Thermo-pH-Salt Environmental Terpolymers Influenced by 2-((Dimethylamino)methyl)-4-methylphenyl Acrylate: A Comparative Study for Tuning Phase Separation Temperature.

Abstract

This study offers a comparison between three different types of thermoresponsive (TR) and thermo-pH-salt (TPR) multiresponsive polymers including homopoly(N-isopropylacrylamide) (PNIPAAm), copolymers with three different monomers, 2-hydroxyethyl methacrylate (HEMA), N,N-dimethylacrylamide (DMAAm), and styrene (S) at three different concentrations (5, 10, and 20 mol %), and a PNIPAAm terpolymer with 5, 10, and 20 mol % 2-((dimethylamino)methyl)-4-methylphenyl acrylate (DMAMCA) and 10 mol % HEMA, DMAAm, and S monomers. All polymers were chemically analyzed with 1H NMR and Fourier transform infrared spectroscopy (FT-IR) as well as gel permeation chromatography (GPC) for the molecular weights and dispersity and differential scanning calorimeter (DSC) for the glass transition temperatures. The cloud point, also known as the phase separation temperature (Cp), was determined for all polymers by a turbidity test using a UV-vis spectrophotometer; a micro-differential scanning calorimeter was used for measuring the cloud point in deionized water. The influence of a tertiary amine cationic group of DMAMCA changed the behavior of TR copolymers into TPR by shifting the cloud point of the TPR to higher values in acidic solutions (lower pH) and to lower values in alkaline solutions. The Cp was measured at different concentrations of Hofmeister kosmotropic and chaotropic anion salt solutions in a range of pH solutions for the terpolymers. It demonstrated the same behavior as mentioned in pH solutions besides the effect of salt ions. By measuring the Tc and Cp of these polymers, we can exploit various applications of stimuli-responsive materials for sensors and biomedical technology.