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Metallocene catalysts for the ring-opening co-polymerisation of epoxides and cyclic anhydrides
Polymer Chemistry ( IF 4.1 ) Pub Date : 2022-05-16 , DOI: 10.1039/d2py00335j Matthew S. Shaw 1 , Morgan R. Bates 1 , Matthew D. Jones 2 , Benjamin D. Ward 1
Polymer Chemistry ( IF 4.1 ) Pub Date : 2022-05-16 , DOI: 10.1039/d2py00335j Matthew S. Shaw 1 , Morgan R. Bates 1 , Matthew D. Jones 2 , Benjamin D. Ward 1
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The ring-opening co-polymerisation (ROCOP) of epoxides and cyclic anhydrides is a versatile route to new polyesters. The vast number of monomers that are readily available means that an effectively limitless number of unique polymeric materials 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 exclusively within the remit of polyolefins. Metallocene complexes [Cp2MCl2] (M = Ti, Zr, Hf, Cp = η5-C5H5) are known to be excellent pre-catalysts for olefin polymerisation and yet have not been reported for ROCOP, despite their supreme pedigree in the polymerisation 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 this therefore represents a highly effective catalyst system for the preparation of bio-derived recyclable polymers.
中文翻译：
用于环氧化物和环状酸酐的开环共聚的茂金属催化剂
环氧化物和环状酸酐的开环共聚 (ROCOP) 是制备新型聚酯的通用途径。大量容易获得的单体意味着可以使用共同的合成路线制备有效无限数量的独特聚合物材料，从而为更可回收的聚合物铺平道路，并且可以用于目前完全属于聚烯烃的范围。茂金属配合物 [Cp 2 MCl 2 ] (M = Ti, Zr, Hf, Cp = η 5 -C 5 H 5) 已知是烯烃聚合的优秀预催化剂，但尚未报道用于 ROCOP，尽管它们在聚合领域具有最高的血统。在此，我们报道了[Cp 2 MCl 2 ]作为环氧化物和酸酐ROCOP催化剂的首次应用，并表明它们是该反应的有效催化剂。催化性能与标准环氧化物如氧化环己烯良好，但对更具挑战性的空间要求的氧化柠檬烯具有优异的催化性能，因此这代表了一种用于制备生物衍生可回收聚合物的高效催化剂体系。
更新日期：2022-05-19
中文翻译：
用于环氧化物和环状酸酐的开环共聚的茂金属催化剂
环氧化物和环状酸酐的开环共聚 (ROCOP) 是制备新型聚酯的通用途径。大量容易获得的单体意味着可以使用共同的合成路线制备有效无限数量的独特聚合物材料，从而为更可回收的聚合物铺平道路，并且可以用于目前完全属于聚烯烃的范围。茂金属配合物 [Cp 2 MCl 2 ] (M = Ti, Zr, Hf, Cp = η 5 -C 5 H 5) 已知是烯烃聚合的优秀预催化剂，但尚未报道用于 ROCOP，尽管它们在聚合领域具有最高的血统。在此，我们报道了[Cp 2 MCl 2 ]作为环氧化物和酸酐ROCOP催化剂的首次应用，并表明它们是该反应的有效催化剂。催化性能与标准环氧化物如氧化环己烯良好，但对更具挑战性的空间要求的氧化柠檬烯具有优异的催化性能，因此这代表了一种用于制备生物衍生可回收聚合物的高效催化剂体系。
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