CN101497507B - High-early strength antifreezing polycarboxylate high performance water reducing agent and preparation - Google Patents
High-early strength antifreezing polycarboxylate high performance water reducing agent and preparation Download PDFInfo
- Publication number
- CN101497507B CN101497507B CN2009100611964A CN200910061196A CN101497507B CN 101497507 B CN101497507 B CN 101497507B CN 2009100611964 A CN2009100611964 A CN 2009100611964A CN 200910061196 A CN200910061196 A CN 200910061196A CN 101497507 B CN101497507 B CN 101497507B
- Authority
- CN
- China
- Prior art keywords
- water reducing
- early
- reducing agent
- polycarboxylate
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/29—Frost-thaw resistance
Abstract
The present invention discloses an early-strength antifreezing polycarboxylate high-performance water reducing agent and a method for preparing the same. The early-strength antifreezing water reducing agent is prepared from a polycarboxylate water reducing agent, an early-strength antifreezing agent, an air entraining agent and water. The method comprises the following steps: A, the synthesis of the polycarboxylate high-performance water reducing agent: (1) esterification reaction; adding methacrylic acid, and the like to a reaction kettle, and (2) polymerization reaction; heating big monomer methoxypolyethyleneglycol methacrylic ester; B, the preparation for the solution of an early-strength antifreezing agent: (1), weighing water and adding the same to the reaction kettle, and adding calcium formate to the reaction kettle, and (2), adding triethanolamine, and the like to the reaction kettle to prepare the early-strength antifreezing agent solution; C, the preparation of the air entraining agent: weighing water and adding the same to the reaction kettle, and adding powdered three-level colophony to the reaction kettle to obtain the air entraining agent; and D, the preparation of the finished product: weighing the polycarboxylate water reducing agent and adding the same to the reaction kettle, and adding the air entraining agent and the early-strength antifreezing agent solution to the reaction kettle. The early-strength antifreezing polycarboxylate high-performance water reducing agent has higher water reducing rate and remarkable enhancing effect, and is suitable to prepare various common concrete and high-performance concrete at a negative temperature range of between 20 DEG C below zero and 0 DEG C.
Description
Technical field
The invention belongs to the concrete additives in building materials technical field, more specifically relate to a kind of early-strength anti-freezing type polycarboxylate dehydragent, the preparation method who also relates to early-strength anti-freezing type polycarboxylate dehydragent simultaneously is applicable to and prepares the concrete and the premixing mortar of various strength grades winter under subzero temperature.
Background technology
The vast northern area weather of China is colder usually, is winter 4-6 month, and is very big to the concrete engineering construction influence.In order to ensure the quality and the progress of concrete construction, most economical effective means is to use concrete admixture---early strength antifreezing agent.Along with the development of building industry, concrete has progressively been realized high performance (high-strength, high workload degree, high-durability).In order to satisfy the concrete requirement of pumping construction in winter, early strength antifreezing agent is all wanted composite superplasticizer, air entrapment agent usually.JC475-2004 " coagulation frostproofer " is divided into five big classes with frostproofer according to composition: the first kind is a chloride salt; Second class is a villaumite resistance rust class; The 3rd class is non-chloride salt; The 4th class is the organic compound class, as: urea, methyl alcohol etc.; The 5th class is the complex class frostproofer.Villaumite type, villaumite resistance rust type, no rate high alkalinity, the low alkali type several stages of no chlorine have been experienced in its development.Normally with naphthalene water reducer, melamine water reducing agent, aliphatic category water reducer etc., accelerating component is vitriol, carbonate etc. to water reducer in the previously used frostproofer, and wherein great majority are sodium salt; Antifreezing component is nitrite, villaumite, urea, ammoniacal liquor etc.Not only alkali content is very high in the water reducer component of these frostproofers, but also contains residual formaldehyde, and in addition, its water-reducing rate neither be very high, and is relatively poor to the suitability of cement, is difficult to satisfy the requirement of current high performance concrete; Alkali content in the accelerating component is very high; Chloride ion content, sulphate content are very high in the antifreezing component, and what have also can discharge ammonia etc. in concrete, are unfavorable for the weather resistance and the environmental protection of coagulation.
The compound antifreezer sodium salt content of mentioning among patent CN92102097.5, the patent CN92110542.8 is all very high; Contain urea in the frostproofer that patent CN94100148.2, patent CN96109810.4 introduce; Contain Sodium Propionate, former bright powder among the patent CN2003107019.8, alkali content is very high.The diminishing component all is naphthalene water reducers in the above-mentioned patent, contains higher sodium sulfate, and alkali content is higher, and the accelerating component alkali content is also very high, and this can cause the generation of alkali-aggregate reaction; Some antifreezing component such as urea etc. also discharge the gas of contaminate environment in concrete, the antifreezing component that has contains the nitrite of severe toxicity.
Though patent CN101186462A and patent CN101289293A all are also very low with polycarboxylate dehydragent component, early-strength anti-freezing component alkali content, chloride ion content, but the bleed component is used separately or the simple composite use in the antifreeze water reducer that patent CN101186462A introduces, the pore size, the homogeneity that form pore in concrete distribute not ideal enough, and do not adopt suds-stabilizing agent in the air entrapment agent, can make the bubble instability in the concrete like this, be easy to break, do not reach the air content requirement of expection, can reduce anti-freezing property; Do not have the bleed component in the frostproofer that patent CN101289293A introduces, just produce air content by water reducer in concrete, air content is on the low side.The size of the size of concrete enclosing pore, the homogeneity of distribution, stability and air content all can exert an influence to the anti-freezing property of frostproofer.
Summary of the invention
Some problems at current early-strength anti-freezing type water reducer existence, the objective of the invention is to be to provide a kind of early-strength anti-freezing type polycarboxylate dehydragent, according to the mechanism of action of early strength antifreezing agent and a large amount of tests, determined the performance perameter index of early-strength anti-freezing type water reducer, invented a kind of freeze proof, endurance quality is better, is adapted under the low temperature environment normal concrete of the various strength grades of preparation and the high-early strength antifreezing polycarboxylate high performance water reducing agent of high performance concrete.
Another object of the present invention is the preparation method who has been to provide a kind of early-strength anti-freezing type polycarboxylate dehydragent, higher, the early stage reinforced effects of the product water-reducing rate of its production is more remarkable, the frost resistance under the low temperature is better, chlorion and alkali content is low, can not discharge poisonous and hazardous gas in concrete, is to prepare various concrete and premixing mortar ideal environmentally friendly machine subzero temperature under.
The present invention is according to concrete freeze injury mechanism, reduce theoretical, ice crystal distortion theory in conjunction with freeze proof critical strength theory, freezing point, determined to select from the following aspects the integral part of preparation high-early strength antifreezing polycarboxylate high performance water reducing agent: (1) selects the high-quality air entrapment agent for use, change concrete pore structure, make the inside concrete pore for be evenly distributed, airtight independently little pore, can effectively sponge frost heave stress that inside concrete produces like this and unlikelyly cause destruction; (2) select the polycarboxylate high performance dehydragent of high water reducing rate for use, reduce the free-water in the concrete significantly, make when freezing and can not produce the concrete expansion stress of enough destruction, water-cement ratio has also obtained reduction simultaneously, the corresponding raising of concrete intensity, thus anti-freezing property improved; (3) select frostproofer for use, reduce the freezing point of inside concrete water, water is not frozen or few freezing; (4) select hardening accelerator for use, improve early strength as early as possible, make concrete meet or exceed the concrete critical strength of enduring cold as early as possible.Good consistency is arranged between these components and the component, can produce early strong, antifreeze synergistic effect again each other.Each component of the present invention is formulated by following mass percent:
Raw materials quality per-cent (%)
Polycarboxylate high performance dehydragent 6%-14%
Early strength antifreezing agent 4%-16%
Air entrapment agent 0.3%-0.8%
Water 70%-92%
Described water reducer is: the methacrylic polycarboxylate high performance dehydragent
Described early strength antifreezing agent comprises accelerating component and antifreezing component, and wherein accelerating component is: trolamine, tri-isopropanolamine, calcium formiate, antifreezing component is: nitrocalcite (Ca (NO
3)
2), ethylene glycol, their mass ratio is: trolamine: tri-isopropanolamine: calcium formiate: Ca (NO
3)
2: ethylene glycol=0.1: 0.1: 3: 3: 2.
A kind of early-strength anti-freezing type polycarboxylate dehydragent, each component of its preferential scope is formulated by following mass percent:
Raw materials quality per-cent (%)
Polycarboxylate high performance dehydragent 8%-12%
Early strength antifreezing agent 6%-14%
Air entrapment agent 0.4%-0.7%
Water 74%-88%
A kind of early-strength anti-freezing type polycarboxylate dehydragent, each component of its better scope is formulated by following mass percent:
Raw materials quality per-cent (%)
Polycarboxylate high performance dehydragent 9%-10%
Early strength antifreezing agent 8%-12%
Air entrapment agent 0.5%-0.6%
Water 78%-84%
A kind of early-strength anti-freezing type polycarboxylate dehydragent, preferably each component of scope is formulated by following mass percent:
Raw materials quality per-cent (%)
Polycarboxylate high performance dehydragent 9.5%
Early strength antifreezing agent 11%
Air entrapment agent 0.5%
Water 79%
A kind of preparation method of early-strength anti-freezing type polycarboxylate dehydragent the steps include:
One, high performance water reducing agent of polyocarboxy acid is synthetic:
1. esterification: in reactor, add dissolved methoxy poly (ethylene glycol) 70-100Kg (molecular weight is 1500), heating heats up, start simultaneously and stir, temperature is controlled at 80-105 ℃, add methacrylic acid 20-30Kg then, add stopper thiodiphenylamine 0.9-1.5Kg, p-methyl benzenesulfonic acid 4-6Kg more successively, be warmed up to 120-130 ℃, be incubated 5-7 hour, obtain the macromer methoxyl-polyethyleneglycol methacrylic ester.
2. polyreaction: 70-80 ℃ of the macromer methoxyl-polyethyleneglycol methacrylic ester heating and melting that the first step reaction is made, add entry 90-120Kg then, when being warmed up to 85-95 ℃, beginning drips the ammonium persulfate solution 35-55Kg of methacrylic acid 6-8Kg and 10% (mass percent concentration) simultaneously, the dropping time is 4 hours, be warmed up to 90-100 ℃ of constant temperature after dripping after 2 hours, naturally cool to below 60 ℃, the sodium hydroxide solution that drips 30% (mass percent concentration) is regulated PH=6-7, promptly make the methacrylic polycarboxylate high performance dehydragent, concentration is about 30% (mass percent concentration).
Two, preparation early-strength anti-freezing agent solution:
A, take by weighing water 1500-2500Kg earlier and add in the reactor, be warmed up to 60-70 ℃, under whipped state, slowly add calcium formiate, the Ca (NO of weighing in proportion then
3)
2
B, treat that solution in the A step dissolves fully after, under whipped state, add trolamine, tri-isopropanolamine more successively, (mass ratio of each component is ethylene glycol: calcium formiate: Ca (NO
3)
2: trolamine: tri-isopropanolamine: ethylene glycol=3: 3: 0.1: 0.1: 2), added the back restir 20 minutes, stop to stir, promptly be mixed with the early-strength anti-freezing agent solution;
Three, the making of air entrapment agent:
Take by weighing water 150-250Kg and add in the reactor, add 40% (mass percent concentration) NaOH solution 15-25Kg then, heat to 80 ℃-90 ℃ after under whipped state, slowly add three grades of rosin 75-175Kg of powdery.After adding material, reacted 2 hours, at this moment the PH=8-10 of material.Take out a small amount of finished product, use 40-60 ℃ hot water dilution,, then can determine to react completely as if clear, muddy, the nothing precipitation of nothing.After reacting completely, add sodium laurylsulfonate 15-30Kg successively, fully after the dissolving, the polyvinyl alcohol solution 15-45Kg, emulsifying agent (OP) 8-13Kg that add trolamine 4-6.5Kg, 4% (mass percent concentration) successively are diluted to the solution that percentage concentration is about 20% (mass percent concentration) with hot water at last and promptly obtain the finished product air entrapment agent.
Four, finished product is made
Take by weighing quantitative polycarboxylate water-reducer and join in another reactor, take by weighing the air entrapment agent in the 3rd step then in proportion, the early-strength anti-freezing agent solution with air entrapment agent, preparation under whipped state adds in the reactor successively, stirs, and to clarification, promptly gets this product.
In order to describe material composition of the present invention, compound method and premium properties in detail, now be listed below embodiment and carry out the performance index simultaneous test according to the existing industry standard of JC457-2004 " concrete antifreezer ".But can not be interpreted as that scope of the present invention only limits to following examples.
The present invention compared with prior art has the following advantages and effect:
A, the removing residue formaldehyde that does not contain contaminate environment and toxic substance can not discharge obnoxious flavour in concrete;
B, chlorion, alkali content are low, do not contain in concrete and cause steel bar corrosion and alkali;
C, water-reducing rate height, early stage reinforced effects be good, slow setting not;
D, in concrete, introduce evenly, sealing, little pore independently, can improve concrete anti-freezing property, improve concrete weather resistance;
E, good to the adaptability of cement is little through time loss.
Embodiment
Embodiment 1:
A kind of early-strength anti-freezing type polycarboxylate dehydragent, each component of its preferential scope is formulated by following mass percent:
Raw materials quality per-cent (%)
Polycarboxylate high performance dehydragent 12%
Early strength antifreezing agent 10.3%
Air entrapment agent 0.7%
Water 77%
A kind of high-early strength antifreezing polycarboxylate high performance water reducing agent, described polycarboxylate high performance dehydragent are the graft copolymer of following general formula, and its structural formula is:
Wherein: R
1For-CH
3Or H; R
2Alkyl for H or 1-4 carbon atom; M is H, monovalent metallic ion, divalent-metal ion, ammonium or amido; A, b are the chain number of multipolymer repeating unit, and its size is determined by the molecular weight of multipolymer; N is oxyethane addition average mol 90-200.
A kind of preparation method of early-strength anti-freezing type polycarboxylate dehydragent the steps include:
(1) esterification: in reactor, add dissolved methoxy poly (ethylene glycol) (molecular weight is 1500) 80Kg, heating heats up, start simultaneously and stir, temperature is controlled at 80 or 85 or 89 or 93 or 97 or 100 or 103 or 105 ℃, add methacrylic acid 26Kg then, add stopper thiodiphenylamine 1.31Kg, p-methyl benzenesulfonic acid 5.0Kg more successively, be warmed up to 120 or 123 or 125 or 128 or 130 ℃, be incubated 5 or 6 or 7 hours, obtain the macromer methoxyl-polyethyleneglycol methacrylic ester.
(2) polyreaction: the first step is reacted the macromer methoxyl-polyethyleneglycol methacrylic ester heating and melting that makes, 70-80 ℃, add entry 105.27Kg then, when being warmed up to 85 or 87 or 89 or 90 or 92 or 95 ℃, beginning drips the ammonium persulfate solution 45Kg of methacrylic acid 7.11Kg and 10% (mass percent concentration) simultaneously, the dropping time is 4 hours, be warmed up to 90 or 93 or 95 or 98 or 100 ℃ of constant temperature after dripping after 2 hours, naturally cool to below 60 ℃, the sodium hydroxide solution that drips 30% (mass percent concentration) is regulated PH=6-7, promptly make the methacrylic polycarboxylate high performance dehydragent, concentration is 30% (mass percent concentration).
Two, preparation early-strength anti-freezing agent solution:
A, take by weighing 1910Kg water earlier and add in the reactor, be warmed up to 60 or 62 or 64 or 66 or 68 or 70 ℃, under whipped state, slowly add calcium formiate 300Kg, the Ca (NO of weighing in proportion then
3)
2300Kg;
B, treat that solution in the A step dissolves fully after, add trolamine 20Kg, tri-isopropanolamine 20Kg, ethylene glycol 200Kg more successively, every stirring 20 minutes is mixed with the early-strength anti-freezing agent solution;
Three, the making of our company's air entrapment agent:
Take by weighing 200Kg water and add in the reactor, add 20Kg40% (mass percent concentration) NaOH solution then, heat to 80 or 82 or 84 or 86 or 88 or 90 ℃ after under whipped state, slowly add three grades of rosin of 100Kg powdery.After adding material, reacted 2 hours, at this moment the PH=8 or 8.5 or 8.8 or 9.2 or 9.6 or 9.8 or 10 of material.Take out a small amount of finished product,,, then can determine to react completely as if clear, muddy, the nothing precipitation of nothing with the hot water dilution.After reacting completely, add sodium laurylsulfonate 20Kg successively, fully after the dissolving, the polyvinyl alcohol solution 25Kg, emulsifying agent (OP) 10Kg that add trolamine 5Kg, 4% (mass percent concentration) successively, being diluted to percentage concentration with hot water at last is that 20% solution promptly obtains the finished product air entrapment agent.
Four, finished product is made
The methacrylic high performance water reducing agent of polyocarboxy acid solution 400Kg that takes by weighing 30% (mass percent concentration) that makes joins in the reactor, under whipped state, add successively then and press the above early-strength anti-freezing agent solution 343Kg of method preparation 30% (mass percent concentration), air entrapment agent solution 35Kg, stir, leave standstill to clarification and promptly get solid content and be about 23.0%, pH value is 8 light yellow liquid product.
Embodiment 2:
(method of the preparation of synthetic, the early strength antifreezing agent of polycarboxylate dehydragent, the making of air entrapment agent is identical with embodiment 1.)
Finished product is made:
Take by weighing above-mentioned high performance water reducing agent of polyocarboxy acid solution 120Kg, join in the reactor, under whipped state, add 97Kg water successively, early-strength anti-freezing agent solution 132Kg, the modification air entrapment agent solution 10.8Kg in the 3rd step among the embodiment 1 obtains solid content about 21.6% and pH value and is 8 light yellow liquid product.
Comparative example 1:
Taking by weighing 1000Kg water adds in the reactor, under whipped state, add naphthalene water reducer 300Kg, trolamine 20Kg, urea 50Kg, Sodium Nitrite 200Kg, calcium nitrite 80Kg then successively, after stirring dissolving fully, obtain the brownish black solid content and be 39.4% and pH value be that 8 diminishing component is the early strength antifreezing agent liquid product of naphthalene water reducer.
Comparative example 2:
In reactor, add entry 377Kg, under whipped state, add polycarboxylate dehydragent 100Kg (40% quality is than concentration), ethylene glycol 30Kg, tetrahydroxypropyl ethylenediamine 10Kg successively, Magnesium sulfocyanate 50Kg, calcium formiate 25Kg and rosin tree lipid air entrapment agent 15Kg, be stirred to fully dissolving, obtain the early strength antifreezing agent product that quality is a polycarboxylate than original diminishing component of concentration about 31.1%.
Implementation result:
1, with the contrast of the adaptability of cement: according to GB/T8077-2000 " concrete admixture uniformity test method " starch only degree of mobilization and through the time loss contrast experiment.The cement that this experiment is adopted be the new P.O42.5 cement of China, and W/C=0.29 surveys the initial flow degree respectively, parks 60 minutes, after 120 minutes, surveys their clean slurry degree of mobilization more respectively, contrast its clean slurry degree of mobilization and through the time lose.Comparing result such as following table: (table 1)
| Frostproofer | Initial clean slurry degree of mobilization (mm) | Degree of mobilization after 1 hour (mm) | Degree of mobilization after 2 hours (mm) |
| Embodiment 1 | 240 | 252 | 250 |
| Embodiment 2 | 220 | 230 | 228 |
| Comparative example 1 | 180 | 150 | 90 |
| Comparative example 2 | 225 | 225 | 220 |
By table 1 result as can be seen the diminishing component be that the clean slurry degree of mobilization of polycarboxylic acid salt's frostproofer is all better, 1 hour, 2 hours very little through time loss, and the situation of growth was arranged in 1 hour, naphthalene is that the initial flow degree of class frostproofer is less, 1 hour, 2 hours very big through time loss, relatively poor with the intermiscibility of cement.
2, frostproofer performance comparison
Measure the admixture of embodiment 1,2 and comparative example 1,2 by JC475-2004 " concrete antifreezer " respectively and do the anti-freezing property contrast:
The parameter of early strength antifreezing agent is 3%, mix proportion is: cement: rubble: sand=330: 1147: 703, water consumption: concrete slump is: 80 ± 10 (mm), wherein, poor, the bleeding rate of the water-reducing rate of concrete mix, ultimate compression strengthization, air content, time of coagulation is than examining and determine by GB8076-97.(table 2)
Table 2: the frostproofer volume is 3% of a gelling material, concrete performance contrast in the time of-15 ℃.
By the detected result of table 2 as can be seen:
＜1〉every index of the embodiment of the invention 1.2 described early-strength anti-freezing formulation polycarboxylate high performance dehydragents has all surpassed the requirement of acceptable end product among the JC475-2004 " concrete antifreezer ".Its water-reducing rate is all more than 20%, the early-strength anti-freezing effect than traditional be that the frostproofer of diminishing group is better with naphthalene;
＜2〉the present invention is that diminishing component, employing do not have the frostproofer of the air entrapment agent of modification as the bleed component on the market owing to having adopted the homemade modification air entrapment agent of our company, its anti-freezing property also obviously to be better than with the polycarboxylate dehydragent.The present invention is to concrete impermeability, and weather resistance also has improvement, is a kind of desirable early-strength anti-freezing type water reducer of preparing high performance concrete under subzero temperature.
A kind of early-strength anti-freezing type polycarboxylate dehydragent, its each component can be formulated by following mass percent:
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | |
| Polycarboxylate high performance dehydragent (%) | 12 | 6 | 8 | 10 | 7 | 4 | 9 | 11 | 14 | 8.5 | 6.5 |
| Early strength antifreezing agent (%) | 10.3 | 8 | 7 | 9 | 11 | 12 | 8 | 7 | 5 | 7.5 | 8.5 |
| Air entrapment agent (%) | 0.7 | 0.5 | 0.3 | 0.4 | 0.6 | 0.8 | 0.3 | 0.5 | 0.7 | 0.8 | 0.85 |
| Water (%) | 77 | 85.5 | 84.7 | 80.6 | 81.4 | 83.2 | 82.7 | 81.5 | 80.3 | 83.2 | 84.15 |
Its preparation process is identical with embodiment 1.
Claims (7)
1. high-early strength antifreezing polycarboxylate high performance water reducing agent, it is made by following raw material mass percent by weight:
Above-mentioned each component sum is 100%;
Described water reducer is: the methacrylic polycarboxylate high performance dehydragent;
Described early strength antifreezing agent comprises accelerating component and antifreezing component, and wherein accelerating component is: trolamine, tri-isopropanolamine, calcium formiate; Antifreezing component is: nitrocalcite, ethylene glycol, their mass ratio is: trolamine: tri-isopropanolamine: calcium formiate: Ca (NO
3)
2: ethylene glycol=0.1: 0.1: 3: 3: 2;
The making method of described air entrapment agent is as follows:
Taking by weighing water 150-250Kg adds in the reactor, add 40%NaOH solution 15-25Kg then, after heating to 80 ℃-90 ℃ under whipped state, add three grades of rosin 75-175Kg of powdery, after adding material, reacted 2 hours, the pH=8-10 of material takes out finished product at this moment, hot water dilution with 40-60 ℃, clear, do not have muddy, do not have precipitation, determine to react completely, after reacting completely, add sodium laurylsulfonate 15-30Kg successively, after the dissolving, add trolamine 4-6.5Kg successively, 4% polyvinyl alcohol solution 15-45Kg, emulsifying agent 8-13Kg, being diluted to percentage concentration with hot water at last is that 20% solution promptly obtains the finished product air entrapment agent.
2. a kind of high-early strength antifreezing polycarboxylate high performance water reducing agent according to claim 1 is characterized in that: it is made by following raw material mass percent by weight:
Above-mentioned each component sum is 100%.
3. a kind of high-early strength antifreezing polycarboxylate high performance water reducing agent according to claim 1 is characterized in that: it is made by following raw material mass percent by weight:
Above-mentioned each component sum is 100%.
4. a kind of high-early strength antifreezing polycarboxylate high performance water reducing agent according to claim 1 is characterized in that: it is made by following raw material mass percent by weight:
5. a kind of high-early strength antifreezing polycarboxylate high performance water reducing agent according to claim 1 is characterized in that: it is made by following raw material mass percent by weight:
6. a kind of high-early strength antifreezing polycarboxylate high performance water reducing agent according to claim 1 is characterized in that: it is made by following raw material mass percent by weight:
7. a kind of high-early strength antifreezing polycarboxylate high performance water reducing agent according to claim 1 is characterized in that: it is made by following raw material mass percent by weight:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100611964A CN101497507B (en) | 2009-03-20 | 2009-03-20 | High-early strength antifreezing polycarboxylate high performance water reducing agent and preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100611964A CN101497507B (en) | 2009-03-20 | 2009-03-20 | High-early strength antifreezing polycarboxylate high performance water reducing agent and preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101497507A CN101497507A (en) | 2009-08-05 |
| CN101497507B true CN101497507B (en) | 2011-10-05 |
Family
ID=40944806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100611964A Expired - Fee Related CN101497507B (en) | 2009-03-20 | 2009-03-20 | High-early strength antifreezing polycarboxylate high performance water reducing agent and preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101497507B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641363A (en) * | 2013-12-06 | 2014-03-19 | 广州市鲁班建筑工程技术有限公司 | Self-repaired vinylon polymer waterproof mortar additive and preparation method thereof |
Families Citing this family (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704934B (en) * | 2009-11-20 | 2012-05-30 | 山东同盛建材有限公司 | Method for synthesizing polycarboxylate superplasticizer at low cost |
| CN101921083B (en) * | 2010-08-19 | 2012-11-14 | 上海固佳化工科技有限公司 | Ester-ether mixed ultra high early strength poly-carboxylic high-performance water reducer and preparation method thereof |
| CN102344535B (en) * | 2011-08-02 | 2012-12-12 | 武汉市奥维邦科技发展有限公司 | Preparation method of modified high-performance polycarboxylic acid water reducing agent |
| CN102320770A (en) * | 2011-09-13 | 2012-01-18 | 武汉理工大学 | Efficient liquid antifreezing agent for concrete, and preparation method thereof |
| CN102392405B (en) * | 2011-11-04 | 2013-09-11 | 广东冠粤路桥有限公司 | Super-early-strength super-rapid-hardening concrete pavement and construction method thereof |
| CN103373832B (en) * | 2012-04-17 | 2015-05-13 | 苏琳 | High-performance anti-cracking anticorrosive water reducing agent composition and preparation method thereof |
| CN102815901B (en) * | 2012-08-31 | 2013-10-16 | 中铁二十局集团有限公司 | Ultralow-temperature high-performance concrete for railway construction in severe cold regions and preparation technique thereof |
| CN102797358B (en) * | 2012-08-31 | 2014-08-06 | 中铁二十局集团有限公司 | Construction technique for ultralow-temperature high-property concrete for railway construction in frigid areas |
| CN102898056A (en) * | 2012-10-17 | 2013-01-30 | 孝感恒盛建筑节能材料有限公司 | Enhancement type water reducer capable of reducing slump loss |
| CN102875052B (en) * | 2012-10-23 | 2014-04-16 | 天津市建筑科学研究院有限公司 | Compound admixture for heat curing-free concrete in winter construction |
| CN103030328A (en) * | 2012-11-27 | 2013-04-10 | 常州大学 | Anti-freezing agent for building materials |
| CN103030754A (en) * | 2012-12-21 | 2013-04-10 | 江西迪特科技有限公司 | Method for preparing polycarboxylic concrete water reducer with high slump retention capacity, and construction method of polycarboxylic concrete water reducer |
| CN103910504A (en) * | 2013-01-25 | 2014-07-09 | 王立巍 | Concrete antifreezing agent |
| CN103145368B (en) * | 2013-03-07 | 2014-04-09 | 北京新奥混凝土集团有限公司 | Early-strength water reducer for recycled aggregate concrete |
| CN103224341B (en) * | 2013-05-13 | 2014-07-30 | 十九冶成都建设有限公司 | High-early-strength antifreezing polycarboxylic-acid composite water reducing agent and application thereof |
| CN103613319A (en) * | 2013-11-08 | 2014-03-05 | 安徽省阜南绿原化工有限公司 | Green and environment-friendly plasticizer |
| CN103755214B (en) * | 2014-01-17 | 2015-07-15 | 东海建设集团有限公司 | Concrete antifreezer |
| CN104529232B (en) * | 2014-12-04 | 2016-08-24 | 同济大学 | Polycarboxylate composite water reducing agent, preparation method and using method thereof for high carbon content concrete |
| CN105778078B (en) * | 2014-12-16 | 2017-11-21 | 辽宁奥克化学股份有限公司 | A kind of polyether ester, its preparation method and Early-strength polycarboxylate superplasticizer and preparation method thereof as made from the polyether ester |
| CN104830277B (en) * | 2015-03-30 | 2017-03-15 | 内蒙古博冉科技有限责任公司 | The antifreeze tackifier of wall built-up |
| CN104876467B (en) * | 2015-04-17 | 2017-07-11 | 浙江老虎山建材有限公司 | A kind of high performance concrete admixture and its preparation technology |
| CN104861122A (en) * | 2015-04-22 | 2015-08-26 | 厦门路桥翔通建材科技有限公司 | Heat-source-free early strength polycarboxylate water reducer and preparation method thereof |
| CN105110694A (en) * | 2015-08-10 | 2015-12-02 | 深圳市科源建设集团有限公司 | Concrete anti-freezing agent |
| CN105503010A (en) * | 2015-12-30 | 2016-04-20 | 新疆玉鑫蕊科技开发有限责任公司 | Polycarboxylic acid type concrete antifreezer |
| EP3333138A1 (en) * | 2016-12-06 | 2018-06-13 | Sika Technology AG | Liquid additive for readying cement screed for laying quickly |
| CN106927712A (en) * | 2017-03-02 | 2017-07-07 | 安徽鑫固环保股份有限公司 | A kind of high-strength antifreeze bicomponent mortar additive and preparation method thereof |
| CN107032656A (en) * | 2017-03-02 | 2017-08-11 | 安徽鑫固环保股份有限公司 | A kind of winter is with composite mortar additive and preparation method thereof |
| CN107021666A (en) * | 2017-03-02 | 2017-08-08 | 萧县沃德化工科技有限公司 | A kind of early-strength anti-freezing type compound additive and preparation method and application |
| CN107010867A (en) * | 2017-03-02 | 2017-08-04 | 安徽鑫固环保股份有限公司 | A kind of compound early-strength anti-freezing wet mixing mortar additive and preparation method thereof |
| CN107032655A (en) * | 2017-03-02 | 2017-08-11 | 安徽鑫固环保股份有限公司 | A kind of wet mixing mortar NEW TYPE OF COMPOSITE additive and preparation method thereof |
| CN106946487A (en) * | 2017-03-02 | 2017-07-14 | 安徽鑫固环保股份有限公司 | A kind of wet mixing mortar antifreeze additive and preparation method thereof |
| CN106927710A (en) * | 2017-03-02 | 2017-07-07 | 安徽鑫固环保股份有限公司 | A kind of wet mixing mortar early-strength anti-freezing type additive and preparation method thereof |
| CN107777907A (en) * | 2017-09-28 | 2018-03-09 | 长沙加美乐素化工有限公司 | The Early-strength polycarboxylate superplasticizer used for undervulcanization cement and Machine-made Sand concrete |
| CN108046667A (en) * | 2017-12-08 | 2018-05-18 | 湖南中大经纬地热开发科技有限公司 | A kind of improvement Loess Filling and its application method for roadbed |
| CN109095814A (en) * | 2018-05-30 | 2018-12-28 | 江苏百瑞吉新材料有限公司 | A kind of rust-proof type poly carboxylic acid series water reducer and preparation method thereof |
| CN108911564B (en) * | 2018-07-13 | 2020-11-13 | 桂林华越环保科技有限公司 | Concrete synergist with composite function |
| CN111533481A (en) * | 2020-05-06 | 2020-08-14 | 黄炳江 | Novel concrete water reducing agent and preparation method thereof |
| CN112960934B (en) * | 2021-03-08 | 2022-11-01 | 合肥元旭环保新型材料有限公司 | Preparation process and equipment of antifreezing concrete additive |
| CN113666660B (en) * | 2021-08-31 | 2022-11-01 | 江西省圣源商品混凝土有限公司 | Concrete antifreezing agent and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1547986A1 (en) * | 2003-12-22 | 2005-06-29 | Mapei S.p.A. | High early strength superplasticizer |
| CN101186462A (en) * | 2007-11-26 | 2008-05-28 | 江苏博特新材料有限公司 | Liquid, chlorine-free, early-strength anti-freezing polycarboxylate composite water reducing agent and preparation method thereof |
| CN101289292A (en) * | 2008-06-13 | 2008-10-22 | 北京工业大学 | Early strength polycarboxylic acid high performance dehydragent and method for preparing same |
-
2009
- 2009-03-20 CN CN2009100611964A patent/CN101497507B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1547986A1 (en) * | 2003-12-22 | 2005-06-29 | Mapei S.p.A. | High early strength superplasticizer |
| CN101186462A (en) * | 2007-11-26 | 2008-05-28 | 江苏博特新材料有限公司 | Liquid, chlorine-free, early-strength anti-freezing polycarboxylate composite water reducing agent and preparation method thereof |
| CN101289292A (en) * | 2008-06-13 | 2008-10-22 | 北京工业大学 | Early strength polycarboxylic acid high performance dehydragent and method for preparing same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641363A (en) * | 2013-12-06 | 2014-03-19 | 广州市鲁班建筑工程技术有限公司 | Self-repaired vinylon polymer waterproof mortar additive and preparation method thereof |
| CN103641363B (en) * | 2013-12-06 | 2015-11-18 | 广州市鲁班建筑工程技术有限公司 | A kind of selfreparing vinylon waterproof polymer mortar admixture and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101497507A (en) | 2009-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101497507B (en) | High-early strength antifreezing polycarboxylate high performance water reducing agent and preparation | |
| CN101508536B (en) | modified aliphatic water reducing agent and preparation method | |
| CN104844047B (en) | Compound antifreezer and anti-freezing pumping agents | |
| CN101580354A (en) | Polycarboxylic retarding high-performance water reducing agent for preparing concrete of middle and low strength grade | |
| CN104788629A (en) | Polycarboxylate water-reducing agent and normal-temperature preparation method thereof | |
| CN103086635A (en) | Pumping agent and application thereof | |
| CN102659365B (en) | Desulfurized ash residue mixed dry mortar | |
| CN108840608A (en) | A kind of frost-resistant concrete and preparation method thereof | |
| CN106904867B (en) | Concrete synergist containing chitosan sodium sulfonate and preparation method thereof | |
| CN111153646A (en) | Seawater sea sand concrete material for 3D printing | |
| CN104119026A (en) | Concrete composite water reducing agent | |
| CN108424030A (en) | A kind of collapse protection type Concrete strength agent and its preparation method and application | |
| CN109336443A (en) | A kind of concrete potent dose and its preparation process | |
| CN103922628B (en) | A kind of high performance water reducing agent of polyocarboxy acid of anti-freeze type and preparation method thereof | |
| CN102101758B (en) | Polyether carboxylic acid water reducer and preparation method thereof | |
| CN105384380A (en) | Tannin extract/polycarboxylate concrete water reducer and preparation method thereof | |
| CN102815898B (en) | Superfine slag powder concrete and preparation method thereof | |
| CN101805147B (en) | Preparation method of liquid cement grinding aid | |
| CN109704620B (en) | Concrete admixture suitable for cold and dry environment and preparation method and application thereof | |
| CN104478280B (en) | Concrete synergist and preparation method thereof | |
| CN104478287B (en) | Multifunctional concrete synergist and preparation method thereof | |
| CN106336138B (en) | A kind of foam control agent and its manufactured bleed diminishing compounding agent, concrete | |
| CN112341116A (en) | Desulfurized gypsum and super-sulfur cement concrete and preparation method thereof | |
| CN103435289A (en) | High-early-strength, freeze-proofing and high-performance polycarboxylate water reducer | |
| CN113173728B (en) | Alkali-free accelerator for resisting aggregate alkali activity reaction and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111005 Termination date: 20180320 |