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作为潜在包装材料的聚(3-羟基丁酸酯)/聚乳酸共混膜中的气体传输现象与聚合物动力学

Gas Transport Phenomena and Polymer Dynamics in PHB/PLA Blend Films as Potential Packaging Materials.

作者信息

Siracusa Valentina, Karpova Svetlana, Olkhov Anatoliy, Zhulkina Anna, Kosenko Regina, Iordanskii Alexey

机构信息

Department of Chemical Science (DSC), University of Catania, Viale A. Doria 6, 95125 Catania, Italy.

Plekhanov Russian University of Economics, Stremyanny per. 36, 117997 Moscow, Russia.

出版信息

Polymers (Basel). 2020 Mar 12;12(3):647. doi: 10.3390/polym12030647.

Abstract

Actually, in order to replace traditional fossil-based polymers, many efforts are devoted to the design and development of new and high-performance bioplastics materials. Poly(hydroxy alkanoates) (PHA) as well as polylactides are the main candidates as naturally derived polymers. The intention of the present study is to manufacture fully bio-based blends based on two polyesters: poly (3-hydroxybutyrate) (PHB) and polylactic acid (PLA) as real competitors that could be used to replace petrol polymers in packaging industry. Blends in the shape of films have been prepared by chloroform solvent cast solution methodology, at different PHB/PLA ratios: 1/0, 1/9, 3/7, 5/5, 0/1. A series of dynamic explorations have been performed in order to characterize them from a different point of view. Gas permeability to N, O, and CO gases and probe (TEMPO) electron spin resonance (ESR) analyses were performed. Blend surface morphology has been evaluated by Scanning Electron Microscopy (SEM) while their thermal behavior was analyzed by Differential Scanning Calorimetry (DSC) technique. Special attention was devoted to color and transparency estimation. Both probe rotation mobility and N, O, and CO permeation have monotonically decreased during the transition from PLA to PHB, for all contents of bio-blends, namely because of transferring from PLA with lower crystallinity to PHB with a higher one. Consequently, the role of the crystallinity was elucidated. The temperature dependences for CO permeability and diffusivity as well as for probe correlation time allowed the authors to evaluate the activation energy of both processes. The values of gas transport energy activation and TEMPO rotation mobility are substantially close to each other, which should testify that polymer segmental mobility determines the gas permeability modality.

摘要

实际上,为了取代传统的化石基聚合物,人们致力于新型高性能生物塑料材料的设计与开发。聚羟基脂肪酸酯(PHA)以及聚乳酸是主要的天然衍生聚合物候选材料。本研究旨在制造基于两种聚酯的全生物基共混物:聚(3-羟基丁酸酯)(PHB)和聚乳酸(PLA),它们是包装行业中可用于替代石油基聚合物的真正竞争对手。通过氯仿溶剂浇铸溶液法,以不同的PHB/PLA比例:1/0、1/9、3/7、5/5、0/1制备了薄膜形状的共混物。为了从不同角度对其进行表征,进行了一系列动态探索。进行了对N、O和CO气体的透气性以及探针(TEMPO)电子自旋共振(ESR)分析。通过扫描电子显微镜(SEM)评估共混物的表面形态,同时通过差示扫描量热法(DSC)技术分析其热行为。特别关注了颜色和透明度的评估。对于所有生物共混物的含量,在从PLA转变为PHB的过程中,探针旋转迁移率以及N、O和CO的渗透率均单调下降,这是因为从结晶度较低的PLA转变为结晶度较高的PHB。因此,阐明了结晶度的作用。CO渗透率和扩散率以及探针相关时间的温度依赖性使作者能够评估这两个过程的活化能。气体传输能量活化值和TEMPO旋转迁移率的值彼此基本接近,这表明聚合物链段迁移率决定了气体渗透方式。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6df1/7182844/531b2c75ba04/polymers-12-00647-g001.jpg

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