Benign Metal Initiators for the Production of Biopolymers and their subsequent depolymerisation

该项目将结合Jones集团在制备Lewis酸性金属配合物方面的专业知识，并将其用于生产新的生物聚合物。最近，一些引发剂已被证明比其他系统更活跃，并且能够在工业相关条件下工作。该项目将分为几个部分：1。配体修饰和改变金属中心（化学浴/卡迪夫）。这将涉及到配体家族的扩展（改变立体，电子）和络合这些到一系列的金属中心。在工业相关条件下（高温和无溶剂），将筛选络合物的环酯（乙酯、己内酯、丁内酯）的同质聚合和环氧化物/二氧化碳和环氧化物/酸酐的共聚合。这是极具挑战性的，然而，我们已经开发出了有希望的催化剂。将最有前途的均相聚合催化剂用于共聚合。这可能会产生嵌段共聚物或根据反应性比而定的交替共聚物。影响高度交替共聚物所需的精确条件是一个知之甚少的领域，因此将是一个有趣的探索途径。根据“循环经济概念”，我们将研究与商业相关的生物聚合物的催化解聚。首先，我们将重点研究聚酯{聚乳酸-PLA}。将塑料垃圾填埋会造成材料价值的损失，也会造成环境问题。当务之急是开发能够回收聚合物以回收单体（或有用的化学原料）的技术。这有可能通过催化解聚来实现

This project will combine expertise in the Jones group in the preparation of Lewis acidic metal complexes and exploitthis in the production of new biopolymers. Recently several initiator have been shown to be significantly more activethan other systems and are able to work at industrially relevant conditions. The project will be split into severalstrands:1. Ligand modification and varying metal centre (Chemistry Bath/Cardiff). This will involve the expansion of the familyof ligands (varying sterics, electronics) and complexing these to a range of metal centres.2. Homo and co-polymerisation the complexes will be screened for the homo-polymerisation of cyclic esters (eglactide, caprolactone, butryolactone) and co-polymerisation of epoxide/CO2 and epoxide/anhydrides underindustrially relevant conditions (high temperature and solvent free). This is extremely challenging, however, we havedeveloped catalysts that show promise. The most promising homo-polymerisation catalysts will be taken forward forco-polymerisations. This, presumably, will lead to either block copolymers or alternating copolymers depending onthe reactivity ratios. The precise conditions required for effecting highly alternating copolymers is an area that ispoorly understood, and will therefore be an interesting avenue to explore.3. In line with the "cyclic economy concept" we will investigate catalytic depolymerisation of commercially relevantbiopolymers. Initially we will focus our investigation on polyesters {polylactide -PLA}. Disposal of plastics into landfillcauses loss of materials' value and also contributes to environmental problems. It is imperative that technology isdeveloped that can recycle polymers to recover the monomer (or useful chemical starting materials). This potentiallycan be achieved by catalytic depolymerisation