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Porous polymer networks prepared from ethynylpyridines
Titlová, Štěpánka ; Sedláček, Jan (advisor) ; Sedláček, Ondřej (referee)
Series of new micro/mesoporous polymer networks with high content of pyridine segments was prepared. For the preparation were used ethynylpyridine type of monomers which were successfully homopolymerized and copolymerized with hydrocarbon diethynylarenes by chain-growth coordination polymerization catalyzed with [Rh(NBD)acac] complex. Polymerizations provided polyacetylene networks with main chains densely cross- linked by pyridine or arylene links. Prepared pyridine networks showed specific surface area SBET from 308 m2 /g to 923 m2 /g and variable content of pyridine segments in an interval from 3,27 mmol/g to 7,86 mmol/g. In networks, pyridine segments made part of interchain links or side groups. Networks with pyridine segments were successfully quaternized by heterogeneous postpolymerization reaction with bromoethane to form well covalently defined networks containing N-ethylpyridinium segments. Quaternized networks containing pyridinim segments in amount from 2,41 mmol/g to 4,24 mmol/g had preserved micro/mesoporous texture with values of SBET from 331 m2 /g to 592 m2 /g. Polyacetylene networks with N-ethylpyridinium segments were prepared also by catalyst-free (spontaneous) quaternization polymerization of diethylpyridines. These networks were worse covalently defined and had proved lower...
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Functionalized microporous polymer networks prepared from ethynylarenes
Stahlová, Sabina ; Sedláček, Jan (advisor) ; Etrych, Tomáš (referee) ; Červený, Libor (referee)
The preparation of a new group of functionalized conjugated polymer networks has been described based on spontaneous quaternization polymerization of ethynylpyridines with bis(bromomethyl)arenes. The networks consisted of polyacetylene chains with pyridyl and pyridiniumyl pendants cross-linked with -CH2(arylene)CH2- links. The variation of the ratio of monomer and quaternization agent in the feed modified the ratio of pyridyl and pyridiniumyl groups in the networks (pyridyl/pyridiniumyl ratios from 0 to 1.32). The networks did not exhibit a permanent microporosity that could be confirmed by nitrogen adsorption at 77 K. Nevertheless, all networks were active in capture of CO2 at 293 K (up to 0.73 mmol CO2/g, 750 Torr). It has been hypothesized that CO2 capture reflected formation of a temporary porous texture of the networks through conformational changes of the network segments enabled by the segments mobility at room temperature. The preparation of functionalized conjugated polymer networks with permanent micro/mesoporosity (SBET up to 667 m2 /g) has been described that was based on chain coordination copolymerization of acetylenic monomers. The copolymerization of 1,4-diethynylbenzene or 4,4'-diethynylbiphenyl with mono or diethynylbenzenes bearing NO2 or CH2OH groups has been demonstrated as...
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Functionalized microporous polymer networks prepared from ethynylarenes
Stahlová, Sabina
The preparation of a new group of functionalized conjugated polymer networks has been described based on spontaneous quaternization polymerization of ethynylpyridines with bis(bromomethyl)arenes. The networks consisted of polyacetylene chains with pyridyl and pyridiniumyl pendants cross-linked with -CH2(arylene)CH2- links. The variation of the ratio of monomer and quaternization agent in the feed modified the ratio of pyridyl and pyridiniumyl groups in the networks (pyridyl/pyridiniumyl ratios from 0 to 1.32). The networks did not exhibit a permanent microporosity that could be confirmed by nitrogen adsorption at 77 K. Nevertheless, all networks were active in capture of CO2 at 293 K (up to 0.73 mmol CO2/g, 750 Torr). It has been hypothesized that CO2 capture reflected formation of a temporary porous texture of the networks through conformational changes of the network segments enabled by the segments mobility at room temperature. The preparation of functionalized conjugated polymer networks with permanent micro/mesoporosity (SBET up to 667 m2 /g) has been described that was based on chain coordination copolymerization of acetylenic monomers. The copolymerization of 1,4-diethynylbenzene or 4,4'-diethynylbiphenyl with mono or diethynylbenzenes bearing NO2 or CH2OH groups has been demonstrated as...
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Porous polymer networks prepared from ethynylpyridines
Titlová, Štěpánka ; Sedláček, Jan (advisor) ; Sedláček, Ondřej (referee)
Series of new micro/mesoporous polymer networks with high content of pyridine segments was prepared. For the preparation were used ethynylpyridine type of monomers which were successfully homopolymerized and copolymerized with hydrocarbon diethynylarenes by chain-growth coordination polymerization catalyzed with [Rh(NBD)acac] complex. Polymerizations provided polyacetylene networks with main chains densely cross- linked by pyridine or arylene links. Prepared pyridine networks showed specific surface area SBET from 308 m2 /g to 923 m2 /g and variable content of pyridine segments in an interval from 3,27 mmol/g to 7,86 mmol/g. In networks, pyridine segments made part of interchain links or side groups. Networks with pyridine segments were successfully quaternized by heterogeneous postpolymerization reaction with bromoethane to form well covalently defined networks containing N-ethylpyridinium segments. Quaternized networks containing pyridinim segments in amount from 2,41 mmol/g to 4,24 mmol/g had preserved micro/mesoporous texture with values of SBET from 331 m2 /g to 592 m2 /g. Polyacetylene networks with N-ethylpyridinium segments were prepared also by catalyst-free (spontaneous) quaternization polymerization of diethylpyridines. These networks were worse covalently defined and had proved lower...
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Functionalized microporous polymer networks prepared from ethynylarenes
Stahlová, Sabina ; Sedláček, Jan (advisor) ; Etrych, Tomáš (referee) ; Červený, Libor (referee)
The preparation of a new group of functionalized conjugated polymer networks has been described based on spontaneous quaternization polymerization of ethynylpyridines with bis(bromomethyl)arenes. The networks consisted of polyacetylene chains with pyridyl and pyridiniumyl pendants cross-linked with -CH2(arylene)CH2- links. The variation of the ratio of monomer and quaternization agent in the feed modified the ratio of pyridyl and pyridiniumyl groups in the networks (pyridyl/pyridiniumyl ratios from 0 to 1.32). The networks did not exhibit a permanent microporosity that could be confirmed by nitrogen adsorption at 77 K. Nevertheless, all networks were active in capture of CO2 at 293 K (up to 0.73 mmol CO2/g, 750 Torr). It has been hypothesized that CO2 capture reflected formation of a temporary porous texture of the networks through conformational changes of the network segments enabled by the segments mobility at room temperature. The preparation of functionalized conjugated polymer networks with permanent micro/mesoporosity (SBET up to 667 m2 /g) has been described that was based on chain coordination copolymerization of acetylenic monomers. The copolymerization of 1,4-diethynylbenzene or 4,4'-diethynylbiphenyl with mono or diethynylbenzenes bearing NO2 or CH2OH groups has been demonstrated as...
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Functionalized microporous polymer networks prepared from ethynylarenes
Stahlová, Sabina
The preparation of a new group of functionalized conjugated polymer networks has been described based on spontaneous quaternization polymerization of ethynylpyridines with bis(bromomethyl)arenes. The networks consisted of polyacetylene chains with pyridyl and pyridiniumyl pendants cross-linked with -CH2(arylene)CH2- links. The variation of the ratio of monomer and quaternization agent in the feed modified the ratio of pyridyl and pyridiniumyl groups in the networks (pyridyl/pyridiniumyl ratios from 0 to 1.32). The networks did not exhibit a permanent microporosity that could be confirmed by nitrogen adsorption at 77 K. Nevertheless, all networks were active in capture of CO2 at 293 K (up to 0.73 mmol CO2/g, 750 Torr). It has been hypothesized that CO2 capture reflected formation of a temporary porous texture of the networks through conformational changes of the network segments enabled by the segments mobility at room temperature. The preparation of functionalized conjugated polymer networks with permanent micro/mesoporosity (SBET up to 667 m2 /g) has been described that was based on chain coordination copolymerization of acetylenic monomers. The copolymerization of 1,4-diethynylbenzene or 4,4'-diethynylbiphenyl with mono or diethynylbenzenes bearing NO2 or CH2OH groups has been demonstrated as...
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