Relatively homogeneous network structures of temperature-responsive gels synthesized <i>via</i> atom transfer radical polymerization.

Abstract

The network structures of poly(<i>N</i>-isopropylacrylamide) (PNIPAAm) gels prepared by atom transfer radical polymerization (ATRP) were compared with those prepared by free radical polymerization (FRP), as a conventional radical polymerization. Temperature-responsive shrinkage was observed in the PNIPAAm gels prepared by ATRP and FRP (ATRP and FRP gels), which depended on the cross-linker content. From the light-scattered intensities, 〈<i>I</i>〉_T, measured at the different sample positions, we used the partial heterodyne method to determine the dynamic fluctuation, 〈<i>I</i>〉_F, spatial component, 〈<i>I</i>〉_C, and correlation length, <i>ξ</i>, of the ATRP and FRP gels, as a function of the cross-linker content and temperature. While there is little difference in 〈<i>I</i>〉_F and <i>ξ</i> between the ATRP and FRP gels, 〈<i>I</i>〉_C of the ATRP gel was smaller than that of the FRP gel. In addition, we calculated the standard deviation of 〈<i>I</i>〉_T for the ATRP and FRP gels, as a function of temperature to quantify the inhomogeneity of the gel networks. The standard deviation revealed that increasing cross-linker content and temperature makes the gel networks more inhomogeneous. The dynamic light scattering (DLS) measurement used to characterize the gel network revealed that ATRP suppresses inhomogeneity more effectively than FRP. The standard deviation of the scattered intensity is used in this study to quantify the inhomogeneity of the network structures. Quantitative evaluations of the inhomogeneity of the network structures by the standard deviation of the scattered intensity are useful in the investigation of the structure-property relationships of gels.