Hobich Jan, Huber Birgit, Theato Patrick, Mutlu Hatice
Soft Matter Synthesis Laboratory, Institute for Biological Interfaces 3 (IBG 3), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen, D-76344, Germany.
Institute for Chemical Technology and Polymer Chemistry (ITCP), Karlsruhe Institute of Technology (KIT), Engesserstr.18, Karlsruhe, D-73131, Germany.
Macromol Rapid Commun. 2021 May;42(10):e2100118. doi: 10.1002/marc.202100118. Epub 2021 Apr 8.
The preparation of polymers containing sulfur-nitrogen bond derivatives, particularly 2,2,6,6-tetramethylpiperidine-1-sulfanyl (TEMPS) dimers (i.e., BiTEMPS), has been limited to free-radical or conventional step-growth polymerization as result of the inherent thermal lability of the BiTEMPS unit. Accordingly, a novel poly(diaminodisulfide) possessing the BiTEMPS functional group is synthesized via acyclic diene metathesis (ADMET) polymerization at 65-75 °C within 3 h with precise control over the primary polymer structure. Polymer is isolated with an M of 20 400 g mol and Ð of 1.9. Importantly, detailed nuclear magnetic resonance (NMR), size exclusion chromatography, attenuated total reflectance Fourier transform infrared (ATR-IR) in addition to elemental analysis studies of the BiTEMPS polymer confirm the successful polymerization, and show that the BiTEMPS unit remains intact during the polymerization process. Furthermore, the previously unexplored UV-responsiveness of the BiTEMPS decorated polymer backbone is investigated for the very first time.
由于双（2,2,6,6-四甲基哌啶-1-硫基）（BiTEMPS）单元固有的热不稳定性，含硫氮键衍生物聚合物，特别是2,2,6,6-四甲基哌啶-1-硫基（TEMPS）二聚体（即BiTEMPS）的制备仅限于自由基聚合或传统的逐步增长聚合。因此，通过无环二烯复分解（ADMET）聚合在65-75°C下3小时内合成了具有BiTEMPS官能团的新型聚（二氨基二硫化物），并对初级聚合物结构进行了精确控制。分离得到的聚合物的分子量为20400 g/mol，分散度为1.9。重要的是，除了对BiTEMPS聚合物进行元素分析研究外，详细的核磁共振（NMR）、尺寸排阻色谱、衰减全反射傅里叶变换红外光谱（ATR-IR）证实了聚合反应的成功，并表明BiTEMPS单元在聚合过程中保持完整。此外，首次研究了BiTEMPS修饰的聚合物主链以前未被探索的紫外线响应性。
