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Poly(methyl methacrylate/butyl acrylate) [P(MMA/BA)] copolymers (Mη ∼2×105) with different mass percentages of MMA were synthesized by the method of solution polymerization. Thermally stimulated depolarization current (TSDC) technique was used to investigate the effect of copolymerization on pendant group and chain segment motions. Three TSDC peaks were observed over the temperature range from 310 to 400 K. The highest temperature, ρ peak originates from the detrapping of trapped charge carriers. The lower temperature, α peak corresponds to the glass transition. The activation energy of the α relaxation decreases from 1.2 eV for PMMA to 0.98 eV for MMA(75)/BA(25). In the fitting process, another peak, β', is separated on the low temperature side. The apparent energy barrier of the β' for PMMA is 0.80 eV. The β' relaxation is thought to correspond to the motion of pendant groups including intra- and inter-molecular interactions. All three peaks move to lower temperatures with an increase in BA component, and the activation energy for the α and β' relaxations also decreases with the increase of BA component in copolymers, indicating that the flexible side groups of BA have an effect of plasticization on the glass transition and motion of pendent groups. The temperatures of the α and β' peaks of P(MMA/BA) copolymers follow the Fox equation. Fitting results gives the α peak at 238 K and β' peak at 225 K for polybutyl acrylate (PBA). [ABSTRACT FROM AUTHOR]

Poly (methyl methacrylate/butyl acrylate) [P(MMA/BA)] copolymers ( M η ∼⃒2×10 5 ) with different mass percentages of PMMA (100/0, 90/10, 81/19, and 75/25), were synthesized by the method of solution polymerization. In addition to the normal α and ρ peak, a third τ peak is observed in thermally stimulated depolarization current (TSDC) spectra of the copolymers in the high temperature region. The α peak‐corresponds to the glass transition, the ρ peak originates from the detrapping of trapped carriers in the bulk amorphous structure related with flexible side groups, and the τ peak can be attributed to the charge detrapping related to the liquid–liquid transition of the copolymers. The three peaks all move to lower temperature with an increase of the BA component, indicating that the flexible side groups of butyl acrylate not only have an effect of plasticization on the glass transition and liquid–liquid transition, but also make the trap depth shallower and the detrapping process easier for the ρ and τ peaks. The experimental results confirm that TSDC analysis is very sensitive for investigating the liquid–liquid transition of polymers. The liquid–liquid transition temperature ( T LL ) of the copolymers follows a type of the Fox equation. Fitting the results gives a T LL of 102°C for polybutyl acrylate. [ABSTRACT FROM AUTHOR]