Addition homo- and copolymerization of 3-triethoxysilyltricyclo[4.2.1.02,5]non-7-ene / D. A. Alentiev, S. A. Korchagina, E. S. Finkel'shtein et al. // Russian Chemical Bulletin . — 2018. — Vol. 67, no. 1. — P. 121–126. [ DOI ]
Bermeshev M. V., Chapala P. P. Addition polymerization of functionalized norbornenes as a powerful tool for assembling molecular moieties of new polymers with versatile properties // Progress in Polymer Science (Oxford) . — 2018. — Vol. 84. — P. 1–46. [ DOI ]
Cross-linking of addition copolymers based on 3-trimethylsilyltricyclo[4.2.1.02,5]non-7-ene / D. A. Alentiev, M. V. Bermeshev, E. V. Bermesheva, E. S. Finkelshtein // AIP Conference Proceedings . — 2018. — Vol. 1981. — P. 020177. [ DOI ]
Extrathermodynamic parameters of sorption of light hydrocarbons on stationary phases prepared from tricyclononene polymers / A. A. Korolev, V. E. Shiryaeva, T. P. Popova et al. // Journal of Chromatography A . — 2018. — Vol. 1533. — P. 174–179.
Janus tricyclononene polymers bearing tri(n-alkoxy)silyl side groups for membrane gas separation / D. A. Alentiev, E. S. Egorova, M. V. Bermeshev et al. // Journal of Materials Chemistry A . — 2018. — Vol. 6, no. 40. — P. 19393–19408. [ DOI ]
Metathesis and additive poly(tricyclononenes) with geminal trimethylsilyl side groups: chain rigidity, molecular and thin film properties / N. Yevlampieva, M. Bermeshev, O. Vezo et al. // Journal of Polymer Research . — 2018. — Vol. 25, no. 8. — P. 162. [ DOI ]
Metathesis-type poly-exo-tricyclononenes with fluoroorganic side substituents: Synthesis and gas-transport properties / G. O. Karpov, M. V. Bermeshev, I. L. Borisov et al. // Polymer . — 2018. [ DOI ]
Microporous materials based on norbornadiene-based cross-linked polymers / D. A. Alentiev, D. M. Dzhaparidze, N. N. Gavrilova et al. // Polymers . — 2018. — Vol. 10, no. 12. — P. 1382. [ DOI ]
Molecular properties of additive poly(bis(trimethylsilyl)tricyclonones) with vicinal and geminal side substituents / N. P. Yevlampieva, M. V. Bermeshev, O. S. Vezo et al. // Polymer Science, Series A . — 2018. — Vol. 60, no. 2. — P. 162–171. [ DOI ]
Nanoporosity of polymer membrane materials and sorbents according to positron annihilation and low-temperature gas sorption data / V. P. Shantarovich, V. G. Bekeshev, I. B. Kevdina et al. // High Energy Chemistry . — 2018. — Vol. 52, no. 4. — P. 275–282.
One-pot two-step stannylation/stille homocoupling of aryl bromides and iodides under solvent-free conditions / P. S. Gribanov, Y. D. Golenko, M. A. Topchiy et al. // Mendeleev Communications . — 2018. — Vol. 28, no. 3. — P. 323–325. A new highly efficient solvent-free method for aryl bromide (iodide) homocoupling comprising the use of Pd(OAc)2/PCy3 system in the presence of CsF is suitable for substrates bearing functional groups not tolerant to lithium-, magnesium-, zincorganic reagents and strong bases. [ DOI ]
Poly(trialkoxysilyltricyclononenes): A new type of polymers for membrane gas separation / D. A. Alentiev, M. V. Bermeshev, L. E. Starannikova et al. // Doklady Chemistry . — 2018. — Vol. 482, no. 2. — P. 225–228. [ DOI ]
Selective catalytic hydrogenation of alicyclic dienes with hydrogen in a liquid phase / M. V. Bermeshev, T. N. Antonova, D. R. Shangareev et al. // Petroleum Chemistry . — 2018. — Vol. 58, no. 10. — P. 861–867.
Selective hydrogenation of 5-vinyl-2-norbornene to 2-vinylnorbornane / S. V. Shorunov, E. S. Piskunova, V. A. Petrov et al. // Petroleum Chemistry . — 2018. — Vol. 58, no. 12. — P. 1056–1063. [ DOI ]
Stereoselective synthesis and polymerization of exo-5-trimethylsilylnorbornene / D. A. Alentiev, M. V. Bermeshev, L. E. Starannikova et al. // Journal of Polymer Science, Part A: Polymer Chemistry . — 2018. — Vol. 56, no. 12. — P. 1234–1248. 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 Na1[B(3,5-(CF3)2C6H3)4]2 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 exoand endo-isomers. [ DOI ]
Structural and morphological features of carbon—silicon-carbide fibers based on cellulose and triethoxyvinylsilane / I. S. Makarov, L. K. Golova, M. V. Mironova et al. // Fibre Chemistry (English Translation of Khimicheskie Volokna) . — 2018. — Vol. 50, no. 2. — P. 1–6. Carbon—silicon-carbide fibers were produced from cellulose and triethoxyvinylsilane and spun using the solid-phase NMMO-process. Scanning and transmission electron microscopy studies, energydispersive x-ray spectrometry, and x-ray structure analysis of composite carbon fibers established and identified the structure and morphology of carbon fibers that varied from an isotropic shell to regularly organized lamellae of graphite-like layers of the fiber core. Distributions of chemical elements were plotted. The nano-sized dimensions of silicon-carbide regions in the carbon fibers were determined. [ DOI ]
Synthesis and properties of metathesis polymer based on 3-silatranyltricyclo[4.2.1.02.5]non-7-ene / D. A. Alentiev, D. M. Dzhaparidze, P. P. Chapala et al. // Polymer Science, Series B . — 2018. — Vol. 60, no. 5. — P. 612–620. [ DOI ]
Synthesis and properties of polynorbornenes containing trialkoxysilyl groups / D. A. Alentiev, M. V. Bermeshev, L. E. Starannikova et al. // AIP Conference Proceedings . — 2018. — Vol. 1981. — P. 020168. [ DOI ]
Synthesis and unusual photochemistry of a highly reactive pyrimidinedione / S. V. Shorunov, M. B. Plutschack, M. V. Bermeshev, I. A. Guzei // Mendeleev Communications . — 2018. — Vol. 28, no. 5. — P. 501–502. [ DOI ]
The effect of geometric confinement on gas separation characteristics of additive poly[3-(trimethylsilyl)tricyclononene-7] / E. A. Chernova, M. A. Bermeshev, D. I. Petukhov et al. // NANOSYSTEMS: PHYSICS, CHEMISTRY, MATHEMATICS, 2018, 9 (2), P. 252–258 . — 2018. — Vol. 2018, no. 9. — P. 252–258. Composite membranes based on a hydrophobic glassy poly[3-(trimethylsilyl)tricyclononene-7](PTCNSi-1) confined in the channels of anodic alumina with different pore diameters are discussed. Formation of continuous polymer film with partial penetration of polymer into the rigid pores of anodic alumina was achieved by spin-coating technique under vacuum suction. Mass-transport characteristics of composite membranes reveal a slight reduction of composite membrane permeability for condensable gases, and many-fold permeability drop for permanent gases as compared to the bulk film. This results in an ideal selectivity rise over 35 for C4H10/CH4 pair compared to 12.6 for bulk PTCNSi-1. The effect is attributed to a solubility-controlled mobility of polymer segments confined in the AAO channels and formation of rigid shallow polymer layer at AAO/polymer interface, which suppress transport of gases. The correlation between intrinsic properties of the polymer (hydrophobicity, Kuhn segment) and its transport characteristics in the confined state is discussed. The evolution of the permeance and puregas selectivity of the composite membranes during ageing is also reported. [ DOI ]
Carbon—silicon-carbide fibers prepared from solid solutions of cellulose in n-methylmorpholine-n-oxide with added tetraethoxysilane / I. S. Makarov, L. K. Golova, G. N. Bondarenko et al. // Fibre Chemistry (English Translation of Khimicheskie Volokna) . — 2017. — Vol. 49, no. 4. — P. 231–236. Composite fibers were prepared by solid-state dissolution of cellulose in N-methylmorpholine-N-oxide with added tetraethoxysilane (TEOS). It was shown that adding TEOS to the cellulose matrix increased up to 16% the fiber carbon residue during heat treatment. Bonds formed between Si and C during their high-temperature treatment according to IR spectra of the composite cellulose fibers. The thermal behavior of the fibers was studied using TGA and TMA. The fiber morphology and the structure of the Si-containing additive particles were examined using SEM and TEM. The mechanical properties of carbon fibers prepared from cellulose-hydrate and composite fibers were compared. [ DOI ]
Chromatographic determination of the diffusion coefficients of light hydrocarbons in polymers / E. E. Yakubenko, A. A. Korolev, P. P. Chapala et al. // Russian Journal of Physical Chemistry A . — 2017. — Vol. 91, no. 1. — P. 175–181. [ DOI ]
Composite fibers based on cellulose and tetraetoxysilane: Preparation, structure and properties / I. S. Makarov, L. K. Golova, L. K. Kuznetsova et al. // Fibre Chemistry (English Translation of Khimicheskie Volokna) . — 2017. — Vol. 49, no. 2. — P. 101–107. A method for producing cellulose-based composite fibers with the addition of tetraethoxysilane (TEOS) with a high degree of dispersion of the additive in the cellulose matrix through a “solid phase” dissolution step of the cellulose in N-methylmorpholine-N-oxide (NMMO) is proposed. Investigation of the phase state and morphological features of mixtures of cellulose solutions with TEOS additives in NMMO has shown that in the entire range of concentrations studied, the solutions are biphasic emulsions, and their dispersity and the shape of dispersed phase droplets depend on the prehistory of solution preparation. It is established that the rheological behavior of cellulose solutions with TEOS additives varies depending on the amount of the additive. A theory about a mechanism for changing the rheological behavior of cellulose solutions with TEOS is formulated. X-ray diffraction analysis, scanning and transmission microscopy and IR spectroscopy were used to characterize the structure and morphology of composite fibers. The mechanical properties of composite cellulose fibers with TEOS are investigated. [ DOI ]
Chapala P. P., Bermeshev M. V., Gavrilova N. N. Microporous structure of highly permeable additive silicon-containing polytricyclononenes // Polymer Science, Series A . — 2017. — Vol. 59, no. 1. — P. 143–148. [ DOI ]
Molecular mobility and physical aging of a highly permeable glassy polynorbornene as revealed by dielectric spectroscopy / H. Yin, P. Chapala, M. Bermeshev et al. // ACS macro letters . — 2017. — Vol. 6, no. 8. — P. 813–818. [ DOI ]
New stationary phases for gas chromatography based on polymers with intrinsic porosity / E. Yakubenko, A. Korolev, P. Chapala et al. // Analytica Chimica Acta . — 2017. — Vol. 986. — P. 153–160.
Polynorbornenes / E. Finkelshtein, M. Gringolts, M. Bermeshev et al. // Membrane Materials for Gas and Vapor Separation . — 2017. — P. 143–221.
Solvent-free buchwald–hartwig amination with low palladium loadings / G. A. Chesnokov, P. S. Gribanov, M. A. Topchiy et al. // Mendeleev Communications . — 2017. — Vol. 27, no. 6. — P. 618–620. A highly efficient ‘green’ solvent-free monoarylation of primary anilines with aryl bromides mediated by the expanded-ring N-heterocyclic carbene palladium complex (THP-Dipp)Pd(cinn)Cl [THP-Dipp is 1,3-bis(2,6-diisopropylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene; cinn is cinnamyl] can be performed at low catalyst loadings (0.1 mol%) to provide excellent yields and remarkable selectivities for various substrates. [ DOI ]
Чапала П. П., Бермешев М. В., Гаврилова Н. Н. МИКРОПОРИСТАЯ СТРУКТУРА ВЫСОКОПРОНИЦАЕМЫХ АДДИТИВНЫХ КРЕМНИЙСОДЕРЖАЩИХ ПОЛИТРИЦИКЛОНОНЕНОВ // Высокомолекулярные соединения. Серия А . — 2017. — Т. 59. — С. 95–100.
Синтез и газотранспортные параметры полипентафторстирола / Н. А. Белов, Р. Ю. Никифоров, М. В. Бермешев и др. // Мембраны и мембранные технологии . — 2017. — Т. 7, № 5. — С. 305–310. Радикальной полимеризацией пентафторстирола получен полипентафторстирол (ППФС) (Mw = 1.7 × 105 Да, Mw/Mn = 1.6, Тg = 110oС). Структура полученного полимера подтверждена спектрами 1H и 19F-ЯМР. Измерены коэффициенты проницаемости и диффузии газов He, H2, O2, N2, CO2, CH4 на барометрической установке. Показано, что в ряду полимеров полистирол-поли(п-фторстирол)-ППФС с возрастанием доли атомов фтора в мономерном звене полимера возрастают коэффициенты проницаемости, диффузии и растворимости газов и убывают идеальные селективности. Эти закономерности связаны с возрастанием доли свободного объема и убыванием плотности энергии когезии в этом ряду полимеров. По сочетанию селективности проницаемости и коэффициента проницаемости для пар газов N2/CH4, CO2/CH4, O2/N2 и др. полимеры на основе стирола и его производных находятся на диаграммах Робсона в общем облаке точек и не представляют интерес для их разделения. [ DOI ]
Хроматографический метод определения коэффициентов диффузии легких углеводородов в полимерах / Е. Е. Якубенко, А. А. Королев, П. П. Чапала и др. // Журнал физической химии . — 2017. — Т. 91, № 1. — С. 171–177.
A new cycloadduct based on quadricyclane and perfluorocyclohexene: synthesis, metathesis polymerization and gas-transport properties of the obtained polymer / I. L. Borisov, T. R. Akmalov, A. O. Ivanov et al. // Mendeleev Communications . — 2016. — Vol. 26, no. 2. — P. 124–126. A new fluorine-containing tricyclononene was synthesized by [2σ + 2σ + 2π]-cycloaddition of quadricyclane with perfluorocyclohexene. This cycloadduct was subjected to ring-opening metathesis polymerization. Gas-transport properties of the obtained polymer were estimated. [ DOI ]
Additive poly[3-(trimethylsilyl)tricyclononene-7]: Molecular properties and chain rigidity / N. P. Yevlampieva, M. V. Bermeshev, A. S. Gubarev et al. // Polymer Science, Series A . — 2016. — Vol. 58, no. 3. — P. 324–335. [ DOI ]
Kinetics and thermochemistry of [2π + 2σ + 2σ]-cycloaddition of quadricyclane to tetracyanoethylene / V. D. Kiselev, D. A. Kornilov, O. V. Anikin et al. // Russian Journal of Organic Chemistry . — 2016. — Vol. 52, no. 6. — P. 777–780. [ DOI ]
Synthesis and gas-transport properties of metathesis polytricyclononenes bearing three me3si groups per monomer unit / P. Chapala, M. Bermeshev, L. Starannikova et al. // Macromolecular Chemistry and Physics . — 2016. — Vol. 217. — P. 1966–1976. A new metathesis polynorbornene containing three SiMe3 groups per monomer unit directly connected to the norbornene moiety via SiC bonds is synthesized. The ring-opening metathesis polymerization of sterically hindered 3,3,4-tris(trimethylsilyl)tricyclononene-7 is successfully conducted in yields 80–85% in the presence of first generation Grubbs catalyst. The corresponding polymer is obtained with molecular weight Mw up to 5.4 × 105 Da. It is an amorphous glassy (Tg = 200 oC) polymer with high thermal stability. Gas permeability and diffusivity coefficients are studied for a range of gases (He, H2, O2, N2, CO2, CH4). This polymer containing three SiMe3 groups per monomer unit turns out to be more permeable (P(O2) = 125 Barrer) than similar polymers with one or two SiMe3 groups per monomer unit (P(O2) = 30–50 Barrer). Wide angle X-ray diffraction, positron annihilating lifetime spectroscopy, as well as Brunauer–Emmett–Teller investigations are also performed and discussed. [ DOI ]
Synthesis and gas-transport properties of novel copolymers based on tricyclononenes containing one and three me3 si-groups / P. Chapala, M. Bermeshev, L. Starannikova et al. // Macromolecular Chemistry and Physics . — 2016. — Vol. 218, no. 3. — P. 1600385. 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 (R3/R4) based on positron annihilating lifetime spectroscopy analysis and Brunauer–Emmett–Teller surface areaup 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. [ DOI ]
Synthesis of 3,4-dihydroxyphenyl-containing polymeric materials from 1,2-polybutadiene and eugenol via thiol—ene addition / P. P. Chapala, M. V. Bermeshev, S. A. Korchagina et al. // Russian Chemical Bulletin . — 2016. — Vol. 65, no. 4. — P. 1061–1066. [ DOI ]
Synthesis of novel tricyclononenes containing alkoxysilyl groups / D. A. Alentiev, P. P. Chapala, M. P. Filatova et al. // Mendeleev Communications . — 2016. — Vol. 26, no. 6. — P. 530–531. [ DOI ]
АДДИТИВНЫЙ ПОЛИ(3-ТРИМЕТИЛСИЛИЛТРИЦИКЛОНОНЕН-7): МОЛЕКУЛЯРНЫЕ СВОЙСТВА И ЖЕСТКОСТЬ ЦЕПИ / Н. П. Евлампиева, М. В. Бермешев, А. С. Губарев и др. // Высокомолекулярные соединения. Серия А . — 2016. — Т. 58. — С. 233–245.
КИНЕТИКА И ТЕРМОХИМИЯ РЕАКЦИИ [2π+2σ+2σ]-ЦИКЛОПРИСОЕДИНЕНИЯ МЕЖДУ КВАДРИЦИКЛАНОМ И ТЕТРАЦИАНОЭТИЛЕНОМ / В. Д. Киселёв, Д. А. Корнилов, О. В. Аникин и др. // Журнал органической химии . — 2016. — Т. 52. — С. 793–795.
Метатезисный полимер на основе 5-триметилсилилбицикло[2.2.2]окт-2-ена: синтез и газотранспортные свойства / Д. А. Алентьев, М. В. Бермешев, Л. Э. Старанникова и др. // Высокомолекулярные соединения. Серия Б . — 2016. — Т. 58, № 6. — С. 450–456. Синтезирован новый кремнийсодержащий бициклический мономер, 5-триметилсилилбицикло[2.2.2]окт-2-ен, изучена его метатезисная полимеризация и газотранспортные свойства полученного на его основе полимера. Синтез мономера осуществлялся по двустадийной схеме с использованием реакции Дильса–Альдера из циклогексадиена-1,3 и винилтрихлорсилана с последующим метилированием реактивом Гриньяра. Полученный 5-триметилсилилбицикло[2.2.2]окт-2-ен в метатезисной гомополимеризации в присутствии катализатора Граббса первого и второго поколений, а также катализатора Граббса–Ховейды неактивен, однако он медленно полимеризуется при наличии в реакционной смеси норборнена. Высокомолекулярный сополимер (Mw = 3.0 × 10^5, Mw/M = 2.8) на основе 5-триметилсилилбицикло[2.2.2]окт-2-ена и норборнена обладает хорошими пленкообразующими свойствами и имеет температуру стеклования 126oC.Исследованы газотранспортные свойства сополимера. [ DOI ]
СИНТЕЗ 3,4-ДИГИДРОКСИФЕНИЛСОДЕРЖАЩИХ ПОЛИМЕРНЫХ МАТЕРИАЛОВ НА ОСНОВЕ 1,2-ПОЛИБУТАДИЕНА И ЭВГЕНОЛА С ПОМОЩЬЮ РЕАКЦИИ ТИОЛ-ЕН-ПРИСОЕДИНЕНИЯ / П. П. Чапала, М. В. Бермешев, С. А. Корчагина и др. // Известия Академии наук. Серия химическая . — 2016. — С. 1061–1066.
СИНТЕЗ И ГАЗОРАЗДЕЛИТЕЛЬНЫЕ СВОЙСТВА МЕТАТЕЗИСНОГО ПОЛИ(5-ЭТИЛИДЕН-2-НОРБОРНЕНА) / П. П. Чапала, И. Л. Борисов, М. В. Бермешев и др. // Мембраны и мембранные технологии . — 2016. — Т. 6. — С. 406–411. [ DOI ]
A novel, highly gas-permeable polymer representing a new class of silicon-containing polynorbornens as efficient membrane materials / P. P. Chapala, M. V. Bermeshev, L. E. Starannikova et al. // Macromolecules . — 2015. — Vol. 48, no. 22. — P. 8055–8061. The synthesis and gas permeation properties of addition-type poly(3,3-bis(trimethylsilyl)-tricyclononene-7)(PTCNSi2g) are first reported. High molecular weight PTCNSi2g was obtained via addition polymerization of 3,3-bis(trimethyl)tricyclononene-7 on a Pd-containing catalyst. It possessed a BET surface area as high as 790 m2/g. This new polymer is distinguished by exta high gas permeability and solubility controlled permeation of hydrocarbons. Positron annihilation lifetime spectroscopy revealed extremely large size of free volume elements (8.3 A). PTCNSi2g is a promising membrane materialfor separation of natural gas. [ DOI ]
Comparative reactivity of me3si-substituted norbornene derivatives in ring-opening metathesis polymerization / M. L. Gringolts, M. V. Bermeshev, M. V. Moskvicheva et al. // Silicon . — 2015. — Vol. 7. — P. 107–115. Silyl substituted norbornenes and their derivatives are effective monomers in the synthesis of new prospective polymer materials for gas separation membranes by metathesis and addition polymerization. Comparative activity of norbornenes (NB), norbornadienes (NBD) and tricyclononenes (TCN) with different spatial arrangement of one or two Me3Si substituents in ring-opening metathesis polymerization (ROMP) in the presence of Grubbs initiator Cl2(PCy3)2Ru=CHPh were studied by NMR and GC. It was shown that the rate of the initiation was lower than the propagation for all monomers and the highest activity was inherent to the exo-5-trimethylsilylnorbornene (5-NBSi) and 3- trimethylsilyltricyclononene (3-TCNSi). Disubstituted TCN turned out to be more active than NB having the same number and position of the substituents. The latter were more active than the corresponding NBD. It was found that syn- and anti-isomers of 3-TCNSi polymerized with close rates in contrast to exo- and endo-substituted 5-NBSi, for which polymerization rates were substantially different. Special behavior of monomers with bulky substituents in the geminal position was observed: 5,5-NBSi2 was inactive in the presence of the 1st generation Grubbs initiator, whereas it was polymerized in the presence of the 2nd generation one. Quantum-chemical calculations were in agreement with experimental data and evidenced the influence of energy, electronic and structural properties of the norbornene-type monomers studied on their activity in ROMP. [ DOI ]
Detailed study of the gas permeation parameters of a glassy poly(tricyclononene) with si-o-si side groups / N. Belov, Y. Nizhegorpdova, M. Bermeshev, Y. Yampolskii // Journal of Membrane Science . — 2015. — Vol. 483. — P. 136–143. Diffusion (D) andpermeability(P) coefficients ofpoly(3,4-bis(trimethylsiloxy) silyl]tricyclononene-7) (PTSOTN), a metathesis ring opening polymer with Si–O–Si containing side groups,were measured for light gases(He,H2, O2, N2, CO2) and hydrocarbon C1–C4. For the hydrocarbons C2–C4 the measurement was conducted in the pressure range of 0–2 atm.Using a novel technique,sorption isotherms in this polymer were obtained for all the aforementioned penetrants in the range of 0–2.5 atm.It was shown that the slope of the correlation of ln D versus d2 for PTSOTN is intermediate between those characteristic for polymers with solubility controlled selectivity and size sieving glassy polymers.A comparison of the permselectivity α, diffusion selectivity αD and sorption selectivity αS indicated that the solubility controlled permeation in PTSOTN is caused by the reduced diffusivity selectivity of this polymer. [ DOI ]
Experimental and theoretical study of [2σ + 2σ + 2π]–cycloaddition of quadricyclane and ethylenes containing three silyl-groups / M. Bermeshev, P. Chapala, V. Lakhtin et al. // Silicon . — 2015. — Vol. 7, no. 2. — P. 117–126. [ DOI ]
Experimental and theoretical study of [2σ + 2σ + 2π]–cycloaddition of quadricyclane and ethylenes containing three silyl-groups / M. Bermeshev, P. Chapala, V. Lakhtin et al. // Silicon . — 2015. — Vol. 7, no. 2. — P. 117–126. [ DOI ]
Gas separation and pervaporation characteristics of poly(3-trimethylsilyltricyclononene) / I. Borisov, G. Golubev, B. Bulgakov et al. // Int. Conference "Ion transport in organic and inorganic membranes". — Krasnodar, 2015. — P. 97–99.
Gas-transport properties of new mixed matrix membranes based on addition poly(3-trimethylsilyltricyclo-nonene-7) and substituted calixarenes / P. P. Chapala, M. V. Bermeshev, L. E. Starannikova et al. // Journal of Membrane Science . — 2015. — Vol. 474, no. 1. — P. 83–91. Herein we report the results of the preparation and investigation of gas permeation parameters of novel membrane composite materials based on highly permeable addition poly(3-trimethylsilyltricyclono-nene-7) (PTCNSi1) and different substituted calixarenes(CA). Calix[4]areneandcalix[8]arene with substituents R1 (R1¼Me, Et,SiMe3) in the lower rim and R2 (R2¼tert-Bu, H)in the upper rim were used as the additives.We explored the correlations between the structure of fillers(calixarenes)and gas permeation parameters of the composites.It is shown that the introduction of calixarenes results in increases in the separation factors, though a decrease in the observed permeability coefficients is observed.Thus,the addition of calix[4]arenewithR1¼Et and R2¼tert-Bu increases the separation factors for H2/N2 gas pair more than twice,from 5.2 to 11.4,while the permeability coefficient P(H2) decreases from 2060 to 1000 Barrer.The increase of calixarene content tends to further enhance the separation factors. The application of positron annihilation lifetime spectroscopy indicated that these changes can be explained by certain reduction of mean size of free volume elements in the compositions containing calixarenes.The data of BET, TEM, WAXD,and mechanical properties of the composites are also reported and discussed. [ DOI ]
Gas-transport properties of new mixed matrix membranes based on addition poly(3-trimethylsilyltricyclononene-7) and substituted calixarenes / P. P. Chapala, M. V. Bermeshev, L. E. Starannikova et al. // Journal of Membrane Science . — 2015. — Vol. 474. — P. 83–91. Herein we report the results of the preparation and investigation of gas permeation parameters of novel membrane composite materials based on highly permeable addition poly(3-trimethylsilyltricyclononene-7) (PTCNSi1) and different substituted calixarenes (CA). Calix[4]arene and calix[8]arene with substituents R1 (R1 = Me, Et, SiMe3) in the lower rim and R2 (R2 = tert-Bu, H) in the upper rim were used as the additives. We explored the correlations between the structure of fillers (calixarenes) and gas permeation parameters of the composites. It is shown that the introduction of calixarenes results in increases in the separation factors, though a decrease in the observed permeability coefficients is observed. Thus, the addition of calix[4]arene with R1 = Et and R2 = tert-Bu increases the separation factors for H2/N2 gas pair more than twice, from 5.2 to 11.4, while the permeability coefficient P(H2) decreases from 2060 to 1000 Barrer. The increase of calixarene content tends to further enhance the separation factors. The application of positron annihilation life time spectroscopy indicated that these changes can be explained by certain reduction of mean size of free volume elements in the compositions containing calixarenes. The data of BET, TEM, WAXD, and mechanical properties of the composites are also reported and discussed. [ DOI ]
Gas-transport properties of novel composites based on addition poly(3-trimethylsilyltricyclononene-7) and substituted cyclodextrines / P. P. Chapala, M. V. Bermeshev, L. E. Starannikova et al. // Polymer Composites . — 2015. — Vol. 36, no. 6. — P. 1029–1038. In this work we report the preparation and properties of composite materials for gas separatuion membranes based on highly permeable addition poly(3-trimethylsilyltricyclononene-7) (PTCNSi1) as a matrix and substituted cyclodextrines (CD) as fillers. CD studied had different structure and this allowed as to explore correlations between the structure of the fillers and gas permeation parameters of the resulting compositions. Namely alpha-,beta - and gamma-cyclodextrines with Me- or Me3Si-substituents were synthesired and the composites containing them were prepared. Permeability coefficients of the obtained composites were determined for He, H2, O2, N2, CO2, CH4. It was found that the introduction of cyclodextrines with bulky Me3Si-groups rather weakly influenced the permeability coefficients for Heand H2, while for other gases a marked decrease in permeability was observed. On the other hand, in the case of the composites containing Me-substituted CD decreases in permeability were observed for all the studied gases.Thechanges of gas permeability dramatically depend on the size of gas molecules and this results in an icrease in selectivities for some gas pairs. Thus, introduction of alpha-CD with Me-groups resulted in increase in selectivity H2/N2 from 5.2 for pure polymer to 9.1. The increase in CD content in a composite gave an extra growth of selectivities. BET, TEM, WAXD, positron annihilation data (free volume) and mechanical properties of the composites also studied and discussed. [ DOI ]
Mobility of the spin probe tempo in glassy metathesis polymers with substituents containing flexible si–o–si groups / I. I. Barashkova, M. V. Bermeshev, A. M. Wasserman, Y. P. Yampolskii // Polymer Science, Series A . — 2015. — Vol. 57, no. 3. — P. 279–284. Glassy metathesis polymers (glass transition temperatures of 110–236oC) containing substituents with flexible Si–O–Si groups are studied by the spinprobe method with the use of the stable nitroxyl radical TEMPO. A high mobility of the spin probe not correlating with the free volume of polymers is reported. These results and the earlier discovered thermodynamic selectivity of the indicated polymers (high permeability coefficients of higher hydrocarbons) make it possible to infer that Si–O–Si groups are responsible for the observed behavior similarly to that in siloxane rubbers. [ DOI ]
Study of glassy polymers fractional accessible volume (fav) by extended method of hydrostatic weighing: Effect of porous structure on liquid transport / A. Yushkin, A. Grekhov, S. Matson et al. // Reactive and Functional Polymers . — 2015. — Vol. 86. — P. 269–281. [ DOI ]
Synthesis and gas permeation parameters of metathesis polytricyclononenes with pendant me3e-groups (e=c, si, ge) / M. Bermeshev, B. Bulgakov, L. Starannikova et al. // Journal of Applied Polymer Science . — 2015. — Vol. 132, no. 5. — P. 41395–42002.
Synthesis and gas permeation parameters of metathesis polytricyclononenes with pendant me3e-groups (e = c, si, ge) / B. Maxim, B. Boris, S. Lyudmila et al. // Journal of Applied Polymer Science . — 2015. — Vol. 132, no. 5. — P. 41395–42002. 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. [ DOI ]
Synthesis and gas-separation properties of metathesis poly(3-fluoro-3-pentafluoroethyl-4,4-bis(trifluoromethyl)tricyclonene-7) / M. V. Bermeshev, L. E. Starannikova, S. R. Sterlin et al. // Petroleum Chemistry . — 2015. — Vol. 55, no. 9. — P. 753–758. Metathesis polymerization of 3-fluoro-3-pentafluoroethyl-4,4-bis(trifluorometyl)tricyclononene-7 was performed and the properties of the obtained polymer F-PTCN wereinvestigated. It wasfound that F-PTCN possessed high thermal stability. The gas permeability of F-PTCN (P(O2) = 60 Barrer, P(CO2) = 240 Barrer was close to the parameters of earlier studied two fluorocontaining polynorbornenes. Although a new synthesided metathesis fluorosubstituted polymer was less permeable than a metathesis polytricyclononene containing two Me3Si-groups per a monomer unit, but it had substantially higher values of ideal selectivities for some pairs of gases. [ DOI ]
[2σ + 2σ + 2π]-cycloaddition of quadricyclane to partially methylated chlorosilylalkenes / P. P. Chapala, M. V. Bermeshev, V. G. Lakhtin et al. // Mendeleev Communications . — 2015. — Vol. 25, no. 5. — P. 344–345. [ DOI ]
Подвижность спинового зонда ТЕМПО в стеклообразных метатезисных полимерах с заместителями, содержащими гибкие группы si–o–si / И. И. Барашкова, М. В. Бермешев, А. М. Вассерман, Ю. П. Ямпольский // Высокомолекулярные соединения. Серия А . — 2015. — Т. 57, № 3. — С. 224–229. Методом спинового зонда с использованием стабильного нитроксильного радикала ТЕМПО изучены стеклообразные метатезисные полимеры (температура стеклования 110–236oC), содержащие заместители с гибкими группами Si–O–Si. Отмечена большая подвижность спинового зонда, не коррелирующая со свободным объемом полимеров. Эти результаты, а также обнаруженная ранее термодинамическая селективность указанных полимеров (бóльшие коэффициенты проницаемости высших углеводородов) позволяют сделать следующий вывод: за наблюдаемое поведение ответственно присутствие групп Si–O–Si, аналогично тому, как это имеет место в силоксановых каучуках. [ DOI ]
Синтез и газоразделительные свойства метатезисного поли(3-фтор-3-пентафторэтил-4,4-бис(трифторметил)трициклононена-7 / М. В. Бермешев, Л. Э. Старанникова, С. Р. Стерлин и др. // Мембраны и мембранные технологии . — 2015. — Т. 5, № 3. — С. 234–240. Изучена полимеризация по метатезисной схеме 3-фтор-3-пентафторэтил-4,4-бис(трифторметил)-трициклононена-7 и исследованы свойства полученного полимера (F-PTCN), в частности, газопроницаемость. Найдено, что F-PTCN обладает высокой термической стабильностью. Его газоразделительные параметры (P(O2) = 60 Баррер, P(CO2) = 240 Баррер) близки к параметрам ранее изученных фторсодержащих полинорборненов. Новый синтезированный метатезисный фторсодержащий политрициклононен уступает по газопроницаемости метатезисному политрициклононену с двумя Me3Si-группами в мономерном звене, но заметно превосходит его по селективности газоразделения для ряда пар газов. [ DOI ]
Cationic polymerization of norbornene derivatives in the presence of boranes / M. V. Bermeshev, B. A. Bulgakov, A. M. Genaev et al. // Macromolecules . — 2014. — Vol. 47, no. 16. — P. 5470–5483. Cationic polymerization of 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, and norbornadiene-2,5 in the presence of boranes was systematically studied. It was found that B(C6F5)3 in combination with caprylic acid, 1-phenylethanol or water was a highly active catalyst for the polymerization of 5-alkylidene-2-norbornenes. The corresponding cationic polymers were obtained with up to yields 95% and with high molecular weights (Mw ≤ 430 000). The activity of 5-alkylidene-2-norbornenes in the polymerization using B(C6F5)3 containing systems was the highest among the other monomers (5-vinyl-2-nobornene, dicyclopentadiene, and norbornadiene-2,5). BF3·O(C2H5)2 based catalysts turned out to be not so active for cationic polymerization of monomers compared with the systems containing B(C6F5)3. They produced polymers predominantly containing the addition (vinyl) units instead of isomerization units. The structure of the polymer main chain units depended on the nature of the monomers: in the case of norbornadiene-2,5, 5-methylene-2-norbornene, and 5-ethylidene-2-norbornene the transannular polymerization proceeded, while dicyclopentadiene and 5-vinyl-2-norbornene formed the addition type polymers under the studied conditions. [ DOI ]
Regeneration of alkanolamine solutions in membrane contactor based on novel polynorbornene / A. A. Shutova, A. N. Trusov, M. V. Bermeshev et al. // Oil and Gas Science and Technology . — 2014. — Vol. 69. — P. 1059–1068.
Solubility controlled permeation of hydrocarbons: new membrane materials and results / Y. Yampolskii, L. Starannikova, N. Belov et al. // Journal of Membrane Science . — 2014. — Vol. 453, no. 3. — P. 532–545. Polymers of different classes are considered as membrane materials for separation of hydrocarbons C1–C4. It has been known for a long time that solubility controlled permeation is characteristic of rubbery polymers and in particular of the most permeable rubber polydimethylsiloxane.The transport properties of these polymers are considered. Discovery of poly(trimethylsilylpropyne)and other polyacetylenes showed that similar properties can be revealed in glassy polymers.As is discussed in this review,the most important properties are reduction of the permeability of light components(CH4) in the presence of more condensable penetrant(C4H10) and higher selectivity of mixture separation ascompared with ideal separation factors measured in the experiments with pure gases.Recently,two other classes of glassy polymers with solubility controlled permeation were discovered:addition type Si-containingnorbornene polymers and metathesis polynorbornenes with flexible Si–O bonds inside groups.The transport properties of these novel polymers are considered in detail.It was shown that for the former group of norbornene polymers the reasons for solubility controlled permeation is great and opened porosity just as is the case for polyacetylenes.For the latter group,the presence of flexible Si–O bonds inside groups is responsible for their transport properties. [ DOI ]
Glassy polynorbornenes with si-o-si containing side groups. novel materials for hydrocarbon membrane separation / M. V. Bermeshev, A. V. Syromolotov, L. E. Starannikova et al. // Macromolecules . — 2013. — Vol. 46. — P. 8973–8979. Polymers of a new class of glassy materials thatdemonstrate unusual solubility controlled permeability-metathesis Si−O−Si containing polynorbornenes-are synthesized. The introduction of bulky Si(OSiMe3)3 substituents into the polynorbornene backbone is shown to provide the polymers with increased gas permeability, higher than all other known metathesis polynorbornenes. The prepared glassy polymers reveal behavior similar to that known for rubbers and, in particular, siloxanes: permeability coefficients increase for the penetrants of larger size. That is, these polymers are capable to remove higher hydrocarbons from natural and associated petroleum gases. [ DOI ]
Glassy polynorbornenes with si-o-si containing side groups – novel materials for hydrocarbon membrane separation / M. V. Bermeshev, A. V. Syromolotov, L. E. Starannikova et al. // Macromolecules . — 2013. — Vol. 46. — P. 8973–8979. Polymers of a new class of glassy materials that demonstrate unusual solubility controlled permeability metathesis Si−O−Si containing polynorbornenes are synthesized. The introduction of bulky Si(OSiMe3)3 substituents into the polynorbornene backbone is shown to provide the polymers with increased gas permeability, higher than all other known metathesis polynorbornenes. The prepared glassy polymers reveal behavior similar to that known for rubbers and, in particular, siloxanes: permeability coefficients increase for the penetrants of larger size. That is, these polymers are capable to remove higher hydrocarbons from natural and associated petroleum gases. [ DOI ]
Membrane separation of multicomponent mixture of alkanes c1-c4 / Y. V. Grinevich, L. E. Starannikova, Y. P. Yampolskii, M. V. Bermeshev // Polymer Science, Series A . — 2013. — Vol. 55, no. 1. — P. 43–47. The membrane separation of the four-component mixture of gaseous alkanes C1-C4 is studied. Homogeneous films based on two high-permeable polymers, namely, addition-type poly[3- (trimethylsilyl)tricyclononene-7] and poly[3,4-bis(trimethylsilyl)tricyclononene-7], are used as membranes. Separation of the multicomponent mixture of hydrocarbons on these polymers follows the same trends as separation of binary mixtures CH4-C4H10 on polyacetylenes. In the presence of higher hydrocarbons, the permeability coefficients of methane decrease and the permeates become enriched with higher hydrocarbons. During separation of the multicomponent mixture, permeability coefficients P(C4H10) attein high values (up to 12000 Barrers). [ DOI ]
Metathesis and addition polymerization of novel m33si- and me3ge-substituted tricyclononene / M. Bermeshev, B. Bulgakov, D. Demchuk et al. // Polymer Journal . — 2013. — Vol. 45, no. 7. — P. 718–726. Addition and ring-opening metathesis polymerizations of new monomers (Me3Si- and Me3Ge-substituted tricyclononene and tricyclononadienes) were carried out on Pd- or Ni-catalyst systems and Grubbs first-generation catalyst, respectively. New addition polymers were obtained with good yields up to 70% and molecular weight (Mw) up to 5.6 × 105. The yields of the first obtained metathesis polymers were higher than 80% and Mw were up to 8.8 × 105. It was shown that the novel addition polymer poly[(3-trimethylgermyl)tricyclononene-7] possesses high gas-transport parameters and solubility-controlled permeation of gaseous hydrocarbons. [ DOI ]
Metathesis and addition polymerization of novel me3si- and me3ge-substituted tricyclononenes / M. Bermeshev, B. Bulgakov, D. Demchuk et al. // Polymer Journal . — 2013. — Vol. 45, no. 7. — P. 718–726. Addn. and ring-opening metathesis polymns. of new monomers (Me3Si- and Me3Ge-substituted tricyclononene and tricyclononadienes) were studied. Addn. polymn. was carried out on Pd- and Ni-catalyst systems activated by B(C6F5)3 and/or methylalumoxane. New addn. polymers were obtained with good yields up to 70% and with mol. wts. (Mw) up to 5.6 × 105. Metathesis polymn. was performed using the first-generation Grubbs catalyst. The yields of the first obtained metathesis polymers were higher than 80%, and the Mw values were up to 8.8 × 105. It was revealed that the cyclobutene double bond in the studied tricyclononadienes is inactive in both metathesis and addn. polymns. The relative activities of the substituted tricyclononene-7 and the corresponding tricyclononadiene-3,7 in the metathesis copolymn. were defined using 1H NMR spectroscopy. It was found that the novel addn. polymer poly[(3-trimethylgermyl)tricyclononene-7] possesses high gas-transport parameters (for example, P(O2)=660 Barrers, P(CO2)=3850 Barrers) and soly.-controlled permeation of gaseous hydrocarbons (α(n-C4H10/CH4)=17.3). [ DOI ]
Мембранное разделение многокомпонентной смеси алканов С1-С4 / Ю. Гриневич, Л. Старанникова, Ю. Ямпольский, М. Бермешев // Высокомолек. соед. А . — 2013. — Т. 55, № 1. — С. 47–52. Исследовано мембранное разделение четырехкомпонентной смеси газообразных алканов С1–С4. В качестве мембран использованы гомогенные пленки двух высокопроницаемых полимеров: адди- тивных поли[3(триметилсилил)трициклононена-7] и поли[3,4-бис(триметилсилил)трициклоно- нена-7]. Показано, что закономерности разделения многокомпонентной смеси углеводородов на этих полимерах такие же, как и при разделении бинарных смесей СН4–С4Н10 на полиацетиленах. В присутствии высших углеводородов коэффициенты проницаемости метана понижаются, а пермеат оказывается обогащенным более тяжелыми углеводородами. При разделении многокомпонентной смеси коэффициенты проницаемости Р(С4Н10) достигают высоких значений (до 12000 Баррер).
Copolymerization of 5-(trimethylsilyl)norbornene and 5-ethylidene-2-norbornene authors authors and affiliations / B. A. Bulgakov, M. V. Bermeshev, M. L. Gringol’ts et al. // Petroleum Chemistry . — 2012. — Vol. 52, no. 2. — P. 119–122. [ DOI ]
Copolymerization of trimethylsilylnorbornene and 5-ethylene-2-norbornene / B. A. Bulgakov, M. V. Bermeshev, M. L. Gringol’ts et al. // Petroleum Chemistry . — 2012. — Vol. 52, no. 2. — P. 119–122.
Si- and ge-substituted polytricyclononenes as new highly permeable polymer materials / M. V. Bermeshev, B. A. Bulgakov, L. E. Starannikova et al. // Procedia Engineering . — 2012. — Vol. 44. — P. 171–172. [ DOI ]
Synthesis of tricyclononenes and tricyclononadienes containing mx3-groups (m = c, si, ge; x = cl, me) / B. A. Bulgakov, M. V. Bermeshev, D. V. Demchuk et al. // Tetrahedron . — 2012. — Vol. 68. — P. 2166–2171. New organoelement-substituted (Si-, Ge-) tricyclononenes and tricyclononadienes were obtained via the [2σ+2σ+2π]-cycloaddn. reaction of the corresponding substituted ethylenes and acetylenes with quadricyclane. The chem. behavior of Si-, Ge-, Sn-contg. olefins and acetylenes under the cycloaddn. conditions was studied. The mol. structures of trimethylsilyl(tosyl)tricyclononadiene and tert-butyltricyclononene were detd. by x-ray crystallog. [ DOI ]
ДВОЙНЫЕ ДВОЙНЫЕ И ТРОЙНЫЕ СОПОЛИМЕРЫ НОРБОРНЕНА И ЕГО ПРОИЗВОДНЫХ С АКРИЛАТАМИ - НОВЫЕ МАТЕРИАЛЫ ДЛЯ ОПТОЭЛЕКТРОНИКИ / В. И. Быков, К. Л. Маковецкий, Д. С. Попов и др. // Высокомолекулярные соединения. Серия А . — 2012. — Т. 54, № 2. — С. 341–345.
Substituted polynorbornenes as promising materials for gas separation membranes / E. S. FINKELSHTEIN, M. V. BERMESHEV, M. L. GRINGOLTS et al. // Russian Chemical Reviews . — 2011. — Vol. 80, no. 4. — P. 341–361. Published results concerning the synthesis and study of the transport characteristics of polynorbornenes are considered and analyzed. Conclusiions are drawn regarding the effect of the backbone rigidity and the nature of side groups on the gas permeability level. The prospects of using addition organosilicon polynorbornenes as gas separating membrane materials are discussed. The bibliography includes 88 references. [ DOI ]
Synthesis of high molecular weight poly[3-{tris(trimethylsiloxy)silyl} tricyclononenes-7] and their gas permeation properties / M. V. Bermeshev, A. V. Syromolotov, M. L. Gringolts et al. // Macromolecules . — 2011. — Vol. 44. — P. 6637–6640. A study was conducted to demonstrate the synthesis of high molecular weight polynorbornenes of poly[3-{tris(trimethylsiloxy)silyl}tricyclononenes-7] containing three pendant Me 3Si-O groups and investigate their gas permeation properties. The aim of the synthetic strategy was in shift of hindered Me 3Si groups from the double bond. This strategy allowed the synthesis of a novel 3-{tris(trimethylsiloxy)silyl}tricyclo[4.2.1.0] non-7-ene (III) on the basis of thermal condensation of vinyltrichlorosilane with quadricyclane. The monomer III was successfully polymerized by ring-opening metathesis polymerization (ROMP) mechanism in the presence of first generation Grubbs catalyst. The assumption of reactivation of norbornene double bond by the removal of bulky -Si(OSiMe 3) 3 groups was also confirmed by successful addition polymerization of III in the presence of Pd-containing catalyst systems. [ DOI ]
Synthesis of silicon-substituted tricyclononenes / M. V. Bermeshev, A. V. Syromolotov, M. L. Gringolts et al. // Tetrahedron Letters . — 2011. — Vol. 52. — P. 6091–6093. A new series of tricyclononene derivatives with two and three silyl groups are successfully synthesized via [2σ+2σ+2π]-cycloaddition of silylethylenes to quadricyclane. The activity of the silylethylenes in the cycloaddition reactions was estimated. [ DOI ]
Замещенные полинорборнены - перспективные материалы для газоразделительных мембран / Е. Ш. Финкельштейн, М. В. Бермешев, М. Л. Грингольц и др. // Успехи химии . — 2011. — Т. 80, № 4. — С. 362–383. Рассмотрены и проанализированы результаты работ по синтезу и изучению транспортных характеристик полинорборненов. Сделаны выводы о влиянии жесткости основной цепи и природы боковых групп на уровень газопроницаемости, а также о перспективности использования аддитивных кремнийсодержащих полинорборненов в качестве газоразделительных мембранных материалов. Библиография - 88 ссылок.
ПОЛИМЕРИЗАЦИЯ НОРБОРНЕНОВ - ПУТЬ К СОЗДАНИЮ НОВЫХ ГАЗОРАЗДЕЛИТЕЛЬНЫХ МЕМБРАННЫХ МАТЕРИАЛОВ / Е. Ш. Финкельштейн, М. В. Бермешев, М. Л. Грингольц и др. // Успехи химии . — 2011. — Т. 80, № 4. — С. 362–383. Рассмотрены и проанализированы результаты работ по синтезу и изучению транспортных характеристик полинорборненов. Сделаны выводы о влиянии жесткости основной цепи и характера боковых групп на уровень газопроницаемости, а также о перспективности использования аддитивных кремнийсодержащих полинорборненов в качестве газоразделительных мембранных материалов. Библиография – 88 ссылок.
СИНТЕЗ И ПОЛИМЕРИЗАЦИЯ 3-ТРИС(ТРИМЕТИЛСИЛОКСИ)СИЛИЛТРИЦИКЛОНОНЕНА-7 / А. В. Сыромолотов, М. В. Бермешев, М. Л. Грингольц и др. // Доклады Академии наук . — 2011. — Т. 437, № 1. — С. 53–55. Найден подход к синтезу новых высокомолекулярных кремнийсодержащих полимеров – аддитивных и метатезисных политрициклононенов, содержащих три Me3Siгруппы в мономерном звене. Полученные полимеры являются перспективными материалами для изучения их газоразделительных характеристик.
New high permeable addition poly(tricyclononenes) with si(ch3)3 side groups. synthesis, gas permeation parameters, and free volume / M. Gringolts, M. Bermeshev, Y. Yampolskii et al. // Macromolecules . — 2010. — Vol. 43. — P. 7165–7172. Addition polymerization of two tricyclononene monomers bearing one and two Si(CH3)3 groups was performed in the presence of Pd-containing catalysts. The polymers were obtained with high yields and were completely saturated. Good mechanical and film forming properties are observed for the polymers prepared in the presence of Pd(OAc)2/B(C6F5)3 catalyst. Their glass transition temperature was not observed until the onset of thermal decomposition (>370 C) and the molecular weights are high (Mw up to 7 х 1000000). Study of gas permeation parameters of the obtained poly[3-(trimethylsilyl)tricyclononene-7] and poly[3,4- bis(trimethylsilyl)tricyclononene-7] showed that both glassy polymers revealed substantially high gas permeability. Other transport characteristics (increase in permeability in the series C1-C4 alkanes and negative activation energies of permeation) indicate that these polymers reveal so-called solubility controlled permeation, which is typical for some extra-high permeability polymers. Positron annihilation lifetime spectroscopy indicated that both polymers are characterized by very large sizes of free volume elements. [ DOI ]
ВЫСОКОПРОНИЦАЕМЫЕ ПОЛИМЕРНЫЕ МАТЕРИАЛЫ НА БАЗЕ КРЕМНИЙЗАМЕЩЕННЫХ НОРБОРНЕНОВ / М. Л. Грингольц, М. В. Бермешев, А. В. Сыромолотов и др. // Нефтехимия . — 2010. — Т. 50, № 5. — С. 363–371. Разработан подход к направленному синтезу высокопроницаемых полимеров на базе кремнийзамещенных норборненов, основанный на синтезе и полимеризации норборненов, норборнадиенов и трициклононенов с различным числом и местоположением кремнийсодержащих заместителей. Показано, что мономеры легко вовлекаются в метатезисную полимеризацию с образованием высокомолекулярных полимеров с хорошими пленкообразующими свойствами. Это позволяет получать полимеры с закономерно изменяемой структурой и выявлять корреляции типа структура полимера − свойства. Аддитивная (винильная) полимеризация норборненов - более сложный процесс, однако получаемые кремнийзамещенные полинорборнены демонстрируют более высокую газопроницаемость, чем соответствующие метатезисные полинорборнены. По уровню проницаемости аддитивные полинорборнены можно отнести к классу высокопроницаемых полимеров. Показано, что Me3Si-заместители, их количество, а также структура основной цепи ответственны за увеличение газопроницаемости полинорборненов.
Catalytic transformations of mono- and bis-silyl substituted norbornadienes / M. L. Gringolts, M. V. Bermeshev, Y. V. Nelyubina, E. S. Finkelshtein // Petroleum Chemistry . — 2009. — Vol. 49, no. 5. — P. 369–376. [ DOI ]
Effect of substituents on addition polymerization of norbornene derivatives with two me3si-groups using ni(ii)/mao catalyst / M. L. Gringolts, M. V. Bermeshev, K. L. Makovetsky, E. S. Finkelshtein // European Polymer Journal . — 2009. — Vol. 45. — P. 2142–2149. Addition polymerization and copolymerization of bis(Me3Si)-substituted norbornene-type monomers such as 5,5-bis(trimethylsilyl)norbornene-2, 2,3-bis(trimethylsilyl)norbornadiene- 2,5 and 3,4-bis(trimethylsilyl)tricyclo[4.2.1.02,5]nonene-7, in the presence of Ni(II) naphtenate/MAO catalyst were studied. Disubstituted norbornene and norbornadiene were found to be practically inactive in homopolymerization. On the other hand, their copolymerization with norbornene proceeded withmoderate yields of copolymers containing predominantly norbornene units. Under studied reaction conditions 2,3-bis(trimethylsilyl) norbornadiene-2,5 was transformed into the only exo-trans-exo-dimer as a result of the [2+2]-cyclodimerization reaction. Moving Me3Si-substituents one carbon atom away from norbornene double bond made 3,4-bis(trimethylsilyl)tricyclo[4.2.1.02,5]nonene-7 active in homopolymerization and allowed to obtain addition homo-polymer with twoMe3Si-substituents in each elementary unit. The reaction mechanism and steric effect of Me3Si-substituents are also discussed. [ DOI ]
New quadricyclane-based cyclic polycarbosilanes / M. L. Gringolts, M. V. Bermeshev, E. S. Finkelshtein, A. G. Kaz'min // Doklady Chemistry . — 2009. — Vol. 424. — P. 49–51. A new reaction for the chemistry of organosilicon compounds, namely, the condensation of quadricyclane with alkenylsilanes was discovered. This approach makes it possible to synthesize new polycarbosilanes— addition and metathesis polytricyclononenes containing more than one Me3Si group in the monomeric unit. [ DOI ]
New membrane materials via catalytic polymerization of bis(trimethylsilyl)-substituted norbornene type monomers / M. Bermeshev, M. Gringolts, L. Starannikova et al. // New Smart Materials via Metal Mediated Macromolecular Engineering. Ed. by E. Khsravi et al. — Springer Science+Business Media B.V Amsterdam, Netherlands, 2009. — P. 319–326.
Synthesis and gas separation properties of metathesis polynorbornenes with different positions of one or two sime3 groups in a monomer unit / M. L. Gringolts, M. V. Bermeshev, L. E. Starannikova et al. // Polymer Science, Series A . — 2009. — Vol. 51, no. 11-12. — P. 1233–1240. The metathesis polymerization of 5,5-bis(trimethylsilyl)norbornene, 2,3-bis(trimethylsilyl)norbornadiene, and exo,endo-3,4-bis(trimethylsilyl)tricyclo[4.2.1.02,5]non-7-ene with the catalysts WCl6/1,1,3,3-tetramethyl-1,3-disilacyclobutane, RuCl3/EtOH, and the Grubbs Ru–carbene complex Cl2(PCy3)2Ru=CHPh has been studied. New polymers with yields of up to 98% and Mw = (2–39) × 100000 are prepared. New metathesis copolymers of 5trimethylsilylnorbonene with 5-(hydroxymethyl)norbornene and 5-(trimethylsiloxymethyl)norbornene are synthesized in the presence of the Cl2(PCy3)2Ru=CHPh catalyst with yields of 78 and 98%. The gas-permeability study of the above series of the metathesis polymers containing one or two Me3Si substituents in each monomer unit shows that the introduction of the second SiMe3 group markedly improves their transport characteristics. A change in the character of the backbone (polynorbornadiene, polytricyclononene) has a small effect on the permeability of the polymers. The metathesis polynorbornene with two vicinal SiMe3 groups exhibits higher gas-permeability coefficients than its isomer with germinal substituents. The homopolymer of 5-trimethylsilylnorbornene is characterized by better transport parameters than its copolymers with –OSiMe3 and –OH substituents. [ DOI ]
КАТАЛИТИЧЕСКИЕ ПРЕВРАЩЕНИЯ МОНО- И БИС-КРЕМНИЙЗАМЕЩЕННЫХ НОРБОРНАДИЕНОВ / М. Л. Грингольц, М. В. Бермешев, Ю. В. Нелюбина, Е. Ш. Финкельштейн // Нефтехимия . — 2009. — Т. 49, № 5. — С. 389–396. Изучены превращения 2-триметилсилилнорборнадиена-2,5 (СНБД) и 2,3-бис(триметилсилил)норборнадиена-2,5 (ДСНБД) в условиях метатезисной и аддитивной полимеризации. При использовании катализаторов WCl6/1,1,3,3-тетраметилдисилациклобутан-1,3 и Cl2(PCy3)2Ru=CHPh с выходами до 98% получены высокомолекулярные кремнийзамещенные полициклопентилиденвинилены. В условиях аддитивной полимеризации на катализаторе нафтенат никеля (II)- МАО СНБД и ДСНБД димеризуются с образованием пентациклических димеров. При этом в случае СНБД зафиксированы три димера, а в случае ДСНБД образуется исключительно экзо-транс-экзо-циклодимер. Будучи неактивными в аддитивной гомополимеризации, СНБД и ДСНБД участвуют в аддитивной сополимеризации с норборненом.
НОВЫЕ ЦИКЛИЧЕСКИЕ ПОЛИКАРБОСИЛАНЫ НА ОСНОВЕ КВАДРИЦИКЛАНА / М. Л. Грингольц, М. В. Бермешев, А. Г. Казьмин, Е. Ш. Финкельштейн // Доклады Академии наук . — 2009. — Т. 424. — С. 774–776. Обнаружена новая для химии кремнийорганических соединений реакция конденсации квадрициклана с алкенилсиланами. В результате, нами найден подход и показана возможность синтеза новых поликарбосиланов – аддитивных и метатезисных политрициклононенов, содержащих более одной Me3Si-группы в мономерном звене.
Синтез и газоразделительные свойства метатезисных полинорборненов с различным положением одной и двух групп sime3 в мономерном звене / М. Л. Грингольц, М. В. Бермешев, Л. Э. Старанникова и др. // Высокмолек. соед., сер. А . — 2009. — Т. 51, № 11. — С. 1970–1977. Изучена метатезисная полимеризация 5,5-бис-(триметилсилил)норборнена, 2,3-бис-(триметилси- лил)норборнадиена и экзо,эндо-3,4-бис-(триметилсилил)трицикло[4.2.1.02,5]нон-7-ена на катали- заторах WCl6/1,1,3,3-тетраметил-1,3-дисилациклобутан, RuCl3/EtOH и Ru-карбеновом комплексе Граббса Cl2(PCy3)2Ru=CHPh. Получены новые полимеры с выходом до 98% и Мw = (2–39) × 100000. Синтезированы новые метатезисные сополимеры 5-триметилсилилнорборнена с 5-(гидроксиме- тил)норборненом и 5-(триметилсилоксиметил)норборненом на катализаторе Cl2(PCy3)2Ru=CHPh с выходом 78 и 98%. Исследование газопроницаемости полученного ряда метатезисных полимеров, содержащих один и два Me3Si-заместителя в каждом мономерном звене, показало, что введение второй группы SiMe3 существенно улучшает их транспортные свойства. Изменение характера ос- новной цепи (полинорборнадиен, политрициклононен) мало влияет на проницаемость полимеров. Метатезисный полинорборнен с двумя вицинальными группами SiMe3 обладает более высокими коэффициентами газопроницаемости, чем его изомер с геминальными заместителями. Гомополи- мер 5-триметилсилилнорборнена характеризуется лучшими транспортными свойствами, чем его сополимеры, содержащие заместители –OSiMe3 и –ОН.
Titanium complexes based on chiral enantiopure dialkanolamines: synthesis, structures and catalytic activity / K. V. Zaitsev, M. V. Bermeshev, A. A. Samsonov et al. // New Journal of Chemistry . — 2008. — Vol. 32, no. 8. — P. 1415–1431. New chiral enantiopure tridentate ligands (dialkanolamines) RN(CHR(3)CR(1)R(2)OH)(CHR(4)CR(5)R(6)OH) 10-17 were synthesized by the opening of the epoxide ring by the action of the amines or alkanolamines. Titanium complexes, viz. [RN(CHR(3)CR(1)R(2)O)(CHR(4)CR(5)R(6)O)]Ti(O-i-Pr)(2) 18-23 and [RN(CHR(3)CR(1)R(2)O)(CHR(4)CR(1)R(6)O)](2)Ti 25-31 were synthesized by treatment of Ti(O-i-Pr)(4) With one or two equivalents of corresponding dialkanolamines. Complex (R)-PhCH(Me)N(CH(2)C(Me)(2)O)(2)TiCl(2)*HNMe(2) 24 was obtained from the reaction of One equivalent of dialkanolamine 10 with (Me(2)N)(2)TiCl(2). The composition and Structure of all novel compounds were established by (1)H and (13)C NMR spectroscopy as well as elemental analysis. The possible Solution structures of 18-31 are discussed. The single-crystal X-ray diffraction study of 23, 25-28, 30 31 indicates monomeric Structures ill the solid state. Chiral complexes 20, 22, 23 25, 26, 30 were tested as chiral catalysts in the Abramov reaction and demonstrated moderate enantiomeric activity. [ DOI ]
Titanium complexes based on chiral enantiopure dialkanolamines: synthesis, structures and catalytic activity / K. V. Zaitsev, M. V. Bermeshev, A. A. Samsonov et al. // New Journal of Chemistry . — 2008. — Vol. 32, no. 8. — P. 1415–1431. New chiral enantiopure tridentate ligands (dialkanolamines) RN(CHR(3)CR(1)R(2)OH)(CHR(4)CR(5)R(6)OH) 10-17 were synthesized by the opening of the epoxide ring by the action of the amines or alkanolamines. Titanium complexes, viz. [RN(CHR(3)CR(1)R(2)O)(CHR(4)CR(5)R(6)O)]Ti(O-i-Pr)(2) 18-23 and [RN(CHR(3)CR(1)R(2)O)(CHR(4)CR(1)R(6)O)](2)Ti 25-31 were synthesized by treatment of Ti(O-i-Pr)(4) With one or two equivalents of corresponding dialkanolamines. Complex (R)-PhCH(Me)N(CH(2)C(Me)(2)O)(2)TiCl(2)*HNMe(2) 24 was obtained from the reaction of One equivalent of dialkanolamine 10 with (Me(2)N)(2)TiCl(2). The composition and Structure of all novel compounds were established by (1)H and (13)C NMR spectroscopy as well as elemental analysis. The possible Solution structures of 18-31 are discussed. The single-crystal X-ray diffraction study of 23, 25-28, 30 31 indicates monomeric Structures ill the solid state. Chiral complexes 20, 22, 23 25, 26, 30 were tested as chiral catalysts in the Abramov reaction and demonstrated moderate enantiomeric activity. [ DOI ]
Synthesis and structure of titanium alkoxides based on tetraphenyl substituted 2,6-dimethanolpyridine moiety / K. V. Zaitsev, M. V. Bermeshev, S. S. Karlov et al. // Inorganica Chimica Acta . — 2007. — Vol. 360, no. 7. — P. 2507–2512. Novel titanocanes and spirobititanocanes based on 2,6-bis[hydroxy(diphenyl)methyl]pyridine (1a) and 2,6-di(hydroxymethyl)pyridine (1b) - [2,6-C5H3N(CPh2O)(2)]Ti(O-i-Pr)(2) (2a), [2,6-C5H3N(CPh2O)(2)](2)Ti (3a), [2,6-C5H3N(CH2O)(2)](2)Ti (3b), [2,6-C5H3N(CPh2O)(2)TriCl(2) (4) - as well as the closely related N-phenyl derivative PhN(CH2CH2O)(2)Ti(Cl)Cp (5) have been synthesized. Complexes 2-5 were characterized by H-1 and C-13 NMR spectroscopy and elemental analysis data. The molecular structure of 3a was determined by X-ray structure analysis. (c) 2006 Elsevier B.V. All rights reserved. [ DOI ]
Synthesis and structure of titanium alkoxides based on tetraphenyl substituted 2,6-dimethanolpyridine moiety / K. V. Zaitsev, M. V. Bermeshev, S. S. Karlov et al. // Inorganica Chimica Acta . — 2007. — Vol. 360, no. 7. — P. 2507–2512. Novel titanocanes and spirobititanocanes based on 2,6-bis[hydroxy(diphenyl)methyl]pyridine (1a) and 2,6-di(hydroxymethyl)pyridine (1b) - [2,6-C5H3N(CPh2O)(2)]Ti(O-i-Pr)(2) (2a), [2,6-C5H3N(CPh2O)(2)](2)Ti (3a), [2,6-C5H3N(CH2O)(2)](2)Ti (3b), [2,6-C5H3N(CPh2O)(2)TriCl(2) (4) - as well as the closely related N-phenyl derivative PhN(CH2CH2O)(2)Ti(Cl)Cp (5) have been synthesized. Complexes 2-5 were characterized by H-1 and C-13 NMR spectroscopy and elemental analysis data. The molecular structure of 3a was determined by X-ray structure analysis. (c) 2006 Elsevier B.V. All rights reserved. [ DOI ]
Hyperfine interactions and local structure of 57fe in la0.6sr0.4fexco1-xo3-y / A. Baranov, O. N. Andreeva, M. V. Bermeshev et al. // The abstracts of International Meeting “ORDER, DISORDER and PROPERTIES of OXIDES”. — Sochi, Russia, 2003. — P. 22–22.
