polycarboxylic acids dehydragent, this invention is by the modification polyoxyalkylenes ether containing unsaturated double-bond, (methyl) vinylformic acid, the sulfonate of unsaturated double-bond, acrylamide four kinds of monomers, use molecular weight regulator, temperature of reaction is under 50-70 DEG C of condition, synthesizes high-early strength type polycarboxylic acids dehydragent.The method needs to complete reaction under the condition of heating, fails to reach energy-conservation object.
Summary of the invention
The object of the present invention is to provide one not need heating, energy efficient, increases work efficiency, and obtained water reducer water-reducing rate is high, the water reducer preparation method that early stage reinforced effects is good.
For achieving the above object, the invention provides a kind of preparation method without thermal source Early-strength polycarboxylate superplasticizer, it is characterized in that, step is,
Get the raw materials ready: take each component by the mol ratio of each monomer, reductive agent, chain-transfer agent, unsaturated acid derivative being mixed obtained mass percent concentration with water is the aqueous solution of 44 ± 3%, is denoted as X material; Unsaturated sulfonic acid salt, monomer a being mixed obtained mass percent concentration with water is the aqueous solution of 26 ± 1%, is denoted as Y material for subsequent use;
Polymerization: unsaturated Soxylat A 25-7 and water are added in polymerization reaction kettle, be stirred to unsaturated Soxylat A 25-7 to dissolve completely, add oxygenant, be stirred to evenly, start to add X material and Y material simultaneously, add time controling at 1-3 hour, 1-2h is incubated after interpolation, polyreaction terminates, and is neutralized to pH=6-7 with the alkaline solution that mass percent concentration is 20 ± 2%, obtained polyethers Early-strength polycarboxylate superplasticizer; Polymer quality percentage concentration is between 40%-55%.
Further, the mol ratio of described unsaturated Soxylat A 25-7, unsaturated acid derivative, unsaturated sulfonic acid salt, monomer a is 1:3-5:0.7-1.5:0.2-0.6; Oxygenant is the 0.8-1.2% of monomer total mass, and reductive agent is the 0.1-0.2% of monomer total mass, and chain-transfer agent is the 0.3-0.5% of monomer total mass; Described monomer total mass is the quality sum of unsaturated Soxylat A 25-7, unsaturated acid derivative, unsaturated sulfonic acid salt and monomer a.
Further, described unsaturated Soxylat A 25-7 is one or more the combination in allyl polyethenoxy ether, methacrylic Soxylat A 25-7 or isopentene Soxylat A 25-7 and derivative thereof, and corresponding molecular weight is 1000-3000.
Further, described unsaturated acid derivative is one or more the combination in (methyl) vinylformic acid, methylene-succinic acid, toxilic acid (acid anhydride).
Further, described unsaturated sulfonic acid salt is one or more the combination in sodium allylsulfonate, methylpropene sodium sulfonate, 2-acrylamide-2-methacrylic sulfonic acid.
Further, described monomer a comprises one or more the combination in trolamine, tri-isopropanolamine, di-alcohol monoisopropanolamine.
Further, described oxygenant comprises one or more the combination in hydrogen peroxide, benzoyl peroxide, tertbutyl peroxide, ammonium persulphate, Potassium Persulphate.
Further, described reductive agent comprises one or more the combination in xitix and sodium bisulfite, tartrate, rongalite, ferrous sulfate, ferrous pyrophosphate.
Further, described chain-transfer agent is the combination of one or more in Thiovanic acid, thiohydracrylic acid, mercaptoethanol, 3-thiohydracrylic acid;
Optional, described alkaline solution is one or more combination in sodium hydroxide, potassium hydroxide, ammoniacal liquor, thanomin.
The present invention also provide the described preparation method without thermal source Early-strength polycarboxylate superplasticizer to prepare without thermal source Early-strength polycarboxylate superplasticizer.
In the present invention, the ratio of unsaturated acid derivative and unsaturated Soxylat A 25-7 increases, Early-strength polycarboxylate superplasticizer water-reducing rate increases, molecular weight increases, but unsaturated acid derivative and unsaturated Soxylat A 25-7 are than excessive, Early-strength polycarboxylate superplasticizer molecular weight is excessive, the dispersiveness of gained Early-strength polycarboxylate superplasticizer is deteriorated, and water-reducing rate reduces rapidly.If the amount of oxygenant, reductive agent and chain-transfer agent exceeds the scope of application claims, the molecular weight of Early-strength polycarboxylate superplasticizer can be affected, cause the water-reducing rate of Early-strength polycarboxylate superplasticizer low.
The present invention adopts aforementioned preparation process to produce water reducer, compared with like product and technique, has following significant beneficial effect:
1, have employed oxidation-reduction trigger system in copolyreaction, suitable Oxidizing and Reducing Agents can be selected to realize optimum initiator proportioning, farthest reduce temperature of reaction, without the need to heating, reaction can be made at room temperature to carry out, simplify production technique, saved cost, improve working efficiency.
2, introduce alcamines material, effectively can improve the water-reducing rate of water reducer and concrete early strength.
3, simple process, be easy to suitability for industrialized production and environmental nonpollution, comparatively like product is more excellent for the application performance of the finished product.
Embodiment
Be described below in detail embodiments of the invention, the example of described embodiment is intended to for explaining the present invention, and can not be interpreted as limitation of the present invention.Unreceipted concrete technology or condition person in embodiment, according to the technology described by the document in this area or condition or carry out according to product description.Agents useful for same or the unreceipted production firm person of instrument, being can by the conventional products of commercial acquisition.
Embodiment 1: without the preparation of thermal source Early-strength polycarboxylate superplasticizer
The first step is got the raw materials ready: Thiovanic acid 0.69g, xitix 0.23g, and vinylformic acid 18g adds 24.08g water, mixes the solution that obtained mass percent concentration is about 44%, is placed in storage tank for subsequent use, is considered as X material; Methylpropene sodium sulfonate 9.2g, tri-isopropanolamine 3.2g, add water 35.3g, mixes the aqueous solution that obtained mass percent concentration is about 26%, stored in for subsequent use in another storage tank, is considered as Y material;
Second step is polymerized: in the four-hole boiling flask being furnished with thermometer and electric blender, add 163.5g water, allyl polyethenoxy ether (M
w=3000) 200g, stirs after fully dissolving, adds the H that mass percent concentration is 20%
2o
21.84g, stirs, and starts to add X material and Y material simultaneously, within 3 hours, adds complete, is incubated 1 hour afterwards, is that the pH value of mixed solution is neutralized to pH=6 ~ 7 by the sodium hydroxide solution of 20%, adds 40.3g water with mass percent concentration.Obtained without thermal source Early-strength polycarboxylate superplasticizer, its solid content is about 40%.
In actual production process, adopt the mol ratio identical with previous embodiment to get the raw materials ready, then carry out polyreaction by identical polymerization technique, be polymerized the reactor of equipment system the temperature control unit common to those skilled in the art and whipping appts used.
With reference to the relevant regulations of GB8076-2008 " concrete admixture ", GB/T50081-2002 " standard for test methods of mechanical properties of ordinary concrete ", concrete test is adopted to detect the performance perameter such as the slump, ultimate compression strength of this product.Concrete mix and effect related data are as shown in table 1,2.
Embodiment 2: without the preparation of thermal source Early-strength polycarboxylate superplasticizer
Adopt the processing step identical with embodiment 1, prepare without thermal source Early-strength polycarboxylate superplasticizer by following raw material dosage and processing parameter, be specially:
The first step is got the raw materials ready: Thiovanic acid 0.99g, xitix 0.37g, and methacrylic acid 28.9g adds 38.5g water, mixes the solution that obtained mass percent concentration is about 44%, is placed in storage tank for subsequent use, is considered as X material; Sodium allylsulfonate 11.88g, tri-isopropanolamine 7.9g, add water 56.3g, mixes the aqueous solution that obtained mass percent concentration is about 26%, stored in for subsequent use in another storage tank, is considered as Y material;
Second step is polymerized: in the four-hole boiling flask being furnished with thermometer and electric blender, add 163.5g water, methacrylic Soxylat A 25-7 (M
w=2400) 200g, stirs after fully dissolving, adds the H that mass percent concentration is 20%
2o
22.49g, stirs, and starts to add X material and Y material simultaneously, and within 3 hours, add complete, being incubated 1 hour afterwards, is that the pH value of mixed solution is neutralized to pH=6 ~ 7 by the sodium hydroxide solution of 20% with mass percent concentration.Obtained without thermal source Early-strength polycarboxylate superplasticizer, its solid content is about 50%.
With reference to the relevant regulations of GB8076-2008 " concrete admixture ", GB/T50081-2002 " standard for test methods of mechanical properties of ordinary concrete ", concrete test is adopted to detect the performance perameter such as the slump, ultimate compression strength of this product.Concrete mix and effect related data are as shown in table 1,2.
Embodiment 3: without the preparation of thermal source Early-strength polycarboxylate superplasticizer
Prepare without thermal source Early-strength polycarboxylate superplasticizer by following raw material dosage and processing parameter, be specially:
The first step is got the raw materials ready: thiohydracrylic acid 1.22g, rongalite 0.49g, and vinylformic acid 26.9g adds 36.4g water, mixes the solution that obtained mass percent concentration is about 44%, is placed in storage tank for subsequent use, is considered as X material; Sodium allylsulfonate 12g, trolamine 5.5g, add water 49.8g, mixes the aqueous solution that obtained mass percent concentration is about 26%, stored in for subsequent use in another storage tank, is considered as Y material;
Second step is polymerized: in the four-hole boiling flask being furnished with thermometer and electric blender, add 163.5g water, isopentene Soxylat A 25-7 (M
w=2400) 200g, stir after fully dissolving, add the tertbutyl peroxide 2.93g that mass percent concentration is 20%, stir, start to add X material and Y material simultaneously, within 3 hours, add complete, be incubated 1 hour afterwards, with mass percent concentration be 20% ammonia soln the pH value of mixed solution is neutralized to pH=6 ~ 7, add 43g water.Obtained without thermal source Early-strength polycarboxylate superplasticizer, its solid content is about 45%.
With reference to the relevant regulations of GB8076-2008 " concrete admixture ", GB/T50081-2002 " standard for test methods of mechanical properties of ordinary concrete ", concrete test is adopted to detect the performance perameter such as the slump, ultimate compression strength of this product.Concrete mix and effect related data are as shown in table 1,2.
Embodiment 4: without the preparation of thermal source Early-strength polycarboxylate superplasticizer
Prepare without thermal source Early-strength polycarboxylate superplasticizer by following raw material dosage and processing parameter, be specially:
The first step is got the raw materials ready: thiohydracrylic acid 0.76g, rongalite 0.51g, and methylene-succinic acid 32.4g adds 42.9g water, mixes the solution that obtained mass percent concentration is about 44%, is placed in storage tank for subsequent use, is considered as X material; Methylpropene sodium sulfonate 3.9g, 2-acrylamide-2-methacrylic sulfonic acid 10.3g, di-alcohol monoisopropanolamine 8.1g, add water 63.5g, mixes the aqueous solution that obtained mass percent concentration is about 26%, stored in for subsequent use in another storage tank, is considered as Y material;
Second step is polymerized: in the four-hole boiling flask being furnished with thermometer and electric blender, add 163.5g water, allyl polyethenoxy ether (M
w=2000) 200g, stir after fully dissolving, add the tertbutyl peroxide 3.06g that mass percent concentration is 20%, stir, start to add X material and Y material simultaneously, within 3 hours, add complete, being incubated 1 hour afterwards, is that the pH value of mixed solution is neutralized to pH=6 ~ 7 by the potassium hydroxide solution of 20% with mass percent concentration.Obtained without thermal source Early-strength polycarboxylate superplasticizer, its solid content is about 50%.
With reference to the relevant regulations of GB8076-2008 " concrete admixture ", GB/T50081-2002 " standard for test methods of mechanical properties of ordinary concrete ", concrete test is adopted to detect the performance perameter such as the slump, ultimate compression strength of this product.Concrete mix and effect related data are as shown in table 1,2.
Embodiment 5: without the preparation of thermal source Early-strength polycarboxylate superplasticizer
Prepare without thermal source Early-strength polycarboxylate superplasticizer by following raw material dosage and processing parameter, be specially:
The first step is got the raw materials ready: Thiovanic acid 0.75g, xitix 0.24g, and vinylformic acid 24g adds 31.8g water, mixes the solution that obtained mass percent concentration is about 44%, is placed in storage tank for subsequent use, is considered as X material; Methylpropene sodium sulfonate 11.9g, tri-isopropanolamine 6g, add water 50g, mixes the aqueous solution that obtained mass percent concentration is about 26%, stored in for subsequent use in another storage tank, is considered as Y material;
Second step is polymerized: in the four-hole boiling flask being furnished with thermometer and electric blender, add 163.5g water, methacrylic Soxylat A 25-7 (M
w=2400) 200g, stir after fully dissolving, add the hydrogen peroxide 1.93g that mass percent concentration is 20%, stir, start to add X material and Y material simultaneously, within 3 hours, add complete, be incubated 1 hour afterwards, with mass percent concentration be 20% sodium hydroxide solution the pH value of mixed solution is neutralized to pH=6 ~ 7, add 22.9g water.Obtained without thermal source Early-strength polycarboxylate superplasticizer, its solid content is about 45%.
With reference to the relevant regulations of GB8076-2008 " concrete admixture ", GB/T50081-2002 " standard for test methods of mechanical properties of ordinary concrete ", concrete test is adopted to detect the performance perameter such as the slump, ultimate compression strength of this product.Concrete mix and effect related data are as shown in table 1,2.
Comparative example 1
Prepare polycarboxylate water-reducer by following raw material dosage and processing parameter, be specially:
The first step is got the raw materials ready: Thiovanic acid 0.9g, xitix 0.25g, and vinylformic acid 26.9g adds 35.7g water, mixes the solution that obtained mass percent concentration is about 44%, is placed in storage tank for subsequent use, is considered as X material; Methylpropene sodium sulfonate 13.1g, add water 37.3g, mixes the aqueous solution that obtained mass percent concentration is about 26%, stored in for subsequent use in another storage tank, is considered as Y material;
Second step is polymerized: in the four-hole boiling flask being furnished with thermometer and electric blender, add 163.5g water, allyl polyethenoxy ether (M
w=2400) 200g, stir after fully dissolving, add the hydrogen peroxide 2.0g that mass percent concentration is 20%, stir, start to add X material and Y material simultaneously, within 3 hours, add complete, be incubated 1 hour afterwards, with mass percent concentration be 20% sodium hydroxide solution the pH value of mixed solution is neutralized to pH=6 ~ 7, add 50g water.Obtained without thermal source Early-strength polycarboxylate superplasticizer, its solid content is about 45%.
Comparative example 2
Prepare without thermal source Early-strength polycarboxylate superplasticizer by following raw material dosage and processing parameter, be specially:
The first step is got the raw materials ready: Thiovanic acid 0.75g, xitix 0.24g, and vinylformic acid 24g adds 31.8g water, mixes the solution that obtained mass percent concentration is about 44%, is placed in storage tank for subsequent use, is considered as X material; Methylpropene sodium sulfonate 11.9g, tri-isopropanolamine 10g, add water 62.3g, mixes the aqueous solution that obtained mass percent concentration is about 26%, stored in for subsequent use in another storage tank, is considered as Y material;
Second step is polymerized: in the four-hole boiling flask being furnished with thermometer and electric blender, add 163.5g water, methacrylic Soxylat A 25-7 (M
w=2400) 200g, stir after fully dissolving, add the hydrogen peroxide 1.93g that mass percent concentration is 20%, stir, start to add X material and Y material simultaneously, within 3 hours, add complete, be incubated 1 hour afterwards, with mass percent concentration be 20% sodium hydroxide solution the pH value of mixed solution is neutralized to pH=6 ~ 7, add 46.5g water.Obtained without thermal source Early-strength polycarboxylate superplasticizer, its solid content is about 45%.
With reference to the relevant regulations of GB8076-2008 " concrete admixture ", GB/T50081-2002 " standard for test methods of mechanical properties of ordinary concrete ", concrete test is adopted to detect the performance perameter such as the slump, ultimate compression strength of this product.Concrete mix and effect related data are as shown in table 1,2.
Table 1 concrete mix table (unit: Kg/m
3)
Label |
Cement |
Water |
Sand |
Stone |
Flyash |
Breeze |
C40 |
312 |
166 |
730 |
1030 |
49 |
49 |
Table 2 mechanical performance of concrete and effect data table related
In sum, the test-results explanation of embodiment 1-5 and comparative example 1-2, the early age strength of concrete (under the condition that volume and the slump are substantially identical) using product of the present invention to prepare is all high than comparative example 1 (common ethers polycarboxylic acid water reducing agent), and other serviceabilitys are all suitable.The test-results of embodiment 1-5 and comparative example 2 illustrates, the volume of monomer a increases, and early age strength of concrete is higher than the intensity of common ethers water reducer, but lower than the early strength of embodiment 5 and cost increases large.Therefore, this product can be applicable to need, in early strong concrete prefabricated element, be significantly improved, and cost performance to be higher to 28d intensity.
Although illustrate and describe embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, those of ordinary skill in the art can change above-described embodiment within the scope of the invention when not departing from principle of the present invention and aim, revising, replacing and modification.