Chromatographic Method for Evaluation of Polymeric GC Stationary Phases Ageing Using the Novel Non-Cross-Linked Poly(3-(Tributoxysilyl)Tricyclononene-7) as the Model Stationary Phase

Abstract

The chromatographic properties and thermal stability are investigated for the polymeric stationary phase based on the norbornene polymer. It was shown that without additional cross-linking, poly(3-(tributoxysilyl)tricyclononene-7) demonstrates properties similar to liquid chromatographic stationary phases. It was also found to be more thermally stable than previously studied trimethylsilyl- and trimethoxysilyl- derivatives. The long-term heating at 170 °C resulted in an increase of mass transfer rate between stationary and mobile phases which could be observed as a decrease of parameter C of Van Deemter equation. This effect is rather unusual, as the polymeric stationary phases tend in decrease of the layer volume and porosity while ageing. Additionally, the values of thermodynamic parameters of sorption are calculated for the polymeric stationary phase: enthalpy of sorption varied −28 to −37 kJ/mol, entropy change was −41 to −51 J/mol K. The compensation curves were plotted for the alkanes, arenes, and alcohols, and the parameters of compensation plot were calculated, demonstrating the different sorption mechanisms both for hydrocarbons and oxygen-containing compounds, and different classes of organic compounds.

Tricyclononenes and tricyclononadienes as efficient monomers for controlled ROMP: understanding structure–propagation rate relationships and enabling facile post-polymerization modification

“…Compared to other exo-substituted NB monomers, which oen require high temperatures [9][10][11] and/or precious metal catalysts 8,12 for their synthesis, exo-TCNs and TCNDs can be conveniently assembled by thermal cycloadditions of activated olens and quadricyclane with perfect exo selectivity. 13,14 While TCN and TCNDbased polymers have been synthesized using Mo (Schrock-type initiators) 15 and Ru (Grubbs 1st and 2nd generation initiators) initiated ROMP 16,17 and studied for applications in gas separations, [18][19][20][21][22][23][24][25] no studies of their performance under "living" ROMP conditions initiated by G3 or post-polymerization functionalization have been reported. We hypothesized that they may be competitive with commonly used exo-NBs in terms of ROMP propagation rates, but that they could offer advantages of facile synthesis and, in some cases, post-polymerization modi-cation.…”

Tricyclononenes and Tricyclononadienes as Efficient Monomers for ROMP: Understanding Structure–Propagation Rate Relationships and Enabling Facile Post-Polymerization Modification

“…License: CC BY 4.0 thermal cycloadditions of activated olefins and quadricyclane with perfect exo selectivity. 13,14 While TCN and TCND-based polymers have been synthesized using Mo (Schrock-type initiators) 15 and Ru (Grubbs 1 st and 2 nd generation initiators) initiated ROMP 16,17 and studied for applications in gas separations, [18][19][20][21][22][23][24][25] no studies of their performance under "living" ROMP conditions initiated by G3 or post-polymerization functionalization have been reported. We hypothesized that they may be competitive with commonly used exo-NBs in terms of ROMP propagation rates, but that they could offer advantages of facile synthesis and, in some cases, post-polymerization modification.…”