Mathias Hehn

Online size exclusion chromatography-NMR for the determination of molar mass distributions of copolymers.

A general approach of size exclusion chromatography (SEC)-NMR is introduced for the determination of the classical molar mass parameters M(W), M(N), and M(P). It can be used for the determination of molar mass distributions of homopolymers and copolymers. The main advantage of SEC-NMR of copolymers is the possibility of detecting each monomer unit simultaneously with NMR as a quantitative concentration detector. Therefore, it is possible to provide the chemical compositions of copolymers at any elution volume without calibrations. In this respect, a new method will be presented for getting correct signal quantities of onflow data with sufficient NMR sensitivities. As the consequence, the chemical composition of copolymers can be correctly quantified under typical chromatographic conditions with respect to sample concentration and flow rate. Finally, the molar mass calibrations of the copolymers can be easily adjusted according to their chemical compositions. The methods were applied to polystyrene-b-poly(methyl methacrylate) block copolymers of different molar masses. The results of the molar mass distributions and the chemical composition distributions obtained by SEC-NMR are in very good agreement with the complex SEC multidetector analysis.

On-line fractionated size exclusion chromatography–nuclear magnetic resonance of polymers with 1H and 2H nuclear magnetic resonance detection

A new approach for on-line SEC-NMR is introduced. The method combines time slicing, fractionation with adjusted loop collection and automatic stop-flow NMR analysis. It will be called on-line fractionated SEC-NMR. This technique allows the precise determination of molar mass distributions for any polymer which can be detected by NMR. It is a significant improvement of sensitivity and accuracy compared to onflow SEC-NMR and exhibits a much easier experimental setup than off-line SEC-NMR fractionation. The new method was applied to protonated and deuterated block copolymers by using ¹H NMR and for the first time also ²H NMR detection. In this case block copolymers can be correctly characterized according to their block length distributions. As the consequence very precise molar mass parameters M(n) and M(w) can be determined. The results of the on-line fractionated SEC-NMR are in very good agreement with the multi detector analysis. The new technique also proposes a method for separating the true copolymer and low molar mass fractions in the mixture, whose structures are confirmed by HPLC-FTIR and 2D chromatography.

Comprehensive two-dimensional liquid chromatography of stereoregular poly(methyl methacrylates) for tacticity and molar mass analysis.

For the first time, stereoregular poly(methyl methacrylates) (PMMAs) were separated according to tacticity on a carbon-based stationary phase using solvent gradient interaction chromatography (SGIC). This stationary phase provides superior separation capabilities, enabling the baseline separation of highly isotactic and syndiotactic PMMAs of different molar masses. Two-dimensional liquid chromatography was performed with the SGIC method separating, according to tacticity in the first dimension coupled to size-exclusion chromatography separating according to molar mass in the second dimension, thus providing comprehensive information on both microstructure and molar mass.

Comprehensive Triblock Copolymer Analysis by Coupled Thermal Field‐Flow Fractionation‐NMR

Thermal field-flow fractionation (ThFFF) is used as a novel fractionation technique to investigate the molecular heterogeneity of PB-b-PVP-b-PtBMA triblock copolymers. Such copolymers cause major problems in liquid chromatography due to very strong polar interactions with the stationary phase. ThFFF separates the copolymers with regard to size and/or chemical composition based on the normal and thermal diffusion coefficients. The separation mechanism in ThFFF and the chemical composition of the separated species is elucidated by online (1) H NMR. Based on the compositional analysis and a calibration of the system with the respective homopolymers, the samples are quantified regarding their molar masses, chemical compositions, and microstructures providing comprehensive information on the complex structure of these block copolymers.

Investigations of Multiple Detection of Polymers

Theoretical and experimental aspects of multiple detection analysis of polymers are critically revised for size exclusion chromatography (SEC). In particular, different combinations of detectors, the importance of the injected mass and the influence of the tacticity of polymers are evaluated in respect to the accuracy of the weight fractions of the polymer components. It is also shown how overlapping detector responses of the chemical components will affect the accuracy of the weight fractions. The calculation of the weight fractions is performed with equations derived for n different chemical components and detectors by using the slopes and intercepts of the linear response equations. Several detector combinations of dual detection in SEC are evaluated with PS-b-PMMA diblock copolymers to determine the comonomer compositions and for the first time different combinations of triple detections are performed for the determination of the weight fractions of a blend of three homopolymers, respectively. The correct determination of the weight fractions of minor and main components of polymers is strongly affected by the chosen combination of detectors, the injected mass and the intercept of the response calibrations. It is shown how these conditions have to be changed to obtain correct quantifications of the weight fractions according to the experimental setups. The experimental results are approved with online SEC-(1)H/NMR where no response factors are required.

Onflow liquid chromatography at critical conditions coupled to 1H and 2H nuclear magnetic resonance as powerful tools for the separation of poly(methylmethacrylate) according to isotopic composition

The present work addresses a major challenge in polymer chromatography by developing a method to separate and analyze polymers with identical molar masses, chemical structures and tacticities that is solely based on differences in isotope composition. For the first time, liquid chromatography at critical conditions (LCCC) was used to separate PMMA regarding the H and D isotopes. At critical conditions of H-PMMA, D-PMMA eluted in the adsorption mode and vice versa. By online onflow LCCC-NMR, both PMMA species were clearly identified. Different from other detectors, NMR can distinguish between H and D. Onflow LCCC-H/NMR and LCCC-D/NMR measurements were carried out and the H/D-blend components were detected. (1)H and (13)C NMR provided the tacticity of protonated PMMA. Double resonance (13)C{H} and triple resonance (13)C{H,D} provided the tacticity of the deuterated samples. Samples with similar tacticities were used to ensure that separation occurs solely regarding the isotope labeling.