Interactions between Water and a Hydrophobic Polymer

Abstract

To investigate the mechanisms of interactions between a hydrophobic polymer and water, molecular dynamics calculations and Raman spectroscopic measurements of cis-1,4polyisoprene (PI)-water systems were performed. The results show that PI in water undergoes a coil−globule transition at around 248 K. The transition is attributed to changes in the density and diffusivity of water. The volume expansion of the supercooled liquid water induces the coil structure of PI. The phase separation of PI from water with an increase in the self-diffusion coefficient of water molecules results in the globule structure of PI. The selfdiffusion coefficient of free water with PI is larger than that of pure water because PI has an effect to decrease the hydrogen-bonding strength of water. The result suggests that the effects of the coexisting water are important factors governing the physical and chemical properties of hydrophobic polymers.