Fundamental Study of Rare-earth-containing Catalytic Reduction Systems for End-group Functionalization of Telechelic Low-molecular-weight Fluoropolymers
LI Donghan1,2,*, NING Shurui2, YU Lu2, LIAO Mingyi3, ZHANG Mengxia1, YOU Shibo1, FANG Qinghong1,2
1 College of Materials Science and Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China 2 Liaoning Provincial Key Laboratory of Rubber & Elastomer, Shenyang University of Chemical Technology, Shenyang 110142, China 3 College of Transportation Engineering, Dalian Maritime University, Dalian 116026, Liaoning, China
Abstract: Herein the use of rare-earth compounds in catalytic reduction systems for the end-group functionalization of carboxyl-terminated low-molecular-weight fluoropolymers was explored. Leveraging the high catalytic activity and selectivity of rare-earth compounds along with no residual impact on polymer product's performance, highly efficient catalytic reduction systems containing sodium borohydride (NaBH4) and rare-earth chloride (RECl3) were specifically designed for a telechelic carboxyl-terminated liquid fluoroeslastomer, aiming to facilitate the conversion of chai-nend carboxyl groups into hydroxyl groups and improvement in end-group reactivity. To achieve this, lanthanum chloride (LaCl3), cerium chloride (CeCl3), and neodymium chloride (NdCl3) were used separately to form catalytic reduction systems with NaBH4. The effects of solvent dosage, reaction temperature, reaction time length, and reductant dosage on carboxylic conversion were investigated, and the molecular chain structure, molecular weight, and functional group content of the raw materials and the products were analyzed and characterized by means of infrared spectroscopy (FTIR), proton nuclear magnetic resonance (1H-NMR), fluorine-19 nuclear magnetic resonance (19F-NMR), gel per-meation chromatography (GPC), and chemical titration. Moreover, the catalytic activity and selectivity of the rare-earth chlorides, as well as the corresponding underlying interactions were discussed. Results indicated that the rare-earth-containing catalytic reduction systems studied in this work could efficiently convert the chain-end carboxyl groups into highly active hydroxyl groups, with a highest conversion up to 87.0% and differing catalytic reduction activities ranked as NaBH4/CeCl3＞NaBH4/LaCl3＞NaBH4/NdCl3. Compared with the conventional lithium aluminum hydride (LiAlH4) reduction system, the NaBH4/RECl3 systems provide multiple advantages such as mild reaction conditions, high conversion ratio with good selectivity, and environmental innocuity, and are potentially applicable as new reduction-catalysis combinations for the synthesis and functionalization of polymer materials.
李东翰, 宁舒蕊, 于璐, 廖明义, 张梦霞, 尤诗博, 方庆红. 稀土催化还原体系用于遥爪型低分子量含氟聚合物端基官能化的基础研究[J]. 材料导报, 2025, 39(3): 23100154-9.
LI Donghan, NING Shurui, YU Lu, LIAO Mingyi, ZHANG Mengxia, YOU Shibo, FANG Qinghong. Fundamental Study of Rare-earth-containing Catalytic Reduction Systems for End-group Functionalization of Telechelic Low-molecular-weight Fluoropolymers. Materials Reports, 2025, 39(3): 23100154-9.
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