Unexpected radical polymerization behavior of oligo(2-ethyl-2-oxazoline) macromonomers

Weber, C.; Babiuch, Krzysztof; Rogers, Sarah E.; Perevyazko, Igor; Hoogenboom, Richard; Schubert, Ulrich S.

doi:10.1039/c2py20479g

Cited by 21 publications

(11 citation statements)

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confidence: 99%

“…Chemical and physical versatility is provided by variation of the side chain of the requisite 2-alkyl/aryl-2-oxazoline monomers, as well as by the use of suitable initiators and terminators for chain-end functionalization. − Notably, end-capping with appropriately designed terminators enables facile introduction of functional groups that would otherwise be incompatible with CROP. Moreover, end-capping with species such as styrenics, − acrylates, − and methacrylates ,− provides macromonomers (MM) that can be used to form graft and comb-like copolymers in subsequent graft-through polymerizations. For instance, RAFT copolymerization of methyl methacrylate and an ω-methacrylated poly(2-ethyl-2-oxazoline) (PEtOx) MM afforded pH- and temperature-responsive graft copolymers .…”

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confidence: 99%

“…For instance, RAFT copolymerization of methyl methacrylate and an ω-methacrylated poly(2-ethyl-2-oxazoline) (PEtOx) MM afforded pH- and temperature-responsive graft copolymers . Nonetheless, attempts to prepare PEtOx-based bottlebrush polymers (BBPs) via free radical, RAFT, or nitroxide-mediated polymerizations revealed a steric crowding effect, preventing the formation of BBPs with degrees of polymerization (DP) > 25 …”

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confidence: 99%

“…31 Nonetheless, attempts to prepare PEtOx-based bottlebrush polymers (BBPs) via free radical, RAFT, or nitroxide-mediated polymerizations revealed a steric crowding effect, preventing the formation of BBPs with degrees of polymerization (DP) > 25. 29 Graft-through ring-opening metathesis polymerization (ROMP) has been applied to the synthesis of a wide range of polymeric architectures including bottlebrush and dendronized polymers. 33−39 ROMP of norbornene-functionalized MMs using ruthenium initiators is particularly suited for the synthesis of side-chain functional polymers with controllable molar masses and low dispersities.…”

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Polyoxazoline-Based Bottlebrush and Brush-Arm Star Polymers via ROMP: Syntheses and Applications as Organic Radical Contrast Agents

et al. 2019

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The synthesis of functional poly(2-alkyl-2-oxazoline) (PAOx) copolymers with complex nanoarchitectures using a graft-through ring-opening metathesis polymerization (ROMP) approach is described. First, well-defined norbornene-terminated poly(2-ethyl-2-oxazoline) (PEtOx) macromonomers (MM) were prepared by cationic ringopening polymerization. ROMP of these MMs produced bottlebrush copolymers with PEtOx side chains. In addition, PEtOx-based branched MMs bearing a terminal alkyne group were prepared and conjugated to an azidecontaining bis-spirocyclohexyl nitroxide via Cu-catalyzed azide-alkyne cycloaddition (CuAAC). ROMP of this branched MM, followed by in situ cross-linking, provided PEtOx-based brush-arm star polymers (BASPs) with nitroxide radicals localized at the core-shell interface. These PEtOx-*

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Polyoxazoline-Based Bottlebrush and Brush-Arm Star Polymers via ROMP: Syntheses and Applications as Organic Radical Contrast Agents

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“…For this purpose, monoacrylated PEtOx polymers are required. Weber et al synthesized acrylated and methacrylated PEtOx macromonomers and studied their polymerization behavior [38,39]. Based on those studies and the end-capping protocol established in our recent work, we aimed to synthesize monoacrylated PEtOx macromonomers with a targeted degree of polymerization (DP) of 10 (PEtOx-A DP10) and 50 (PEtOx-A DP50) in a larger scale (Scheme 1).…”

Section: Synthesis and Structural Characterization Of Poly(2-oxazolinmentioning

confidence: 99%

Two-Photon Polymerized Poly(2-Ethyl-2-Oxazoline) Hydrogel 3D Microstructures with Tunable Mechanical Properties for Tissue Engineering

et al. 2020

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The main task of tissue engineering (TE) is to reproduce, replicate, and mimic all kinds of tissues in the human body. Nowadays, it has been proven useful in TE to mimic the natural extracellular matrix (ECM) by an artificial ECM (scaffold) based on synthetic or natural biomaterials to regenerate the physiological tissue/organ architecture and function. Hydrogels have gained interest in the TE community because of their ability to absorb water similar to physiological tissues, thus mechanically simulating the ECM. In this work, we present a novel hydrogel platform based on poly(2-ethyl-2-oxazoline)s, which can be processed to 3D microstructures via two-photon polymerization (2PP) with tunable mechanical properties using monomers and crosslinker with different degrees of polymerization (DP) for future applications in TE. The ideal parameters (laser power and writing speed) for optimal polymerization via 2PP were obtained using a specially developed evaluation method in which the obtained structures were binarized and compared to the computer-aided design (CAD) model. This evaluation was performed for each composition. We found that it was possible to tune the mechanical properties not only by application of different laser parameters but also by mixing poly(2-ethyl-2-oxazoline)s with different chain lengths and variation of the crosslink density. In addition, the swelling behavior of different fabricated hydrogels were investigated. To gain more insight into the viscoelastic behavior of different fabricated materials, stress relaxation tests via nanoindentation experiments were performed. These new hydrogels can be processed to 3D microstructures with high structural integrity using optimal laser parameter settings, opening a wide range of application properties in TE for this material platform.

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Poly(2‐oxazoline)s

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Encyclopedia of Polymer Science and Technology

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Research in the field of poly(2‐oxazoline)s (PAOx) is rapidly expanding as this polymer class combines high synthetic versatility and biocompatibility, opening up the way to highly functional (biocompatible) materials. PAOx are prepared by living cationic ring‐opening polymerization (CROP) of 2‐oxazolines. The variety of 2‐oxazoline monomers that are readily available or can easily be synthesized allows for tuning of polymer properties and introduction of diverse functionalities. Moreover, thanks to the living nature of CROP, well‐defined polymers with narrow molar mass distribution and high end group fidelity can be obtained. This article covers all aspects of PAOx ranging from the synthesis of 2‐oxazoline monomers, via in‐depth discussion on the CROP mechanism to the synthesis and properties of functional PAOx (co)polymers. The presented research demonstrates that owing to their structural adaptability and the so‐called “stealth” behavior, PAOx are well suited for a range of biomedical applications, including polymer therapeutics, scaffolds for three‐dimensional cell culture, surface modification, matrix excipient for solid dispersions, and antimicrobial agents.

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Unexpected radical polymerization behavior of oligo(2-ethyl-2-oxazoline) macromonomers

Cited by 21 publications

References 61 publications

Polyoxazoline-Based Bottlebrush and Brush-Arm Star Polymers via ROMP: Syntheses and Applications as Organic Radical Contrast Agents

Polyoxazoline-Based Bottlebrush and Brush-Arm Star Polymers via ROMP: Syntheses and Applications as Organic Radical Contrast Agents

Two-Photon Polymerized Poly(2-Ethyl-2-Oxazoline) Hydrogel 3D Microstructures with Tunable Mechanical Properties for Tissue Engineering

Poly(2‐oxazoline)s

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