Norioka Chisa, Kawamura Akifumi, Miyata Takashi
Department of Chemistry and Materials Engineering, Kansai University, 3-3-35, Yamate-cho, Suita, Osaka 564-8680, Japan.
Organization for Research and Development of Innovative Science and Technology, Kansai University, 3-3-35, Yamate-cho, Suita, Osaka 564-8680, Japan.
Soft Matter. 2023 Apr 5;19(14):2505-2513. doi: 10.1039/d3sm00044c.
The network structures of poly(-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, 〈〉, measured at the different sample positions, we used the partial heterodyne method to determine the dynamic fluctuation, 〈〉, spatial component, 〈〉, and correlation length, , of the ATRP and FRP gels, as a function of the cross-linker content and temperature. While there is little difference in 〈〉 and between the ATRP and FRP gels, 〈〉 of the ATRP gel was smaller than that of the FRP gel. In addition, we calculated the standard deviation of 〈〉 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.
将通过原子转移自由基聚合(ATRP)制备的聚(N-异丙基丙烯酰胺)(PNIPAAm)凝胶的网络结构与通过自由基聚合(FRP,一种传统的自由基聚合方法)制备的凝胶网络结构进行了比较。在通过ATRP和FRP制备的PNIPAAm凝胶(ATRP凝胶和FRP凝胶)中观察到了温度响应收缩现象,这种收缩取决于交联剂含量。根据在不同样品位置测量的光散射强度〈I〉,我们使用部分外差法来确定ATRP凝胶和FRP凝胶的动态波动〈δI²〉、空间分量〈I(x)²〉以及相关长度ξ,它们是交联剂含量和温度的函数。虽然ATRP凝胶和FRP凝胶的〈δI²〉和ξ几乎没有差异,但ATRP凝胶的〈I(x)²〉小于FRP凝胶的〈I(x)²〉。此外,我们计算了ATRP凝胶和FRP凝胶的〈I〉的标准偏差,作为温度的函数,以量化凝胶网络的不均匀性。标准偏差表明,增加交联剂含量和温度会使凝胶网络更加不均匀。用于表征凝胶网络的动态光散射(DLS)测量表明,ATRP比FRP更有效地抑制了不均匀性。本研究中使用散射强度的标准偏差来量化网络结构的不均匀性。通过散射强度的标准偏差对网络结构不均匀性进行定量评估,对于研究凝胶的结构-性能关系很有用。