Relative concentration changes of glassy polymer and small molecules may cause vitrification. Bulk polymerization is one example where the monomer/polymer concentration changes via a chemical reaction. During bulk polymerization, reaction acceleration (Trommsdorff effect) and subsequent reaction deceleration (glass effect) may occur. Herein, we systematically investigated the Trommsdorff and glass effects of methyl methacrylate, ethyl methacrylate and butyl methacrylate. The conversion as a function of the reaction time was elucidated based on isothermal differential scanning calorimetry (DSC) data. Under all examined experimental conditions, at the onset of the Trommsdorff effect, apparent phase separation was observed. We examined these effects in conjunction with glass transition as well as the change in the amorphous structure during bulk polymerization.
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The synchrotron radiation experiments were performed at BL40B2 of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal Nos. 2020A1144 and 2021A1069). The authors acknowledge experimental support received from Dr. Noboru Ohta and Dr. Hiroshi Sekiguchi at SPring-8. YS acknowledges the financial support by JSPS KAKENHI Grant Number 22K14015 and the 2022 Osaka Metropolitan University (OMU) Strategic Research Promotion Project (Young Researcher).
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Suzuki, Y., Mishima, R., Kato, E. et al. Analysis of the glass effect and Trommsdorff effect during bulk polymerization of methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Polym J 55, 229–238 (2023). https://doi.org/10.1038/s41428-022-00746-5