CN101734879B - 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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- CN101734879B CN101734879B CN2009103123568A CN200910312356A CN101734879B CN 101734879 B CN101734879 B CN 101734879B CN 2009103123568 A CN2009103123568 A CN 2009103123568A CN 200910312356 A CN200910312356 A CN 200910312356A CN 101734879 B CN101734879 B CN 101734879B
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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
-
- 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
-
- 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
-
- 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)
- Polyurethanes Or Polyureas (AREA)
- Curing Cements, Concrete, And Artificial Stone (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; Like 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 is claimed 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 wc, 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 superior to 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 superior to 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 mechanical property and the engineering use technology etc. of relevant fresh concrete serviceability and maturing 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 TEB 3K 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, and equipment requirements is high, 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 T 46155 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 compound 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 practical application; The consistency of poly carboxylic acid and polyoxyethylene glycol is bad, and 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, and water-reducing rate is high, 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 through 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 sulfite anhy 96 blocked polyurethane, and described polyacrylic ester contains hydroxyl and carboxyl; The reaction of grafting unblocked takes place 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 ABVN or Diisopropyl azodicarboxylate
The preparation method of water reducer of the present invention may further comprise the steps:
(1) Preparation of Emulsion-terminated polyurethane: first polyisocyanate, a polyol, a hydrophilic monomer, and a chain extender at a temperature of 60 to 100 ° C, the reaction of 2 to 4 hours to prepare a polyurethane prepolymer, then add sodium bisulfite blocking agent, the reaction temperature is 60 to 100 ° C, reaction time is 1 to 2 hours to prepare a blocked polyurethane, and finally deionized water was prepared capped polyurethane emulsion;
(2) preparation polyacrylate emulsion: 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 emulsion;
(3) the end-sealed type polyaminoester emulsion is mixed with polyacrylate emulsion and initiator, join in the concrete of the state of mixing and stirring, the reaction of grafting unblocked takes place, obtain with urethane as graft side chain cross-linking type multipolymer.
The described POLYMETHYLENE POLYPHENYLISOCYANATE of step (1) is selected from TDI, MDI, HDI, IPDI or TMXDI; Said polyvalent alcohol has the pure and mild polyether glycol of polyester polyols, and molecular weight is 400～1000; Said hydrophilic monomer chain extender is a dimethylol propionic acid.
The described acrylic ester monomer mixture of step (2) is TEB 3K (MMA), Bing Xisuandingzhi (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 ABVN or Diisopropyl azodicarboxylate, and its consumption accounts for 0.1%～0.2% of described polymkeric substance total amount.
Step (2) Preparation of seed emulsion, and the reaction temperature of the emulsion polyacrylate is 60 ~ 100 ° C, and the reaction time is 2 to 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 is in the Concrete Construction process; Its end-sealed type urethane utilizes the hydration heat of cement that the unblocked reaction can take place 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 such as the sulfonic group introduced more in the past, polyoxyethylene groups is compared, and 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 dispersivity, and concrete slump loss is little.The bleed of urethane side chain, infilling and polymkeric substance and hydrated cementitious product run through each other, 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 explain the present invention rather than to further qualification of the present invention.
Embodiment 1:
(1) preparation of end-sealed type polyaminoester emulsion
Basic recipe:
| Isophorone diisocyanate (IPDI) | 40g |
| W 166 (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 W 166 (molecular weight 400), stir, reaction 2h under 70～75 ℃ temperature condition; 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 sulfite anhy 96 end-sealed type polyaminoester emulsion.
(2) preparation of polyacrylic ester
Basic recipe:
| TEB 3K (MMA) | 20g |
| Bing Xisuandingzhi (BA) | 80g |
| Vinylformic acid (AA) | 10g |
| 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 propenoate 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 propenoate 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, and PH is between 8～9 in adjustment.
(3) taking mass ratio is 7: 3 above-mentioned two kinds of polymkeric substance and the ABVN that accounts for polymkeric substance total amount 0.2%, joins in the concrete mortar that is mixing and stirring, and can in concrete mortar, obtain urethane/gather carboxylic concrete composite water-reducing agent.
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 |
| ETHYLE ACETATE | 23.0g |
| 35%NaHSO3 solution | 13g |
| Acetone | 18g |
Concrete preparation method is with the step (1) of embodiment 1
(2) vinyl resin of synthetic hydroxyl
Basic recipe:
| TEB 3K (MMA) | 24g |
| Bing Xisuandingzhi (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 ABVN that accounts for polymkeric substance total amount 0.3%, joins in the concrete mortar that is mixing and stirring, and can in concrete mortar, obtain urethane/gather carboxylic concrete composite water-reducing agent.
Embodiment 3:
(1) synthetic blocked polyurethane
Basic recipe:
| Diphenylmethanediisocyanate (MDI) | 21g |
| Polycaprolactone (molecular weight 800, dry) | 98g |
| Dimethylol propionic acid (DMPA) | 6.5g |
| ETHYLE ACETATE | 17.0g |
| 35%NaHSO3 solution | 9.0g |
| Acetone | 18.0g |
Concrete preparation method is with the step (1) of embodiment 1
(2)) vinyl resin of synthetic hydroxyl
Basic recipe:
| TEB 3K (MMA) | 20g |
| Bing Xisuandingzhi (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 ABVN that accounts for polymkeric substance total amount 0.1%, joins in the concrete mortar that is mixing and stirring, and can in concrete mortar, obtain urethane/gather carboxylic concrete composite water-reducing agent.
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 through 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 each item performance of the synthetic embodiment of institute 1～4.Making the initial slump through 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 (8)
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 sulfite anhy 96 blocked polyurethane, and described polyacrylic ester contains hydroxyl and carboxyl; The reaction of grafting unblocked takes place in described water reducer mixed emulsion 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 ABVN 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 POLYMETHYLENE POLYPHENYLISOCYANATE, polyvalent alcohol, hydrophilic monomer chain extender under 60～100 ℃ temperature; React and made polyurethane prepolymer in 2～4 hours; Add the sodium sulfite anhy 96 end-capping reagent again, temperature of reaction is 60～100 ℃, and the 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 emulsion: 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 emulsion; Described acrylic ester monomer mixture is TEB 3K, Bing Xisuandingzhi, 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; The described initiator of step (2) is a Potassium Persulphate;
(3) the end-sealed type polyaminoester emulsion is mixed with polyacrylate emulsion and initiator, join in the concrete of the state of mixing and stirring, the reaction of grafting unblocked takes place, obtain with urethane as graft side chain cross-linking type multipolymer; The described initiator of step (3) is ABVN or Diisopropyl azodicarboxylate.
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 POLYMETHYLENE POLYPHENYLISOCYANATE of step (1) is selected from TDI, MDI, HDI, IPDI or TMXDI; Said polyvalent alcohol has the pure and mild polyether glycol of polyester polyols, and molecular weight is 400～1000; Said 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 is characterized in that, described initiator ABVN of step (3) or Diisopropyl azodicarboxylate, and its consumption accounts for 0.1%～0.2% of polymkeric substance total amount.
8. 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 emulsion temperature are 60～100 ℃ in the step (2), and the reaction times is 2～4 hours.
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| CN102351998B (en) * | 2011-07-11 | 2012-11-07 | 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 |
| CN105036595B (en) * | 2015-07-30 | 2017-05-24 | 新疆德蓝股份有限公司 | High-liquidity polycarboxylic acid water reducing agent and preparation method thereof |
| CN106117460B (en) * | 2016-08-26 | 2018-09-28 | 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 |
| 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 |
| CN112175148B (en) * | 2020-09-22 | 2022-07-08 | 德州中科新材料有限公司 | Crosslinking type early-strength carboxylic acid water reducing agent, and preparation method and application thereof |
| CN112390927A (en) * | 2020-10-30 | 2021-02-23 | 武汉善达化工有限公司 | Retarder for refractory material |
| CN112456992B (en) * | 2021-02-03 | 2021-07-06 | 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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