|
Authors
|
Muza, U. L.; Smith, M.-P.; Johani, J. T.; Klumperman, B.; Lederer, A.
|
|
Title
|
Introduction of temperature-gradient elution in three-dimensional correlation thermal field-flow fractionation with quintuple detection for monitoring compositional dynamics of ultrahigh-molar-mass poly(styrene-co-maleic anhydride)
|
|
Date
|
01.01.2026
|
|
Number
|
0
|
|
Abstract
|
Analogous to temperature-gradient interaction chromatography, temperature-gradient elution three-dimensional correlation thermal field-flow fractionation (TGE-3DCoTF3) coupled with quintuple-detection provides high-resolution analysis of ultrahigh-molar-mass poly(styrene-co-maleic anhydride) synthesized via biradical photoinitiation. TGE-3DCoTF3 resolves more than 3 orders of magnitude in molar-mass, cleanly separating residual monomers and oligomers from megadalton copolymers while preserving their integrity. Multidetector correlation yields molar-mass, three independent radii, intrinsic viscosity, diffusion coefficient, thermal diffusion coefficient (DT) and UV–vis spectra. Differential UV–vis absorptivity distinguishes unreacted monomers from copolymers, enabling conversion analysis. DT serves as a pseudospectroscopic probe, confirming constant styrene-to-maleic anhydride ratios and truly alternating copolymerization. Comparative analysis of “lower” and “higher” ultrahigh-molar-mass copolymers differing by a factor of 2 in degrees of polymerization reveals identical thermophoretic behavior but distinct coil compactness, evidencing transitions toward denser core–shell morphology. Collectively, TGE-3DCoTF3 offers a nondestructive, multidimensional benchmark for elucidating molar-mass, size, and compositional dynamics in polymers that challenge conventional SEC characterization.
|
|
Publisher
|
American Chemical Society
|
|
Wikidata
|
|
|
Citation
|
ACS Macro Letters 15 (2026) 46-52
|
|
DOI
|
https://doi.org/10.1021/acsmacrolett.5c00593
|
|
Tags
|
|
