Metallocene catalysts for the ring-opening co-polymerisation of epoxides and cyclic anhydrides - data

The ring-opening co-polymerization (ROCOP) of epoxides and cyclic anhydrides is a versatile route to polyester materials. The vast number of monomers that are readily available means that an effectively limitless number of unique polymeric substances can be prepared using a common synthetic route, thereby paving the way to polymers that are more recyclable and could be used in applications that currently lie within the remit of polyolefins alone. Metallocene complexes [Cp2MCl2] (M = Ti, Zr, Hf, Cp = η5-C5H5) are known to be excellent pre-catalysts for olefin polymerization and yet have not been reported for ROCOP, despite their supreme pedigree in the polymerization realm. Herein, we report the first application of [Cp2MCl2] as catalysts for the ROCOP of epoxides and anhydrides and show that they are effective catalysts for this reaction. The catalytic performances are good with standard epoxides such as cyclohexene oxide but are excellent with more challenging sterically demanding limonene oxide, and therefore represents a highly effective catalyst system for the preparation of bio-derived recyclable polymers. The dataset contains NMR data (Bruker), DFT input and output files (Gaussian 09), and chromatographic data (GPC traces, Excel) which together form chracterising data relating to the polymers, catalyst performance, and mechanistic analyses.

环氧化物与环状酸酐的开环共聚（ring-opening co-polymerization，ROCOP）是制备聚酯材料的通用合成路径。当前市售单体品类丰富，可通过该通用路线制备近乎无限多种独特的聚合物，从而为开发更具可回收性的聚合物提供了可能，这类聚合物可应用于目前仅由聚烯烃覆盖的领域。金属茂配合物（metallocene complexes）[Cp2MCl2]（M = Ti, Zr, Hf, Cp = η5-C5H5）是公认的烯烃聚合优异预催化剂，尽管其在聚合领域拥有深厚的学术积淀，但此前尚未见其用于ROCOP的相关报道。本文首次报道了[Cp2MCl2]作为催化剂用于环氧化物与酸酐的ROCOP，并证实其对该反应具有高效催化活性。该催化体系对环氧环己烷等常规环氧化物表现出良好的催化性能，对更具挑战性的空间位阻型柠檬烯氧化物则展现出优异的催化效果，因此可作为制备生物基可回收聚合物的高效催化体系。本数据集包含核磁共振（nuclear magnetic resonance，NMR）数据（Bruker）、密度泛函理论（density functional theory，DFT）输入输出文件（Gaussian 09）以及色谱数据（凝胶渗透色谱（gel permeation chromatography，GPC）谱图、Excel格式文件），上述数据共同构成了用于聚合物表征、催化性能评价及机理分析的完整表征数据集。