CN102936109A - Polycarboxylic acid water reducing agent, preparation method and application thereof - Google Patents
Polycarboxylic acid water reducing agent, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a polycarboxylic acid water reducing agent, a preparation method and an application thereof, and belongs to the technical field of concrete additives. The polycarboxylic acid water reducing agent is prepared by using industrializedly produced isobutenol polyether or isoamylenol polyether with relatively good performances as a monomer A, unsaturated carboxylic acid, unsaturated acid anhydride or unsaturated ester as a monomer B and unsaturated sulfonic acid and salts thereof as a monomer C, according to a water reducing agent functional group theory and a polycarboxylic acid water reducing agent molecule design theory; and co-polymerizing the monomer A, B and C. A polycarboxylic acid water reducing agent product is obtained in a water solution via a one-step method, under initiation of a redox initiation system, by introducing carboxyls or ester groups having the functions of delayed coagulation and slump resistance, and the sulfonic acid groups having high water reducing effect into the molecular structure of the water reducing agent and controlling a material ratio and material-feeding modes. Besides, cost can be further reduced by selecting a proper redox system to make the polymerization carried out at a low temperature. The method is suitable for industrialize production.
Description
Technical field
The present invention relates to a kind of poly carboxylic acid series water reducer, its preparation method and application, belong to technical field of concrete additives.
Background technology
Concrete is maximum, the most widely used material of construction of consumption in the world.Since the thirties in 20th century, the appearance of water reducer and be successfully applied to concrete field, the appearance of especially efficient and high-performance water reducing agent, promoted the development of concrete technology greatly, become gradually in concrete, particularly indispensable component in modern concrete.Although volume is few, can improve to a great extent concrete construction process, improve the properties of concrete material, reduce costs etc., be referred to as " industrial monosodium glutamate " by industry circle.Water reducer was through the development of more than 70 years, by take the first-generation ordinary water-reducing agent that sulfonated lignin are representative, the s-generation high efficiency water reducing agent that naphthalene system, amido sulfoacid series and melamine based water reducer are representative, develop into and take the high-performance water reducing agent that poly carboxylic acid series water reducer is representative.The molecular designing degree of freedom that poly carboxylic acid series water reducer is larger with it, can prepare as required high guarantor collapses, high diminishing, early strong, slow setting, bleed, the water reducer product of different performance such as reduces, the concrete of the performances such as suitable preparation is high-strength, superelevation strong, high workability, high-durability, obtained the consistent high praise of engineering circles, add its raw material sources abundant, the production technique greenization, become the main development direction of water reducer.
Poly carboxylic acid series water reducer, since 20th century, researched and developed successfully the eighties, has experienced the development of ester type, ether type, acid amides/imide-type, polymeric amide-type products such as polyethylene glycol type.What suitability for industrialized production and application were ripe at present is mainly ester type and ether type polycarboxylic acid water reducer product.Ester type poly carboxylic acid need to first synthesize the large monomer of ester, with the copolymerization monomer copolymerization, make again, although this type of poly carboxylic acid series water reducer excellent performance, but esterification production technology complexity, esterification temperature is high, and esterification time is long, using and removing all and will increase enterprise's production cost with aqua in reaction process, it is larger that product performance are affected by the structure of the large monomer of ester and purity, limited the industrialization promotion of this type of water reducer.Large monomer preparation technology is comparatively simple for the ether type, product performance are stable, at present existing many enterprises can provide the large monomer of ether of various structures and molecular weight, cost also reduces gradually, and the large monomer of ether and comonomer single stage method synthesizing polycarboxylic acid product, technique is simple, and process " green " is changed, product performance are similar to ester class poly carboxylic acid product, are the focuses of studying at present.For example: publication number is CN101955333, name is called " a kind of poly carboxylic acid series water reducer of low-dosage high water reducing rate, synthetic method and using method " Chinese invention patent application disclose by polyethylene glycol monomethyl ethermethacrylic acid esters, the 2-methyl allyl alcohol polyoxyethylene ether, vinylformic acid, methylpropene sodium sulfonate is main polymerization single polymerization monomer, by ammonium persulphate, cause, polymerization in the aqueous solution of 60-100 ℃, the water reducer obtained is due to the sulfonic group of having introduced efficient diminishing, just there is higher water-reducing rate under low-dosage, but applied the large monomer of esterification of complicated process of preparation in synthetic, use nitrogen protection, do not adopt suitable redox system, cause polymeric reaction temperature high.Publication number is CN102140019, the Chinese invention patent application that name is called " a kind of poly carboxylic acid series water reducer and preparation method thereof " discloses by the large monomer of ether, olefin(e) acid class monomer, with the maleinamide polymerization single polymerization monomer at redox initiation system, polymerization under 50-90 ℃ of condition, utilize the absorption of two carboxyls raising Water-reducing Admixtures To Cements of maleinamic acid, obtain the water reducer that a kind of slump has kept, but polymerization temperature is higher, and synthetic maleinamide polymerization single polymerization monomer technique is comparatively complicated.Publication number is CN102010487, the Chinese invention patent application that name is called " a kind of preparation method of polycarboxylate water-reducer " discloses that a kind of to take poly glycol monomethyl ether (MPEG) and maleic anhydride (MAH) be main raw material, by esterification synthesizing polyethylene glycol monomethyl ether maleic anhydride surface-active macromonomer (PAM), again with PAM, methylpropene sodium sulfonate, methylene-succinic acid is main raw material, in the initiator system of hydrogen peroxide and vitamins C composition, the method of the synthetic polycarboxylate water-reducer of terpolymer under 30-50 ℃ of condition, the product water-reducing rate is high, slump retaining is good, but need esterif iotacation step, processing condition are had relatively high expectations.Although above method can access comparatively desirable product, complex process is had relatively high expectations, and is unfavorable for industrial production.
Summary of the invention
The technical problem to be solved in the present invention is: the defect existed for prior art, a kind of high performance water reducing agent of polyocarboxy acid, its preparation method and application are proposed, and when guaranteeing quality product, optimized production process, cost is lower, applicable to industrial production.
The present invention is the technical solution problem by the following technical programs: a kind of poly carboxylic acid series water reducer comprises the following component by mass parts:
100 parts of the large monomer A of methyl thiazolinyl Soxylat A 25-7
Unsaturated carboxylic acid, acid anhydrides or esters monomer B 4-20 part
Unsaturated sulfonic acid or its esters monomer C 2-15 part
Oxygenant 0.5-5 part
Reductive agent 0.008-0.5 part
Chain-transfer agent 0.05-1 part
40% sodium hydroxide solution 5-20 part
Water 100-200 part.
Wherein, the chemical formula of described monomer A is R
1-O-[CH
2-CH
2O]
m-R
2, R in formula
1For
Or
, R
2For the alkyl group that hydrogen atom or carbonatoms are 1-5, the number of repeat unit of m is 15-80, and the weight-average molecular weight of described monomer A is 600-3000; Described unsaturated carboxylic acid, acid anhydrides or esters monomer B are at least one in vinylformic acid, maleic anhydride, methyl acrylate, ethyl propenoate; Described unsaturated sulfonic acid or its esters monomer C are at least one in sodium vinyl sulfonate, sodium allyl sulfonate, methylpropene sodium sulfonate, Sodium styrene sulfonate, 2-acrylamide-2-methyl propane sulfonic (sodium).
Described oxygenant is at least one in Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen peroxide.
Described reductive agent is at least one in sodium bisulfite, S-WAT, glucose, vitamins C, ferrous sulfate, rongalite.
Described chain-transfer agent is at least one in Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, mercaptoethanol.
The preparation method of above-mentioned poly carboxylic acid series water reducer comprises the following steps:
Step 1, described monomer A is added in reactor by described mass parts, add water heated and stirred and make its dissolving;
Step 2, described oxygenant and described monomer C are dissolved in water by described mass parts after, add in reactor;
Step 3, under whipped state, add reductive agent, described monomers B and chain-transfer agent mixing solutions by described mass parts, the mode that adds is to drop in advance in reactor by described reductive agent, start again to drip described monomers B and chain-transfer agent mixing solutions, and the time that dropwises of control reductive agent is later than the time that dropwises of monomers B and chain-transfer agent mixing solutions;
Step 4, insulation reaction 1-2 hour;
Step 5, add 40% sodium hydroxide solution by described mass parts, regulate the pH value of product to 6-7, obtain poly carboxylic acid series water reducer.
Wherein, in described step 3, the time that described reductive agent drips in advance is 15-45 minute, and the time that dropwises of described reductive agent is later than the time that the dropwises 15-40 minute of monomers B and chain-transfer agent mixing solutions.
In described step 2 to four, temperature is 20-40 ℃.
The 0.05%-0.3% that solid volume when the polycarboxylate water-reducer that aforesaid method is obtained is applied to concrete is gelling material quality in concrete, preferably 0.08%-0.18%.
The present invention is theoretical and poly carboxylic acid series water reducer molecular design theory according to water reducer functional group, utilize the isobutene alcohol polyethers of the better performances of suitability for industrialized production or prenol polyethers as the large monomer A of methyl thiazolinyl Soxylat A 25-7, with unsaturated carboxylic acid or its ester, acid anhydride is as monomers B, using unsaturated sulfonic acid base or its esters as monomer C, by monomer A, B, C carries out copolymerization, owing in the water reducer molecular structure, introducing and thering is slow setting, the carboxyl of slump retaining effect or ester group, with the sulfonic acid group with high water-reduction, by controlling material proportion and feed way, under redox initiation system causes, make a kind of high diminishing that has with single stage method polymerization in the aqueous solution, the high poly carboxylic acid series water reducer product of protecting the effect of collapsing, and select suitable redox system that polymerization temperature is carried out at low temperatures, further reduced cost.The advantage of such scheme is: (1) is used iso-butylene Soxylat A 25-7 and the isopentene Soxylat A 25-7 of suitability for industrialized production, preparation technology is simpler than the large monomer of ester class, cost is low, product structure is easy to control, thereby the product performance that make are more stable, and the large monomer of this type of polyethers has higher activity than the allyl group ether of birdsing of the same feather flock together, easily, with unsaturated acids and derivative generation copolyreaction thereof, the product performance that make are better.Through repeatability and expansion property proof test, the prepared product performance of the method for the invention are stable, and raw material sources are abundant, and technique is simple, and cost is low, is conducive to suitability for industrialized production.(2) according to dispersion diminishing mechanism---sterically hindered theory and functional group's theory of poly carboxylic acid series water reducer, select the polyether monomer of suitable molecular weight, introduce the side chain of suitable length, by with unsaturated carboxylic acid or esters monomer, the sulphonic acids monomer carries out copolymerization, introducing has slow setting, guarantor collapse carboxylic acid or the ester functional group of function, and the sulfonate functional groups with high diminishing dispersiveness, find optimum process condition by test, make the water reducer molecular size range and distribute moderate, functional group's ratio and distribution are suitable, thereby obtain a kind of high diminishing, the water reducer product of high function of slump protection.(3) polymerization technique adopts oxygenant all to add in reaction system, and the mode that reductive agent drips, controlled free radical polymerization rate, product structure and stable performance; Be conducive to simplify technique, reduce production costs, and large-scale industrialization production.(4) it is worth mentioning that: the mode that adopts reductive agent to splash in advance, before making acids and esters monomer solution splash into, certain density free radical is arranged, make the large monomer of ether and unsaturated sulfonic acid and the activation of unsaturated sulfonic acid salt monomer of active less, being conducive to graft copolymerization occurs, monomer conversion increases, and active larger unsaturated acids and esters monomer homopolymerization side reaction reduce, and the water reducer performance effectively improves.(5) select suitable redox system, make reaction be able to can carry out at low temperatures, not only further reduced production cost, and reduced the generation of side reaction in the polymerization process, the product made has the advantages such as volume is low, water-reducing rate is high, slump retention is good, applied widely, cost performance is high, is conducive to apply.
Embodiment
The iso-butylene Soxylat A 25-7 adopted in the embodiment of the present invention, isopentene Soxylat A 25-7 are purchased from Huangma Chemical Group Co., Zhejiang and Liaoning AoKe Chemical Co., Ltd, other raw materials are commercially available technical grade or reagent, the consumption of material described in embodiment " part ", be mass parts, described per-cent (concentration) is mass percent (concentration), repeats no more herein.
Embodiment mono-
Getting 100 parts of iso-butylene Soxylat A 25-7s (weight-average molecular weight 2400) adds in reactor, add 80 parts of water, heating up to stir is dispersed in the aqueous solution it, 1.4 parts of ammonium persulphates and 4 parts of sodium allyl sulfonates are added in reactor by 10 parts of water dissolution, stir and be warming up to 35 ℃, keep temperature fluctuation range in whole reaction process to be no more than 2 ℃, start to drip 0.35 part of glucose and be dissolved in the solution formed in 30 parts of water, start to drip 7.5 parts of vinylformic acid after 20min and 0.2 part of Thiovanic acid is dissolved in the solution formed in 25 parts of water, the former is controlled at 3h and dropwises, latter 2h dropwises, all dropwise rear insulation reaction 1.5h, regulating pH with 40% sodium hydroxide solution is 6-7, obtain the polycarboxylate water-reducer product.
Embodiment bis-
Getting 100 parts of iso-butylene Soxylat A 25-7s (weight-average molecular weight 2000) adds in reactor, add 80 parts of water, heating up to stir is dispersed in the aqueous solution it, 1.5 parts of Sodium Persulfates and 4.5 parts of methallylsulfonic acid sodium are added in reactor by 10 parts of water dissolution, stir and be warming up to 35 ℃, keep temperature fluctuation range in whole reaction process to be no more than 2 ℃, start to drip 0.3 part of vitamins C and be dissolved in the solution formed in 30 parts of water, start to drip 8 parts of vinylformic acid after 20min, 2 parts of maleic anhydrides and 0.15 part of mercaptoethanol are dissolved in the solution formed in 25 parts of water, the former is controlled at 3h and dropwises, latter 2h dropwises, all dropwise rear insulation reaction 1.5h, regulating pH with 40% sodium hydroxide solution is 6-7, obtain the polycarboxylate water-reducer product.
Embodiment tri-
Getting 100 parts of iso-butylene Soxylat A 25-7s (weight-average molecular weight 1200) adds in reactor, add 80 parts of water, heating up to stir is dispersed in the aqueous solution it, 1.7 parts of Potassium Persulphates and 4.5 parts of sodium vinyl sulfonates with adding in reactor after 10 parts of water dissolution, stir and be warming up to 30 ℃, keep temperature fluctuation range in whole reaction process to be no more than 2 ℃, start to drip 0.4 part of glucose and be dissolved in the solution formed in 30 parts of water, start to drip 9 parts of vinylformic acid after 20min and 0.25 part of 2 mercaptopropionic acid is dissolved in the solution formed in 25 parts of water, the former is controlled at 3h and dropwises, latter 2h dropwises, all dropwise rear insulation reaction 1.5h, regulating pH with 40% sodium hydroxide solution is 6-7, obtain the polycarboxylate water-reducer product.
Embodiment tetra-
Getting 100 parts of isopentene Soxylat A 25-7s (weight-average molecular weight 2400) adds in reactor, add 80 parts of water, heating up to stir is dispersed in the aqueous solution it, 1.4 parts of ammonium persulphates and 4 parts of methallylsulfonic acid sodium are added in reactor by 10 parts of water dissolution, stir and be warming up to 35 ℃, keep temperature fluctuation range in whole reaction process to be no more than 2 ℃, start to drip 0.35 part of glucose and be dissolved in the solution formed in 30 parts of water, start to drip 6.5 parts of vinylformic acid after 30min, 1.5 part methyl acrylate and 0.15 part of Thiovanic acid are scattered in the solution formed in 25 parts of water, the former is controlled at 3h and dropwises, latter 2h dropwises, all dropwise rear insulation reaction 1.5h, regulating pH with 40% sodium hydroxide solution is 6-7, obtain the polycarboxylate water-reducer product.
Embodiment five
Getting 100 parts of isopentene Soxylat A 25-7s (weight-average molecular weight 2000) adds in reactor, add 80 parts of water, heating up to stir is dispersed in the aqueous solution it, 1.5 parts of Potassium Persulphates and 4.5 parts of Sodium styrene sulfonate with adding in reactor after 10 parts of water dissolution, stir and be warming up to 35 ℃, keep temperature fluctuation range in whole reaction process to be no more than 2 ℃, start to drip 0.35 part of sodium bisulfite and 0.01 part of ferrous sulfate is dissolved in the solution formed in 30 parts of water, start to drip 8 parts of vinylformic acid after 30min and 0.15 part of Thiovanic acid is scattered in the solution formed in 25 parts of water, the former is controlled at 3h and dropwises, latter 2h dropwises, all dropwise rear insulation reaction 1.5h, regulating pH with 40% sodium hydroxide solution is 6-7, obtain the polycarboxylate water-reducer product.
Embodiment six
Getting 100 parts of isopentene Soxylat A 25-7s (weight-average molecular weight 1200) adds in reactor, add 80 parts of water, heating up to stir is dispersed in the aqueous solution it, 1.4 parts of ammonium persulphates, 2.5 part sodium allyl sulfonate and 2 parts of 2-acrylamide-2-methyl propane sulfonic sodium add in reactor by 10 parts of water dissolution, stir and be warming up to 35 ℃, keep temperature fluctuation range in whole reaction process to be no more than 2 ℃, start to drip 0.35 part of S-WAT and 0.01 part of ferrous sulfate is dissolved in the solution formed in 30 parts of water, start to drip 8 parts of vinylformic acid after 30min, 1.5 part ethyl propenoate and 0.25 part of 3-thiohydracrylic acid are scattered in the solution formed in 25 parts of water, the former is controlled at 3h and dropwises, latter 2h dropwises, all dropwise rear insulation reaction 1.5h, regulating pH with 40% sodium hydroxide solution is 6-7, obtain the polycarboxylate water-reducer product.
Embodiment seven
Getting 100 parts of iso-butylene Soxylat A 25-7s (weight-average molecular weight 2400) adds in reactor, add 80 parts of water, heating up to stir is dispersed in the aqueous solution it, 0.8 part of 30% hydrogen peroxide and 3 parts of sodium allyl sulfonates are added in reactor by 10 parts of water dissolution, stir and be warming up to 25 ℃, keep temperature fluctuation range in whole reaction process to be no more than 2 ℃, start to drip 0.2 part of rongalite and 0.015 part of ferrous sulfate is dissolved in the solution formed in 30 parts of water, start to drip 7.5 parts of vinylformic acid after 20min, 1.5 part ethyl propenoate and 0.2 part of Thiovanic acid are scattered in the solution formed in 25 parts of water, the former is controlled at 3h and dropwises, latter 2h dropwises, all dropwise rear insulation reaction 1.5h, regulating pH with 40% sodium hydroxide solution is 6-7, obtain the polycarboxylate water-reducer product.
Contrast experiment's example
Contrast experiment's example one
Getting 100 parts of iso-butylene Soxylat A 25-7s (weight-average molecular weight 2400) adds in reactor, add 80 parts of water, heating up to stir is dispersed in the aqueous solution it, 1.4 parts of ammonium persulphates and 4 parts of sodium allyl sulfonates are added in reactor by 10 parts of water dissolution, stir and be warming up to 35 ℃, keep temperature fluctuation range in whole reaction process to be no more than 2 ℃, start to drip 0.35 part of glucose simultaneously and be dissolved in the solution formed in 30 parts of water, reach 7.5 parts of vinylformic acid and 0.2 part of Thiovanic acid and be scattered in the solution formed in 25 parts of water, being controlled at 3h dropwises, all dropwise rear insulation reaction 1.5h, regulating pH with 40% sodium hydroxide solution is 6-7, obtain the polycarboxylate water-reducer product.
Contrast experiment's example two
Getting 100 parts of isopentene Soxylat A 25-7s (weight-average molecular weight 2400) adds in reactor, add 80 parts of water, heating up to stir is dispersed in the aqueous solution it, 1.2 parts of ammonium persulphates are added in reactor by 10 parts of water dissolution, stir and be warming up to 35 ℃, keep temperature fluctuation range in whole reaction process to be no more than 2 ℃, start to drip 0.35 part of sodium bisulfite and 0.01 part of ferrous sulfate is dissolved in the solution formed in 30 parts of water simultaneously, reach 10 parts of vinylformic acid and 0.2 part of Thiovanic acid and be scattered in the solution formed in 25 parts of water, being controlled at 3h dropwises, all dropwise rear insulation reaction 1.5h, regulating pH with 40% sodium hydroxide solution is 6-7, obtain the polycarboxylate water-reducer product.
The water reducer product of above contrast experiment and embodiment mono-to seven is made clean slurry test and concrete test, and test result is as follows:
Clean slurry test:
Adopt conch P.O 42.5R cement, carry out according to GB/T 8077-2000 " Methods for testing uniformity of concrete admixture ", W/C=0.29, the water reducer volume is the solid volume of folding, test-results is in Table 1:
Table 1 flowing degree of net paste of cement experimental result
By table 1 data, can be found out, than under low-dosage, the product of synthesized of the present invention can make cement paste have large initial flow and good mobility hold facility.From Comparative Examples experimental example one, can find out, the preferential monomer dropping technique of selective reduction agent is better than reductive agent and monomer drips the product made simultaneously, this is because reductive agent first adds in reaction system, the active lower large monomer of ether is activated, more be conducive to occur graft copolymerization, monomer conversion improves, and minor comonomer homopolymerization probability reduces, thereby in the water reducer product obtained, active constituent content increases, performance effectively improves; Can obtain from contrast experiment's example two, introduce a certain proportion of sulfonic group, can make the dispersiveness of water reducer be improved largely.
Concrete test:
Gelling material adopts conch P.O 42.5R cement, fine aggregate adopts medium sand (fineness modulus 2.8, silt content 0.3%), coarse aggregate is used rubble (particle diameter 5-20mm, continuous grading, porosity 40%), according to the requirement of GB/T 8076-2008, carry out concrete test, controlling the slump is (210 ± 10), and test-results is in Table 2:
Table 2 concrete test result
From the concrete application example, can find out, the prepared water reducer of the present invention has the characteristics such as volume is low, water-reducing rate is high, slump retaining is good, bleed is little.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (10)
1. a poly carboxylic acid series water reducer comprises the following component by mass parts:
100 parts of the large monomer A of methyl thiazolinyl Soxylat A 25-7
Unsaturated carboxylic acid, acid anhydrides or esters monomer B 4-20 part
Unsaturated sulfonic acid or its esters monomer C 2-15 part
Oxygenant 0.5-5 part
Reductive agent 0.008-0.5 part
Chain-transfer agent 0.05-1 part
40% sodium hydroxide solution 5-20 part
Water 100-200 part.
2. poly carboxylic acid series water reducer according to claim 1, it is characterized in that: the chemical formula of described monomer A is R
1-O-[CH
2-CH
2O]
m-R
2, R in formula
1For
Or
, R
2For the alkyl that hydrogen atom or carbonatoms are 1-5, the number of repeat unit of m is 15-80, and the weight-average molecular weight of described monomer A is 600-3000; Described unsaturated carboxylic acid, acid anhydrides or esters monomer B are at least one in vinylformic acid, maleic anhydride, methyl acrylate, ethyl propenoate; Described unsaturated sulfonic acid or its esters monomer C are at least one in sodium vinyl sulfonate, sodium allyl sulfonate, methylpropene sodium sulfonate, Sodium styrene sulfonate, 2-acrylamide-2-methyl propane sulfonic (sodium).
3. poly carboxylic acid series water reducer according to claim 1, it is characterized in that: described oxygenant is at least one in Potassium Persulphate, Sodium Persulfate, ammonium persulphate, hydrogen peroxide.
4. poly carboxylic acid series water reducer according to claim 1, it is characterized in that: described reductive agent is at least one in sodium bisulfite, S-WAT, glucose, vitamins C, ferrous sulfate, rongalite.
5. poly carboxylic acid series water reducer according to claim 1, it is characterized in that: described chain-transfer agent is at least one in Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, mercaptoethanol.
6. the preparation method of poly carboxylic acid series water reducer according to claim 1 comprises the following steps:
Step 1, described monomer A is added in reactor by described mass parts, add water heated and stirred and make its dissolving;
Step 2, described oxygenant and described monomer C are dissolved in water by described mass parts after, add in reactor;
Step 3, under whipped state, add reductive agent, described monomers B and chain-transfer agent mixing solutions by described mass parts, the mode that adds is to drop in advance in reactor by described reductive agent, start again to drip described monomers B and chain-transfer agent mixing solutions, and the time that dropwises of control reductive agent is later than the time that dropwises of monomers B and chain-transfer agent mixing solutions;
Step 4, insulation reaction 1-2 hour;
Step 5, add 40% sodium hydroxide solution by described mass parts, regulate the pH value of product to 6-7, obtain poly carboxylic acid series water reducer.
7. the preparation method of poly carboxylic acid series water reducer according to claim 6, it is characterized in that: in described step 3, the time that described reductive agent drips in advance is 15-45 minute, and the time that dropwises of described reductive agent is later than the time that the dropwises 15-40 minute of monomers B and chain-transfer agent mixing solutions.
8. the preparation method of poly carboxylic acid series water reducer according to claim 6, it is characterized in that: in described step 2 to four, temperature is 20-40 ℃.
9. the application of poly carboxylic acid series water reducer according to claim 1 is characterized in that: the solid volume while being applied to concrete is gelling material quality 0.05%-0.3% in concrete.
10. the application of poly carboxylic acid series water reducer according to claim 9 is characterized in that: the 0.08%-0.18% that the solid volume while being applied to concrete is gelling material quality in concrete.
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