Forecasting linear aliphatic copolyester degradation through modular block design

Abstract

a b s t r a c tThe development of efficient methods to predict the degradation of renewable polymeric materials is continuously sought in the field of polymer science. Herein, we present a modular build-up approach to create polyester-based materials with forecasted degradation rates based on the hydrolysis of the constituent polymer blocks. This involved the strategic combination of critical factors affecting polyester hydrolysis, i.e. hydrophobicity and degree of crystallinity. The starting point of this method was a toolbox of polymers with different hydrophobicities and degrees of crystallinity, as well as an understanding of their inherent differences in hydrolysis rate. Knowledge of the hydrolysis of each polymer block module enabled the prediction of the overall degradation behavior of the constructed copolymers. Taking advantage of the primary factors that affect polymer degradation, block copolymers could be independently designed to incorporate soft or rigid and faster or slower degradation properties. This approach generated a shift for how molecular design can be used to predict the degradation behavior of intended materials for different applications.

Switching from Controlled Ring-Opening Polymerization (cROP) to Controlled Ring-Closing Depolymerization (cRCDP) by Adjusting the Reaction Parameters That Determine the Ceiling Temperature

“…5−7 These polymers, which are most often obtained by ring-opening polymerization of the respective cyclic monomers, allow, through different addition schemes or inherent reactivity behavior, the construction of refined macromolecular architectural features. 8−10 This enables control of many polymer properties, such as degradation, 11−13 mechanical performance, 11,14 and the placement of functional groups along the polymer chain. 15,16 …”

Acetalised Galactarate Polyesters: Interplay between Chemical Structure and Polymerisation Kinetics

“…Crystallinity and thus also the difference in the crystallisation rate can have a significant role in the hydrolytic stability and a correlation is possible i.e., between the relatively higher amount of formed crystalline regions and the better resistance to hydrolysis of the GxMe-16HD samples [ 39 , 40 ]. Nevertheless, it is worth mentioning that since the analysed polymer films were 0.1 mm thick, the diffusion rate through the sample is neglected.…”

N-Heterocyclic Olefin-Based (Co)polymerization of a Challenging Monomer: Homopolymerization of ω-Pentadecalactone and Its Copolymers with γ-Butyrolactone, δ-Valerolactone, and ε-Caprolactone

“…The formation of aliphatic polyester from lactones via ring-opening polymerization (ROP) is nowadays an established, intensively researched field of polymer chemistry. − The intrinsic properties of the materials combined with the convenient characteristics of ROP render them attractive for a number of applications, broadly ranging from drug delivery to tissue engineering and beyond. − Part of this allure is the considerable scope of readily available lactone monomers which can be used as building blocks. This flexibility is further accentuated by the ability to copolymerize various lactones, enabling a manipulation of almost all mechanical, thermal, and chemical properties, including degradation times, and a tailoring of the polymer composition (block copolymers, random copolymers). − However, to exploit this potential to its full extent, powerful catalysts are needed; the ability to (co)­polymerize lactones at will is presently still elusive. This is essentially down to two interlocked issues.…”