Solvent-Dependent Sequence-Controlled Copolymerization of Lactones: Tailoring Material Properties from Robust Plastics to Tough Elastomers

IF 16.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Chaoqun Weng, Dr. Xiao Li, Prof. Dr. Xiaoyan Tang
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Abstract

Copolymerization stands as a versatile and potent method for tailoring polymer properties by adjusting structural unit composition and sequence distribution. However, achieving sequence-controlled copolymerization in a one-step and one-pot process remains challenging. This study introduces a solvent-dependent sequence-controlled copolymerization strategy to produce block and statistical copolyesters from 4-phenyl-2-oxabicyclo[2.1.1]hexan-3-one (4Ph-BL) and ϵ-caprolactone (ϵ-CL). The distinct kinetics of the two monomers enable the facile synthesis of diblock and triblock copolyesters, PCL-b-P(4Ph-BL) and P(4Ph-BL)-b-PCL-b-P(4Ph-BL), in non-coordinating solvents, such as dichloromethane and toluene. Conversely, coordinating solvents like tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane facilitate frequent transesterifications, yielding statistical copolyesters P[CL-stat-(4Ph-BL)] with varying ratios of heterosequences. Density functional theory (DFT) calculations confirmed that coordinating solvents stabilize the transition state for transesterification, thereby validating their role in triggering this process. By varying the microstructures and compositions, the resultant copolyesters display tunable thermal and mechanical properties, evolving from robust plastics with an ultimate tensile strength of up to 46.3±3.1 MPa to tough elastomers with >99.3 % elastic recovery. All the copolyesters exhibit remarkable thermal stability (Td,5%=376 °C) and maintain desirable chemical circularity (>92 %), supporting a closed-loop life cycle for sustainable material economy.

Abstract Image

内酯的溶剂依赖性序列控制共聚:从强韧塑料到韧性弹性体的材料特性定制
共聚是通过调整结构单元组成和序列分布来定制聚合物特性的一种通用而有效的方法。然而,在一步法和一锅法工艺中实现序列控制共聚仍然具有挑战性。本研究介绍了一种依赖溶剂的序列控制共聚策略,以 4-苯基-2-氧杂双环[2.1.1]己烷-3-酮(4Ph-BL)和ε-己内酯(ε-CL)为原料生产嵌段共聚物和统计共聚物。由于这两种单体的动力学特性不同,因此可以在二氯甲烷和甲苯等非配位溶剂中轻松合成二嵌段和三嵌段共聚聚酯 PCL-b-P(4Ph-BL)和 P(4Ph-BL)-b-PCL-b-P(4Ph-BL) 。相反,四氢呋喃、2-甲基四氢呋喃、2,5-二甲基四氢呋喃、1,4-二氧六环和 1,2-二甲氧基乙烷等配位溶剂则可促进频繁的酯交换反应,产生具有不同杂环比例的统计共聚物 P[CL-stat-(4Ph-BL)]。密度泛函理论(DFT)计算证实,配位溶剂能稳定酯交换的过渡状态,从而验证了它们在引发这一过程中的作用。通过改变微结构和成分,由此产生的共聚多酯显示出可调的热性能和机械性能,从极限拉伸强度高达 46.3 ± 3.1 兆帕的坚固塑料到弹性恢复率高达 99.3% 的强韧弹性体。所有共聚聚酯都表现出卓越的热稳定性(Td,5% = 376 °C),并保持理想的化学循环性(>92%),支持可持续材料经济的闭环生命周期。
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来源期刊
CiteScore
26.60
自引率
6.60%
发文量
3549
审稿时长
1.5 months
期刊介绍: Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.
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