ε-Caprolactone-Tetrahydrofuran High-Molar-Mass Copolymers: Polymerization in Bulk above Tc of THF and Ordered Copolymers with Two-Dimensional NMR and DFT Analysis

IF 5.2 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2025-10-20 DOI:10.1021/acs.macromol.5c02033

Julia Pretula, Marta K. Dudek, Krzysztof Kaluzynski, Sławomir Kaźmierski, Marek Cypryk, Stanislaw Penczek

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Abstract

Copolymers of ε-caprolactone (CL) and tetrahydrofuran (THF) with high molar masses (M_n ∼ 10⁵ g/mol) were synthesized in bulk at ∼80 °C, i.e., above the ceiling temperature (T_c) of THF. This thermodynamic limitation reduced the length of units to monads and dyads, allowing the synthesis of ordered (alternating) copolymers, [(thf-thf)-cl]_n, at a sufficiently high [THF]₀/[CL]₀ feed ratio. The presence of the -thf-thf-dyads (apparently against thermodynamic predictions) results from the antepenultimate influence of the -cl- fragment. A combination of COSY, TOCSY, and ROESY spectra enabled the identification of all chemical shifts in the most detailed copolymer spectrum. Thus, whenever copolymers with -cl- and/or -thf- units are to be analyzed, the present analysis provides the corresponding reference points. According to the kinetic data, both comonomers polymerize at an identical rate at the chosen feed ratio. The particular rates of the four major reactions in the copolymerization scheme were analyzed using the DFT method.

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ε-己内酯-四氢呋喃高摩尔质量共聚物：THF和有序共聚物在Tc以上的整体聚合与二维NMR和DFT分析

ε-己内酯（CL）与四氢呋喃（THF）的共聚物在~ 80℃下（即高于THF的上限温度（Tc））批量合成，具有高摩尔质量（Mn ~ 105 g/mol）。这种热力学限制将单元的长度减少到单体和双单体，允许在足够高的[THF]0/[CL]0进料比下合成有序（交替）共聚物[(THF - THF)-cl]n。-thf-thf-dyads的存在（显然与热力学预测相反）是由-cl-片段的倒数影响造成的。COSY， TOCSY和ROESY光谱的组合能够识别最详细的共聚物光谱中的所有化学位移。因此，每当要分析-cl-和/或-thf-单元的共聚物时，本分析提供了相应的参考点。根据动力学数据，两种共聚单体在选择的投料比下以相同的速率聚合。用离散傅立叶变换方法分析了共聚方案中四个主要反应的特定速率。

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.