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利用红外光谱法研究HO/Fenton体系中天然橡胶解聚时羟基增长的动力学

Kinetics of Hydroxyl Growth on Natural Rubber Depolymerization with HO/Fenton Using Infrared Spectroscopy.

作者信息

Wibowo Heri Budi, Sutrisno Sutrisno, Sitompul Hamonangan Rekso Diputro, Ardianingsih Retno, Abdilah Luthfia Hajar, Hartaya Kendra, Witjakso Ario

机构信息

Research Centre for Rocket Technology, Research Organization of Aeronautics and Space, National Research and Innovation Agency, Bogor 16350, West Java, Indonesia.

Energy Conversion and Conservation Research Centre, Research Organization of Energy and Manufacture, National Research and Innovation Agency, Bogor 16340, West Java, Indonesia.

出版信息

Polymers (Basel). 2025 Jul 1;17(13):1847. doi: 10.3390/polym17131847.

Abstract

The kinetics of the depolymerization of natural rubber (NR) to hydroxyl-terminated natural rubber (HTNR) by hydrogen peroxide (HO) in the presence of a Fenton catalyst within an acidic milieu and under ultraviolet radiation has been rigorously examined utilizing infrared spectroscopy to determine the alterations in molar mass and the functional characteristics. The kinetic model was analyzed in accordance with the elementary reaction, encompassing the following mechanisms: the interaction between hydroxyl radicals and NR, producing radical NR and hydroxylated NR; the reaction wherein radical NR and hydroxyl radicals yield hydroxylated NR; and the subsequent reaction of hydroxylated NR with hydroxyl radicals producing lower radical NR, hydroxylated terminated NR, radical NR, and hydroxylated NR. The conversion of the NR polymer and the total hydroxyl content were discerned at the absorption bands of the CH-CH and OH groups located at 850 cm and 3400 cm, respectively. The absorption peak at 1850 cm attributed to CH was employed as the reference group for calibration. The influence of the temperature on the depolymerization process conformed to the Arrhenius equation, characterized by activation energies of 750 K and 1200 K. The impact of the HO/Fenton ratio on the depolymerization process follows a power law with power coefficients of 1.97 and 1.82.

摘要

在酸性环境中,于紫外线辐射下,在芬顿催化剂存在的情况下,利用过氧化氢(HO)将天然橡胶(NR)解聚为端羟基天然橡胶(HTNR)的动力学过程已通过红外光谱进行了严格研究,以确定摩尔质量和功能特性的变化。根据基元反应对动力学模型进行了分析,包括以下机制:羟基自由基与NR之间的相互作用,生成自由基NR和羟基化NR;自由基NR与羟基自由基反应生成羟基化NR;以及随后羟基化NR与羟基自由基反应生成较低自由基NR、羟基化端基NR、自由基NR和羟基化NR。分别在位于850 cm和3400 cm的CH-CH和OH基团的吸收带处识别出NR聚合物的转化率和总羟基含量。将归因于CH的1850 cm处的吸收峰用作校准的参考基团。温度对解聚过程的影响符合阿伦尼乌斯方程,其活化能分别为750 K和1200 K。HO/芬顿比 对解聚过程的影响遵循幂律,幂系数分别为1.97和1.82。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bbf4/12252367/bfc124ec2a1e/polymers-17-01847-g001.jpg

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