ROP and crystallization behaviour of partially renewable triblock aromatic-aliphatic copolymers derived from L-lactide

Tuning the Properties of Furandicarboxylic Acid-Based Polyesters with Copolymerization: A Review

“…The vast majority of these copolymers were prepared by melt polycondensation reactions at high temperatures. A number of alternative approaches has also been investigated; the synthesis of cyclic furanoate oligomers has allowed for the preparation of furanoate copolymers, notably PBF copolymers, by ring-opening polymerization (ROP) [ 64 , 66 , 83 , 86 , 98 , 105 ]. Additionally, the use of enzymatic polymerization has been employed, which warrants a more sustainable synthetic procedure and milder reaction conditions [ 80 , 86 , 93 ].…”

“…When copolymerization aims at the introduction of lactyl or ε -oxycaproate units, two different strategies have been adopted. On the one hand, the previously mentioned two-step polymerization process is adapted, and an ROP stage is introduced [ 49 , 67 , 87 , 95 , 98 ]. In other words, esterification or transesterification yields furanoate oligomers; then, ε -caprolactone or lactide and a catalyst are added, and ROP takes place.…”

“…Otherwise, as previously stated, TBT or Sb 2 O 3 are used for the two other steps. A noteworthy exception is the use of a metal-free catalyst, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, for the ROP of lactide by PHF oligomers, which was conducted at room temperature for 5 min [ 98 ]. Very high average molecular weights were not achieved, but lower ones have also been reported.…”

“…Block or multiblock copolymers are obtained in copolymers incorporating polyether segments, such as poly(ethylene glycol) (PEG) or poly(tetramethylene glycol) (PTMG) [ 46 , 47 , 48 , 56 , 88 , 89 , 90 , 91 , 93 , 94 , 101 ]. When ROP with CL or lactide is included in the polymerization, the outcome depends on the experimental conditions, and both random [ 49 , 54 , 85 ] and block copolymers [ 54 , 87 , 95 , 98 ] have been obtained. The structure depends mainly on whether monomers or oligomers are employed as starting products and on whether the conditions are harsh enough to cause some depolymerization of PLA or PCL oligomers, or favor transesterification reactions.…”

“…The high stiffness of the furan ring can benefit the formation of 2,5-FDCA block copolymers, where the furan-based polyesters act as the hard segment and can be considered as physical crosslinking points. A number of polymers were used in the literature as a soft segment for the creation of 2,5-FDCA-based copolymers such as PEG [ 47 , 48 , 88 , 89 ], poly(tetramethylene glycol) (PTMG) [ 56 , 94 ], PPO [ 93 ], and PLA [ 98 ]. The thermal behavior of these materials is quite similar and heavily dependent on the block length, as well as to the content of each block.…”