CN101289292A - Early strength polycarboxylic acid high performance dehydragent and method for preparing same - Google Patents
Early strength polycarboxylic acid high performance dehydragent and method for preparing same Download PDFInfo
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- CN101289292A CN101289292A CNA2008101149450A CN200810114945A CN101289292A CN 101289292 A CN101289292 A CN 101289292A CN A2008101149450 A CNA2008101149450 A CN A2008101149450A CN 200810114945 A CN200810114945 A CN 200810114945A CN 101289292 A CN101289292 A CN 101289292A
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- 239000002253 acid Substances 0.000 title claims description 20
- 238000000034 method Methods 0.000 title abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims description 26
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 20
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 229960004418 trolamine Drugs 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims 3
- 239000004567 concrete Substances 0.000 abstract description 53
- 239000003513 alkali Substances 0.000 abstract description 11
- 229910000831 Steel Inorganic materials 0.000 abstract description 7
- 239000010959 steel Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 2
- 229920005646 polycarboxylate Polymers 0.000 abstract 3
- 229920000642 polymer Polymers 0.000 abstract 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 12
- 239000004568 cement Substances 0.000 description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 239000008030 superplasticizer Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Diphosphoinositol tetrakisphosphate Chemical compound OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 230000003389 potentiating effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009440 infrastructure construction Methods 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- 229920001427 mPEG Polymers 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011513 prestressed concrete Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000009955 starching Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a high performance early-strength polycarboxylate water reducer and a preparation method thereof, which pertains to the water reducer field. The early-strength water reducer is prepared mainly based on graft copolymeric carboxylic polymer and compounded with a preferred early strength component; wherein, the copolymeric carboxylic polymer refers to the polymer polymerized by methoxy polyethylene glycol acrylate and acrylic acid/methyl acrylic acid by a free radical initiator in water. The high performance early-strength polycarboxylate water reducer prepared by the invention is characterized by small doping, low alkali content, no chloride ion and no sulfate, and the like, and does not result in the corrosion and alkali aggregate reaction, and the like, of the steel bars in the concrete structure, which is helpful for guaranteeing the duration of the concrete structure. The high performance early-strength polycarboxylate water reducer manufactured by the invention can be widely applied to the construction of various concrete projects and the construction of concrete at low temperature, and is particularly suitable for the low energy consumptive production technique of concrete prefabricated parts and has promising application prospect.
Description
Technical field
The present invention relates to a kind of concrete early strength polycarboxylic acid high performance dehydragent of normal silicate that is used for.
Background technology
In recent years; enter the new period of sustained, rapid and sound development along with China's economy; the continuous increase that China drops into infrastructure constructions such as dwelling house, traffic, water conservancy and hydropowers; concrete admixture requirements at the higher level have also been proposed; require to have good serviceability on the one hand, guarantee the weather resistance of concrete structure on the other hand again.
In many engineerings, because the requirement that has certain singularity thereby clearly proposed in very short limited period, must be completed, these needs of just having to add concrete early strength agent to accelerate hydrated cementitious, improve the concrete strength tempo, thereby accelerating construction progress is completed smoothly to guarantee engineering.In addition, in concrete prefabricated element was produced, hardening accelerator can shorten the steam-cured time even exempt steam curing process, thereby has remarkable economic efficiency.In the practical application, adopt the early-strength type composite water-reducing agent mostly, guaranteed fresh concrete good construction performance under the low water-cement ratio condition on the one hand, also accelerated concrete early strength tempo on the other hand.
The sulfonic acid group content that adopts 30~100 parts among the CN1312324A is the modified waste old polystyrene water reducer of 20mol%~98mol%, with 5~20 parts sodium sulfate, 40~70 parts composite the forming of sulfonated lignin.When the solid volume of folding was about 6%, its water-reducing rate was 20~28%, and 1d ultimate compression strength rises to 41%~48% approximately.This invention is owing to mainly be to focus on to utilize the modified waste old polystyrene water reducer, thereby significantly reduces the cost of early strong composite water-reducing agent, but volume is big, and contains sodium sulfate, and the effect that improves early strength still is not very desirable.Adopt 600~800 parts Calcium Chloride Powder Anhydrous, 200~400 parts flyash, 5~15 parts myo-Inositol hexaphosphate, 10~30 parts trolamine, 2~10 parts Sodium Benzoate to be composited among the CN101024565A.Under-5 ℃~-25 ℃ temperature on average, when volume 2.5%, can make 1~7 day ultimate compression strength of concrete improve 20~100%.This invention mainly is to focus on that antifreeze morning, powerful was a early strength under the low temperature, only illustrated under the normal temperature and can improve early strong, saving cement, not mentioned concrete effect, and wherein contain villaumite, forbid being used for Steel Concrete and prestressed concrete structure engineering, forbid basically on important engineering, using.Mentioning employing acrylate copolymer water reducer and alkanolamine, morpholine derivative etc. among the US6767399 is composited.Do not illustrate in this patent that acrylate copolymer water reducer structure belongs to pectination, the improvement of still needing of its mobile hold facility.
Domestic about hardening accelerator or early strong composite water-reducing agent patent also seldom, and adopt naphthalene system or s-generation water reducer composite high-early strength effects such as melamine system, amido sulfoacid series villaumite or vitriol etc. preferably in the existing patent mostly, but have that volume is big, serviceability is easily lost, undesirable, the environment of potent fruit shortcoming such as close friend inadequately early, some easily causes the generation of steel bar corrosion, alkali in the concrete structure, thereby reduced the weather resistance of concrete structure, caused very big society's waste.Begun to turn to 21st century to use the poly carboxylic acid series water reducer of tool prospect or composite with accelerating component in the external issued patents, but owing to part material reasons such as not clear or price is high, application is subjected to very big restriction.So press for exploitation be fit to China's feelings have not chloride ion-containing and sulfate ion, low alkali content, volume little, early potent fruit significantly, the concrete admixture of advantages of environment protection, can significantly improve the early strength tempo, can not produce problems such as steel bar corrosion, alkali in the concrete structure again, ensure the weather resistance of concrete structure conscientiously.
Summary of the invention
The present invention is according to the compound principle and the functional design principle of compound additive, it is good and significantly improve the high performance water reducing agent of polyocarboxy acid of early strength to have invented a kind of concrete water-reducing effect of ordinary Portland cement that is used for, and has overcome traditional morning strong composite water-reducing agent defectives such as steel bar corrosion, alkali easily take place.
Early strength polycarboxylic acid high performance dehydragent provided by the invention, it is characterized in that: utilize the acrylic acid or the like high efficiency water reducing agent to be main raw material, behind functional design, with reasonable composite the forming of early strong useful component such as trolamine, Sodium Thiocyanate 99, nitrocalcite, meter comprises by weight:
80~125 parts of acrylic acid or the like poly carboxylic acid series water reducers
3~7 parts of trolamines
5~30 parts of Sodium Thiocyanate 99s
14~42 parts in nitrocalcite
24~70 parts in water
The production method of early strength polycarboxylic acid high performance dehydragent provided by the invention, with parts by weight is 80~125 acrylic acid or the like poly carboxylic acid series water reducers of part, 3~7 parts trolamine, 5~30 parts Sodium Thiocyanate 99, the above-mentioned composition of 14~42 parts nitrocalcite place 24~70 parts water promptly to get this early-strength type polycarboxylic acid series composite water-reducing agent after the mixing stirring is fully water-soluble.
Effect of the present invention: find a kind of have efficient diminishing, no slow setting and early strong high performance water reducing agent of polyocarboxy acid and the accelerating component etc. of chloride ion-containing, sulfate ion etc. not, good synergetic property is arranged between several components, after science is composite, have characteristics such as volume is little, water-reducing rate is high, alkali content is low, environmental friendliness, the fresh concrete workability is good, can significantly improve early strength such as 12h, 24h, the 3d ultimate compression strength in the length of time, and can not produce problems such as steel bar corrosion, alkali in the concrete structure, ensure the weather resistance of concrete structure conscientiously.
For describing various material composition of the present invention, compound method and excellent results more in detail, be listed below embodiment and test according to the character index of GB/T8077-2000 " Methods for testing uniformity of concrete admixture ", GB 8076-1997 " concrete admixture ".But scope of the present invention is not limited only to the following examples.
Embodiment:
Embodiment 1:
Carry out the synthetic of acrylic acid or the like poly carboxylic acid high efficiency water reducing agent with reference to following steps:
The first step esterification: in reactor, add molecular weight M=1000 methoxy poly (ethylene glycol) 100 grams, heated and stirred is to fully melting, temperature is controlled at 130 ℃, add hydroquinone of polymerization retarder 0.014 gram, react after 15 minutes, in turn with vinylformic acid 14.4 grams, tosic acid 1.14 grams, hexanaphthene 23 grams carry out esterification again; After the isothermal reaction 4.5 hours, remove band aqua hexanaphthene, obtain the macromer methoxyl-polyethyleneglycol acrylate by vacuumizing.
The second step polyreaction: the big monomer that the first step reaction is made places four neck flasks, add entry 150.52 grams after the heating and melting, be warmed up to 65 ℃, fully add sodium allyl sulfonate 7.9 grams after the stirring and dissolving successively, the aqueous solution 32.4 grams of the POTASSIUM PERSULFATE mass percent concentration 10% of butyl acrylate 19.2 gram preparations join in the reactor, be warmed up to 90 ℃ of temperature of reaction, isothermal reaction adds 10% persulfate aqueous solution, 28.35 grams after 1 hour, react again and add remaining 10% potassium persulfate solution 20.25g after 1 hour, after the isothermal reaction 2 hours, naturally cool to 44 ℃, add 40% quadrol regulator solution to pH=7, promptly get acrylic acid or the like poly carboxylic acid high efficiency water reducing agent, mass percent concentration is 40.0%.But thin up is to required different mass percentage concentration, as 20%, 30%.
Acrylic acid or the like poly carboxylic acid series water reducer 62.5 grams that take by weighing 20% concentration place plastic containers, add 12.0 gram water, 3.5 gram trolamines, 15 gram Sodium Thiocyanate 99s, 7.0 gram nitrocalcite then under whipped state successively, fully dissolving is left standstill and is promptly got early-strength type polycarboxylic acid series composite superplasticizer.Solid content 36.0%, pH 7.2, and it is clarifying light brown that outward appearance is, volume 2.0%;
Embodiment 2:
Synthesize according to embodiment 1 and to obtain acrylic acid or the like poly carboxylic acid high efficiency water reducing agent, and with the solution dilution to 20.0% of gained 40.0%.
Acrylic acid or the like poly carboxylic acid series water reducer 40 grams that take by weighing 20% concentration place Glass Containers, add 35.0 gram water, 1.5 gram trolamines, 2.5 gram Sodium Thiocyanate 99s, 21.0 gram nitrocalcite then under whipped state successively, fully dissolving is left standstill and is promptly got early-strength type polycarboxylic acid series composite superplasticizer.Solid content 27%, pH 7.1, and it is clarifying light brown that outward appearance is, volume 2.0%;
Embodiment 3:
Synthesize according to embodiment 1 and to obtain acrylic acid or the like poly carboxylic acid high efficiency water reducing agent, and with the solution dilution to 20.0% of gained 40.0%.
Acrylic acid or the like poly carboxylic acid series water reducer 50 grams that take by weighing 20% concentration place stainless steel vessel, add 21.5 gram water, 2.5 gram trolamines, 5 gram Sodium Thiocyanate 99s, 21.0 gram nitrocalcite then under whipped state successively, fully dissolving is left standstill and is promptly got light brown clarifying early-strength type polycarboxylic acid series composite superplasticizer.Solid content 33.5%, pH 7.2, and it is clarifying light brown that outward appearance is, volume 2.0%;
Embodiment 4:
Synthesize according to embodiment 1 and to obtain acrylic acid or the like poly carboxylic acid high efficiency water reducing agent, and with the solution dilution to 20.0% of gained 40.0%.
Acrylic acid or the like poly carboxylic acid series water reducer 60 grams that take by weighing 20% concentration place stainless steel vessel, be incorporated in 24.5 gram water, 3.5 gram trolamines, 5 gram Sodium Thiocyanate 99s, 7.0 gram nitrocalcite then under whipped state successively, fully dissolving is left standstill and is promptly got early-strength type polycarboxylic acid series composite superplasticizer.Solid content 25.5%, pH 7.3, and it is clarifying light brown that outward appearance is, volume 2.0%;
Comparative example 1: take by weighing water 333g and place plastic containers, add naphthalene series high-efficiency water-reducing agent 35g, trolamine 7g, calcium chloride 125g then successively under whipped state, fully dissolving is left standstill and is got promptly that to clarify brown early-strength type naphthalene be composite water-reducing agent.Solid content 33.4%, pH 7.5, and outward appearance is the clarification brown, volume 4.0%;
Comparative example 2: take by weighing water 305g and place plastic containers, add naphthalene series high-efficiency water-reducing agent 40g, trolamine 5g, sodium sulfate 150g then successively under whipped state, fully dissolving is left standstill and is got promptly that to clarify brown early-strength type naphthalene be composite water-reducing agent.Solid content 39.0%, pH 7.5, and outward appearance is the clarification brown, volume 5.0%;
Implementation result
1. flowing degree of net paste of cement and retentivity thereof
Flowing degree of net paste of cement and degree of mobilization carry out with reference to GB/T8077-2000 " Methods for testing uniformity of concrete admixture " through the measuring method of time loss.Adopt coloured glaze river P.O.42.5 cement, W/C=0.29.Concrete testing method is that sheet glass is placed on level attitude,, makes its surface wettability and is not with water stain sheet glass, truncated cone circle mould, agitator and the even wiping of agitator kettle with wet towel.Truncated cone circle mould is placed on sheet glass central authorities, the cement paste that stirs (water cement ratio 0.29) is injected rapidly in the truncated cone circle mould, behind the floating upper surface of scraper, truncated cone circle mould is vertically mentioned with hand, timing simultaneously, appoint and starch on sheet glass unrestricted flow only and on 2 orthogonal directions, measure clean slurry maximum and sprawl diameter, average as the value of starching degree of mobilization only to 30s.To remain the clean slurry container of packing into, and cover, park 1h, 2h respectively, stir 1min then to prevent that water from dividing evaporation, repeat again the aforesaid operations method measure its degree of mobilization through the time lose.As seen, under the same terms, the flowability and the mobile retentivity product tool than before of the early strength polycarboxylic acid high performance dehydragent of the inventive method preparation have greatly improved.
Table 1 flowing degree of net paste of cement and the comparison that keeps performance thereof
Group number | The early-strength type composite water-reducing agent | 5min(mm) | 30min(mm) | 60(mm) |
1 | Embodiment 1 | 265 | 260 | 240 |
2 | Embodiment 2 | 235 | 230 | 220 |
3 | Embodiment 3 | 250 | 245 | 225 |
4 | Embodiment 4 | 255 | 240 | 230 |
5 | Comparative example 1 | 190 | 150 | - |
6 | Comparative example 2 | 220 | 175 | 130 |
2. the technical feature of early strength polycarboxylic acid high performance dehydragent
To carrying out mortar and concrete performance detection according to the early-strength type polycarboxylic acid series composite water-reducing agent of the inventive method preparation and traditional early strong composite water-reducing agent of naphthalene system.Concrete performance test ginseng GB/T 50080-2002 " Standard for test methods of properties of ordinary concrete mixture standard ", GB/T 50081-2002 " standard for test methods of mechanical properties of ordinary concrete " measure the various performances of fresh concrete and maturing respectively.Test ambient temperature is (20 ± 3) ℃.
The normal concrete proportioning designs by JGJ55-2000 " design of common concrete proportioning rules ", mixes early the constant rate of the cement of the concrete of composite water-reducing agent and normal concrete, sand, stone by force.The proportioning design should meet following provisions: cement consumption: when adopting cobble, and (310 ± 5) kg/m
3When adopting rubble, (330 ± 5) kg/m
3Because stone belongs to crushed gravel, the employing single cement consumption is 320kg.Sand coarse aggregate ratio: the concrete sand coarse aggregate ratio of composite water-reducing agent is 36%~40% to normal concrete with mixing early by force.Here all get sand coarse aggregate ratio 40%.
Early strong composite water-reducing agent volume: regulation liquid volume is respectively 2.0%; Water consumption: should make the concrete slump reach (80 ± 10) mm.Draw folk prescription concrete mix cement in view of the above: sand: stone: water=320: 760: 1140: 200.
Concrete mixture characteristic water-reducing rate, bleeding rate ratio, air content and mensuration and calculating that time of coagulation, difference was carried out according to GB 8076-1997 " concrete admixture ".The slump should be finished in the 5min after concrete goes out machine.Concrete sample making, maintenance and detection etc. are carried out with reference to GB/T50080-2002 " Standard for test methods of properties of ordinary concrete mixture standard ", GB/T50081-2002 " standard for test methods of mechanical properties of ordinary concrete ", the concrete slump of composite water-reducing agent is not (80 ± 10) mm with not mixing early by force but mix, test specimen is made should adopt shaking table jolt ramming, and time of vibration is 10~15 seconds.That mixes early strong composite water-reducing agent is examined concrete sample going to the standard curing room maintenance after the maintenance 12h form removal under (20 ± 3) ℃ envrionment temperature, measures corresponding age strength respectively, and test-results sees Table 2~3.
The test of table 2C50 mechanical performance of concrete
Concrete performance test result when table 3 volume is 15 ℃ of 2.0% curing temperatures
Annotate: "-" expression shifts to an earlier date time of coagulation, and "+" expression delays time of coagulation.
This novel early strength polycarboxylic acid high performance dehydragent volume is little, early effective by force; Chloride ion-containing has not been eliminated the possibility of being brought into chlorion by admixture, has reduced the potentially dangerous of steel bar corrosion; Sulfur-bearing acid group not, alkali content is low, and when mixing with 2.0% liquid mass, it is atomic to introduce alkali number, only about 0.05%, has reduced the possibility that alkali takes place equally.These all help ensureing concrete weather resistance.
Claims (2)
1. early strength polycarboxylic acid high performance dehydragent is characterized in that: based on the acrylic acid or the like poly carboxylic acid series water reducer, with accelerating component trolamine, Sodium Thiocyanate 99, nitrocalcite is composite forms, and presses mass fraction in following ranges:
80~125 parts of acrylic acid or the like poly carboxylic acid series water reducers
3~7 parts of trolamines
5~30 parts of Sodium Thiocyanate 99s
14~42 parts in nitrocalcite
24~70 parts in water.
2. the preparation method of early strength type polycarboxylic acid series high-performance dehydragent as claimed in claim 1, it is characterized in that: the acrylic acid or the like poly carboxylic acid series water reducer that with mass fraction is 80~125 parts, 3~70 parts trolamine, 5~30 parts Sodium Thiocyanate 99, the above-mentioned composition of 14~42 parts nitrocalcite place 24~70 parts water promptly to get early-strength type polycarboxylic acid series composite water-reducing agent after the mixing stirring is fully water-soluble.
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