TAD Click Chemistry on Aliphatic Polycarbonates: A First Step Toward Tailor‐Made Materials

Abstract

For the first time, the effectiveness of triazolinedione (TAD) click chemistry onto aliphatic polycarbonates (APC) is demonstrated. Statistic copolymers carrying click‐reactive conjugated diene (in a ratio of 10%) are synthesized via organocatalyzed ring‐opening polymerization. The highly efficient click reaction of TADs carrying simple butyl and phenyl functions are confirmed by 1H‐NMR and DSC. Network formation using a bivalent TAD is also performed and simply characterized by DSC. This post‐polymerization functionalization of biocompatible and biodegradable APC pave the way to easy and versatile “on‐demand” materials design.

Amphiphilic tri- and tetra-block co-polymers combining versatile functionality with facile assembly into cytocompatible nanoparticles

“…22 In addition, main-chain substituted polycarbonates can be synthesised from functionalised cyclic carbonate monomers through relatively simple chemistry, thus allowing ready access to covalently-linked polymer-drug conjugates. 23 There are now several reports that both lactide and cyclic carbonate monomers can be ring-opened under ambient conditions with organocatalysts, such as 1,8-diazabicyclo [5.4.0] undec-5-ene (DBU), [24][25][26][27] thus negating the need for metal catalysts or high temperatures which might otherwise generate toxic or degraded components in the final polymer product. These data suggest that functionalised materials which are (a) biodegradable and (b) adaptable for a variety of therapeutic formats might be produced through ring-opening polymerisations of carbonates under mild reaction conditions.…”

Versatile, Highly Controlled Synthesis of Hybrid (Meth)acrylate–Polyester–Carbonates and their Exploitation in Tandem Post‐Polymerization–Functionalization

“…In contrast, DBU is a milder organocatalyst which should result in fewer side‐reactions, while also allowing for ROP at room temperature and in “fumehood” conditions, in order to make these reactions more accessible in non‐specialist chemical laboratories …”

“…[21][22][23] In contrast, DBU is a milder organocatalyst which should result in fewer side-reactions, while also allowing for ROP at room temperature and in "fumehood" conditions, in order to make these reactions more accessible in non-specialist chemical laboratories. [22,[24][25][26][27] Based on this, this work reports the synthesis of a series of (bis)(meth)acrylate macromonomers produced via copolymerization of lactide and a BOC protected serinol-based cyclic carbonate monomer (tBSC). Succsseful variation of the nature of the initiator provided various end-chain functionalities to the final materials, to broaden the scope of materials achieveable through ROP syntheses.…”

Role of self‐assembly conditions and amphiphilic balance on nanoparticle formation of PEG‐PDLLA copolymers in aqueous environments

“…However, a major drawback with LA‐based polymers and copolymers is the toxic catalyst and stringent reaction conditions typically utilized in their production . Recently, we demonstrated a more friendly catalytic approach for ROP of LA in ambient conditions and at room temperature, using mild organocatalysts such as 1,8‐diazabicyclo[5.4.0]undec‐5‐ene (DBU) . This synthetic approach negates the need for toxic catalysts, high temperature reactions (over 120°C), and more extensive purifications, thereby facilitating further access to these materials across nonspecialist chemical laboratories.…”

“…[15][16][17] Recently, we demonstrated a more friendly catalytic approach for ROP of LA in ambient conditions and at room temperature, [18][19][20] using mild organocatalysts such as 1,8diazabicyclo [5.4.0]undec-5-ene (DBU). [21][22][23][24] This synthetic approach negates the need for toxic catalysts, high temperature reactions (over 120 C), and more extensive purifications, thereby facilitating further access to these materials across nonspecialist chemical laboratories.…”