Nazarov Ivan V, Bakhtin Danila S, Gorlov Ilya V, Potapov Konstantin V, Borisov Ilya L, Lounev Ivan V, Makarov Igor S, Volkov Alexey V, Finkelshtein Eugene Sh, Bermeshev Maxim V
A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky Prospekt, 119991 Moscow, Russia.
Faculty of Fundamental Physical and Chemical Engineering, The Moscow State University, 1 Leninskie Gory, 119991 Moscow, Russia.
Polymers (Basel). 2022 Jun 30;14(13):2697. doi: 10.3390/polym14132697.
Polymers from norbornenes are of interest for applications in opto- and microelectronic (low dielectric materials, photoresists, OLEDs). Norbornenes with ester motifs are among the most readily available norbornene derivatives. However, little is known about dielectric properties and the gas-transport of polynorbornenes from such monomers. Herein, we synthesized a new metathesis polymer from -5-norbornenecarboxylic acid and 1,1'-bi-2-naphthol. The designed monomer was obtained via a two-step procedure in a good yield. This norbornene derivative with a rigid and a bulky binaphthyl group was successfully polymerized over the 1st generation Grubbs catalyst, affording high-molecular-weight products (M ≤ 1.5·10) in yields of 94-98%. The polymer is amorphous and glassy (T = 161 °C), and it shows good thermal stability. Unlike most, polyNBi is a classic low-permeable glassy polymer. The selectivity of polyNBi was higher than that of polyNB. Being less permeable than polyNB, polyNBi unexpectedly showed a lower value of dielectric permittivity (2.7 for polyNBi vs. 5.0 for polyNB). Therefore, the molecular design of polynorbornenes has great potential to obtain polymers with desired properties in a wide range of required characteristics. Further tuning of the gas separation efficiency can be achieved by attaching an appropriate substituent to the ester and aryl group.
降冰片烯类聚合物因其在光电子和微电子领域（低介电材料、光刻胶、有机发光二极管）的应用而备受关注。带有酯基序的降冰片烯是最容易获得的降冰片烯衍生物之一。然而，对于由这类单体合成的聚降冰片烯的介电性能和气体传输性能却知之甚少。在此，我们由5-降冰片烯羧酸和1,1'-联-2-萘酚合成了一种新型的易位聚合物。通过两步法以良好的产率得到了设计的单体。这种带有刚性且庞大的联萘基的降冰片烯衍生物在第一代格拉布催化剂作用下成功聚合，得到了高分子量产物（M ≤ 1.5·10），产率为94 - 98%。该聚合物为无定形玻璃态（T = 161 °C），具有良好的热稳定性。与大多数聚合物不同，聚NBi是一种典型的低渗透性玻璃态聚合物。聚NBi的选择性高于聚NB。聚NBi的渗透性比聚NB低，但其介电常数却意外地较低（聚NBi为2.7，聚NB为5.0）。因此，聚降冰片烯的分子设计在获得具有广泛所需特性的聚合物方面具有巨大潜力。通过在酯基和芳基上连接合适的取代基，可以进一步调节气体分离效率。
