Poly(phosphoester)s via Olefin Metathesis

介绍了通过烯烃歧化反应合成几种聚磷酸酯(PPEs)。这项建议的目的是实现对分子结构和微观结构的控制，以控制这一极有希望的聚合物类别在生物应用方面的降解动力学。通过非环二烯歧化(ADMET)聚合，合成了线型聚磷酸盐、S和-膦酸酯。特别是，由于与聚磷酸盐S相比，水解动力学发生了变化，因此聚膦酸类化合物S的合成引起了人们的极大兴趣，ADMET首次以系统的方式获得了这类聚合物。此外，将通过在聚合物主干中引入支化来改变体系结构。将研究不同的支化聚合途径(AB2、A2+B3或B3方法)来设计具有不同支化度的PPE。所有这些新材料都将被应用于合成可降解的纳米粒子，这些纳米粒子可以负载药物等，并在体外进行测试。

This proposal describes the synthesis of several polyphosphoesters (PPEs) via olefin metathesis reactions. The aim of this proposal is to achieve control over molecular architecture and microstructure to control the degradation kinetics of this highly promising polymer class with respect to bioapplications. Linear poly(phosphate)s and -phosphonates will be synthesized via acyclic diene metathesis (ADMET) polymerization. Especially the synthesis of the poly(phosphonate)s is of high interest due to the altered hydrolysis kinetics compared to poly(phosphate)s and ADMET allows access to this class of polymers for the first time in a systematic manner. Further, the architecture will be altered by introducing branches in the polymer backbone. Different pathways for a branching ADMET polymerization (AB2, A2+B3 or B3 approaches) will be investigated to design PPEs with a variable degree of branching. All these novel materials will be applied for the synthesis of degradable nanoparticles that can be loaded with drugs etc. and tested in vitro.