文献类型：期刊文献

英文题名：Polymerization of 1,3-Propanediol to Poly(trimethylene ether) Glycol: Process Optimization Under Sulfuric Acid Catalysis and Performance of p-Toluenesulfonic Acid

作者：Ni, Yisong[1];Jiang, Yu[2];Zong, Yuan[1];Zheng, Sixian[2]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]Zhejiang Ecowel Biomat Co Ltd, Lishui 323000, Peoples R China

年份：2026

卷号：14

期号：11

外文期刊名：PROCESSES

收录：;EI(收录号：20262420889983);WOS:【SCI-EXPANDED(收录号:WOS:001789929400001)】；

语种：英文

外文关键词：PO3G; polycondensation; catalyst; PTSA

摘要：Poly(trimethylene ether) glycol (PO3G), a bio-based polyether polyol with excellent flexibility and superior hydrolytic stability, has emerged as a critical raw material for the preparation of high-performance polymer materials. This work optimized the sulfuric acid-catalyzed polymerization process and assessed the feasibility of using p-toluenesulfonic acid (PTSA) as an alternative catalyst. A parametric study was conducted to establish a reliable operating window for the sulfuric acid system. DFT calculations demonstrated that the driving force for chain growth decreases with increasing chain length, that recombination between chains of significantly different lengths is more favorable than between chains of equal length, and that the formation of disulfate esters is thermodynamically more favorable. Although PTSA required a higher catalyst loading, the resulting polymer had a markedly lower yellowness index. Prolonged reaction times lead to a molecular weight plateau, especially at high PTSA concentrations, while the yellowness index continues to increase after reaching the plateau. 1H NMR analysis indicated the formation of benzenesulfonate monoester intermediates during PTSA catalysis, suggesting a potentially milder pathway and possibly fewer side reactions compared to the sulfuric acid system. This paper provides theoretical and experimental foundations for the green, efficient synthesis of PO3G and the catalyst optimization for analogous bio-based polyether polyols.