Claisen thermally rearranged (CTR) polymers

Tena, Alberto; Rangou, Sofia; Shishatskiy, Sergey; Filiz, Volkan; Abetz, Volker

doi:10.1126/sciadv.1501859

Cited by 37 publications

(18 citation statements)

References 39 publications

(51 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The auxiliary liquid for the measurement was isooctane as a liquid with low density and very low solubility in studied polymers. FFV was calculated according to the method described elsewhere [ 18 ].…”

Section: Methodsmentioning

confidence: 99%

Gas Separation Properties of Polyimide Thin Films on Ceramic Supports for High Temperature Applications

et al. 2018

Self Cite

View full text Add to dashboard Cite

Novel selective ceramic-supported thin polyimide films produced in a single dip coating step are proposed for membrane applications at elevated temperatures. Layers of the polyimides P84®, Matrimid 5218®, and 6FDA-6FpDA were successfully deposited onto porous alumina supports. In order to tackle the poor compatibility between ceramic support and polymer, and to get defect-free thin films, the effect of the viscosity of the polymer solution was studied, giving the entanglement concentration (C*) for each polymer. The C* values were 3.09 wt. % for the 6FDA-6FpDA, 3.52 wt. % for Matrimid®, and 4.30 wt. % for P84®. A minimum polymer solution concentration necessary for defect-free film formation was found for each polymer, with the inverse order to the intrinsic viscosities (P84® ≥ Matrimid® >> 6FDA-6FpDA). The effect of the temperature on the permeance of prepared membranes was studied for H2, CH4, N2, O2, and CO2. As expected, activation energy of permeance for hydrogen was higher than for CO2, resulting in H2/CO2 selectivity increase with temperature. More densely packed polymers lead to materials that are more selective at elevated temperatures.

show abstract

Section: Methodsmentioning

confidence: 99%

Gas Separation Properties of Polyimide Thin Films on Ceramic Supports for High Temperature Applications

et al. 2018

Self Cite

View full text Add to dashboard Cite

show abstract

“…Tena et al 42 have reported a novel low-temperature chemistry using a Claisen rearrangement reaction (CR) for the preparation of microporous polymers. The reaction was reported to occur at temperatures of ca 300 ∘ C (Scheme 10).…”

Section: Macromolecular Tr Chemistry Tr: Polybenzoxazolesmentioning

confidence: 99%

“…Tena et al . have reported a novel low‐temperature chemistry using a Claisen rearrangement reaction (CR) for the preparation of microporous polymers.…”

Section: Macromolecular Tr Chemistrymentioning

confidence: 99%

Understanding structure and composition of thermally rearranged polymers based on small‐molecule chemistry: a perspective

Murugesan¹,

Sivaram

2019

Polymer International

View full text Add to dashboard Cite

We provide a critical perspective of the burgeoning literature on microporous polymers prepared using thermal rearrangement (TR) processes based on the learning derived from analogous chemistry involving small‐molecular‐weight compounds. TR polymers have shown interesting permeability–selectivity relationships in gas separation and, thus, have generated wide interest as potential membrane materials for industrial applications. The intractable nature of the products obtained by TR processes has precluded rigorous structural elucidation of the polymers. Based on small‐molecule chemistry, we conclude that structures are likely to be more complex than generally depicted in the published literature. Interestingly, a simpler chemistry, namely thermal dehydrocyclization (TCD), leads to products identical to those derived from TR, but at significantly lower temperatures. However, TCD chemistry does not involve a skeletal rearrangement of the kind purported in TR during the conversion of imide to oxazole ring resulting in spatially confined heterocyclic ring polymers. Yet, they show similar fractional free‐volume elements as exhibited by TR polymers. This is intriguing and points to a need for more careful examination of the factors responsible for microporosity in such materials. TR chemistry as currently practiced appears limited to only benzoxazole‐type structures. The ability to precisely control and reproducibly produce materials with well‐defined structure and properties will be a key to large‐scale manufacture and industrial applications of such materials. Seen from this perspective, TR processes leave much to be desired and further improvements are clearly warranted. © 2019 Society of Chemical Industry

show abstract

“…[3,3]-Sigmatropic rearrangement is another powerful and reliable pericyclic reaction, allowing for the stereoselective construction of C-C bond. 11 However, this rearrangement cannot be applied to polymerization other than the post-modification of side-chains [12][13][14][15][16] because it is an intramolecular reaction, which intrinsically forms and breaks the bond simultaneously (Scheme 1Ab).…”

Section: Introductionmentioning

confidence: 99%

Tandem diaza-Cope rearrangement polymerization: turning intramolecular reaction into powerful polymerization to give enantiopure materials for Zn²⁺ sensors

Hwang

Choi

2021

Chem. Sci.

View full text Add to dashboard Cite

show abstract

Claisen thermally rearranged (CTR) polymers

Abstract: Second generation of thermally rearranged polymers presents low temperatures for a complete rearrangement.

Cited by 37 publications

References 39 publications

Gas Separation Properties of Polyimide Thin Films on Ceramic Supports for High Temperature Applications

Gas Separation Properties of Polyimide Thin Films on Ceramic Supports for High Temperature Applications

Understanding structure and composition of thermally rearranged polymers based on small‐molecule chemistry: a perspective

Tandem diaza-Cope rearrangement polymerization: turning intramolecular reaction into powerful polymerization to give enantiopure materials for Zn²⁺ sensors

Contact Info

Product

Resources

About

Claisen thermally rearranged (CTR) polymers

Abstract: Second generation of thermally rearranged polymers presents low temperatures for a complete rearrangement.

Cited by 37 publications

References 39 publications

Gas Separation Properties of Polyimide Thin Films on Ceramic Supports for High Temperature Applications

Gas Separation Properties of Polyimide Thin Films on Ceramic Supports for High Temperature Applications

Understanding structure and composition of thermally rearranged polymers based on small‐molecule chemistry: a perspective

Tandem diaza-Cope rearrangement polymerization: turning intramolecular reaction into powerful polymerization to give enantiopure materials for Zn2+ sensors

Contact Info

Product

Resources

About

Tandem diaza-Cope rearrangement polymerization: turning intramolecular reaction into powerful polymerization to give enantiopure materials for Zn²⁺ sensors