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红外光谱法表征 PLA 可生物降解塑料的降解行为。

Characterization of degradation behaviors of PLA biodegradable plastics by infrared spectroscopy.

机构信息

College of Electronic Engineering, Nanjing XiaoZhuang University, Nanjing 211171, People's Republic of China; College of Information Science and Technology, Nanjing Forestry University, Nanjing 210037, People's Republic of China.

Nanjing Institute of Product Quality Inspection, Nanjing 210019, People's Republic of China.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2022 Oct 15;279:121376. doi: 10.1016/j.saa.2022.121376. Epub 2022 May 18.

Abstract

In this paper, the degradation behavior of two kinds of polylactic acid (PLA) biodegradable material products (pure PLA cup cover and modified PLA straw) was studied. It was found that under the composting environment specified in the International Standard, in the first 35 days, the degradation rate of the straw (with 50%-60% poly butylenes succinate (PBS)) was faster than that of the pure PLA cup cover, but in the later stage, the PLA cup cover exceeded the straw and disintegrated preferentially, and both could be degraded in about 70 days. After further analyzing the far-infrared (FIR, can also be called THz) and mid infrared (MIR) spectra of cup cover and straw, we observed that the material structure had not changed until disintegration, only the ester bond was hydrolyzed, the polymers became oligomers, which could be reflected in the change of the effective area of the characteristic peak at 7.15 THz (cup cover, labeled 1921) and 6.99 THz (straw, labeled 4386) in the THz spectrum. With the degradation, the effective area decreased continuously. Due to the strong absorption of the material in MIR band, most characteristic peaks were flattened and lost analytical value. The bivariate correlation of degradation time, biodegradation rate, total carbon dioxide release and the effective area of the characteristic peak at 7.15 THz (1921) and 6.99 THz (4386) in THz spectrum was analyzed by SPSS software. We discovered that the degradation time was significantly positively correlated with biodegradation rate and carbon dioxide release at the level of 0.01 and negatively correlated with the effective area of characteristic peak at the level of 0.05. The biodegradation rate was significantly negatively correlated with the effective area of characteristic peak at the level of 0.01. Taking the degradation time as the independent variable and the biodegradation rate, carbon dioxide release and effective area of characteristic peak as the dependent variables, we got that the THz spectrum could be used to describe the degradation behavior of PLA products as long as appropriate coefficient correction was made. In this way, we could separate from the laboratory environment, study the impact of environmental diversification on material degradation performance, and reduce the cost of material degradation performance identification. Using density functional theory (DFT), reduced density gradient (RDG) method and visualization software, the changes of weak interaction position and intensity in the molecule during the polymerization of lactic acid into PLA were further analyzed. We found that the vibration of ester bond corresponded to the characteristic peak with weak intensity in the spectrum, and the peak with large intensity mainly originated from the out-of-plane swing of O-H bond in the molecule.

摘要

本文研究了两种聚乳酸(PLA)可生物降解材料制品(纯 PLA 杯盖和改性 PLA 吸管)的降解行为。结果表明,在国际标准规定的堆肥环境下,在最初的 35 天内,吸管(含有 50%-60%聚丁二酸丁二醇酯(PBS))的降解速度快于纯 PLA 杯盖,但在后期,PLA 杯盖超过了吸管并优先分解,两者都可以在大约 70 天内降解。进一步分析杯盖和吸管的远红外(FIR,也称为太赫兹)和中红外(MIR)光谱后,我们观察到在分解之前,材料结构没有变化,只是酯键被水解,聚合物变成低聚物,这可以反映在太赫兹光谱中 7.15 THz(杯盖,标记为 1921)和 6.99 THz(吸管,标记为 4386)处特征峰的有效面积变化。随着降解的进行,有效面积不断减小。由于材料在 MIR 波段的强烈吸收,大多数特征峰变平,失去了分析价值。利用 SPSS 软件对降解时间、生物降解率、总二氧化碳释放与太赫兹光谱中 7.15 THz(1921)和 6.99 THz(4386)处特征峰有效面积的二元相关性进行分析。我们发现,降解时间与生物降解率和二氧化碳释放呈显著正相关(在 0.01 水平上),与特征峰有效面积呈显著负相关(在 0.05 水平上)。生物降解率与特征峰有效面积呈显著负相关(在 0.01 水平上)。以降解时间为自变量,生物降解率、二氧化碳释放和特征峰有效面积为因变量,通过适当的系数修正,得出太赫兹光谱可以用来描述 PLA 制品的降解行为。这样,我们就可以脱离实验室环境,研究环境多样化对材料降解性能的影响,降低材料降解性能鉴定的成本。利用密度泛函理论(DFT)、约化密度梯度(RDG)方法和可视化软件,进一步分析了乳酸聚合形成 PLA 过程中分子中弱相互作用位置和强度的变化。结果表明,酯键的振动对应于光谱中弱强度的特征峰,而强度较大的峰主要来源于分子中 O-H 键的面外摆动。

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