CN105130269A - High-water-reduction high-early-strength type polycarboxylic acid water reducing agent and pyrogen-free preparation method thereof - Google Patents
High-water-reduction high-early-strength type polycarboxylic acid water reducing agent and pyrogen-free preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of concrete admixture in building materials, and provides a high-water-reduction high-early-strength type polycarboxylic acid water reducing agent and a pyrogen-free preparation method thereof. Firstly, a high-early-strength type polycarboxylic acid water reducing agent mother liquid is obtained by using a redox initiation system under a pyrogen-free condition, then an optimized early-strength component, a defoaming agent and water are added, and compounding is carried out to obtain the product, wherein the high-early-strength type polycarboxylic acid water reducing agent mother liquid is prepared from unsaturated polyoxyethylene ether (MW=3800-4000), a chain transfer agent, unsaturated acid and/or an unsaturated acid derivative, an oxidant, a reductant and water. The water reducing agent has low mixing amount, and has the advantages of high water reducing rate, good early strength effect, good cement adaptability and the like; moreover, the process does not need additional pyrogen, can be carried out at normal temperature, has less equipment investment and low cost, and is suitable for large-area popularization and application. The water reducing agent can greatly improve the early strength of concrete, improves the template turnover speed, improves the work efficiency, is beneficial for improving constructional engineering quality and improving the production efficiency, reduces energy consumption, and reduces construction costs.
Description
Technical field
The present invention relates to the reinforcement of concrete admixture technical field in material of construction, particularly relate to a kind of high diminishing height high-early strength type polycarboxylic acids dehydragent and without thermal source method for making.
Background technology
Culture's material that in the concrete world today, consumption is maximum.Concrete admixture is before mixing concrete mixing or mixes to improve the material of concrete performance in mix process, can effectively improve concrete performance, become material indispensable in concrete.
Modern age, concrete admixture originated from early 1930s, experienced by s-generation high efficiency water reducing agent that first-generation ordinary water-reducing agent that wooden calcium is representative, naphthalene system and trimeric cyanamide are representative, third generation high-performance water reducing agent three phases that polycarboxylic acid series is representative, the developing history of existing more than 80 year so far.Water reducer, slump retaining agent, accelerating chemicals, retardant, defoamer, hardening accelerator etc. is mainly divided into by the function of admixture.Polycarboxylate water-reducer uses more and more extensive in the engineering of China as third generation water reducer, relative to water reducers such as naphthalene system and melamine series, its dissemination is effective, and the hold-time is long, and concrete can be made to have good serviceability.
After mixing polycarboxylate water-reducer, concrete can be made to have good serviceability and mechanical property, at structure durabilities such as high-speed railways, it requires that in high engineering, advantage is particularly outstanding.Its excellent performance derives from its special comb shaped molecular structure, main chain is adsorbed in cement particle surface, forms firmly adsorption layer, is that fine hair shape stretches in aqueous by polyethylene oxide side chains, form strong sterically hindered effect, make cement granules obtain significant dissemination.But, coventional type polycarboxylate water-reducer significantly can delay the aquation of cement, especially under cryogenic, early strength slower development, common polycarboxylate water-reducer is constructed in the winter time and the use of cold environment is restricted, also constrain and requiring the use in early strong engineering and concrete prefabricated element.
During concrete prefabricated element is produced, in order to increase production efficiency, improve template turn-around speed, not only require that polycarboxylate water-reducer has good diminishing dissemination, also requirement can improve early age strength of concrete; In addition, in order to accelerate speed of application under cold condition, also require that concrete has desirable epistasis energy morning.
At present, improve early age strength of concrete and have three kinds of main paties: (1) uses extraordinary strength cement and increases cement consumption (output and price is restricted can not generally adopt); (2) adopt vapor cure, even the technological approaches of microwave curing improves early age strength of concrete as far as possible.(be unfavorable for the raising of volume stability of concrete and weather resistance, vapor cure and microwave curing are unfavorable for environmental protection, energy-conservation requirement); (3) early-strength admixture (working method is simple, with low cost) is used.
The mode that early-strength admixture adopts naphthalene water reducer (or melamine system water reducer) or common poly carboxylic acid series water reducer and hardening accelerator (trolamine, sodium sulfate, sodium-chlor etc.) composite usually, but there is with hardening accelerator is composite the shortcoming that concrete plasticity is poor, slump-loss is large that water-reducing rate is not high enough, prepare in naphthalene water reducer (or melamine system water reducer); Adopt common poly carboxylic acid series water reducer and hardening accelerator (trolamine, sodium sulfate, sodium-chlor etc.) composite, there is the shortcomings such as unstable product quality, easily layering.
Patent CN201410220236 utilizes isobutene alcohol Soxylat A 25-7 (HPEG), vinylformic acid (AA), 2-acrylamide-2-methyl propane sulfonic (AMPS) polymerization obtains a kind of high-early strength type polycarboxylic acids dehydragent, but needs to synthesize at the temperature of 40-45 DEG C; The modification polyoxyalkylenes ether of patent CN201110291956 utilization containing unsaturated double-bond, (methyl) vinylformic acid, the sulfonate of unsaturated double-bond, acrylamide four kinds of monomers are under molecular weight regulator existence condition, carry out aqueous solution copolymerization by free radical initiation and obtain high-early strength type polycarboxylic acids dehydragent, but needing to synthesize at the temperature of 50-70 DEG C.
In the high-early strength type polycarboxylic acids dehydragent synthetic method that above-mentioned patent is announced, all need steam or boiler heating, add energy consumption and facility investment, production cost is high, is unfavorable for energy-saving and emission-reduction and reduces costs.
Summary of the invention
In order to overcome above-mentioned defect, invention has been and study extensively and profoundly, by being main macromonomer with unsaturated Soxylat A 25-7, design for poly carboxylic acid series water reducer comb shaped molecular structure, by selecting suitable polymeric monomer and polymerization technique, adjustment molecular architecture and functional group densities and kind, synthesis high-early strength type polycarboxylic acids dehydragent mother liquor, compound, with subsidiary material such as various high-quality accelerating component, defoamers, obtains high diminishing height early-strength type polycarboxylic admixture.Make full use of the high high water reducing rate of diminishing height early-strength type polycarboxylic admixture and the feature of works fine performance, change the hydration influences of poly carboxylic acid series water reducer to cement, shorten concrete coagulating time, improve early age strength of concrete, enhance productivity, save cost.
The object of the invention is to overcome in the past water reducer complex manufacturing, produce that power consumption is high, quality is unstable shortcomings such as (as layerings etc.), provide that a kind of technique is simple, energy-conserving and environment-protective, excellent performance high diminishing height high-early strength type polycarboxylic acids dehydragent and without thermal source method for making.
The technical solution adopted for the present invention to solve the technical problems is: a kind of high diminishing height high-early strength type polycarboxylic acids dehydragent, is characterized in that: be made up of the raw material of following weight percent, high-early strength type polycarboxylic acids dehydragent mother liquor 10% ~ 30%; Accelerating component 1% ~ 15%; Defoamer 0.005% ~ 0.02%; Water surplus;
Wherein, high-early strength type polycarboxylic acids dehydragent mother liquor is made up of the raw material of following weight percent:
Unsaturated Soxylat A 25-7 33% ~ 37%; Unsaturated acid and/or unsaturated acid derivative 2% ~ 6%; Chain-transfer agent 0.1% ~ 0.8%; Oxygenant 0.1% ~ 0.3%; Reductive agent 0.03% ~ 0.08%; Alkali 0.5% ~ 1.0%; All the other are water;
The molecular-weight average of described unsaturated Soxylat A 25-7 is at 3800-4000.
Described alkali is preferably sodium hydroxide.
The preparation method of described high-early strength type polycarboxylic acids dehydragent mother liquor comprises the steps:
1. get the raw materials ready: reductive agent is mixed the obtained reductive agent aqueous solution with water, be denoted as a material; By chain-transfer agent, unsaturated acid and/or unsaturated acid derivative, the obtained aqueous solution of water mixing, be denoted as b material;
2. be polymerized: unsaturated Soxylat A 25-7 and water are added in reactor, is stirred to dissolving, add oxygenant; After stirring, add a material and b material, when controlling reinforced, temperature in the kettle is 15 ~ 40 DEG C simultaneously, and after reinforced, continue reaction 1.5 ~ 3 hours, being neutralized to pH with alkaline solution is 7 ~ 9, obtains high-early strength type polycarboxylic acids dehydragent mother liquor.
Described add a material and b expect time controling at 2 ~ 4 hours.
Described accelerating component is one or more in trolamine, sodium sulfate and sodium-chlor, is preferably one or more in trolamine and sodium sulfate.
Described defoamer is at least one in machine silicon defoaming agent and polyethers defoamer.
Preferred b material is the aqueous solution that chain-transfer agent, unsaturated acid, unsaturated acid derivative and water obtain, and can obtain the early better water reducer of potent fruit like this.
Described unsaturated acid is vinylformic acid; Unsaturated acid derivative is one or more in acrylamide, ethyl propenoate, butyl acrylate.
Described oxygenant is one or more in hydrogen peroxide, ammonium persulphate, Potassium Persulphate and Sodium Persulfate, and preferred oxidant is hydrogen peroxide.
Described chain-transfer agent is one or more in thiohydracrylic acid, methylpropene sodium sulfonate, Thiovanic acid.
Described reductive agent is one or more in L-AA, ferrous sulfate and sodium bisulfite.
The present invention also provides a kind of preparation method of high diminishing height high-early strength type polycarboxylic acids dehydragent, comprises the steps:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor is prepared
1. get the raw materials ready: reductive agent is mixed the obtained reductive agent aqueous solution with water, be denoted as a material; By chain-transfer agent, unsaturated acid and/or unsaturated acid derivative, the obtained aqueous solution of water mixing, be denoted as b material;
2. be polymerized: unsaturated Soxylat A 25-7 and water are added in reactor, is stirred to dissolving, add oxygenant; After stirring, add a material and b material, when controlling reinforced, temperature in the kettle is 15 ~ 40 DEG C simultaneously, and after reinforced, continue reaction 1.5 ~ 3 hours, being neutralized to pH with alkaline solution is 7 ~ 9, obtains high-early strength type polycarboxylic acids dehydragent mother liquor;
(2) high diminishing height high-early strength type polycarboxylic acids dehydragent is prepared
Add water, defoamer, high-early strength type polycarboxylic acids dehydragent mother liquor in a reservoir successively, mixing and stirring, then add accelerating component and stir and obtain high diminishing height high-early strength type polycarboxylic acids dehydragent.
The time controling of a material and b material is added at 2 ~ 4 hours preferably.
In this programme, the synthesis of high-early strength type polycarboxylic acids dehydragent mother liquor without the need to thermal source, add a material and b expect time be thermopositive reaction, when controlling reinforced, temperature in the kettle is 15 ~ 40 DEG C, the high-early strength type polycarboxylic acids dehydragent mother liquor that synthesis and accelerating component act synergistically, cost is low, and technique is simple.
The present invention, compared with like product and technique, has significant beneficial effect:
1, high-early strength type polycarboxylic acids dehydragent mother liquor of the present invention is according to molecular design theory, by preferred polymeric monomer, adjustment polycarboxylate water-reducer molecular backbone chain and side-chain structure, because molecular side chain is longer (lower to cement granules parcel property, cause hydrated cementitious to accelerate) and polymerization time introduce there is early powerful monomer, high-early strength type polycarboxylic acids dehydragent mother liquor effectively can be polymerized with powerful monomer morning, concrete coagulating time is shortened than coventional type poly carboxylic acid series water reducer mother liquor, improve early age strength of concrete, thus it is long for time of coagulation to solve traditional poly carboxylic acid series water reducer, early strength is low, the shortcoming of quality instability, realize the high early strong dual-use function of polycarboxylate water-reducer height diminishing,
The advantages such as the high diminishing height high-early strength type polycarboxylic acids dehydragent that 2, prepared by the present invention has high diminishing, high morning is strong, cement adaptability is wide, energy-conserving and environment-protective, can significantly reduce concrete water cement ratio, after composite accelerating component, concrete coagulating time can be shortened further, improve early age strength of concrete, the concrete serviceability of remarkable improvement, mechanical property and endurance quality, significant to aspects such as construction cost of enhancing productivity, reduce, saving reduce discharging, improve construction engineering quality and increase the service life.
3, preparation technology of the present invention is simple; and carry out at normal temperature; steam or boiler is not needed to provide thermal source; reaction system is stablized, and easily controls, and overcomes in traditional high performance water reducing agent of polyocarboxy acid preparation process the shortcoming needing to heat; whole reaction process is solvent-free; environmental protection, belongs to cleaner production, is conducive to energy-saving and emission-reduction and environment protection.
Embodiment
Comparative example 1
Prepare common poly carboxylic acid series water reducer P-1 by following material quantity and technique, be specially:
1. get the raw materials ready: L-AA 0.30g, add in 13g deionized water, mix, A tank is for subsequent use, is be a material; Vinylformic acid 23.0g, methylpropene sodium sulfonate 4.0 grams, adds in 40g deionized water, mixes, and B tank is for subsequent use, is be b material;
2. be polymerized: in the glass reactor being furnished with thermometer and electric blender, add deionized water 283.45g and allyl polyethenoxy ether (MW=2400) 200g, stir after fully dissolving, be warming up to 60 DEG C, add the H that mass concentration is 30%
2o
20.50g, stir, then drip a material and b material simultaneously, a gob adds 3 hours, b gob adds 2.5 hours, and a material dropwises rear continuation reaction response 2 hours, is neutralized to pH value to 6.8 ~ 7.2 with 30% aqueous sodium hydroxide solution 15 grams, obtain coventional type poly carboxylic acid series water reducer mother liquor P-1, its solid content is about 40%.
Comparative example 2
In container C, add deionized water 862.4 grams, silicone antifoam agent 0.1 gram, coventional type poly carboxylic acid series water reducer mother liquor P-1125 gram successively, mix and blend, adds accelerating component trolamine 12.5 grams, stirs, obtain poly carboxylic acid series water reducer F-1.
Embodiment 1
Prepare high diminishing high collapse protection type polycarboxylate high performance water-reducing agent by following material quantity and technique, be specially:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor T-1 is prepared
1. get the raw materials ready: L-AA 0.20g, add in 13g deionized water, mix, A tank is for subsequent use, is be a material; Vinylformic acid 12.0g, acrylamide 5.0g, methylpropene sodium sulfonate 2.16 grams, adds in 40g deionized water, mixes, and B tank is for subsequent use, is be b material;
2. be polymerized: in the glass reactor being furnished with thermometer and electric blender, add deionized water 289.5g, unsaturated Soxylat A 25-7 (MW=4000) 210g, stir after fully dissolving, add the H that mass concentration is 30%
2o
21.45g, stir, constant temperature to 15 DEG C, drips a material and b material simultaneously, controls polymerization temperature at 15 ~ 40 DEG C, a gob adds 3 hours, b gob adds 2.5 hours, and a material dropwises rear continuation reaction response 2 hours, is neutralized to pH value to 6.8 ~ 7.2 with 30% aqueous sodium hydroxide solution 15 grams, obtain high-early strength type polycarboxylic acids dehydragent mother liquor T-1, its solid content is about 40%.
(2) high diminishing height high-early strength type polycarboxylic acids dehydragent Z-1 is prepared
Deionized water 862.4 grams, silicone antifoam agent 0.05 gram, high-early strength type polycarboxylic acids dehydragent mother liquor T-1125 gram is added successively in container C, mix and blend, add accelerating component trolamine 12.5 grams, stir, obtain high diminishing height high-early strength type polycarboxylic acids dehydragent Z-1.
Embodiment 2
Prepare high diminishing high collapse protection type polycarboxylate high performance water-reducing agent by following material quantity and technique, be specially:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor T-2 is prepared
1. get the raw materials ready: L-AA 0.35g, add in 13g deionized water, mix, A tank is for subsequent use, is be a material; Vinylformic acid 16.0g, acrylamide 6.0g, 3-thiohydracrylic acid 0.45g, add in 40g deionized water, mix, B tank is for subsequent use, is be b material;
2. be polymerized: in the glass reactor being furnished with thermometer and electric blender, add deionized water 187.3g and unsaturated Soxylat A 25-7 (MW=4000) 140g, stir after fully dissolving, add the H that mass concentration is 30%
2o
20.57g, stir, constant temperature to 18 DEG C, drips a material and b material simultaneously, controls polymerization temperature at 15 ~ 40 DEG C, a gob adds 3 hours, b gob adds 2.5 hours, and a material dropwises rear continuation reaction response 2 hours, is neutralized to pH value to 6.8 ~ 7.2 with 30% aqueous sodium hydroxide solution 16 grams, obtain high-early strength type polycarboxylic acids dehydragent mother liquor T-2, its solid content is about 40%.
(2) high diminishing height high-early strength type polycarboxylic acids dehydragent Z-2 is prepared
Deionized water 862.4 grams, silicone antifoam agent 0.05 gram, high-early strength type polycarboxylic acids dehydragent mother liquor T-2125 gram is added successively in container C, mix and blend, add accelerating component trolamine 12.5 grams, stir, obtain high diminishing height high-early strength type polycarboxylic acids dehydragent Z-2.
Embodiment 3
Prepare high diminishing high collapse protection type polycarboxylate high performance water-reducing agent by following material quantity and technique, be specially:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor T-3 is prepared
1. get the raw materials ready: L-AA 0.21g, add in 13g deionized water, mix, A tank is for subsequent use, is be a material; Vinylformic acid 12.0g, acrylamide 5.0g, methylpropene sodium sulfonate 2.28 grams adds in 40g deionized water, mixes, and B tank is for subsequent use, is be b material;
2. be polymerized: in the glass reactor being furnished with thermometer and electric blender, add deionized water 228.7g, unsaturated Soxylat A 25-7 (MW=3800) 170g, stir after fully dissolving, add the H that mass concentration is 30%
2o
20.57g, stir, constant temperature to 27 DEG C, drips a material and b material simultaneously, controls polymerization temperature at 15 ~ 40 DEG C, a gob adds 3 hours, b gob adds 2.5 hours, and a material dropwises rear continuation reaction response 2 hours, is neutralized to pH value to 6.8 ~ 7.2 with 30% aqueous sodium hydroxide solution 14.5 grams, obtain high-early strength type polycarboxylic acids dehydragent mother liquor T-3, its solid content is about 40%.
(2) high diminishing height high-early strength type polycarboxylic acids dehydragent Z-3 is prepared
Deionized water 862.4 grams, silicone antifoam agent 0.05 gram, high-early strength type polycarboxylic acids dehydragent mother liquor T-3125 gram is added successively in container C, mix and blend, add accelerating component trolamine 12.5 grams, stir, obtain high diminishing height high-early strength type polycarboxylic acids dehydragent Z-3.
Embodiment 4
Prepare high diminishing high collapse protection type polycarboxylate high performance water-reducing agent by following material quantity and technique, be specially:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor T-4 is prepared
1. get the raw materials ready: L-AA 0.45g, add in 13g deionized water, mix, A tank is for subsequent use, is be a material; Vinylformic acid 11.0g, acrylamide 3.0g, 2 mercaptopropionic acid 0.39 gram, adds in 40g deionized water, mixes, and B tank is for subsequent use, is be b material;
2. be polymerized: in the glass reactor being furnished with thermometer and electric blender, add deionized water 281.4g and unsaturated Soxylat A 25-7 (MW=4000) 210g, stir after fully dissolving, add the H that mass concentration is 30%
2o
20.62g, stir, constant temperature to 13 DEG C, drips a material and b material simultaneously, controls polymerization temperature at 15 ~ 40 DEG C, a gob adds 3 hours, b gob adds 2.5 hours, and a material dropwises rear continuation reaction response 2 hours, is neutralized to pH value to 6.8 ~ 7.2 with 30% aqueous sodium hydroxide solution 16 grams, obtain high-early strength type polycarboxylic acids dehydragent mother liquor T-4, its solid content is about 40%.
(2) high diminishing height high-early strength type polycarboxylic acids dehydragent Z-4 is prepared
Deionized water 862.4 grams, silicone antifoam agent 0.05 gram, high-early strength type polycarboxylic acids dehydragent mother liquor T-4125 gram is added successively in container C, mix and blend, add accelerating component trolamine 12.5 grams, stir, obtain high diminishing height high-early strength type polycarboxylic acids dehydragent Z-4.
Embodiment 5
Deionized water 862.3 grams, silicone antifoam agent 0.20 gram, high-early strength type polycarboxylic acids dehydragent mother liquor T-3125 gram is added successively in container C, mix and blend, add accelerating component trolamine 12.5 grams, stir, obtain high diminishing height high-early strength type polycarboxylic acids dehydragent Z-5.
Embodiment 6
Deionized water 749.8 grams, silicone antifoam agent 0.20 gram, high-early strength type polycarboxylic acids dehydragent mother liquor T-3125 gram is added successively in container C, mix and blend, add 125 grams, accelerating component sodium sulfate, stir, obtain high diminishing height high-early strength type polycarboxylic acids dehydragent Z-6.
Embodiment 7
Deionized water 737.3 grams, silicone antifoam agent 0.20 gram, high-early strength type polycarboxylic acids dehydragent mother liquor T-3125 gram is added successively in container C, mix and blend, add 125 grams, accelerating component sodium sulfate, trolamine 12.5 grams, stir, obtain high diminishing height high-early strength type polycarboxylic acids dehydragent Z-7.
Embodiment 8
Prepare high diminishing high collapse protection type polycarboxylate high performance water-reducing agent by following material quantity and technique, be specially:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor T-5 is prepared
1. get the raw materials ready: L-AA 0.21g, add in 13g deionized water, mix, A tank is for subsequent use, is be a material; Vinylformic acid 12.0g, methylpropene sodium sulfonate 2.28 grams adds in 40g deionized water, mixes, and B tank is for subsequent use, is be b material;
2. be polymerized: in the glass reactor being furnished with thermometer and electric blender, add deionized water 221.2g, unsaturated Soxylat A 25-7 (MW=3800) 170g, stir after fully dissolving, add the H that mass concentration is 30%
2o
20.57g, stir, constant temperature to 27 DEG C, drips a material and b material simultaneously, controls polymerization temperature at 15 ~ 40 DEG C, a gob adds 3 hours, b gob adds 2.5 hours, and a material dropwises rear continuation reaction response 2 hours, is neutralized to pH value to 6.8 ~ 7.2 with 30% aqueous sodium hydroxide solution 14.5 grams, obtain high-early strength type polycarboxylic acids dehydragent mother liquor T-5, its solid content is about 40%.
(2) high diminishing height high-early strength type polycarboxylic acids dehydragent Z-8 is prepared
Deionized water 862.4 grams, silicone antifoam agent 0.05 gram, high-early strength type polycarboxylic acids dehydragent mother liquor T-5125 gram is added successively in container C, mix and blend, add accelerating component trolamine 12.5 grams, stir, obtain high diminishing height high-early strength type polycarboxylic acids dehydragent Z-8.
Embodiment 9
Prepare high diminishing high collapse protection type polycarboxylate high performance water-reducing agent by following material quantity and technique, be specially:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor T-6 is prepared
1. get the raw materials ready: L-AA 0.45g, add in 13g deionized water, mix, A tank is for subsequent use, is be a material; Vinylformic acid 11.0g, acrylamide 3.0g, 2 mercaptopropionic acid 0.39 gram, adds in 40g deionized water, mixes, and B tank is for subsequent use, is be b material;
2. be polymerized: in the glass reactor being furnished with thermometer and electric blender, add deionized water 281.4g and unsaturated Soxylat A 25-7 (MW=4000) 210g, stir after fully dissolving, add the ammonium persulphate 0.62g that mass concentration is 30%, stir, constant temperature to 13 DEG C, drip a material and b material simultaneously, control polymerization temperature at 15 ~ 40 DEG C, a gob adds 3 hours, b gob adds 2.5 hours, a material dropwises rear continuation reaction response 2 hours, pH value is neutralized to 6.8 ~ 7.2 with 30% aqueous sodium hydroxide solution 16 grams, obtain high-early strength type polycarboxylic acids dehydragent mother liquor T-6, its solid content is about 40%.
Described ammonium persulphate can also be at least one of Potassium Persulphate and Sodium Persulfate.
(2) high diminishing height high-early strength type polycarboxylic acids dehydragent Z-9 is prepared
Deionized water 862.4 grams, polyethers defoamer 0.05 gram, high-early strength type polycarboxylic acids dehydragent mother liquor T-6125 gram is added successively in container C, mix and blend, add accelerating component trolamine 12.5 grams, stir, obtain high diminishing height high-early strength type polycarboxylic acids dehydragent Z-9.
Embodiment 10
Prepare high diminishing high collapse protection type polycarboxylate high performance water-reducing agent by following material quantity and technique, be specially:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor T-7 is prepared
1. get the raw materials ready: L-AA 0.45g, add in 13g deionized water, mix, A tank is for subsequent use, is be a material; Vinylformic acid 14.0g, 2 mercaptopropionic acid 0.39 gram, adds in 40g deionized water, mixes, and B tank is for subsequent use, is be b material;
2. be polymerized: in the glass reactor being furnished with thermometer and electric blender, add deionized water 281.4g and unsaturated Soxylat A 25-7 (MW=4000) 210g, stir after fully dissolving, add the H that mass concentration is 30%
2o
20.62g, stir, constant temperature to 13 DEG C, drips a material and b material simultaneously, controls polymerization temperature at 15 ~ 40 DEG C, a gob adds 3 hours, b gob adds 2.5 hours, and a material dropwises rear continuation reaction response 2 hours, is neutralized to pH value to 6.8 ~ 7.2 with 30% aqueous sodium hydroxide solution 16 grams, obtain high-early strength type polycarboxylic acids dehydragent mother liquor T-7, its solid content is about 40%.
(2) high diminishing height high-early strength type polycarboxylic acids dehydragent Z-10 is prepared
Deionized water 862.4 grams, polyethers defoamer 0.05 gram, high-early strength type polycarboxylic acids dehydragent mother liquor T-7125 gram is added successively in container C, mix and blend, add accelerating component trolamine 12.5 grams, stir, obtain high diminishing height high-early strength type polycarboxylic acids dehydragent Z-10.
Embodiment 11
Prepare high diminishing high collapse protection type polycarboxylate high performance water-reducing agent by following material quantity and technique, be specially:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor T-8 is prepared
1. get the raw materials ready: L-AA 0.21g, add in 13g deionized water, mix, A tank is for subsequent use, is be a material; Vinylformic acid 12.0g, acrylamide 5.0g, methylpropene sodium sulfonate 3.80 grams adds in 40g deionized water, mixes, and B tank is for subsequent use, is be b material;
2. be polymerized: in the glass reactor being furnished with thermometer and electric blender, add deionized water 228.7g, unsaturated Soxylat A 25-7 (MW=3800) 170g, stir after fully dissolving, add the H that mass concentration is 30%
2o
20.57g, stir, constant temperature to 27 DEG C, drips a material and b material simultaneously, controls polymerization temperature at 15 ~ 40 DEG C, a gob adds 3 hours, b gob adds 2.5 hours, and a material dropwises rear continuation reaction response 2 hours, is neutralized to pH value to 6.8 ~ 7.2 with 30% aqueous sodium hydroxide solution 14.5 grams, obtain high-early strength type polycarboxylic acids dehydragent mother liquor T-8, its solid content is about 40%.
(2) high diminishing height high-early strength type polycarboxylic acids dehydragent Z-11 is prepared
Deionized water 862.4 grams, silicone antifoam agent 0.05 gram, high-early strength type polycarboxylic acids dehydragent mother liquor T-8125 gram is added successively in container C, mix and blend, add accelerating component trolamine 12.5 grams, stir, obtain high diminishing height high-early strength type polycarboxylic acids dehydragent Z-11.
Embodiment 12
Deionized water 687.45 grams, machine silicon defoaming agent defoamer 0.05 gram, high-early strength type polycarboxylic acids dehydragent mother liquor T-3300 gram is added successively in container C, mix and blend, add accelerating component trolamine 12.5 grams, stir, obtain high diminishing height high-early strength type polycarboxylic acids dehydragent Z-12.
Respectively following test is carried out to high diminishing height high-early strength type polycarboxylic acids dehydragent prepared by above example:
1, product of the present invention and domestic and international product water cement mortar Experimental comparison
This experiment cement is little wild field 42.5R, cement 1000g, and standard sand 2000 grams, water 305g, specific experiment result is as shown in table 1.
Table 1 sand-cement slurry contrast experiment
As can be seen from Table 1, height diminishing height high-early strength type polycarboxylic acids dehydragent of the present invention all has good water-reducing effect and higher dispersive ability, and effect is suitable with external product effect.
2, product of the present invention and domestic and international product concrete experiments contrast
This experiment cement is little wild field 42.5R, and flyash is Huaneng Group secondary ash.Silt content is 2.2%, the medium sand of fineness modulus 2.6.Silt content 0.5%, the stone of particle diameter 5 ~ 25.Churning time is 90 seconds, vibrating time 15 seconds.Proportioning is cement: flyash: breeze: sand: stone: water=190:80:80:1000:840:160.Specific experiment result is as shown in table 2.
Table 2 concrete performance experimental result
As can be seen from Table 2, high diminishing height high-early strength type polycarboxylic acids dehydragent of the present invention has the advantages such as water-reducing effect is good, early strength is high, later strength is not lost, energy-conserving and environment-protective, good stability, excellent combination property.
The foregoing is only specific embodiments of the invention; be not limited to the present invention; for a person skilled in the art, can be improved according to above-described embodiment or convert, and all these improve and conversion all should be included in the protection domain of claims of the present invention.
Claims (10)
1. a high diminishing height high-early strength type polycarboxylic acids dehydragent, is characterized in that: be made up of the raw material of following weight percent, high-early strength type polycarboxylic acids dehydragent mother liquor 10% ~ 30%; Accelerating component 1% ~ 15%; Defoamer 0.005% ~ 0.02%; Water surplus;
Wherein, high-early strength type polycarboxylic acids dehydragent mother liquor is made up of the raw material of following weight percent:
Unsaturated Soxylat A 25-7 33% ~ 37%; Unsaturated acid and/or unsaturated acid derivative 2% ~ 6%; Chain-transfer agent 0.1% ~ 0.8%; Oxygenant 0.1% ~ 0.3%; Reductive agent 0.03% ~ 0.08%; Alkali 0.5% ~ 1.0%; All the other are water;
The molecular-weight average of described unsaturated Soxylat A 25-7 is 3800-4000.
2. high diminishing height high-early strength type polycarboxylic acids dehydragent according to claim 1, is characterized in that: described accelerating component is one or more in trolamine, sodium sulfate and sodium-chlor.
3. high diminishing height high-early strength type polycarboxylic acids dehydragent according to claim 1, is characterized in that: described defoamer is at least one in machine silicon defoaming agent and polyethers defoamer.
4. high diminishing height high-early strength type polycarboxylic acids dehydragent according to claim 1, is characterized in that: described unsaturated acid is vinylformic acid; Unsaturated acid derivative is one or more in acrylamide, ethyl propenoate, butyl acrylate.
5. high diminishing height high-early strength type polycarboxylic acids dehydragent according to claim 1, is characterized in that: described b material is the aqueous solution that chain-transfer agent, unsaturated acid, unsaturated acid derivative and water obtain.
6. high diminishing height high-early strength type polycarboxylic acids dehydragent according to claim 1, is characterized in that: described oxygenant is one or more in hydrogen peroxide, ammonium persulphate, Potassium Persulphate and Sodium Persulfate.
7. high diminishing height high-early strength type polycarboxylic acids dehydragent according to claim 1, is characterized in that: described chain-transfer agent is one or more in thiohydracrylic acid, methylpropene sodium sulfonate, Thiovanic acid.
8. high diminishing height high-early strength type polycarboxylic acids dehydragent according to claim 1, is characterized in that: described reductive agent is one or more in L-AA, ferrous sulfate and sodium bisulfite.
9. the preparation method of a kind of high diminishing height high-early strength type polycarboxylic acids dehydragent piece according to any one of claim 1-8, is characterized in that: comprise the steps:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor is prepared
1. get the raw materials ready: reductive agent is mixed the obtained reductive agent aqueous solution with water, be denoted as a material; By chain-transfer agent, unsaturated acid and/or unsaturated acid derivative, the obtained aqueous solution of water mixing, be denoted as b material;
2. be polymerized: unsaturated Soxylat A 25-7 and water are added in reactor, is stirred to dissolving, add oxygenant; After stirring, add a material and b material, when controlling reinforced, temperature in the kettle is 15 ~ 40 DEG C simultaneously, and after reinforced, continue reaction 1.5 ~ 3 hours, being neutralized to pH with alkaline solution is 7 ~ 9, obtains high-early strength type polycarboxylic acids dehydragent mother liquor;
(2) high diminishing height high-early strength type polycarboxylic acids dehydragent is prepared
Add water, defoamer, high-early strength type polycarboxylic acids dehydragent mother liquor in a reservoir successively, mixing and stirring, then add accelerating component and stir and obtain high diminishing height high-early strength type polycarboxylic acids dehydragent.
10. high diminishing height high-early strength type polycarboxylic acids dehydragent according to claim 9, is characterized in that: described in add a material and b expect time controling at 2 ~ 4 hours.
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