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Cyclopropanation of poly(isoprene) using NHC‐Cu(I) catalysts: Introducing carboxylates
Journal of Polymer Science ( IF 3.9 ) Pub Date : 2020-09-03 , DOI: 10.1002/pol.20200404 Kshitij Sanjay Shinde 1 , Philipp Michael 1 , Michael Rössle 2 , Sven Thiele 2 , Wolfgang H. Binder 1
Journal of Polymer Science ( IF 3.9 ) Pub Date : 2020-09-03 , DOI: 10.1002/pol.20200404 Kshitij Sanjay Shinde 1 , Philipp Michael 1 , Michael Rössle 2 , Sven Thiele 2 , Wolfgang H. Binder 1
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The incorporation of functional groups into unsaturated polyolefine‐polymers often represent a challenging task. Based on the known cyclopropanation of double bonds with diazoesters in the presence of metal‐catalysts of low molecular weight compounds, we in this article develop an approach to decorate the polymer backbone of poly(diene)s with ester as well as carboxylic groups via cyclopropanation. Therefore, predominantly cis‐1,4‐poly(isoprene)s are converted with ethyl or tert‐butyl diazoacetate using copper(I) N‐heterocyclic carbene (NHC) catalysts, while focusing on the technically relevant cyclohexane as solvent. The application of commercially available NHC‐Cu(I) catalysts results in modification degrees of 4–5%, while an increased solvent polarity, like dichloromethane, results in up to 17% modification. The resulting esters were further converted to the corresponding free carboxylic groups by deprotection using trifluoroacetic acid. Thus, an introduction of functional groups along the polymer backbone with a wide variety of application, like ionic interaction or hydrogen bonding motifs, was successfully demonstrated. Its potential for upscaling makes this approach feasible for an application in large‐scale production processes, such as for manufacturing of modified synthetic rubbers.
中文翻译：
使用NHC-Cu（I）催化剂对聚异戊二烯进行环丙烷化：引入羧酸盐
将官能团掺入不饱和聚烯烃聚合物中通常是一项艰巨的任务。基于已知的在低分子量化合物的金属催化剂存在下双键与重氮酸酯的环丙烷化作用，我们在本文中开发了一种通过环丙烷化作用用酯和羧基修饰聚二烯的聚合物主链的方法。因此，主要是使用铜（I）N将顺式-1,4-聚（异戊二烯）与重氮乙基乙酸乙酯或叔丁基重氮乙酸酯转化杂环卡宾（NHC）催化剂，同时侧重于技术上相关的环己烷作为溶剂。使用市售的NHC-Cu（I）催化剂可实现4-5％的改性度，而增加溶剂极性（如二氯甲烷）可实现17％的改性。通过使用三氟乙酸脱保护，将所得的酯进一步转化为相应的游离羧基。因此，成功地证明了沿着聚合物主链引入具有广泛应用的官能团，例如离子相互作用或氢键基序。它具有扩大规模的潜力，使该方法可用于大规模生产过程中，例如用于制造改性合成橡胶。
更新日期：2020-10-17
中文翻译：
使用NHC-Cu（I）催化剂对聚异戊二烯进行环丙烷化：引入羧酸盐
将官能团掺入不饱和聚烯烃聚合物中通常是一项艰巨的任务。基于已知的在低分子量化合物的金属催化剂存在下双键与重氮酸酯的环丙烷化作用，我们在本文中开发了一种通过环丙烷化作用用酯和羧基修饰聚二烯的聚合物主链的方法。因此，主要是使用铜（I）N将顺式-1,4-聚（异戊二烯）与重氮乙基乙酸乙酯或叔丁基重氮乙酸酯转化杂环卡宾（NHC）催化剂，同时侧重于技术上相关的环己烷作为溶剂。使用市售的NHC-Cu（I）催化剂可实现4-5％的改性度，而增加溶剂极性（如二氯甲烷）可实现17％的改性。通过使用三氟乙酸脱保护，将所得的酯进一步转化为相应的游离羧基。因此，成功地证明了沿着聚合物主链引入具有广泛应用的官能团，例如离子相互作用或氢键基序。它具有扩大规模的潜力，使该方法可用于大规模生产过程中，例如用于制造改性合成橡胶。
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