A kind of modified melamine high-efficiency water reducing agent with low cost
Technical field:
The invention belongs to additive for building material and chemosynthesis technical field, be specifically related to a kind of modified melamine high-efficiency water reducing agent with low cost and preparation method thereof.
Background technology:
The production of modern concrete, application be unable to do without concrete admixture, and admixture has become the 5th kind of integral part except cement, water, sand, stone in the concrete.Water reducer is that application surface is the widest in the admixture, and usage quantity is also maximum a kind of, and its consumption accounts for more than 80% of the total consumption of admixture.High efficiency water reducing agent is that a kind of water-reducing rate is high, neither the also water reducer of not bleed of slow setting.Because the appearance of high efficiency water reducing agent just makes high strength, high flowability concrete be achieved, and has guaranteed the development of concrete construction novel process.High efficiency water reducing agent commonly used has naphthalene water reducer, thionamic acid salt water reducer, aliphatics based water reducer, melamine class water reducer and poly carboxylic acid series water reducer etc. at present.
Compare with the general concrete water reducer, melamine superplasticizer can significantly improve concrete intensity and weather resistance; Without bleed, can not form a large amount of bubbles at inside concrete: the fine aluminium acid salt cement is had good adaptability, and other kind admixture consistency is good, can uses together or be re-dubbed multi-functional compound additive and use; Steam curing process adaptability is better than other type high efficiency water reducing agent; The main ingredient that can be used as water-proof material is used, and in polychromy concrete, heat resistant fire-proof concrete, oil well reinforced concrete and some special engineerings good application prospect is arranged.But such water reducer exists production cost high, is difficult to make pulvis, and stock and trucking costs are high, and the shortcomings such as reaction is harsh strict, difficult quality control.These mass production and marketing that greatly affected it are used.Number of patent application is that 200310115062.9 disclosed modified melamine high-efficiency water-reducing agents are that melamine high-efficiency water-reducing agent is in the past carried out modification, delay concrete time of coagulation, solve concrete large problem of slump-loss in transportation, construction process, but its cost is higher.
Summary of the invention:
The present invention has done many exploration work at the reduction cost, when keeping the melamine superplasticizer premium properties, replace the expensive trimeric cyanamide monomer of part with comparatively cheap reactive monomer urea, synthesized the comparatively cheap melamine superplasticizer of cost.
For achieving the above object, the present invention is by the following technical solutions:
Modified melamine high-efficiency water reducing agent with low cost of the present invention, it is characterized in that: it is take urea, trimeric cyanamide, formaldehyde, sodium bisulfite, Sodium Pyrosulfite as main raw material, be aided with sodium hydroxide and sulfuric acid as pH adjusting agent, under 50~95 ℃ temperature condition, through four reactions steps such as 4~8 hours methylolations, sulfonation, condensation reaction, alkalescence reformations, generate faint yellow transparent melamine high-efficiency water-reducing agent.
Above-mentioned low-cost modified melamine water reducing agent is characterized in that: the content of each component (weight) per-cent is: trimeric cyanamide 4~20%, urea 4~20%, sodium bisulfite 5~10%, formaldehyde 2~30%, Sodium Pyrosulfite 5~10%, sodium hydroxide 0.05%~5%, sulfuric acid 0.05~5%, water 10~70%.
Melamine high-efficiency water-reducing agent of the present invention, each process condition is as follows:
The step 1 methylolation stage
(1) mol ratio of reactant is:
Trimeric cyanamide: urea: formaldehyde=(0.2~0.8): (0.2~1): (1.5~6);
(2) temperature of reaction: 70~85 ℃;
(3) reaction times: 50~60min;
(4) pH value: between 8~10.
The step 2 sulfonation reaction stage
(1) mol ratio of reactant is:
Sodium bisulfite: Sodium Pyrosulfite: trimeric cyanamide: urea
=(0.5~1.5)∶(0.5~1)∶(0.5~1)∶(0.5~1);
(2) temperature of reaction: 80~90 ℃;
(3) reaction times: 100~120min;
(4) pH value: between 10~12.
The step 3 condensation reaction stage
(1) temperature of reaction: 50~60 ℃;
(2) reaction times: 100~140min;
(3) pH value: between 4.5~6.
The alkaline reformation stage of step 4
(1) temperature of reaction: 85~95 ℃;
(2) reaction times: 60~90min;
(3) pH value: between 8.5~10.5.
Compared with prior art, the present invention has the following advantages:
(1) water-reducing rate is high, stable performance, and volume is lower, without obvious bleed and slow setting, good fluidity in practical engineering application, time of coagulation is short.
(2) cost is lower, utilizes rational modification scheme and suitable replacement amount, in the situation that keeps the water reducer use properties, successfully replaces the expensive trimeric cyanamide monomer of part, decrease production cost with urea.
(3) effect is better than other kind water reducer in steam-curing concrete, in the situation that does not change concrete mix, adds water reducer of the present invention, can make steam-cured rear intensity improve 35~40%, shortens 1.5~2.5 hours steam-cured time.
Embodiment:
Embodiment 1 (proportioning is mol ratio)
In four-hole boiling flask, add 0.4 part of trimeric cyanamide, 0.2 part of urea and 1.5 parts of formaldehyde (37% aqueous solution), stir, regulate pH=8, heat to 70 ℃, reacted 50 minutes; Drop into 0.4 part of sodium bisulfite, 0.2 part of Sodium Pyrosulfite and a part of deionized water, regulate pH=10, be heated to 80 ℃, reacted 100 minutes; Cool to 50 ℃, regulate pH=4.5, reacted 100 minutes; Be warming up to 85 ℃, regulate pH=8.5, reaction 60min.Be down to normal temperature, both got melamine high-efficiency water-reducing agent of the present invention.
Embodiment 2 (proportioning is mol ratio)
In four-hole boiling flask, add 0.3 part of (mole number) trimeric cyanamide, 0.3 part of urea and 1.8 parts of formaldehyde (37% aqueous solution), stir, regulate pH=8.5, heat to 70 ℃, reacted 50 minutes; Drop into 0.4 part of sodium bisulfite, 0.3 part of Sodium Pyrosulfite and a part of deionized water, regulate pH=10, be heated to 80 ℃, reacted 100 minutes; Cool to 50 ℃, regulate pH=4.5, reacted 100 minutes; Be warming up to 85 ℃, regulate pH=8.5, reaction 60min.Be down to normal temperature, both got melamine high-efficiency water-reducing agent of the present invention.
Embodiment 3 (proportioning is mol ratio)
In four-hole boiling flask, add 0.3 part of trimeric cyanamide, 0.4 part of urea and 2.0 parts of formaldehyde (37% aqueous solution), stir, regulate pH=8.5, heat to 80 ℃, reacted 60 minutes; Drop into 0.4 part of sodium bisulfite, 0.3 part of Sodium Pyrosulfite and a part of deionized water, regulate pH=10, be heated to 85 ℃, reacted 100 minutes; Cool to 50 ℃, regulate pH=4.5, reacted 100 minutes; Be warming up to 85 ℃, regulate pH=8.5, reaction 60min.Be down to normal temperature, both got melamine high-efficiency water-reducing agent of the present invention.
Embodiment 4 (proportioning is mol ratio)
In four-hole boiling flask, add 0.3 part of trimeric cyanamide, 0.2 part of urea and 1.8 parts of formaldehyde (37% aqueous solution), stir, regulate pH=8.5, heat to 70 ℃, reacted 50 minutes; Drop into 0.4 part of sodium bisulfite, 0.1 part of Sodium Pyrosulfite and a part of deionized water, regulate pH=10, be heated to 80 ℃, reacted 100 minutes; Cool to 50 ℃, regulate pH=4.5, reacted 100 minutes; Be warming up to 90 ℃, regulate pH=9, reaction 80min.Be down to normal temperature, both got melamine high-efficiency water-reducing agent of the present invention.
Embodiment 5 (proportioning is mol ratio)
In four-hole boiling flask, add 0.3 part of trimeric cyanamide, 0.2 part of urea and 1.8 parts of formaldehyde (37% aqueous solution), stir, regulate pH=8.5, heat to 70 ℃, reacted 50 minutes; Drop into 0.4 part of sodium bisulfite, 0.1 part of Sodium Pyrosulfite and a part of deionized water, regulate pH=10, be heated to 80 ℃, reacted 100 minutes; Cool to 50 ℃, regulate pH=4.5, reacted 120 minutes; Be warming up to 90 ℃, regulate pH=9, reaction 80min.Be down to normal temperature, both got melamine high-efficiency water-reducing agent of the present invention.