Online Detection of Functional Groups in SEC via Quantum Cascade Laser IR Spectroscopy

Abstract

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.