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Conjugated porous polymers derived from diethynylarenes by chain-growth polymerization and polycyclotrimerization
Slováková, Eva ; Sedláček, Jan (advisor) ; Merna, Jan (referee) ; Červený, Libor (referee)
4 ABSTRACT The synthesis has been described yielding a new type of rigid conjugated polymer networks which possess a high content of permanent micropores and macropores and exhibit high surface areas up to 1469 m2/g. The networks have been prepared via chain-growth coordination polymerization catalysed with insertion catalysts based on Rh complexes. This polymerization has been newly applied to bifunctional acetylenic monomers of diethynylarene type (1,4-diethynylbenzene, 1,3-diethynylbenzene and 4,4'-diethynylbiphenyl). The covalent structure of the networks consists of the polyacetylene main chains densely connected by arylene struts. The W and Mo metathesis catalysts have been revealed as inefficient for the synthesis of these networks. The increase in the polymerization temperature and time has been shown to affect positively the content and the diameter (up to 22 nm) of the mesopores in the networks. A mechanism has been proposed that explains the mesopores formation as a result of mutual knitting of small particles of the microporous polymer. The application of emulsion polymerization technique allowed to prepare texturally hierarchical polyacetylene networks possessing interconnected open macropores (diameter up to 4,8 μm) the walls of which exhibited micro/mesoporous texture. It was demonstrated...
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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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Conjugated porous polymers derived from diethynylarenes by chain-growth polymerization and polycyclotrimerization
Slováková, Eva
The synthesis has been described yielding a new type of rigid conjugated polymer networks which possess a high content of permanent micropores and macropores and exhibit high surface areas up to 1469 m2/g. The networks have been prepared via chain-growth coordination polymerization catalysed with insertion catalysts based on Rh complexes. This polymerization has been newly applied to bifunctional acetylenic monomers of diethynylarene type (1,4-diethynylbenzene, 1,3-diethynylbenzene and 4,4'-diethynylbiphenyl). The covalent structure of the networks consists of the polyacetylene main chains densely connected by arylene struts. The W and Mo metathesis catalysts have been revealed as inefficient for the synthesis of these networks. The increase in the polymerization temperature and time has been shown to affect positively the content and the diameter (up to 22 nm) of the mesopores in the networks. A mechanism has been proposed that explains the mesopores formation as a result of mutual knitting of small particles of the microporous polymer. The application of emulsion polymerization technique allowed to prepare texturally hierarchical polyacetylene networks possessing interconnected open macropores (diameter up to 4,8 μm) the walls of which exhibited micro/mesoporous texture. It was demonstrated that...
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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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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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Conjugated porous polymers derived from diethynylarenes by chain-growth polymerization and polycyclotrimerization
Slováková, Eva ; Sedláček, Jan (advisor) ; Merna, Jan (referee) ; Červený, Libor (referee)
4 ABSTRACT The synthesis has been described yielding a new type of rigid conjugated polymer networks which possess a high content of permanent micropores and macropores and exhibit high surface areas up to 1469 m2/g. The networks have been prepared via chain-growth coordination polymerization catalysed with insertion catalysts based on Rh complexes. This polymerization has been newly applied to bifunctional acetylenic monomers of diethynylarene type (1,4-diethynylbenzene, 1,3-diethynylbenzene and 4,4'-diethynylbiphenyl). The covalent structure of the networks consists of the polyacetylene main chains densely connected by arylene struts. The W and Mo metathesis catalysts have been revealed as inefficient for the synthesis of these networks. The increase in the polymerization temperature and time has been shown to affect positively the content and the diameter (up to 22 nm) of the mesopores in the networks. A mechanism has been proposed that explains the mesopores formation as a result of mutual knitting of small particles of the microporous polymer. The application of emulsion polymerization technique allowed to prepare texturally hierarchical polyacetylene networks possessing interconnected open macropores (diameter up to 4,8 μm) the walls of which exhibited micro/mesoporous texture. It was demonstrated...
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Synthesis of microporous polymer networks with azomethine links
Hašková, Alena ; Sedláček, Jan (advisor) ; Balcar, Hynek (referee)
A series of following Schiff base type monomers with two terminal ethynyl groups and one or two azomethine groups have been synthesized: N-(4-ethynylbenzylidene)(4-ethynylaniline), positional isomers of N,N'-(1,4-phenylene)bis(1-(ethynylphenyl)methanimine) and positional isomers of 1,1'-(1,4-phenylene)bis[(N-ethynylphenyl)methanimine]. These monomers have been successfully polymerized in chain-growth mode with the use of [Rh(NBD)acac] as the coordination catalyst into densely cross-linked polyacetylene networks with micro/mesoporous texture and specific surface in hundreds of m2 /g. The positive correlation between the conversion of ethynyl groups and specific surface area on one hand and the increase in reaction temperature and reaction time on the other side was proven. Varying the composition and architecture of polymerized monomers affected particularly the distribution of micropores and mesopores in the networks. The postpolymerization modification of poly[N-(4-ethynylbenzylidene)(4- ethynylaniline)] network has been performed consisting in a partial releasing the links connecting the linear segments of the network. It was confirmed that despite this modification the network preserved the micro/mesoporous texture.
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Conjugated porous polymers derived from diethynylarenes by chain-growth polymerization and polycyclotrimerization
Slováková, Eva
The synthesis has been described yielding a new type of rigid conjugated polymer networks which possess a high content of permanent micropores and macropores and exhibit high surface areas up to 1469 m2/g. The networks have been prepared via chain-growth coordination polymerization catalysed with insertion catalysts based on Rh complexes. This polymerization has been newly applied to bifunctional acetylenic monomers of diethynylarene type (1,4-diethynylbenzene, 1,3-diethynylbenzene and 4,4'-diethynylbiphenyl). The covalent structure of the networks consists of the polyacetylene main chains densely connected by arylene struts. The W and Mo metathesis catalysts have been revealed as inefficient for the synthesis of these networks. The increase in the polymerization temperature and time has been shown to affect positively the content and the diameter (up to 22 nm) of the mesopores in the networks. A mechanism has been proposed that explains the mesopores formation as a result of mutual knitting of small particles of the microporous polymer. The application of emulsion polymerization technique allowed to prepare texturally hierarchical polyacetylene networks possessing interconnected open macropores (diameter up to 4,8 μm) the walls of which exhibited micro/mesoporous texture. It was demonstrated that...
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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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