Bridging Reaction Engineering and Polymers Design: Solvent Effects in Continuous Flow Copolymerization

Poly(glycidyl methacrylate-co-methyl methacrylate) [poly(GMA-co-MMA)] is a promising functional copolymer for photoresist applications due to its reactive epoxy groups and tunable physicochemical properties. This thesis is focused on this polymer and integrates theoretical solubility prediction, thermodynamic modeling, and continuous-flow synthesis to establish quantitative structure–process–property relationships for their use in microelectronic-grade solvents.

Solubility behavior in dimethyl sulfoxide (DMSO), propylene glycol monomethyl ether (PGME), and propylene glycol monomethyl ether acetate (PGMEA) was investigated using the Hildebrand and Hansen models, Hoy group-contribution method, Polymer Genome machine-learning platform, and Flory–Huggins thermodynamic analysis of Gibbs free energy of mixing. Experimental saturation solubility measurements at 25 °C confirmed apparent saturation at ≈ 0.3 g cm-3 in DMSO and PGMEA. Flory–Huggins [delta]Gm values aligned well with experiment for good solvents but highlighted the concentration dependence and specific interaction limitations of the models for PGME.

Copolymers were synthesized in a Vapourtec tubular microreactor via free-radical copolymerization, and through systematically varying temperature (75–120 °C), monomer feed ratio, and residence time (5–80 min) in DMSO and PGMEA. ¹H NMR provided composition and conversion; GPC yielded Mw, dispersity (PDI), and degree of polymerization (DPn) The use of DMSO resulted in higher molecular weight polymers compared to PGMEA under identical conditions, consistent with solvent effects on radical polymerization kinetics and chain transfer behavior. Temperature and feed ratio enabled independent tuning of composition and chain length, with narrow dispersity (PDI = 1.2 – 2.3) across all condition, indicating improved control compared to conventional batch processing.

This work demonstrates that continuous-flow synthesis, combined with multi-model solubility prediction and experimental validation, enables reproducible control over key polymer quality attributes. The established solvent–process–property relationships provide practical guidelines for tailoring poly(GMA-co-MMA) molecular weight, composition, and rheological behavior, advancing the scalable production of high-performance materials for advanced microelectronics and lithographic applications.

Equipment used in this paper: Tubular Reactor 

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