CN101787137B - Polycarboxylic water reducer having reducing function, synthesis method and application method thereof - Google Patents
Polycarboxylic water reducer having reducing function, synthesis method and application method thereof Download PDFInfo
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- CN101787137B CN101787137B CN2010101020930A CN201010102093A CN101787137B CN 101787137 B CN101787137 B CN 101787137B CN 2010101020930 A CN2010101020930 A CN 2010101020930A CN 201010102093 A CN201010102093 A CN 201010102093A CN 101787137 B CN101787137 B CN 101787137B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000001308 synthesis method Methods 0.000 title abstract 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 59
- 239000004567 concrete Substances 0.000 claims abstract description 39
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 amine compounds Chemical class 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000005886 esterification reaction Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 239000004568 cement Substances 0.000 claims description 19
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 17
- 125000005518 carboxamido group Chemical group 0.000 claims description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 17
- 239000004570 mortar (masonry) Substances 0.000 claims description 13
- 230000032050 esterification Effects 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 150000007942 carboxylates Chemical class 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010348 incorporation Methods 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims 4
- 238000002360 preparation method Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000010276 construction Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000002202 Polyethylene glycol Substances 0.000 abstract 2
- 229920002125 Sokalan® Polymers 0.000 abstract 2
- 125000003368 amide group Chemical group 0.000 abstract 2
- 239000004584 polyacrylic acid Substances 0.000 abstract 2
- 229920001223 polyethylene glycol Polymers 0.000 abstract 2
- 239000004035 construction material Substances 0.000 abstract 1
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 22
- 239000000047 product Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 4
- 230000008602 contraction Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004574 high-performance concrete Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 206010011376 Crepitations Diseases 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention belongs to the technical field of construction materials, and specifically relates to a polycarboxylic water reducer having the reducing function, a synthesis method and an application method thereof. The synthesis method comprises the following steps: selecting polyacrylic acid, amine compounds with amide groups, polyethylene glycol, p-toluenesulfonic acid, sodium hydroxide and water as raw materials, weighing the polyacrylic acid and the amine compounds with amide groups according to the mass ratio, orderly adding to a reaction kettle, mixing, and stirring; introducing protective nitrogen gas to the reaction kettle, plugging a water separator and a condenser pipe, and reacting at 100-240 DEG C for 0.5-5 hours; adding the polyethylene glycol and the p-toluenesulfonic acid which are weighed according to the mass ratio to the polymer while stirring to be subjected to the esterification reaction at 50-120 DEG C for 2-8 hours; and adding water to the ester to prepare a solution, adding the sodium hydroxide to adjust the PH value, and uniformly mixing to obtain the required product. The invention has the advantages of simple synthesis process, stable process product performance, high water reducing rate, good reducing function, better slump retentivity and low admixture, can meet higher construction requirements, and improves the concrete strength to a certain extent, thereby having good market prospects.
Description
Technical field
The invention belongs to building material technical field, be specifically related to a kind of poly carboxylic acid series water reducer, compound method and method of use thereof with reducing function.
Background technology
Concrete structure is owing to be under the different restrained conditions because of contraction causes tensile stress, when concrete tensile strength during less than this tensile stress, will cause crack on concrete.Concrete shrinkage is meant the volume-diminished phenomenon that in concrete coagulation initial stage or process of setting, occurs.Generally be divided into plastic shrinkage, chemical shrinkage, dry shrinkage and carbonization and shrink, when shrinking greatly, will cause concrete cracking.And these crackles that produce or crack can cause concrete strength and weather resistance to reduce, and shorten concrete work-ing life, even influence concrete structural safety.Therefore, the contraction and the cracking problem of high performance concrete (HPC) have become problem extremely general and serious in the engineering practice, have caused the great attention of construction work circle.Along with the widespread use of low water binder ratio and mineral admixture HPC, the seriousness of concrete cracking and self-constriction problem is also strengthening.
Mix an amount of water reducer in the concrete, can significantly improve the serviceability and the concrete over-all properties in sclerosis back of fresh concrete.Poly carboxylic acid series water reducer is as new generation product, has that volume is low, water-reducing rate is high, a distinct advantages such as little, environmental protection of slow setting, slump-loss not.Though the concrete shrinkage of much reporting the admixture poly carboxylic acid series water reducer is less than other water reducers, but still be difficult to satisfy actual engineering demand.Therefore, China concrete admixture standard GB8076-1997 mixes cement water reducing agent, hardening accelerator, retardant, air entrapment agent concrete performance index regulation, and the concrete shrinkage ratio of mixing high efficiency water reducing agent is not more than 135%.And foreign study shows: when synthesizing polycarboxylic acid dehydragent, add and reduce component and can obtain having the poly carboxylic acid series water reducer that reduces the concrete shrinkage function.
The synthesis technique of poly carboxylic acid series water reducer mainly is in the market: prepare poly carboxylic acid series water reducer by starting material such as MPEG, methylacrylic acid, stopper, catalyzer and initiators through over-churning, polyreaction.Methylacrylic acid is on the high side in the used starting material of this type of technology, causes the poly carboxylic acid series water reducer cost to increase lacking of market competition ability; And this synthesis technique is complicated, and esterification process is difficult to control, and esterification products is very big to the performance impact of polyreaction and the finished product.Next is to produce poly carboxylic acid series water reducer by starting material such as APEG, maleic anhydride, initiators through copolyreaction.This type of technology did not need for two steps synthetic, and the prices of raw and semifnished materials are cheap, but product performance are not as good as MPEG class poly carboxylic acid series water reducer.Now, develop poly carboxylic acid series water reducer, could obtain to use widely with performance characteristics.The present invention is a main raw material(s) with ROHM (PAA), the aminated compounds (PN-220) that has carboxamido-group, polyoxyethylene glycol (PEG); Adopt the synthesis technique of esterification after the first copolymerization; (also) shrinkage that component is improved poly carboxylic acid series water reducer is reduced in introducing; Guaranteeing that water reducer has on the basis of low-dosage, high water reducing rate, practicing thrift use cost.At present, the domestic temporary transient not achievement in research of relevant synthesis technique aspect.
Summary of the invention
The object of the present invention is to provide a kind of good effect of reducing that has, synthesis technique is simple, the poly carboxylic acid series water reducer that product performance are stable, compound method and method of use thereof.
The poly carboxylic acid series water reducer that the present invention proposes with reducing function, starting material are ROHM, have the aminated compounds of carboxamido-group, polyoxyethylene glycol, tosic acid, sodium hydroxide and water that the weight ratio of each component is:
ROHM 100
The aminated compounds 30～180 that has carboxamido-group
Polyoxyethylene glycol 20～200
Tosic acid 2～10
Sodium hydroxide 2～10
Water 200～1700.
The preferable weight ratio of each component is:
ROHM 100
The aminated compounds 50～150 that has carboxamido-group
Polyoxyethylene glycol 60～160
Tosic acid 3～8
Sodium hydroxide 2～6
Water 400～1500.
Among the present invention, said polyacrylic molecular weight is 1000～5000.
Among the present invention, the said aminated compounds that has carboxamido-group adopts PN-220 (trade mark that refers to product).
Among the present invention, the molecular weight of said polyoxyethylene glycol is 400～2000.
The compound method of the poly carboxylic acid series water reducer that the present invention proposes with reducing function, concrete steps are:
(1) takes by weighing ROHM, has the aminated compounds of carboxamido-group by mass ratio, add reaction kettle successively, mix, stir;
(2) copolymerization: in reaction kettle, feed shielding gas nitrogen, plug water trap and prolong, under 100～240 ℃ of temperature, reacted 0.5～5 hour;
(3) esterification: go on foot in the polymkeric substance of preparing (2), add the polyoxyethylene glycol and the tosic acid that take by weighing by mass ratio while stirring, under 50～120 ℃ of temperature, carried out esterification 2～8 hours;
(4) go on foot in the carboxylate of preparing (3), add entry and be mixed with solution, add sodium hydroxide again and regulate the pH value, mix, promptly get required product to 6.8-7.2.
Among the present invention, replace MPEG or APEG, form side chain, produce the steric restriction effect of physics, prevent the cement granules cohesion, keep dispersed with PAA; The poly carboxylic acid series water reducer of long side chain has degree of mobilization retentivity preferably, and the poly carboxylic acid series water reducer of short-side chain has initial flow degree preferably.PAA can with the PN-220 polymerization reaction take place, the aminated compounds (PN-220) that has carboxamido-group has the enhancing diminishing, improves effects such as slump-loss.The more important thing is the introducing polyoxyethylene glycol, have reducing function.Tosic acid is as the catalyzer of esterification.Sodium hydroxide is used for the pH value of conditioned reaction product solution.
Synthetic product of the present invention is a light yellow transparent liquid; Concentration is 20%～70%; The water reducer incorporation is 0.10%～0.50% of a cement weight in the clean slurry; The water reducer incorporation is 0.30%～1.00% of a cement weight in the mortar, and the water reducer incorporation is 0.40%～2.00% of a cement weight in the concrete.Can make it have high water reducing rate and good reducing function and slump retentivity preferably, can satisfy higher construction requirement, and improve concrete strength to a certain extent.Compare with existing processes; With ROHM (PAA), the aminated compounds (PN-220) that has carboxamido-group, polyoxyethylene glycol (PEG) is the compound method reaction times weak point of the poly carboxylic acid series water reducer with reducing function of main raw material(s); Technology is simple; The stable performance of reaction product especially can improve contraction.
The present invention can supply admixture factory to produce; Be widely used in sand-cement slurry and the concrete; Reinforcing bar is not had corrosion, can spray to the surface of concrete or mortar member and goods yet, be applicable to great concrete construction engineering and various normal concrete construction works such as factory building, road, bridge, tunnel, dam, airport; Also being fit to the materials for wall production of articles, is the ideal economization agent for concrete.
Embodiment
Further specify the present invention through embodiment below.
Embodiment 1; With ROHM (PAA), the aminated compounds (PN-220) that has carboxamido-group, polyoxyethylene glycol (PEG) is the poly carboxylic acid series water reducer with reducing function of main raw material(s), and its weight ratio is: PAA (molecular weight 1000) 100, PN-22030, PEG (molecular weight 400) 20, tosic acid 2, sodium hydroxide 10, water 200.Adopt following compound method: PAA, PN-220 to add reaction kettle successively, feed nitrogen protection, plug water trap and prolong, react 5h down at 100 ℃; The polymkeric substance limit is stirred to wherein adding PEG and tosic acid in the limit then, reacts 2h down at 50 ℃; In carboxylate, add entry and process certain density solution, add sodium hydroxide at last, regulate pH value to 6.8, mix, promptly get desired product.Mix this water reducer of by mass of cement 0.10%, can make wc is that 0.29 flowing degree of net paste of cement is 270mm; In mortar, mix this water reducer of 0.30%, the 3d decrement of mortar is 60%, and the 28d decrement is 38%; In concrete, mix this water reducer of 0.40%, concrete water-reducing ratio reaches 20%, and the 3d decrement is 40%, and the 28d decrement is that 24%, 2 hour slump-loss is 25mm, and compressive strength rate reached 110% in 28 days.
Embodiment 2; With ROHM (PAA), the aminated compounds (PN-220) that has carboxamido-group, polyoxyethylene glycol (PEG) is the poly carboxylic acid series water reducer with reducing function of main raw material(s), and its weight ratio is: PAA (molecular weight 2500) 100, PN-220100, PEG (molecular weight 1000) 60, tosic acid 6, sodium hydroxide 6, water 800.Adopt following compound method: PAA, PN-220 to add reaction kettle successively, feed nitrogen protection, plug water trap and prolong, react 3h down at 160 ℃; The polymkeric substance limit is stirred to wherein adding PEG and tosic acid in the limit then, reacts 5h down at 90 ℃; In carboxylate, add entry and process certain density solution, add sodium hydroxide at last, regulate pH value to 7.0, mix, promptly get desired product.Mix this water reducer of by mass of cement 0.30%, can make wc is that 0.29 flowing degree of net paste of cement is 255mm; In mortar, mix this water reducer of 0.60%, the 3d decrement of mortar is 76%, and the 28d decrement is 60%; In concrete, mix this water reducer of 1.00%, concrete water-reducing ratio reaches 25%, and the 3d decrement is 65%, and the 28d decrement is that 50%, 2 hour slump-loss is 20mm, and compressive strength rate reached 130% in 28 days.
Embodiment 3; With ROHM (PAA), the aminated compounds (PN-220) that has carboxamido-group, polyoxyethylene glycol (PEG) is the poly carboxylic acid series water reducer with reducing function of main raw material(s), and its weight ratio is: PAA (molecular weight 5000) 100, PN-220180, PEG (molecular weight 2000) 200, tosic acid 10, sodium hydroxide 2, water 1700.Adopt following compound method: PAA, PN-220 to add reaction kettle successively, feed nitrogen protection, plug water trap and prolong, react 0.5h down at 240 ℃; The polymkeric substance limit is stirred to wherein adding PEG and tosic acid in the limit then, reacts 8h down at 120 ℃; In carboxylate, add entry and process certain density solution, add sodium hydroxide at last, regulate pH value to 7.2, mix, promptly get desired product.Mix this water reducer of by mass of cement 0.50%, can make wc is that 0.29 flowing degree of net paste of cement is 245mm; In mortar, mix this water reducer of 1.00%, the 3d decrement of mortar is 85%, and the 28d decrement is 65%; In concrete, mix this water reducer of 2.00%, concrete water-reducing ratio reaches 30%, and the 3d decrement is 85%, and the 28d decrement is that 62%, 2 hour slump-loss is 15mm, and compressive strength rate reached 120% in 28 days.
Embodiment 4; With ROHM (PAA), the aminated compounds (PN-220) that has carboxamido-group, polyoxyethylene glycol (PEG) is the poly carboxylic acid series water reducer with reducing function of main raw material(s), and its weight ratio is: PAA (molecular weight 5000) 100, PN-22060, PEG (molecular weight 2000) 80, tosic acid 8, sodium hydroxide 4, water 1000.Adopt following compound method: PAA, PN-220 to add reaction kettle successively, feed nitrogen protection, plug water trap and prolong, react 1.5h down at 200 ℃; The polymkeric substance limit is stirred to wherein adding PEG and tosic acid in the limit then, reacts 3h down at 100 ℃; In carboxylate, add entry and process certain density solution, add sodium hydroxide at last, regulate pH value to 7.0, mix, promptly get desired product.Mix this water reducer of by mass of cement 0.40%, can make wc is that 0.29 flowing degree of net paste of cement is 250mm; In mortar, mix this water reducer of 0.80%, the 3d decrement of mortar is 65%, and the 28d decrement is 47%; In concrete, mix this water reducer of 1.60%, concrete water-reducing ratio reaches 28%, and the 3d decrement is 80%, and the 28d decrement is that 58%, 2 hour slump-loss is 20mm, and compressive strength rate reached 120% in 28 days.
Embodiment 5; With ROHM (PAA), the aminated compounds (PN-220) that has carboxamido-group, polyoxyethylene glycol (PEG) is the poly carboxylic acid series water reducer with reducing function of main raw material(s), and its weight ratio is: PAA (molecular weight 2500) 100, PN-220150, PEG (molecular weight 1000) 120, tosic acid 4, sodium hydroxide 8, water 1200.Adopt following compound method: PAA, PN-220 to add reaction kettle successively, feed nitrogen protection, plug water trap and prolong, react 2h down at 180 ℃; The polymkeric substance limit is stirred to wherein adding PEG and tosic acid in the limit then, reacts 6h down at 70 ℃; In carboxylate, add entry and process certain density solution, add sodium hydroxide at last, regulate pH value to 7.0, mix, promptly get desired product.Mix this water reducer of by mass of cement 0.20%, can make wc is that 0.29 flowing degree of net paste of cement is 260mm; In mortar, mix this water reducer of 0.50%, the 3d decrement of mortar is 58%, and the 28d decrement is 43%; In concrete, mix this water reducer of 1.20%, concrete water-reducing ratio reaches 25%, and the 3d decrement is 70%, and the 28d decrement is that 52%, 2 hour slump-loss is 15mm, and compressive strength rate reached 110% in 28 days.
Claims (4)
1. poly carboxylic acid series water reducer with reducing function is characterized in that starting material are ROHM, have aminated compounds, polyoxyethylene glycol, tosic acid, sodium hydroxide and the water of carboxamido-group, and the weight ratio of each component is:
Wherein: said polyacrylic molecular weight is 1000～5000, and the said aminated compounds that has carboxamido-group adopts PN-220, and the molecular weight of said polyoxyethylene glycol is 400～2000;
The preparation method is following:
(1) takes by weighing ROHM, has the aminated compounds of carboxamido-group by mass ratio, add reaction kettle successively, mix, stir;
(2) copolymerization: in reaction kettle, feed shielding gas nitrogen, plug water trap and prolong, under 100～240 ℃ of temperature, reacted 0.5～5 hour;
(3) esterification: go on foot in the polymkeric substance of preparing (2), add the polyoxyethylene glycol and the tosic acid that take by weighing by mass ratio while stirring, under 50～120 ℃ of temperature, carried out esterification 2～8 hours;
(4) go on foot in the carboxylate of preparing (3), add the entry obtain solution, add sodium hydroxide again and regulate the pH value, mix, promptly get required product to 6.8-7.2.
2. the poly carboxylic acid series water reducer with reducing function according to claim 1 is characterized in that the weight ratio of each component is:
3. compound method with poly carboxylic acid series water reducer of reducing function as claimed in claim 1 is characterized in that concrete steps are:
(1) takes by weighing ROHM, has the aminated compounds of carboxamido-group by mass ratio, add reaction kettle successively, mix, stir;
(2) copolymerization: in reaction kettle, feed shielding gas nitrogen, plug water trap and prolong, under 100～240 ℃ of temperature, reacted 0.5～5 hour;
(3) esterification: go on foot in the polymkeric substance of preparing (2), add the polyoxyethylene glycol and the tosic acid that take by weighing by mass ratio while stirring, under 50～120 ℃ of temperature, carried out esterification 2～8 hours;
(4) go on foot in the carboxylate of preparing (3), add the entry obtain solution, add sodium hydroxide again and regulate the pH value, mix, promptly get required product to 6.8-7.2.
4. method of use with poly carboxylic acid series water reducer of reducing function as claimed in claim 1; It is characterized in that this water reducer incorporation is 0.10%～0.50% of a cement weight in the clean slurry; This water reducer incorporation is 0.40%～1.00% of a cement weight in the mortar, and this water reducer incorporation is 0.40%～2.00% of a cement weight in the concrete.
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| CN103626419B (en) * | 2012-08-23 | 2016-06-08 | 上海东大化学有限公司 | Take polyethers as poly carboxylic acid series water reducer, its method of preparation and use of raw material |
| CN104761173B (en) * | 2014-12-23 | 2017-01-18 | 水利部交通运输部国家能源局南京水利科学研究院 | Polycarboxylate water reducer with good reducing effect and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5880182A (en) * | 1993-10-29 | 1999-03-09 | Mbt Holding Ag | Water-reducing admixtures for cementitious compositions |
| CN1636921A (en) * | 2004-12-09 | 2005-07-13 | 武汉科技大学 | Concrete water reducing agent of polyacrylic acid and its synthesis process |
| CN1802330A (en) * | 2004-06-25 | 2006-07-12 | 日本西卡株式会社 | Cement dispersant and concrete composition containing the dispersant |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5880182A (en) * | 1993-10-29 | 1999-03-09 | Mbt Holding Ag | Water-reducing admixtures for cementitious compositions |
| CN1802330A (en) * | 2004-06-25 | 2006-07-12 | 日本西卡株式会社 | Cement dispersant and concrete composition containing the dispersant |
| CN1636921A (en) * | 2004-12-09 | 2005-07-13 | 武汉科技大学 | Concrete water reducing agent of polyacrylic acid and its synthesis process |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2001-19512A 2001.01.23 |
| 孙振平等.烯丙基聚乙二醇系聚羧酸类减水剂的研究.《建筑材料学报》.2009,第12卷(第4期),407-412. * |
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