TY - JOUR TI - Synthesis and structure-property correlations of y-substituted pyrrolidone-based polymers DO - https://doi.org/doi:10.7282/t3-06rq-ba63 PY - 2017 AB - Synthesis and characterization of novel y-substituted pyrrolidone-based polymers and PEG-PPS based polymers have been reported. In this thesis, pyrrolidone-based polymers have been explored with an interest to study the influence of substituents on the y-position. Synthesis of 5-methoxy-2-pyrrolidone was carried out using anodic decarboxylation of pyroglutamic acid. Acid catalyzed alkoxy/thioate exchange of 5-methoxy-2-pyrrolidone, derivatization with acryloyl moiety and subsequent polymerization of the monomers, yielded pyrrolidone-based polymers that varied in their ?-substituents. Polymerization was initially carried out via conventional free radical polymerization but later on was carried out via reversible addition-fragmentation transfer (RAFT) polymerization in order to get molecular weight control and narrower dispersity. The glass transition temperature Tg was found to be significantly influenced by both substituent structure (e.g., saturated linear aliphatic vs cyclic aliphatic vs aromatic) and chemical class. Inspired by these findings, amphiphilic block copolymers comprising of pyrrolidone-based polymers as the hydrophilic and hydrophobic blocks were synthesized. These block copolymers comprised of poly(MeOEtONP) as the hydrophilic block and poly(N-acryloyl-2-pyrrolidone) (NP), poly (N-acryloyl-5-ethoxy-2-pyrrolidone) (EtONP) or poly(N-acryloyl-5-ethylthiolate-2-pyrrolidone) (EtSNP) as the hydrophobic block. Studies were conducted to assess the influence of the length of hydrophilic block and the chemical class of bridging unit in the hydrophobic block. Critical micelle concentration, turbidimetry and hydrodynamic radii studies indicate an increase in hydrophobicity on addition of a ?-substituent on the pyrrolidone ring. Drug-encapsulation and release studies conducted on the block copolymers suggested that the structure of the hydrophobic block in the copolymer plays an important role in determining the performance of these polymeric nanocarriers. In a collaborative project with Prof. Robert K. Prud'homme of Princeton University, amphiphilic poly(ethylene glycol)-b- poly(propylene sulfide) (PEG-PPS) block copolymers of variable lengths were synthesized via anionic initiation method for flash nanoprecipitation of drug-loaded polymeric nanoparticle. PEG-PPS based block copolymers of variable lengths were synthesized and thermal properties were analyzed through differential scanning calorimetry and thermal gravimetric analysis. Initial studies conducted in the Prud'homme laboratory indicate a significant change in polymeric nanoparticle size upon subjecting it to oxidizing conditions. This indicates promising applications of the synthesized polymers in the field of drug-delivery. KW - Chemistry KW - Pyrrolidone KW - Polymers -- Synthesis LA - English ER -