Dynamics of the Phase Separation in a Thermoresponsive Polymer: Accelerated Phase Separation of Stereocontrolled Poly( N, N-diethylacrylamide) in Water.

We studied the dependence on tacticity of the dynamic phase separation behavior of thermoresponsive poly( N, N-diethylacrylamide) (PDEA) in an aqueous solution. Using a laser temperature-jump technique combined with transient photometry, we determined the time constants of the phase separation and found that both atactic and isotactic-rich PDEAs had fast and slow phase separation processes (τ _fast and τ _slow ). The fast process (τ _fast ) was independent of the tacticity, irrespective of the concentration. On the other hand, the slow process had a strong dependence on the tacticity. We found the slow phase separation process got considerably faster with increasing isotacticity in dilute solutions. This effect due to the tacticity of the PDEA is totally different from that of poly( N-isopropylacrylamide) and can be explained on the basis of the difference between the hydrophobicity of atactic PDEA and that of isotactic-rich PDEA.