The State-of-the-art Synthesis Techniques of Polycarboxylate Superplasticizer
SHA Shengnan, SHI Caijun, XIANG Shuncheng, JIAO Dengwu
Key Laboratory for Green & Advanced Civil Engineering Materials and Application Technology of Hunan Province, College of Civil Engineering, Hunan University, Changsha 410082
Abstract: Polycarboxylate superplasticizers (PCE) has become an indispensable component of high-performance or ultra-high performance concrete, owing to its low dosage, high water reducing rate (>40%), significant positive effects on the workability, mechanical and durability properties of concrete. PCE. is usually composed of a backbone containing anionic groups (like carboxyl group, sulfonic acid group and phosphate group) and grafted side chains with neutral charge. The anionic groups are adsorbed on the surface of cement particles, providing the electrosta-tic repulsion forces, while the PEO-grafted side chains extend from the cement particle surface into the pore solution to create steric hindrance forces. The synergistic effects of the two forces break down the flocculated clusters and improve the dispersion of cement paste. Diverse modified PCE with different side chains, grafting density, anchoring functional group and length of backbone show various effects and can be employed by concrete with different demand in performance. However, with the continuous raise in requirements of concrete performance and the decrease in quality of raw materials, the performance of PCE may be more sensitive to the mixture proportion parameters (cement type, w/c, etc.) and production conditions such as operating temperature and mixing time. The incompatibility between PCE with carboxyl and polyethylene oxide (PEO) side chains and cementitious materials is increasingly serious. Besides, with the increasing requirements of ultra-high performance concrete, a series of PCE with performances of shrinkage reduction, low viscosity and high slump retention have emerged as the times require. PCE can be primarily classified into two categories. One is polyester-type PCE, which made from α-methoxy poly (ethylene glycol) methacrylate ester (MPEG-MA) by aqueous free radical copolymerization or esterification/transesterification reaction. The other is polyether-type PCE, which is synthesize by free radical copolymerization in bulk or in aqueous solution with α-allyl-α-methoxy or α-hydroxy poly (ethylene glycol) (APEG) ether and maleic anhydride as key monomers, or copolymerization via isoprenyl oxy poly (ethylene glycol, acrylic acid, and α-methallyl-α-methoxy or α-hydroxy poly (ethylene glycol) ether. Polycarboxylate superplasticizer (PCE) features low dosage and high water reducing rate. Different functional groups of PCE exhibit different effects, for example, carboxylic groups show retarding effect and water reducibility, sulfonic groups exert dispersing effect, and hydroxyl groups retarding and soaking wetting effects, and polyethoxy groups present flowability retention capability. The water reducing rate and ability of delayed hydration inhibition of ester-PCE are slightly lower than that of ether-PCE. The method of free radical polymerization possesses easy process and mild synthesis conditions, nevertheless, it is difficult to control the synthetic products due to the irreversible reaction.While reversible addition-fragmentation chain transfer (RAFT) polymerization can prepare the block PCE with controlled molecular weight and narrow molecular weight distribution. In this article, the development of synthesis techniques of PCE is comprehensively reviewed from the aspects of raw materials, synthesis conditions, synthesis methods and post-processing. The impacts of these factors on the performance of PCE are discussed in detail. Finally, the development trend of PCE is also proposed.
作者简介: 沙胜男,2017年6月毕业于河南理工大学,获得理学学士学位。现为湖南大学土木工程学院博士研究生,在史才军教授的指导下进行研究。目前主要研究领域为聚羧酸的制备及其应用。史才军,国家第二批《千人计划》特聘专家、湖南省特聘专家、亚洲混凝土联合会副主席、湖南大学985工程创新平台首席科学家、特聘教授、中国建筑材料科学研究总院特聘教授、博士生导师,Taylor and Francis学术期刊Journal of Sustainable Cement-based Materials创刊主编, Journal of Ceramics in Modern Technologies共同主编、中国硅酸盐学会会刊《硅酸盐学报》副主编,Elsevier著名学术期刊Cement and Concrete Research和Cement and Concrete Composites、Construction and Building Materials、Taylor & Francis学术期刊Journal of Structural Integrity and Maintenance、西班牙Materiales de Construccion、《材料导报》、《建筑材料学报》、《重庆交通大学学报》及《中国水泥》等期刊编委。cshi@hnu.edu.cn
引用本文:
沙胜男, 史才军, 向顺成, 焦登武. 聚羧酸减水剂的合成技术研究进展[J]. 材料导报, 2019, 33(3): 558-568.
SHA Shengnan, SHI Caijun, XIANG Shuncheng, JIAO Dengwu. The State-of-the-art Synthesis Techniques of Polycarboxylate Superplasticizer. Materials Reports, 2019, 33(3): 558-568.
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2019, Vol. 33 
