Polycarboxylate superplasticizers of acrylic acid–isobutylene polyethylene glycol copolymers: monomer reactivity ratios, copolymerization behavior and performance

Acrylic acid–isobutylene polyethylene glycol (AA-TPEG) copolymers are typical of polycarboxylate superplasticizers (PCEs). AA-TPEG copolymers are prepared via free-radical polymerization with potassium persulfate as the initiator. The obtained copolymers were characterized by gel permeation chromatography (GPC) and infrared spectra (FTIR). The GPC method can break through the former limitations of the instruments and receive instantaneous unreacted and instantaneous monomer concentrations and not the initial monomer feeds. Since TPEG monomer is highly bulky, the common calculation methods for determining monomer reactivity ratios in copolymerization based on terminal copolymerization equation are not suitable. However, this study created non-linear least squares curve fitting of terminal copolymerization equation (NLLSQ-T) and penultimate copolymerization equation (NLLSQ-P) methods, which used Python’s NumPy, SciPy, and SymPy libraries to generate code and did numerical computations, bringing greater accuracy of monomer reactivity ratios. The monomer reactivity ratios were calculated with Fineman–Ross, Kelen–Tüdös, YBR, NLLSQ-T, and NLLSQ-P methods and found to be rAA = 10.888, r′AA = 1.131, rTPEG = 0.012, and r′TPEG = 0.042 for AA-TPEG copolymers. Moreover, this study also explored specific copolymerization behavior of similar structure of copolymers with steric hindrance under penultimate copolymerization equation, such as dependence of the mole fractions in the copolymer on the mole fractions of unreacted monomers in solution, variation of copolymer compositions with conversion and sequence length distribution. The fluidity and flow loss of pastes containing PCEs were investigated, and the appropriate PCEs dosages resulted in a better workability of cement pastes.