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用于氧化聚合物降解的环境设想方案。

Environmental scenarii for the degradation of oxo-polymers.

机构信息

Université Clermont Auvergne, CNRS, Sigma, Institut de Chimie de Clermont-Ferrand, F-63000, Clermont-Ferrand, France.

Université Clermont Auvergne, CNRS, Sigma, Institut de Chimie de Clermont-Ferrand, F-63000, Clermont-Ferrand, France.

出版信息

Chemosphere. 2018 May;198:182-190. doi: 10.1016/j.chemosphere.2018.01.153. Epub 2018 Feb 3.

Abstract

The fate of oxo-polymers in nature is strongly dependent on environmental conditions, mainly on the intensity and duration of sunshine, which vary with the season and the climate. In this work, we report the effect of different scenarii on the production and the molecular composition of oligomers released from oxo-biodegradable HDPE films. Under our experimental conditions, the duration of accelerated weathering corresponded to a period of 3 months to 3 years of exposure to outside conditions under temperate climate. In addition, the oligomers were extracted in three different solvents: i) water to mimics the natural environment; ii) acetone and chloroform to identify oligomers trapped in the polymer matrix. The combination of high-resolution mass spectrometry and H NMR spectroscopy gives an extensive picture of the relative concentrations and the structural compositions of the extracted oligomers in the different tested conditions. In particular, the masses, the number of oxygen and carbon atoms could be determined for up to 2283 molecules. Globally the concentration and the size of oligomers increased with the duration of extraction, the level of aging of the polymer and the use of non-polar solvents. Surprisingly, the presence of highly oxidized molecules in acetone and chloroform extract, suggested an important swelling of HPDE films in these solvents and a better diffusion of these oligomers in the matrix. In nature, the biodegradability of oligomers could result from processes occurring both at the molecular (oxidation) and the macromolecular (diffusion and release) levels.

摘要

氧代聚合物在自然界中的命运强烈依赖于环境条件,主要是阳光的强度和持续时间,而这些条件又随季节和气候而变化。在这项工作中,我们报告了不同情景对从氧生物降解高密度聚乙烯薄膜中释放的低聚物的产生和分子组成的影响。在我们的实验条件下,加速风化的持续时间相当于在温带气候下暴露于外部条件 3 个月至 3 年的时间。此外,用三种不同的溶剂提取低聚物:i)水模拟自然环境;ii)丙酮和氯仿,以鉴定被困在聚合物基质中的低聚物。高分辨率质谱和 1H NMR 光谱的组合提供了在不同测试条件下提取低聚物的相对浓度和结构组成的广泛情况。特别是,可以确定多达 2283 个分子的质量、氧和碳原子的数量。总体而言,随着提取时间的延长、聚合物老化程度的增加和使用非极性溶剂,低聚物的浓度和大小都增加了。令人惊讶的是,在丙酮和氯仿提取物中存在高度氧化的分子,这表明 HPDE 薄膜在这些溶剂中发生了明显的溶胀,并且这些低聚物在基质中的扩散性更好。在自然界中,低聚物的生物降解性可能源于分子(氧化)和高分子(扩散和释放)水平上发生的过程。

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