Facile synthesis of tertiary amine functionalized liquid polyisoprene rubber by LAP with 1,2-Dipiperidinoethane derivatives as modifier

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal Pub Date : 2025-06-01 DOI:10.1016/j.eurpolymj.2025.114020

Kun Liu , Qiqi Dai , Yi Xiao , Xupeng Han , Yujie Wang , Yao Long , Zhifang Chen , Wenjun Yi , Xiaoxing Gu , Lijun Li

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引用次数: 0

Abstract

The properties of polydiene-based liquid rubber are controlled by the microstructure, sequence distribution and degree of functionalization. The living anionic polymerization (LAP) initiation (alkyl-metal nucleophiles) and regulation (electron-rich Lewis bases) systems and polymerization conditions (such as temperature, solvent and charging mode) as well as the functionality comonomer need to be optimized to achieve excellent control of polymer structure. Herein, with the assistance of the 1,2-dipiperidinoethane (DPE) derivatives with different steric hindrance and electron effect substituents, the high vinyl polyisoprene (HVPI, 80 % < 3,4- & 1,2-units < 92 %, 1,2-units up to 26 %) liquid rubber was obtained with n-BuLi as initiator in cyclohexane. Furthermore, the synthesis of HVPI with quantitatively tertiary-amine functionalization, ranging from 0 % to 25 % molar ratio, was achieved through in-situ living anionic polymerization (LAP) using 4-dimethylaminomethylstyrene (VBN) as a polar comonomer. Precise control of molecular weight and tertiary amine functionalization can be achieved above room temperature. The fine structure of the product was analyzed using FTIR, GPC, ¹H NMR, ¹³C NMR, and DSC techniques. The polymerization mechanism was also proposed to explain the formation of highly selective vinyl side groups.

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以1,2-二哌替乙烷衍生物为改性剂，LAP法合成叔胺功能化液态聚异戊二烯橡胶

聚乙烯烃基液体橡胶的性能受其微观结构、序列分布和功能化程度的控制。活性阴离子聚合（LAP）引发体系（烷基-金属亲核试剂）和调控体系（富电子路易斯碱）、聚合条件（如温度、溶剂和充电方式）以及功能化单体需要优化，以实现对聚合物结构的优异控制。在具有不同位阻和电子效应取代基的1,2-二哌替啶乙烷（DPE）衍生物的辅助下，高乙烯基聚异戊二烯(HVPI, 80% <；3, 4 -,1、2单位& lt;以n-BuLi为引发剂，在环己烷中制得92%（1,2 ~ 26%）的液态橡胶。此外，以4-二甲氨基甲基苯乙烯（VBN）为极性单体，通过原位活阴离子聚合（LAP）合成了具有定量叔胺功能化的HVPI，摩尔比为0% ~ 25%。室温以上可实现分子质量和叔胺功能化的精确控制。采用FTIR、GPC、1H NMR、13C NMR、DSC等技术对产物的精细结构进行了分析。聚合机理也被提出来解释高选择性乙烯基侧基的形成。

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来源期刊

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.