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Star polymers (CD-POEGMAs and CD-PNIPAMs), and pseudo-graft polymer (PADMA-(CD-POEGMAs) x ) formed from PADMA with adamantyl(Ad) pendants and CD-POEGMAs by host–guest inclusion complexation were prepared and characterized. This work compared the thermoresponsive and self-assembly mechanisms of the POEGMAs as branches to that of PNIPAMs branched cyclodextrin cored star polymers. In contrast to CD-PNIPAMs which behaved abrupt and intensive dehydration process near its LCST, CD-POEGMAs exhibited thermally induced aggregation process with consecutive conformation changes during the temperature increase process, and gradually self-assembled into cyclodextrin centered aggregates with hydrophobic methacrylate backbone and dehydrated POEGMAs side chains. Moreover, this work provided a supramolecular method controlling and adjusting the thermoresponsive properties of pseudo-graft PADMA-(CD-POEGMAs) x formed from CD-POEGMAs and PADMA via inclusion complexation, which underwent a reversible thermally induced transition from micelle to nano-aggregates. Pseudo-graft PADMA-(CD-POEGMAs) x behaved gradually conformation changes as temperature rising, and self-assembled into aggregates with hydrophobic methacrylate backbone, residual Ads, and dehydrated POEGMAs side chains. [ABSTRACT FROM AUTHOR]

Poly(amino acid)-type macromolecules (PAAs), poly(ethylene glycol) -b- poly(aspartic acid) (PEG-PAAs), and poly(ethylene glycol)- b -poly(glutamic acid) (PEG-PGAs) were synthesized, and their states in aqueous solutions were studied. PEG-PAAs and PEG-PGAs were first used as novel polycarboxylate superplasticizers, and their dispersion and adsorption behaviors were investigated in cement slurries in the absence and presence of montmorillonite (MMT) clay. The results demonstrated that both PEG-PAAs and PEG-PGAs not only showed excellent water reducing and fluidity retention capabilities but also exhibited remarkable MMT clay tolerance. In contrast to the stretched molecular conformation of traditional polycarboxylate superplasticizers (PCEs), the hydrophobic main chain and the side methylene and ethylene linkers connected to the carboxylic groups of PAA and PGA segments resulted in self-assembly of the PEG-PAAs and PEG-PGAs in aqueous solutions, and the self-assembled nanosized aggregates exhibited relatively uniform spherical morphologies with average sizes of 30–100 nm. Carboxylic groups located on the periphery of the nanoaggregates acted as anchors and adsorbed on the surfaces of the cement particles. The nanoaggregates and the stretched hydrophilic PEG side chains, which jointly produced and enhanced the steric hindrance to prevent cement particle aggregation and hydration, resulted in notable dispersion capabilities. Total organic carbon (TOC), X-ray diffraction (XRD), and thermogravimetry–differential scanning calorimetry (TG-DSC) analyses revealed that the adsorption between the MMT clay and PAA nanoaggregates was surface adsorption (rather than interlayer adsorption), and this significant finding could be ascribed to the enlarged steric hindrance of the PAA nanoaggregates, which prevented the interlamination adsorption consumption of MMT clay to PAAs and revealed the outstanding clay insensitivity. This study provides a new perspective and strategy to design novel poly(amino acid)-type superplasticizers (PAAs) with excellent dispersion performances and improved clay tolerance. [Display omitted] • Poly(amino acid)-type superplasticizers (PAAs) with enhanced dispersing performance for cement doped with clay impurities. • The self-assembled nanoaggregates of PAAs enhanced steric hindrance and resulted in notable dispersion capabilities. • The enlarged steric hindrance of PAAs prevented interlamination adsorption and revealed outstanding clay insensitivity. [ABSTRACT FROM AUTHOR]