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Controlled Polymerization of Ethyl Glyoxylate Using Alkyllithium and Alkoxide Initiators
Macromolecules ( IF 5.5 ) Pub Date : 2018-07-16 00:00:00 , DOI: 10.1021/acs.macromol.8b01007
Amir Rabiee Kenaree 1 , Elizabeth R. Gillies 1, 2
Affiliation  

The synthesis of poly(ethyl glyoxylate)s (PEtGs) by anionic polymerization was explored. PEtGs are a subclass of stimulus-responsive self-immolative polymers with promising properties for applications as coatings, sensors, and drug delivery vehicles. In this paper, a new purification procedure for the preparation of highly pure ethyl glyoxylate (EtG), suitable for anionic polymerization reactions, and the first successful examples of controlled polymerization of EtG are described. n-BuLi, PhLi, and t-BuLi were employed as initiators under different experimental conditions, and their behavior was examined using NMR spectroscopy, size exclusion chromatography, and thermal analysis to develop an optimized procedure. As functional alkoxide initiators, propargyl alkoxide was employed in optimization studies and poly(ethylene glycol) (PEG) dialkoxide was utilized for the direct synthesis of PEtG–PEG–PEtG copolymers. The new polymerization method revealed many features of controlled polymerization reactions, yielding PEtGs with predictable molar masses and relatively low dispersity values.

中文翻译:

使用烷基锂和醇盐引发剂控制乙醛酸乙酯的聚合

探索了通过阴离子聚合反应合成聚乙醛酸乙酯(PEtGs)的方法。PEtG是刺激响应性自消融聚合物的一个子类,具有前景广阔的性能,可用于涂料,传感器和药物运输工具。在本文中,描述了一种适用于阴离子聚合反应的高纯度乙醛酸乙酯(EtG)制备的新纯化工艺,以及控制下EtG聚合的第一个成功实例。n -BuLi,PhLi和t-BuLi在不同实验条件下用作引发剂,并使用NMR光谱,尺寸排阻色谱法和热分析法检查其行为,以开发优化程序。作为功​​能性醇盐引发剂,炔丙基醇盐用于优化研究,而聚乙二醇(PEG)二烷醇盐用于直接合成PEtG–PEG–PEtG共聚物。新的聚合方法显示出受控聚合反应的许多特征,得到具有可预测的摩尔质量和相对较低的分散度值的PEtG。
更新日期:2018-07-16
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