Controlled Ring-Opening Polymerization of Macrocyclic Monomers Based on Ring-Opening/Ring-Closing Cascade Reaction,Journal of the American Chemical Society

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Controlled Ring-Opening Polymerization of Macrocyclic Monomers Based on Ring-Opening/Ring-Closing Cascade Reaction
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-11-06 , DOI: 10.1021/jacs.3c10765
Wensen Chen _{1,

2} , Changjuan Guo _{1,

2} , Hao Ding _{1,

2} , Xingyu Yang _{1,

2} , Ke Zhang _{1,

2}

Affiliation

The development of a controlled ring-opening polymerization (ROP) method for synthesizing backbone-functionalized and sequence-controlled polymers with well-defined architectures from macrocyclic monomers is highly desirable in polymer chemistry. Herein, we developed a novel general controlled ROP of macrocycles for producing backbone functional and sequence-controlled polyurethanes and polyamides with controlled molecular weights and narrow dispersities (Đ < 1.1). The key to this method is the introduction of a trimethyl lock unit, an efficient cyclization-based self-immolative spacer, into the macrocyclic monomer ring as a “ring-opening trigger.” ROP is initiated by the attack of a primary amine nucleophile on the ring-activated carbonate/ester group, leading to the ring opening of the macrocyclic monomer. Subsequently, spontaneous 6-exo-trig cyclization of the trimethyl lock unit occurs, detaching this ring-opening trigger and regenerating the primary amine end group. The regenerated primary amine group can then be used to propagate the polymer chain by iterating the ring-opening-ring-closing cascade reaction. The versatile ROP method can be applied in the synthesis of water-soluble polyurethanes, backbone-degradable polyurethanes and poly(ester amide)s, and sequence-controlled poly(amino acid)s with well-defined macromolecular architectures.

中文翻译：

基于开环/闭环级联反应的大环单体可控开环聚合

聚合物化学中非常需要开发一种受控开环聚合（ROP）方法，用于从大环单体合成具有明确结构的主链官能化和序列控制聚合物。在此，我们开发了一种新型的通用受控大环ROP，用于生产具有受控分子量和窄分散度（Đ < 1.1）的主链功能和序列控制的聚氨酯和聚酰胺。该方法的关键是将三甲基锁单元（一种基于环化的高效自毁间隔基）引入大环单体环中作为“开环触发器”。ROP 是通过伯胺亲核试剂攻击环活化的碳酸酯/酯基团引发的，导致大环单体开环。随后，三甲基锁单元发生自发的 6- exo -trig 环化，分离该开环触发器并重新生成伯胺端基。然后，再生的伯胺基团可用于通过重复开环-闭环级联反应来增长聚合物链。多功能的ROP方法可应用于水溶性聚氨酯、主链可降解聚氨酯和聚(酯酰胺)以及具有明确大分子结构的序列控制聚(氨基酸)的合成。

更新日期：2023-11-06

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