摘要
针对传统金属催化剂在聚合物合成中的局限性,采用非金属TEB PPNCl双组分Lewis酸碱对催化体系,通过环氧丙烷与CO_(2)的交替共聚反应制备了聚碳酸亚丙酯(PPC)。核磁共振与凝胶渗透色谱分析证实,该催化体系可实现高效可控聚合,所得PPC相对分子质量随反应时间延长呈现线性增长,且具有较窄的多分散指数;热重分析揭示PPC在150~250℃范围内呈现单步降解行为。采用Kissinger法、Kissinger-Akahira-Sunose法、Madhusudanan-Krishnan-Ninan法和Flynn-Wall-Ozawa法计算得到表观活化能,结合Coats-Redfern模型确定其热降解遵循反应级数n为1/3的随机成核与随后生长机制。
To overcome the limitations of conventional metal-based catalysts in polymer synthesis,poly(propylene carbonate)was synthesized through the alternating copolymerization of propylene oxide and CO_(2) using a metal-free two-component Lewis acid-base pair catalytic system comprising triethylborane and bis(triphenylphosphine)iminium chloride.Nuclear magnetic resonance and gel permeation chromatography analyses confirmed the capability of system to mediate efficient and controlled polymerization,with the resulting poly(propylene carbonate)showing a linear molecular weight increase over time and a narrow polydispersity index.Thermogravimetric analysis revealed a single-step thermal degradation process occurring between 150℃and 250℃.The apparent activation energies were determined using the Kissinger,Kissinger-Akahira-Sunose,Madhusudanan-Krishnan-Ninan,and Flynn-Wall-Ozawa methods.Further kinetic analysis using the Coats-Redfern model indicated consistency with a reaction order of n=1/3,corresponding to a stochastic nucleation and subsequent growth mechanism.
作者
王宪飞
杨金生
路忠凯
王贤山
Wang Xianfei;Yang Jinsheng;Lu Zhongkai;Wang Xianshan(Technology R&D Center,Zhenghe Group Co.,Ltd.,Dongying,Shangdong 257399)
出处
《石油炼制与化工》
北大核心
2025年第11期34-40,共7页
Petroleum Processing and Petrochemicals
关键词
聚碳酸亚丙酯
热降解
动力学
非金属催化剂
poly(propylene carbonate)
thermal degradation
kinetics
metal-free catalyst
