Free Radical Copolymerization of N-Isopropylacrylamide and 2,3-Dihydroxypropyl Methacrylate: Reaction Kinetics and Characterizations

Poly(<i>N</i>-isopropylacrylamide) (PNIPAm) undergoes a sharp phase transition in aqueous solutions at around 32 °C, which is called the lower critical solution temperature; the tuning of the LCST of PNIPAm could be achieved by the copolymerization of <i>N</i>-isopropylacrylamide (NIPAm) with other hydrophilic/hydrophobic monomers to regulate the solvation state of PNIPAm and meet the requirements of possible applications. Herein, a hydrophilic monomer, 2,3-dihydroxypropyl methacrylate (DHPMA), w introduced to regulate the phase transition behavior of PNIPAm via free radical copolymerization. A series of poly(<i>N</i>-isopropylacrylamide-<i>co</i>-2,3-dihydroxypropyl methacrylate) (P(NIPAm-<i>co</i>-DHPMA)) was synthesized and characterized. The reaction kinetics were investigated in detail. In this copolymerization, the reactivity ratios of DHPMA and NIPAm were found to be 3.09 and 0.11, suggesting that DHPMA had greater preference for homopolymerization than for copolymerization, while NIPAm had greater preference for copolymerization than for homopolymerization. The phase transition temperature of P(NIPAm-<i>co</i>-DHPMA) copolymers varied from 31 to 42 °C by controlling the content of DHPMA in the copolymers from 0 to 58 mol%. Finally, the good cytocompatibility of P(NIPAm-<i>co</i>-DHPMA) was confirmed. These results provide insights into designing thermo-responsive polymers with suitable responsive behaviors that meet the requirements of different applications.