The investigation of the relationship between the structure and properties of branched polymers heavily relies on the branched morphology. In this study, we explored the electron-rich and electron-poor effects that arise from different types of double bonds in inimers using self-condensing atom transfer radical polymerization (ATRP). A comparative analysis of polymerization systems using various inimers as branching monomers revealed notable differences. Specifically, when examining styrene-based initiator (St-inimer) systems, the absence of a discernible nucleation feature and the non-conformance to the “core-first-arm-later” method for synthesizing star-shaped polystyrene (branching morphology factor ε is higher than 1.0) were observed. On the other hand, the methacrylate-based initiator (MA-inimer) systems exhibited a clear nucleation process during polymerization, followed by linear molecular weight growth and a constant polydispersity characteristic, consistent with the “core-first-arm-later” approach for synthesizing star-shaped polystyrene (ε is about 0.6, lower than 1.0). The maleimide-based initiator (Mal-inimer) systems demonstrated an initial nucleation phase, a mid-stage linear growth phase with a constant polydispersity characteristic, and a late-stage nonlinear growth phase resulting in a broader polydispersity index. As a result, the polymerization process in maleimide-based initiator systems conforms to the law of preparing star branched polymers with multi-core structures (ε is about 0.8).
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