Novel functional materials obtained by catalytic polymerization

我们提出了通过催化烯烃聚合来制备创新聚合物材料的平台。乙烯和高碳烯烃的聚合被广泛用于制备聚乙烯等商品塑料，但很少被用于制备功能材料，主要是因为催化剂对官能团几乎没有耐受性。我们预计，以聚烯烃为基础的功能材料的制备将提供相当大的好处，例如优异的耐化学性和环保性，可能利用主要重复单元的容易结晶，能够定制材料的结构，可能利用这些聚合物独特的机械性能范围和相对较低的成本。我们的研究计划将以钯膦磺酸盐为基础，这是一种表现出前所未有的多功能性的催化剂家族，允许插入迄今从未催化聚合的功能性单体。我们计划的第一个方面是改善这些催化剂的性能。然后，我们提出了一种基于甲酸钯分解成氢化物或氢硅烷氧化加成合成端官能化低聚物的新策略。生成的低聚物和含有主链官能团的聚合物将在自组装成选择性溶剂后用于形成结晶度可调的纳米颗粒。

We propose to prepare a platform of innovating polymeric materials by catalytic polymerization of olefins. The polymerization of ethylene and higher olefins is widely used for preparing commodity plastics such as polyethylene but it is rarely exploited to prepare functional materials, mostly because the catalysts have little to no tolerance to functional groups. We envision that the preparation of functional materials based on polyolefins would offer considerable benefits such as an excellent chemical and environmental resistance, the possibility to take advantage of the facile crystallization of the main repeat unit, the ability to tailor the architecture of the material, the possibility to take advantage of the unique range of mechanical properties and of the relative low cost of these polymers. Our research program will be based on Pd phosphine sulfonates, a family of catalysts which exhibits an unprecedented versatility, allowing the insertion of functional monomers never catalytically polymerized so far. A first facet of our program consists in improving the performance of these catalysts. Then, we propose to develop a novel strategy to synthesize end-functionalized oligomers based either on the decomposition of palladium formates into hydrides or on the oxidative addition of hydrosilanes. The resulting oligomers and polymers containing main-chain functional units will be then used for the formation of nanoparticles with tunable crystallinity upon self-assembly into a selective solvent.