Molecular Design of Core‐Shell Type Allylic Nanoparticles Based on Crosslinking Multiallyl/Multivinyl Copolymerizations

Abstract

AbstractThis article is referred to the clarification of polymerization characteristics of microgel‐like network polymer precursor (NPP), closely related to the inhomogeneous polymer network formation, in the free‐radical crosslinking (co)polymerization of multivinyl monomers. Firstly, the gelation in free‐radical crosslinking allyl benzoate/diallyl terephthalate (DAT) copolymerization governed by Flory‐Stockmayer gelation theory was explored in the presence of ethylene glycol dimethacrylate (EGDMA) as a typical multivinyl monomer. Since the copolymerizability of allyl monomer with methacrylate monomer is very poor, the crosslinking EGDMA polymerization accompanied by in situ nanogel‐ or microgel‐like methacrylate‐NPP formation was preceded. Secondly, DAT polymerization was carried out with in situ inhomogeneous network formation by a preceded crosslinking EGDMA polymerization. The structures of resulting NPPs were characterized by SEC‐MALLS‐viscometry. Here, the preceded in situ methacrylate‐NPP formation promoted the gelation, never leading to delayed gelation. Finally, our aforementioned discussion was extended to the preparation of novel core‐shell type allylic nanoparticles based on crosslinking multiallyl/multivinyl copolymerizations.