Nonlinear polystyrenes (PS) with similar molecular weights but with different molecular structures having star-, figure-8-, and cage-shaped architectures were synthesized by combining atom transfer radical polymerization (ATRP) and click chemistry. Figure-8- and cage-shaped PS were fractionated by using a gradient normal phase liquid chromatography as confirmed by SEC-LS, MALDI-TOF MS, 1H NMR, and FT-IR spectrometry. Their purities were estimated by using a two-dimensional liquid chromatography (2D-LC). The glass transition temperatures of these topologically different polymers were in the order of cage-, figure-8-, and star-shaped polymers possibly due to the multiple links that constrain the overall molecular diffusivity in the case of multicyclic polymers (figure-8, and cage). Monte Carlo simulation on the glass transition behavior of model system also agreed well with the experimental results.
Bibliographical noteFunding Information:
This work was supported by the Active Polymer Center for Pattern Integration (No. R11-2007-0056091) and Basic Science Research Program through the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIP) (2013R1A2A2A01068818). T.C. acknowledges the support from NRF-Korea (2015R1A2A2A01004974). J.H. acknowledges support from NRF-Korea (2013R1A1A2064112).
© 2016 American Chemical Society.
ASJC Scopus subject areas
- Organic Chemistry
- Polymers and Plastics
- Inorganic Chemistry
- Materials Chemistry