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Functionalized hyper-cross-linked porous polyacetylenes
Havelková, Lucie
An atom-economic one-step chain-growth coordination homopolymerization providing high yields of functionalized hyper-cross-linked polyacetylenes with permanent micro/mesoporous texture and specific surface area up to 1062 m2 /g was introduced and optimized. Substituted 1,3-diethynylbenzenes served as monomers simultaneously providing functionalization and hyper-cross-linking of the networks. The homopolymerization was compatible with the heteroatom groups of the monomers and allowed to prepare polyacetylene networks with the wide spectrum of univalent functional groups: -F, -Cl, -Br, -NO2, -COOCH3, -CH2OH, -COOH and -CH=O decorating the aromatic segments of the networks in a high extent (7.87 mmol/g). A novel two-step synthesis of functionalized hyper-cross-linked polyacetylenes was introduced combining chain-growth coordination polymerization of acetylenic monomers and covalent templating using acetal and Schiff base protecting groups. By postpolymerization hydrolytic removal of the protecting segments from the primary networks, the networks with a high content (up to 9.61 mmol/g) of univalent functional groups -CH2OH, -CH=O and -NH2 were prepared. These groups were placed either on the cross-linking or linear (aromatic and aliphatic) network segments, even in the vicinity of the main...
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Functionalized hyper-cross-linked porous polyacetylenes
Havelková, Lucie ; Sedláček, Jan (advisor) ; Brožek, Jiří (referee) ; Balcar, Hynek (referee)
An atom-economic one-step chain-growth coordination homopolymerization providing high yields of functionalized hyper-cross-linked polyacetylenes with permanent micro/mesoporous texture and specific surface area up to 1062 m2 /g was introduced and optimized. Substituted 1,3-diethynylbenzenes served as monomers simultaneously providing functionalization and hyper-cross-linking of the networks. The homopolymerization was compatible with the heteroatom groups of the monomers and allowed to prepare polyacetylene networks with the wide spectrum of univalent functional groups: -F, -Cl, -Br, -NO2, -COOCH3, -CH2OH, -COOH and -CH=O decorating the aromatic segments of the networks in a high extent (7.87 mmol/g). A novel two-step synthesis of functionalized hyper-cross-linked polyacetylenes was introduced combining chain-growth coordination polymerization of acetylenic monomers and covalent templating using acetal and Schiff base protecting groups. By postpolymerization hydrolytic removal of the protecting segments from the primary networks, the networks with a high content (up to 9.61 mmol/g) of univalent functional groups -CH2OH, -CH=O and -NH2 were prepared. These groups were placed either on the cross-linking or linear (aromatic and aliphatic) network segments, even in the vicinity of the main...
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Templating as a new method of creating and modifying the porous texture of polyacetylene networks
Sokol, Jiří ; Sedláček, Jan (advisor) ; Balcar, Hynek (referee)
A new method of introducing permanent micropores into hyper-cross-linked polyacetylene networks has been developed. The method used a combination of polyacetylene chemistry and Schiff base chemistry. Through the coordination chain-growth polymerization of monomers with polymerizable ethynyl groups, a wide series of homopolymer and copolymer networks with rigid polyene main chains interconnected by arylene links was prepared. The networks carried substituents of the predominantly aromatic Schiff-base-type in the pendant groups. With increasing content and volume of these substituents the specific surface area of the networks decreased. The networks with a high content of Schiff-base-type substituents were non-porous. The prepared networks were subsequently hydrolyzed under the conditions optimized in this diploma thesis. The hydrolysis led to a highly efficient cleavage of the Schiff base methanimine linkages and to the removal of the cleaved low molecular weight aromatic amine and aldehyde segments from the networks. In this way, new functional groups were generated in the networks, either CH=O or NH2. The hydrolytic modification had a fundamental effect on the texture parameters of the networks. The modification of the originally microporous networks mostly led to an increase in the specific...
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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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Preparation of polyacetylenes with N-benzylidene-2-hydroxyaniline groups
Zhernakova, Yulia ; Sedláček, Jan (advisor) ; Vyskočilová, Eliška (referee)
The following monoethynylated N-benzylidene-2-hydroxyanilines were prepared: N-(4- ethynylbenzylidene)-2-hydroxyaniline, N-(3-ethynylbenzylidene)-2-hydroxyaniline, N-(4- ethynylbenzylidene)-2-hydroxy-5-nitroaniline and N-(3-ethynylbenzylidene)-2-hydroxy-5- nitroaniline, which differed in the position of the ethynyl group on the benzylidene ring and the substitution of the hydroxyaniline ring. Monoethynylated N-benzylidene-2- hydroxyanilines were used as the monomers for the chain-growth coordination homo- and copolymerization. The homopolymerization resulted in linear polyacetylene homopolymers with N-benzylidene-2-hydroxyaniline substituents. The copolymerization with multiethynylarene-type cross-linkers provided densely cross-linked copolymeric polyacetylene networks. The linear units of the networks carried N-benzylidene-2- hydroxyaniline substituents, the interconnection between the chains of the networks being realized by arene links. The texture parameters of the prepared networks significantly depended on the type of comonomers used. The highest specific surface area values (~530 m2 /g) were achieved with networks prepared by copolymerization of N-(4- ethynylbenzylidene)-2-hydroxyaniline or N-(3-ethynylbenzylidene)-2-hydroxyaniline,with 4,4'-diethynylbiphenyl used as a cross-linker. Selected...
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Preparation of functionalized polyacetylene networks by one-step polymerization
Trnková, Kristýna ; Sedláček, Jan (advisor) ; Faukner, Tomáš (referee)
Three new compounds of the aromatic-aliphatic Schiff base type have been prepared via a condensation of 4-ethynylbenzaldehyde with various configurational isomers of 1,2- diaminocyclohexane. The compounds contained two azomethine links and two identical ethynyl groups located at terminal benzene rings. By means of a condensation of 4- ethynylaniline with 5-ethynyl-1,3-benzenedicarbaldehyde an aromatic Schiff base has been prepared which contained two azomethine links interconnecting three benzene rings each of which being substituted with one ethynyl group. All the prepared compounds were used as the monomers of the coordination chain growth polymerization in which the ethynyl groups of the monomers were transformed while the azomethine groups remained preserved. The polymerizations provided polymer networks in which the polyacetylene main chains (formed via polymerization) were extensively interconnected with aromatic-aliphatic or aromatic segments containing azomethine groups. The quantitative conversion of ethynyl groups was achieved in the polymerizations of diethynylated monomers. The polymerization of a triethynylated monomer proceeded under the conversion of the ethynyl groups of the monomer up to 90 %. The triethynylated monomer provided networks with microporous texture manifested by a...
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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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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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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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