Thermodynamic interactions and characterisation of poly[(glycidyl methacrylate- co-methyl, ethyl, butyl) methacrylate] by inverse gas chromatography

Abstract

Poly(glycidyl methacrylate- co-methyl methacrylate) poly(GMA- co-MMA), poly(glycidyl methacrylate- co-ethyl methacrylate) poly-(GMA- co-EMA) and poly(glycidyl methacrylate- co-butyl methacrylate) poly(GMA- co-BMA) were synthesized in 1,4-dioxane solution using 2,2′-azobisisobutyronitrile (AIBN) as initiator at 60 °C. The copolymer compositions were determined by 1H NMR analysis. The FT-IR and 13C NMR spectra of the copolymers have been discussed. According to TG, carbonaceous residue values of poly(GMA- co-MMA), poly(GMA- co-EMA) and poly(GMA- co-BMA) were found to be 3.00, 4.00 and 4.20%, respectively, at 500 °C. Some thermodynamic quantities such as the sorption enthalpy, ΔH 1 s, the sorption entropy, TΔ S 1 s, the sorption free energy, Δ G 1 s, the partial molar free energy, Δ G 1 ∞, the partial molar heat of mixing, Δ H 1 ∞, at infinite dilution were obtained for the interactions of poly[(glycidyl methacrylate- co-methyl, ethyl, butyl) methacrylate] with n-alkanes, aromatics, CCl 4, 1-chloro-propane, 1-chloro-butane and 1,4-dioxane by inverse gas chromatography method in the temperature range of 363–453 K. The specific retention volumes, V g 0, the weight fraction activity coefficients of solute probes at infinite dilution, Ω 1 ∞, Flory–Huggins thermodynamic interaction parameters, χ 12 ∞ between polymers and solvents were determined. Also, the solubility parameters, δ 2, of the poly(GMA- co-MMA), poly(GMA- co-EMA) and poly(GMA- co-BMA) was found to be 30.85, 25.83, 25.00 (J cm −3) 0.5 and 31.94, 26.59, 25.71 (J cm −3) 0.5 from slope and intercept of [( δ 1 2/ RT)− χ 12 ∞/ V 1]=(2 δ 2/ RT) δ 1− δ 2 2/ RT equation, at 433, 423 and 393 K, respectively. The glass transition temperature, T g, of the poly(GMA- co-MMA), poly(GMA- co-EMA) and poly(GMA- co-BMA) was found to be 373, 355 and 334 K, respectively, by DSC and inverse gas chromatography.