Summary: A strong viscosity increase upon polymerization hinders cavitation and subsequent radical formation during an ultrasound‐induced bulk polymerization. In this work, ultrasound‐induced radical polymerizations of methyl methacrylate (MMA) have been performed in CO2‐expanded MMA in order to reduce the viscosity of the reaction mixture. For this purpose, the phase behavior of CO2/MMA systems has been determined. With temperature oscillation calorimetry, the influence of CO2 on the viscosity and on the reaction kinetics of ultrasound‐induced polymerizations of MMA has been studied. In contrast to polymerizations in bulk, this technique shows that a low viscosity is maintained during polymerization reactions in CO2‐expanded MMA. As a consequence, a constant or even increasing polymerization rate is observed when pressurized CO2 is applied. Moreover, the ultrasound‐induced polymer scission in CO2‐expanded MMA is demonstrated, which appears to be a highly controlled process. Finally, a preliminary sustainable process design is presented for the production of 10 kg/h pure PMMA (specialty product) in CO2‐expanded MMA by ultrasound‐induced initiation.Process flow diagram of the ultrasound‐induced polymerization of MMA in CO2‐expanded MMA.magnified imageProcess flow diagram of the ultrasound‐induced polymerization of MMA in CO2‐expanded MMA.

Ultrasound-induced polymer scission is a nonrandom process which alters the molecular weight distribution of polymers. However, transient cavitation, and consequently polymer scission, is not possible in concentrated polymer solutions due to the high liquid viscosity. The addition of an antisolvent can be used to circumvent this problem because the antisolvent decreases the gyration radius of polymer chains, which induces a reduction in liquid viscosity. To determine the influence of carbon dioxide (CO2) as an antisolvent on the ultrasound-induced scission rate, ultrasonic scission experiments of poly(methyl methacrylate) have been performed in bulk methyl methacrylate (MMA) as well as in CO2-expanded MMA. Modeling the experimental time-dependent molecular weight distributions (MWD) has revealed the scission kinetics at different polymer concentrations and CO2 fractions. At low polymer concentrations, the scission rate is decreased upon an increased CO2 content. This is a result of the higher vapor pressure of CO2, which cushions the cavitation. However, at higher polymer concentrations, this effect is counteracted by the viscosity reduction induced by CO2. As a consequence, the scission rate in CO2-expanded MMA is higher as compared to bulk MMA for solutions with a high polymer concentration. The results show that ultrasound-induced scission in pressurized CO2 can alter and control the MWD of polymers even in concentrated polymer solutions, whereas ultrasound-induced scission in bulk solutions is limited to relatively low polymer concentrations.

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