Synthesis of cardo-polymers using Tröger's base formation

Carta, Mariolino; Croad, Matthew; Jansen, Johannes C.; Bernardo, Paola; Clarizia, Gabriele; McKeown, Neil B.

doi:10.1039/c4py00607k

Cited by 68 publications

(50 citation statements)

References 39 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…PIMs [23,24] provide a new generation of highly rigid microporous materials with (i) excellent processability, (ii) highly rigid pore structures in which guest catalyst molecules can be readily embedded, (iii) good access of solvent and substrate to the catalyst through rigid pores and (iv) robustness towards corrosion. In our previous work, the poly-amine structure PIM-EA-TB [25] (synthesised based on a Tröger's base reaction [26][27][28]) has been employed to electrochemically grow palladium lamellae [29], to act as a host for molecular Fe(II)-porphyrinato electrocatalyst [30] and to protect gold nanoparticles [31] and fuel cell catalysts [32]. Recently, we have demonstrated proof of concept for the immobilisation of the molecular electrocatalyst 4-benzoyloxy-TEMPO (or 4B-TEMPO) into a porous PIM-EA-TB host film for the electrocatalytic oxidation of saccharides [33].…”

Section: Introductionmentioning

confidence: 99%

Polymer of Intrinsic Microporosity Induces Host-Guest Substrate Selectivity in Heterogeneous 4-Benzoyloxy-TEMPO-Catalysed Alcohol Oxidations

et al. 2015

Self Cite

View full text Add to dashboard Cite

The free radical 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4B-TEMPO) is active as an electrocatalyst for primary alcohol oxidations when immobilised at an electrode surface and immersed into an aqueous carbonate buffer solution. In order to improve the catalytic process, a composite film electrode is developed based on (i) carbon microparticles of 2-12 μm diameter to enhance charge transport and (ii) a polymer of intrinsic microporosity (here PIM-EA-TB with a BET surface area of 1027 m 2 g −1 ). The latter acts as a highly rigid molecular framework for the embedded free radical catalyst with simultaneous access to aqueous phase and substrate. The resulting mechanism for the oxidation of primary alcohols is shown to switch in reaction order from first to zeroth with increasing substrate concentration consistent with a kinetically limited process with competing diffusion of charge at the polymer layer-electrode interface (here the BLEk^case in Albery-Hillman notation). Reactivity optimisation and screening for a wider range of primary alcohols in conjunction with DFT-based relative reactivity correlation reveals substrate hydrophobicity as an important factor for enhancing catalytic currents. The PIM-EA-TB host matrix is proposed to control substrate partitioning and thereby catalyst reactivity and selectivity.

show abstract

Section: Introductionmentioning

confidence: 99%

Polymer of Intrinsic Microporosity Induces Host-Guest Substrate Selectivity in Heterogeneous 4-Benzoyloxy-TEMPO-Catalysed Alcohol Oxidations

et al. 2015

Self Cite

View full text Add to dashboard Cite

show abstract

“…Recently, Carta et al evaluated adamantane-containing Tr€ oger's base-PIMs for CO 2 separation. 25 The incorporation of adamantane and Tr€ oger's base units in polymers imparted intrinsic microporosity and improved gas separation performance owing to the rigid and contorted structure.…”

Section: Synthesized Polyamidesmentioning

confidence: 99%

“…Similar observations have been documented in the literature concerning effect of physical aging on gas permeability characteristics of PIMs. 20,25 The gas permeation data of PIMs were plotted on Robeson plot (Fig. 5) To gauge the relative performance of these PIMs, the gas permeability data was correlated with commercially available polymers and adamantane-containing polymers reported in the literature.…”

Section: Articlementioning

confidence: 99%

“…PIM-1 is a widely studied candidate in the class of PIMs due to its rigid and contorted structure. 9 Since then, several examples of PIMs containing units such as triptycene, 10,11 spirobisindane, 12,13 Tr€ oger's base, [14][15][16][17] spirobischromane, 18 spirobifluorene, 19 hexaphenylbenzene, 20 naphthalene, 21 tetraphenylethylene, 22 phthalimide, 23 tribenzotriquinacene, 24 cardo PIMs, and so on 25 have been synthesized and evaluated as membrane materials for gas separation.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Synthesis, characterization, and gas permeation properties of adamantane‐containing polymers of intrinsic microporosity

Shrimant

Shaligram

Kharul

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

View full text Add to dashboard Cite

A new bis(catechol) monomer, namely, 4,4 0 -((1r,3r)-adamantane-2,2-diyl)bis(benzene-1,2diol) (THADM) was synthesized by condensation of 2-adamantanone with veratrole followed by demethylation of the formed (1r,3r)-2,2-bis(3,4 dimethoxyphenyl)adamantane. Polycondensation of THADM and various compositions of THADM and 5,5,6 0 ,6 0 -tetrahydroxy-3,3,3 0 ,3 0 -tetramethylspirobisindane was performed with 2,3,5,6-tetrafluoroterephthalonitrile (TFTPN) to obtain the homopolymer and copolymers. These polymers demonstrated good solubility in common organic solvents such as dichloromethane, chloroform, and tetrahydrofuran and could be cast into tough films from their chloroform solutions. GPC analysis revealed that number average molecular weights of polymers were in the range 48,100-61,700 g mol 21 , suggesting the formation of reasonably high molecular weight polymers. They possessed intrinsic microporosity with Brunauer-Emmett-Teller (BET) surface area in the range 703-741 m 2 g 21 . Thermogravimetric analysis of polymers indicated that 10% weight loss temperature was in the range 513-518 8C demonstrating their excellent thermal stability. THADM-based polymer of intrinsic microporosity (PIM) showed P(CO 2 ) 5 1080, P(O 2 ) 5 232 and appreciable selectivity [a(CO 2 /CH 4 ) 5 22.6, a(CO 2 /N 2 ) 5 26.7, and a(O 2 /N 2 )5 5.7]. The gas permeability measurements revealed that with increase in the content of adamantane units in PIMs, selectivity increased and permeability decreased, following the trade-off relationship. The gas separation properties of PIMs containing adamantane units were located close to 2008 Robeson upper bound for gas pairs such as CO

show abstract

“…The cardo moiety imparts also a significant increase in T g and thermal stability [27][28][29][30]. Additionally, the aromatic cardo polyimides reported in the literature exhibit high gas selectivity values [23,31,32]. According to these observations, the target of this work was to prepare novel polyimides containing tert-butyl or hexafluoroisopropylidene groups and cardo moieties in the repeat unit ( Figure 1) and to explore their effect on solubility, thermal stability and gas separation properties.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and gas separation properties of novel polyimides containing cardo and tert-butyl-m-terphenyl moieties

Bermejo¹,

Álvarez²,

Maya³

et al. 2018

Express Polym. Lett.

View full text Add to dashboard Cite

Abstract.A series of aromatic polyimides has been obtained by the reaction of two dianhydrides, the commercial 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and another having a 5′-tert-butyl-m-terphenyl moiety (BTPDA), with several diamines, including two that have a cardo structure (derived from 9H-fluorene), one of them bearing methyl groups ortho to the amino functionalities (TMeCardo). The solubility, and also the thermal, mechanical, and gas separation properties of the corresponding polyimide membranes were evaluated and compared in order to explore the effect of the different groups in the polyimide backbone. The novel polyimides, which were derived from BTPDA and the cardo diamines, showed high thermal stability, excellent solubility in organic solvents and good gas separation properties, especially the polyimide that bore the ortho methyl substituents. The behavior was especially good for the pair O 2 /N 2 , where the TMeCardo polymer overpassed the Robeson upper bound.

show abstract

Synthesis of cardo-polymers using Tröger's base formation

Cited by 68 publications

References 39 publications

Polymer of Intrinsic Microporosity Induces Host-Guest Substrate Selectivity in Heterogeneous 4-Benzoyloxy-TEMPO-Catalysed Alcohol Oxidations

Polymer of Intrinsic Microporosity Induces Host-Guest Substrate Selectivity in Heterogeneous 4-Benzoyloxy-TEMPO-Catalysed Alcohol Oxidations

Synthesis, characterization, and gas permeation properties of adamantane‐containing polymers of intrinsic microporosity

Synthesis, characterization and gas separation properties of novel polyimides containing cardo and tert-butyl-m-terphenyl moieties

Contact Info

Product

Resources

About