Silicon Photonic Microring Resonator Arrays for Mass Concentration Detection of Polymers in Isocratic Separations.

Molecular weight distribution (MWD) is often the most informative analytical parameter in polymer analysis, with gel permeation chromatography (GPC) being the most common approach for determining the MWD for polymer samples. Many industrially relevant polymers lack chromogenic or fluorogenic signatures, precluding use of spectroscopy-based detection. Universal detectors, such as evaporative light scattering and charged aerosol detectors, are nonlinear, limiting quantitative polymer analysis. Differential refractive index (dRI) detectors show linear mass concentration sensitivity but are limited for some analyses given that they are incompatible with gradient-based separations, have a limited dynamic range, and require extended thermal equilibration times. In this study, we investigated the utility of silicon photonic microring resonator arrays as a quantitative mass concentration detector for industrial polymer analysis. Microring resonators have optical properties that are sensitive to changes in refractive index, offer an extended dynamic range, have a broad solvent compatibility, and have a linear mass concentration detection for a range of molecular weights. Linear mass concentration detection for microrings was demonstrated through a series of isocratic GPC separations using narrow MWD polystyrene (PS) standards. This detection technology was then utilized in conjunction with conventional GPC detectors to analyze a series of broad MWD PS standards, with results in good agreement with dRI and UV/visible. These results demonstrate the potential of the microring resonator platform as a detector for industrial polymer analysis.

Separating effective high density polyethylene segments from olefin block copolymers using high temperature liquid chromatography with a preloaded discrete adsorption promoting solvent barrier.

Recent advances in catalyst technology have enabled the synthesis of olefin block copolymers (OBC). One type is a "hard-soft" OBC with a high density polyethylene (HDPE) block and a relatively low density polyethylene (VLDPE) block targeted as thermoplastic elastomers. Presently, one of the major challenges is to fractionate HDPE segments from the other components in an experimental OBC sample (block copolymers and VLDPE segments). Interactive high temperature liquid chromatography (HTLC) is ineffective for OBC separation as the HDPE segments and block copolymer chains experience nearly identical enthalpic interactions with the stationary phase and co-elute. In this work we have overcome this challenge by using liquid chromatography under the limiting conditions of desorption (LC LCD). A solvent plug (discrete barrier) is introduced in front of the sample which specifically promotes the adsorption of HDPE segments on the stationary phase (porous graphitic carbon). Under selected thermodynamic conditions, VLDPE segments and block copolymer chains crossed the barrier while HDPE segments followed the pore-included barrier solvent and thus enabled separation. The barrier solvent composition was optimized and the chemical composition of fractionated polymer chains was investigated as a function of barrier solvent strength using an online Fourier-transform infrared (FTIR) detector. Our study revealed that both the HDPE segments as well as asymmetric block copolymer chains (HDPE block length≫VLDPE block length) are retained in the separation and the barrier strength can be tailored to retain a particular composition. At the optimum barrier solvent composition, this method can be applied to separate effective HDPE segments from the other components, which has been demonstrated using an experimental OBC sample.

Toward absolute chemical composition distribution measurement of polyolefins by high-temperature liquid chromatography hyphenated with infrared absorbance and light scattering detectors.

Chemical composition distribution (CCD) is a fundamental metric for representing molecular structures of copolymers in addition to molecular weight distribution (MWD). Solvent gradient interaction chromatography (SGIC) is commonly used to separate copolymers by chemical composition in order to obtain CCD. The separation of polymer in SGIC is, however, not only affected by chemical composition but also by molecular weight and architecture. The ability to measure composition and MW simultaneously after separation would be beneficial for understanding the impact of different factors and deriving true CCD. In this study, comprehensive two-dimensional chromatography (2D) was coupled with infrared absorbance (IR5) and light scattering (LS) detectors for characterization of ethylene-propylene copolymers. Polymers were first separated by SGIC as the first dimension chromatography (D1). The separated fractions were then characterized by the second dimension (D2) size exclusion chromatography (SEC) with IR5 and LS detectors. The concentrations and compositions of the separated fractions were measured online using the IR5 detector. The MWs of the fractions were measured by the ratio of LS to IR5 signals. A metric was derived from online concentration and composition data to represent CCD breadth. The metric was shown to be independent of separation gradients for an "absolute" measurement of CCD breadth. By combining online composition and MW data, the relationship of MW as a function of chemical composition was obtained. This relationship was qualitatively consistent with the results by SEC coupled to IR5, which measures chemical composition as a function of logMW. The simultaneous measurements of composition and MW give the opportunity to study the SGIC separation mechanism and derive chain architectural characteristics of polymer chains.