Synthesis of Isohexide Diyne Polymers and Hydrogenation to Their Saturated Polyethers,ACS Macro Letters

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Synthesis of Isohexide Diyne Polymers and Hydrogenation to Their Saturated Polyethers
ACS Macro Letters ( IF 5.1 ) Pub Date : 2021-08-03 , DOI: 10.1021/acsmacrolett.1c00422
Ethan A Gormong ₁ , Theresa M Reineke ₁ , Thomas R Hoye ₁

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The incorporation of renewable feedstocks into polymer backbones is of great importance in modern polymer science. We report the synthesis of 1,3-diyne polymers derived from the bispropargyl ethers of isosorbide, isomannide, and isoidide. The dialkyne monomers can be polymerized through an adaptation of the Glaser–Hay coupling using a nickel(II) cocatalyst. These well-defined diyne polymers bear an iodoalkyne end group, afforded through an unanticipated reductive elimination pathway, and display glass transition temperatures (T_g) from 55 to 64 °C. Fully saturated, analogous polyethers can be prepared from the hydrogenation of the diyne polymers, and these show T_g values between −10 and −2 °C. Both the 1,3-diyne polymers and the saturated analogues display similar trends in their T_g values vis-à-vis the stereochemical features of the isohexide unit within the backbone. This polymerization provided access to two series of isohexide-based polyethers, the thermal properties of which are influenced by the nature of the 2,4-hexadiynyl and hexamethylene linkers as well as the relative configuration of the bicyclic subunit in the backbone. The reported method represents an important step toward accessing well-defined polyethers from renewable feedstocks using readily available catalysts and convenient ambient conditions.

中文翻译：

异己二炔聚合物的合成及其饱和聚醚的加氢反应

将可再生原料掺入聚合物主链在现代聚合物科学中非常重要。我们报告了从异山梨醇、异甘露醇和异艾杜醇的双炔丙基醚衍生的 1,3-二炔聚合物的合成。二炔单体可以通过使用镍 (II) 助催化剂的 Glaser-Hay 偶联进行聚合。_{这些定义明确的二炔聚合物带有一个碘代炔烃端基}，通过意想不到的还原消除途径提供，并显示出 55 至 64 °C 的玻璃化转变温度 (Tg) 。完全饱和的类似聚醚可以从二炔聚合物的氢化中制备，这些显示T _g-10 和 -2 °C 之间的值。1,3-二炔聚合物和饱和类似物的T _g值相对于主链内异己酯单元的立体化学特征都显示出相似的趋势。这种聚合提供了获得两种基于异己酯的聚醚的途径，它们的热性能受 2,4-己二炔基和六亚甲基连接体的性质以及主链中双环亚基的相对构型的影响。所报道的方法代表了使用现成的催化剂和便利的环境条件从可再生原料中获得定义明确的聚醚的重要一步。

更新日期：2021-08-17

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