Pressure-assisted solvent- and catalyst-free production of well-defined poly(1-vinyl-2-pyrrolidone) for biomedical applications

Paulina Maksym; Magdalena Tarnacka; Dawid Heczko; Justyna Knapik-Kowalczuk; Anna Mielańczyk; Roksana Bernat; Grzegorz Garbacz; Kamil Kaminski; Marian Paluch

doi:10.1039/d0ra02246b

Pressure-assisted solvent- and catalyst-free production of well-defined poly(1-vinyl-2-pyrrolidone) for biomedical applications

RSC Adv. 2020 Jun 5;10(36):21593-21601. doi: 10.1039/d0ra02246b. eCollection 2020 Jun 2.

Authors

Paulina Maksym^{1

2}, Magdalena Tarnacka^{1

2}, Dawid Heczko³, Justyna Knapik-Kowalczuk^{1

2}, Anna Mielańczyk⁴, Roksana Bernat^{2

5}, Grzegorz Garbacz⁶, Kamil Kaminski^{1

2}, Marian Paluch^{1

2}

Affiliations

¹ Institute of Physics, University of Silesia ul. 75 Pułku Piechoty 1 41-500 Chorzów Poland paulina.maksym@smcebi.edu.pl kamil.kaminski@smcebi.edu.pl +48323497610.
² Silesian Center of Education and Interdisciplinary Research, University of Silesia ul. 75 Pulku Piechoty 1A 41-500 Chorzow Poland.
³ Department of Pharmacognosy and Phytochemistry, Medical University of Silesia in Katowice, School of Pharmacy with the Division of Laboratory Medicine in Sosnowiec Jagiellonska 4 41-200 Sosnowiec Poland.
⁴ Department of Physical Chemistry and Technology of Polymers, Faculty of Chemistry, Silesian University of Technology ul. M. Strzody 9 44-100 Gliwice Poland.
⁵ Institute of Chemistry, University of Silesia ul. Szkolna 9 40-007 Katowice Poland.
⁶ Physiolution GmbH Walther-Rathenau-Str. 49a 17489 Greifswald Germany.

Abstract

In this work, we developed a fast, highly efficient, and environmentally friendly catalytic system for classical free-radical polymerization (FRP) utilizing a high-pressure (HP) approach. The application of HP for thermally-induced, bulk FRP of 1-vinyl-2-pyrrolidone (VP) allowed to eliminate the current limitation of ambient-pressure polymerization of 'less-activated' monomer (LAM), characterized by the lack of temporal control yielding polymers of unacceptably large disperisites and poor result reproducibility. By a simple manipulation of thermodynamic conditions (p = 125-500 MPa, T = 323-333 K) and reaction composition (two-component system: monomer and low content of thermoinitiator) well-defined poly(1-vinyl-2-pyrrolidone)s (PVP) in a wide range of molecular weights and low/moderate dispersities (M _n = 16.2-280.5 kg mol^-1, Đ = 1.27-1.45) have been produced. We have found that HP can act as an 'external' controlling factor that warrants the first-order polymerization kinetics for classical FRP, something that was possible so far only for reversible deactivation radical polymerization (RDRP) systems. Importantly, our synthetic strategy adopted for VP FRP enabled us to obtain polymers of very high M _n in a very short time-frame (0.5 h). It has also been confirmed that VP bulk polymerization yields polymers with significantly lower glass transition temperatures (T _g) and different solubility properties in comparison to macromolecules obtained during the solvent-assisted reaction.