Cp(π-Allyl)Pd-Initiated Polymerization of Diazoacetates: Reaction Development, Kinetic Study, and Chain Transfer with Alcohols,Macromolecules

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Cp(π-Allyl)Pd-Initiated Polymerization of Diazoacetates: Reaction Development, Kinetic Study, and Chain Transfer with Alcohols
Macromolecules ( IF 5.1 ) Pub Date : 2021-11-16 , DOI: 10.1021/acs.macromol.1c01966
Xing-Qi Yao ₁ , Yi-Song Wang ₁ , Jianbo Wang _{1,

2}

Affiliation

A new initiating system, (cyclopentadienyl) (π-allyl)palladium(II) [Cp(π-allyl)Pd], for the polymerization of diazoacetate monomers has been developed. Homo- and copolymers bearing an ester substituent at every main-chain carbon atom were efficiently synthesized from various alkyl and aryl diazoacetates. In particular, this polymerization system can tolerate various functional groups, which allows for effective postpolymerization functionalization of the resultant polymers. Detailed kinetic study indicates that this polymerization has the characteristics of slow initiation and rapid propagation. Furthermore, alcohols were found to function as chain transfer agents as confirmed by polymerization experiments and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analyses of the polymer products, thus providing an effective method for controlling the molecular weight of the polymer.

中文翻译：

Cp(π-烯丙基)Pd 引发的重氮乙酸聚合：反应发展、动力学研究和链转移与醇

已开发出一种新的引发系统（环戊二烯基）（π-烯丙基）钯（II）[Cp（π-烯丙基）Pd]，用于重氮乙酸酯单体的聚合。在每个主链碳原子上带有酯取代基的均聚物和共聚物由各种重氮乙酸烷基酯和芳基酯有效合成。特别是，这种聚合体系可以容忍各种官能团，这允许对所得聚合物进行有效的聚合后官能化。详细的动力学研究表明，该聚合具有慢引发和快速增长的特点。此外，通过聚合实验和聚合物产物的基质辅助激光解吸电离飞行时间质谱 (MALDI-TOF-MS) 分析证实，醇类可用作链转移剂，

更新日期：2021-12-14

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