Radical Copolymerization of Vinyl Ethers and Cyclic Ketene Acetals as a Versatile Platform to Design Functional Polyesters

Abstract

Free-radical copolymerization of cyclic ketene acetals (CKAs) and vinyl ethers (VEs) was investigated as an efficient yet simple approach for the preparation of functional aliphatic polyesters. The copolymerization of CKA and VE was first predicted to be quasi-ideal by DFT calculations. The theoretical prediction was experimentally confirmed by the copolymerization of 2-methylene-1,3-dioxepane (MDO) and butyl vinyl ether (BVE), leading to r =0.73 and r =1.61. We then illustrated the versatility of this approach by preparing different functional polyesters: 1) copolymers functionalized by fluorescent probes; 2) amphiphilic copolymers grafted with poly(ethylene glycol) (PEG) side chains able to self-assemble into PEGylated nanoparticles; 3) antibacterial films active against Gram-positive and Gram-negative bacteria (including a multiresistant strain); and 4) cross-linked bioelastomers with suitable properties for tissue engineering applications.

Simulation of the Degradation of Cyclic Ketene Acetal and Vinyl‐Based Copolymers Synthesized via a Radical Process: Influence of the Reactivity Ratios on the Degradability Properties

“…We first studied the evolution of the cumulative (average) mole fraction of different vinyl monomers units in the copolymer ( F vinyl ) with the overall molar conversion ( Figure ). Styrene and methacrylics illustrate the case where the vinyl reactivity ratio ( r vinyl ) is very high compared to r CKA ( r MDO = 0.021 and r S = 22.6; r MDO = 0.04 and r MMA = 3.5), whereas VAc and VE are examples of vinyl monomers where r vinyl and r CKA are both close to 1 ( r VE = 1.61 and r MDO = 0.73; r VAc = 1.53 and r MDO = 0.47). Please note here that whatever the radical process (controlled or free radical polymerization), the evolution of F vinyl with the overall molar conversion is similar.…”

“…This phenomenon can be explained by the strong difference between the vinyl and CKA reactivity ratios ( r vinyl and r CKA , respectively) with r CKA values generally very low (and close to 0) compared to the r vinyl ones (e.g., r MDO = 0.023 and r MA = 26.53; r MDO = 0.021 and r S = 22.6; r MDO = 0.04 and r MMA = 3.5). The only noticeable exceptions concern the systems MDO/VAc and MDO/VE with reactivity ratios both close to 1 ( r VE = 1.61 and r MDO = 0.73; r VA = 1.53 and r MDO = 0.47). In this case, one can expect a more homogeneous and statistical repartition of the cleavable ester units all along the polymer chain and consequently a narrow distribution of the fragmented chains length after degradation.…”

“…In particular, five and seven‐membered ring monomers like 2‐methylene‐4‐phenyl‐1,3‐dioxolane (MPDL) and 2‐methylene‐1,3‐dioxepane (MDO), or 5,6‐benzo‐2‐methylene‐1,3‐dioxepane (BMDO), respectively are of great interest thanks to their good stability and their well‐described synthesis. Their copolymerization by rROP with vinyl monomers like styrene (S), methyl acrylate (MA), methyl methacrylate (MMA), vinyl acetate (VA), or vinyl ether (VE) enables the elaboration of degradable vinyl materials . Their hydrolytic degradation that can be performed under different conditions (few hours to several days in deionized water, phosphate‐buffered saline (PBS) or under accelerated conditions in presence of KOH or HCl) is nevertheless difficult to precisely quantify and can be reported according to different criteria (soluble or not in the medium, weight loss measurements etc.).…”

Direct Metal‐Free Preparation of Functionalizable Polylactic Acid‐Ethisterone Conjugates in a One‐Pot Approach

“…Polyesters are one of the most widely used biodegradable materials . Moreover, polylactic acid (PLA) represents a biocompatible, nontoxic, and biorenewable polymer, it offers diverse and potent fields of application particularly in biomedical and pharmaceutical areas, such as the production of resorbable sutures, bioabsorbable implants for bone fixation, scaffolds for tissue engineering, and carriers for controlled drug release systems …”

Académie des Sciences Prizes 2018

“…Heute ist sie Te chnische Direktorin am Centre de RØsonance MagnØtique Nucleaire à trsh auts Champs,L yon, (Europäisches Zentrum fürH ochfeld-NMR) und stellvertretende Direktorin der Infrastructure de Recherche dØcentralisØeRMN Tr sHauts Champs (Franzçsische Hochfeld-NMR-Forschungseinrichtungen). [4] ValØrie Gabelica (Institut EuropØen de Chimie et Biology (IECB), UniversitØ de Bordeaux) studierte an der UniversitØ de Lige und promovierte dort 2002 unter Anleitung von Edwin De Pauw. [3a] Sie ist außerdem Koautorin eines Berichts über gefrorene Acrylamidgele als DNP-Matrix.…”