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The determination of molar masses and their distributions is crucial in polymer synthesis and design. This work presents the current performance and limitations of diffusion‐ordered spectroscopy (DOSY) on a low‐field (benchtop) NMR spectrometer (at 90 MHz) as an alternative to size exclusion chromatography (SEC) for determining diffusion coefficient distributions (DCDs) and molar mass distributions (MMDs). After optimization for narrowly distributed homopolymers, MMDs obtained with inverse Laplace transformation (ILT) and log‐normal distribution are compared with average molar masses obtained with mono‐ and bi‐exponential fits, as well as MMDs obtained from SEC. This approach enables ILT to determine DCDs and MMDs even for bimodal homopolymers with fully spectrally overlapping signals and block copolymers with various chemical compositions, for which chemical composition profiles are determined. The feasibility of low‐field diffusion NMR with samples dissolved in non‐deuterated solvents is further demonstrated and methods for solvent suppression are discussed. [ABSTRACT FROM AUTHOR]

Abstract: A state‐of‐the‐art, medium‐resolution 1H‐NMR spectrometer (62 MHz) is used as a chemically sensitive online detector for size‐exclusion chromatography of polymers such as polymethylmethacrylate (PMMA) and polystyrene (PS). The method uses protonated eluents and works at typical chromatographic conditions with trace amounts of analytes (<0.5 g L−1 after separation). Strong solvent suppression, e.g., by a factor of 500, is achieved by means of T1‐filtering and mathematical subtraction methods. Substantial improvements are made with respect to previous work in terms of the sensitivity (signal‐to‐noise ratio up to 130:1, PMMA OCH3) and selectivity (peak width, full width half maximum (FWHM) 4 Hz on‐flow). Typical homopolymers and a blend are investigated to deformulate their composition along the dimensions of molecular weight and NMR chemical shift. These results validate this new hyphenated chromatography method, which can greatly facilitate analysis and is much more effective than previously published results. [ABSTRACT FROM AUTHOR]

The development of coupled techniques based on chemically sensitive detectors, such as FTIR or NMR spectrometers, for size exclusion chromatography (SEC) provides sophisticated methods for determining the molecular-weight-dependent chemical composition in polymers. However, the detection of rare functionalities such as end groups or branching points presents a challenge, especially for online coupled SEC detection, which is based on low-concentration chromatography. To address this issue, for the first time, an external cavity quantum cascade laser (EC-QCL) infrared spectrometer is coupled to an SEC. The system is evaluated using polystyrene/poly(methyl methacrylate) (PS/PMMA) blends. The current limit of detection for the carbonyl (PMMA) stretch vibration at 1730 cm -1 with this technique is 3.5 µg PMMA on a semipreparative column (typical load of 2.5 mg polymer in total). That equals 0.15 mol% of PMMA in the PS/PMMA blend and corresponds to one carbonyl group per 70 kg mol -1 polymer., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)