Control of the temperature responsiveness of poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) copolymer using ultrasonic irradiation

Poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) (poly(NIPAM-co-HEMA)) is a temperature-responsive copolymer that is expected to be applicable as an advanced functional polymeric material in various fields. In this study, a novel method was developed to control the responsive temperature of poly(NIPAM-co-HEMA) using an ultrasonic polymerization technique. Initially, the behavior of the reaction was investigated using NIPAM and HEMA monomers under ultrasonic irradiation. A high ultrasonic power was found to produce a high reaction rate and low number average molecular weight of the copolymer. The polydispersity of the synthesized copolymer was approximately 1.5 for all ultrasonic powers examined. In the early stage of the reaction, the molar fraction of NIPAM in the copolymer was lower than the initial molar fraction of the monomers. It was concluded that ultrasonic irradiation affected the initiation reaction and polymer degradation, but did not affect the propagation reaction. Furthermore, the effect of the ultrasonic irradiation conditions on the temperature responsiveness of the copolymer was investigated. The lower critical solution temperature (LCST) of the copolymer was found to increase with increasing ultrasonic irradiation time. In addition, in the early stages of the reaction, the measured values of the LCST were higher than the estimated values using copolymer composition. This can be attributed to some parts of the copolymer chain possessing a higher NIPAM fraction than the overall fraction due to different reactivities of the monomers and terminated radicals. This hypothesis was indirectly verified by the synthesis of a block copolymer from the PNIPAM homopolymer and HEMA monomer.