CN101041571A - Air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent and preparation method thereof - Google Patents
Air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent and preparation method thereof Download PDFInfo
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- CN101041571A CN101041571A CNA2007100205660A CN200710020566A CN101041571A CN 101041571 A CN101041571 A CN 101041571A CN A2007100205660 A CNA2007100205660 A CN A2007100205660A CN 200710020566 A CN200710020566 A CN 200710020566A CN 101041571 A CN101041571 A CN 101041571A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The invention discloses an absorbing gas and keeping collapse type polycarboxylate concrete highly effective dehydragent and preparation, which comprises the following steps: (1) choosing polyalkylene glycol acrylate monomer, carboxylic monomer and allyl sulphonic acid as raw material; adding polyalkylene glycol monomer and carboxylic acid monomer into reactor incorporating condense diverting device; proceeding react; getting polyalkylene glycol acrylate monomer; (2) copolymerizing polyalkylene glycol acrylate monomer, carboxylic acid monomer and allyl sulphonic acid monomer; getting product; controlling the reacting condition with low temperature and normal pressure. When the blending quantity is 0.2% gelling material, the diminishing ratio can reach 30% and the gas content can reach 3.0-6.0%. The concrete 28d intensity can reach 130-150% and the slump of concrete nearly loss-free in 2 h, which possesses good workability without bleeding phenomenon under normal pressure.
Description
Technical field
The present invention relates to a kind of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent and preparation thereof, with polyalkene glycol acrylates class monomer, carboxylic-acid monomer, allyl sulphonic acid class monomer etc. is the feedstock production high efficiency water reducing agent, belongs to technical field of concrete additives in the chemical building material.
Background technology
Along with China's rapid economic development, the construction of heavy construction is more and more, and constantly to high strength, high-durability, high workability or special property development, admixture has become one of requisite component of concrete to concrete technology.High efficiency water reducing agent, be use in the concrete admixture maximum a kind of.
At present, the cement water reducing agent of domestic use is based on naphthalene water reducer, its production technique and utilisation technology comparative maturity, higher, the low price of water-reducing rate, but exist, the slump good inadequately with cement adaptability through the time problems such as loss big and consequent poor durability, and contain toxic substances such as formaldehyde in the product, very easily cause environmental pollution, be detrimental to health; Its main raw material NAPTHALENE FLAKES. (INDUSTRIAL GRADE source of goods anxiety in recent years, price constantly raises, and causes production cost to rise steadily.The method of traditional solution naphthalene water reducer slump-loss mainly contains multiaddition method, latter admixing method, with the retardant composite algorithm etc., but all can not fundamentally overcome its defective.
By comparison, novel polycarboxylate concrete high efficiency water reducing agent then because have low-dosage, highly flow, big plurality of advantages and the research focus that becomes international rapidly such as collapse, cement adaptability is good, the molecular structure variable factor is many protected.Meanwhile, because the proposition of " high performance concrete " this novel concept, making people see simple pursuit intensity by the past to concrete quality begins to change into and pays attention to concrete durability, workability and the adaptability in harsh environment for use simultaneously, this just requires water reducer that certain bleed and good slump retentivity will be arranged, and novel polycarboxylate concrete high efficiency water reducing agent will become the first-selection that people prepare low water binder ratio, high-strength, high durability concrete.And abroad, especially Japanese, the efficient carboxylic acid water reducer of bleed has been widely used in water conservancy, road etc. and has required in the concrete works of high-durability.
Reported a kind of preparation method of vinyl class in polymer type cement water reducing agent among the patent CN1562853A, though this water reducer has adopted some carboxylic-acid monomers when synthetic, but do not relate to the steric repulsion effect of long-chain branch during molecular designing, water reducer is protected collapsing property and is affected adversely.
Reported a kind of preparation method of poly-carboxylic-acid cement dispersant among the patent CN1847187A, but it directly uses the polyoxyalkylenes ether monomer in building-up process, this monomer external product in Chinese market seldom is difficult to guarantee the continuity of suitability for industrialized production; Domestic production producer is few, and impurity content exceeding index often in the product, and the water reducer over-all properties is had a negative impact.
Reported a kind of polycarboxylic acid series water reducing agents for efficient aerocrote among the patent CN1316398A, but it is in copolymerization process, the employing butanone is a solvent, after reaction finishes, needs to steam through underpressure distillation and desolventize, and technological process is comparatively complicated.
Reported a kind of multi-functional carboxylic acid comb grafted copolymer concrete high efficiency water reducing agent among the patent CN1721361A, but its solvent recovering rate is low, causes the product cost height, and causes environmental pollution easily.
Summary of the invention
The objective of the invention is provides a kind of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent and preparation thereof at above-mentioned weak point, production technique of the present invention is simple relatively, easy control of reaction conditions, production unit is required lower, be a kind of have low-dosage, big diminishing, high protect collapse, the suitable polycarboxylate concrete high efficiency water reducing agent of bleed.
A kind of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent and preparation thereof are to take following scheme to realize:
A kind of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent is characterized in that it is to carry out graft copolymer that copolyreaction makes in adding alkali and the superpolymer salts solution of gained by following several monomers by certain ratio, promptly
With the polyalkene glycol acrylates class monomer of general formula (1) expression,
R
1Alkyl for H or carbonatoms 1-5; R
2Be OH, the alkyl of H or carbonatoms 1-10;
M is the average addition mole number of oxyalkylene group, is the integer of 1-99;
And the carboxylic-acid monomer of using general formula (2) to represent,
R
3Alkyl for H or carbonatoms 1-5; M
1Be H, Na
+Or carbonatoms is the alkyl of 1-4; With olefin sulfonic acid class monomer with general formula (3) expression,
R
4Alkyl for H or carbonatoms 1-5; M
2Be H, Na
+
In adding alkali and the copolymer salt solution of gained, reaction formula is as follows through polyreaction synthetic multipolymer:
In the formula, a, b, c represent the mole number of corresponding monomeric unit, a: b: c=0-3: 2-7: 1-5; N represents the mole number of repeating unit, is the integer of 1-99.
A kind of preparation method of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent is characterized in that adopting following technology synthetic:
(1) prepare big monomer with reactive behavior: polyalkene glycol acrylates class monomer,
Polyalkylene glycol mono body and carboxylic-acid monomer are joined in the reactor that the condensation part flow arrangement is housed, add stopper, catalyzer, solvent, stir, be warming up to 82～125 ℃, reacted 5-15 hour, desolventize and reclaim by the underpressure distillation steaming, promptly get and contain the monomeric polyalkene glycol acrylates class of excess carboxylic acid class monomer;
Wherein, adding the polyalkylene glycol mono body with the monomeric amount of substance ratio of carboxylic-acid is: 1: 1.25-4.0; Add the 1-10% of catalytic amount for add total monomer weight; Adding the stopper amount is the 0.1-2.5% of total monomer weight; Adding quantity of solvent is the 15-35% of grafted monomer gross weight; When the employing solvent was toluene, temperature of reaction was 110～125 ℃; When the employing solvent was hexanaphthene, temperature of reaction was 82～95 ℃; Solvent recovering rate reaches 98-100%;
(2) synthetic polycarboxylate concrete high efficiency water reducing agent,
1) preparation of monomer solution:
Polyalkene glycol acrylates class monomer, carboxylic-acid monomer and the monomeric mixture of allyl sulphonic acid class are added water be made into water solution system, the concentration of monomer solution is 20-70%;
2) preparation of initiator solution:
Persulphate is added water be made into initiator solution, the concentration of initiator solution is 0.1-2.5%;
3) free radical solution polymerization:
Adding total monomer weight 1.0-2.5 water doubly in reactor is dispersion medium, stir, be warmed up to 75～95 ℃, adopt dripping method or repeatedly feeding method adding monomer solution and initiator solution at a slow speed, reacted 4-8 hour, cooling adds alkali with the gained multipolymer and is neutralized to PH=6.5-8, promptly gets copolymer salt solution;
Wherein, the initiator add-on is the 0.1-5% of total monomer weight, and monomer dropped in 0-5 hour fully, and initiator dropped into fully at 2-6 hour.
Have in the big monomer process of reactive behavior in preparation, described polyalkylene glycol mono body is selected a kind of or mixture in different molecular weight polyethylene glycol, the methoxy poly (ethylene glycol) for use; Described carboxylic-acid monomer is selected one or more the mixture in vinylformic acid, methacrylic acid, methyl acrylate, the methyl methacrylate for use; Described catalyzer is selected a kind of or mixture in the vitriol oil, the tosic acid for use; Described stopper is selected a kind of or mixture in thiodiphenylamine, the phenol derivatives for use; Described solvent is selected a kind of or mixture in toluene, the hexanaphthene for use.
In building-up reactions, described polyalkene glycol acrylates class monomer is selected a kind of or mixture in different molecular weight polyethylene glycol mono acrylic ester, the methoxy poly (ethylene glycol) mono acrylic ester for use; Described carboxylic-acid monomer is selected one or more the mixture in vinylformic acid, methacrylic acid, methyl acrylate, the methyl methacrylate for use; Described olefin sulfonic acid class monomer is selected a kind of or mixture in allylsulfonate, the methallyl sulfonate for use; Described initiator is selected a kind of or mixture in Sodium Persulfate, Potassium Persulphate, the ammonium persulphate for use; It is 30% liquid caustic soda or a kind of or mixture in the ammoniacal liquor that described neutralization bases is selected strength of solution for use.
The synthesis technique of above-mentioned a kind of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent, can select polyalkene glycol acrylates class monomer difference or while and the carboxylic-acid monomer and the allyl sulphonic acid class monomer copolymerization of different molecular weight for use, the synthetic product can independent or composite use.
Above-mentioned a kind of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent, production technique is simple relatively, easy control of reaction conditions, production unit is required lower, be a kind of have low-dosage, big diminishing, high protect collapse, the suitable polycarboxylate concrete high efficiency water reducing agent of bleed.
The synthetic of above-mentioned a kind of air entrained collapse-preventing type polycarboxylate bleed type concrete high efficiency water reducing agent is to utilize polyoxyalkylenes ethers monomer, have in preparation and to introduce two keys in the big monomer process of reactive behavior, with carboxylic-acid monomer, allyl sulphonic acid class monomer copolymerization takes place again in solution, introduce long side chain, preparation technology is very simple, reaction conditions is easy to control, production process does not produce three industrial wastes, reusable edible after the solvent recuperation, and solvent recovering rate reaches 98-100%, promptly guaranteed economic benefit, again non-environmental-pollution.
The solid content that adopts the present invention to make is the concrete of 20% polycarboxylate bleed type concrete high efficiency water reducing agent configuration, and when the water reducer volume was gelling material weight 1%, water-reducing rate can reach more than 30%; Air content is between 3.0-6.0%, and concrete antifreezing melts ability and weather resistance significantly improves; The concrete strength height, slump retaining is good, basic free of losses in the concrete slump 2 hours; Workability is good, and normal pressure is no excreting water phenomenon down, but the concrete pumping is good, and education resistance can be good; Alkali content is low, can avoid alkali-aggregate reaction; Chloride ion content is extremely low, to the effect of reinforcing bar non-corroding; Volume stability is good, and concrete 28d does not almost have contraction; The product cement adaptability is good, is adapted to the cement of multiple different size, model; Product performance are stable, and long storage does not have precipitation, not stratified.
Description of drawings
The invention will be further described below with reference to accompanying drawing:
Fig. 1 is that a kind of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent prepares synoptic diagram.
With reference to accompanying drawing 1, a kind of synthesis technique of air entrained collapse-preventing type polycarboxylate research work of air entrained type concrete high efficiency water reducing agent is:
(1) prepares the large monomer with reactivity: polyalkene glycol acrylates class monomer, polyalkylene glycol mono body and carboxylic acids monomer are joined in the reactor that the condensation part flow arrangement is housed, add polymerization inhibitor, catalyst, solvent, stir, be warming up to reaction temperature, reacted 5-15 hour, and desolventized and reclaim by the decompression distillation steaming, namely get the polyalkene glycol acrylates class monomer that contains excess carboxylic acid class monomer;
(2) synthetic polycarboxylate concrete high efficiency water reducing agent,
Be warmed up to 75～95 ℃, under the condition that stirs, in reactor, adopt at a slow speed dripping method or repeatedly feeding method adding monomer solution and initiator solution, reacted 4-8 hour, cooling adds alkali with the gained copolymer and is neutralized to PH=6.5-8, namely gets copolymer salt solution;
Embodiment
Embodiment 1:
With molecular weight is that 600 Liquid Macrogol g and vinylformic acid 45.04g join in the reactor that the condensation part flow arrangement is housed, add stopper thiodiphenylamine 0.345g, catalyzer vitriol oil 3.45g, toluene 51.76g stirs, be warming up to 110 ℃, reacted 9 hours, and desolventized, promptly get esterification products 348.83g by the underpressure distillation steaming, be weighed as 51.32g after the solvent recuperation, solvent recovering rate is 99.15%; In esterification products, add sodium methallyl sulfonate 47.445g and methacrylic acid 57.57g, obtain the 453.845g monomer, adding 543.58g water, to be made into concentration be 50% monomer solution, and adding water 21.22g with the ammonium persulphate 0.544g that accounts for total monomer weight 0.1%, to be made into concentration be 2.5% initiator solution; In reactor, add water 1250.58g, stir, be warming up to 75 ℃, drip monomer solution and initiator solution simultaneously, monomer solution dropwised in 5 hours, initiator solution dropwised in 6 hours, after agent solution to be triggered dropwises, 85 ℃ of insulations 2 hours, cooling, to be cooled to 45 ℃, adding concentration is that 30% liquid caustic soda is neutralized to PH=6.5, i.e. high-efficiency water-reducing agent of poly-carboxylic acid a.
Embodiment 2:
With molecular weight is that 1000 polyoxyethylene glycol 500g and methacrylic acid 107.61g join in the reactor that the condensation part flow arrangement is housed, add hydroquinone of polymerization retarder 6.076g, catalyzer tosic acid 30.38g, solvent toluene 182.28g stirs, be warming up to 125 ℃, reacted 5 hours, and desolventized and reclaim, promptly get esterification products 635g by the underpressure distillation steaming, be weighed as 179.55g after the solvent recuperation, solvent recovering rate is 98.50%; Add 96.58g sodium allyl sulfonate and 18g vinylformic acid in esterification products, adding 321.25g water, to be made into concentration be 70% monomer solution, adds water 200g with Potassium Persulphate 5g and be made into 2.44% initiator solution; Add water 2477g in reactor, stir, be warming up to 85 ℃, added monomer solution once in per 0.5 hour, drop into 178.47g at every turn, monomer solution being fed intake in 3 hours finishes; Initiator solution adopts dripping method at a slow speed, dropwises in 4 hours, after initiator dropwises, is warming up to 90 ℃ of insulations 2 hours, cooling, and to be cooled to 45 ℃, adding concentration is that 30% ammoniacal liquor is neutralized to PH=7.0, i.e. high-efficiency water-reducing agent of poly-carboxylic acid b.
Embodiment 3:
With molecular weight is that 750 methoxy poly (ethylene glycol) 375g and methyl methacrylate 150g join in the reactor that the condensation part flow arrangement is housed, add stopper thiodiphenylamine 13.125g, catalyzer tosic acid 52.5g, solvent hexanaphthene 131.25g stirs, be warming up to 82 ℃, reacted 12 hours, and desolventized and reclaim, promptly get esterification products 574.2g by the underpressure distillation steaming, be weighed as 129g after the solvent recuperation, solvent recovering rate is 98.29%; Adding 1000g water in esterification products, to be made into concentration be 36.48% monomer solution, and adding water 410g with Sodium Persulfate 10.36g, to be made into concentration be 2.46% initiator solution; In reactor, add water 960g, stir, disposable input monomer solution is warming up to 85 ℃ then, initiator solution adopts dripping method at a slow speed, dropwised in 2 hours, after initiator dropwises, 95 ℃ of insulations 2 hours, cooling, to be cooled to 45 ℃, adding concentration is that 30% liquid caustic soda is neutralized to PH=7.5, i.e. high-efficiency water-reducing agent of poly-carboxylic acid c.
Embodiment 4:
With molecular weight is that 2000 methoxy poly (ethylene glycol) 1000g and methyl acrylate 172g join in the reactor that the condensation part flow arrangement is housed, add stopper thiodiphenylamine 5.86g, catalyzer vitriol oil 46.88g, solvent hexanaphthene 410.2g stirs, be warming up to 95 ℃, reacted 15 hours, and desolventized and reclaim, promptly get esterification products 1208.2g by the underpressure distillation steaming, be weighed as 403.6g after the solvent recuperation, solvent recovering rate is 98.39%; Add 216.225g sodium allyl sulfonate and 86.09g methacrylic acid in esterification products, adding 2265g water, to be made into concentration be 40% monomer solution, and adding water 730g with ammonium persulphate 7.92g, to be made into concentration be 1.08% initiator solution; In reactor, add water 3000g, drip monomer solution and initiator solution while stirring simultaneously at 95 ℃, monomer solution dropwised in 3 hours, initiator solution dropwised in 3.5 hours, after initiator dropwises, 95 ℃ of insulations 0.5 hour, cooling then, to be cooled to 45 ℃, add concentration and be 30% ammoniacal liquor and be neutralized to PH=8, be i.e. high-efficiency water-reducing agent of poly-carboxylic acid d.
Embodiment 5:
With molecular weight 1000 methoxy poly (ethylene glycol) 700g, vinylformic acid 200g joins in the reactor that the condensation part flow arrangement is housed, and adds stopper thiodiphenylamine 45g, catalyzer vitriol oil 18g, solvent toluene 300g is 110 ℃ of stirring reactions 8 hours, after reaction finishes, adopting the underpressure distillation mode to steam desolventizes and reclaims, promptly get esterification products 950g, reclaiming the toluene amount is 294g, and solvent recovering rate is 98%; Esterification products is added 1000g water, and to be made into concentration be 48.72% monomer solution, take by weighing ammonium persulphate 20g, add the 1000g water dissolution and make 1.96% initiator solution, in reactor, add water 1800g, stir, be warming up to 90 ℃ and drip monomer solution and initiator solution simultaneously, dropwised in 4 hours, 95 ℃ of insulations 1.5 hours, cooling, to be cooled to 45 ℃, adding concentration is that 30% liquid caustic soda is neutralized to PH=7.0, promptly gets high-efficiency water-reducing agent of poly-carboxylic acid e.(performance see Table 1 and table 2)
Embodiment 6:
With molecular weight 800 polyoxyethylene glycol 240g, vinylformic acid 90g joins in the reactor that the condensation part flow arrangement is housed, and adds stopper phenol derivatives 0.8g, catalyzer vitriol oil 6.18g, solvent toluene 60g is 115 ℃ of stirring reactions 5 hours, after reaction finishes, adopting the underpressure distillation mode to steam desolventizes and reclaims, make 337g esterification products 1, reclaiming the toluene amount is 59.5g, and solvent recovering rate is 99.17%; With molecular weight 2000 polyoxyethylene glycol 540g, vinylformic acid 80g, join in the reactor that the condensation part flow arrangement is housed, add hydroquinone of polymerization retarder 0.405g, catalyzer vitriol oil 11.9g, solvent toluene 200g, 115 ℃ of stirring reactions 8 hours, adopt underpressure distillation that toluene is steamed in order to recycle, make 627g esterification products 2, recovery toluene is 198g, and solvent recovering rate is 99%; Getting esterification products 1 weight is that 337g and esterification products 2 weight are that 105g mixes in same container for stirring, adding 733g water, to be made into concentration be 37.62% monomer solution, getting ammonium persulphate 4.42g adds 300g water and is made into 1.45% initiator solution, in reactor, add 735g water, be warming up to 83 ℃, dripped monomer, initiator simultaneously each 2 hours, then 92 ℃ of insulations 2.5 hours, adding concentration is that 30% ammoniacal liquor is neutralized to PH=7.0, promptly gets high-efficiency water-reducing agent of poly-carboxylic acid f.(performance see Table 1 and table 2)
Embodiment 7:
With molecular weight 600 methoxy poly (ethylene glycol) 200g, tosic acid 5.22g, thiodiphenylamine 0.72g, vinylformic acid 85g, toluene 60g, put into reaction vessel, 115 ℃ of stirring reactions 5 hours, adopt underpressure distillation that toluene is put in order out in order to recycle, promptly get 290g esterification products 1, recovery toluene is 59g, and solvent recovering rate is 98.33%; With molecular weight 2000 methoxy poly (ethylene glycol) 540g, tosic acid 11.9g, Resorcinol 0.525g, vinylformic acid 35g, toluene 150g, put into reaction vessel, 115 ℃ of stirring reactions 8 hours, adopt underpressure distillation that toluene is put in order out in order to recycle, promptly get 587g esterification products 2, recovery toluene is 149g, and solvent recovering rate is 99.33%; Getting esterification products 1 weight is that 290g and esterification products 2 weight are that 105g mixes in same container for stirring, adding 700g water, to be made into concentration be 36.07% monomer solution, getting ammonium persulphate 4.42g adds 300g water and is made into 1.45% initiator solution, in reactor, add 580g water, be warming up to 85 ℃, dripped monomer, initiator simultaneously each 3 hours, then 90 ℃ of insulations 2.5 hours, adding concentration is that 30% ammoniacal liquor is neutralized to PH=7.0, promptly gets high-efficiency water-reducing agent of poly-carboxylic acid g.(performance see Table 1 and table 2)
Embodiment 8:
The polycarboxylate water-reducer that polycarboxylate water-reducer that embodiment 1 is made and embodiment 4 make is that 1: 3.5 ratio mixes according to weight ratio, promptly gets high-efficiency water-reducing agent of poly-carboxylic acid h.
Embodiment 9:
The polycarboxylate water-reducer that polycarboxylate water-reducer that polycarboxylate water-reducer that embodiment 1 is made and embodiment 3 make and embodiment 4 make mixes according to 1: 4.5: 2 ratio of weight ratio, promptly gets high-efficiency water-reducing agent of poly-carboxylic acid i.
Embodiment 10:
The polycarboxylate water-reducer that polycarboxylate water-reducer that embodiment 5 is made and embodiment 7 make is that 1: 2.5 ratio mixes according to weight ratio, promptly gets high-efficiency water-reducing agent of poly-carboxylic acid j.
Table 1 is mixed the high efficiency water reducing agent of the present invention's preparation and the concrete performance index of naphthalene water reducer
| Interventions Requested | Detected result | |||
| e | f | g | Naphthalene water reducer | |
| Water-reducing rate/% | 30.0 | 32.0 | 30.5 | 14.8 |
| Air content/% | 5.5 | 5.0 | 3.0 | 2.3 |
| Slump retention value/mm | 30min | 210 | 215 | 212 | —— |
| 60min | 208 | 217 | 215 | —— | |
| Time of coagulation is poor/min | Initial set | +20 | +10 | +15 | -15 |
| Final set | +10 | +0 | +25 | -20 | |
| Compressive strength rate/% | 1d | 140 | 156 | 147 | 148 |
| 7d | 152 | 160 | 158 | 140 | |
| 28d | 130 | 141 | 144 | 123 | |
| Normal pressure bleeding rate ratio/% | 0 | 0 | 0 | 78 | |
| Pressure bleeding rate ratio/% | 22 | 15 | 8 | —— | |
| Relative durability index/%, 200 times | —— | —— | —— | —— | |
| 28d shrinkage ratio/% | 100 | 100 | 102 | 106 | |
| Reinforcing bar is had or not action of rust | Do not have | Do not have | Do not have | Do not have | |
According to " concrete admixture " (GB/T8076-1997) and " concrete pump-feed agent " (JC473-2001) detects and mixes the high efficiency water reducing agent that the present invention prepares and the concrete performance of naphthalene water reducer.
The high efficiency water reducing agent of table 2 the present invention preparation and the homogeneity index of naphthalene water reducer
| Interventions Requested | Detected result | |||||||
| e | f | g | Naphthalene water reducer | |||||
| Solid content/% | 20 | 20 | 20 | 90 | ||||
| Chloride ion content/% | 0.13 | 0.16 | 0.12 | 0.15 | ||||
| Flowing degree of net paste of cement/mm | Initially | One hour | Initially | One hour | Initially | One hour | Initially | One hour |
| 300 | 298 | 313 | 307 | 317 | 317 | 200 | —— | |
| Surface tension/mN/m | 57.2 | 56.2 | 53.8 | —— | ||||
| PH | 7.0 | 7.0 | 7.0 | 8.0 | ||||
| Total alkali content (Na 2O+ 0.658K 2O)/％ | 0.75 | 0.60 | 0.68 | 7.1 | ||||
Annotate: synthetic institute water is a tap water; The naphthalene series high-efficiency water-reducing agent of surveying is FDN (high dense) commercially available prod.
(GB/T8077-2000) detect the high efficiency water reducing agent of the present invention preparation and the homogeneity index of naphthalene water reducer according to " Methods for testing uniformity of concrete admixture ".
Claims (10)
1, a kind of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent is characterized in that it is to carry out graft copolymer that copolyreaction makes in adding alkali and the superpolymer salts solution of gained by following several monomers by certain ratio, promptly
With the polyalkene glycol acrylates class monomer of general formula (1) expression,
R
1Alkyl for H or carbonatoms 1-5; R
2Be OH, the alkyl of H or carbonatoms 1-10;
M is the average addition mole number of oxyalkylene group, is the integer of 1-99;
And the carboxylic-acid monomer of using general formula (2) to represent,
R
3Alkyl for H or carbonatoms 1-5; M
1Be H, Na
+Or carbonatoms is the alkyl of 1-4; With olefin sulfonic acid class monomer with general formula (3) expression,
R
4Alkyl for H or carbonatoms 1-5; M
2Be H, Na
+
In adding alkali and the copolymer salt solution of gained, reaction formula is as follows through polyreaction synthetic multipolymer:
In the formula, a, b, c represent the mole number of corresponding monomeric unit, a: b: c=0-3: 2-7: 1-5; N represents the mole number of repeating unit, is the integer of 1-99.
2, the preparation method of the described air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent of claim 1 is characterized in that adopting following technology synthetic:
(1) prepare big monomer with reactive behavior: polyalkene glycol acrylates class monomer,
Polyalkylene glycol mono body and carboxylic-acid monomer are joined in the reactor that the condensation part flow arrangement is housed, add stopper, catalyzer, solvent, stir, be warming up to 82～125 ℃, reacted 5-15 hour, desolventize and reclaim by the underpressure distillation steaming, promptly get and contain the monomeric polyalkene glycol acrylates class of excess carboxylic acid class monomer;
Wherein, adding the polyalkylene glycol mono body with the monomeric amount of substance ratio of carboxylic-acid is: 1: 1.25-4.0; Add the 1-10% of catalytic amount for add total monomer weight; Adding the stopper amount is the 0.1-2.5% of total monomer weight; Adding quantity of solvent is the 15-35% of grafted monomer gross weight; When the employing solvent was toluene, temperature of reaction was 110～125 ℃; When the employing solvent was hexanaphthene, temperature of reaction was 82～95 ℃; Solvent recovering rate reaches 98-100%;
(2) synthetic polycarboxylate concrete high efficiency water reducing agent,
1) preparation of monomer solution:
Polyalkene glycol acrylates class monomer, carboxylic-acid monomer and the monomeric mixture of olefin sulfonic acid class are added water be made into water solution system, the concentration of monomer solution is 20-70%;
2) preparation of initiator solution:
Persulphate is added water be made into initiator solution, the concentration of initiator solution is 0.1-2.5%;
3) free radical solution polymerization:
Adding total monomer weight 1.0-2.5 water doubly in reactor is dispersion medium, stirs, and is warmed up to 75～95 ℃, add monomer solution and initiator solution, reacted 4-8 hour, cooling, the gained multipolymer is added alkali be neutralized to PH=6.5-8, promptly get copolymer salt solution;
Wherein, the initiator add-on is the 0.1-5% of total monomer weight, and monomer dropped in 0-5 hour fully, and initiator dropped into fully at 2-6 hour.
3, the preparation method of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent according to claim 2 is characterized in that having polyalkylene glycol mono body described in the big monomer process of reactive behavior in preparation selects a kind of or mixture in different molecular weight polyethylene glycol, the methoxy poly (ethylene glycol) for use; Described carboxylic-acid monomer is selected one or more the mixture in vinylformic acid, methacrylic acid, methyl acrylate, the methyl methacrylate for use.
4, the preparation method of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent according to claim 2 is characterized in that having catalyzer described in the big monomer process of reactive behavior in preparation selects a kind of or mixture in the vitriol oil, the tosic acid for use.
5, the preparation method of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent according to claim 2 is characterized in that having stopper described in the big monomer process of reactive behavior in preparation selects a kind of or mixture in thiodiphenylamine, the phenol derivatives for use.
6, the preparation method of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent according to claim 2 is characterized in that solvent described in the graft reaction selects a kind of or mixture in toluene, the hexanaphthene for use.
7, the preparation method of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent according to claim 2 is characterized in that the class of polyalkene glycol acrylates described in building-up reactions monomer selects a kind of or mixture in different molecular weight polyethylene glycol mono acrylic ester, the methoxy poly (ethylene glycol) mono acrylic ester for use; Described carboxylic-acid monomer is selected one or more the mixture in vinylformic acid, methacrylic acid, methyl acrylate, the methyl methacrylate for use; Described olefin sulfonic acid class monomer is selected a kind of or mixture in allylsulfonate, the methallyl sulfonate for use.
8, the preparation method of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent according to claim 2 is characterized in that initiator described in the building-up reactions selects a kind of or mixture in Sodium Persulfate, Potassium Persulphate, the ammonium persulphate for use; It is 30% liquid caustic soda or a kind of or mixture in the ammoniacal liquor that described neutralization bases is selected strength of solution for use.
9, the preparation method of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent according to claim 2, it is characterized in that monomer solution and initiator solution all adopt at a slow speed dripping method or repeatedly feeding method add in the reactor.
10, the preparation method of air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent according to claim 2, the synthesis technique that it is characterized in that above-mentioned air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent, can select polyalkene glycol acrylates class monomer difference or while and the carboxylic-acid monomer and the allyl sulphonic acid class monomer copolymerization of different molecular weight for use, the synthetic product can independent or composite use.
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