Metathesis and addition polymerization of novel Me3Si- and Me3Ge-substituted tricyclononenes

Abstract

Addition and ring-opening metathesis polymerizations of new monomers (Me 3 Si-and Me 3 Ge-substituted tricyclononene and tricyclononadienes) were studied. Addition polymerization was carried out on Pd-and Ni-catalyst systems activated by B(C 6 F 5) 3 and/or methylalumoxane. New addition polymers were obtained with good yields up to 70% and with molecular weights (M w) up to 5.6 Â 10 5. Metathesis polymerization was performed using the first-generation Grubbs catalyst. The yields of the first obtained metathesis polymers were higher than 80%, and the M w values were up to 8.8 Â 10 5. It was revealed that the cyclobutene double bond in the studied tricyclononadienes is inactive in both metathesis and addition polymerizations. The relative activities of the substituted tricyclononene-7 and the corresponding tricyclononadiene-3,7 in the metathesis copolymerization were defined using 1 H NMR spectroscopy. It was found that the novel addition polymer poly[(3trimethylgermyl)tricyclononene-7] possesses high gas-transport parameters (for example, P(O 2) ¼ 660 Barrers, P(CO 2) ¼ 3850 Barrers) and solubility-controlled permeation of gaseous hydrocarbons (a (n-C 4 H 10 /CH 4) ¼ 17.3).

Synthesis and Gas-Transport Properties of Metathesis Polytricyclononenes Bearing Three Me3 Si Groups per Monomer Unit

“…It was shown that addition type polynorbornenes are more permeable than metathesis polymers but the latter are more readily obtained due to the high driving force of metathesis polymerization of high strain norbornene monomers . High gas permeability level of these polymers was caused by the presence of spherical bulky groups (e.g., trimethylsilyl groups or trimethylgermyl groups) and rigid polymer chains which disrupt a dense polymer chain package . Bulky SiMe 3 groups were also introduced into other classes of polymers (polyacetylenes, polystyrenes, polysulfones, poly(phenylene oxide), polyolefins).…”

Synthesis and gas permeation parameters of metathesis polytricyclononenes with pendant Me3E‐groups (E = C, Si, Ge)

“…In general, ROMP polymerization of tricyclononenes proceeds readily due to a high strain energy of the norbornene fragment and the exo ‐orientation of cyclobutane ring . Earlier we have demonstrated that ROMP polymerization of tricyclononenes and tricyclononadienes proceeds effectively in the presence of the 1st generation Grubbs catalyst at high monomer/catalyst ratios resulting in high molecular weight polymers. This process is characterized by a good reproducibility and tolerance to the strain cyclobutene ring in the case of polymerization of tricyclononadienes .…”

“…Earlier we have demonstrated that ROMP polymerization of tricyclononenes and tricyclononadienes proceeds effectively in the presence of the 1st generation Grubbs catalyst at high monomer/catalyst ratios resulting in high molecular weight polymers. This process is characterized by a good reproducibility and tolerance to the strain cyclobutene ring in the case of polymerization of tricyclononadienes . So all the polymers studied in this work were synthesized on the above catalyst according to Scheme (Table ).…”

“…On the basis of these and other studies, one can ask a natural question: is the strong effect of Me 3 Si‐group caused by its bulky and symmetric shape or by the presence of silicon atom in it? Some studies were performed to answer this question, i.e., several glassy polymers with Me 3 C‐ and Me 3 Ge‐side groups were studied . Usually, comparisons of gas permeability were made only between Me 3 Si‐ and Me 3 Ge‐substituted polymers which were synthesized by the similar scheme.…”

Experimental and Theoretical Study of [2σ + 2σ + 2π]–Cycloaddition of Quadricyclane and Ethylenes Containing Three Silyl-Groups

“…It has been recently shown that among norbornene derevatives exo-tricyclononenes were more attractive due to their enhanced activities in polymerization [5][6][7][8][9]. We have demonstrated previously that quadricyclane (Q) entered into [2σ + 2σ + 2π] stereoand regiospecific cycloaddition reaction with silicon-and germanium-substituted ethylenes and acetylenes resulting in a formation of substituted tricyclo[4.2.1.0 2,5 ]nonenes and tricyclo[4.2.1.0 2,5 ]nonadienes [7,[10][11][12][13]. Methylation of these cycloadducts led to highly active monomers.…”