Solvent effects on surface-grafted and solution-born poly[N-(2-hydroxypropyl)methacrylamide] during surface-initiated RAFT polymerization

0586100 - ÚMCH 2025 RIV GB eng J - Journal Article
Wang, Yu-Min - Kálosi, A. - Halahovets, Y. - Beneš, Hynek - de los Santos Pereira, Andres - Pop-Georgievski, Ognen
Solvent effects on surface-grafted and solution-born poly[N-(2-hydroxypropyl)methacrylamide] during surface-initiated RAFT polymerization.
Polymer Chemistry. Roč. 15, č. 20 (2024), s. 2070-2080. ISSN 1759-9954. E-ISSN 1759-9962
R&D Projects: GA ČR(CZ) GA22-02836S; GA ČR(CZ) GA22-27329S; GA MŠMT LX22NPO5102
Institutional support: RVO:61389013
Keywords : p(HPMA) * solvent effects * SI-RAFT
OECD category: Polymer science
Impact factor: 4.6, year: 2022
Method of publishing: Open access
https://pubs.rsc.org/en/content/articlelanding/2024/py/d4py00177j

The difference in the molar mass between surface-grafted and solution-born polymers grown during surface-initiated (SI) polymerization has caused controversy for years. To understand it, we study the solvent effects on the polymer formed on the surface and in the solution by investigating their macromolecular parameters. We utilized reversible addition fragmentation chain-transfer (RAFT) polymerization to grow surface-grafted and solution-born poly[N-(2-hydroxypropyl)methacrylamide] (p(HPMA)) under different solvent conditions. Changing the solvent proticity and/or polarity influences the solution propagation rate, leading to mass transfer limitations and a concomitant discrepancy in the molar masses of the polymer formed in solution and grafted from the surface. Moreover, the solvent effects were found to directly determine the grafting density of surface-grafted p(HPMA). These results highlight how decisive the solvent effects on the SI-RAFT polymerization of HPMA are and that they may be key to regulate the physical and macromolecular parameters of the obtained surface-grafted p(HPMA) brushes.
Permanent Link: https://hdl.handle.net/11104/0353675