Karpov Gleb O, Borisov Ilya L, Volkov Alexey V, Finkelshtein Eugene Sh, Bermeshev Maxim V
A.V. Topchiev Institute of Petrochemical Synthesis of Russian Academy of Sciences, 29 Leninsky Prospekt, 119991 Moscow, Russia.
Polymers (Basel). 2020 Jun 3;12(6):1282. doi: 10.3390/polym12061282.
Polynorbornenes represent a fruitful class of polymers for structure-property study. Recently, vinyl-addition polynorbornenes bearing side groups of different natures were observed to exhibit excellent gas permeation ability, along with attractive CH/CH and CO/N separation selectivities. However, to date, the gas transport properties of fluorinated addition polynorbornenes have not been reported. Herein, we synthesized addition polynorbornene with fluoroorganic substituents and executed a study on the gas transport properties of the polymer for the first time. A norbornene-type monomer with a CF group, 3-pentafluorophenyl--tricyclononene-7, was successfully involved in addition polymerization, resulting in soluble, high-molecular-weight products obtained in good or high yields. By varying the monomer concentration and monomer/catalyst ratio, it was possible to reach M values of (2.93-4.35) × 10. The molecular structure was confirmed by NMR and FTIR analysis. The contact angle with distilled water revealed the hydrophobic nature of the synthesized polymer as expected due to the presence of fluoroorganic side groups. A study of the permeability of various gases (He, H, O, N, CO, and CH) through the prepared polymer disclosed a synergetic effect, which was achieved by the presence of both bulky perfluorinated side groups and rigid saturated main chains. Addition poly(3-pentafluorophenyl--tricyclononene-7) was more permeable than its metathesis analogue by a factor of 7-21, or the similar polymer with flexible main chains, poly(pentafluorostyrene), in relation to the gases tested. Therefore, this investigation opens the door to fluorinated addition polynorbornenes as new potential polymeric materials for membrane gas separation.
聚降冰片烯是一类在结构-性能研究方面成果丰硕的聚合物。最近，人们观察到带有不同性质侧基的乙烯基加成聚降冰片烯表现出优异的气体渗透能力，以及吸引人的CH/CH和CO/N分离选择性。然而，迄今为止，含氟加成聚降冰片烯的气体传输性能尚未见报道。在此，我们合成了带有氟代有机取代基的加成聚降冰片烯，并首次对该聚合物的气体传输性能进行了研究。一种带有CF基团的降冰片烯型单体，3-五氟苯基- -三环壬烯-7，成功参与加成聚合反应，得到了可溶的、高分子量的产物，产率良好或较高。通过改变单体浓度和单体/催化剂比例，可以得到(2.93 - 4.35)×10的M值。通过核磁共振（NMR）和傅里叶变换红外光谱（FTIR）分析确定了分子结构。与蒸馏水的接触角表明，由于存在氟代有机侧基，合成的聚合物具有预期的疏水性。对各种气体（He、H、O、N、CO和CH）透过制备的聚合物的渗透性研究揭示了一种协同效应，这是由庞大的全氟侧基和刚性饱和主链共同存在实现的。对于所测试的气体，加成聚(3-五氟苯基- -三环壬烯-7)的渗透性比其复分解类似物高7 - 21倍，或者比具有柔性主链的类似聚合物聚（五氟苯乙烯）高。因此，这项研究为含氟加成聚降冰片烯作为用于膜气体分离的新型潜在高分子材料打开了大门。
