Degradable Vinyl Polymer Nanoparticles/Latexes by Aqueous Nitroxide-Mediated Polymerization-Induced Self-Assembly

Abstract

The synthesis of degradable vinyl polymer nanoparticles/latexes in aqueous dispersed media is receiving much attention, particularly for biomedical applications and plastic pollution control, as it can circumvent the severe limitations associated with emulsification of preformed degradable polymers. Polymerisation-induced self-assembly (PISA), which enables the in-situ formation of aqueous suspensions of diblock copolymer nano-objects of high solids content, has become a very popular polymerization process due to its many advantages in terms of simplicity, robustness, scalability and versatility. However, the preparation of degradable vinyl polymer nanoparticles by direct aqueous PISA has never been reported. This severely limits the use of PISA in biomedical and environmental applications. Herein, we report the first aqueous emulsion PISA able to generate degradable vinyl polymer nanoparticles. It relies on radical ring-opening polymerization-induced self-assembly (rROPISA) of traditional vinyl monomers (n-butyl acrylate or styrene) with dibenzo[c,e]oxepane-5-thione (DOT), a thionolactone that features high stability in protic solvents and favourable reactivity with many vinyl monomers, and is a precursor of labile thioester groups in the main chain. Stable aqueous suspensions of thioester-containing diblock copolymer nanoparticles were obtained with both vinyl monomers. Extensive degradation of the copolymers and the nanoparticles was successfully demonstrated under aminolytic or basic conditions. Given the success of the PISA process within the polymer community, this work has the potential to greatly expand its use in many areas, from nanomedicine (providing an extension to biocompatible vinyl polymers) to sustained materials in the context of the polymer circular economy.

Dynamic Worm-Gel Materials as Tunable, Regenerable Adsorbents for Water Treatment

“…License: CC BY-NC-ND 4.0 3 accessing a diverse range of polymeric nanoparticles (NPs) with various morphologies and sizes. [1][2][3][4][5][6][7] These methodologies address significant barriers to scaling up traditional self-assembly procedures, enabling the streamlined synthesis of concentrated polymeric NP dispersions with typical solids content (SC%) ranging from SC% = 25 -50 w%. Reversible additionfragmentation chain transfer (RAFT) dispersion polymerization have been extensively investigated yielding detailed phase diagrams for many systems.…”

Degradable Linear and Bottlebrush Thioester-Functional Copolymers through Atom-Transfer Radical Ring-Opening Copolymerization of a Thionolactone

“…6 copolymerization of n-butyl acrylate and styrene with up to 2 mol % DOT. 15 Atom-transfer radical polymerization (ATRP) 16 is, arguably, more complex than RAFT polymerization. 17 However, it has a distinct advantage over (thermally initiated) RAFT in that it does not require a radical initiator (such as AIBN).…”

“…RDRP of thionolactones has been achieved exclusively through RAFT polymerization with which TARO radical polymerization appears to be fully compatible. During the writing of this article, Lages et al reported the successful nitroxide-mediated copolymerization of n -butyl acrylate and styrene with up to 2 mol % DOT …”

Degradable linear and bottlebrush thioester-functional copolymers through atom transfer radical ring-opening copolymerization of a thionolactone

“…During the writing of this manuscript, Lages et al reported the successful nitroxide-mediated copolymerization of n-butyl acrylate and styrene with up to 2 mol-% DOT. 15 Atom transfer radical polymerization 16 is, arguably, more complex than RAFT polymerization. 17 But it has a distinct advantage over (thermally initiated) RAFT in that it does not require a radical initiator (such as AIBN).…”