molecular weight of 44.8 kDa with 85% of conversion. The short- coming of this process is that enzymes such as Novozym 435 which provides good results for e-ROP are expensive. Therefore, the feasi- bility of the process most likely depends on the catalyst reuse that might be limited to two cycles [13] with the use of carbon dioxide as solvent.
Several studies have shown that the use of carbon dioxide as solvent leads to the reduction of enzymatic activity by three different sorts of interaction as explained by Rosso et al. [13]: (1) pH reduction due to the production of carbonic acid derived from the reaction between CO2 and water present in the enzyme micro-environment [14]; (2) CO2 and lysine residues tend to form carbamates [14–16], and (3) enzyme essential water removal by the hydrophilic CO2 [17,18].
To overcome these drawbacks this work proposes the use of liquefied petroleum gas as polymerization solvent medium for polycaprolactone production through e-ROP of the monomer. When compared to carbon dioxide, the major components of LPG, propane and n-butane, present positive effect on enzymatic activity [18] while presenting a similar dielectric constant (solvent polar- ity) which is in the range from 1.6 to 1.9 for LPG and 1.6 for carbon dioxide [19]. Since liquid propane and n-butane exhibit low com- pressibility and very low solubility in water, the literature indicates that they have a hydrostatic behavior working as mechanical press or piston fluid that increases the system pressure changing favor- ably the enzyme conformation [20].
Besides, LPG is plenty available, cheaper and it can be used in much lower pressures compared to carbon dioxide. For example, at 65 ◦ C and 25 bar, LPG exhibits a density of 9.27 mol/L, while carbon dioxide will reach a similar density only at 124 bar [21]. In addition, as any pressurized gas, LPG has the advantage over liquid organic solvents of being easily separated from the final product by system depressurization. Furthermore, compared to pure propane and n- butane, LPG has a very much lower price and its composition is almost invariant with time, which guarantees safe working with expected reliable polymerization results.
Still, the selection of the reactor type, to drive the polymer- ization process in pressurized medium, is noteworthy because it exerts a strong influence on the quality of the final polymer obtained and the economic viability of the process [22]. Studies on the production of polycaprolactone in scCO2 with enzyme as cat- alyst have been performed in batch mode, in reactors/autoclaves of constant volume [9,10,23] and, more recently, using a variable volume reactor [13]. However, processes performed in continuous mode are generally more advantageous because of its good process control, high productivity and low cost (per mass of product) [24]. Moreover, the use of the packed bed reactor (PBR) allows the con- tinuous removal of inhibitory substances thereby facilitating the reuse of the enzymes, this being the most suitable reactor for long- term production on industrial scale as well as for the use of ratios higher of enzyme/substrate, being therefore more cost effective than those conventional operations carried out by batch reactors [25]. In this context, the only works found in the literature for e-ROP of