使用碱金属烷氧基化合物和冠醚双重催化体系合成交替聚酯

IF 5.8 2区 化学 Q1 POLYMER SCIENCE European Polymer Journal Pub Date : 2024-10-11 DOI:10.1016/j.eurpolymj.2024.113497
Yiru Li , Zhizhuang Li , Weihong Zeng , Yuxin Shen , Yanian Fang , Yunliang Wang , Heng Li
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引用次数: 0

摘要

本研究在邻苯二甲酸酐(PA)和环氧丙烷(PO)的开环交替聚合(ROAP)中采用了冠醚与碱金属烷氧基化合物(AMA)的双催化体系。这种方法简化了聚酯的生产过程,其特点是序列完全交替、摩尔质量可调(最高可达 59.3 kg mol-1)以及摩尔质量分布窄(ÐM <1.26)。对各种市售 AMAs(特别是乙醇钠 (EtONa)、甲醇钠和乙醇锂)与冠醚(15-冠醚-5 和 18-冠醚-6)进行的分析表明,EtONa 和 18-冠醚-6 配对具有更高的催化效率。效率的提高归功于冠醚与碱金属离子的配位,从而增强了末端氧化烷阴离子的亲核性。该方法已成功应用于 PA、降冰片烯酐和多种环氧化物的 ROAP,同时还简化了从 PA、PO 和内酯混合物中生成脂肪族芳香族嵌段聚酯的过程。该策略提供了一种直接的聚酯生产方法,从而为聚酯合成技术的发展做出了重大贡献。
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Synthesis of alternating polyesters using a dual catalytic system of alkali metal alkoxides and crown ether
In this study, a dual catalytic system that merges crown ether with alkali metal alkoxides (AMA) is utilized in the ring-opening alternating polymerization (ROAP) of phthalic anhydride (PA) and propylene oxide (PO). This method streamlines the production of polyesters characterized by a fully alternating sequence, a modifiable molar mass (achieving up to 59.3 kg mol−1), and a narrow molar mass distribution (ÐM < 1.26). Analysis of various commercially available AMAs, notably sodium ethoxide (EtONa), sodium methoxide, and lithium ethoxide, in tandem with crown ethers (15-crown-5 and 18-crown-6), underscores the superior catalytic efficacy of the EtONa and 18-crown-6 pairing. This heightened efficiency is attributed to the coordination of crown ether with alkali metal ions, thereby boosting the nucleophilicity of terminal alkoxide anions. The methodology has been successfully deployed in the ROAP of PA, norbornene anhydride, and multiple epoxides, while also simplifying the creation of aliphatic–aromatic block polyesters from a mixture of PA, PO, and lactide. This strategy presents a straightforward approach to polyester production, thus making significant contributions to the evolution of polyester synthesis technology.
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来源期刊
European Polymer Journal
European Polymer Journal 化学-高分子科学
CiteScore
9.90
自引率
10.00%
发文量
691
审稿时长
23 days
期刊介绍: European Polymer Journal is dedicated to publishing work on fundamental and applied polymer chemistry and macromolecular materials. The journal covers all aspects of polymer synthesis, including polymerization mechanisms and chemical functional transformations, with a focus on novel polymers and the relationships between molecular structure and polymer properties. In addition, we welcome submissions on bio-based or renewable polymers, stimuli-responsive systems and polymer bio-hybrids. European Polymer Journal also publishes research on the biomedical application of polymers, including drug delivery and regenerative medicine. The main scope is covered but not limited to the following core research areas: Polymer synthesis and functionalization • Novel synthetic routes for polymerization, functional modification, controlled/living polymerization and precision polymers. Stimuli-responsive polymers • Including shape memory and self-healing polymers. Supramolecular polymers and self-assembly • Molecular recognition and higher order polymer structures. Renewable and sustainable polymers • Bio-based, biodegradable and anti-microbial polymers and polymeric bio-nanocomposites. Polymers at interfaces and surfaces • Chemistry and engineering of surfaces with biological relevance, including patterning, antifouling polymers and polymers for membrane applications. Biomedical applications and nanomedicine • Polymers for regenerative medicine, drug delivery molecular release and gene therapy The scope of European Polymer Journal no longer includes Polymer Physics.
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