Double Modification of Polymer End Groups through Thiolactone Chemistry

Abstract

A straightforward synthetic procedure for the double modification and polymer-polymer conjugation of telechelic polymers is performed through amine-thiol-ene conjugation. Thiolactone end-functionalized polymers are prepared via two different methods, through controlled radical polymerization of a thiolactone-containing initiator, or by modification of available end-functionalized polymers. Next, these different linear polymers are treated with a variety of amine/acrylate-combinations in a one-pot procedure, creating a library of tailored end-functionalized polymers. End group conversions are monitored via SEC, NMR, and MALDI-TOF analysis, confirming the quantitative modification after each step. Finally, this strategy is applied for the synthesis of block copolymers via polymer-polymer conjugation and the successful outcome is analyzed via LCxSEC measurements.

Automated Synthesis Protocol of Sequence‐Defined Oligo‐Urethane‐Amides Using Thiolactone Chemistry

“…The ring‐opening of homocysteine‐γ‐thiolactone with a primary amine releases the protected thiol, which can then undergo a subsequent in situ Michael addition with, for example, an acrylate or an acrylamide . This chemistry can be carried out in a one‐pot fashion, allowing double modification of the structure . While these reactions do not fulfill all of the criteria of click‐chemistry, they remain nonetheless very versatile and efficient for the preparation of defined structures …”

Polyoxazolines with a Vicinally Double-Bioactivated Terminus for Biomacromolecular Affinity Assessment

“…Multicomponent reactions (MCRs) have most recently emerged as one method to ligate multiple low molecular reaction partners, usually in one-pot syntheses [ 23 ]. However, due to reactive impediments, only a few polymers have since been used for MCR, with the main focus lying on (poly)saccharides [ 24 , 25 , 26 , 27 ], which so far leaves this set of reactions as an unsuitable synthesis method for the aforementioned system [ 28 ].…”

Two Pathways of Thiolactone Incorporation into Polyurethanes and Their One-Pot Double Postfunctionalization

“…The use of γ-thiolactones in polymer chemistry has recently gained considerable interest . Apart from their application as monomer in various step-growth polymerization strategies by thiol–ene reaction preceded by opening of the thiolactone ring, ,− the introduction of thiolactone groups either at chain ends , or laterally on the chains − is more and more considered. It opens nearly endless possibilities of polymer chain postmodifications.…”

“…Postpolymerization modification is a convenient approach for the preparation of a great variety of functional polymers with programmed properties from a single precursor polymer platform. ,, The large range of possibilities offered by thiolactone chemistry opens up a broad horizon for the preparation of tailor-made PUs. Advantageously, thiolactones are nonreactive during PU synthesis and thereby do not require any protection/deprotection step.…”