Ullmann缩聚合成含二氮杂萘酮给受体结构聚合物

Donor-Acceptor Copolymers Containing Phthalazinone Structure Synthesized by Ullmann Polymerization

廉价Cu催化的Ullmann缩聚是一种用于合成聚芳醚经典聚合方法。在过去几十年的研究中，由于Ullmann反应对单体本身的活性具有很大的依赖性，所以聚合用单体局限在缺电子结构的双卤单体范围内。作者研究团队在强碱Cs2CO3的催化效果下，成功的实现了二氮杂萘酮受体和噻吩强给体结构之间的聚合。对合成的聚合物进行了凝胶渗透色谱（GPC）和氢核磁共振（1H-NMR）的结构表征。在氮气中质量损失5％时的温度均高于382℃，800℃残炭率在63％-76％。表明所得聚合物具有优异的热稳定性。满足光学器件对热性能的使用要求。同时，通过改变主链之中噻吩的含量来控制受体和给体之间的相互作用，成功地对聚合物的最大发射波长和发光颜色实现了调控。上述工作对于扩展聚芳醚合成方法和开发新类型的聚芳醚产品具有重要的研究价值。并且基于Ullmann缩合聚合的特点，可以扩大含二氮杂萘酮结构的聚合物种类。对于开发新型功能化的聚合物具有指导意义。

There has been a great deal of recent effort centered on low-cost copper catalyst Ullmann polycondcnsation. In the past decade, the monomers used in Ullmann polycondensation are mostly electron-deficient di-halogenated compounds. The molecular weight are highly dependent on the reaction activities of monomers. In this research, the polymerizations are success- fully proceed between the electron-deficient phthalazinone structure and strong electron donating thiophene structure. The ob- tained copolymers are fully characterized by GPC and 1H-NMR. Their 5% weigh loss temperatures are higher than 382 ℃. The char yield of the investigated polymers in the nitrogen atmosphere is in the range of 63% -76% at 800 ℃, confirming their excellent thermal stability and meeting the demand of the optical device for thermal performance. Also, the wavelength of the luminescence can be controlled by changing the content of thiophene structures in the polymer backbones. Further- more, our research could enrich and diversify the typical polyarylether family containing phthalazinone structure. And it is of great guiding significance for developing the novel functional polymers based on Ullmann polymerization.