Christian Wold

The identification and quantification of a high molecular weight light stabilizer in polycarbonate by application of an online coupling of size exclusion chromatography in stopped flow mode with pyrolysis gas chromatography time of flight mass spectroscopy

The identification and quantification of a high molecular weight light stabilizer (Uvinul 3030™) in an unknown polycarbonate sample was achieved through the application of SEC-Py-TOF-GCMS. A size exclusion column optimized to achieve resolution in the lower mass range was applied to allow the fractionation of an individual additive peak. A commercially available sampling interface was operated in stop flow mode and fractions were pyrolyzed to allow chromatographic separation of the fragments of the otherwise non-volatile stabilizer. After identification on the basis of accurate mass and elemental composition of the additive the quantification was compared using the available SEC-UV and SEC-PY-GC-TOFMS data. The resulting method provided a high degree of certainty in identification and flexibility in quantification expected to be applicable to other additives of similar volatilities or functional class.

Separation of Branched Poly(bisphenol A carbonate) Structures by Solvent Gradient at Near-Critical Conditions and Two-Dimensional Liquid Chromatography

Branching is a molecular metric that strongly influences the application properties of polymers. Consequently, detailed information on the microstructure is required to gain a deeper understanding of structure-property relationships. In the present case, we employ high-performance liquid chromatography to characterize the branching in a poly(bisphenol A carbonate) (PC). To this end, a method was developed based on a mobile phase gradient in a very narrow range (±1.4 vol %) around the point of adsorption (98.9/1.1 vol % chloroform/methyl tert-butyl ether), which we refer to as solvent gradient at near-critical conditions. Application of such gentle gradient enabled separation of PC according to end-groups. The separation mechanism was confirmed by collecting fractions of a separated sample and subsequently analyzing these by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Hyphenating the developed gradient method with size-exclusion chromatography as the second dimension (2D-LC) enabled separation of linear and branched PC chains and determination of the molar mass distribution of the fractions. A reversed elution order was observed for branched species in 2D-LC, meaning that low molar mass chains exhibited higher elution volumes in the first dimension than higher molar masses. This finding was explained by influences of end-groups as well as the architecture of the branched polymer chains.

Selective chromatographic separation of polycarbonate according to hydroxyl end-groups using a porous graphitic carbon column

Porous graphitic carbon (PGC) has shown unique separation efficiency in liquid chromatography for a wide range of substance classes. In the characterization of polymers PGC has particularly been used for analysis of polyolefins. Its retention mechanisms differ dramatically from those of silica-based stationary phases and therefore allow interesting applications. Due to its unprecedented retention mechanisms PGC does not only promise good separation performance for polyolefins but also for more polar polymers such as Polycarbonate (PC). In this study, we determined the critical conditions of PC on PGC using CHCl3/dichlorobenzene (DCB) and CHCl3/trichlorobenzene (TCB) as eluents achieving separations according to hydroxyl end-groups, which was confirmed by MALDI-TOF-MS analysis. As the content of TCB at the critical point was lower compared to that of DCB, it was concluded that TCB is a stronger desorption promoting eluent than DCB for the present system. The temperature influence on the critical point was then investigated revealing that with increasing temperature the content of desorption promoting eluent has to be raised in order to achieve critical conditions. Furthermore, a peak shifting over time was observed using TCB as desorption promoting eluent, which was attributed to irreversibly adsorbed PC on the column material. However, when a flow cell-IR detector was applied monitoring the eluted samples, a recovery rate close to 100% was found.