Molecular Properties of Additive Poly(bis(trimethylsilyl)tricyclonones) with Vicinal and Geminal Side Substituents

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

doi:10.1134/s0965545x18020050

Cited by 6 publications

(5 citation statements)

References 20 publications

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“…No doubt, the main reason for the phenomenon is the presence of flexible side alkyl‐groups, which provides local small‐scale mobility reducing energy barriers of gas diffusion. The considered polymers combine contradictory properties: they are glassy polymers by their thermal and mechanical properties due to the high rigidity of main chains (Table ), but the trend of hydrocarbons permeation in them is similar to that of rubbers. So, addition poly(5‐ n ‐alkylnorbornenes) studied here can be considered as comb‐shaped polymers, where the permeation properties of both components (glassy and rubbery) appeared and good performance is revealed.…”

Section: Methodsmentioning

confidence: 74%

Addition Polyalkylnorbornenes: A Promising New Class of Si‐Free Membrane Materials for Hydrocarbons Separation

Wozniak

Bermesheva

Borisov

et al. 2019

Macromol. Rapid Commun.

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ated petroleum gases. The realization of this process allows avoiding problems with the condensation of hydrocarbons (i.e., to reduce the dew point) and pre-detonating coking in compressor engines. [4,5] The separated C 2+ fraction will be a valuable feed for further chemical processing, or it can be used as a fuel. For a successful solution of the abovementioned task, membranes that show solubilitycontrolled permeation (i.e., which are characterized by higher permeability of heavier components of a mixture) seem to be the most attractive. For a long time, it was believed that the solubility-controlled permeation is a feature of rubbery polymers. In particular, it took place for the most permeable rubber-polydimethylsiloxane, while for convenient glassy polymers the permeability of hydrocarbons usually reduces with the size of penetrants mole cules. [5,6] At the same time, the use of glassy polymers in this process could extend frames and conditions of its application owing to high glass transition temperatures, good mechanical properties, and the promising combination of membrane characteristics of glassy polymers (glassy polymers dominate the polymers near or on the upper bound in contrast to rubbery polymers [7] ). The discovery of glassy poly(trimethylsilylpropyne) (PTMSP) and other highly permeable polyacetylenes in the last decades of the twentieth century quite unexpectedly revealed that glassy polymers indeed could possess the solubility controlled gas permeation of hydrocarbons. [8,9] Later it was shown that some other glassy polymers with large free volume polymers of intrinsic microporosity (PIM's) [10,11] and addition polynorbornenes bearing Me 3 Si-side groups [12,13] ) also exhibited the solubility controlled permeation. The main reasons for this phenomenon were the nanoporous nature of these glassy polymers and the presence of large free volume. Unfortunately, the abovementioned nanoporous polymers have not found a practical application for separation of hydrocarbons mainly due to the significant aging over time. These materials, as well as polysiloxanes, are extremely permeable membranes, so higher permeable polymers are not apparently required. Therefore, the process of hydrocarbon separation would be improved if the separation selectivity and polymers stability could be enhanced. To overcome these problems, low free volume glassy polynorbornenes [14][15][16][17] and polyacetylenes [18][19][20] have been successfully developed. The solubility-controlled permeation of hydrocarbons in these polymers Addition Poly(alkylnorbornenes) 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 polym...

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Section: Methodsmentioning

confidence: 74%

Addition Polyalkylnorbornenes: A Promising New Class of Si‐Free Membrane Materials for Hydrocarbons Separation

Wozniak

Bermesheva

Borisov

et al. 2019

Macromol. Rapid Commun.

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“…Обратим внимание на то, что мономер ПТЦН имеет вицинальное расположение боковых заместителей (рис. 1), тo есть группы Si(Ме) 3 находятся по одну сторону от плоскости квадроцикла трициклононена (exoмономер) [5,8].…”

Section: обсуждение результатовunclassified

“…Несмотря на то, что при переходе из раствора в пленку, имеет место изменение невозмущенных конформаций полимерных молекул за счет возникновения сетки зацеплений и их взаимопроникновения, в цепях сохраняется характерная для данного полимера локальная корреляция в расположении звеньев, которую обычно характеризуют длиной сегмента Куна [9,10]. Этот параметр цепи ПТЦН был определен недавно методом гидродинамического анализа в разбавленных растворах в работе [8]…”

Section: обсуждение результатовunclassified

“…Составленные из порядка тридцати спиральных фрагментов (сегментов Куна) цепи детектируются в рассеянии нейтронов на фоне полимерной матрицы. Однако наблюдаемые радиусы инерции R G ∼ 18 nm на ∼ 30% ниже размера макромолекул в растворах [8], т. к. они сильно перекрываются в блочном полимере. При упаковке цепей в блоке доля свободного объема в полученной пленке достигает 15%, превышая значение для идеальной модели упаковки цилиндрических фрагментов цепей без взаимопроникновения (9%).…”

Section: заключениеunclassified

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Структура Пленок Кремнийзамещенного Политрициклононена По Данным Малоуглового Рассеяния Нейтронов

Лебедев¹,

Евлампиева²,

Бермешев³

et al. 2018

Физика Твердого Тела

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Политрициклононены-новые полимеры, обладающие высокими показателями проницаемости не только для атмосферных газов, но и газообразных углеводородов. Для целевого улучшения газотранспортных свойств этого класса полимеров необходимо изучение тонких пленок (≤ 100 µm), применяющихся в газоразделительных мембранных технологиях. В данной работе методом малоуглового рассеяния нейтронов исследована структура пленок политрициклононена с вицинальным расположением двух боковых заместителей Si(CH 3) 3 в мономерном звене, синтезированного по схеме аддитивной полимеризации. Показано, что в целом аморфная пленка характеризуется наличием локального ориентационного порядка, связанного с сохранением фрагментами цепей спиральной конформации. Размер упорядоченных областей сопоставим с длиной корреляционных взаимодействий в цепи полимера (сегментом Куна) и соответствует 8−9 nm. Определены также величина свободного объема и тип пустот (пор), формирующихся в пленке полимера за счет неоднородной упаковки. Финансирование: Петербургский институт ядерной физики им. Б.П. Константинова НИЦ " Курчатовский институт", Санкт-Петербургский государственный университет.

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“…The crosslinking could stabilize the membrane materials against the deterioration by swelling or dissolution in hydrocarbons that can occur during gas‐separation process. At the same time, these polymers are saturated and chemically inert, and their main chains are very rigid . All this makes their crosslinking difficult.…”

Section: Introductionmentioning

confidence: 99%

Crosslinking of addition copolymers from tricyclononenes bearing (CH₃)₃Si‐ and (C₂H₅O)₃Si‐groups as a modification of membrane gas separation materials

Alentiev

Egorova

Бермешев

et al. 2019

Polymer Engineering & Sci

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Here, we report the synthesis and the study of gas‐transport properties of crosslinked highly permeable copolymers from Si‐containing norbornene derivatives. The initial high‐molecular‐weight copolymers were prepared via addition copolymerization of 3‐trimethylsilyltricyclo[4.2.1.02,5]non‐7‐ene (TCNSi1) with 3‐triethoxysilyltricyclo[4.2.1.02,5]non‐7‐ene (TCNSiOEt) in good or high yields using a Pd‐catalyst. The obtained copolymers included up to 10 mol% of TCNSiOEt units bearing reactive Si–O–C‐containing substituents. The crosslinking was readily realized by using simple sol–gel chemistry in the presence of Sn‐catalyst. The formed crosslinked copolymers were insoluble in common organic solvents. Permeability coefficients of various gases (He, H2, O2, N2, CO2, CH4, C2H6, C3H8, n‐C4H10) in these copolymers before and after crosslinking were determined and the influence of the incorporated TCNSiOEt units as well as the crosslinking on gas transport properties were established. As a result, it was found that only a small reduction of gas‐permeability was observed when TNCSiOEt units were incorporated into the main chains, and the copolymers were crosslinked. At the same time, the selectivity for C4H10/CH4 pair was increased. The suggested approach has allowed obtaining crosslinked polymers from Si‐containing monomers without a loss of the main membrane characteristics. POLYM. ENG. SCI., 59:2502–2507, 2019. © 2019 Society of Plastics Engineers

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Molecular Properties of Additive Poly(bis(trimethylsilyl)tricyclonones) with Vicinal and Geminal Side Substituents

Cited by 6 publications

References 20 publications

Addition Polyalkylnorbornenes: A Promising New Class of Si‐Free Membrane Materials for Hydrocarbons Separation

Addition Polyalkylnorbornenes: A Promising New Class of Si‐Free Membrane Materials for Hydrocarbons Separation

Структура Пленок Кремнийзамещенного Политрициклононена По Данным Малоуглового Рассеяния Нейтронов

Crosslinking of addition copolymers from tricyclononenes bearing (CH₃)₃Si‐ and (C₂H₅O)₃Si‐groups as a modification of membrane gas separation materials

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Molecular Properties of Additive Poly(bis(trimethylsilyl)tricyclonones) with Vicinal and Geminal Side Substituents

Cited by 6 publications

References 20 publications

Addition Polyalkylnorbornenes: A Promising New Class of Si‐Free Membrane Materials for Hydrocarbons Separation

Addition Polyalkylnorbornenes: A Promising New Class of Si‐Free Membrane Materials for Hydrocarbons Separation

Структура Пленок Кремнийзамещенного Политрициклононена По Данным Малоуглового Рассеяния Нейтронов

Crosslinking of addition copolymers from tricyclononenes bearing (CH3)3Si‐ and (C2H5O)3Si‐groups as a modification of membrane gas separation materials

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Crosslinking of addition copolymers from tricyclononenes bearing (CH₃)₃Si‐ and (C₂H₅O)₃Si‐groups as a modification of membrane gas separation materials