410: Exploring the effects of polymer topologies on the properties of Poly(tert-butyl acrylate)

Polymer topology plays a crucial role in physical properties and determines potential material applications.¹ The shape and interconnectedness of polymer chains significantly influence their behavior, such as solution and thermal properties. We explored advanced polymer architectures including a cyclic and 8-shaped with precise molecular designs in addition to the conventional linear polymer. By studying these polymer architectures, material properties can be fine-tuned at the molecular level as advanced new possibilities in materials design.

In this work, we synthesized poly(tert-butyl acrylate) with various shapes including linear, tetra-arm, cyclic, and 8-shaped polymers using ARGET-ATRP and click chemistry.² This approach allowed us to control both the size and structure of the polymers. Comprehensive analysis using ¹H NMR, FT-IR, SEC, DSC, and MALDI-TOF mass spectrometry techniques confirmed the successful synthesis of these polymers. Our investigation revealed that the topologies significantly influenced the properties. Cyclic polymers exhibited higher glass transition temperatures compared to their linear precursors, attributing to their more compact rigid structures.³ Further,  the intrinsic viscosity decreased with increasing structural compactness across different topologies. These findings demonstrate the profound impact of polymer topology on material properties, offering new avenues for fine-tuning polymer behavior in both solution and bulk states.⁴ This research covers the way for developing advanced materials with tailored properties, which can potentially revolutionize applications in fields such as drug delivery, smart coatings, and high-performance polymers.

Figure. Intrinsic viscosity ([η]) and glass transition temperature (T_g) of various topological polymers. The [η] was measured using a triple detector-equipped SEC, while T_g  was measured using DSC.

Reference:

[1]        Gu Y., Zhao J., Johnson J. A., A macromolecular level understanding of polymer network topology. Trends in Chemistry 2019, 1 (3), 318, DOI:10.1016/j.trechm.2019.02.017.

[2]        Yamamoto T., Tezuka Y., Topological polymer chemistry by programmed self-assembly and effective linking chemistry European Polymer Journal 2011, 47 (4), 535, DOI:10.1016/j.eurpolymj.2010.10.020.

[3]        Hossain M. D., Lu D., Jia Z., Monteiro M. J., Glass transition temperature of cyclic polymers ACS Macro Letters 2014, 3 (12), 1254, DOI:10.1021/mz500684v.

[4]        Romio M., Trachsel L., Morgese G., Ramakrishna S. N., Spencer N. D., Benetti E. M., Topological polymer chemsitry enters materials science: expanding the appicability of cyclic polymers ACS Macro Letters 2020, 9 (7), 1024, DOI:10.1021/acsmacrolett.0c00358.