2‐Methyltetrahydrofuran (2‐MeTHF) as a versatile green solvent for the synthesis of amphiphilic copolymers via ROP, FRP, and RAFT tandem polymerizations

Abstract

2-methyltetrahydrofuran (2-MeTHF) is a readily available, inexpensive, neoteric, bio-based solvent. It has been adopted across a wide range of chemical processes including the batch manufacture of fine chemicals, enzymatic polycondensations and ring opening polymerizations. To reduce the environmental burden related to the synthesis of pharmaceutical-grade polymers based on lactide and caprolactone, we envisaged the use of 2-MeTHF. For the first time, we combined a series of metal-free and enzymatic ROPs with free radical and controlled RAFT polymerizations (carried out separately and in tandem) in 2-MeTHF, in order to easily tune the chemistry and the architecture of the final polymers. After a simple purification, the amphiphilic polymers were formulated into nanoparticles and tested for their cytocompatibility in three model cell lines, to assess their application as potential polymeric excipients for nanomedicines. K E Y W O R D S2-MeTHF, green solvent, organo-enzymatic ROP, ROP-free radical tandem polymerizations, ROP-RAFT tandem polymerizations

Lignin Nanoparticles Support Lipase‐Tyrosinase Enzymatic Cascade in the Synthesis of Lipophilic Hydroxytyrosol Ester Derivatives

“…Irrespective from the experimental conditions, the highest yield of 5 was generally obtained using the 1 : 1 ratio of the two reagents. 2‐MeTHF is a bio‐renewable reaction solvent [60] widely applied in bio‐catalysis and esterification processes [36,61] . Among the different experimental conditions tested with 2‐MeTHF, Catalyst II afforded 5 in yield higher than Catalyst I (Table 4, entry 16 versus entry 13).…”

Tuneable N‐Substituted Polyamides with High Biomass Content via Ugi 4 Component Polymerization

“…[23] From a sustainability perspective, there are several preferential solvents such as dimethyl carbonate, 2-methyltetrahydrofuran (Me-THF), or cyclopentyl methyl ether. [36][37][38] To test the versatility of the reaction to proceed in only sustainable solvents, the polymerization was also repeated in a single solvent, Me-THF, and the ob-tained polymer (P1F) was analyzed in the same manner as the previous polymers (Table 1, Figure 1A). The polymerization proceeded in Me-THF, and there were no observed solubility issues, however, the MW achieved was lower than with the optimal 2:1 MeOH/THF system.…”

On-line polymerisation monitoring in scCO2: a reliable and inexpensive sampling method in high pressure applications

“…In an attempt to investigate the kinetics of two simultaneous competing reactions, the HEMA initiated eROP of εcaprolactone in scCO2 was studied. The hydroxyl group of HEMA can act as an initiator in ROP to yield functional polymers [63,64]. While in the presence of Novozym 435, HEMA is known to undergo transesterification with itself, resulting in a lack of control over the polymers produced [65,66].…”