Abstract

Post‐polymerization modification provides an elegant way to introduce chemical functionalities onto macromolecules to produce tailor‐made materials with superior properties. This concept was adapted to well‐defined block copolymers of the poly(2‐oxazoline) family and demonstrated the large potential of these macromolecules as universal toolkit for numerous applications. Triblock copolymers with separated water‐soluble, alkyne‐ and alkene‐containing segments were synthesized and orthogonally modified with various low‐molecular weight functional molecules by copper(I)‐catalyzed azide‐alkyne cycloaddition (CuAAC) and thiol‐ene (TE) click reactions, respectively. Representative toolkit polymers were used for the synthesis of gold, iron oxide and silica nanoparticles.

Highlights

  • Post-polymerization modification provides an elegant way to introduce chemical functionalities onto macromolecules to produce tailor-made materials with superior properties

  • Every chemical functionality is tolerated in cationic polymerizations, though this limitation can be overcome by the use of protecting group chemistry or by suitable post-polymerization modification approaches

  • Zeta-potential measurements reveal a significant reduction of the positive value of cetylpyridinium chloride (CPC)-stabilized AuNCs in the presence of the polymer emphasizing the macromolecular surface modification and ion complex formation between the CPC ammonium and the polymer carboxylate (Figure 3D). This experiment was repeated with the multifunctional block copolymer P3-OH-SAc. The thioester (SAc) (PMeOx52-PPentynOx32(OH)32-PButenOx13(SAc)13) having a polyhydroxyl middle segment instead of polycarboxylate and the zeta potential stayed in the region of 40 mV as for the initial CPC-stabilized AuNCs (Figure 3D)

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Summary

Introduction

Post-polymerization modification provides an elegant way to introduce chemical functionalities onto macromolecules to produce tailor-made materials with superior properties. We combine well-established CuAAC and TE click reactions into one universal synthetic protocol for the orthogonal post-polymerization modification of triblock coPOxs aiming to generate a modular toolkit of multifunctional polymers (Figure 1).

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