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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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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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Preparation of functionalized polyacetylenes with linear and cross-linked architecture
Havelková, Lucie ; Sedláček, Jan (advisor) ; Balcar, Hynek (referee)
The phenylacetylene type monomers with benzene ring substituted with one or two aldehyde groups (besides an ethynyl group) were efficiently polymerized into linear mostly high-molecular-weight polyacetylenes with aldehyde groups in pendants if the complex [Rh(NBD)acac] was used as the polymerization catalyst. To achieve high yield and molecular weight of the polymer the positioning of the aldehyde group to meta position with respect to the ethynyl group was most appropriate. It was confirmed that polyacetylenes with aldehyde groups were modifiable by a reaction with p-toluidine under formation of Schiff base type pendant groups. 1,3-Diethynylbenzenes with various substituents in position 5 on the ring (R = H, F, Cl, Br, HCO, NO2, COOCH3) were efficiently polymerized with [Rh(NBD)acac] catalyst into microporous or micro/mesoporous polyacetylene networks that exhibited specific surface area from 311 to 1146 m2 /g. In the case of the networks with HC=O groups, the positive effect of these groups was confirmed on the capacity of the network in CO2 and methanol vapor capture. The composition and texture of the networks possessing HC=O groups were partly reversibly modifiable in reaction with p-toluidine.
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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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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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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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Preparation of functionalized polyacetylenes with linear and cross-linked architecture
Havelková, Lucie ; Sedláček, Jan (advisor) ; Balcar, Hynek (referee)
The phenylacetylene type monomers with benzene ring substituted with one or two aldehyde groups (besides an ethynyl group) were efficiently polymerized into linear mostly high-molecular-weight polyacetylenes with aldehyde groups in pendants if the complex [Rh(NBD)acac] was used as the polymerization catalyst. To achieve high yield and molecular weight of the polymer the positioning of the aldehyde group to meta position with respect to the ethynyl group was most appropriate. It was confirmed that polyacetylenes with aldehyde groups were modifiable by a reaction with p-toluidine under formation of Schiff base type pendant groups. 1,3-Diethynylbenzenes with various substituents in position 5 on the ring (R = H, F, Cl, Br, HCO, NO2, COOCH3) were efficiently polymerized with [Rh(NBD)acac] catalyst into microporous or micro/mesoporous polyacetylene networks that exhibited specific surface area from 311 to 1146 m2 /g. In the case of the networks with HC=O groups, the positive effect of these groups was confirmed on the capacity of the network in CO2 and methanol vapor capture. The composition and texture of the networks possessing HC=O groups were partly reversibly modifiable in reaction with p-toluidine.
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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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