UiO-66-NH2/路易斯碱二元体系催化环氧化物与环酸酐开环共聚
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福州大学

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国家自然科学基金项目(面上项目,重点项目,重大项目)


Ring-opening copolymerization of epoxide with cyclic anhydride catalyzed by UIO-66-NH2/Lewis base binary system
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Fuzhou University

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The National Natural Science Foundation of China (General Program, Key Program, Major Research Plan)

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    摘要:

    环氧化物与环酸酐的开环共聚反应(ROCOP)在聚酯的制备中起着至关重要的作用。以四氯化锆和2-氨基对苯二甲酸为原料,经水热反应制备氨基修饰的金属有机框架材料UiO-66-NH2,将其作为主催化剂,与助催化剂组成二元路易斯酸碱,用于催化环氧环己烷(CHO)和马来酸酐(MA)的开环共聚反应,采用FTIR、XRD表征UiO-66-NH2的结构组成,基于1HNMR表征,考察主催化剂类型、反应温度、催化剂用量对CHO和MA开环共聚反应的CHO转化率、聚合物酯键含量以及催化剂周转频率的影响,并探究其反应动力学。通过SEM、XRD、ICP-OES表征,分析UiO-66-NH2的循环使用性能。结果表明,以双(三苯基正膦基)氯化铵(PPNCl)为助催化剂,在n(UiO-66-NH2)∶n(PPNCl)∶n(MA)∶n(CHO)=1∶1∶100∶100,反应温度80 ℃,反应时间1 h的条件下,制备聚酯P(MA-CHO)中酯键含量最高可达99.9%,CHO转化率78.6%,催化剂周转频率78.6 h–1。UiO-66-NH2/PPNCl催化MA和CHO开环聚合反应为一级动力学反应,表观活化能约为66.51 kJ/mol。UiO-66-NH2具有良好的物理和化学稳定性,重复使用3次催化活性稍降低,CHO的转化率从78.6%降至77.5%。

    Abstract:

    The ring-opening copolymerization reaction of epoxides with cyclic anhydride (ROCOP) plays a crucial role in the preparation of polyesters. In this thesis, the amino-modified metal-organic framework material UiO-66-NH2 was synthesized, and the ring-opening copolymerization of epoxide with cyclic anhydride catalyzed by the UiO-66-NH2/Lewis acid-base binary system was investigated. It was shown that the UiO-66-NH2/PPNCl catalytic system presented the best catalytic performance, and the ester bond content in the prepared polyester was up to 99.9%. Meanwhile, the effects of temperature, catalyst ratio and co-catalyst on the ring opening copolymerization reaction were investigated. The kinetic study showed that the reaction was a first-order kinetic reaction with an apparent activation energy Ea of about 66.51 kJ?mol-1. The cycling test proved that UiO-66-NH2 had good physical and chemical stability, and could be reused 3 times without decreasing the catalytic activity.

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胡从意,蓝云洪,肖龙强,侯琳熙. UiO-66-NH2/路易斯碱二元体系催化环氧化物与环酸酐开环共聚[J].精细化工,2025,42(6):

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  • 收稿日期:2024-06-30
  • 最后修改日期:2024-09-02
  • 录用日期:2024-08-12
  • 在线发布日期: 2025-06-06
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