Anionic ring-opening polymerization of ferrocenylcyclosiloxanes: a comprehensive structural study

IF 4.5 3区工程技术 Q1 CHEMISTRY, APPLIED

Reactive & Functional Polymers Pub Date : 2024-08-22 DOI:10.1016/j.reactfunctpolym.2024.106029

{"title":"Anionic ring-opening polymerization of ferrocenylcyclosiloxanes: a comprehensive structural study","authors":"","doi":"10.1016/j.reactfunctpolym.2024.106029","DOIUrl":null,"url":null,"abstract":"<div>In this study, a comprehensive structural analysis of the linear redox-active ferrocenyl-containing polysiloxanes (FPSs) was performed by the liquid-state 1H, 13C, and 29Si nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography (GPC), and cyclic voltammetry. FPSs with tunable Fc unit content ranging from 20 to 100 mol% were obtained by anionic ring-opening polymerization (AROP). The 29Si NMR spectroscopy indicates the successful anionic homopolymerization of the mono- and tetraferrocenyl-substituted cyclotetrasiloxanes (Fc4D4 and Fc1D4) by appearance of new signals of Si atoms corresponding to a polymer backbone. An analysis of pentad assignments in 29Si NMR determined the anionic copolymerization of Fc4D4 with D4 by indicating signals of neighboring Si atoms from different types of polymer units (DF and D), which differ from the signals of homopolymers. The Mayo-Lewis copolymerization constants of Fc4D4 and D4 were determined by the Fineman–Ross method. The molecular masses and unimodal molecular weight distribution of FPSs were estimated by using GPC. FPSs possess redox-activity. Thus, the proposed comprehensive approach analyzes structural features of the functional silicones with enhanced redox properties, which can be applied in (opto)electronics, coatings, and biomedicine.</div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":null,"pages":null},"PeriodicalIF":4.5000,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Reactive & Functional Polymers","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1381514824002049","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}

引用次数: 0

Abstract

In this study, a comprehensive structural analysis of the linear redox-active ferrocenyl-containing polysiloxanes (FPSs) was performed by the liquid-state ¹H, ¹³C, and ²⁹Si nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography (GPC), and cyclic voltammetry. FPSs with tunable Fc unit content ranging from 20 to 100 mol% were obtained by anionic ring-opening polymerization (AROP). The ²⁹Si NMR spectroscopy indicates the successful anionic homopolymerization of the mono- and tetraferrocenyl-substituted cyclotetrasiloxanes (Fc₄D₄ and Fc₁D₄) by appearance of new signals of Si atoms corresponding to a polymer backbone. An analysis of pentad assignments in ²⁹Si NMR determined the anionic copolymerization of Fc₄D₄ with D₄ by indicating signals of neighboring Si atoms from different types of polymer units (D^F and D), which differ from the signals of homopolymers. The Mayo-Lewis copolymerization constants of Fc₄D₄ and D₄ were determined by the Fineman–Ross method. The molecular masses and unimodal molecular weight distribution of FPSs were estimated by using GPC. FPSs possess redox-activity. Thus, the proposed comprehensive approach analyzes structural features of the functional silicones with enhanced redox properties, which can be applied in (opto)electronics, coatings, and biomedicine.

Abstract Image

查看原文本刊更多论文

二茂铁环硅氧烷的阴离子开环聚合：全面的结构研究

本研究通过液态 1H、13C 和 29Si 核磁共振 (NMR) 光谱、凝胶渗透色谱 (GPC) 和循环伏安法对线性氧化还原活性二茂铁聚硅氧烷 (FPS) 进行了全面的结构分析。通过阴离子开环聚合（AROP）获得了 Fc 单元含量可调的 FPS，Fc 单元含量从 20 摩尔%到 100 摩尔%不等。29Si NMR 光谱显示，单二茂铁基和四二茂铁基取代的环四硅氧烷（Fc4D4 和 Fc1D4）成功地进行了阴离子均聚，出现了与聚合物骨架相对应的 Si 原子新信号。通过对 29Si NMR 中的五位分配进行分析，确定了 Fc4D4 与 D4 的阴离子共聚，显示了来自不同类型聚合物单元（DF 和 D）的相邻 Si 原子的信号，这些信号与均聚物的信号不同。Fc4D4 和 D4 的马约-路易斯共聚常数是通过 Fineman-Ross 法测定的。采用 GPC 方法估算了 FPS 的分子质量和单峰分子量分布。FPSs 具有氧化还原活性。因此，所提出的综合方法分析了具有增强氧化还原特性的功能有机硅的结构特征，可应用于（光）电子、涂层和生物医学领域。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Reactive & Functional Polymers 工程技术-高分子科学

CiteScore

8.90

自引率

5.90%

发文量

259

审稿时长

27 days

期刊介绍： Reactive & Functional Polymers provides a forum to disseminate original ideas, concepts and developments in the science and technology of polymers with functional groups, which impart specific chemical reactivity or physical, chemical, structural, biological, and pharmacological functionality. The scope covers organic polymers, acting for instance as reagents, catalysts, templates, ion-exchangers, selective sorbents, chelating or antimicrobial agents, drug carriers, sensors, membranes, and hydrogels. This also includes reactive cross-linkable prepolymers and high-performance thermosetting polymers, natural or degradable polymers, conducting polymers, and porous polymers. Original research articles must contain thorough molecular and material characterization data on synthesis of the above polymers in combination with their applications. Applications include but are not limited to catalysis, water or effluent treatment, separations and recovery, electronics and information storage, energy conversion, encapsulation, or adhesion.