A kind of concrete polycarboxylate water-reducer and its preparation method
Technical field
The present invention relates to a kind of concrete admixture, particularly a kind of concrete polycarboxylate water-reducer and its preparation method.
Background technology
Along with the develop rapidly of China's infrastructure construction, the especially Large scale construction of high ferro recent years engineering, in construction process, the specification of quality of commerical ready-mixed concrete is more and more stricter, basic demand all uses high performance concrete. In high performance concrete, adding the water reducer of similar naphthalene system, sulfamate system, these tradition polycondensation types of close amine system, its water-reducing rate is general, and can produce to pollute to environment in the water reducer production processes such as naphthalene system. Therefore, widely, application quantity also increases year by year in the use of eco-friendly polycarboxylate water-reducer.
Now, for pursuing high water reducing rate, cause many polycarboxylate water-reducers in actual applications, shortcomings such as occurring easily secreting water, harden, workability is poor, and be difficult to be solved by composite mode, owing to China is to the research of polycarboxylate water-reducer starting relatively evening compared with the developed country such as Japanese, American-European, many technology are not also very ripe, raw-material quality yet less stable; In addition, China cement mill is numerous, and production technique, cement type, composition, fineness, blended material source varies. The polycarboxylate water-reducer overwhelming majority domestic at present all exists and cement poor compatibility, and the adaptability of environment is weak, the defects such as loss of slump is fast, brings very big difficulty to construction.
Published patent documentation is recorded, patent of invention such as publication number CN101575403 discloses a kind of polymerization process preparing polycarboxylic acid series high efficiency water reducing agent, the homogenizing system that the method adopts is at normal temperature not polymerization reaction take place, and need to be warmed to more than 80 DEG C and can react, the patent of invention that publication number is CN101774779 discloses the poly-little slump concrete plasticity-retention agent of sulfonic acid structure of a kind of combed, need to by even for each starting monomer aqueous solution, drip when temperature is 65-98 DEG C and add initiator solution, preserving heat after reaction ends 1 hour, it is cooled to room temperature, adding alkali neutralization, the method temperature of reaction is too high, length consuming time, energy consumption height, the patent of invention that publication number is CN101792281A discloses a kind of polycarboxylate water-reducer and its preparation method, reacting initial temperature 70-90 DEG C, reaction times reaches 6-8h, need after reaction to be cooled to normal temperature, still temperature of reaction is too high for it, length consuming time, energy consumption height, and it adopts method for preparing raw material complexity and uses organic solvent toluene easily to produce to pollute to environment, in addition, publication number is the synthetic method that the patent of invention of CN102336845A discloses a kind of polycarboxylate water-reducer, use organic solvent reaction raw materials such as alcohol, ketone, aromatic hydrocarbon, aliphatic hydrocarbon, one or more in ester or ketone, reaction also needs after terminating to remove organic solvent, it it is a kind of non-green polycarboxylate water-reducer, environment is polluted, preparation process length consuming time, and above water reducer and its preparation method raw material and complicated process of preparation, preparation technology's overlong time, energy consumption is big, production efficiency is low, therefore, research and development strong adaptability, reduction production energy consumption polycarboxylate water-reducer that is low and minimizing environmental pollution is a difficult problem urgently to be resolved hurrily at present.
Summary of the invention
It is an object of the invention to provide a kind of stable performance, water-reducing rate height, what cement adaptability was strong has concrete polycarboxylate water-reducer and its preparation method of excellent water reducing ability and function of slump protection, it has, and preparation process technique is simple, the time is short, and energy consumption of reaction is low, workable and the feature of environmentally safe.
The technical solution adopted in the present invention is: a kind of concrete polycarboxylate water-reducer, and it is the weight-average molecular weight become by monomer A and monomers B copolymerization is the polymkeric substance of 5000 ~ 30000; Monomer A is methacrylic Soxylat A 25-7, and the chemical structure formula I of monomer A is:
(I)
Wherein m is the integer of 14 ~ 66, n is the integer of 0 ~ 40, and the molecular weight of monomer A is 2000 ~ 3000, and the mass ratio of monomer A and monomers B is 4.8 ~ 11:1, monomers B is the mixture of one or more in vinylformic acid, methacrylic acid or maleic anhydride, and the chemical structure of general formula (II) of polymkeric substance is:
(II)
Wherein R1For H or COOH; R2For H or CH3, the molecular weight of described monomer A is preferably 2400.
Described polymkeric substance by described monomer A and B and is added copolymerization in the aqueous solution of chain-transfer agent and complete under redox system initiator existence condition.
Oxygenant in described redox initiator is that one or more of ammonium persulphate, Potassium Persulphate or hydrogen peroxide are composite; Reductive agent is that one or more in sodium bisulfite, xitix, rongalite or hypophosphite are composite; Oxidizer accounts for the 0.17% ~ 1.33% of total monomer weight, it is preferable to 0.23% ~ 1.1%, and reductive agent consumption accounts for the 0.06% ~ 0.4% of total monomer weight, it is preferable to 0.08% ~ 0.34%.
Described chain-transfer agent is that in mercaptoethanol, Thiovanic acid, 2-Thiovanic acid, 3-thiohydracrylic acid or Dodecyl Mercaptan, one or more are composite, and its Chain transfer agent consumption accounts for the 0.35% ~ 1.48% of total monomer weight, it is preferable to 0.5% ~ 1.25%.
Present invention also offers the preparation method of a kind of concrete polycarboxylate water-reducer, comprise: in the reactor, the monomer A of described mass ratio and B are carried out copolyreaction in aqueous, and complete copolyreaction when adding redox system initiator and chain-transfer agent, reaction process carries out at normal temperatures, time is 1.5 ~ 5h, regulates PH value to 5.5 ~ 8 after having reacted, and namely obtains poly carboxylic acid series water reducer multipolymer.
As the preferred preparation method improved further, concrete steps are as follows:
1) in the reactor, first adding monomer A and water, stirring at normal temperature is dissolved to monomer A;
2) reaction system obtained to step 1) is dripped the oxygenant added as redox system initiator;
3) to step 2) drip in the reaction system that obtains simultaneously and add described monomers B, reductive agent and chain-transfer agent, drip that to add the time be 1.2 ~ 4h;
4) reaction is cooled to room temperature after terminating, and completes to regulate PH value to be 5.5 ~ 8 with aqueous sodium hydroxide solution, obtains described polycarboxylate water-reducer polymkeric substance.
Described step 2) the mode that adds of dripping be at the uniform velocity drip to add or one that speed change is dripped in adding.
Described oxygenant is that one or more of ammonium persulphate, Potassium Persulphate or hydrogen peroxide are composite; Reductive agent is that one or more in sodium bisulfite, xitix, rongalite or hypophosphite are composite; Oxidizer accounts for the 0.17% ~ 1.33% of total monomer weight, it is preferable to 0.23% ~ 1.1%, and reductive agent consumption accounts for the 0.06% ~ 0.4% of total monomer weight, it is preferable to 0.08% ~ 0.34%.
Described chain-transfer agent is that in mercaptoethanol, Thiovanic acid, 2-Thiovanic acid, 3-thiohydracrylic acid or Dodecyl Mercaptan, one or more are composite, and its Chain transfer agent consumption accounts for the 0.35% ~ 1.48% of total monomer weight, it is preferable to 0.5% ~ 1.25%.
The advantage that the present invention has and positively effect be:
(1) the polycarboxylate water-reducer strong adaptability that prepared by the present invention, water-reducing rate height;
(2) comparing with other products domestic, volume is low;
(3) the present invention carries out at normal temperatures, energy consumption is low, it is to increase operability, reduces production cost;
(4) the preparation process used time is short, it is to increase preparation efficiency;
(5) add hybrid mode by adopting further to drip, change rate of addition, it is achieved control molecular designing, reaches the excellent properties compatible from different cement; Dripping at a slow speed and add, molecular weight distribution is extensive, and slump retentivity is good; Dripping fast and add, molecular weight distribution is concentrated, water-reducing rate height;
(6) environment is polluted by minimizing;
(7) raw material sources of the present invention enriches, and comprehensive cost performance height, has the very strong market competitiveness.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail: a kind of concrete polycarboxylate water-reducer of preparation, raw material can adopt monomer A and monomers B, monomer A is methacrylic Soxylat A 25-7, monomers B is the mixture of one or more in vinylformic acid, methacrylic acid or maleic anhydride, can react in redox system, namely add as the oxygenant in initiator, reductive agent, and add chain-transfer agent, wherein, oxygenant selects one or more of ammonium persulphate, Potassium Persulphate or hydrogen peroxide composite; Reductive agent selects one or more in sodium bisulfite, xitix, rongalite or hypophosphite composite; Chain-transfer agent selects in mercaptoethanol, Thiovanic acid, 2-Thiovanic acid, 3-thiohydracrylic acid or Dodecyl Mercaptan one or more composite, and reaction process carries out at normal temperatures, and the time is 1.5 ~ 5h. The proterties of this polymkeric substance is light yellow viscous liquid.
Embodiment one: a kind of concrete polycarboxylate water-reducer of preparation, raw material adopts monomer A and vinylformic acid, and the chemical structure formula I of monomer A is:
(I)
Wherein m=50, n=2, each component selected and mass ratio be: methacrylic Soxylat A 25-7: vinylformic acid: ammonium persulphate: inferior sodium phosphate: Thiovanic acid=7.27:1:0.036:0.023:0.064, in the reaction vessel that agitator is housed, add 160g monomer A (molecular weight 2400) and 130g water, it is stirred to monomer A to dissolve, add 0.8g ammonium persulphate, stir after evenly, drip simultaneously and add acrylic acid aqueous solution (wherein vinylformic acid 22g, water 50g) and Thiovanic acid, the aqueous solution (the wherein Thiovanic acid 1.4g of inferior sodium phosphate, inferior sodium phosphate 0.5g, water 45g), front 45min drip add three/bis-, after residue 1/3rd, 45min dropwises, reaction is cooled to normal temperature after terminating, by NaOH aqueous solution adjust ph to neutrality can also be, obtain poly carboxylic acid series water reducer, its chemical structural formula is formula (II-1):
(II-1)
Wherein m=50, n=2. This embodiment adopts speed change to drip the mode of adding, drip the added-time fast, a large amount of hydroxy-acid group is introduced in short period of time, it is that anionic charge density increases that more polar group is grafted on main chain, polycarboxylate water-reducer molecule is stronger in the adsorptive power of cement particle surface, it is to increase the dispersing property of polycarboxylate water-reducer; Later stage drips at a slow speed and adds, mild access polar group, makes polycarboxylate water-reducer on the basis that water-reducing rate improves, still keeps good dispersion stabilization, macroscopic body now through time fluidity loss little. This speed change drips polycarboxylate water-reducer prepared by adding method, and with existing water reducer when volume is identical, water-reducing rate can improve more than 20%, and function of slump protection is good, and cement adaptability is strong.
Embodiment two, a kind of concrete polycarboxylate water-reducer of preparation, raw material adopts monomer A and methacrylic acid, m=39 in monomer A chemical structure formula I, n=10, each component selected and mass ratio are monomer A: methacrylic acid: hydrogen peroxide: xitix: 3-thiohydracrylic acid=7:1:0.0532:0.016:0.056; In the reaction vessel that agitator is housed, add 350g monomer A (molecular weight 2400) and 180g water, it is stirred to monomer A to dissolve, add 2.66g hydrogen peroxide, stir after evenly, drip simultaneously and add acrylic acid aqueous solution (wherein vinylformic acid 50g, water 80g) and 3-thiohydracrylic acid, Vitamin C aqueous acid (wherein 3-Thiovanic acid 2.8g, xitix 0.8g, water 96g), drip that to add the time be 3.5h, reaction is cooled to normal temperature after terminating, by NaOH aqueous solution adjust ph to neutral, obtaining poly carboxylic acid series water reducer, its chemical structural formula is (II-2):
(II-2)
Wherein m=39, n=10, adopts the mode dripped at a slow speed and add monomers B in this embodiment, the water reducer molecular weight distribution obtained is extensive, has better function of slump protection.
Embodiment three, a kind of concrete polycarboxylate water-reducer of preparation, raw material adopts monomer A and monomers B (vinylformic acid and maleic anhydride), m=17 in monomer A chemical structure formula I, n=31, each component selected and mass ratio are monomer A: vinylformic acid: maleic anhydride: ammonium persulphate: sodium bisulfite: 2-Thiovanic acid=11.25:1:1.3:0.12:0.1:0.054, in the reaction vessel that agitator is housed, add 225g monomer A (molecular weight 2600) and 260g water, it is stirred to monomer A to dissolve, add 2.4g ammonium persulphate, stir after evenly, drip simultaneously and add vinylformic acid, the aqueous solution (the wherein vinylformic acid 20g of maleic anhydride, maleic anhydride 26g, water 56g) and 2-Thiovanic acid, the aqueous solution (the wherein 2-Thiovanic acid 2.0g of sodium bisulfite, sodium bisulfite 1.08g, water 45g), drip that to add the time be 2h, reaction is cooled to normal temperature after terminating, by NaOH aqueous solution adjust ph to neutral, obtain poly carboxylic acid series water reducer, its chemical structural formula is (II-3):
(II-3)
Wherein m=17, n=31.
Embodiment four: a kind of concrete polycarboxylate water-reducer of preparation, raw material adopts monomer A and monomers B (vinylformic acid), m=44 in monomer A chemical structure formula I, n=0, each component selected and mass ratio be: monomer A: vinylformic acid: Potassium Persulphate: sodium bisulfite: rongalite: mercaptoethanol=11:1:0.022:0.011:0.019:0.022, in the reaction vessel that agitator is housed, add 198g monomer A (molecular weight 2000) and 120g water, it is stirred to monomer A to dissolve, add 0.4g Potassium Persulphate, stir after evenly, drip simultaneously and add acrylic acid aqueous solution (wherein vinylformic acid 18g, water 70g) and rongalite, mercaptoethanol, the aqueous solution (the wherein rongalite 0.35g of sodium bisulfite, mercaptoethanol 0.4g, sodium bisulfite 0.2g, water 85g), drip that to add the time be 70min, reaction is cooled to normal temperature after terminating, by NaOH aqueous solution adjust ph to neutral, obtain poly carboxylic acid series water reducer, its chemical structural formula is (II-4):
(II-4)
Wherein m=44, n=0.
Embodiment five: a kind of concrete polycarboxylate water-reducer of preparation, raw material adopts monomer A and monomers B (maleic anhydride), m=65 in monomer A chemical structure formula I, n=1, each constituent mass is than being monomer A: maleic anhydride: hydrogen peroxide: Potassium Persulphate: inferior sodium phosphate: Thiovanic acid: Dodecyl Mercaptan=9.78:1:0.09:0.052:0.0087:0.087:0.07, in the reaction vessel that agitator is housed, add 225g monomer A (molecular weight 3000) and 140g water, it is stirred to monomer A to dissolve, add 2.065g hydrogen peroxide and 1.2g Potassium Persulphate, stir after evenly, drip the aqueous solution (the wherein maleic anhydride 23g adding maleic anhydride simultaneously, water 95g) and Thiovanic acid, Dodecyl Mercaptan, the aqueous solution (the wherein Thiovanic acid 2.0g of inferior sodium phosphate, Dodecyl Mercaptan 1.6g, inferior sodium phosphate 0.2g, water 78g), front 1.5h drip add four/tri-, after residue 1/4th, 1h dropwises, reaction is cooled to normal temperature after terminating, by NaOH aqueous solution adjust ph to neutral, obtain poly carboxylic acid series water reducer, its chemical structural formula is (II-5):
(II-5)
Wherein m=65, n=1.
Embodiment six, a kind of concrete polycarboxylate water-reducer of preparation, raw material adopts monomer A and monomers B (methacrylic acid), m=7 in monomer A chemical structure formula I, n=40, each component selected and mass ratio are monomer A: methacrylic acid: ammonium persulphate: Potassium Persulphate: xitix: Dodecyl Mercaptan=6.4:1:0.033:0.009:0.019:0.024, in the reaction vessel that agitator is housed, add 270g monomer A (molecular weight 2700) and 210g water, it is stirred to monomer A to dissolve, add 1.4g ammonium persulphate and 0.4g Potassium Persulphate, stir after evenly, drip simultaneously and add methacrylic aqueous acid (wherein methacrylic acid 42g, water 70g) and Dodecyl Mercaptan, Vitamin C aqueous acid (wherein Dodecyl Mercaptan 1.0g, xitix 0.8g, water 88g), 1.5h dropwise, reaction is cooled to normal temperature after terminating, by NaOH aqueous solution adjust ph to neutral, obtain poly carboxylic acid series water reducer, its chemical structural formula is (II-6):
(II-6)
Wherein: m=7, n=40.
The embodiment of the present invention one is carried out flowing degree of net paste of cement detection to product and the standard specimen of embodiment six by GB/T8077-2000 Methods for testing uniformity of concrete admixture. Wherein, standard specimen is the polycarboxylate water-reducer that commercially available routine uses. Using reference cement in detection, water cement ratio is 0.29, and water reducer volume is the 0.4% of cement, and water reducer is admittedly containing being 40%, and detected result is as follows:
Cement type |
Water reducer title |
Initial flow degree (mm) |
1h degree of mobilization (mm) |
2h degree of mobilization (mm) |
Reference cement |
Embodiment one |
285*280 |
275*275 |
270*265 |
Reference cement |
Embodiment two |
260*260 |
265*260 |
265*255 |
Reference cement |
Embodiment three |
270*265 |
260*260 |
260*255 |
Reference cement |
Embodiment four |
275*265 |
265*260 |
255*250 |
Reference cement |
Embodiment five |
280*280 |
275*270 |
270*265 |
Reference cement |
Embodiment six |
280*275 |
275*275 |
270*270 |
Reference cement |
Standard specimen |
255*250 |
250*240 |
240*235 |
By above result it will be seen that contrast each sample between initial flow degree with through time degree of mobilization, patent of the present invention synthesis polycarboxylate water-reducer be all better than standard specimen. Initial flow degree is more big, shows that water-reducing rate is more high, through time degree of mobilization retention value more big, show that slump retaining is more good, above result shows, the water reducer of the present invention's synthesis has excellent water-reducing property and function of slump protection.