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具有聚乙烯亚胺核和聚丙交酯多臂的多臂星形聚合物的分子动力学研究

Study of the Molecular Dynamics of Multiarm Star Polymers with a Poly(ethyleneimine) Core and Poly(lactide) Multiarms.

作者信息

Román Frida, Colomer Pere, Calventus Yolanda, Hutchinson John M

机构信息

Laboratori de Termodinàmica i Físicoquímica, TERFIQ, Departament de Màquines i Motors Tèrmics, ESEIAAT, Universitat Politècnica de Catalunya, Barcelona Tech, Carrer Colom 11, Terrassa 08222, Spain.

出版信息

Materials (Basel). 2017 Feb 4;10(2):127. doi: 10.3390/ma10020127.

DOI:10.3390/ma10020127
PMID:28772486
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5459105/
Abstract

Multiarm star polymers, denoted PEI-PLA and containing a hyperbranched poly(ethyleneimine) (PEI) core of different molecular weights and poly(lactide) (PLA) arms with ratio of lactide repeat units to N links were used in this work. Samples were preconditioned to remove the moisture content and then characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS). The glass transition temperature, , is between 48 and 50 °C for all the PEI-PLA samples. The dielectric curves show four dipolar relaxations: γ, β, α, and α' in order of increasing temperature. The temperatures at which these relaxations appear, together with their dependence on the frequency, allows relaxation maps to be drawn, from which the activation energies of the sub- γ- and β-relaxations and the Vogel-Fulcher-Tammann parameters of the α-relaxation glass transition are obtained. The dependence of the characteristic features of these relaxations on the molecular weight of the PEI core and on the ratio of lactide repeat units to N links permits the assignation of molecular motions to each relaxation. The γ-relaxation is associated with local motions of the -OH groups of the poly(lactide) chains, the β-relaxation with motions of the main chain of poly(lactide), the α-relaxation with global motions of the complete assembly of PEI core and PLA arms, and the α'-relaxation is related to the normal mode relaxation due to fluctuations of the end-to-end vector in the PLA arms, without excluding the possibility that it could be a Maxwell-Wagner-Sillars type ionic peak because the material may have nano-regions of different conductivity.

摘要

本研究使用了多臂星形聚合物（记为PEI-PLA），其包含不同分子量的超支化聚（乙烯亚胺）（PEI）核以及丙交酯重复单元与N键比例不同的聚（丙交酯）（PLA）臂。对样品进行预处理以去除水分含量，然后通过热重分析（TGA）、差示扫描量热法（DSC）和介电弛豫光谱法（DRS）进行表征。所有PEI-PLA样品的玻璃化转变温度(T_g)在48至50°C之间。介电曲线显示出四个偶极弛豫：按温度升高顺序为γ、β、α和α'。这些弛豫出现的温度及其对频率的依赖性使得能够绘制弛豫图谱，从中获得亚γ和β弛豫的活化能以及α弛豫玻璃化转变的Vogel-Fulcher-Tammann参数。这些弛豫的特征对PEI核的分子量以及丙交酯重复单元与N键比例的依赖性允许将分子运动分配给每个弛豫。γ弛豫与聚（丙交酯）链的-OH基团的局部运动相关，β弛豫与聚（丙交酯）主链的运动相关，α弛豫与PEI核和PLA臂的完整组装体的整体运动相关，而α'弛豫与由于PLA臂中端到端向量的波动引起的正常模式弛豫有关，但不排除它可能是麦克斯韦-瓦格纳-西勒斯型离子峰的可能性，因为该材料可能具有不同电导率的纳米区域。

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本文引用的文献

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