CN104926183A - High-adaptability and high-performance polycarboxylic water-reducing agent and preparation method for same - Google Patents
High-adaptability and high-performance polycarboxylic water-reducing agent and preparation method for same Download PDFInfo
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title description 6
- 239000000178 monomer Substances 0.000 claims abstract description 74
- 239000003999 initiator Substances 0.000 claims abstract description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 methyl butyl Chemical group 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
- 239000007788 liquid Substances 0.000 claims description 46
- 229920005646 polycarboxylate Polymers 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004448 titration Methods 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000004160 Ammonium persulphate Substances 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 6
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 3
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004567 concrete Substances 0.000 abstract description 36
- 239000004568 cement Substances 0.000 abstract description 15
- 239000004576 sand Substances 0.000 abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 241001494479 Pecora Species 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003467 diminishing effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a high-adaptability and high-performance polycarboxylic water-reducing agent, which is obtained by polymerizing a monomer a (methyl allyl polyethenoxy ether or methyl butyl polyethenoxy ether), a monomer b (acrylic acid) and a monomer c (one or a mixture of more than two of maleic anhydride, methacrylic acid, sodium methallyl sulfonate and the like) in an aqueous solution system under the action of an initiator. The prepared high-performance polycarboxylic water-reducing agent has high adaptability with cement, and also has higher adaptability with concrete aggregate, particularly concrete prepared from manufactured sand; compared with an ordinary polycarboxylic water-reducing agent, the prepared polycarboxylic water-reducing agent has the advantages that the slump flow of concrete is higher under the condition that the slump of the concrete is kept the same, and the concrete can freely flow more favorably.
Description
Technical field
The present invention relates to polycarboxylate water-reducer technical field, be specifically related to a kind of wide apaptability high performance water reducing agent of polyocarboxy acid and preparation method thereof.
Background technology
In recent years, along with the construction of Chinese large-sized infrastructure project, the especially enforcement of National Highway railway and freeway network planning, cumulative to the demand of high performance water reducing agent of polyocarboxy acid.Compared with traditional naphthalene series high-efficiency water-reducing agent, polycarboxylate water-reducer has that volume is low, water-reducing rate is high, slump retaining is good, advantages of environment protection, obtains the generally accreditation of concrete works circle.But, polycarboxylate water-reducer and the adaptability between cement and mineral admixture (flyash, breeze etc.) still exist, simultaneously due to shortage of resources, a large amount of engineering adopts Machine-made Sand to replace natural river sand, causes adaptability new between polycarboxylate water-reducer and Machine-made Sand.Adaptability problem main manifestations is that fresh concrete workability is poor, slump-loss large, usually can affect the structure of maturing, finally make concrete durability decline.For adaptability problem, common measure is by composite to improve concrete workability to polycarboxylate water-reducer and workability conditioning agent, slump retaining agent, retardant etc., wherein relate to the consistency between these component and polycarboxylate water-reducers, sometimes even there is layering, but fundamentally can not solve adaptability problem by composite.Therefore, set about from the performance of polycarboxylate water-reducer own, the adaptability solved between itself and concrete raw material is very necessary.
Publication date is on June 13rd, 2012, publication number is that the Chinese invention patent application of CN 102491674 adopts batch charging mode and continuous dropping mode to produce diminishing formulation and collapse protective poly-carboxylic acid mother liquor respectively, then by composite for two kinds of mother liquors, arrange by the composite ratio both changing the adaptability adjusting polycarboxylate water-reducer.The method effectively improves the function of slump protection of composite rear polycarboxylate water-reducer, but general owing to protecting the guarantor of mother liquor of collapsing ability of collapsing itself, and concrete slump-loss is still comparatively large, and damage of collapsing for 1 hour is up to 4cm.
Summary of the invention
The object of the invention is to the shortcomings and deficiencies overcoming prior art, there is provided a kind of with short production cycle, cost performance is high, the high performance water reducing agent of polyocarboxy acid of adaptability wide ranges, another object of the present invention is to provide a kind of preparation method of wide apaptability high performance water reducing agent of polyocarboxy acid.
First object of the present invention is achieved through the following technical solutions:
A kind of wide apaptability high performance water reducing agent of polyocarboxy acid, this water reducer is polymerized by under the water solution system of following monomer under initiator effect:
1) monomer a: methacrylic Soxylat A 25-7, structural formula is as follows:
Or methyl alkene butyl Soxylat A 25-7, structural formula is as follows:
Wherein: n is the integer of 20 ~ 70, m is the integer of 20 ~ 70, and monomer a accounts for 50% ~ 95% of polymerization single polymerization monomer total mass in reaction system;
2) monomer b: vinylformic acid, structural formula is as follows:
Monomer b accounts for 2% ~ 30% of polymerization single polymerization monomer total mass in reaction system;
3) monomer c: be selected from one or more the mixture in maleic anhydride, methacrylic acid, methylpropene sodium sulfonate, acrylamide, methyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hy-droxybutyl, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, hydroxyethyl methylacrylate, Rocryl 410, monomer c accounts for 0.2% ~ 40% of polymerization single polymerization monomer total mass in reaction system.
Preferably, it is the integer of 20 ~ 60 that described monomer a accounts for 60% ~ 90%, n of reactant total mass, and m is the integer of 20 ~ 60.
Preferably, described monomer b accounts for 2% ~ 25% of reactant total mass.
Preferably, described monomer c accounts for 0.2% ~ 30% of reactant total mass.
Preferably, it is the integer of 20 ~ 60 that described monomer a accounts for 80% ~ 90%, n of reactant total mass, and m is the integer of 20 ~ 60; Described monomer b accounts for 2% ~ 18% of reactant total mass; Described monomer c accounts for 0.2% ~ 18% of reactant total mass.
Described initiator is water soluble starter, especially preferred in Sodium Persulfate, Potassium Persulphate, ammonium persulphate, hydrogen peroxide, xitix, sodium bisulfite one or both or two or more composite, initiator amount is 0.2 ~ 15% of polymerization single polymerization monomer total mass in reaction system.
Preferably, described initiator be in ammonium persulphate or hydrogen peroxide or xitix one or both or two or more composite, its consumption is 0.3 ~ 10% of reaction system polymerization single polymerization monomer total mass.
Second object of the present invention is achieved through the following technical solutions:
Prepare a method for as above arbitrary described wide apaptability high performance water reducing agent of polyocarboxy acid, carry out as follows:
1) monomer a and water are added reaction vessel, stir and heat, all dissolve to monomer a;
2) when temperature is increased to 60 ~ 90 DEG C, start respectively to drip A liquid and B liquid, wherein A liquid is the mixing solutions of monomer b, monomer c and water simultaneously, and B liquid is the mixing solutions containing initiator and water; A liquid Continuous Titration 3h, B liquid Continuous Titration 3.5h;
3) dropwise rear insulation 80 DEG C reaction 1 ~ 3h, after cool to 30 ~ 50 DEG C, adding alkali regulator solution pH value is 5 ~ 7, namely obtains described polycarboxylate water-reducer.
Further, described B liquid is also containing molecular weight regulator.
Preferably, described molecular weight regulator selects thiohydracrylic acid or Thiovanic acid.
As another kind of embodiment, the second object of the present invention can also be achieved through the following technical solutions:
Prepare a method for as above arbitrary described wide apaptability high performance water reducing agent of polyocarboxy acid, carry out as follows:
1) monomer a and water are added reaction vessel, stir and heat, all dissolve to monomer a;
2) when temperature is increased to 60 ~ 90 DEG C, the first initiator and water is added;
2) drip A liquid and B liquid, wherein A liquid is the mixing solutions of monomer b, monomer c and water simultaneously, and B liquid is the mixing solutions containing the second initiator and water; A liquid Continuous Titration 3h, B liquid Continuous Titration 3.5h;
3) dropwise rear insulation 80 DEG C reaction 1 ~ 3h, after cool to 30 ~ 50 DEG C, adding alkali regulator solution pH value is 5 ~ 7, namely obtains described polycarboxylate water-reducer;
Second initiator and the first initiator can be identical or different.
As preferably, the polycarboxylate water-reducer strength of solution of final preparation is 40% ~ 50%.In above preparation method, in each step 1 or step 2, the addition of water all can in this, as consideration foundation.
Compared with existing public technology, the present invention has following advantage:
(1) high performance water reducing agent of polyocarboxy acid prepared of the present invention except the adaptability between cement well except, and also show good adaptability between aggregate, particularly with the concrete of Machine-made Sand configuration; Compared with existing common polycarboxylate water-reducer, polycarboxylate water-reducer prepared by the present invention is keeping under the condition that concrete slump is identical, and concrete divergence is larger, is more conducive to concrete unrestricted flow.
(2) polycarboxylate water-reducer prepared of the present invention, introduce the diminishing such as sulfonic group, polyoxyethylene group in the molecular structure, introduce hydroxyl, ester group, acid amides etc. simultaneously and protect the group that collapses, by ratio and the distribution thereof of both optimization, water reducer can be made with higher dispersiveness and slump retaining, improve the adaptability of polycarboxylate water-reducer in molecular structure aspect.
(3) polycarboxylate water-reducer prepared of the present invention, raw material sources is wide, and synthesis technique is simple, and with short production cycle, cost performance is high, and market outlook are good, is more suitable for industrialization scale operation.
Embodiment
Below in conjunction with embodiment, the invention will be further described, and contriver to the present invention after research and testing, has many successful examples, enumerates some embodiments below, but the scope of protection of present invention is not limited to the scope of embodiment statement.
In an embodiment, unless otherwise stated, " % " expression " quality % ".
Embodiment 1
Monomer a and 15g deionized water that 200g concentration is 60% is added, stirring heating, and letting nitrogen in and deoxidizing in the reaction vessel being furnished with agitator, reflux condensing tube, dropping equipment.When the temperature of question response container rises to 80 DEG C, start to drip the A liquid that be made up of 0.5232g monomer c, 10.80g monomer b, 22.50g water and by 1.0464g ammonium persulphate, the B liquid that 39.00g water forms simultaneously; Control to drip speed, A liquid drips off for 3 hours, and B drips off for 3.5 hours, and after B liquid dropwises, insulation 2h, then cools to 40 DEG C, regulates pH to 6, namely obtain the wide apaptability polycarboxylate water-reducer that concentration is 45%, be designated as HSPC-1 by 35% concentration NaOH solution.
Embodiment 2
180g monomer a and 142.5g deionized water is added, stirring heating, and letting nitrogen in and deoxidizing in the reaction vessel being furnished with agitator, reflux condensing tube, dropping equipment.When the temperature of question response container rises to 80 DEG C, start to drip the A liquid be made up of 6.2784g monomer c, 16.20g monomer b, 33.0g water and the B liquid be made up of 1.1772g ammonium persulphate, 64.5g water simultaneously; Control to drip speed, A liquid drips off for 3 hours, and B drips off for 3.5 hours, and after B liquid dropwises, insulation 2h, then cools to 40 DEG C, regulates pH to 6, namely obtain the wide apaptability polycarboxylate water-reducer that concentration is 45%, be designated as HSPC-2 by 35% concentration NaOH solution.
Embodiment 3
Monomer a and 8g deionized water that 240g concentration is 60% is added, stirring heating, and letting nitrogen in and deoxidizing in the reaction vessel being furnished with agitator, reflux condensing tube, dropping equipment.When the temperature of question response container rises to 60 DEG C, add the solution be made up of 1.12 gram of 30% concentration hydrogen peroxide and 8g water, stir after 5 minutes, start to drip the A liquid that be made up of 14.37g monomer c, 10.81g monomer b, 40.0g water and by 0.4359g xitix, 0.71g thiohydracrylic acid, the B liquid that 52g water forms simultaneously; Control to drip speed, A liquid drips off for 3 hours, and B drips off for 3.5 hours, and after B liquid dropwises, insulation 2h, then cools to 40 DEG C, regulates pH to 6, namely obtain the wide apaptability polycarboxylate water-reducer that concentration is 45%, be designated as HSPC-3 by 35% concentration NaOH solution.
Embodiment 4
Monomer a and 8g deionized water that 240g concentration is 60% is added, stirring heating, and letting nitrogen in and deoxidizing in the reaction vessel being furnished with agitator, reflux condensing tube, dropping equipment.When the temperature of question response container rises to 60 DEG C, add the solution be made up of 1.29 gram of 30% concentration hydrogen peroxide and 8g water, stir after 5 minutes, start to drip the A liquid that be made up of 21.55g monomer c, 9.94g monomer b, 45.0g water and by 0.4993g xitix, 0.82g thiohydracrylic acid, the B liquid that 54g water forms simultaneously; Control to drip speed, A liquid drips off for 3 hours, and B drips off for 3.5 hours, and after B liquid dropwises, insulation 2h, then cools to 40 DEG C, regulates pH to 6, namely obtain the wide apaptability polycarboxylate water-reducer that concentration is 45%, be designated as HSPC-4 by 35% concentration NaOH solution.
Comparative example 1
Monomer a methacrylic Soxylat A 25-7 accounts for 91.21% of monomer total mass
Monomer b vinylformic acid accounts for 8.79% of monomer total mass
Monomer a and 87.15g deionized water that 412.1g concentration is 60% is added, stirring heating, and letting nitrogen in and deoxidizing in the reaction vessel being furnished with agitator, reflux condensing tube, dropping equipment.When the temperature of question response container rises to 60 DEG C, add the solution be made up of 1.04 gram of 30% concentration hydrogen peroxide and 9.8g water, stir after 5 minutes, start to drip the A liquid that be made up of 23.83g monomer b, 42.7g water and by 0.379g xitix, 0.690g Thiovanic acid, the B liquid that 81.9g water forms simultaneously; Control to drip speed, A liquid drips off for 3 hours, and B drips off for 3.5 hours, and after B liquid dropwises, insulation 2h, then cools to 40 DEG C, regulates pH to 6, namely obtain the wide apaptability polycarboxylate water-reducer that concentration is 40%, be designated as HSPC-5 by 35% concentration NaOH solution.
Application Example 1
The poly carboxylic acid (HSPC-1 ~ HSPC-4) that this present invention is synthesized and comparative example polycarboxylate water-reducer (HSPC-5) contrast properties under clean slurry system, cement used is golden sheep P.O42.5R cement, flowing degree of net paste of cement test is carried out according to standard GB/T/T 8077-2012, and test-results is as shown in table 1.
Table 1 flowing degree of net paste of cement test-results
As seen from the data in Table 1, the present invention synthesizes polycarboxylate water-reducer HSPC-1 ~ HSPC-4 and shows good dispersion retentivity, through time 60min after paste flowing degree free of losses; The dispersion retentivity of comparative example polycarboxylate water-reducer HSPC-5 is obviously poor, and after 60min, paste flowing degree declines obviously.
Application Example 2
Choose of the present invention polycarboxylate water-reducer HSPC-2 good with golden sheep P.O42.5R cement adaptability, investigate the adaptability between itself and other cement, as shown in table 2.Under fixing water reducer volume and water cement ratio condition, carry out paste flowing degree test according to standard GB/T/T8077-2012.Result show, the dispersiveness of water reducer HSPC-2 in reference cement and P.O42.5R ordinary Portland cement and dispersion retentivity all higher, through time 120min after paste flowing degree free of losses; In P.II42.5R silicate cement, the dispersiveness of water reducer declines relatively, through time 120min after paste flowing degree slightly lose, but paste flowing degree free of losses in 60min.Generally, good adaptability is shown between the HSPC-2 water reducer prepared of the present invention and five kinds of cement.
Table 2 HSPC-2 water reducer and cement adaptability test-results
Application Example 3
Under concrete system, the adaptability between water reducer HSPC-2 of the present invention and cement is investigated respectively in C30 and C50 grade concrete, and compare with comparative example water reducer HSPC-5 performance, concrete raw material and proportioning as shown in table 3, concrete test the results are shown in Table 4.The test of concrete slump, slump-loss requires to carry out according to standard GB/T 8076-2008 " concrete admixture ".From table 4 result, HSPC-2, in C30 and C50 grade concrete, all shows good adaptability to two kinds of different cement, through time 60min after concrete still there is higher mobility; The slump retaining of existing water reducer is poor, and concrete slump loss obviously wants large, especially C30 concrete, and no matter is C30 or C50 grade concrete, through time 60min after concrete divergence loss want obviously large.
Table 3 C30 and C50 concrete raw material and proportioning
Table 4 C30 and C50 concrete test result
Application Example 4
Under concrete system, in C20, C25 and C30 grade concrete, investigate the adaptability between water reducer HSPC-2 of the present invention and Machine-made Sand respectively, concrete raw material and proportioning as shown in table 5, concrete test the results are shown in Table 6.From table 6 result, HSPC-2 water reducer all with Machine-made Sand configuration C20 ~ C30 grade concrete in showing good workability, through time 60min after, the slump change very little, and divergence even increases, what illustrate between HSPC-2 water reducer and Machine-made Sand is well-adjusted.
Table 5 C20 and C30 concrete raw material and proportioning
Table 6 C20 and C30 concrete test result
Claims (10)
1. a wide apaptability high performance water reducing agent of polyocarboxy acid, is characterized in that: this water reducer is polymerized by under the water solution system of following monomer under initiator effect:
1) monomer a: monomer a is methacrylic Soxylat A 25-7, and structural formula is as follows:
Or methyl alkene butyl Soxylat A 25-7, structural formula is as follows:
Wherein: n is the integer of 20 ~ 70, m is the integer of 20 ~ 70, and monomer a accounts for 50% ~ 95% of polymerization single polymerization monomer total mass in reaction system;
2) monomer b: be vinylformic acid, structural formula is as follows:
Monomer b accounts for 2% ~ 30% of polymerization single polymerization monomer total mass in reaction system;
3) monomer c: be selected from one or more the mixture in maleic anhydride, methacrylic acid, methylpropene sodium sulfonate, acrylamide, methyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hy-droxybutyl, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, hydroxyethyl methylacrylate, Rocryl 410, monomer c accounts for 0.2% ~ 40% of polymerization single polymerization monomer total mass in reaction system.
2. wide apaptability high performance water reducing agent of polyocarboxy acid according to claim 1, is characterized in that: it is the integer of 20 ~ 60 that described monomer a accounts for 60% ~ 90%, n of reactant total mass, and m is the integer of 20 ~ 60.
3. wide apaptability high performance water reducing agent of polyocarboxy acid according to claim 1, is characterized in that: described monomer b accounts for 2% ~ 25% of reactant total mass.
4. wide apaptability high performance water reducing agent of polyocarboxy acid according to claim 1, is characterized in that: described monomer c accounts for 0.2% ~ 30% of reactant total mass.
5. wide apaptability high performance water reducing agent of polyocarboxy acid according to claim 1, is characterized in that: it is the integer of 20 ~ 60 that described monomer a accounts for 80% ~ 90%, n of reactant total mass, and m is the integer of 20 ~ 60; Described monomer b accounts for 2% ~ 18% of reactant total mass; Described monomer c accounts for 0.2% ~ 18% of reactant total mass.
6. wide apaptability high performance water reducing agent of polyocarboxy acid according to claim 1, it is characterized in that: described initiator is water soluble starter, be selected from Sodium Persulfate, Potassium Persulphate, ammonium persulphate, hydrogen peroxide, xitix, sodium bisulfite one or both or two or more composite, initiator amount is 0.2 ~ 15% of polymerization single polymerization monomer total mass in reaction system.
7. wide apaptability high performance water reducing agent of polyocarboxy acid according to claim 5, it is characterized in that: described initiator be in ammonium persulphate or hydrogen peroxide or xitix one or both or two or more composite, its consumption is 0.3 ~ 10% of reaction system polymerization single polymerization monomer total mass.
8. prepare as arbitrary in claim 1 ~ 7 as described in the method for wide apaptability high performance water reducing agent of polyocarboxy acid, it is characterized in that carrying out as follows:
1) monomer a and water are added reaction vessel, stir and heat, all dissolve to monomer a;
2) when temperature is increased to 60 ~ 90 DEG C, start respectively to drip A liquid and B liquid, wherein A liquid is the mixing solutions of monomer b, monomer c and water simultaneously, and B liquid is the mixing solutions containing initiator and water; A liquid Continuous Titration 3h, B liquid Continuous Titration 3.5h;
3) dropwise rear insulation 80 DEG C reaction 1 ~ 3h, after cool to 30 ~ 50 DEG C, adding alkali regulator solution pH value is 5 ~ 7, namely obtains described polycarboxylate water-reducer.
9. method according to claim 7, is characterized in that: described B liquid also contains molecular weight regulator, the preferred thiohydracrylic acid of described molecular weight regulator or Thiovanic acid.
10. prepare as arbitrary in claim 1 ~ 7 as described in the method for wide apaptability high performance water reducing agent of polyocarboxy acid, it is characterized in that carrying out as follows:
1) monomer a and water are added reaction vessel, stir and heat, all dissolve to monomer a;
2) when temperature is increased to 60 ~ 90 DEG C, the first initiator and water is added;
2) drip A liquid and B liquid, wherein A liquid is the mixing solutions of monomer b, monomer c and water simultaneously, and B liquid is the mixing solutions containing the second initiator and water; A liquid Continuous Titration 3h, B liquid Continuous Titration 3.5h;
3) dropwise rear insulation 80 DEG C reaction 1 ~ 3h, after cool to 30 ~ 50 DEG C, adding alkali regulator solution pH value is 5 ~ 7, namely obtains described polycarboxylate water-reducer;
Second initiator and the first initiator can be identical or different.
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