Thioacetate‐Based Initiators for the Synthesis of Thiol‐End‐Functionalized Poly(2‐oxazoline)s,Macromolecular Rapid Communications

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Thioacetate‐Based Initiators for the Synthesis of Thiol‐End‐Functionalized Poly(2‐oxazoline)s
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2020-08-16 , DOI: 10.1002/marc.202000320
Gabriela Gil Alvaradejo ₁ , Mathias Glassner ₂ , Ravi Kumar _{3,

4} , Vanessa Trouillet _{4,

5} , Alexander Welle _{4,

6} , Yangxin Wang ₁ , Victor R de la Rosa ₂ , Sylwia Sekula-Neuner _{4,

7} , Michael Hirtz _{3,

4} , Richard Hoogenboom ₂ , Guillaume Delaittre _{1,

8}

Affiliation

Institute of Biological and Chemical Systems (IBCS), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen, 76344, Germany.
Supramolecular Chemistry Group, Centre of Macromolecular Chemistry (CMaC), Department of Organic and Macromolecular Chemistry, Ghent University, Krijgslaan 281-S4, Ghent, 9000, Belgium.
Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen, 76344, Germany.
Karlsruhe Institute of Technology (KIT), Karlsruhe Nano Micro Facility, Hermann-von Helmholtz-Platz 1, Eggenstein-Leopoldshafen, 76344, Germany.
Institute for Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen, 76344, Germany.
Karlsruhe Institute of Technology (KIT), Institute of Functional Interfaces, Hermann-von Helmholtz-Platz 1, Eggenstein-Leopoldshafen, 76344, Germany.
n.able GmbH, Hermann-von Helmholtz-Platz 1, Eggenstein-Leopoldshafen, 76344, Germany.
Organic Functional Molecules, Organic Chemistry, University of Wuppertal, Gaußstrasse 20, Wuppertal, 42119, Germany.

New functional initiators for the cationic ring‐opening polymerization of 2‐alkyl‐2‐oxazolines are described to introduce a thiol moiety at the α terminus. Both tosylate and nosylate initiators carrying a thioacetate group are obtained in multigram scale, from commercial reagents in two steps, including a phototriggered thiol–ene radical addition. The nosylate derivative gives access to a satisfying control over the cationic ring‐opening polymerization of 2‐ethyl‐2‐oxazoline, with dispersity values lower than 1.1 during the entire course of the polymerization, until full conversion. Cleavage of the thioacetate end group is rapidly achieved using triazabicyclodecene, thereby leading to a mercapto terminus. The latter gives access to a new subgeneration of α‐functional poly(2‐oxazoline)s (butyl ester, N‐hydroxysuccinimidyl ester, furan) by Michael addition with commercial (meth)acrylates. The amenability of the mercapto‐poly(2‐ethyl‐2‐oxazoline) for covalent surface patterning onto acrylated surfaces is demonstrated in a microchannel cantilever spotting (µCS) experiment, characterized by X‐ray photoelectron spectroscopy (XPS) and time‐of‐flight secondary‐ion mass spectrometry (ToF‐SIMS).

中文翻译：

硫代乙酸基引发剂用于合成巯基末端官能化聚（2-恶唑啉）

描述了2-烷基-2-恶唑啉阳离子开环聚合的新功能引发剂，可在α末端引入硫醇部分。带有硫代乙酸酯基团的甲苯磺酸酯和nosylate引发剂都是以克级形式从商业试剂中分两步获得的，包括光引发的硫醇-烯基的加成。壬酸酯衍生物可以令人满意地控制2-乙基-2-恶唑啉的阳离子开环聚合反应，在整个聚合过程中直至完全转化之前，分散度值均低于1.1。使用三氮杂双环癸烯可快速实现硫代乙酸酯端基的切割，从而形成巯基末端。后者使人们可以使用新一代的α-官能聚（2-恶唑啉）（丁酯，N-羟基琥珀酰亚胺基酯，呋喃），由Michael加成并与市售（甲基）丙烯酸酯。巯基聚（2-乙基-2-恶唑啉）在丙烯酸通道表面上共价表面构图的适应性在微通道悬臂点样（µCS）实验中得到了证明，其特征在于X射线光电子能谱（XPS）和时间飞行二次离子质谱（ToF-SIMS）。

更新日期：2020-09-22

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