No abstract

The emulsion polymerization of butyl acrylate was monitored by online nuclear magnetic resonance spectroscopy at 20 MHz 1H frequency. The reaction progress could be followed, monitoring the conversion of the reactant time-resolved without any need of sample preparation. Experimental data were analyzed with kinetic models for free-radical polymerization. The data comprised the polymerization rate in seeded batch emulsion polymerizations of butyl acrylate with doubly deionized water and D2O as solvent. The polymerization rate versus conversion curve behaves compatible with the three rate intervals model, typically observed in emulsion polymerizations. Zero−one kinetics explains the experimental results appropriately, leading to the determination of entry and termination rate coefficients.

Current results and limitations of a novel SEC–MR–NMR (size‐exclusion chromatography–medium resolution nuclear magnetic resonance) system are presented, delivering a direct correlation of chemical structure and molecular weight. A 20 MHz 1H NMR spectrometer based on permanent magnets was combined with a SEC setup. The NMR sensitivity was improved by digital filters, shims, and a self‐built flow probe when compared with time‐domain instruments. For optimum NMR signal‐to‐noise ratio (S/N) of polymer fractions and concomitantly reduced S/N of solvent signals, deuterated solvents or protonated solvents, with solvent suppression, were applied. Results are presented after optimization of both NMR and chromatographic components such as column dimension and volume flow.

Online coupling of size exclusion chromatography together with medium resolution nuclear magnetic resonance (SEC-MR-NMR) might be one solution to the problem of chemically sensitive detection in liquid polymer chromatography. By use of a combination of SEC with a table-top, specially designed 20 MHz NMR spectrometer, based on a permanent magnet, online (1) H NMR spectra of SEC fractions can be obtained. The integration of digital filters, mechanical shims and electronic shims led to substantially improved sensitivity and chemical selectivity compared to former TD (time domain) 20 MHz instruments. (1) H NMR spectra of PMMA and PS homopolymers as well as PS-PMMA block copolymers were of sufficient quality to enable detection and de-formulation of unknown polymer compounds. (1) H NMR spectra of acceptable resolution and S/N ratio were collected online during the chromatography. The SEC separation online with the NMR measurements performed well and resulted in the proof of principle of the SEC-MR-NMR combination.