CN103964734B - High-strength high-performance concrete high molecular polymer admixture and preparation method thereof - Google Patents
High-strength high-performance concrete high molecular polymer admixture and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high-strength high-performance concrete high molecular polymer admixture and preparation method thereof, belong to technical field of concrete additives.It is made up of following raw material: 37% formaldehyde, phenol, urea, sodium sulfanilate, sodium naphthalene sulfonate, aliphatic water reducing agent, 98% sulfuric acid, 30%NaOH solution, Walocel MT 20.000PV, K12 (dodecyl sulphate), Sulfothiorine, ammonium persulphate, water.Its preparation process is urea, formaldehyde, phenol, sulfuric acid, sodium sulfanilate, sodium naphthalene sulfonate, aliphatic water reducing agent and ammonium persulphate add retort successively and react, then cool, add 30%NaOH again to neutralize, then add bleed, the sticky guarantor of guarantor moulds and accelerating component (sodium lauryl sulphate and Walocel MT 20.000PV Sulfothiorine), drying, obtains high-strength and high performance water reducer.This material is for preparing strong concrete, and product water-reducing rate ultimate compression strength obviously increases, and collapses to damage to reduce.
Description
Technical field
The present invention relates to technical field of concrete additives, especially a kind of high-strength high-performance concrete high molecular polymer admixture.
Background technology
Concrete admixture refers to the material for improving and regulate concrete performance and admixture.The application of concrete admixture in engineering more and more comes into one's own, and the interpolation of admixture plays a role to the concrete performance of improvement.
At present, conventional admixture mainly contains following four classes both at home and abroad: 1. naphthalene series high-efficiency water-reducing agent, 2. aminosulfonate-based superplasticizer, 3. aliphatic water reducing agent, 4. poly carboxylic acid series water reducer.Wherein naphthalene series high-efficiency water-reducing agent price is low, but water-reducing rate is lower, concrete strength rate of increase is low, and and inferior suitability, preparation more than C60 high-strength concrete is quite difficult, need application other additional functionality materials a large amount of to prepare successfully, and concrete mix slump-loss is fast, later concrete shrinking percentage is larger.Aminosulfonate-based superplasticizer water-reducing rate is higher, and concrete strength rate of increase is higher, good with cement adaptability, little loss of slump, but concrete coagulating time is longer, and the easy bleeding of concrete, even hardens, and amino water reducer affects by starting material, and its cost is higher.Aliphatic high-efficiency water reducing agent, water-reducing rate is between naphthalene system and amino, better with cement adaptability, but bleed is comparatively large, and concrete rate of increase is not high, and preparation high-strength concrete difficulty is comparatively large separately, is generally applied to low-grade concrete, and early collapsing by force, it is little to damage.Polycarboxylic acid high-performance water reducer affects by polymeric monomer raw material, occur that fluctuation is comparatively large, and cost is higher during quality product application, and harsh to ingredient requirements such as cement, sand, stones, poor with cement adaptability, concrete strength rate of increase is large, good endurance.
Above four class materials, 1. 2. 3. compatible, with 4. incompatible, if can develop a kind of product, than 4. cost is low, performance is suitable, and have again 1. the advantage of 2. 3. three kinds of product performance, its market outlook must be bright.
Summary of the invention
The object of the present invention is to provide a kind of high-strength high-performance concrete high molecular polymer admixture and preparation method thereof.Admixture of the present invention is used for concrete batching, and compared with polycarboxylic acids dehydragent, better with the adaptability to raw material such as cement, sand, stone, quality product is more stable, and cost is lower, and, suitable with polycarboxylic acids dehydragent with weather resistance at strength growth rate; Compared to naphthalene system, amino and aliphatic water reducing agent, when water reducer of the present invention is used for concrete, product water-reducing rate ultimate compression strength obviously increases, and collapses to damage to reduce, and overcomes above-mentioned the deficiencies in the prior art.
The technical solution adopted in the present invention is:
A kind of high-strength high-performance concrete high molecular polymer admixture, is characterized in that, be made up of following raw material:
37% formaldehyde, phenol, urea, sodium sulfanilate, sodium naphthalene sulfonate, aliphatic water reducing agent, 98% sulfuric acid, 30%NaOH solution, Walocel MT 20.000PV, sodium lauryl sulphate (K12), Sulfothiorine, ammonium persulphate, water.
Preferably, be made up of the raw material of following weight percent:
37% formaldehyde 8-12%, phenol 2-5%, urea 1-5%, sodium sulfanilate 3-8%, sodium naphthalene sulfonate (naphthalene water reducer) 10-15%, aliphatic water reducing agent 4-9%, 98% sulfuric acid 3-8%, 30%NaOH solution 8-14%, Walocel MT 20.000PV 0.05-0.2%, sodium lauryl sulphate (K12) 0.1-0.4%, Sulfothiorine 0.5-2.2%, ammonium persulphate 0.05-0.12%, water 40-60%, the weight percent of above each component is 100%.
Preferably, be made up of the raw material of following weight percent:
37% formaldehyde 9.6%, phenol 3%, urea 2%, sodium sulfanilate 6%, sodium naphthalene sulfonate 12%, aliphatic water reducing agent 6%, 98% sulfuric acid 5%, 30%NaOH solution 10%, Walocel MT 20.000PV 0.1%, sodium lauryl sulphate (K12) 0.2%, Sulfothiorine 1%, ammonium persulphate 0.1%, water 45%, the weight percent of above each component is 100%.
Present invention also offers a kind of preparation method of high-strength high-performance concrete high molecular polymer admixture, it is characterized in that, comprise the following steps:
1. raw material is taken by above-mentioned weight percent;
2. by step 1. in the urea that takes and formaldehyde soluble in water, be placed in hold-up vessel, under 40-50 DEG C of condition, react 1-2h, obtain mixed solution one;
3. by step 1. in the phenol, the sulfuric acid that take add in retort, mix, then the mixed solution one of 1/3rd volumes dropped in retort, be heated to 60-70 DEG C, reaction 1h;
4. by step 1. in the sodium sulfanilate, sodium naphthalene sulfonate, aliphatic water reducing agent and the ammonium persulphate that take add step 3. in retort in, mix, then the mixed solution one of residue 2/3rds volume is dropped in retort, be heated to 80-90 DEG C, reaction 3-4h;
5. step 4. in mixture temperature be down to 55-65 DEG C, proceed in neutralization tank, then add step 1. in the 30%NaOH solution that takes, mix;
6. by step 1. in the sodium lauryl sulphate that takes and Walocel MT 20.000PV be added in neutralization tank, mix;
7. by step 1. in the Sulfothiorine that takes be added in the mixture 6. processed through step, stir, then dry, obtain high-strength and high performance water reducer.
Beneficial effect of the present invention:
This material is used for concrete batching, and compared with polycarboxylic acids dehydragent, better with the adaptability to raw material such as cement, sand, stone, quality product is more stable, and cost is lower, and, suitable with polycarboxylic acids dehydragent with weather resistance at strength growth rate; Compared to naphthalene system, amino and aliphatic water reducing agent, when water reducer of the present invention is used for concrete, product water-reducing rate ultimate compression strength obviously increases, and collapses to damage to reduce, and overcomes the deficiencies in the prior art described in background technology.
Concrete,
(1) add the concrete 3 days intensity that water reducer of the present invention obtains and reach more than 50% of 28 days intensity percent, 28 days strength growth rates are greater than 80% simultaneously;
(2) add the concrete durability that water reducer of the present invention obtains and improve more than 2 times;
(3) add the concrete water-reducing ratio that water reducer of the present invention obtains and be greater than 25%;
(4) early age strength of concrete that water reducer of the present invention obtains is added high, later strength sustainable growth;
(5) concrete 1 day compressive strength rate >=170% that water reducer of the present invention obtains is added;
(6) concrete 28 days compressive strength rate >=150% that water reducer of the present invention obtains are added;
(7) add concrete 1h that water reducer of the present invention obtains damage of collapsing and be less than 20mm;
(8) water reducer of the present invention may be used for the concrete preparing C15-C100, namely preparation C60-C100 concrete is used in, also above effect (more difficult when existing a lot of water reducer is for preparing the concrete of more than C60, often need to add other supplies) can be reached;
(9) water reducer cost of the present invention is low, and compared to polycarboxylic acid high-performance water reducer, cost reduces 10-20%, and performance is high.
Accompanying drawing explanation
Accompanying drawing 1 is the schema of preparation method of the present invention.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples, embodiment should not regard as limiting the scope of the present invention.
The present invention in order to develop the high-performance water reducing agent of novel environmental type resin type, by polymerization, physics and chemical reaction, a kind of Multifunctional tree epoxy-type of composition generation water reducer.To the theoretical foundation of this high efficiency water reducing agent, formula, technique, parameter, reaction mechanism, on the impact of concrete workability, slump-loss, time of coagulation, impermeability, mechanical property and and cement adaptability, the performances such as concrete contraction are studied, and make development nonpoisonous and tasteless without the cold high-performance water reducing agent scheme of ammonia.
The theoretical investigation of water reducer of the present invention:
1. Concrete Additive metal surface promoting agent category, add in concrete and significantly can reduce solvent and its liquid-liquid interface tension force, have hydrophilic, lipophilic group, hydrophilic radical generally has-OH ,-COOH ,-C-NH
2,
(carbonyl) ,-SO
3r, these groups not only make molecule have wetting ability, but also molecule can be made to have dispersiveness, oilness, thickening property etc., if use proper, these performances can show preferably.
2. concerning solid-liquid interface, because surface has intrinsic shape, surfactant adsorption makes surface tension γ decline, and thus produces a series of surface phenomena, as dispersion, wetting, foaming, emulsification, washing, lubricates, improves system stability.Water reducer dissociates, and the electrokinetic potential ζ of micelle is improved, and electrostatic repulsion increases, and forms adsorption film with cement grains, and release free-water, has diminishing and plastify effect.
3. in admixture, some functional group can be combined into hydrogen bond in grout, makes water particle microparticle surfaces form the stable solvent hydration shell of one deck, has inhibition, thus reaches guarantor and mould effect.
4., in concrete mixture, introduce certain micro-bubble and can play thickening, water retention.
5. the Ca (OH) that reactive polymer and hydrated cementitious are separated out is utilized
2complex reaction, makes cement surface form one deck complex compound and hinders cement early hydration, have slow setting, protects and mould effect.
6. in admixture, sulfo group can play water-reduction, and-OH ,-COOH etc. play guarantor's effect of collapsing, and therefore, make-SO
3r and the-functional group such as OH ,-COOH are grafted in water-soluble polymer.
Reaction mechanism of the present invention and countermeasure:
According to above theory, sodium sulfanilate, sodium naphthalene sulfonate, aliphatic water reducing agent, phenol is selected to be main raw material, general-SO
3r ,-NH
2the functional groups such as ,-OH pass through CH
2the bridging effect of O, connects into the flexible macromolecule of a gear-like by various functional group.Its reaction mechanism is as follows:
Therefore, according to theoretical foundation and reaction mechanism, following measures is taked:
Therefore, introducing-OH ,-COOH ,-C-NH in water-soluble polymer
2,
(carbonyl) ,-SO
3the hydrophilic radicals such as R, its molecular weight of strict control, makes macromolecular structure be the soft line style of gear-like, adjustment pH, itself and cement grains are spatially adsorbed, surface tension reduces, and increases its space repulsion, and 2eta current potential declines reduction at any time, dispersion effect is better, little loss of slump, and mixture cohesiveness, the increase of trickling property can be made, thickening Water-saving effect is desirable.
Early strong, thickening, guarantor are moulded, thickening, strengthen, the component such as to intensify and carry out composite, thus cement water reducing agent is had superly to mould, protect mould, anti-segregation, thickening, early strong, enhancing etc. are multi-functional.
Below in conjunction with example, the present invention will be further described:
Embodiment 1:
Proportioning raw materials 1:37% formaldehyde 9.6%, phenol 3%, urea 2%, sodium sulfanilate 6%, sodium naphthalene sulfonate 12%, aliphatic water reducing agent 6%, 98% sulfuric acid 5%, 30%NaOH solution 10%, Walocel MT 20.000PV 0.1%, sodium lauryl sulphate (K12) 0.2%, Sulfothiorine 1%, ammonium persulphate 0.1%, water 45%.
Proportioning raw materials 2:37% formaldehyde 8%, phenol 4%, urea 3%, sodium sulfanilate 7%, sodium naphthalene sulfonate 11%, aliphatic water reducing agent 8%, 98% sulfuric acid 5%, 30%NaOH solution 12%, Walocel MT 20.000PV 0.15%, sodium lauryl sulphate (K12) 0.3%, Sulfothiorine 1.5%, ammonium persulphate 0.05%, water 40%, the weight percent of above each component is 100%.
The preparation method of above-mentioned two kinds of proportionings is all as follows:
1. raw material is taken by above-mentioned weight percent;
2. by step 1. in the urea that takes and formaldehyde soluble in water, be placed in hold-up vessel, under 40-50 DEG C of condition, react 1-2h, obtain mixed solution one;
3. by step 1. in the phenol, the sulfuric acid that take add in retort, mix, then the mixed solution one of 1/3rd volumes dropped in retort, be heated to 60-70 DEG C, reaction 1h;
4. by step 1. in the sodium sulfanilate, sodium naphthalene sulfonate, aliphatic water reducing agent and the ammonium persulphate that take add step 3. in retort in, mix, then the mixed solution one of residue 2/3rds volume is dropped in retort, be heated to 80-90 DEG C, reaction 3-4h;
5. by step 4. in mixture temperature be down to 55-65 DEG C, proceed in neutralization tank, then add step 1. in the 30%NaOH solution that takes, mix;
6. by step 1. in the sodium lauryl sulphate that takes and Walocel MT 20.000PV be added in neutralization tank, mix;
7. by step 1. in the Sulfothiorine that takes be added in the mixture 6. processed through step, stir, then dry, obtain high-strength and high performance water reducer.
Embodiment 2:
High-strength high-performance concrete high molecular polymer admixture (filling a prescription 1 in embodiment) is strangled in mine (main shaft, auxiliary shaft, ventilating shaft) C80P12 at the dejected height of Ordos, inner Mongolia Hangjin Banner Shenhua Group and is applied.
It is 1,200 ten thousand tons that the dejected height of Shenhua Group strangles colliery annual output designed productive capacity, dark 650 meters of mine; Concrete inner wall adopts C80P12 concrete, and the slump keeps 220mm after requiring one hour; By experimental study and concrete proportion design, successful Application high-strength and high performance admixture preparation C80P12 concrete reaches 30000m
3by construction, check through construction engineering quality monitoring station, Erdos, concrete strength, imperviously all reach design requirements, achieve good techno-economic effect, its weather resistance is evaluated, compared to the concrete not adding water reducer, weather resistance improves 2.4 times, and other design parameters are as shown in table 1 below.
The technical parameter in mine construction strangled by table 1 concrete of the present invention high molecular polymer admixture at the dejected height of Shenhua Group
| 3 days ultimate compression strength (MPa) | Within 3 days, intensity reaches per-cent | 28 days ultimate compression strength (MPa) | Strength growth rate | 1h collapses damage | Water-reducing rate |
| 47.2 | 50.8％ | 92.9 | 96.8％ | <20mm | 27.8％ |
Embodiment 3:
High-strength high-performance concrete high molecular polymer admixture (filling a prescription 1 in embodiment) is examined at Ordos, inner Mongolia state electricity and is breathed out application in plain mine (main shaft, auxiliary shaft, ventilating shaft).
State's electricity is examined and is breathed out plain Coal Mines Hebei electric power and state's electricity jjoint venture investment, year designed productive capacity is that 1,500 ten thousand tons of state's electricity are examined and breathed out element to strangle mine (auxiliary shaft, ventilating shaft) be vertical, dark 580 meters, main shaft is inclined shaft, auxiliary shaft and ventilating shaft inwall adopt concrete C70P10, and the slump keeps 200mm after requiring one hour; Successful Application high-strength and high performance admixture preparation C70P10 concrete reaches 18000m
3by construction, detect unit through construction engineering quality monitoring station, Erdos and coal system to detect, concrete strength, imperviously all reach design requirements, achieve good techno-economic effect, its weather resistance is evaluated, compared to the concrete not adding water reducer, weather resistance improves 2.3 times, and other design parameters are as shown in table 2 below.
Table 2 concrete of the present invention high molecular polymer admixture examines at state's electricity the technical parameter breathed out in plain mine construction
| 3 days ultimate compression strength (MPa) | Within 3 days, intensity reaches per-cent | 28 days ultimate compression strength (MPa) | Strength growth rate | 1h collapses damage | Water-reducing rate |
| 44.4 | 53.6％ | 82.9 | 86.7％ | <20mm | 28.6％ |
Embodiment 4:
High-strength high-performance concrete high molecular polymer admixture (filling a prescription 1 in embodiment) is applied high the strangling in coal mine (main shaft, auxiliary shaft, ventilating shaft) of Ordos, inner Mongolia Wushen Banner Ba Yan.
Wushen Banner Ba Yan is high, and to strangle colliery be invested by Shandong Zibo mineral group company, year designed productive capacity be 8,000,000 tons, main shaft, auxiliary shaft, ventilating shaft inwall adopt C65-C80 concrete, and successful Application high-strength and high performance admixture preparation C65-C80 concrete reaches 20000m
3concrete workability is good, and formation of concrete is bright and clean, without pitted skin, crackle, concrete strength, impervious, freeze-thaw-all meets design requirement, and achieves good techno-economic effect, its weather resistance is evaluated, compared to the concrete not adding water reducer, weather resistance improves 2.52 times, and other design parameters are as shown in table 3 below.
Table 3 concrete of the present invention high molecular polymer admixture is at the high technical parameter strangled in coal mine engineering of Wushen Banner Ba Yan
| 3 days ultimate compression strength (MPa) | Within 3 days, intensity reaches per-cent | 28 days ultimate compression strength (MPa) | Strength growth rate | 1h collapses damage | Water-reducing rate |
| 46.2 | 50.8％ | 90.8 | 96.9％ | <20mm | 29％ |
Embodiment 5:
High-strength high-performance concrete high molecular polymer admixture (filling a prescription 1 in embodiment), in walnut valley, Gansu coal mine (auxiliary shaft, ventilating shaft), is applied in Xin Zhuan colliery (main shaft, auxiliary shaft).Colliery year, designed productive capacity was 8,000,000 tons, and dark 900 meters of vertical, (auxiliary shaft, ventilating shaft) outer wall adopts C80P8, and inwall adopts C80P10, and having applied C80P8 concrete has 20000m
3, C80P10 concrete has 30000m
3, by the checking of construction engineering quality inspection center of Shaanxi Province, and obtain good techno-economic effect, evaluate its weather resistance, compared to the concrete not adding water reducer, weather resistance improves 2.45 times, and other design parameters are as shown in table 4 below.
The technical parameter of table 4 concrete high molecular polymer of the present invention admixture in the coal mine engineering of walnut valley, Gansu
| 3 days ultimate compression strength (MPa) | Within 3 days, intensity reaches per-cent | 28 days ultimate compression strength (MPa) | Strength growth rate | 1h collapses damage | Water-reducing rate |
| 49 | 53.4％ | 91.7 | 87.1％ | <20mm | 26.8％ |
Embodiment 6:
High-strength high-performance concrete high molecular polymer admixture (filling a prescription 1 in embodiment) application in Shanxi Gao Jiabao coal mine (main shaft, auxiliary shaft, ventilating shaft), the outer wall thickness of main shaft, auxiliary shaft, ventilating shaft is 500-700mm, adopt C30-C50 chutable concrete, interior wall thickness 800-1500mm, adopt C60-C70 high slump concrete, concrete total amount is about 120000m
3formation of concrete is bright and clean, without pitted skin, crackle, concrete strength, impervious, freeze-thaw-all meets design requirement, achieve good techno-economic effect, its weather resistance is evaluated, compared to the concrete not adding water reducer, weather resistance improves 2.7 times, and other design parameters are as shown in table 5 below.
The technical parameter of table 5 concrete high molecular polymer of the present invention admixture in the coal mine engineering of walnut valley, Gansu
| 3 days ultimate compression strength (MPa) | Within 3 days, intensity reaches per-cent | 28 days ultimate compression strength (MPa) | Strength growth rate | 1h collapses damage | Water-reducing rate |
| 40.9 | 50.2％ | 81.5 | 99.3％ | <20mm | 25.9％ |
Claims (3)
1. a high-strength high-performance concrete high molecular polymer admixture, is characterized in that, is made up of following raw material:
37% formaldehyde, phenol, urea, sodium sulfanilate, sodium naphthalene sulfonate, aliphatic water reducing agent, 98% sulfuric acid, 30%NaOH solution, Walocel MT 20.000PV, sodium lauryl sulphate, Sulfothiorine, ammonium persulphate, water;
The weight percent of above-mentioned raw materials is:
37% formaldehyde 8-12%, phenol 2-5%, urea 1-5%, sodium sulfanilate 3-8%, sodium naphthalene sulfonate 10-15%, aliphatic water reducing agent 4-9%, 98% sulfuric acid 3-8%, 30%NaOH solution 8-14%, Walocel MT 20.000PV 0.05-0.2%, sodium lauryl sulphate 0.1-0.4%, Sulfothiorine 0.5-2.2%, ammonium persulphate 0.05-0.12%, water 40-60%, the weight percent of above each component is 100%.
2. high-strength high-performance concrete high molecular polymer admixture according to claim 1, is characterized in that, be made up of the raw material of following weight percent:
37% formaldehyde 9.6%, phenol 3%, urea 2%, sodium sulfanilate 6%, sodium naphthalene sulfonate 12%, aliphatic water reducing agent 6%, 98% sulfuric acid 5%, 30%NaOH solution 10%, Walocel MT 20.000PV 0.1%, sodium lauryl sulphate 0.2%, Sulfothiorine 1%, ammonium persulphate 0.1%, water 45%, the weight percent of above each component is 100%.
3. a preparation method for the high-strength high-performance concrete high molecular polymer admixture according to the arbitrary claim of claim 1-2, is characterized in that, comprise the following steps:
1. raw material is taken by the weight percent described in claim 1-2;
2. by step 1. in the urea that takes and formaldehyde soluble in water, be placed in hold-up vessel, under 40-50 DEG C of condition, react 1-2h, obtain mixed solution one;
3. by step 1. in the phenol, the sulfuric acid that take add in retort, mix, then the mixed solution one of 1/3rd volumes dropped in retort, be heated to 60-70 DEG C, reaction 1h;
4. by step 1. in the sodium sulfanilate, sodium naphthalene sulfonate, aliphatic water reducing agent and the ammonium persulphate that take add step 3. in retort in, mix, then the mixed solution one of residue 2/3rds volume is dropped in retort, be heated to 80-90 DEG C, reaction 3-4h;
5. by step 4. in mixture temperature be down to 55-65 DEG C, proceed in neutralization tank, then add step 1. in the 30%NaOH solution that takes, mix;
6. by step 1. in the sodium lauryl sulphate that takes and Walocel MT 20.000PV be added in neutralization tank, mix;
7. by step 1. in the Sulfothiorine that takes be added in the mixture 6. processed through step, stir, then dry, obtain high-strength and high performance water reducer.
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