In this study, the binary aqueous free radical copolymerization process of ethylene‐glycol monovinyl polyethylene glycol (EPEG) and acrylic acid (AA) was studied. The influence of monomer type and molar ratio on the conversion ratio of EPEG and the molar ratio of copolymer were investigated via gel permeation chromatography (GPC) by comparing the macromonomer molecular structures, side chain densities, and carboxyl group concentrations. According to the results, the reactivity of EPEG copolymerized with AA was higher than that of isoprenyl oxypoly (ethylene glycol) ether (IPEG, also referred to as TPEG) with AA. The copolymerization reaction between EPEG and AA could be completed within 30 min at 10–20°C. At the initial stage, the copolymer content quickly attained 60% within 15 min, reflecting the short induction period and high chain propagation rate constant. The fluidity tests in cement mortar revealed that polycarboxylate superplasticizers (PCEs) with short side chains and high conversion ratio exhibited better dispersion capacity than PCEs with long side chains.

Through molecular structure design, modified polycarboxylate superplasticizers (PCEs) were synthesized via copolymerization using isoprenyl oxy poly(ethylene glycol) ether (TPEG), acrylic acid, and hydroxyethyl methacrylate phosphate. TPEG-PCEs were selected as potential dispersants for Na/Cabentonite containing cement mortar. Other two kinds of commercial PCE that were obtained based on methallyl ether (HPEG) and ethylene-glycol monovinyl polyethylene glycol (EPEG) as macromonomers were also applied in the mortar. The effects of the type of bentonite and its dosage, as well as the monomer structure of PCEs and the type of cement, on the dispersion properties of the bentonite-containing mortar were studied. According to the findings, the initial fluidity of the mortar was reduced by about 20 mm when two kinds of bentonite were used. Applying 3% Ca-bentonite resulted in 40% flow loss in the mortar after 1 h. The fluidity of the mortar with Na-bentonite exhibited lower dispersion ability than that with Ca-bentonite when HPEG-PCE and EPEG-PCE were chosen as dispersants. The TPEG-PCE exhibited superior dispersing performance over HPEG-PCE and EPEG-PCE and exerted a retarding effect on cement, being also weakly sensitive to clay content. Thus, TPEG-PCEs with phosphate groups present a viable alternative to conventional PCEs.