Transesterification of Poly(ethyl glyoxylate): A Route to Structurally Diverse Polyglyoxylates,Macromolecules

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Transesterification of Poly(ethyl glyoxylate): A Route to Structurally Diverse Polyglyoxylates
Macromolecules ( IF 5.1 ) Pub Date : 2020-09-16 , DOI: 10.1021/acs.macromol.0c01197
Rebecca E. Yardley ₁ , Amir Rabiee Kenaree ₁ , Xiaoli Liang ₁ , Elizabeth R. Gillies _{1,

2}

Affiliation

Polyglyoxylates are a class of self-immolative polymers that depolymerize in solution and the solid state. The glyoxylic acid degradation product is a metabolite in the glyoxylate cycle and can also be processed in the liver in humans, making polyglyoxylates attractive for applications in the environment and in medicine. Although expanding the scope of available polyglyoxylates would enable new properties and applications, highly pure glyoxylate monomers are required for polymerization, and this level of purity is difficult to achieve for many potential monomers. To address this challenge, we report here the 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)-catalyzed post-polymerization transesterification of poly(ethyl glyoxylate) (PEtG) as a general method for the synthesis of directly inaccessible polyglyoxylates. Using a new end-capping strategy, PEtG compatible with the transesterification reaction was developed. n-Propanol, i-propanol, n-butanol, t-butanol, n-pentanol, n-hexanol, n-octanol, and benzyl alcohol were employed and the reactivities of these different alcohols were investigated. The resulting polyglyoxylates were characterized chemically and their thermal properties were compared. In all cases, the transesterified polyglyoxylates retained the stimuli-responsive depolymerization properties of the parent PEtG. In addition, functional polyglyoxylates based on allyl, propargyl, and furfuryl esters, which are suitable for subsequent click reactions, were prepared. The propargyl-functionalized polyglyoxylate was used to conjugate pyrene, and the resulting molecules underwent a change in fluorescence properties upon depolymerization.

中文翻译：

聚乙醛酸乙酯的酯交换反应：结构多样的聚乙醛酸的途径

聚乙醛酸酯是一类在溶液和固态下解聚的自消旋聚合物。乙醛酸降解产物是乙醛酸循环中的代谢产物，也可以在人的肝脏中加工，从而使聚乙醛酸酯在环境和医学中具有吸引力。尽管扩大可用的聚乙醛酸酯的范围将能够实现新的性能和应用，但是聚合仍需要高纯度的乙醛酸酯单体，并且对于许多潜在的单体而言，难以达到这种纯度。为了解决这一挑战，我们在此报告1,5,7-三氮杂双环[4.4.0]癸-5-烯（TBD）催化的聚乙醛酸乙酯（PEtG）的聚合后酯交换反应，作为该方法的一般方法直接合成的聚乙醛酸酯的合成。使用新的封顶策略，Ñ丙醇，我丙醇，Ñ丁醇，吨丁醇，Ñ戊醇，Ñ己醇，Ñ使用了辛醇和苄醇，并研究了这些不同醇的反应性。对所得的聚乙醛酸酯进行化学表征，并比较其热性能。在所有情况下，酯交换的聚乙醛酸酯都保留了母体PEtG的刺激响应解聚特性。另外，制备了适用于随后的点击反应的基于烯丙基，炔丙基和糠酸酯的官能聚乙醛酸酯。炔丙基官能化的聚乙醛酸酯用于缀合pyr，并且解聚后所得分子的荧光性质发生变化。

更新日期：2020-10-13

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