聚羧酸系高效减水剂的研究现状和应用前景

高效减水剂的研究已成为混凝土材料科学中的一个重要分支,并推动混凝土材料向高强、高性能化不断发展,其中聚羧酸系高效减水荆是新一代绿色高效减水剂的代表.结合国内外资料综述了聚羧酸系高效减水刑的研究现状、性能特点、分散稳定机理以及今后的发展方向.指出对聚羧酸系高效减水剂的基础理论研究还有待进一步加强;开发、合成、生产多元化和不同性能的系列聚羧酸系减水荆母体、多功能的聚羧酸系减水剂衍生产品,已成为当今聚羧酸系高效减水荆发展的必然趋势.     

疏水烷基酯侧链对聚羧酸系减水剂分散及保坍性能的影响

为了研究聚羧酸系减水剂(PCA)分子结构中疏水侧链对新拌混凝土坍落度及其损失的影响,以马来酸酐(MA)、异戊烯醇聚氧乙烯醚(TPEG)和丙烯酸烷基酯为原料,过硫酸铵为引发剂,通过自由基聚合合成了4种不同疏水侧链长度(疏水侧链含碳个数分别为4、8、12和18)的聚羧酸系减水剂。通过水泥净浆流动度、流动性损失等指标检验了聚羧酸系减水剂的分散性能及保坍性能,结果表明随着疏水侧链长度的增加,聚羧酸系减水剂的分散性能逐渐提高,保坍性能有所改善。吸附量和zeta电位测试结果解释了这种现象的原因,随着疏水侧链长度的增加,水泥颗粒表面zeta电位绝对值逐渐增加,水泥颗粒表面上的持续吸附能力逐渐增强。     

聚羧酸类高效减水剂的研究进展

聚羧酸高效减水剂是高效减水剂的新品种，具有很多良好的使用性能。通过对近年来国内外的文献综合，讨论了反应单体，聚氧烷基链和端基的选择，聚合物相对分子质量及其分布，减水剂添加量等对减水剂性能的影响因素。     

聚羧酸系高性能减水剂的合成技术

介绍了国内外聚羧酸系高性能减水剂的研究发展现状、分子结构特征以及聚羧酸类高性能减水剂的合成方法,分析了聚羧酸系高效减水剂的不同合成技术的优缺点,认为制备具有聚合活性的大单体的技术是聚羧酸系高性能减水剂需要解决的紧迫问题,提出了聚羧酸系高性能减水剂的研究方向和研究过程面临的问题及解决措施.     

聚羧酸混凝土减水剂的研究现状与发展趋势

聚羧酸减水剂的研发和推广是混凝土材料科学中的一个研究热点,推动混凝土材料向高强、高性能化不断发展.结合国内外资料综述了聚羧酸系高效减水剂的研究现状、作用杌理、合成方法,分析了聚羧酸减水剂结构与性能的关系,总结了当前研究与应用中存在的主要问题,展望了今后的发展趋势.     

低收缩型混凝土用聚羧酸系减水剂的制备及性能

采用自由基共聚法,以苯乙烯磺酸钠(SS)和2-羟乙基乙烯基聚氧乙烯聚氧丙烯醚大单体(IPEG-PPG)为主要合成原料,并加入自制减缩组分(RS)共聚,制备了低收缩聚羧酸系减水剂(SRPC),通过凝胶渗透色谱、红外光谱和核磁共振测试分析了其相对分子质量及其分布以及特征官能团。测定了表面张力、对水泥颗粒吸附行为、混凝土自收缩及各项混凝土应用性能(减水率、含气量、抗压强度),并分析其吸附-降低表面张力的减缩机理。结果表明,当侧链接枝密度(EO∶PO)为3∶1,侧链长度为23且摩尔比RS∶SS∶IPEG-PPG=3∶0.6∶1时合成的聚羧酸系减水剂具有高减水性能且对混凝土具有低收缩的作用。     

超早强聚羧酸对低坍落度混凝土流变与气泡结构经时变化的影响

分别采用两种超长侧链聚羧酸减水剂与一种常规聚羧酸减水剂制备低坍落度混凝土,通过测试分析湿筛砂浆流动度、流变性、气泡结构参数以及三维重构气泡形态,对比研究了超长侧链聚羧酸减水剂对混凝土工作性能与气泡特征经时变化的影响.结果表明:低坍落度混凝土湿筛砂浆符合宾汉姆流体特征,流动度与屈服应力具有强线性相关性,减水剂种类对其影响较小,但超长侧链聚羧酸对砂浆流动度的经时保持作用明显弱于普通聚羧酸.超长侧链聚羧酸在砂浆中的引气数量和小孔径气泡占比均低于普通聚羧酸,并且超长侧链聚羧酸加速了砂浆中小孔径气泡向大孔径气泡的转变.CT三维重构试验直观地证实了砂浆中相邻小气泡聚并成大气泡现象的存在,超长侧链聚羧酸使得砂浆中气泡聚并发生的时间比普通聚羧酸更早.     

长侧链两性聚羧酸系减水剂对水泥早期水化的影响

考察了不同阳离子含量的长侧链两性聚羧酸系减水剂(APCs)对水泥早期水化的影响。结果表明,相较于纯阴离子型的普通聚羧酸系减水剂PCs,含阳离子的APCs能够加速水泥的水化,促进早期水化产物生成,从而提高水泥早期强度。当共聚物中阳离子的含量为10%时(APC-10),水泥浆体最快进入水化加速反应阶段。热重与扫描电镜的结果也证实,在相同的龄期内,掺APC-10的样品中生成更多的羟钙石和簇状水化产物。但随着阳离子含量的进一步增加,长侧链两性聚羧酸减水剂对水化的促进作用减弱甚至消失,试件的早期强度反而有所降低。     

聚羧酸型梳状共聚物超分散剂的构性关系研究

以聚氧乙烯甲基烯丙基二醚（APEO－n)，顺丁烯二酸酐（MAn)，苯乙烯（St)等为共聚单体，合成了一系列聚羧酸型梳状共聚物，研究了共聚物的结构，组成等对分散性能的影响，结果表明，接枝链的长度和密度影响超分散剂的性能，当接枝链长度为20－60，St%(mol%)为5％－20％时，分散性能良好。     

化学外加剂在低水泥浇注料中的作用机理与应用分析

分析了在低水泥浇注料中,由于微粉粒子在水中产生电离、吸附和晶格取代等现象导致其表面荷电形成双电层结构、微粉粒子产生絮凝的现象;阐述了化学外加剂对微粉粒子的分散作用机理,即DLVO理论和HVO理论;分别介绍了萘系(FDN)、脂肪族、氨基磺酸盐系、聚羧酸系高效减水剂的具体作用机理;分析了在低水泥浇注料中三聚磷酸钠、六偏磷酸钠、柠檬酸钠、密胺树脂、聚丙烯酸钠、氨基磺酸盐、聚羧酸系高效减水剂等化学外加剂的应用现状。认为聚羧酸系高效减水剂具有较好的减水效果,其生产与应用研究将越来越广泛和深入。     

Effects of the molecular architecture of comb-shaped superplasticizers on their performance in cementitious systems

The objective of this study is to link the molecular structure of polycarboxylate-ether-type superplasticizers with the performance of cementitious systems in order to develop new products with enhanced properties, e.g. improved water reduction with a wide range of cements or a reduced retardation of cement hydration. Different experimental superplasticizers have been synthesized varying length and density of the polyether chains as well as the molecular weight of the polymer. The influence of these polymers on the properties of cement pastes and mortars was determined using various characterization methods like mortar flow, rheological and calorimetric measurements, adsorption measurements and mortar compressive strength.Characteristic connections between molecular structure of the polycarboxylate-type water reducers, adsorption behaviour, workability and retarding effect have been determined allowing the synthesis of new superplasticizers with improved performance.     

Interaction of polycarboxylate-based superplasticizers with cements containing different C3A amounts

This parametric study links the molecular structure of a carboxylate-type of superplasticizer with their performance in cement pastes with different C₃A-contents. Beside the variation of the C₃A-content, the experimental synthesized superplasticizers have been varied by polyethylene-oxide side chain density and length. The connection between the superplasticizers, their effect on workability properties and retardation phenomenon and the dependency of C₃A-content in the cement paste has been investigated.The characteristic interaction phenomenons between different PCE-architectures and different C₃A-contents have been examined by calorimetric, rheological, adsorption, and zeta potential measurements. This study shows that with decreasing side chain density the PCE molecules adsorb stronger and thus, lower the yield stress of a cement paste by steric stabilization. It is also shown that PCE molecules with long side chains delaying the setting of the cement paste to less extend than PCE molecules with shorter side chains. Consequently, in terms of optimization of the molecular architecture, good workability can be achieved by addition of highly charged PCE with long side chains. The latter minimizes undesired retardation phenomena.     

Influence of superplasticizer type and mix design parameters on the performance of them in concrete mixtures

The use of superplasticizers in concrete manufacture was a milestone in the history of concrete, and this played a central role in the development of high strength and performance concrete. Superplasticizers are admixtures, which are added to concrete mixture in very small dosages. Their addition results in significant increase of the workability of the mixture, in reduction of water/cement ratio or even of cement quantity. Their performance depends on the type of the superplasticizer, the composition of the concrete mixture, the time of addition and the temperature conditions during mixing and concreting.Measurements of workability, slump loss, air content, as well as of strength development have been made to reach a conclusion about superplasticizers performance with the use of two kinds of aggregate: one natural (river) and one crushed limestone. Apart from this, it seems that the quantity of fines in a mixture influences the performance of superplasticizers.     

含聚氧乙烯链段的嵌段共聚物和接枝共聚物的合成及性能

综述了由聚氧乙烯链段与聚二烯烃、聚异丁烯、聚乙烯基吡啶、聚丙烯腈、聚丙烯酰胺或聚丙烯酸链段组成的各种嵌段共聚物及接枝共聚物的合成,并对其各种性能,包括两亲性质、络合碱金属离子性及微观相分离等进行了总结。     

马来酸酐在聚羧酸盐减水剂合成中的应用

随着聚羧酸盐减水剂的不断发展,马来酸酐在其合成中的应用也越来越多.根据马来酸酐与丙烯酸(以及甲基丙烯酸)各自的特性和聚羧酸盐减水剂合成的技术要求,分析了它们在合成过程中的作用和主要差别,并概述了马来酸酐在合成中的应用情况,最后提出了马来酸酐在合成中应用的几点建议.马来酸酐及其酯的分子结构和化学活性独特,应用于聚羧酸盐减水剂的合成必将有广阔的前景.     

The Effects of Side Chains on the Charge Mobilities and Functionalities of Semiconducting Conjugated Polymers beyond Solubilities

Recent decades have witnessed the rapid development of semiconducting polymers in terms of high charge mobilities and applications in transistors. Significant efforts have been made to develop various conjugated frameworks and linkers. However, studies are increasingly demonstrating that the side chains of semiconducting polymers can significantly affect interchain packing, thin film crystallinity, and thus semiconducting performance. Ways to modify the side alkyl chains to improve the interchain packing order and charge mobilities for conjugated polymers are first discussed. It is shown that modifying the branching chains by moving the branching points away from the backbones can boost the charge mobilities, which can also be improved through partially replacing branching chains with linear ones. Second, the effects of side chains with heteroatoms and functional groups are discussed. The siloxane‐terminated side chains are utilized to enhance the semiconducting properties. The fluorinated alkyl chains are beneficial for improving both charge mobility and air stability. Incorporating H bonding group side chains can improve thin film crystallinities and boost charge mobilities. Notably, incorporating functional groups (e.g., glycol, tetrathiafulvalene, and thymine) into side chains can improve the selectivity of field‐effect transistor (FET)‐based sensors, while photochromic group containing side chains in conjugated polymers result in photoresponsive semiconductors and optically tunable FETs.     

Improving Cooperative Interactions Between Halogenated Aromatic Additives and Aromatic Side Chain Acceptors for Realizing 19.22% Efficiency Polymer Solar Cells

Processing additive plays an important role in the standard operation procedures for fabricating top performing polymer solar cells (PSCs) through efficient interactions with key photovoltaic materials. However, improving interaction study of acceptor materials to high performance halogenated aromatic additives such as diiodobenzene (DIB) is a widely neglected route for molecular engineering toward more efficient device performances. In this work, two novel Y-type acceptor molecules of BTP-TT and BTP-TTS with different aromatic side chains on the outer positions are designed and synthesized. The resulting aromatic side chains significantly enhanced the interactions between the acceptor molecules and DIB through an arene/halogenated arene interaction, which improved the crystallinity of the acceptor molecules and induced a polymorph with better photovoltaic performances. Thus, high power conversion efficiencies (PCEs) of 18.04% and 19.22% are achieved in binary and ternary blend devices using BTP-TTS as acceptor and DIB as additive. Aromatic side chain engineering for improving additive interactions is proved to be an effective strategy for achieving much higher performance photovoltaic materials and devices.     

Design of High‐Mobility Diketopyrrolopyrrole‐Based π‐Conjugated Copolymers for Organic Thin‐Film Transistors

Since the report of the first diketopyrrolopyrrole (DPP)‐based polymer semiconductor, such polymers have received considerable attention as a promising candidate for high‐performance polymer semiconductors in organic thin‐film transistors (OTFTs). This Progress Report summarizes the advances in the molecular design of high‐mobility DPP‐based polymers reported in the last few years, especially focusing on the molecular design of these polymers in respect of tuning the backbone and side chains, and discussing the influences of structural modification of the backbone and side chains on the properties and device performance of corresponding DPP‐based polymers. This provides insights for the development of new and high‐mobility polymer semiconductors.     

不同梳状键接结构聚羧酸在高性能混凝土中的应用性能和作用机理

梳状结构聚羧酸具有优异的分子结构可设计性,为绿色混凝土的生态化、高性能化提供了理论基础和技术支撑。本研究以聚丙烯酸(PAA)、羟基甲氧基聚氧乙烯丙烯醚(HMPEPG)、氨基甲氧基聚氧乙烯丙烯醚(AMPEPG)为反应原料,根据酯化和酰胺化反应,分别设计合成了以酯基和酰胺键接主侧链的梳状结构聚羧酸(PCE),并通过红外光谱(IR)和分子量测试证明了分子结构符合预期设计。水泥净浆和混凝土应用性能结果表明,酯基键接聚羧酸的初始净浆流动度和混凝土早期强度更优,酰胺键接聚羧酸的净浆流动度保持能力和混凝土扩展度更优。二者的作用机理存在显著差异,酯基键接聚羧酸的吸附行为更稳定,更易快速成核水化,酰胺键接聚羧酸的表面张力更低,气-液界面取向能力更强。本研究合成的酯键和酰胺键两种方式连接主侧链的梳状结构聚羧酸可分别应用于高早强要求和高泵送要求的混凝土,具有较好的应用前景和推广价值。     

Effect of repeated dosages of superplasticizers on slump,strength and freeze-thaw resistance of concrete

Superplasticizers, when added to fresh concrete, cause large increases in its slump. However, this increase in slump is not sustained over long periods and within 60 minutes or so the concrete reverts to its original slump. In actual field applications of superplasticizers it may be necessary to add additional dosages to maintain the increased slump. This paper gives results of a laboratory investigation to determine the effect of repeated dosages of superplasticizers on workability, strength and durability of concrete. A series of air-entrained concrete mixes was made at a water/ cement ratio of 0.42 with a slump of 50 mm. Four commonly available superplasticizers were repeatedly added to the concrete, at the manufacture's recommended dosage rates, after completion of initial mixing. This was followed by additional mixing for 2 minutes. The properties of the fresh concrete were determined and test cylinders were cast after the addition of each dosage. Test prisms were also cast for strength and durability studies after the addition of the last dosage. The test results indicate that large increases in slumps of superplasticized concretes can be maintained for several hours by the addition of a second dosage. Apart from one instance, the addition of the third dosage is not considered desirable. The repeated additions of sulphonated melamine- and naphthalene-based superplasticizers caused substantial loss in entrained air content of the concrete; however, for concrete incorporating the lignosulphonate based superplasticizer, the reverse was true. The loss of entrained air adversely affected the performance of the concrete in freeze-thaw tests.