Structure-property relationships for polycarboxylate ether superplasticizers by means of RAFT polymerization

Polycarboxylate ether (PCE) comb-copolymers are widely used as water reducing agents in the concrete industry while maintaining a high fluidity via the polymer adsorption to the cement particles. PCE copolymers with a broad range of structures are well established by Free radical polymerization, however, understanding the structure-property relationship is still complex due to the high polydispersity of PCE copolymers prepared by conventional polymerization. The influence of different structural parameters using well-defined polymeric structures is yet to be explored.

In this study, two different types of comb-like random copolymers, namely polycarboxylate ether (PCE; poly(oligo(ethylene glycol) methyl ether methacrylate/methacrylic acid)) and polysulfonate ether (PSE; poly(oligo(ethylene glycol) methyl ether acrylate/sodium 4-styrenesulfonate)), were synthesized by RAFT polymerization to enable the synthesis of polymers with controlled features. The effect of charge types and side chain lengths on the adsorption, rheology, and dispersing ability of cement pastes have been studied.

RAFT polymerization could be used to prepare PCE random copolymers with good control over the polymer molecular weight and narrow polydispersity (Đ < 1.3). Results revealed that the ζ-potential values depend on both the charge type and side chain lengths. Copolymers containing SO₃^- exhibited higher absolute negative ζ-potential values than COO^- while PCE copolymers with shorter side chains developed higher absolute negative ζ-potential values. On the other hand, the adsorption study demonstrated that decreasing the side chain lengths lead to higher adsorption of PCE copolymers while Copolymers with COO^- groups were found to be adsorbed more than SO₃^- counterparts. These results are further confirmed with the rheological studies and it is found that the shorter the side chain, the lower the yield stress and the higher the dispersion of cement pastes but to a limited effect. Additionally, the charge types have a major influence on the performance of superplasticizers. This study could make further progress in establishing superplasticizers with controlled architectures for better performance.