This work focuses on a two-stage polymerisation process for the production of uniform polymer beads. Highly uniform droplets were firstly produced by a stirred-vessel membrane emulsification device.Methyl methacrylate (MMA) and a specific grade of polyvinyl alcohol (PVA) were used as monomer and stabiliser, respectively. The effects of various process parameters affecting the droplet size and uniformity including feeding policy, agitation speed, stabiliser concentration, and flowrate were investigated. The evolution of droplet size and its coefficient of variation (CV) were monitored over the course of emulsification. A new start-up policy, validated by monitoring droplet formation at the membrane surface, was introduced that eliminated the non-uniformity in the size of droplets formed early during emulsification. The mechanisms contributing to droplet size distribution broadening at the membrane surface during formation were decoupled from those acting in the emulsification vessel during circulation. The high CV obtained at low PVA concentration and high agitation speed was attributed to drop breakup and coalescence occurring in the emulsification vessel, respectively, after droplets formed. The emulsification was followed by a shear-controlled suspension polymerisation to convert the discrete droplets of monomer to polymer beads. A wide range of reactor impeller speeds and PVA concentrations was studied to find the conditions under which the droplets formed via membrane emulsification would not undergo further break-up or coalesce during polymerisations and a one-to-one copy of the initial droplets with the same CV can be achieved.
In a typical suspension polymerization, both emulsification and polymerization occur simultaneously in a single-stirred vessel reactor using a constant stirring speed and stabilizer concentration. This work introduces a novel two-stage stirring protocol for improving the uniformity of polymer beads produced in suspension polymerization reactors . In the two-stage stirring protocol proposed, the polymerization stage was carried out at a reduced stirring speed. This policy, verified by mathematical modeling, led to the drops coalescence being suppressed, and as a result, the drops average size and size distribution being maintained in the course of polymerization. The particle size distribution narrowing was more significant if the emulsification stage was carried out at room temperature, the stabilizer concentration was low, and the difference between the stirring speeds used in the two stages was large. The two-stage stirring protocol was extended to include a two-stage stabilizer-addition protocol, which further improved the quality of the beads.
A microfluidic platform with dual photopolymerization zones has been developed for production of novel uniform interconnected porous particles with shapes imposed either by the geometry of the external capillary or by the thermodynamic minimisation of interfacial area. Double w/o/w drops with well-defined internal droplet size and number were produced and then exposed to online photopolymerization to create the porous particles. Cylindrical interconnected porous particles were produced in a segmented flow where the drops took the shape of the capillary. The microfluidic set up included an extension capillary where the drops relaxed and conformed to their thermodynamically favoured morphology. Window opening of the particles occurred "on-the-fly" during UV polymerization without using any offline auxiliary methods. A distinction was made between critically and highly packed arrangements in double drops. The window opening occurred consistently for highly packed spherical drops, but only for critically packed drops containing more than 6 internal cores at internal phase ratio as low as 0.35. The size and number of cores, shape and structure of double drops could be precisely tuned by the flowrate and by packing structure of the inner droplets.
Polypropylene carbonate (PPC) derived from carbon dioxide has been used as a precursor for the synthesis of polyurethane (PU). The high viscosity of the PPC is the key parameter hindering its processability during PU synthesis. Herein, a PPC nanocomposite with highly exfoliated nanoclay was prepared through a solution intercalation process. A wide range of nanoclay concentrations incorporated into the PPC were studied. The impacts of the nanoclay on the PPC were investigated in order to maintain the polymer structure while improving its physical properties. The characterizations of PPC nanocomposites showed that the highly exfoliated nanoclay contributed to a viscosity reduction, and a slight reduction in the molecular weight. The polymer degradation was indicated by the formation of cyclic propylene carbonate. The minimum or critical concentration of nanoclay was found to be between ∼0.5 and 2.0 wt %. Within this range, the polymer degradation is minimal. The PPC nanocomposites with a lower viscosity showed excellent precursors for making PU coating materials. The PU coating derived from the PPC nanocomposite has higher anticorrosive properties in comparison with the non-modified PU coating.
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