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Well-defined benzoxazine/triphenylamine-based hyperbranched polymers with controlled degree of branching.

ABSTRACT: Well-defined thermally polymerizable hyperbranched polymers (TPA-BZs) containing various numbers of triphenylamine (TPA) and benzoxazine (BZ) units have been prepared using a "click-like" reaction concept, through one-pot Mannich condensations of 4-(bis(4-aminophenyl)amino)phenol (TPA-2NH₂-OH, as the AB₂ branching groups), aniline (as the focal groups), CH₂O, and phenol in 1,4-dioxane, with a unique feeding approach. Two design strategies for the chemical construction were applied: (i) simple hyperbranched TPA-BZs, such as those containing one or three TPA units, developed from the focal or the terminal group direction to form the resultant monomers; (ii) three dendritic TPA-BZs containing four TPA units possessing different degrees of branching (DBs) for the conformation study. The exothermic temperature for the dendritic TPA-BZs decreased upon increasing the DB. The bathochromic shifts of the dendritic TPA-BZs increased upon increasing the number of TPA units, in UV-Vis absorption and PL emission spectra, presumably because of an increase in the effective conjugation length. In addition, the polymerized dendritic TPA-BZ DG1 possessed thermal properties superior to those of the hyperbranched TPA-BZ polybenzoxazines, possibly because the segmental mobility in the polymer network was restricted by the dendrimer core group and because of its symmetrical construction. The hyperbranched TPA-BZ possessed unique photophysical properties, suggesting potential applications in optoelectronic devices.

SUBMITTER: Lin RC

PROVIDER: S-EPMC9079809 | biostudies-literature | 2018 Apr

REPOSITORIES: biostudies-literature

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Well-defined benzoxazine/triphenylamine-based hyperbranched polymers with controlled degree of branching.

Lin Ruey-Chorng RC Kuo Shiao-Wei SW

RSC advances 20180411 24

Well-defined thermally polymerizable hyperbranched polymers (TPA-BZs) containing various numbers of triphenylamine (TPA) and benzoxazine (BZ) units have been prepared using a "click-like" reaction concept, through one-pot Mannich condensations of 4-(bis(4-aminophenyl)amino)phenol (TPA-2NH2-OH, as the AB2 branching groups), aniline (as the focal groups), CH2O, and phenol in 1,4-dioxane, with a unique feeding approach. Two design strategies for the chemical constru ...[more]

PMID: 35542500

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Project description:Application of redox-active polymers (RAPs) in redox flow batteries (RFBs) can potentially reduce the stack cost through substitution of costly ion-exchange membranes by cheap size-exclusion membranes. However, intermolecular interactions of polymer molecules, i.e., entanglements, particularly in concentrated solutions, result in relatively high electrolyte viscosities. Furthermore, the large size and limited mobility of polymers lead to slow diffusion and more sluggish heterogeneous electron transfer rates compared to quickly diffusing small molecules. Although a number of RAPs with varying electrolyte viscosities have been reported in the literature, the relation between the RAP structure and the hydrodynamic properties has not been thoroughly investigated. Herein, hyperbranched 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO)-based polymers intended for application as low-viscosity catholytes for RFBs are presented and the influence of the structure and the molar mass distribution on the hydrodynamic properties is investigated. A new synthesis approach for TEMPO-based polymers is established based on step-growth polymerization of a TEMPO-containing monomer using an aza-Michael addition followed by a postpolymerization modification to improve solubility in aqueous solutions. The compact structure of hyperbranched polymers was demonstrated using size-exclusion chromatography (SEC) with viscometric detection and the optimum molar mass was found based on the results of viscometric and crossover investigations. The resulting RAP revealed a viscosity of around 21 mPas at a concentration corresponding to around 1 M TEMPO-containing units, according to the calculated mass of the repeating unit, showing potential for high capacity polymer-based catholytes for RFBs. Nevertheless, possible partial deactivation of TEMPO units lowered the active TEMPO concentration of the hyperbranched RAPs. A faster diffusion and higher charge transfer rate were observed for the hyperbranched polymer compared to the previously reported linear polymers. However, in RFB tests, a poor performance was observed, which is attributed to the side reactions of the oxidized TEMPO moieties. Finally, pathways for overcoming the main remaining challenges, i.e., high loss of material during dialysis as an indication of being prone to crossover, the partial deactivation of TEMPO moieties, and the subsequent side reactions under battery conditions, are suggested.

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Well-defined benzoxazine/triphenylamine-based hyperbranched polymers with controlled degree of branching.

Publications

Well-defined benzoxazine/triphenylamine-based hyperbranched polymers with controlled degree of branching.

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