Commercial Processes for the Manufacture of Polystyrene

Modern Styrenic Polymers Polystyrene and Styrenic Copolymers. Edited by J. Scheirs and D. B. Priddy ( 2003 John Wiley Sons Ltd 

2 TECHNICAL CONSTRAINTS THAT INFLUENCE REACTOR SELECTION 

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COMMERCIAL PROCESSES FOR THE MANUFACTURE OF POLYSTYRENE 65 3.3 STEAM STRIPPING... 

Since polystyrene is one of the oldest commercial polymers with over 9 million tonnes/yr of sales, there have been thousands of patents issued covering all aspects of its manufacture and property enhancement. The styrene monomer readily polymerizes to polystyrene either thermally or with free-radical initiators (see Chapter 6 on free-radical polymerization and Chapter 8 on nitroxide-mediated polymerization). Commercial processes for the manufacture of polystyrene are described in Chapter 3 while process modelling and optimization of styrene polymerization is examined in Chapter 5. Styrene also can be polymerized via anionic and Ziegler-Natta chemistries using organometallic initiators. Using free radical and anionic polymerization chemistries, the... 

The commercial manufacture of polystyrene was batch mode through the 1930s and 1940s, with a gradual transition to continuous bulk polymerization beginning in the 1950s. Suspension polymerization was a common early polystyrene production process, where a single reactor produced a polymer slurry that had to be separated from the water and dried. This process was ideal for free radical... 

Styrene is one of the oldest and most studied monomers. It spontaneously generates free radials upon heating above 100 °C and polymerizes yielding amorphous polystyrene (PS). Styrene can also be polymerized by other mechanisms (anionic, cationic, or Zeigler-Natta) with the aid of chemical initiators. Commercially, over twenty billion pounds of PS are produced annually worldwide. All of this polystyrene is produced via free radical (FR) chemistry, and mostly via continuous solution polymerization processes. The commercial preference for the continuous solution process is due mainly to economic factors. Non-solution polymerization processes (suspension and emulsion) have lower reactor efficiency (product/reactor volume) due to reactor volume occupied by the water which adds to the manufacturing cost. 

While bulk or emulsion polymerization can also be used for the purpose, the commercial manufacture of polystyrene is mostly carried out in a solution process using a free-radical initiator. The solvent, typically ethylbenzene, used at a level of 2-30%, controls the viscosity of the solution. High-impact-grade polymer used in injection-molding and extrusion is modified with butadiene rubber incorporated during polymerization. The solvent and residual monomer in the crude resin is removed by flash evaporation or in a devolatilizing extruder (at about 225°C). Figure 2.9 is a schematic of the polymerization process. 

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