CN101817657A - Polycarboxylic acid slump retaining agent - Google Patents

Polycarboxylic acid slump retaining agent Download PDF

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Publication number
CN101817657A
CN101817657A CN200910009492A CN200910009492A CN101817657A CN 101817657 A CN101817657 A CN 101817657A CN 200910009492 A CN200910009492 A CN 200910009492A CN 200910009492 A CN200910009492 A CN 200910009492A CN 101817657 A CN101817657 A CN 101817657A
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Prior art keywords
agent
polycarboxylic acid
acid
concrete
structural formula
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CN200910009492A
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Inventor
田凤兰
段文锋
熊卫锋
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Beijing Oriental Yuhong Waterproof Technology Co Ltd
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Beijing Oriental Yuhong Waterproof Technology Co Ltd
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Priority to CN200910009492A priority Critical patent/CN101817657A/en
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688Copolymers containing at least three different monomers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641Polyacrylates; Polymethacrylates
    • C04B24/2647Polyacrylates; Polymethacrylates containing polyether side chains
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/308Slump-loss preventing agents

Abstract

The invention aims at preparing a novel additive for cement, mortar and concrete, which is composed of polycarboxylic acid super plasticizers resulted from partial crosslinking polymerization of monomers in structural formulas 1, 2. The product can prominently improve the slump retaining ability of traditional concrete water reducer while enhancing the dispersion ability thereof, and the setting time of the concrete is not prolonged. The product is suitable for the preparation of high-flow concrete required for long-range transportation. The product can be prepared according to the following method: the monomers in structural formulas 1, 2 are partially crosslinking-polymerized, and a reaction medium is then added with initiator and chain transfer agent for the preparation in a manner of free radical polymerization reaction. The product can be slowly hydrolyzed by alkaline hydration products in cement paste, carboxylate ions capable of being anchored on the surface of cement particles are gradually released, and flowability of the concrete can be enhanced prominently as the number of the carboxylate ions in cement grout increases. Aiming at the current situation that the cement in our country has various types and complex admixtures, the product solves the problem of inferior suitability of the additive and the cement effectively.

Description

Polycarboxylic acid slump retaining agent
Technical field:
The present invention relates to functional type concrete admixture field, particularly a kind of preparation method of new sustained release type poly carboxylic acid slump retaining agent.
Background technology:
At the modern concrete building field, along with the raising of high span bridge, skyscraper and various Hydraulic and Hydro-Power Engineering to the concrete performance requirement, and the fast development of commerical ready-mixed concrete and concrete construction process change rapidly, all promoted the develop rapidly of concrete admixture technology.At present, concrete admixture has become most important component in the concrete, and habitually is referred to as concrete industry " salt ".Poly carboxylic acid series admixture is the new concrete admixture that fast development is in recent years got up, such admixture has the characteristics of good water solubility, stable performance, add in the concrete as water reducer, can under the very little situation of consumption, play significant dissemination, and this dissemination also can obviously not reduce along with the prolongation of time, and promptly showing preferably, the slump keeps performance.And can be under the condition that keeps concrete workability and high workability, it is minimum that concrete water cement ratio is reduced to, thereby greatly improve concrete ultimate compression strength.But; because the cement type of China is various; Additive is extremely complicated, therefore, and in concrete actual use; problems such as the slump is big through time loss, bleeding segregation appear through regular meeting; though and the polycarboxylate dehydragent water-reducing rate is very high, dispersion effect is splendid, because of its volume low; to cement, sand, building stones comparatively responsive (as: silt content in the sandstone can greatly increase the poly carboxylic acid adsorptive capacity), equally the too fast problem of slump-loss can appear in some cases.Therefore, studying the concrete slump retaining agent that has controlled absorption and can slowly discharge in the hydrated cementitious environment has great importance.
At present, Japan and American-European many based on vinylformic acid and maleic anhydride to the research that gathers carboxylic class acid water reducer, and how synthetic in solvent-based system, as JP2007-200342, JP2005-131355, JP11-209124, JP09-336737.Its complex process, the production cycle is long, is not suitable for applying.Domestic also have many correlative study reports to polycarboxylic acids dehydragent, as CN 1326794C, CN1944477A etc., these prior aries or in polymer molecular chain, introduce the unsaturated polyether side chain and sulfonic group or in polymer molecular chain, introduce polyester and sulfonic group, the adhesive aggregation type is bigger, and stability and adaptive faculty are relatively poor.Simultaneously because China's cement type is various, Additive is complicated, also standard not to the utmost of relevant cement standard, therefore, in actual use, through regular meeting occur that slump-loss is too fast, time of coagulation is oversize, to phenomenons such as sandstone material mass-sensitives.
CN 101050255A has introduced a kind of preparation method of the co-poly carboxylic acid class efficient cement water reducing agent with the polyalkylene glycol ethers side chain, it has introduced carboxylic acid group, carboxylic acid ester groups, sulfonic group and polyalkylene glycol ethers side chain simultaneously in polymer molecular chain, advantage is polymer architecture than horn of plenty, overcomes single by small molecules carboxylic acid and prepared polycarboxylate water-reducer slow setting and the too fast problem of slump-loss of poly-alkoxy glycol ether to a certain extent.But it fails further to solve the adaptability problem of polycarboxylate water-reducer, and the problem of the rapid variation of performance still can take place along with the variation of cement kind, Additive kind and consumption in actual use.
CN1667009A has introduced a kind of preparation method of carboxylic acids graft copolymer concrete strengthening agent, this material is by monoalkyl polyethers or two hydroxy polyethers and binary unsaturated carboxylic acid or acid anhydrides the medium reaction to take place under acid anhydrides catalyzer condition to generate the big monomer of band C=C and then carry out copolymerization and form, though this material can solve the too fast problem of concrete slump loss that is mixed with traditional water reducers such as naphthalene system to a certain extent, but still can not overcome this problem fully.
Summary of the invention:
The present invention is intended to prepare a kind of new sustained release type poly carboxylic acid slump retaining agent that is used for cement, mortar and concrete.Compare with traditional polycarboxylate dehydragent, the prepared polycarboxylate superplasticizer of the present invention had both overcome long shortcoming of external polycarboxylate dehydragent complex process, production cycle, and adopt partial cross-linked technology that adsorption group is carried out end-blocking, playing the effect of slowly-releasing, thereby improved the problem of conventional concrete admixture and inferior suitability to a great extent.
The invention provides the crosslinked polycarboxylic acid concrete slump retaining agent of a kind of slow release type, it is characterized in that forming by the crosslinked post polymerization gained of the monomer segment of following structural formula polycarboxylic acid super-plasticizer:
Structural formula 1
Figure B200910009492XD0000031
Wherein: R 1Be hydrogen atom or C 1-3Alkyl, R 2Be hydrogen atom, alkali metal cation, ammonium or C 1-4Aliphatic alkyl;
Structural formula 2
Figure B200910009492XD0000032
Wherein: R 3Be hydrogen atom or C 1-3Aliphatic alkyl, R 4Be C 1-3Aliphatic alkyl, A is C 2-4Alkylidene group, n=15-100.
Wherein structural formula 1 and structural formula 2 monomer mole ratios are 1: 0.5~2.
In the molecular structure of the polycarboxylic acid super-plasticizer of the crosslinked polycarboxylic acid concrete slump retaining agent of described slow release type, further contain following structural unit
Structural formula 3
Figure B200910009492XD0000033
R wherein 5Be C 1-5Alkyl
R 6Be H or CH 3
The unitary content of calculating described structural formula 3 by weight percentage is 0~80% of polycarboxylic acid super-plasticizer.
The present invention also provides the preparation method of the crosslinked polycarboxylic acid concrete slump retaining agent of described slow release type, comprises following processing step:
A. exist the lower section crosslinked at linking agent structural formula 1 and 2 monomers, wherein, linking agent is monoene propyl diester or methylallyl ester or its salt that contains the unsaturated dicarboxylic acid of 2 end carboxyls.In reactor, add a certain amount of deionized water, when temperature reaches 70~100 ℃, the mixing solutions of adding formula 1 and formula 2 and the linking agent that accounts for mixing solutions total mass 0.03~0.7%, reaction 1~3h;
B. deionized water is made monomer solution with methacrylic acid or acrylamide and after even transfer agent mixes;
C. in 3h~5h, respectively the initiator solution of step b gained monomer solution and monomer solution total mass 0.03~0.1% is added dropwise in the reactor, dropwises, and then insulation reaction 1~2h; Obtain cross-linking copolymer;
D. step c gained solution and additive compound are obtained the crosslinked polycarboxylic acid concrete slump retaining agent of slow release type.
Wherein linking agent is monoene propyl diester or methylallyl ester or its salt of unsaturated dicarboxylic acid.
Wherein said unsaturated dicarboxylic acid is selected from: toxilic acid, maleic anhydride, methylene-succinic acid, fumaric acid, toxilic acid monoene propyl ester
Wherein said auxiliary agent comprises defoamer, air entrapment agent, retardant and hardening accelerator and acceleration curing agent.
Wherein said defoamer is the water-soluble poly ether defoaming agent, and retardant is a Sunmorl N 60S.
The prepared sustained-release polycarboxylic slump retaining agent of the present invention is faint yellow to red-brown clear liquid, and system viscosity increases along with the increase of concentration.
The prepared sustained-release polycarboxylic slump retaining agent of the present invention is high-strength in preparation, when high performance concrete, pump concrete, chutable concrete, self-compacting concrete, have superior slump hold facility and to the adaptability of cement.
Embodiment:
Following examples will be carried out concrete description to the present invention from chemosynthesis and two aspects of concrete performance test, but the present invention not produced any restriction.In following examples, except as otherwise noted, all umbers are weight fraction, and percentage ratio is weight percentage.
Molecular weight described in the embodiment is the weight-average molecular weight that reference material is measured with the polyoxyethylene glycol for using gel chromatography.
Synthetic embodiment 1
Disposing agitator, thermometer, the deionized water that adds 50 weight parts in the 1000ml round-bottomed flask of reflux condensing tube and tear drop device, be heated with stirring to 80 ℃, to be mixed with the methoxy polyoxyethylene methacrylic ester of 300 weight parts then, 26.1 the toxilic acid monoene propyl ester of part methacrylic acid and 40 mass parts carries out crosslinking reaction, reaction 2h, adding 1.83 weight part 3-thiohydracrylic acids and 100 parts by weight of deionized water and 5.2 weight part methacrylic acids after reaction finishes is mixed with monomer solution and is mixed with 1.02 weight part ammonium persulphates, the initiator solution of 30 parts by weight of deionized water dropwises in 3 ± 0.5h and 4 ± 0.5h respectively, and insulation is 1 hour under same temperature.After dropwising, cool, treat that temperature reduces to below 40 ℃, when becoming clear, the NaOH solution with 30% is neutralized to neutrality to solution, at last system is diluted to 20% by muddy.Obtain copolymer 1 of the present invention thus, its weight-average molecular weight is 25000.
Synthetic embodiment 2
Disposing agitator, thermometer, the deionized water that adds 50 weight parts in the 1000ml round-bottomed flask of reflux condensing tube and tear drop device, be heated with stirring to 80 ℃, to be mixed with the methoxy polyoxyethylene methacrylic ester of 200 weight parts and the polyoxyethylene glycol allyl ethers of 100 total amount parts then, 26.1 the toxilic acid monoene propyl ester of weight part methacrylic acid and 40 mass parts carries out crosslinking reaction, reaction 2h, after finishing, reaction adds 1.83 weight part 3-thiohydracrylic acids and 100 parts by weight of deionized water, 5.2 the monomer solution of weight part methacrylic acid preparation and be mixed with 1.02 weight part ammonium persulphates, the initiator solution of 30 parts by weight of deionized water dropwises in 3 ± 0.5h and 4 ± 0.5h respectively, and insulation is 1 hour under same temperature.After dropwising, cool, treat that temperature reduces to below 40 ℃, when becoming clear, the NaOH solution with 30% is neutralized to neutrality to solution, at last system is diluted to 20% by muddy.Obtain copolymer 1 of the present invention thus, its weight-average molecular weight is 18500.
Synthetic embodiment 3
Disposing agitator, thermometer, the deionized water that adds 50 weight parts in the 1000ml round-bottomed flask of reflux condensing tube and tear drop device, be heated with stirring to 80 ℃, to be mixed with the methoxy polyoxyethylene methacrylic ester of 150 weight parts and the polyoxyethylene glycol allyl ethers of 150 total amount parts then, 26.1 the toxilic acid monoene propyl ester of weight part methacrylic acid and 40 mass parts carries out crosslinking reaction, reaction 2h, after finishing, reaction adds 1.83 weight part 3-thiohydracrylic acids and 100 parts by weight of deionized water, 3.5 the weight part methacrylic acid is prepared monomer solution and is mixed with 1.02 weight part ammonium persulphates, the initiator solution of 30 parts by weight of deionized water dropwises in 3 ± 0.5h and 4 ± 0.5h respectively, and insulation is 1 hour under same temperature.After dropwising, cool, treat that temperature reduces to below 40 ℃, when becoming clear, the NaOH solution with 30% is neutralized to neutrality to solution, at last system is diluted to 20% by muddy.Obtain copolymer 1 of the present invention thus, its weight-average molecular weight is 22500.
Synthetic embodiment 4
Disposing agitator, thermometer, the deionized water that adds 50 weight parts in the 1000ml round-bottomed flask of reflux condensing tube and tear drop device, be heated with stirring to 80 ℃, to be mixed with the methoxy polyoxyethylene methacrylic ester of 75 weight parts and the polyoxyethylene glycol allyl ethers of 225 total amount parts then, the toxilic acid monoene propyl ester of 35 weight part methacrylic acids and 25 weight parts carries out crosslinking reaction, reaction 2h, after finishing, reaction adds 2.0 weight part 3-thiohydracrylic acids and 100 parts by weight of deionized water, 7.8 the monomer solution of weight part methacrylic acid preparation and be mixed with 1.52 weight part ammonium persulphates, the initiator solution of 30 parts by weight of deionized water dropwises in 3 ± 0.5h and 4 ± 0.5h respectively, and insulation is 1 hour under same temperature.After dropwising, cool, treat that temperature reduces to below 40 ℃, when becoming clear, the NaOH solution with 30% is neutralized to neutrality to solution, at last system is diluted to 20% by muddy.Obtain copolymer 1 of the present invention thus, its weight-average molecular weight is 18500.
Synthetic embodiment 5
Disposing agitator, thermometer, the deionized water that adds 50 weight parts in the 1000ml round-bottomed flask of reflux condensing tube and tear drop device, be heated with stirring to 80 ℃, to be mixed with the polyoxyethylene glycol allyl ethers of 300 total amount parts then, the toxilic acid monoene propyl ester of 35 weight part methacrylic acids and 25 weight parts carries out crosslinking reaction, reaction 2h, after finishing, reaction adds 2.0 weight part 3-thiohydracrylic acids and 100 parts by weight of deionized water, 5.2 the weight part methacrylic acid is mixed with monomer solution and is mixed with 1.52 weight part persulfuric acid acid ammonium, the initiator solution of 30 parts by weight of deionized water dropwises in 3 ± 0.5h and 4 ± 0.5h respectively, and insulation is 1 hour under same temperature.After dropwising, cool, treat that temperature reduces to below 40 ℃, when becoming clear, the NaOH solution with 30% is neutralized to neutrality to solution, at last system is diluted to 20% by muddy.Obtain copolymer 1 of the present invention thus, its weight-average molecular weight is 29500.

Claims (9)

1. crosslinked polycarboxylic acid concrete slump retaining agent of slow release type is characterized in that being made up of the crosslinked post polymerization gained of the monomer segment of following structural formula polycarboxylic acid super-plasticizer:
Structural formula 1
Figure F200910009492XC0000011
Wherein: R 1Be hydrogen atom or C 1-3Alkyl, R 2Be hydrogen atom, alkali metal cation, ammonium or C 1-4Aliphatic alkyl;
Structural formula 2
Figure F200910009492XC0000012
Wherein: R 3Be hydrogen atom or C 1-3Aliphatic alkyl, R 4Be C 1-3Aliphatic alkyl, A is C 2-4Alkylidene group, n=15-100.
2. the crosslinked polycarboxylic acid concrete slump retaining agent of slow release type according to claim 1 is characterized in that structural formula 1 and structural formula 2 monomer mole ratios are 1: 0.5~2.
3. as the crosslinked polycarboxylic acid concrete slump retaining agent of slow release type as described in the right 1, it is characterized in that, in the molecular structure of polycarboxylic acid super-plasticizer, further contain following structural unit
Structural formula 3
R wherein 5Be C 1-5Alkyl
R 6Be H or CH 3
4. as the crosslinked polycarboxylic acid concrete slump retaining agent of slow release type as described in the right 1, the unitary content that it is characterized in that calculating by weight percentage described structural formula 3 is 0~80% of polycarboxylic acid super-plasticizer.
5. as the preparation method of the crosslinked polycarboxylic acid concrete slump retaining agent of slow release type as described in the right 1, comprise following processing step:
A. exist the lower section crosslinked at linking agent structural formula 1 and 2 monomers, wherein, linking agent is monoene propyl diester or methylallyl ester or its salt that contains the unsaturated dicarboxylic acid of 2 end carboxyls.In reactor, add a certain amount of deionized water, when temperature reaches 70~100 ℃, the mixing solutions of adding formula 1 and formula 2 and the linking agent that accounts for mixing solutions total mass 0.03~0.7%, reaction 1~3h;
B. deionized water is made monomer solution with methacrylic acid or acrylamide and after even transfer agent mixes;
C. in 3h~5h, respectively the initiator solution of step b gained monomer solution and monomer solution total mass 0.03~0.1% is added dropwise in the reactor, dropwises, and then insulation reaction 1~2h; Obtain cross-linking copolymer;
D. step c gained solution and additive compound are obtained the crosslinked polycarboxylic acid concrete slump retaining agent of slow release type.
6. preparation method as claimed in claim 5, wherein linking agent is monoene propyl diester or methylallyl ester or its salt of unsaturated dicarboxylic acid.
7. preparation method as claimed in claim 5, wherein said unsaturated dicarboxylic acid is selected from: toxilic acid, maleic anhydride, methylene-succinic acid, fumaric acid, toxilic acid monoene propyl ester
8. preparation method as claimed in claim 5, wherein said auxiliary agent comprises defoamer, air entrapment agent, retardant and hardening accelerator and acceleration curing agent.
9. preparation method as claimed in claim 8, wherein said defoamer is the water-soluble poly ether defoaming agent, retardant is a Sunmorl N 60S.
CN200910009492A 2009-02-26 2009-02-26 Polycarboxylic acid slump retaining agent Pending CN101817657A (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102173635A (en) * 2010-12-17 2011-09-07 上海华联建筑外加剂厂有限公司 Polycarboxylic acid high-slump-retaining zero-bleeding high-performance water reducing agent
CN102390950A (en) * 2011-07-29 2012-03-28 北京建筑工程学院 Slow-release type polycarboxylate slump-retaining agent and preparation method thereof
EP2644578A1 (en) 2012-03-30 2013-10-02 Technische Universität München Copolymer for dispersant for cement, dispersant for cement, and cement composition
WO2014059765A1 (en) * 2012-10-18 2014-04-24 江苏博特新材料有限公司 Super plasticizer for precast concrete component
CN103923276A (en) * 2014-04-28 2014-07-16 中海油能源发展股份有限公司惠州石化分公司 Method for synthesizing polyether-type polycarboxylate water reducer
CN104261722A (en) * 2014-10-10 2015-01-07 科之杰新材料集团有限公司 Polycarboxylate slump retaining agent and preparation method thereof
JP2015516480A (en) * 2012-03-30 2015-06-11 テクニシェ ユニバーシタット ミュンヘン Concrete admixture
CN106365493A (en) * 2015-07-23 2017-02-01 南京理工大学 Plasticity-retention and mud-resistance type dispersing agent and preparation method thereof
CN106519140A (en) * 2016-11-15 2017-03-22 湖北工业大学 Delayed-release alkali-resistant polycarboxylic acid slump retaining agent master batch
CN106699985A (en) * 2016-11-15 2017-05-24 湖北工业大学 Super-long super slow release type polycarboxylic acid slump-retaining agent master batch
CN108249807A (en) * 2018-01-15 2018-07-06 江苏苏博特新材料股份有限公司 A kind of new polycarboxylic acid water reducer, preparation method and application
CN109956701A (en) * 2017-12-22 2019-07-02 中国铁道科学研究院集团有限公司铁道建筑研究所 A kind of non-fragment orbit Workability of Self-compacting Concrete retention agent and preparation method thereof
CN113135686A (en) * 2021-04-25 2021-07-20 重庆富普新材料有限公司 Ultra-long slump retaining type polycarboxylic acid pumping agent and preparation method thereof

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102173635A (en) * 2010-12-17 2011-09-07 上海华联建筑外加剂厂有限公司 Polycarboxylic acid high-slump-retaining zero-bleeding high-performance water reducing agent
CN102173635B (en) * 2010-12-17 2013-03-20 上海华联建筑外加剂厂有限公司 Polycarboxylic acid high-slump-retaining zero-bleeding high-performance water reducing agent
CN102390950A (en) * 2011-07-29 2012-03-28 北京建筑工程学院 Slow-release type polycarboxylate slump-retaining agent and preparation method thereof
JP2015516480A (en) * 2012-03-30 2015-06-11 テクニシェ ユニバーシタット ミュンヘン Concrete admixture
US9328022B2 (en) 2012-03-30 2016-05-03 Nippon Shokubai Co., Ltd. Copolymer for dispersant for cement, dispersant for cement, and cement composition
WO2013144332A1 (en) 2012-03-30 2013-10-03 Technische Universität München Copolymer for dispersant for cement, dispersant for cement, and cement composition
EP2644578A1 (en) 2012-03-30 2013-10-02 Technische Universität München Copolymer for dispersant for cement, dispersant for cement, and cement composition
WO2014059765A1 (en) * 2012-10-18 2014-04-24 江苏博特新材料有限公司 Super plasticizer for precast concrete component
CN103923276A (en) * 2014-04-28 2014-07-16 中海油能源发展股份有限公司惠州石化分公司 Method for synthesizing polyether-type polycarboxylate water reducer
CN104261722B (en) * 2014-10-10 2016-06-29 科之杰新材料集团有限公司 A kind of polycarboxylic acid slump retaining agent and preparation method thereof
CN104261722A (en) * 2014-10-10 2015-01-07 科之杰新材料集团有限公司 Polycarboxylate slump retaining agent and preparation method thereof
CN106365493A (en) * 2015-07-23 2017-02-01 南京理工大学 Plasticity-retention and mud-resistance type dispersing agent and preparation method thereof
CN106519140A (en) * 2016-11-15 2017-03-22 湖北工业大学 Delayed-release alkali-resistant polycarboxylic acid slump retaining agent master batch
CN106699985A (en) * 2016-11-15 2017-05-24 湖北工业大学 Super-long super slow release type polycarboxylic acid slump-retaining agent master batch
CN109956701A (en) * 2017-12-22 2019-07-02 中国铁道科学研究院集团有限公司铁道建筑研究所 A kind of non-fragment orbit Workability of Self-compacting Concrete retention agent and preparation method thereof
CN108249807A (en) * 2018-01-15 2018-07-06 江苏苏博特新材料股份有限公司 A kind of new polycarboxylic acid water reducer, preparation method and application
CN108249807B (en) * 2018-01-15 2020-10-23 江苏苏博特新材料股份有限公司 Polycarboxylate superplasticizer, and preparation method and application thereof
CN113135686A (en) * 2021-04-25 2021-07-20 重庆富普新材料有限公司 Ultra-long slump retaining type polycarboxylic acid pumping agent and preparation method thereof

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Application publication date: 20100901