The equilibrium and kinetic rigidity of additive poly(trimethylsilyltricyclononenes) with one and two Si(CH3)3 groups in monomer unit

Yevlampieva, N. P.; Бермешев, М. В.; Komolkin, Andrei V.; Везо, О. С.; Chapala, P. P.; Il’yasova, Yu. V.

doi:10.1134/s0965545x17040010

Cited by 8 publications

(3 citation statements)

References 18 publications

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“…The reason of this phenomenon is the difference of the polymer chain rigidity of addition and ROMP polynorbornenes. Addition polynorbornenes possess more rigid polymer main chains . This leads to a more loose packing of polymer chains and as a result addition polynorbornenes with bulky and rigid side groups are microporous materials with large free volume (Tables ).…”

Section: Resultsmentioning

confidence: 99%

Stereoselective synthesis and polymerization of Exo‐5‐trimethylsilylnorbornene

Alentiev

Bermeshev

Старанникова

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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Herein the stereoselective two‐step synthesis of pure exo‐5‐trimethylsilylnorbornene is reported. The monomer proved to be highly reactive in both metathesis and addition polymerization. ROMP polymerization was catalyzed by the first‐generation Grubbs catalyst. High‐molecular‐weight saturated addition polymers were prepared using nickel or palladium complexes as precatalysts and Na+[B(3,5‐(CF3)2C6H3)4]− and/or MAO as cocatalysts. The obtained addition polynorbornenes are highly gas permeable and microporous materials possessing large free volume and BET surface area (up to 540 m2/g). The influence of the substituent orientation (exo‐ vs. exo‐/endo‐mixture) on polymer properties was established. The metathesis polymer based on exo‐isomer exhibits 1.5‐ to 2‐fold increase of permeability coefficients for all gases in comparison to the similar polymer based on the mixture of exo‐ and endo‐isomers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1234–1248

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Section: Resultsmentioning

confidence: 99%

Stereoselective synthesis and polymerization of Exo‐5‐trimethylsilylnorbornene

Alentiev

Bermeshev

Старанникова

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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“…This difference in the properties of two isomeric polymers might be explained by various rigidity of polymer main chains. Thus, it was shown that addition polynorbornenes possess more rigid main chains than the similar metathesis polymers [31,32]. So, in the case of addition polymers, a looser packing of polymer chains should be formed due to more rigid main chains, which could not be packed densely.…”

Section: Resultsmentioning

confidence: 99%

Microporous Materials Based on Norbornadiene-Based Cross-Linked Polymers

et al. 2018

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New microporous homopolymers were readily prepared from norbornadiene-2,5, its dimer and trimer by addition (vinyl) polymerization of the corresponding monomers with 60–98% yields. As a catalyst Pd-N-heterocyclic carbene complex or Ni(II) 2-ethylhexanoate activated with Na+[B(3,5-(CF3)2C6H3)4]− or methylaluminoxane was used. The synthesized polynorbornenes are cross-linked and insoluble. They are glassy and amorphous polymers. Depending on the nature of the catalyst applied, BET surface areas were in the range of 420–970 m2/g. The polymers with the highest surface area were obtained in the presence of Pd-catalysts from the trimer of norbornadiene-2,5. The total pore volume of the polymers varies from 0.39 to 0.79 cm3/g, while the true volume of micropores was 0.14–0.16 cm3/g according to t-plot. These polymers gave CO2 uptake from 1.2 to 1.9 mmol/g at 273 K and 1 atm. The porous structure of new polymers was also studied by means of wide-angle X-ray diffraction and positron annihilation lifetime spectroscopy.

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“…Polynorbornenes, synthesized via the addition mechanism of polymerization, possess rigid and saturated main chains [ 10 , 11 ]. Furthermore, it was shown [ 12 ] that polymer properties can be varied in a wide range by the introduction of side groups of different types.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Gas Transport Properties of Addition Polynorbornene with Perfluorophenyl Side Groups

et al. 2020

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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 C4H10/CH4 and CO2/N2 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 C6F5 group, 3-pentafluorophenyl-exo-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 Mw values of (2.93–4.35) × 105. 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, H2, O2, N2, CO2, and CH4) 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-exo-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.

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The equilibrium and kinetic rigidity of additive poly(trimethylsilyltricyclononenes) with one and two Si(CH3)3 groups in monomer unit

Cited by 8 publications

References 18 publications

Stereoselective synthesis and polymerization of Exo‐5‐trimethylsilylnorbornene

Stereoselective synthesis and polymerization of Exo‐5‐trimethylsilylnorbornene

Microporous Materials Based on Norbornadiene-Based Cross-Linked Polymers

Synthesis and Gas Transport Properties of Addition Polynorbornene with Perfluorophenyl Side Groups

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