The hyperbranched epoxy resins (HBE) composed of bisphenol A (BPA) and polyethylene glycol (PEG) as reactants and pentaerythritol as branching point were successfully synthesized via A2 + B4 polycondensation reaction at various BPA/PEG ratios. The 13C NMR spectra revealed that the synthesized HBE mainly had a dendritic structure as confirmed by the high degree of branching (DB). The addition of PEG in the resin enhanced degree of branching (DB) (from 0.82 to 0.90), epoxy equivalent weight (EEW) (from 697 g eq−1 to 468 g eq−1) as well as curing reaction. Adding 5–10 wt.% PEG in the resin decreased the onset and peak curing temperatures and glass transition temperature; however, adding 15 wt.% PEG in the resin have increased these thermal properties due to the lowest EEW. The curing kinetics were evaluated by fitting the experimental data of the curing behavior of all resins with the Šesták–Berggren equation. The activation energy increased with the increase of PEG in the resins due to HBE’s steric hindrance, whereas the activation energy of HBE15P decreased due to a large amount of equivalent active epoxy group per mass sample. The curing behavior and thermal properties of obtained hyperbranched BPA/PEG epoxy resin would be suitable for using in electronics application.

This paper investigates the photo-initiated cationic polymerization of diglycidyl ether of bisphenol A (DGEBA) modified with bisphenol A (BPA)/polyethylene glycol (PEG) hyperbranched epoxy resin. The relationship between curing behavior, rheological, and thermal properties of the modified DGEBA is investigated using photo-differential scanning calorimetry (DSC) and photo-rheometer techniques. It is seen that the addition of the hyperbranched epoxy resin can increase UV conversion (αUV) and reduce gelation time (tgel). After photo-initiation polymerization (dark reaction) occurred, a second exothermic peak in the DSC thermogram takes place: namely, the occurrence of curing reaction owing to the activated monomer (AM) mechanism. Consequently, the glass transition temperature decreased, and at the same time, UV intensity increased which was due to the molecular weight between crosslinking points (Mc). Furthermore, the radius of gyration (Rg) of the network segment is determined via small-angle X-ray scattering (SAXS). It is noted that the higher the Mc, the larger the radius of gyration proves to be, resulting in low glass transition temperature.