A series of networks is introduced with systematically varied network heterogeneity and high overall values of average glass transition temperature (T_g), based on polymerization of rigid acrylate and aromatic thiol monomers. The curing behavior, chain dynamics, and microstructure of these networks were investigated through a combination of dynamic mechanical analysis and infrared spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and x-ray scattering, respectively. The maximum T_g achieved during cure can be related to the breadth of the mechanical loss tangent, as others have previously suggested, as well as the temperature dependence of the chain dynamics in the network as monitored by ¹H NMR. In addition, the microstructures of the networks are characterized by periodic, fractal microgels with characteristic length scales of ca. 20–40 nm. Intriguingly, this structural motif persists in the more homogeneous networks exhibiting comparatively narrow glass transitions and chain dynamics, indicating that dynamically homogeneous networks can still exhibit significant compositional heterogeneity at the mesoscale.

基于刚性丙烯酸酯和芳族硫醇单体的聚合反应，引入了一系列网络，这些网络具有系统地变化的网络异质性和较高的平均玻璃化转变温度（T _g）总体值。通过动态力学分析和红外光谱，核磁共振（NMR）光谱和X射线散射相结合，分别研究了这些网络的固化行为，链动力学和微观结构。固化过程中达到的最大T _g可能与机械损耗角正切的广度有关，正如其他人先前所建议的那样，以及网络中链动力学的温度依赖性，如¹1 H NMR。此外，网络的微结构通过用的特征长度尺度周期，分形微凝胶特征在于CA。20-40 nm。有趣的是，这种结构基序仍存在于显示出较窄的玻璃化转变和链动力学的更均质的网络中，表明动态均质的网络在中尺度上仍可表现出明显的组成异质性。