Controlled ATRP Synthesis of PtBA and PNIPAM for Surface Grafting onto Graphene with Tunable Thermoresponse

Enhancing the solubility and processability of graphene remains a critical challenge, limiting its integration into advanced materials systems. In this work, poly(tert-butyl acrylate) (PtBA) and poly(N-isopropyl acrylamide) (PNIPAM) were grafted onto graphene via controlled atom transfer radical polymerization (ATRP) to create well-defined polymer–graphene hybrids with tunable interfacial properties. ATRP enabled the synthesis of PtBA and PNIPAM homopolymers with narrow molecular weight distributions and systematically varied chain lengths (4–18 kDa), allowing direct correlation between polymer architecture and material performance. Notably, the thermos-responsive behavior of PNIPAM was strongly dependent on chain length, highlighting the importance of controlled polymer design. Raman and FTIR spectroscopy confirmed successful grafting and chemical modification of the graphene surface. In addition, pilot studies demonstrate the ATRP synthesis of PtBA-b-PNIPAM block copolymers and their hydrolysis to PAA-b-PNIPAM, providing a platform for future development of multifunctional graphene interfaces. Overall, this study establishes a versatile and precisely controlled route for engineering polymer-grafted graphene with enhanced solubility and tunable functionality, enabling broader applications in smart materials and hybrid nanocomposites.