The ring-opening copolymerization (ROCOP) of epoxides and CO₂ provides an alternative approach towards polycarbonates and due to their aliphatic nature, they represent an interesting alternative to bisphenol-A based polycarbonates. A Lewis acidic β-diiminate (BDI)^CF3-Zn-(SiMe₃)₂ complex 1 is used in the ROCOP of CO₂ with cyclohexene oxide (CHO) and limonene oxide (LO), respectively. The knowledge gained from polymerizations monitored via in situ IR spectroscopy was used to upscale the reactions to a 1 L reactor. The two products poly(cyclohexene carbonate) (PCHC) and poly(limonene carbonate) (PLC) were then characterized via thermal analysis, a multiaxial pressure test, and dynamic mechanical analysis and compared with commercial polymers. While PCHC and PLC were both thermally stable at 150 °C for 20 min and only minor decomposition occurred at 180 °C, PLC is prone to cross-linking at elevated temperatures. This could be prevented by hydrogenation of the double bond or by the addition of an antioxidant. In the mechanical performance, the aliphatic polymers ranged between the highly impact resistant Durabio® and the brittle PMMA but broke without a splintering of the material. Overall, this study enabled a classification of CO₂-based polycarbonates, especially of the novel PLC. Additionally, complex 1 was active in the terpolymerization of CHO, LO, and CO₂. The formation of an actual terpolymer was confirmed via aliquot gel-permeation chromatography and diffusion-ordered NMR spectroscopy. High-pressure NMR techniques reveal an interesting kinetic feature. CHO gets copolymerized with CO₂ exclusively, and LO incorporation only starts when CHO is fully consumed.

环氧化物和CO ₂的开环共聚（ROCOP）为聚碳酸酯提供了一种替代方法，由于它们的脂族性质，它们代表了双酚A基聚碳酸酯的一种令人感兴趣的替代方法。甲路易斯酸性β-diiminate（BDI）^CF3 -Zn-（森达₃）₂配合物1在CO ROCOP使用₂分别使用环己烯氧化物（CHO）和环氧丁烯（LO）。通过原位红外光谱监测聚合反应所获得的知识可用于将反应规模扩大至1 L反应器。然后通过热分析，多轴压力测试和动态力学分析对聚碳酸亚环己酯（PCHC）和聚碳酸亚柠檬酯（PLC）这两种产品进行表征，并与市售聚合物进行比较。PCHC和PLC在150°C的温度下均能保持20分钟的热稳定性，而在180°C时仅发生少量分解，而PLC在高温下易于发生交联。这可以通过双键的氢化或通过添加抗氧化剂来防止。在机械性能上 脂族聚合物的强度介于高度耐冲击的Durabio®和脆性PMMA之间，但在不破裂的情况下破裂。总体而言，这项研究可以对CO进行分类₂基聚碳酸酯，尤其是新型PLC。此外，配合物1在CHO，LO和CO ₂的三聚反应中具有活性。通过等分凝胶渗透色谱法和扩散有序NMR光谱法确认了实际三元共聚物的形成。高压NMR技术揭示了有趣的动力学特征。CHO仅与CO ₂共聚，LO掺入仅在CHO被完全消耗时才开始。