An efficient strategy for achieving controlled ring-opening polymerization of O-carboxyanhydrides via amine initiation in collaboration with metal-alkoxide catalysis†,Polymer Chemistry

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An efficient strategy for achieving controlled ring-opening polymerization of O-carboxyanhydrides via amine initiation in collaboration with metal-alkoxide catalysis†
Polymer Chemistry ( IF 4.1 ) Pub Date : 2018-09-15 00:00:00 , DOI: 10.1039/c8py01090k
Yanzhao Nie _{1,

2,

3,

4,

5} , Pei Wang _{1,

2,

3,

4,

5} , Haifeng Du _{6,

7,

8,

9,

10} , Wei Meng _{6,

7,

8,

9,

10} , Jing Yang _{1,

2,

3,

4,

5}

Affiliation

The ring-opening polymerization (ROP) of O-carboxyanhydrides (OCAs) is a versatile alternative for generating well-defined functional poly(α-hydroxy acids) (PAHAs). In contrast to the ROP of lactides, which has countless successful examples, exploring new catalysts and polymerization pathways for the controlled ROP of OCAs remains an attractive challenge. Considering the polymerization characteristics of OCAs, we herein describe an effective catalytic system containing Zn(C₆F₅)₂ and amines that mediates the controlled ROP of OCAs. The strong nucleophilic attack of the amines combined with the effective switching of Zn(C₆F₅)₂ to Zn alkoxide during polymerization provides a collaborative catalytic pathway of amine initiation and metal-alkoxide-promoted chain propagation for the ROP of OCAs. The ROP of OCAs catalyzed by Zn(C₆F₅)₂ and amines enables the controlled polymerization of PAHA, as evidenced by the afforded homopolymers and block polymers with the expected molecular weights and narrow molecular weight distributions (M_w/M_n < 1.1). Careful analysis of the polymerization system and computational studies verify a Lewis pair composed of amines and Zn(C₆F₅)₂ for polymerization initiation and functionality switch from Zn(C₆F₅)₂ to a metal-alkoxide species for coordination–insertion chain propagation.

中文翻译：

一种有效的策略，可通过胺引发与金属醇盐催化共同实现O-羧基酐的可控开环聚合†

O-羧基酐（OCA）的开环聚合（ROP）是一种通用的替代方法，可用于生成定义明确的功能性聚（α-羟基酸）（PAHA）。与丙交酯的ROP相比，丙交酯具有无数成功的例子，探索可控OCA的ROP的新催化剂和聚合途径仍然是一个有吸引力的挑战。考虑到OCA的聚合特性，我们在本文中描述了一种有效的催化体系，该体系含有Zn（C ₆ F ₅）₂和胺，可调节OCA的受控ROP。胺的强亲核攻击与Zn（C ₆ F ₅）₂的有效转换相结合聚合过程中的烷氧基化锌为OCA的ROP提供了胺引发和金属醇盐促进的链增长的协同催化途径。由Zn（C ₆ F ₅）₂和胺催化的OCA的ROP使得PAHA的控制聚合成为可能，这可通过提供具有预期分子量和窄分子量分布（M _w / M _n <1.1的均聚物和嵌段聚合物）来证明。）。对聚合体系的仔细分析和计算研究证实，由胺和Zn（C ₆ F ₅）₂组成的路易斯对可引发聚合反应并从Zn（C ）进行功能转换₆ F₅）₂形成金属-醇盐，用于配位-插入链的传播。

更新日期：2018-09-15

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