CN104761689A - Preparation method of super high-early-strength polycarboxylate superplasticizer - Google Patents
Preparation method of super high-early-strength polycarboxylate superplasticizer Download PDFInfo
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Abstract
The invention relates to a preparation method of a super high-early-strength polycarboxylate superplasticizer. The super high-early-strength polycarboxylate superplasticizer is prepared by performing a free radical polymerization reaction on a low-foam polyether macromonomer A, a polyether macromonomer B, a micromonomer C and a micromonomer D in an aqueous medium under the action of a water-soluble redox system, wherein the molar ratio of the monomers A, B, C and D is (0.2-1):(3-9):(0.5-3). The functional polycarboxylate superplasticizer has the advantages of obviously improving the early hydration of the cement, improving the early strength of the concrete, improving the early strength of the concrete and remarkably enhancing the compressive strength of the concrete, and the advantages of excellent working performance, low apparent viscosity and convenience for construction of the newly mixed concrete.
Description
Technical field
The present invention relates to a kind of preparation method of ultra early-strength polycarboxylate water-reducer, this polycarboxylate water-reducer promotes hydrated cementitious under the prerequisite ensureing dispersion preferably and dispersion retention, improve early age strength of concrete and ensure later strength steady development, optimize maturing internal porosity parameter and distribution consistency degree, remarkable Concrete Structure intensity, belongs to concrete admixture field.
Background technology
Poly carboxylic acid series water reducer has the advantages such as volume is low, good dispersity, Molecular Structure Design degree of freedom are large compared with the condensation polymer type admixtures such as traditional naphthalene system, trimeric cyanamide.On polycarboxylate water-reducer molecular backbone chain, electronegative hydroxy-acid group is adsorbed on cement particle surface, and plays sterically hindered effect by long side chain, thus produces dispersion effect.At present, the poly carboxylic acid series water reducer on market also can delay hydrated cementitious to a certain extent while disperse cement particles, the development of restriction concrete strength.
Improve concrete early strength, mainly through improving the early stage extent of hydration of cement.Current by this one side of admixture, the technological approaches realizing super hardening function has two kinds, a kind of poly carboxylic acid series water reducer being synthesis itself and there is super hardening function, another kind is that the conventional poly carboxylic acid series water reducer of synthesis and hardening accelerator are composite, by strong problem morning of composite solution poly carboxylic acid series water reducer.Mainly rely on the method for composite hardening accelerator in poly carboxylic acid series water reducer to improve concrete early strength at present, but there is certain problem in hardening accelerator in current application, such as inorganic salts hardening accelerator is due to containing Cl-and alkali, easily cause the problems such as removing blunt of reinforcing steel bar corrosion, there is many defects and application limitation, and salt is all soluble, thus morely residue in concrete liquid phase, form concrete surface and saltout and cause concrete surface white pollution.In concrete, introduce the risk that a large amount of alkali adds alkali aggregate reaction simultaneously, reduce concrete weather resistance; Organic Alcohol amine hardening accelerator then needs to control well volume, what such as TEA showed is determined by its specific volume in cementitious material system to hydrated cementitious acceleration or slow action effect, degradation problem under the serious slow setting of concrete and concrete strength can be caused when volume is too much, and do not urge solidifying effect when being used alone, as the addO-on therapy of some mixed chemical admixture, the course of hydrated cementitious can only be changed by its chemical catalysis effect; Organic and inorganic composite type hardening accelerator increases to early potent fruit and other a series of effect improving concrete performance, but still does not change the one side of traditional hardening accelerator to concrete disadvantageous effect.The poly carboxylic acid series water reducer by the method preparation of synthesis with super hardening function is present study hotspot, in recent years, Sequa Corp of Switzerland, catalyst company of Japan, BASF Corp. of Germany is proposed the polycarboxylate water-reducer product with super hardening effect one after another, oneself produces and requires through being used for concrete prefabricated element the concrete that preparation is early strong, but there is esterification in its water reducer preparation process and transesterify difficulty is large, macromole class synthon starting material not easily obtain, complex process and cost is higher, the problems such as water-reducing rate is not enough, therefore enter and produce the practical stage and also have certain difficulty
To sum up, it is poor that traditional early-strength admixture has with water reducer interoperability, is unfavorable for Engineering Control, and difficulty of construction is large, the shortcomings such as poor durability; Existing ultra high early strength poly-carboxylic water reducer production technique exists that esterification and transesterify difficulty are large, macromole class synthon starting material not easily obtain, complex process and the problem such as cost is higher, and water-reducing rate is not enough.
Summary of the invention
Research purpose of the present invention is a kind of polycarboxylate water-reducer with super hardening performance of development, overcomes the shortcoming described in background technology.Products production technology of the present invention is simple, and product water-reducing rate is high, flowing hold facility is strong, amount of air entrainment is low, can effectively Concrete Structure early strength and later strength development be well.
Technical scheme of the present invention is: applicant finds after deliberation, and the side chain lengths of polycarboxylate water-reducer is the key factor affecting hydrated cementitious.Polyethenoxy ether class monomer molecule amount is larger, and hydrated cementitious is faster, more favourable Concrete Structure early strength.Meanwhile, longer side chain is also conducive to the dispersing property increasing water reducer, accelerates hydrated cementitious, promotes cement early strength development.
Applicant finds with propylene oxide (PO) block, the polyether macromonomer of oxyethane (EO) end-blocking has lower HLB value and surface tension, its bubble and steady bubble ability all slightly poor than common polyether, therefore the polycarboxylate water-reducer self that prepared by this polyethers has certain foam control effect that disappears, and optimize maturing internal porosity parameter and distribution consistency degree, and then Concrete Structure intensity.
Applicant finds the sulfonate ion introducing suitable proportion on main chain, can improve the absorption behavior of multipolymer, increases the adsorptive capacity of multipolymer at cement particle surface, and then improves dispersive ability, accelerate hydrated cementitious, promotes early strength development.In addition, concrete apparent viscosity can also be reduced.
Concrete technical scheme of the present invention is: a kind of preparation method of ultra early-strength polycarboxylate water-reducer, and its concrete steps are as follows:
(1) bed material preparation: take monomer A and monomers B respectively, and pour in identical vessel, add oxygenant, be dissolved in water and mix stand-by:
(2) drip material 1. to prepare: take mercaptan type chain transfer agent and reductive agent, add water and fully dissolve and mix stand-by;
(3) drip material 2. to prepare: take monomer C and D respectively, add water and fully dissolve and mix stand-by;
(4) copolyreaction: heating bed material limit, limit is stirred, drip in bed material when temperature rises to 30 ~ 55 DEG C simultaneously material 1. with dropping material 2., dripping material time for adding 1. controls at 3 ~ 4 hours, dripping material time for adding 2. controls at 2 ~ 3.5 hours, copolyreaction temperature controls at 30 ~ 60 DEG C, control the reaction times from dropping to reaction end be 3.5 ~ 6 hours, copolymerization system monomer A, B, C and D total mass concentration control 40 ~ 80%;
(5) neutralization reaction: it is 6 ~ 7 that copolyreaction terminates to add basic cpd adjusted to ph in backward reaction product, final obtained ultra early-strength polycarboxylate water-reducer;
Wherein the mol ratio of monomer A, B, C, D is (0.2 ~ 1): 1:(3 ~ 9): (0.5 ~ 3);
Above-mentioned monomer A is block type polyether macromonomer, represents with general formula (1):
R in general formula (1)
1for H or methyl; R
2for H or methyl, A is O, CH
2o, CH
2cH
2o; EO, PO are respectively oxyethane and propylene oxide; X is the integer of 1 ~ 50, and y is the integer of 30 ~ 150.
Above-mentioned polyether macromonomer B is active polyethenoxy ether class polymeric monomer, represents with general formula (2)
R in general formula (2)
3for H or methyl; B is O, CH
2o, CH
2cH
2o; N is the integer of 90 ~ 150.
Above-mentioned monomer C is unsaturated carboxylic acid class minor comonomer, represents with general formula (3):
R in general formula (3)
4for H or methyl.
Above-mentioned monomer D is unsaturated sulfonic acid or Sulfonates minor comonomer, represents with general formula (4):
R
5——SO
3M （４）(4)
R in general formula (4)
5for the alkyl containing a unsaturated double-bond, M is H or alkalimetal ion.
The monomer A that general formula (1) represents is copolymerized in main chain, and its special long branched chain structure provides space steric effect on the one hand, gives the dispersing property of graft copolymer excellence; Also play on the other hand and reduce graft copolymer surface tension and HLB value, and then reduce bleed performance, optimize maturing internal porosity parameter and distribution consistency degree, improve concrete strength.If monomer A ratio is too low, low bleed DeGrain, ratio too high then multipolymer dissemination is more weak.
The polyether monomer A of preferred above-mentioned general formula (1) is the affixture by vinyl carbinol, butenol, isobutene alcohol or prenol and oxyethane and propylene oxide, and these polyether monomers can be used alone also can be used in combination with two or more arbitrary proportion.
The monomers B that general formula (2) represents is copolymerized in main chain, and its overlength branched structure provides good space steric effect, gives the dispersiveness of graft copolymer excellence on the one hand, effectively can promote hydrated cementitious on the other hand, improves early age strength of concrete.If the ratio of monomers B is too low, early strong DeGrain, the dissemination of too high then multipolymer is more weak.Polyether macromonomer B in preferred formula (2) is the affixture by vinyl carbinol, butenol, isobutene alcohol or prenol and oxyethane, and these polyether monomers can be used alone also can be used in combination with two or more arbitrary proportion.
The hydroxy-acid group of monomer C (general formula 3) mainly provides adsorption site and electrostatic repulsion in graft copolymer, monomer C content is too low, and graft copolymer fully can not be adsorbed on cement particle surface, therefore can not give full play to dissemination and bad to the adaptability of cement, the graft copolymer early strength that too high levels is then generated is lower.Minor comonomer C represented in preferred formula (3) is unsaturated carboxylic acid class minor comonomer, is preferably one or more in acrylic or methacrylic acid.
Sulfonic acid or Sulfonates monomer D are absolutely necessary, its sulfonate ion has stronger electronegativity, in graft copolymer, introduce appropriate sulfonate ion can improve the absorption of graft copolymer at cement particle surface, and then lifting is to the dissemination of cement and the early strength improving cement, in addition, increase graft copolymer and can also reduce intergranular friction resistance at the degree of absorption of cement particle surface, and then reduce concrete apparent viscosity.Monomer D very little then early potent fruit and viscosity reducing effect not obvious, then disperse hold facility lower too much, collapsing, it is fast to damage.Minor comonomer D represented in preferred formula (4) is preferably sodium allyl sulfonate, Sodium styrene sulfonate, sodium vinyl sulfonate, methylpropene sodium sulfonate or 2-acrylamide-2-methylpro panesulfonic acid.
Preferably above-mentioned oxygenant is the mixture of one or more arbitrary proportions in hydrogen peroxide, tertbutyl peroxide or isopropyl benzene hydroperoxide, more preferably hydrogen peroxide, and mass concentration is not less than 25%; The consumption of preferred oxidant is 2 ~ 8% of A, B, C, D tetra-kinds of total moles monomer; Preferably above-mentioned reductive agent is the mixture of one or more arbitrary proportions in vitamins C, rongalite or Mohr's salt, more preferably vitamins C; The consumption of preferred reductive agent is 0.1 ~ 2% of A, B, C, D tetra-kinds of total moles monomer.
Preferably above-mentioned mercaptan type chain transfer agent be in Thiovanic acid, thiohydracrylic acid and mercaptoethanol one or more with arbitrary proportion mixing application; Chain-transfer agent consumption is 1 ~ 8% of A, B, C, D tetra-kinds of total moles monomer.
Preferred above-mentioned basic cpd is the mixture of oxyhydroxide and alcamine compound; Wherein alcamine compound accounts for 5% ~ 100% of oxyhydroxide mole dosage.Wherein said oxyhydroxide is sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonium hydroxide; Described alcamine compound is diethanolamine, trolamine, tri-isopropanolamine, monoisopropanolamine, diisopropanolamine (DIPA), N, N-dimethylethanolamine or N, N-diethylethanolamine.
When implementing of the present invention, first monomer A and B are joined in reaction vessel (four-hole boiling flask) before starting the reaction, thus improve the transformation efficiency of monomer A and B.Monomer C, D are added drop-wise in reaction vessel when reacting and starting simultaneously, can be synthesized the graft copolymer blends of different composition distribution by the rate of addition of monomer and mol ratio.
The present invention's preparation-obtained ultra early-strength polycarboxylate water-reducer number-average molecular weight controls 30000 ~ 100000, and dispersion and the dispersion hold facility of the too little or too large graft copolymer of molecular weight all can be deteriorated.
During use, conventional volume of the present invention is 0.1 ~ 0.3% of glue material total mass, volume be less than 0.1% dispersing property and reinforced effects not obvious, volume obviously can not increase higher than 0.3% reinforced effects but also can bring waste economically.
Except graft copolymerization beyond the region of objective existence of the present invention.Accelerating component, swelling agent and economization agent etc. can also be added.
Beneficial effect:
The present invention is under low-temp reaction condition, and by the control to reaction process condition, the transformation efficiency of monomer A and B is higher, makes the molecular weight of graft copolymer and molecular weight distribution all very good.Graft copolymer volume lower in practical application just can obtain good dispersiveness, good to concrete adaptability in addition.These technique starting material are easy to get, and be convenient to production, reproducible, energy consumption is low and environmental protection.
The present invention, compared with water reducer existing in the market, has following features:
(1) polyether macromonomer of appropriate design significantly can improve stomatal parameters and the distribution consistency degree of maturing inside, the ultimate compression strength of remarkable Concrete Structure;
(2) obviously improve the early hydration of cement, in different cement, all embody obvious super hardening effect;
(3) there is well dispersion and dispersion hold facility under lower volume, remarkable Concrete Structure intensity and early remarkably productive by force;
(4) fresh concrete serviceability is good and apparent viscosity is low, constructability.
Embodiment
The more detailed preparation process describing ultra early-strength polycarboxylate water-reducer of the present invention of following case study on implementation; and these case study on implementation provide by way of illustration; the technician being familiar with this project can be allowed can to understand content of the present invention and be implemented, but these case study on implementation never limit the scope of the invention.All equivalences done according to spirit of the present invention change or modification all should be encompassed in protection scope of the present invention.
A), in the invention process case, the number-average molecular weight of multipolymer adopts wyatt technologycorporation gel permeation chromatograph to measure.Specific experiment condition is as follows: 1. gel column: ShodexSB806+803 two root chromatogram column is connected; 2. eluant: 0.1M NaNO3 solution; 3.: moving phase speed 0.8ml/min; 4. inject: 20 μ 10.5% aqueous solution; 5. detector: Shodex RI-71 type differential refraction detector; 6. standard substance: polyoxyethylene glycol GPC standard specimen (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,447000,18600,6690,1960,628,232).
B) in the invention process case, according to USS ASTM C457-98, adopt opticmicroscope control method, select the pore interval coefficient of straight-line method test maturing.
C) in application example of the present invention, except special instruction, adopt cement to be Yadong PO52.5 level ordinary Portland cement; It is continuous that river sand meets two district's gratings, and fineness modulus is 2.5, silt content 0.4%; Stone is the rubble of 5 ~ 20mm continuous grading, elongated particles≤36%, silt content 0.2%, without clod, without land waste; Breeze is the S95 level breeze that Ma Gangjia China produces, specific surface area 444m2/kg; Terra alba specific surface area 542m2/kg.
D) flowing degree of net paste of cement test is carried out with reference to GB/T8077-2000 standard, and sheet glass measures the maximum diameter that cement paste freely trickles on vial face.The mensuration of time of coagulation is carried out with reference to GB/T1346-2001 standard.
E) water-reducing rate, content measurement perform with reference to the relevant regulations of GB8076-2008 " concrete admixture ".Concrete test is carried out according to the standard regulation in GB_T50080-2002 " Standard for test methods of properties of ordinary concrete mixture standard ".
Table 1
Synthetic example 1
In the four-hole boiling flask that thermometer, agitator, constant flow pump are housed, add 32.3gA-1 (0.012mol), 233.8gB-1 (0.058mol), hydrogen peroxide (effective concentration 27.5%,) 0.675g (0.0055mol), suitable quantity of water, uniform bed material is made in stirring, and heats up; Take 2.318g (0.0218mol) thiohydracrylic acid, 0.048g (0.000273mol) vitamins C, in right amount aqueous phase mix, stir to make to drip uniformly and expect 1.; Take 12.53gC-1 (0.174mol), 4.186g D-1 (0.029mol), appropriate aqueous phase mixes, stir and make uniform dropping material 2.; Drip in bed material when temperature rises to 30 DEG C simultaneously material 1. with dropping material 2., wherein drip material and 1. drip 3 hours, drip material and 2. drip 2 hours, copolymerization system monomer A, B, C and D total mass concentration control 40%, after 1. dropping material is added dropwise to complete, temperature rises to 45 DEG C, then 45 DEG C of insulation reaction 0.5 hour, be cooled to room temperature to add diethanolamine and sodium hydroxide solution (mass concentration 32%) and regulate pH value to be 6, wherein diethanolamine accounts for 5% of sodium hydroxide mole number.The made sample of the present embodiment is micro-yellow transparent liquid, molecular weight 30600 (PE-1).
Synthetic example 2
In the four-hole boiling flask that thermometer, agitator, constant flow pump are housed, add 100.31gA-2 (0.035mol), 187.29gB-2 (0.035mol), hydrogen peroxide (effective concentration 27.5%,) 4.85g (0.0392mol), suitable quantity of water, uniform bed material is made in stirring, and heats up; Take 0.52g (0.0049mol) thiohydracrylic acid, 1.716g (0.0098mol) vitamins C, in right amount aqueous phase mix, stir to make to drip uniformly and expect 1.; Take 27.09gC-2 (0.315mol), 21.735g D-2 (0.105mol), appropriate aqueous phase mixes, stir and make uniform dropping material 2.; Drip in bed material when temperature rises to 35 DEG C simultaneously material 1. with dropping material 2., wherein drip material and 1. drip 3.5 hours, drip material and 2. drip 2.5 hours, copolymerization system monomer A, B, C and D total mass concentration control 50%, after 1. dropping material is added dropwise to complete, temperature rises to 50 DEG C, then 50 DEG C of insulation reaction 1 hour, be cooled to room temperature to add trolamine and sodium hydroxide solution (mass concentration 32%) and regulate pH value to be 7, wherein trolamine accounts for 100% of sodium hydroxide mole number.The made sample of the present embodiment is micro-yellow transparent liquid, molecular weight 89600 (PE-2).
Synthetic example 3
In the four-hole boiling flask that thermometer, agitator, constant flow pump are housed, add 36.36gA-1 (0.013mol), 96.02gA-3 (0.013mol), 88.28gB-1 (0.0219mol), 146.4gB-3 (0.0219mol), hydrogen peroxide (effective concentration 27.5%,) 2.6g (0.021mol), suitable quantity of water, uniform bed material is made in stirring, and heats up; Take 2.229g (0.021mol) thiohydracrylic acid, 0.741g (0.0042mol) vitamins C, in right amount aqueous phase mix, stir to make to drip uniformly and expect 1.; Take 6.307gC-1 (0.0876mol), 15.566gC-2 (0.181mol), 4.205g D-1 (0.0292mol), 12.089g D-3 (0.0584mol), in right amount aqueous phase mix, stir to make to drip uniformly and expect 2.; Drip in bed material when temperature rises to 40 DEG C simultaneously material 1. with dropping material 2., wherein drip material and 1. drip 4 hours, drip material and 2. drip 3 hours, copolymerization system monomer A, B, C and D total mass concentration control 60%, after 1. dropping material is added dropwise to complete, temperature rises to 55 DEG C, then 55 DEG C of insulation reaction 1 hour, be cooled to room temperature to add tri-isopropanolamine and sodium hydroxide solution (mass concentration 32%) and regulate pH value to be 6.5, wherein tri-isopropanolamine accounts for 55% of sodium hydroxide mole number.The made sample of the present embodiment is micro-yellow transparent liquid, molecular weight 70800 (PE-3).
Synthetic example 4
In the four-hole boiling flask that thermometer, agitator, constant flow pump are housed, add 29.81gA-2 (0.0104mol), 47.49gA-4 (0.0206mol), 69.563gB-2 (0.013mol), 172.72gB-4 (0.026mol), hydrogen peroxide (effective concentration 27.5%,) 2.127g (0.0172mol), suitable quantity of water, uniform bed material is made in stirring, and heats up; Take 1.826g (0.0172mol) thiohydracrylic acid, 0.604g (0.0.00343mol) vitamins C, in right amount aqueous phase mix, stir to make to drip uniformly and expect 1.; Take 16.848gC-1 (0.234mol), 8.034gD-2 (0.039mol), appropriate aqueous phase mixes, stir and make uniform dropping material 2.; Drip in bed material when temperature rises to 50 DEG C simultaneously material 1. with dropping material 2., wherein drip material and 1. drip 4 hours, drip material and 2. drip 3.5 hours, copolymerization system monomer A, B, C and D total mass concentration control 70%, after 1. dropping material is added dropwise to complete, temperature rises to 60 DEG C, then 60 DEG C of insulation reaction 2 hours, be cooled to room temperature to add monoisopropanolamine and sodium hydroxide solution (mass concentration 32%) and regulate pH value to be 6.5, wherein monoisopropanolamine accounts for 55% of sodium hydroxide mole number.The made sample of the present embodiment is micro-yellow transparent liquid, molecular weight 69600 (PE-4).
Synthetic example 5
In the four-hole boiling flask that thermometer, agitator, constant flow pump are housed, add 114.48gA-3 (0.0155mol), 35.681gA-4 (0.0155mol), 130.358gB-3 (0.0195mol), 129.539gB-4 (0.0195mol), hydrogen peroxide (effective concentration 27.5%,) 2.127g (0.0172mol), suitable quantity of water, uniform bed material is made in stirring, and heats up; Take 0.91g (0.00858mol) thiohydracrylic acid, 0.604g (0.0.00343mol) vitamins C, in right amount aqueous phase mix, stir to make to drip uniformly and expect 1.; Take 16.848gC-1 (0.234mol), 8.034gD-2 (0.039mol), appropriate aqueous phase mixes, stir and make uniform dropping material 2.; Drip in bed material when temperature rises to 60 DEG C simultaneously material 1. with dropping material 2., wherein drip material and 1. drip 4 hours, drip material and 2. drip 3.5 hours, copolymerization system monomer A, B, C and D total mass concentration control 70%, 60 DEG C of insulation reaction 2 hours after 1. dropping material is added dropwise to complete, be cooled to room temperature and add N, N-diethylethanolamine and sodium hydroxide solution (mass concentration 32%) regulate pH value to be 6.5, wherein N, N-diethylethanolamine accounts for 55% of sodium hydroxide mole number.The made sample of the present embodiment is micro-yellow transparent liquid, molecular weight 95600 (PE-5).Comparative example 1
In the four-hole boiling flask that thermometer, agitator, constant flow pump are housed, add 282.17gB-1 (0.07mol), hydrogen peroxide (effective concentration 27.5%) 0.0.779g (0.0063mol), suitable quantity of water, uniform bed material is made in stirring, and heats up; Take 2.675g (0.0252mol) thiohydracrylic acid, 0.055g (0.000315mol) vitamins C, in right amount aqueous phase mix, stir to make to drip uniformly and expect 1.; Take 15.12gC-1 (0.21mol), 5.04gD-1 (0.035mol), appropriate aqueous phase mixes, stir and make uniform dropping material 2.; Drip in bed material when temperature rises to 30 DEG C simultaneously material 1. with dropping material 2., wherein drip material and 1. drip 3 hours, drip material and 2. drip 2 hours, copolymerization system monomer A, B, C and D total mass concentration control 40%, after 1. dropping material is added dropwise to complete, temperature rises to 45 DEG C, then 45 DEG C of insulation reaction 0.5 hour, be cooled to room temperature to add diethanolamine and sodium hydroxide solution (mass concentration 32%) and regulate pH value to be 6, wherein diethanolamine accounts for 5% of sodium hydroxide mole number.The made sample of the present embodiment is micro-yellow transparent liquid, molecular weight 38700 (PC-1).Comparative example 2
In the four-hole boiling flask that thermometer, agitator, constant flow pump are housed, add 32.3gA-1 (0.012mol), 233.8gB-1 (0.058mol), hydrogen peroxide (effective concentration 27.5%,) 0.603g (0.00488mol), suitable quantity of water, uniform bed material is made in stirring, and heats up; Take 1.295g (0.0122mol) thiohydracrylic acid, 0.043g (0.00024mol) vitamins C, in right amount aqueous phase mix, stir to make to drip uniformly and expect 1.; Take 12.53gC-1 (0.174mol), appropriate aqueous phase mixes, stir and make uniform dropping material 2.; Drip in bed material when temperature rises to 30 DEG C simultaneously material 1. with dropping material 2., wherein drip material and 1. drip 3 hours, drip material and 2. drip 2 hours, copolymerization system monomer A, B, C and D total mass concentration control 40%, after 1. dropping material is added dropwise to complete, temperature rises to 45 DEG C, then 45 DEG C of insulation reaction 0.5 hour, be cooled to room temperature to add diethanolamine and sodium hydroxide solution (mass concentration 32%) and regulate pH value to be 6, wherein diethanolamine accounts for 5% of sodium hydroxide mole number.The made sample of the present embodiment is micro-yellow transparent liquid, molecular weight 30740 (PC-2).
Comparative example 3
In the four-hole boiling flask that thermometer, agitator, constant flow pump are housed, add 32.3gA-1 (0.012mol), 209.1gB-5 (0.058mol), hydrogen peroxide (effective concentration 27.5%,) 0.675g (0.0055mol), suitable quantity of water, uniform bed material is made in stirring, and heats up; Take 2.318g (0.0218mol) thiohydracrylic acid, 0.048g (0.000273mol) vitamins C, in right amount aqueous phase mix, stir to make to drip uniformly and expect 1.; Take 12.53gC-1 (0.174mol), 4.186g D-1 (0.029mol), appropriate aqueous phase mixes, stir and make uniform dropping material 2.; Drip in bed material when temperature rises to 30 DEG C simultaneously material 1. with dropping material 2., wherein drip material and 1. drip 3 hours, drip material and 2. drip 2 hours, copolymerization system monomer A, B, C and D total mass concentration control 40%, after 1. dropping material is added dropwise to complete, temperature rises to 45 DEG C, then 45 DEG C of insulation reaction 0.5 hour, be cooled to room temperature to add diethanolamine and sodium hydroxide solution (mass concentration 32%) and regulate pH value to be 6, wherein diethanolamine accounts for 5% of sodium hydroxide mole number.The made sample of the present embodiment is micro-yellow transparent liquid, molecular weight 29100 (PC-3).
Application examples 1
Adopt Yadong PO52.5 level ordinary Portland cement, cement 300g, water 87g.Flowing degree of net paste of cement hold facility and the time of coagulation of each graft copolymer is listed in table 3, each data from table 3 can find out that ultra early-strength polycarboxylate water-reducer of the present invention has high dispersive and disperses hold facility preferably, and can promote cement early hydration.By contrast, the polymer PC-2 not adding Sulfonates monomer promotes that the effect of hydrated cementitious is on the weak side, and the too low polymer PC-3 of Soxylat A 25-7 molecular weight does not just possess the effect promoting hydrated cementitious.
Table 3
Application examples 2
The concrete water-reducing ratio of each multipolymer, air content, maturing air-void spacing factor, different larval instar concrete crushing strength is listed in table 4.Testing concrete mix used is: cement: sand: stone: water=330:750:1125:170.Find through contrast, ultra early-strength polycarboxylate water-reducer of the present invention has excellent dispersing property, effectively can improve early age strength of concrete.Compared to the copolymer p C-1 of Soxylat A 25-7 synthesis, air content reduces about 43%, and bubble structure size is good and be evenly distributed, and concrete strength improves about 9%; Not containing the copolymer p C-2 of sulfonate synthesis, early age strength of concrete and later strength are all on the low side; Compared to the copolymer p C-3 of lower molecular weight Soxylat A 25-7 synthesis, concrete 1d, 3d, 7d, 28d intensity improves 53%, 14.3%, 12.28%, 13.6% respectively.
Table 4
Claims (10)
1. a preparation method for ultra early-strength polycarboxylate water-reducer, its concrete steps are as follows:
(1) bed material preparation: take monomer A and monomers B respectively, and pour in identical vessel, add oxygenant, be dissolved in water and mix stand-by:
(2) drip material 1. to prepare: take mercaptan type chain transfer agent and reductive agent, add water and fully dissolve and mix stand-by;
(3) drip material 2. to prepare: take monomer C and D respectively, add water and fully dissolve and mix stand-by;
(4) copolyreaction: heating bed material limit, limit is stirred, drip in bed material when temperature rises to 30 ~ 55 DEG C simultaneously material 1. with dropping material 2., dripping material time for adding 1. controls at 3 ~ 4 hours, dripping material time for adding 2. controls at 2 ~ 3.5 hours, copolyreaction temperature controls at 30 ~ 60 DEG C, control the reaction times from dropping to reaction end be 3.5 ~ 6 hours, copolymerization system monomer A, B, C and D total mass concentration control 40 ~ 80%;
(5) neutralization reaction: it is 6 ~ 7 that copolyreaction terminates to add basic cpd adjusted to ph in backward reaction product, final obtained ultra early-strength polycarboxylate water-reducer;
Wherein the mol ratio of monomer A, B, C, D is (0.2 ~ 1): 1:(3 ~ 9): (0.5 ~ 3);
Above-mentioned monomer A is block type polyether macromonomer, represents with general formula (1):
R in general formula (1)
1for H or methyl; R
2for H or methyl, A is O, CH
2o, CH
2cH
2o; EO, PO are respectively oxyethane and propylene oxide; X is the integer of 1 ~ 50, and y is the integer of 30 ~ 150.
Above-mentioned polyether macromonomer B is active polyethenoxy ether class polymeric monomer, represents with general formula (2)
R in general formula (2)
3for H or methyl; B is O, CH
2o, CH
2cH
2o; N is the integer of 90 ~ 150.
Above-mentioned monomer C is unsaturated carboxylic acid class minor comonomer, represents with general formula (3):
R in general formula (3)
4for H or methyl.
Above-mentioned monomer D is unsaturated sulfonic acid or Sulfonates minor comonomer, represents with general formula (4):
R
5-SO
3M (4)
R in general formula (4)
5for the alkyl containing a unsaturated double-bond, M is H or alkalimetal ion.
2. preparation method as claimed in claim 1, is characterized in that the polyether monomer A of general formula (1) is the affixture by vinyl carbinol, butenol, isobutene alcohol or prenol and oxyethane and propylene oxide.
3. preparation method as claimed in claim 1, the polyether macromonomer B that it is characterized in that in general formula (2) is the affixture by vinyl carbinol, butenol, isobutene alcohol or prenol and oxyethane.
4. preparation method as claimed in claim 1, the minor comonomer C represented by it is characterized in that in general formula (3) is one or more in acrylic or methacrylic acid.
5. preparation method as claimed in claim 1, is characterized in that minor comonomer D represented in general formula (4) is sodium allyl sulfonate, Sodium styrene sulfonate, sodium vinyl sulfonate, methylpropene sodium sulfonate or 2-acrylamide-2-methylpro panesulfonic acid.
6. preparation method as claimed in claim 1, is characterized in that described oxygenant is the mixture of one or more arbitrary proportions in hydrogen peroxide, tertbutyl peroxide or isopropyl benzene hydroperoxide; The consumption of oxygenant is 2 ~ 8% of A, B, C, D tetra-kinds of total moles monomer; Described reductive agent is the mixture of one or more arbitrary proportions in vitamins C, rongalite or Mohr's salt; The consumption of reductive agent is 0.1 ~ 2% of A, B, C, D tetra-kinds of total moles monomer.
7. preparation method as claimed in claim 1, is characterized in that described mercaptan type chain transfer agent is that one or more in Thiovanic acid, thiohydracrylic acid and mercaptoethanol are with arbitrary proportion mixing application; Chain-transfer agent consumption is 1 ~ 8% of A, B, C, D tetra-kinds of total moles monomer.
8. preparation method as claimed in claim 1, is characterized in that described basic cpd is the mixture of oxyhydroxide and alcamine compound; Wherein alcamine compound accounts for 5% ~ 100% of oxyhydroxide mole dosage.
9. preparation method as claimed in claim 8, is characterized in that described oxyhydroxide is sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonium hydroxide; Described alcamine compound is diethanolamine, trolamine, tri-isopropanolamine, monoisopropanolamine, diisopropanolamine (DIPA), N, N-dimethylethanolamine or N, N-diethylethanolamine.
10. preparation method as claimed in claim 1, is characterized in that the number-average molecular weight of the ultra early-strength polycarboxylate water-reducer prepared is 30000 ~ 100000.
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| CN105199060A (en) * | 2015-10-14 | 2015-12-30 | 广东红墙新材料股份有限公司 | Super-early-strength PCE (polycarboxylate ether) superplasticizer and preparation method thereof |
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