Comparative Study of Continuous-Flow Reactors for Emulsion Polymerization.

Polymer fouling in batch and tubular reactors creates safety hazards from heat buildup and blockages. The continuous Corning Advanced-Flow™ Reactor (AFR) offers enhanced mass and heat transfer, improving safety and efficiency. This study evaluated three reactor systems-a monolithic AFR, an AFR with an external pipe, and a conventional tubular reactor-for the mini-emulsion polymerization of styrene and subsequent styrene-acrylic acid copolymerization. The AFR operability under varying monomer concentrations was assessed and investigated, with the residence time's effects on conversion. For styrene polymerization at 20-35 wt% monomer, the highest conversions achieved were 88.0% in the AFR, 85.8% in the tubular reactor, and 98.9% in the AFR with pipe. Uniform particles were obtained at ≤30 wt%, whereas at 35 wt%, the monolithic AFR experienced clogging and loss of particle uniformity. Similarly, in styrene-acrylic acid copolymerization (15-17.5 wt% monomer), the maximum conversions reached 80.1% in the AFR and 95.4% in the AFR with pipe, while the monolithic AFR again experienced blockage at 17.5 wt%. In conclusion, integrating an external pipe with the AFR, coupled with higher flow rates, significantly improved initiator diffusion, enhanced monomer conversion, and mitigated blockage. This approach enabled the efficient, continuous production of nanoscale, uniformly sized polystyrene and styrene-acrylic acid copolymers even at high monomer concentrations.