AbstractIn order to explore the feasibility for preparing defined crosslinked particulate structures, oligo(ε-caprolactone) [oCL] derived microparticles (MPs) were crosslinked in non-molten, non-dissolved, i.e. solid state in aqueous suspension by applying a controlled regime with well-defined polymer network precursors either with or without photoinitiator. The MPs (diameter ∼ 40 μm) were prepared by an oil-in-water emulsion process from linear 2oCL or 4-arm star-shaped 4oCL with methacrylate end groups. Crosslinking was initiated by UV-laser irradiation (308 nm) at room temperature. Conversion of methacrylate was monitored by ATR-FTIR spectroscopy and crosslinking was confirmed by a lack of MP dissolution in dichloromethane. In a quantitative evaluation of swelling by dynamic light scattering, higher swelling ratios were detected for particles synthesized with photoinitiator. Wrinkled particle surfaces and distorted particle shapes were observed by light microscopy in the solvent-swollen state and by scanning electron microscopy after deswelling. This work indicated some limitations due to internal inhomogeneity of the MP, but particle crosslinking in solid state was generally possible and may be further improved by higher chain mobility during crosslinking.