Tunable crystallization behavior, memory effect, and thermo-mechanical properties of biobased polyamides PA5X

IF 4.1 2区 化学 Q2 POLYMER SCIENCE Polymer Pub Date : 2024-10-05 DOI:10.1016/j.polymer.2024.127687
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Abstract

To reduce carbon dioxide emissions, the development of sustainable bio-based polyamides with performance advantages has become the focus of widespread attention. 1,5-Pentanediamine (PDA) is a renewable monomer produced by decarboxylation of lysine, which can be used as a sustainable alternative to traditional petroleum-based diamines and play a crucial role in the synthesis of bio-based polyamides. Herein, a series of bio-based aliphatic polyamides (PA5X) synthesized from PDA and aliphatic diacids with different methylene groups were successfully prepared via melt polycondensation. Their chemical structures were characterized, and the effects of diacid chain length on crystallization behavior, memory effect, and thermo-mechanical properties were emphatically investigated. The results show that the melting and crystallization temperatures of PA5X decrease with increasing diacid chain length. Meanwhile, the PA5X exhibits high thermal stability, with Td,5 % exceeding 380 °C. Unlike the even-even polyamide, the crystalline form of PA5X is γ-form, and the crystallization behavior and spherulitic morphology change significantly with diacid chain length, which is attributed to the complex entanglement effects. More particularly, the correlation between the diacid chain length and the melt memory effect is explored. PA56 with shorter methylene groups exhibits stronger melt memory effects due to the memory effects being directly affected by segmental chain interactions. Moreover, PA5X exhibits comparable or even superior tensile strength and ductility compared with hexamethylenediamine-based polyamide (PA6X) and reported fully bio-based PA11. This work provides a comprehensive investigation into the structure-property relationship of the bio-based polyamide PA5X, demonstrating great potential for application in high-performance eco-friendly materials.

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生物基聚酰胺 PA5X 的可调结晶行为、记忆效应和热机械特性
为减少二氧化碳排放,开发具有性能优势的可持续生物基聚酰胺已成为广泛关注的焦点。1,5-戊二胺(PDA)是一种由赖氨酸脱羧生成的可再生单体,可作为传统石油基二胺的可持续替代品,在合成生物基聚酰胺中发挥着重要作用。本文以 PDA 和具有不同亚甲基的脂肪族二元酸为原料,通过熔融缩聚法成功制备了一系列生物基脂肪族聚酰胺(PA5X)。对它们的化学结构进行了表征,并重点研究了二元酸链长对结晶行为、记忆效应和热机械性能的影响。结果表明,随着二元酸链长度的增加,PA5X 的熔化和结晶温度降低。同时,PA5X 具有很高的热稳定性,Td,5% 超过 380°C。与偶偶聚酰胺不同,PA5X 的结晶形式为 γ 形,其结晶行为和球状形态随二酸链长度的增加而发生显著变化,这归因于复杂的缠结效应。研究还特别探讨了二元酸链长度与熔体记忆效应之间的相关性。亚甲基较短的 PA56 具有更强的熔体记忆效应,这是因为记忆效应直接受到段链相互作用的影响。此外,与六亚甲基二胺基聚酰胺(PA6X)和已报道的全生物基 PA11 相比,PA5X 具有相当甚至更高的拉伸强度和延展性。这项研究对生物基聚酰胺 PA5X 的结构-性能关系进行了全面研究,显示了其在高性能环保材料中的巨大应用潜力。
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来源期刊
Polymer
Polymer 化学-高分子科学
CiteScore
7.90
自引率
8.70%
发文量
959
审稿时长
32 days
期刊介绍: Polymer is an interdisciplinary journal dedicated to publishing innovative and significant advances in Polymer Physics, Chemistry and Technology. We welcome submissions on polymer hybrids, nanocomposites, characterisation and self-assembly. Polymer also publishes work on the technological application of polymers in energy and optoelectronics. The main scope is covered but not limited to the following core areas: Polymer Materials Nanocomposites and hybrid nanomaterials Polymer blends, films, fibres, networks and porous materials Physical Characterization Characterisation, modelling and simulation* of molecular and materials properties in bulk, solution, and thin films Polymer Engineering Advanced multiscale processing methods Polymer Synthesis, Modification and Self-assembly Including designer polymer architectures, mechanisms and kinetics, and supramolecular polymerization Technological Applications Polymers for energy generation and storage Polymer membranes for separation technology Polymers for opto- and microelectronics.
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