Microporous Materials Based on Norbornadiene-Based Cross-Linked Polymers

Abstract

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.

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

“…Furthermore, it was shown [ 12 ] that polymer properties can be varied in a wide range by the introduction of side groups of different types. As a result, various addition polymers derived from norbornenes were successfully developed for applications such as adhesives [ 13 ], OLEDs [ 14 , 15 , 16 ], catalyst supports [ 17 , 18 ], membrane materials [ 9 , 19 , 20 ], gas storage materials [ 21 ], and dielectrics [ 22 , 23 , 24 ]. Different norbornene-based membrane materials possessing extremely high gas permeability accompanied by high C 4 H 10 /CH 4 and CO 2 /N 2 selectivities were reported [ 9 , 25 , 26 , 27 , 28 , 29 , 30 ]; in some cases, these polymers possess good long-term stability of their gas transport properties [ 25 , 29 ].…”

Polyvinylnorbornene Gas Separation Membranes

“…Polynorbornene with trimethylsilyl groups showed an extremely high CO 2 permeability of 4350 Barrer but a low CO 2 /CH 4 selectivity of 5.5 [15]. Recently, high CO 2 permeabilities were achieved (1350 Barrer) with a CO 2 /N 2 selectivity of 17 by using a triethylsiloxane pendant side group [9] and impressive BET surface areas (420–970 m 2 /g) were achieved with derivatized polynorbornenes [16]. From the wide variety of functionalized norbornene monomers that were used for gas separation membranes, 5-vinyl-2-norbornene (VNB) was still missing.…”

Features of heterogeneous catalytic transformations of strained carbocyclic compounds of the norbornene series

“…2022;17(4):275-297 ВВЕДЕНИЕ Норборнадиен (НБД), норборнен (НБН) и их производные занимают важное место в органическом и нефтехимическом синтезе [1]. За 70-летнюю историю эти соединения нашли применение в парфюмерной промышленности [2][3][4][5], медицине [6][7][8][9], сельском хозяйстве [10][11][12] в производстве полимерных материалов с уникальными свойствами [13][14][15][16][17][18][19][20][21][22], микроэлектронике и фотонике [23][24][25][26][27], в качестве конвертеров солнечной энергии [28][29][30][31][32][33][34], топлив с различными свойствами [35][36][37][38][39][40][41][42][43][44][45][46][47] и так далее. Количество публикаций и патентов, связанных с получением и использованием производных НБН и НБД, в 2022 г. превысило 35 тыс.…”

“…21 Hβ-25 -это молекулярный цеолитный катализатор водородного типа Hβ с каркасным отношенияем Si/Al = 25.Tonkie Khimicheskie Tekhnologii = Fine Chemical Technologies. 2022;17(4):275-297 Таблица 3.…”