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    基于硼酸酯键的CO2基聚碳酸酯聚合后改性

    Post-Polymerization Modification of CO2-Based Polycarbonate Based on Borate Ester Bond

    • 摘要: 以CO2、环氧丙烷(PO)和烯丙基缩水甘油醚(AGE)为原料,通过三元共聚制备了侧链含有双键的CO2基聚碳酸酯(PAGC)。利用紫外光引发的巯基-烯点击反应将2, 2′-(1, 4-苯基)-双(4-巯基1, 3, 2-二氧硼杂环戊烷)(BDB)引入PAGC侧链实现聚合后改性,制备了系列PAGC-BDB改性材料。实验结果表明,点击反应所形成的交联网络结构可以明显改善材料的力学和热学性能。性材料的抗拉强度从32.4 MPa提高到51.6 MPa,玻璃化转变温度(Tg)从24.7 ℃升高到38.5 ℃,热稳定性也得到了有效提高。得益于硼酸酯键的动态可逆特性,PAGC-BDB改性材料表现出良好的自修复性能,并且使用后可以回收并实现再加工。在160 ℃和5 MPa下热压1 h后,回收材料保留了其初始抗拉强度的95%。这些结果充分证实了该聚合后修饰改性策略在提升CO2基聚碳酸酯综合性能方面的有效性,有助于拓展其应用领域。

       

      Abstract: Carbon dioxide (CO2)-based polycarbonates represent a class of green and sustainable polymers that have attracted considerable attention due to their CO2 utilization and biodegradability. However, as an emerging polymer material, research on their modification and applications remains in the exploratory stage. In this study, CO2, propylene oxide (PO), and allyl glycidyl ether (AGE) were used as raw materials to synthesize CO2-based polycarbonate (PAGC) bearing pendant double bonds through terpolymerization. The structure and composition of the target polymer were confirmed by nuclear magnetic resonance spectroscopy (1H-NMR), Fourier transform infrared spectroscopy (FT-IR), and gel permeation chromatography (GPC). Post-polymerization modification was achieved by introducing 2,2'-(1,4-phenylene)-bis(4-mercapto-1,3,2-dioxaborolane) (BDB) into PAGC side-chains through UV-initiated thiol-ene click reaction, yielding a series of PAGC-BDB modified materials. Experimental results demonstrated that the crosslinked network structure formed by the click reaction significantly enhanced the material properties. The tensile strength of the modified material increased from 32.4 MPa to 51.6 MPa. Differential scanning calorimetry (DSC) analysis revealed an increase in glass transition temperature (Tg) from 24.7 ℃ to 38.5 ℃, and thermal stability was also effectively enhanced. Further investigation showed that the material exhibited excellent self-healing properties and recyclability, benefiting from the dynamic reversibility of boronic ester bonds. After hot-pressing at 160 ℃ and 5 MPa for 1 h, the recycled material retained 95% of its initial tensile strength. These results collectively demonstrate the efficacy of this post-polymerization modification strategy in improving the overall performance of PAGC, thereby broadening its potential applications.

       

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