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Detecting the Rouse and Sub-Rouse Modes in Poly(Butyl Acrylate) and Poly(Ethyl Acrylate) Through Two-Dimensional Dynamic Mechanical Spectra

The difficulties of observing sub-Rouse modes (SRM) and Rouse modes (RM) in acrylate polymers has resulted in many arguments and disputes concerning the nature of their glass-rubber transition. Because different modes have different sensitivity to external perturbations, the two-dimensional dynamic analysis mechanical spectra (2D-DMS) was introduced to detect the local segments motion (LSM), SRM, and RM in poly(butyl acrylate) (PBA) and poly(ethyl acrylate) (PEA). The results of the asynchronous spectra showed the LSM, SRM, and RM of PBA and PEA are located, respectively, at about (−46 ∼ −29°C), (−28 ∼ −10°C), (−4 ∼ 27°C), and about (−12 ∼ −5°C), (−3 ∼ 6°C), and (10 ∼ 44°C). Furthermore, the LSM and SRM of PBA and PEA have an overlap in the synchronous spectra. This is suggested to be caused by the higher coupling effect in PBA and PEA when compared with strong glass formation polymers, like polyisobutylene (PIB).