CN101734879A - Polyurethane/polycarboxylic acid compound water reducer for concrete and preparation thereof - Google Patents
Polyurethane/polycarboxylic acid compound water reducer for concrete and preparation thereof Download PDFInfo
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- CN101734879A CN101734879A CN200910312356A CN200910312356A CN101734879A CN 101734879 A CN101734879 A CN 101734879A CN 200910312356 A CN200910312356 A CN 200910312356A CN 200910312356 A CN200910312356 A CN 200910312356A CN 101734879 A CN101734879 A CN 101734879A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/282—Polyurethanes; Polyisocyanates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/283—Polyesters
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0059—Graft (co-)polymers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a polyurethane/polycarboxylic acid compound water reducer for concrete and preparation thereof. Emulsion polymerization is firstly adopted to synthesize terminated polyurethane emulsion, then acrylate hybrid monomers are introduced and polymerization of acrylate is carried out in the presence of an initiator to obtain polyurethane/polycarboxylic acid compound emulsion. The high performance concrete prepared by the water reducer has high water reducing ratio, early strength, fast setting and good permeability resistance. The water reducer simultaneously improves the impact toughness of the concrete and is environmentally friendly and highly efficient.
Description
Technical field
The invention belongs to concrete additives in building materials, be specifically related to a kind of polyurethane/polycarboxylic acid compound water reducer for concrete and preparation thereof.
Background technology
The concrete technology development be unable to do without chemical admixture, as the development of novel materials such as pump concrete, self-leveling concrete, non-dispersible underwater concrete, sprayed concrete, polymer concrete, high-strength high-performance concrete, high efficiency water reducing agent has all played keying action.High efficiency water reducing agent claims superplasticizer again, is used for concrete mix, mainly play a part three different: 1, under the condition that does not change concrete strength, improve workability of concrete; 2, under given workability condition, reduce water cement ratio, improve concrete intensity and weather resistance; 3, under the condition that guarantees concrete depositing performance and intensity, reduce water and cement consumption, reduce creep, the factor of concrete initial imperfection that drying shrinkage, hydration heat of cement etc. cause.Used high efficiency water reducing agent mainly contains naphthalene water reducer, melamine system water reducer, amido sulfoacid series high-efficiency water reducer and novel poly carboxylic acid series water reducer at present.Though naphthalene water reducer is with low cost, the consistency of itself and cement is not good, and slump-loss is bigger, has certain environmental pollution, and loses its cost advantage along with the rising of NAPTHALENE FLAKES. (INDUSTRIAL GRADE price.Though melamine system water reducer is better than naphthalene water reducer on various performances, it keeps mobile difference and higher price to limit to its use range.The amido sulfoacid series high-efficiency water reducer synthesis technique is simple, and brings concrete and be better than the above two high-performance, but to have limited its use model amount smaller owing to its sensitivity to volume.Polycarboxylate water-reducer, be referred to as the 3rd generation the new polymers water reducer, have low-dosage, slump retaining is good, advantages such as the big and environmental protection of molecular structure degree of freedom.Abroad mainly bias toward the exploitation poly carboxylic acid series water reducer and study the mechanical property of relevant fresh concrete serviceability and maturing and engineering use technology etc. about the research and development direction of polycarboxylic acids dehydragent.Domestic poly carboxylic acid series water reducer does not nearly all reach the practicability stage.The alternative starting material of synthesizing polycarboxylic acid dehydragent are also very limited, choose production technique, reduce cost, improve many aspects such as performance and all need systematic study from the water reducer starting material
Present domestic preparation polycarboxylic acid series diminishing adopts the direct copolymerization method of polymerisable monomer more.Report among the CN316398, utilize the esterification of methyl methacrylate and methyl Soxylat A 25-7 on methyl Soxylat A 25-7 long-chain, to introduce two keys, synthesize the big monomer that polymerization activity is arranged, and obtain the polyocarboxy acid type water reducer with other monomer copolymerizations.Disclosed water reducer is to be obtained by the polyalkylene glycol mono ester monomer that contains long-chain oxyalkylene propenyl group and Acrylic Acid Monomer/unsaturated dicarboxylic acid monomer and the copolymerization of propenyl sulfonic acid monomer among the CN1041816C.The difficult point of this method is to prepare the big monomer (being generally methoxy polyethylene glycol methacrylate-styrene polymer) with polymerization activity, separation and purification process in the technology is more loaded down with trivial details, the equipment requirements height, and processing condition are wayward, and cost is higher, is not suitable for industrialized production.
The disclosed poly carboxylic acid series water reducer of CN1712381A, adopt sulfonation reaction to obtain the sulfonated phenylethylene copolymer-maleic anhydride earlier, under 100～120 ℃ temperature, react the co-poly carboxylic acid that obtains containing the polyoxyethylene side chain with polyoxyethylene glycol and sulfonated phenylethylene copolymer-maleic anhydride generation graft esterification, regulate pH value and obtain polyether grafting type cement water reducing agent.The disclosed poly carboxylic acid series water reducer of CN 1724447A, obtain having the high molecular polymer of sulfonic acid group with vinylformic acid and methylpropene sodium sulfonate generation copolymerization, again with paratoluenesulfonic acid sodium salt as catalyzer make polyoxyethylene glycol under hot conditions with the first step in synthetic polymkeric substance generation esterification obtain poly carboxylic acid series water reducer.Above synthetic method all is a functionalization method after the first polymerization of employing, this method has been avoided difficult, the unsettled bottleneck problem of big monomer preparation of polymerisable monomer method to a certain extent, but in actual applications, the consistency of poly carboxylic acid and polyoxyethylene glycol is bad, temperature of reaction is higher, the actually operating difficulty of esterification.
Summary of the invention:
The objective of the invention is to overcome the difficulty that adopts aforesaid method to run into, a kind of polyurethane/polycarboxylic acid compound water reducer for concrete and preparation method thereof is provided.Water reducer of the present invention is a kind of crosslinking polymer, the water-reducing rate height, and early strong rapid hardening can significantly improve concrete anti-permeability performance and impelling strength, is a kind of efficient cement water reducing agent of environment-friendly type.Present method is utilized the heat production condition in the mixed construction process of concrete, carries out grafting with end-sealed type urethane and polyacrylic ester, prepares polyurethane/polycarboxylic acid compound water reducer for concrete.
The objective of the invention is to realize by following manner.
Water reducer of the present invention is the mixed emulsion that contains end-sealed type urethane, polyacrylic ester and initiator, and described end-sealed type urethane is the sodium bisulfite blocked polyurethane, and described polyacrylic ester contains hydroxyl and carboxyl; Grafting takes place and separates the end-blocking reaction in the mixed emulsion of described water reducer in concrete, end-sealed type urethane discharges the reaction of the OH base in NCO group and the polyacrylic ester, obtain with urethane as graft side chain cross-linking type multipolymer, molecular weight of copolymer 7000～10000.
Described end-sealed type urethane solid content is preferably 35～45%.Most preferably solid content is 40%.
The mass ratio of urethane and polyacrylic ester is: 7～9: 3～5.
Described initiator is 2,2'-Azobis(2,4-dimethylvaleronitrile) or Diisopropyl azodicarboxylate
The preparation method of water reducer of the present invention may further comprise the steps:
(1) preparation end-sealed type polyaminoester emulsion: earlier by polyisocyanates, polyvalent alcohol, hydrophilic monomer and chainextender under the temperature of 60～100 Fei, react and made polyurethane prepolymer in 2～4 hours, add the sodium bisulfite end-capping reagent again, temperature of reaction is 60～100 Fei, reaction times is 1～2 hour, preparation end-sealed type urethane adds deionized water at last and prepares the end-sealed type polyaminoester emulsion;
(2) preparation polyacrylate dispersion: get a part of acrylic ester monomer mixture, emulsifying agent and initiator earlier and prepare seed emulsion, add residual acrylic acid esters monomer mixture, emulsifying agent and initiator again and PH buffer reagent prepared in reaction goes out polyacrylate dispersion;
(3) the end-sealed type polyaminoester emulsion is mixed with polyacrylate dispersion and initiator, join in the concrete of the state of mixing and stirring, grafting takes place separate the end-blocking reaction, obtain with urethane as graft side chain cross-linking type multipolymer.
The described polyisocyanates of step (1) is selected from TDI, MDI, HDI, IPDI or TMXDI; Described polyvalent alcohol has the pure and mild polyether glycol of polyester polyols, and molecular weight is 400～1000; Described hydrophilic monomer chain extender is a dimethylol propionic acid.
The described acrylic ester monomer mixture of step (2) is methyl methacrylate (MMA), butyl acrylate (BA), vinylformic acid (AA) and Hydroxyethyl acrylate (HEA); Mass ratio between them is: 10～20: 30～40: 5～10: 10～14; The twice monomeric additional proportion in front and back is 1～2: 3～4; Described emulsifying agent is preferably sodium laurylsulfonate (SDS) and polyoxyethylene octylphenol ether (OP-10).
The described initiator of step (2) is preferably Potassium Persulphate.
The described initiator of step (3) is preferably 2,2'-Azobis(2,4-dimethylvaleronitrile) or Diisopropyl azodicarboxylate, and its consumption accounts for 0.1%～0.2% of described polymkeric substance total amount.
Prepared in reaction seed emulsion and polyacrylate dispersion temperature are 60～100 Fei in the step (2), and the reaction times is 2～4 hours.
Advantage of the present invention:
Preparation technology of the present invention is simple, be fit to suitability for industrialized production, the polyurethane/polycarboxylic acid compound water reducer for concrete of preparation, in the Concrete Construction process, its end-sealed type urethane utilizes the hydration heat of cement can separate the end-blocking reaction and discharges isocyanic ester (NCO) group, utilize the reaction of the hydroxyl (OH) in NCO group and the poly carboxylic acid to carry out grafting, generate the cross-linking type graft copolymer of urethane and poly carboxylic acid, its reaction conditions is lower.
The present invention introduces polyurethane component in the polyocarboxy acid type water reducer system first, with urethane as graft side chain, functional group of Yin Ruing such as sulfonic group more in the past, polyoxyethylene groups is compared, polyurethane chain has better kindliness and elasticity, the greater room inhibition effect can be provided, improve the hold facility of the slump to a certain extent.
Water reducer of the present invention is (0.04%～0.07%) under lower volume, and water-reducing rate is reached more than 30%, good dispersity, and concrete slump loss is little.The bleed of urethane side chain, infilling and polymkeric substance and hydrated cementitious product run through mutually, interweave and constitute the reticulated structure system be unfavorable for the water infiltration in the water reducer, pore structure to sand-cement slurry has bigger improvement, and has improved the anti-permeability performance and the anti-freezing property of sand-cement slurry.With the high performance concrete that water reducer of the present invention is prepared, have the water-reducing rate height, early strong rapid hardening, well anti-permeability performance significantly improves concrete impelling strength simultaneously, is a kind of efficient cement water reducing agent of environment-friendly type.
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1:
(1) preparation of end-sealed type polyaminoester emulsion
Basic recipe:
| Isophorone diisocyanate (IPDI) | 40g |
| Polypropylene glycol (molecular weight 400) | 100g |
| Polyoxyethylene glycol (molecular weight 600) | 20g |
| Butyleneglycol | 5g |
| 35%NaHSO3 solution | 14g |
Concrete preparation method: in four-hole boiling flask, add isophorone diisocyanate (IPDI) and polypropylene glycol (molecular weight 400), stir, under 70～75 ℃ temperature condition, react 2h, add polyoxyethylene glycol (molecular weight 400), 80～85 ℃ temperature condition continues reaction 1h down, cools the temperature to 30 ℃ then, adds the NaHSO3 aqueous solution, reaction 30min, adding 200ml deionized water carries out decentralized system and gets sodium bisulfite end-sealed type polyaminoester emulsion.
(2) preparation of polyacrylic ester
Basic recipe:
| Methyl methacrylate (MMA) | 20g |
| Butyl acrylate (BA) | 80g |
| Vinylformic acid (AA) | 10g |
| Methyl methacrylate (MMA) | 20g |
| Hydroxyethyl acrylate (HEA) | 20g |
| OP-10 | Add-on: 0.3g add-on: 1.5g for the first time for the first time |
| SDS | Add-on: 1.8g add-on: 3g for the first time for the first time |
| K 2S 2O 8 | Add-on: 0.5g add-on: 1.1g for the first time for the first time |
| Triethylamine (TEA) | 3.2g |
In four-hole boiling flask, add OP-10, SDS and deionized water, be warming up to 80 ℃, get the acrylate mixing monomer and the K of 10% total amount
2S
2O
8Join simultaneously in the system, constant temperature stirs when treating that system is blue light about 30min, with acrylate mixing monomer, SDS, OP-10 and the K of surplus amount
2S
2O
8Drip in the system simultaneously, drip off in the 2h, be incubated 30min again.System is cooled to 50 ℃, adds triethylamine, adjusts PH between 8～9.
(3) taking mass ratio is 7: 3 above-mentioned two kinds of polymkeric substance and the 2,2'-Azobis(2,4-dimethylvaleronitrile) that accounts for polymkeric substance total amount 0.2%, joins in the concrete mortar that is mixing and stirring, and can obtain urethane/poly-carboxylic concrete composite water-reducing agent in concrete mortar.
Embodiment 2:
(1) synthetic blocked polyurethane
Basic recipe:
| Tolylene diisocyanate (TDI) | 32g |
| Polyether glycol (molecular weight 1000, dry) | 100g |
| Dimethylol propionic acid (DMPA) | 10.4g |
| Ethyl acetate | 23.0g |
| 35%NaHSO3 solution | 13g |
| Acetone | 18g |
Concrete preparation method is with the step (1) of embodiment 1
(2) acrylic resin of synthetic hydroxyl
Basic recipe:
| Methyl methacrylate (MMA) | 24g |
| Butyl acrylate (BA) | 60g |
| Vinylformic acid (AA) | 10g |
| Hydroxyethyl acrylate (HEA) | 20g |
| OP-10 | Add-on: 0.5g add-on: 1.5g for the first time for the first time |
| SDS | Add-on: 2g add-on: 3g for the first time for the first time |
| K 2S 2O 8 | Add-on: 0.5g add-on: 1.0g for the first time for the first time |
| Triethylamine (TEA) | 3.0g |
The preparation method is with the step (2) of embodiment 1
(3) taking mass ratio is 8: 5 above-mentioned two kinds of polymkeric substance and the 2,2'-Azobis(2,4-dimethylvaleronitrile) that accounts for polymkeric substance total amount 0.3%, joins in the concrete mortar that is mixing and stirring, and can obtain urethane/poly-carboxylic concrete composite water-reducing agent in concrete mortar.
Embodiment 3:
(1) synthetic blocked polyurethane
Basic recipe:
| Diphenylmethanediisocyanate (MDI) | 21g |
| Polycaprolactone (molecular weight 800, dry) | 98g |
| Dimethylol propionic acid (DMPA) | 6.5g |
| Ethyl acetate | 17.0g |
| 35%NaHSO3 solution | 9.0g |
| Acetone | 18.0g |
Concrete preparation method is with the step (1) of embodiment 1
(2)) acrylic resin of synthetic hydroxyl
Basic recipe:
| Methyl methacrylate (MMA) | 20g |
| Butyl acrylate (BA) | 60 |
| Vinylformic acid (AA) | 12g |
| Hydroxyethyl acrylate (HEA) | 28g |
| OP-10 | Add-on: 0.5g add-on: 1.5g for the first time for the first time |
| SDS | Add-on: 2g add-on: 3g for the first time for the first time |
| K 2S 2O 8 | Add-on: 0.5g add-on: 1.0g for the first time for the first time |
| Triethylamine (TEA) | 2.6g |
The preparation method is with the step (2) of embodiment 1
(3) taking mass ratio is 7: 5 above-mentioned two kinds of polymkeric substance and the 2,2'-Azobis(2,4-dimethylvaleronitrile) that accounts for polymkeric substance total amount 0.1%, joins in the concrete mortar that is mixing and stirring, and can obtain urethane/poly-carboxylic concrete composite water-reducing agent in concrete mortar.
Embodiment 4:
Get embodiment 1 and be research object, relatively its volume is to the influence of fresh mixing concrete property.Making the initial slump by the adjustment water consumption is 20 ± 2cm.It is as shown in the table for experimental result.
The cement that is adopted among the embodiment is changde, hunan province crossdrift conch P.O42.5, and sand is that fineness modulus is 2.55 medium sand, and cobble-stone diameter is 5～20mm.Comparative example is commercially available UNF-5 naphthalene water reducer.Concrete mix is: cement: sand: stone=550: 1200: 2200.
The mensuration of the slump and the loss that collapses: with reference to JC473-2001 " concrete pump-feed agent "; The mensuration of water-reducing rate, time of coagulation: with reference to GB8076-97 " concrete admixture is tested "; The mensuration of ultimate compression strength: with reference to GB/T50081-2002 " mechanical performance of concrete experimental technique standard ".
Embodiment 5:
Present embodiment comprehensively compares every performance of the synthetic embodiment of institute 1～4.Making the initial slump by the adjustment water consumption is 20 ± 2cm.It is as shown in the table for experimental result.
The cement that is adopted in each example is changde, hunan province crossdrift conch P.O42.5, and sand is that fineness modulus is 2.55 medium sand, and cobble-stone diameter is 5～20mm.Comparative example is commercially available UNF-5 naphthalene water reducer.Concrete mix is: cement: sand: stone=550: 1200: 2200.
The mensuration of the slump and the loss that collapses: with reference to JC473-2001 " concrete pump-feed agent "; The mensuration of water-reducing rate, time of coagulation: with reference to GB8076-97 " concrete admixture is tested "; The mensuration of ultimate compression strength: with reference to GB/T50081-2002 " mechanical performance of concrete experimental technique standard ".
Claims (10)
1. polyurethane/polycarboxylic acid compound water reducer for concrete, it is characterized in that: water reducer is the mixed emulsion that contains end-sealed type urethane, polyacrylic ester and initiator, described end-sealed type urethane is the sodium bisulfite blocked polyurethane, and described polyacrylic ester contains hydroxyl and carboxyl; Grafting takes place and separates the end-blocking reaction in the mixed emulsion of described water reducer in concrete, end-sealed type urethane discharges the reaction of the OH base in NCO group and the polyacrylic ester, obtain with urethane as graft side chain cross-linking type multipolymer, molecular weight of copolymer 7000～10000.
2. a kind of polyurethane/polycarboxylic acid compound water reducer for concrete according to claim 1 is characterized in that: described end-sealed type urethane solid content is 35～45%.
3. a kind of polyurethane/polycarboxylic acid compound water reducer for concrete according to claim 1 is characterized in that: the mass ratio of urethane and polyacrylic ester is: 7～9: 3～5.
4. a kind of polyurethane/polycarboxylic acid compound water reducer for concrete according to claim 1 is characterized in that: described initiator is 2,2'-Azobis(2,4-dimethylvaleronitrile) or Diisopropyl azodicarboxylate.
5. the preparation method of a polyurethane/polycarboxylic acid compound water reducer for concrete is characterized in that, may further comprise the steps:
(1) preparation end-sealed type polyaminoester emulsion: earlier by polyisocyanates, polyvalent alcohol, hydrophilic monomer and chainextender under the temperature of 60～100 Fei, react and made polyurethane prepolymer in 2～4 hours, add the sodium bisulfite end-capping reagent again, temperature of reaction is 60～100 Fei, reaction times is 1～2 hour, preparation end-sealed type urethane adds deionized water at last and prepares the end-sealed type polyaminoester emulsion;
(2) preparation polyacrylate dispersion: get a part of acrylic ester monomer mixture, emulsifying agent and initiator earlier and prepare seed emulsion, add residual acrylic acid esters monomer mixture, emulsifying agent and initiator again and PH buffer reagent prepared in reaction goes out polyacrylate dispersion;
(3) the end-sealed type polyaminoester emulsion is mixed with polyacrylate dispersion and initiator, join in the concrete of the state of mixing and stirring, grafting takes place separate the end-blocking reaction, obtain with urethane as graft side chain cross-linking type multipolymer.
6. the preparation method of a kind of polyurethane/polycarboxylic acid compound water reducer for concrete according to claim 5 is characterized in that, the described polyisocyanates of step (1) is selected from TDI, MDI, HDI, IPDI or TMXDI; Described polyvalent alcohol has the pure and mild polyether glycol of polyester polyols, and molecular weight is 400～1000; Described hydrophilic monomer chain extender is a dimethylol propionic acid.
7. the preparation method of a kind of polyurethane/polycarboxylic acid compound water reducer for concrete according to claim 5, it is characterized in that the described acrylic ester monomer mixture of step (2) is methyl methacrylate, butyl acrylate, vinylformic acid and Hydroxyethyl acrylate; Mass ratio between them is: 10～20: 30～40: 5～10: 10～14; The twice monomeric additional proportion in front and back is 1～2: 3～4; Described emulsifying agent is sodium laurylsulfonate and polyoxyethylene octylphenol ether.
8. the preparation method of a kind of polyurethane/polycarboxylic acid compound water reducer for concrete according to claim 5 is characterized in that, the described initiator of step (2) is a Potassium Persulphate.
9. the preparation method of a kind of polyurethane/polycarboxylic acid compound water reducer for concrete according to claim 5, it is characterized in that, the described initiator of step (3) is 2,2'-Azobis(2,4-dimethylvaleronitrile) or Diisopropyl azodicarboxylate, and its consumption accounts for 0.1%～0.2% of described polymkeric substance total amount.
10. the preparation method of a kind of polyurethane/polycarboxylic acid compound water reducer for concrete according to claim 5 is characterized in that, prepared in reaction seed emulsion and polyacrylate dispersion temperature are 60～100 Fei in the step (2), and the reaction times is 2～4 hours.
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| CN102351998A (en) * | 2011-07-11 | 2012-02-15 | 贵州科之杰新材料有限公司 | Preparation method for high-dispersity polycarboxylic acid water reducing agents |
| CN102432330A (en) * | 2011-09-16 | 2012-05-02 | 上海浦莲预拌混凝土有限公司 | Earthquake-resistant and pressure-resistant concrete and preparation method thereof |
| CN104945633A (en) * | 2015-06-02 | 2015-09-30 | 江苏奥莱特新材料有限公司 | Preparation method of novel polycarboxylic acid type water-reducer |
| CN105036595A (en) * | 2015-07-30 | 2015-11-11 | 新疆德蓝股份有限公司 | High-liquidity polycarboxylic acid water reducing agent and preparation method thereof |
| CN106117460A (en) * | 2016-08-26 | 2016-11-16 | 科之杰新材料集团有限公司 | A kind of preparation method of ethers viscosity reduction type polycarboxylate water-reducer |
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| CN112456992A (en) * | 2021-02-03 | 2021-03-09 | 北京利尔高温材料股份有限公司 | Pouring material for tundish working lining and preparation method thereof |
| CN115322307A (en) * | 2022-09-05 | 2022-11-11 | 李娜 | Polycarboxylic acid high-performance water reducing agent and preparation method thereof |
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| DE10226088A1 (en) * | 2002-06-12 | 2004-03-04 | Elotex Ag | Additive for hydraulically setting systems, hydraulically setting compounds and their use |
| CN101531479A (en) * | 2009-04-03 | 2009-09-16 | 南京瑞迪高新技术公司 | Method for preparing low cost aliphatic high efficiency water reducing agent |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102351998A (en) * | 2011-07-11 | 2012-02-15 | 贵州科之杰新材料有限公司 | Preparation method for high-dispersity polycarboxylic acid water reducing agents |
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| CN111848067B (en) * | 2020-07-30 | 2022-02-01 | 石家庄铁道大学 | Grouting material for large bridge support and preparation method thereof |
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| CN112456992A (en) * | 2021-02-03 | 2021-03-09 | 北京利尔高温材料股份有限公司 | Pouring material for tundish working lining and preparation method thereof |
| CN115322307A (en) * | 2022-09-05 | 2022-11-11 | 李娜 | Polycarboxylic acid high-performance water reducing agent and preparation method thereof |
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