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Nanoporous glassy polymers are perspective materials for the fabrication of gas separation membranes, especially for the application of gaseous hydrocarbon separation. However, the drawback of such materials is the pronounced physical aging resulting in the dramatic drop of gas transport properties due to relaxation of high-free-volume fraction in time. Herein, a novel and readily available group of such glassy polymers is reported based on 5-alkylnorbornenes. These polymers are easily synthesized from dicyclopentadiene and α-olefins by Diels-Alder reaction and vinyl (addition) polymerization of the formed cycloadducts in the presence of ([(η3 -C3 H5 )PdCl]2 /PCy3 /Na+ [B(3,5-(CF3 )2 C6 H3 )4 ]- catalyst. The obtained polymers display low-fraction free volume, stable gas permeability over time, and possess a unique feature for the glassy polymers-solubility controlled permeation of hydrocarbons and enhanced C4 H10 /CH4 selectivity.

Metathesis polytricyclononenes were synthesized via ROMP polymerization in the presence of the 1-st generation Grubbs catalyst and their gas-transport properties were studied for the first time. The aim of this work was to evaluate the influence of Me3E-groups (E = C, Si, Ge) on gas permeation parameters of ROMP materials. New metathesis poly(3-tert-butyltricyclononene-7) and poly(3-trimethylgermyltricyclononene-7) were obtained with high yields (up to 95%) and high-molecular weights (Mw∼3–7×105 g mol−1). The glass transition temperatures of the ROMP polytricyclononenes with Me3E-groups decreased when E was changed from C to Si and then to Ge. It was shown that the polytricyclononene containing Me3Si-groups has the highest gas permeability while the polytricyclononene containing Me3C-substituents has the lowest gas permeability. In addition, the gas permeation parameters were estimated for ROMP Me3Si- and Me3Ge-substituted polytricyclonona-3,7-dienes. So the influence of the second double bond in the monomer units on the permeability of the polymers obtained was studied. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41395.

A new polymer, poly[5-(trimethylgermylmethyl)-1,3-cyclopentylenevinylene], was synthesized via ROMP of 5-(trimethylgermylmethyl)-2-norbornene in the presence of RuCl 3 .3H 2 O, RuCl 3 (PPh 3 ) 3 and RuCl 2 (PPh 3 ) 3 catalysts. The structure of the synthesized polymer was determined on the basis of IR, 1 H NMR and 13 C NMR spectra. The gas transport properties for this polymer have been studied.

In this work the authors report the preparation of new addition copolymers based on 3-trimethylsilyltricyclononene-7 (TCNSi1) and 3,3,4-tris(trimethylsilyl)tricyclononene-7 (TCNSi3). A number of high molecular weight copolymers are synthesized with the content of TCNSi3 units from 5 up to 20 mol% in the presence of catalyst Pd(OAc)2/[Ph3C]+[B(C6F5)4]− with the yields of 50%–80%. The obtained copolymers are amorphous. They possess large free volume elements (R 3/R 4) based on positron annihilating lifetime spectroscopy analysis and Brunauer–Emmett–Teller surface area up to 640 m2 g−1. Permeability coefficients of the obtained copolymers are determined for a wide range of gases He, H2, O2, N2, CO2, CH4, C2H6, C3H8, n-C4H10. The correlation between the content of TCNSi3 units and gas permeation parameters of the resulting copolymers is explored. It is found that the introduction of TCNSi3 moieties results in the rise in gas permeability of the corresponding copolymers. Moreover, increase in TCNSi3 content in the copolymer leads to an increase of gas permeability.

Unusually high vapor solubilities of hydrocarbons in the rubbery polymer [Si(Me)(CH 2 SiMe 3 )CH 2 CH 2 CH 2 ] n are reported

A novel syntheses of Z-5-decenol, Z-5-decenyl acetate, Z-7-dodecenol, Z-7-dodecenyl acetate, Z-9-tricosene, Z-7,8-epoxy-2-methyloctadecane which are sex pheromone components of Lepidoptera and Diptera orders, have been realized via stereoselective cometathesis of 1,5-cyclooctadiene with ethylene in the presence of MoCl 5 /SiO 2 -SnMe 4 as a key reaction. The main cometathesis product, 1,Z-5,9-decatriene, has been converted into pheromone components mentioned above by regioselective partial hydroboration or hydrozirconation with help of 9-BBN and Cp 2 ZrHCl, correspondingly. The protonolysis of the obtained zirconosene derivative gave 1,Z-5-decadiene. Hydroboration-oxidation or hydroboration-C 2 -homologation of the latter led to Z-5- or Z-7 monoene pheromone components. Hydroboration-iodination of terminal double bond in 1,Z-5,9-decatriene, and further cross-coupling of the obtained iodine derivative with convenient lithium cuprates resulted in Z-9-tricosene, the main sex pheromone component of House Fly ( Musca Domestica ), or in 2-methyl-Z-7-octadecene, the precursor of Gypsy Moth ( Lymantria Dispar ) sex attractant.