High-temperature High-performance Liquid Chromatography Research Articles

Unraveling the comonomer distribution in ethylene – vinyl ester terpolymers through liquid chromatography with infrared detection

Polyolefins are the most commercially relevant polymers by volume. A readily available feedstock and their tailor-made microstructure allow to adapt polyolefins to many fields of application. Important molecular design features of olefin copolymers are the molar mass distribution (MMD) with the corresponding average values, comonomer type, chemical composition distribution (CCD) with the corresponding average and the tacticity distribution (TD). Advanced separation techniques i.e., high-temperature gel permeation chromatography (HT-GPC) as well as its hyphenation with high-temperature high performance liquid chromatography (HT-HPLC) in the form of high-temperature two-dimensional liquid chromatography (HT 2D-LC) have been successfully applied in this work. This allowed to deeply analyze the molecular heterogeneities of complex polyolefin terpolymers consisting of ethylene, vinyl acetate and branched vinyl ester monomers. By using filter-based infrared detection, the capabilities of HT-GPC are further extended so that the distribution of methyl- and carbonyl groups could be obtained along the molar mass axis. Using porous graphitic carbon (PGC) as a stationary phase for HT-HPLC separation provided information about the CCD of these complex polyolefins from experimental data as part of the hyphenated approach of HT 2D-LC. The latter revealed the full MMD x CCD distribution function, which is the key for a comprehensive analysis of the bivariate molecular structure of the polyolefin terpolymers.

Characterization of the chemical composition distribution of polyolefin plastomers/elastomers (ethylene/1-octene copolymers) and comparison to theoretical predictions

Ethylene/1-olefin copolymers with a 1-olefin content >10 wt%, known as polyolefin plastomers (POP) and elastomers (POE), are materials of growing commercial importance. A relevant example are ethylene/1-octene (EO) copolymers. The thermal properties of nine 1-octene based POP/POE were studied by differential scanning calorimetry (DSC). The obtained thermograms were indicative of an asymmetric chemical composition distribution (CCD), triggering further investigations. At first, analytical temperature rising elution fractionation (a-TREF) was employed which gave further evidence of an asymmetric CCD for some samples. Given the low crystallinity of many of the samples, their CCD could, however, only be studied by high temperature high performance liquid chromatography (HT-HPLC). The hypothesis about an asymmetric CCD could be confirmed for all samples. The results were compared with theoretically calculated CCD (Stockmayer distributions) which are symmetrical. In a semiquantitative comparison, the main peak of the experimental CCD was found to be in good agreement with Stockmayer distributions.

Separation of maleic anhydride grafted polypropylene using multidimensional high-temperature liquid chromatography

Functionalization addresses a property gap of polyolefins and opens new perspectives due to improved surface properties in applications like composites (e.g., glass fiber reinforced polypropylene) and anti-corrosive coatings for metals. Various techniques have been developed to characterize functionalized polyolefins, yet no analytical approach addressing their chemical heterogeneity exists. Using High Temperature Size Exclusion Chromatography (HT-SEC) coupled to infrared spectroscopy we could show for two model samples of polypropylene grafted maleic anhydride (PP-g-MA), differing in their nominal MA content, that the grafting density increases with decreasing molar mass. Crystallization Analysis Fractionation (CRYSTAF) does not enable to separate these samples according to their composition to the extent required. Yet, when using High Temperature High Performance Liquid Chromatography (HT-HPLC), with either silica gel or Mica as stationary phase and a gradient mobile phase, a deformulation into a grafted and a non-grafted fraction could be achieved. This was confirmed by analyzing the eluted fractions by infrared spectroscopy. Hyphenating the separation according to composition with a separation according to molar mass (HT-HPLC x HT-SEC) enabled for the first time to reveal the bivariate distribution of PP-g-MA with regard to the molar mass and composition. Using on-line infrared detection quantitative information on the compositional and molar mass parameters of the individual fractions could be obtained.

High-temperature high-performance liquid chromatography on a porous graphitized carbon column coupled to an Orbitrap mass spectrometer with atmospheric pressure photoionization for screening exogenous anabolic steroids in human urine.

The presence in a urinary matrix of a large number of endogenous steroids and corticosteroids with similar structures can hamper the detection of specific exogenous steroids using liquid chromatography/mass spectrometry (LC/MS) with reversed-phase columns. Therefore, the development of LC/MS methods using alternative columns is of great interest. Porous graphitized carbon is a unique stationary phase for high-performance liquid chromatography (HPLC), with properties differing from traditional silica-based and polymeric stationary phases. The new method involves enzymatic hydrolysis, liquid-liquid extraction, and determination by high-temperature HPLC/Orbitrap mass spectrometry (HTLC/Orbitrap MS) with atmospheric pressure photoionization (APPI). To achieve APPI of doping substances, the mobile phase consisted of 0.1% CF3COOH (A) and a mixture of acetonitrile/2-propanol (25:75 v/v), containing 0.1% CF3COOH (B), which was used as an effective proton source. A screening method for the detection of 57 exogenous steroids has been developed. The method was validated by spiking 10 different blank urine samples at different concentration levels. Validation parameters included limit of detection (LOD), selectivity, ion suppression, extraction recovery, and repeatability. All studied compounds had an LOD lower than the minimum required performance level. Of the 57 steroids studied, 55 showed recovery better than 70%. For all of the analytes, the relative retention times proved to be stable between days, with relative standard deviations (RSDs) smaller than 0.3%. In addition, the interday RSDs of the peak area ratios ranged between 0.7% and 14.5%. The proposed method matches the basic requirements of all methods used to analyze drugs or metabolites in an antidoping laboratory, i.e., sensitivity, selectivity, and specificity. The acquisition of full-scan mass spectra with accurate masses can be a valuable tool in the retrospective evaluation of analyzed samples for anabolic steroids recently added to the prohibited list.

On the Homogeneity of Metallocene Ethylene–Propylene Copolymers as Investigated by Multiple Fractionation Techniques

The chemical heterogeneity of ethylene–propylene copolymers by multiple fractionation techniques is addressed. Three metallocene copolymer samples with different ethylene contents, ranging from 30 to 50 mol% are analyzed using bulk methods to confirm their molecular heterogeneity. In a second step, the samples are fractionated by temperature rising elution fractionation (TREF) to obtain fractions at 30, 60, 90, and 130 °C. These fractions are subsequently analyzed regarding their thermal and molecular properties. Differential scanning calorimetry, crystallization analysis fractionation, and high‐temperature high performance liquid chromatography (HT‐HPLC) results reveal that the TREF fractions collected at 130 °C are mainly due to polypropylene homopolymer, which is rather unexpected considering the high ethylene contents of the bulk samples. Most importantly, HT‐HPLC reveals a remarkably high chemical heterogeneity of the fractions and thus the bulk samples. Solution 13C NMR provides the comonomer contents and sequence distributions of the fractions. These indicate that the same TREF fractions from different samples have distinctively different chemical compositions. image

On the multimodality of preparative TREF fractionation as detected by advanced analytical methods.

Preparative temperature rising elution fractionation (prepTREF) is the standard technique for the preparative fractionation of polyolefins according to crystallisability. For olefin copolymers such as linear low-density polyethylene (LLDPE), it was believed that the TREF elution temperature correlates directly with the copolymer composition. For copolymers having different bulk comonomer contents, the prepTREF fractions of different samples collected at a given temperature were assumed to have the same chemical composition. It was acknowledged quite early that co-crystallisation effects may disturb TREF fractionation and fractions are obtained that are not completely homogeneous. This, however, has not been investigated quantitatively so far. The fundamental statement of prepTREF is challenged for the first time quantitatively using advanced analytical techniques including high-temperature high-performance liquid chromatography (HPLC). Ethylene-1-octene copolymers having bulk comonomer contents ranging from 0.3 to 6.4mol% were fractionated by prepTREF, and the fractions were analysed by high-temperature size exclusion chromatography, crystallisation analysis fractionation, differential scanning calorimetry and high-temperature HPLC. All analytical results prove that the TREF fractions collected from different samples at the same elution temperature have different chemical compositions. The chemical compositions of the fractions correlate with the compositions of the bulk samples in that the comonomer contents of similar TREF fractions increase with an increase of the comonomer content of the bulk samples. These results are in clear contrast to the previous assumption that the TREF fraction composition is independent of the bulk copolymer composition for a given copolymer type. Graphical abstract Advanced analysis of LLDPE by combination of HT-HPLC, DSC and CRYSTAF.

Molecular heterogeneity of ethylene-propylene rubbers: New insights through advanced crystallization-based and chromatographic techniques

For a long time ethylene-propylene rubber (EPR) copolymers with high comonomer contents were believed to be amorphous materials with a random copolymer composition. This is not completely correct as has been shown by temperature rising elution fractionation (TREF) combined with differential scanning calorimetry (DSC), crystallization analysis fractionation (CRYSTAF), and high temperature–high-performance liquid chromatography (HT-HPLC). When using only conventional crystallization-based fractionation methods, the comprehensive compositional analysis of EPR copolymers was impossible due to the fact that large fractions of these copolymers do not crystallize under CRYSTAF conditions. In the present work, HT-HPLC was used for the separation of the EPR copolymers according to their ethylene and propylene distributions along the polymer chains. These investigations showed the existence of long ethylene sequences in the bulk samples which was further confirmed by DSC. The results on the bulk samples prompted us to conduct preparative fractionations of EPR copolymers having varying ethylene contents using TREF. Surprisingly, significant amounts of crystallizing materials were obtained that were analyzed using a multistep protocol. CRYSTAF and DSC analyses of the TREF fractions revealed the presence of components with large crystallizable sequences that had not been detected by the bulk samples analyses. HT-HPLC provided a comprehensive separation and characterization of both the amorphous and the crystalline TREF fractions. The TREF fractions eluting at higher temperatures showed the presence of ethylene-rich copolymers and PE homopolymer. In order to obtain additional structural information on the separated fractions, HT-HPLC was coupled to Fourier transform-infrared (FT-IR) spectroscopy. The FT-IR data confirmed that the TREF fractions were separated according to the ethylene contents of the eluted samples. Preparative TREF analysis together with a combination of various analytical methods proved to be useful tools in understanding the complex molecular composition of these rubber samples. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 863–874

One-Step Method for Separation and Identification of n-Alkanes/Oligomers in HDPE Using High-Temperature High-Performance Liquid Chromatography

n-Alkanes are often an important ingredient of waxes, oils, gasoline, and a byproduct in polyolefins. Separation and identification of alkanes in commercial high-density polyethylene (HDPE) are of vital importance from various points of view. Currently used chromatographic techniques require extraction and laborious preconcentration. Porous graphite Hypercarb as a stationary phase in high-performance liquid chromatography (HPLC) in combination with a mobile phase gradient n-decane → 1,2-dichlorobenzene (ODCB) enables a selective separation of C40–C160 n-alkanes at temperatures between 100 and 160 °C. Thus, it is possible to resolve the individual alkanes in HDPE of 1 kg/mol. An unambiguous assignment of the individual homologues in the chromatogram was possible by doping the HDPE with a C60 standard, and the results were also confirmed by MALDI TOF. Using this method, the presence of alkanes in a HDPE sample with a weight-average molar mass of 70 kg/mol could be shown. n-Hexane as isocratic mobile phase e...

Influence of temperature on peak shape and solvent compatibility: Implications for two‐dimensional liquid chromatography

Solvent compatibility is a limiting factor for the success of two-dimensional liquid chromatography (2-D LC). In the second dimension, solvent effects can result in overpressures as well as in peak broadening or even distortion. A peak shape study was performed on a one-dimensional high-performance liquid chromatography (HPLC) system to simulate the impact of peak distorting solvent effects on a reversed-phase second dimension separation operated at high temperatures. This study includes changes in injection volume, solute concentration, column inner diameter, eluent composition and oven temperature. Special attention was given to the influence of high temperatures on the solvent effects. High-temperature HPLC (HT-HPLC) is known to enhance second dimension separations in terms of speed, selectivity and solvent compatibility. The ability to minimise the viscosity contrast between the mobile phases of both dimensions makes HT-HPLC a promising tool to avoid viscosity mismatch effects like (pre-)viscous fingering. In case of our study, viscosity mismatch effects could not be observed. However, our results clearly show that the enhancement in solvent compatibility provided by the application of high temperatures does not include the elimination of solvent strength effects. The additional peak broadening and distortion caused by this effect is a potential error source for data processing in 2-D LC.

High Temperature Interaction Chromatography of Olefin Copolymers

AbstractSummary: The synthesis and characterization of polyolefins continues to be one of the most important areas for academic and industrial polymer research. One consequence of the development of new “tailor‐made” polyolefins is the need for new and improved analytical techniques for the analysis of polyolefins with respect to molar mass and chemical composition distribution. The present article briefly reviews different new and relevant chromatographic techniques for polyolefin analysis. For the fast analysis of the chemical composition distribution of polyolefins a new high‐temperature gradient high‐performance liquid chromatography (HPLC) system has been introduced. The efficiency of this system for the separation of various olefin copolymers is demonstrated. The correlation between elution volume and chemical composition can be accessed by on‐line coupling of high temperature HPLC with FTIR spectroscopy. For the elucidation of the chemical composition as a function of molar mass high‐temperature size exclusion chromatography and 1H‐NMR spectroscopy can be coupled. It is shown that the on‐line NMR analysis of chromatographic fractions yields information on microstructure and chemical composition in addition to molar mass distribution.

Solvent-resistant sol–gel polydimethyldiphenylsiloxane coating for on-line hyphenation of capillary microextraction with high-performance liquid chromatography

A sol–gel polydimethyldiphenylsiloxane (PDMDPS) coating was developed for capillary microextraction on-line hyphenated with high-performance liquid chromatography (HPLC). This coating was created using methyltrimethoxysilane (MTMS) as the sol–gel precursor and di-hydroxy-terminated PDMDPS as the sol–gel active polymer. The methyl and phenyl groups on the sol–gel active polymer and the methyl groups on the sol–gel precursor ultimately turned into pendant groups providing the ability to extract non-polar analytes. A 40-cm segment of 0.25 mm I.D. fused silica capillary containing the sol–gel PDMDPS coating was installed as an external sampling loop in an HPLC injection port. Aqueous samples containing polycyclic aromatic hydrocarbons (PAHs), aromatic compounds, ketones, and aldehydes were passed through this capillary wherein the analytes were extracted by the sol–gel coating. The extracted analytes were then transferred to the HPLC column using isocratic or gradient elution with an acetonitrile/water mobile phase. This capillary demonstrated excellent extraction capability for non-polar (e.g., polycyclic aromatic hydrocarbons and aromatic compounds) as well as moderately polar compounds, such as aromatic amines, ketones, and aldehydes. The test results indicate that PDMDPS can be successfully immobilized into a sol–gel network and that the resulting solvent-resistant sol–gel organic-inorganic hybrid coating can be effectively used for on-line hyphenation of capillary microextraction with high-performance liquid chromatography. The test results also indicate that the sol–gel PDMDPS coated capillary is resistant to high-temperature solvents, making it suitable for applications in high-temperature HPLC. To the best of our knowledge, this is the first report on the creation of a silica-based sol–gel PDMDPS coating used in capillary microextraction on-line hyphenated to HPLC.