Recyclable Vinyl-Functionalized Polyesters via Chemoselective Organopolymerization of Bifunctional alpha-Methylene-delta-Valerolactone
Recyclable Vinyl-Functionalized Polyesters via Chemoselective Organopolymerization of Bifunctional alpha-Methylene-delta-Valerolactone
复制标题
通过双官能α-亚甲基-δ-戊内酯的化学选择性有机聚合制备可回收乙烯基官能化聚酯
DOI：
10.1002/macp.201900150
复制
发表时间：
2019
影响因子：
2.5
通讯作者：
Zhang Xue Min
中科院分区：
文献类型：
--
作者：
Xu Tie Qi;Yu Zhi Qi;Zhang Xue Min
α-亚甲基-δ-戊内酯是一种由高度稳定的六元δ-戊内酯环和高活性C--C键组成的双功能单体。以前，乙烯基加成聚合(VAP)的产物，即P(MVL)VAP是专门形成的。在这项研究中，这种传统的化学选择性发生了逆转，其中有机催化剂用于实现MVL的第一次开环聚合(ROP)，专门提供了一种不含金属的不饱和聚酯，即P(MVL)ROP。这个具有挑战性的目标是通过研究不同的催化剂、引发剂和反应条件来实现的。此外，P(MVL)ROP和P(MVL)VAP这两种聚合物的形成很容易通过改变聚合溶剂来调节。由此得到的P(MVL)ROP可以很容易地进行后官能化以形成交联或硫化材料；值得注意的是，它可以通过热化学几乎完全转化为其单体。
α‐Methylene‐δ‐valerolactone (MVL) is a bifunctional monomer comprising of a highly stable six‐membered δ‐valerolactone ring and highly reactive CC bond. Previously, the vinyl‐addition polymerization (VAP) product, namely P(MVL)VAP, has been formed exclusively. In this study, this conventional chemoselectivity is reversed, wherein organic catalysts are used to enable the first ring‐opening polymerization (ROP) of MVL, exclusively affording a metal‐free, unsaturated polyester, namely P(MVL)ROP. This challenging goal is achieved by investigating different catalysts, initiators, and reaction conditions. In addition, the formation of two polymers, namely P(MVL)ROPand P(MVL)VAP, is easily regulated by varying the polymerization solvent. The resulting P(MVL)ROPcan be easily post‐functionalized to form crosslinked or sulfurized materials; notably, it can be almost completely converted into its monomer thermochemically.