Poly(o‐xylylene)s via Cobalt‐Catalyzed Reductive Polymerization†,Chinese Journal of Chemistry

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Poly(o‐xylylene)s via Cobalt‐Catalyzed Reductive Polymerization†
Chinese Journal of Chemistry ( IF 5.5 ) Pub Date : 2020-03-28 , DOI: 10.1002/cjoc.202000084
Si Chen ₁ , Yanchuan Zhao _{1,

2}

Affiliation

Poly(p‐xylylene)s (PPX) have found wide applications in various fields owing to their chemical robustness, low gas permeability and excellent dielectric properties. As a structural isomer of PPX, poly(o‐xylylene)s (POX), possessing a distinct main‐chain connectivity, are excellent candidates to pursue high‐performance materials; however, the investigation of POX is hampered by the lack of efficient synthetic methods. Herein, we report a straightforward way to access POXs through a cobalt‐catalyzed reductive polymerization. This method not only allows the direct preparation of electronically unmodified POXs, but also enables the copolymerization between o‐xylylene dibromides bearing different aryl or benzylic substituents. The glass transition temperatures of the copolymers can be finely tuned by varying the ratio between comonomers. The obtained POXs are solvent processible and amenable for thin‐film fabrication. As aryl bromide moiety remains untouched during the polymerization, post‐polymerization functionalization is easily achieved through Suzuki‐Miyaura coupling reaction. The chemistry also enables the copolymerization of xylylene dibromide regioisomers, thereby leading to diversified non‐conjugated polymers, whose backbones are rich in arylene moieties. Moreover, the use of the polymerization strategy to synthesize structurally novel porous polymers is demonstrated.

中文翻译：

通过钴催化还原聚合的聚邻二甲苯†

聚对二甲苯（PPX）由于其化学稳定性，低透气性和出色的介电性能而在各个领域得到了广泛的应用。作为PPX的结构异构体，具有独特的主链连接性的聚邻二甲苯（POX）是追求高性能材料的极佳候选者。然而，缺乏有效的合成方法阻碍了对POX的研究。本文中，我们报告了一种通过钴催化的还原聚合反应访问POX的直接方法。这种方法不仅可以直接制备电子未修饰的POX，而且还可以在邻位之间进行共聚。带有不同芳基或苄基取代基的亚苄基二溴化物。共聚物的玻璃化转变温度可以通过改变共聚单体之间的比例来微调。所获得的POX可以进行溶剂处理，并且适合薄膜制造。由于芳基溴化物部分在聚合过程中保持不变，因此通过Suzuki-Miyaura偶联反应可轻松实现聚合后功能化。该化学方法还可以实现亚二甲苯基二溴化物区域异构体的共聚，从而形成多样化的非共轭聚合物，其主链富含亚芳基部分。此外，证明了使用聚合策略合成结构上新颖的多孔聚合物。

更新日期：2020-03-28

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