Leibniz-Institut für Polymerforschung Dresden e.V, Hohe Straße 6, 01069, Dresden, Germany; Technische Universität Dresden, Center for Advancing Electronics Dresden (cfaed) and Chair of Organic Chemistry of Polymers, 01062, Dresden, Germany.
Macromol Rapid Commun. 2013 Nov;34(22):1772-8. doi: 10.1002/marc.201300707. Epub 2013 Oct 22.
A powerful variation of traditional radical thiol-yne reaction with diphenylacetylene (DPA)-based starting materials leading to the quantitative and selective formation of the corresponding vinyl sulfides is reported. A variety of different thiols are shown to undergo reaction with DPA and the influence of their structure on reactivity is studied. The results obtained from the model reactions are then used to guide the efficient synthesis of hyperbranched poly(vinyl sulfide) (hb-PVS) systems by employing a dithiol and a trialkyne in an A2 + B3 approach. The polymers obtained show excellent solubility in common organic solvents and exhibit high refractive indices (e.g., 1.70 at 589 nm). The combined ease of processability and potential for cross-linking make these materials very interesting for applications, such as coatings for optical devices. The selective mono-addition thiol-yne reaction on DPA serves not only as a synthetic method for the preparation of PVS but could also be applied to the general modification of acetylene-containing materials.
报道了一种强大的传统自由基硫醇-炔反应变体，以二苯乙炔（DPA）为起始原料，可定量且选择性地形成相应的乙烯基硫醚。研究了多种不同的硫醇与 DPA 的反应，以及它们的结构对反应性的影响。然后，从模型反应中获得的结果用于通过在 A2 + B3 方法中使用二硫醇和三炔来指导超支化聚（乙烯基硫醚）（hb-PVS）系统的有效合成。得到的聚合物在常见有机溶剂中具有优异的溶解性，并表现出高折射率（例如，在 589nm 处为 1.70）。这些材料易于加工且具有交联的潜力，因此非常适合应用，例如用于光学器件的涂层。DPA 上的选择性单加成硫醇-炔反应不仅是制备 PVS 的合成方法，也可应用于含乙炔材料的一般修饰。
