Developing a Novel, Green, and Efficient Synthesis Method for Polycarboxylate Superplasticizers Through Mechanochemical Internal Mixing Polymerization.

Polycarboxylate superplasticizers (PCEs) are the most important polymer admixtures in cement and concrete. Developing novel, green, and efficient synthesis methods is essential for lowering energy consumption. Here, a mechanochemical internal mixing polymerization was used to synthesize high-concentration PCEs (INPCEs) for the first time. The optimum reaction temperature, reaction rotating speed, and reaction time were determined using the orthogonal method. The optimum acid-ether ratio (i.e., the molar ratio of acrylic acid (AA) to isopentenyl polyoxyethylene ether (TPEG)) and concentrations of ammonium persulfate (APS) and sodium methacrylate sulfonate (MAS) were also determined. Finally, the molecular structures of the INPCEs were characterized using Fourier transform infrared spectroscopy (FT-IR) and gel permeation chromatography (GPC), and their performance and energy consumption were compared with PCE synthesized via an aqueous solution polymerization (TPCE). The results showed that the optimum reaction temperature, rotating speed, and time were 60 °C, 70 R/min, and 60 min, respectively. In addition, the acid-ether ratio, the concentrations of MAS and APS, and the polymerization method affected the molecular weight and PDI of INPCEs but did not alter the functional groups. At an AA:TPEG:MAS molar of 3.0:1:0.12 and an APS concentration of 1 wt% (relative to TPEG), the initial fluidity of cement paste with INPCE was 312.5 mm at an INPCE dosage of 0.20 wt% and a water-cement ratio of 0.35. Further, the concentrations of the INPCEs were >99.00 wt%, which is much higher than the TPCE concentration of 39.73 wt%, and the dispersion and dispersion retention of INPCE was almost as good as that of TPCE while requiring much less energy for synthesis. These findings can contribute to the reduction in energy consumption in the concrete industry.