Study on the feasibility of TLC/FID to reveal chemical composition distributions of copolymers obtained by emulsion processes

The CCD (chemical composition distribution) of poly(styrene-co-ethyl methacrylate) has been determined by thin layer chromatography/flame ionization detection (TLC/FID). It appeared that a mixture of five reference copolymers obtained by solution polymerization each having a narrow CCD, could be separated in five distinct peaks, provided a modified spotting procedure and a concentration gradient elution technique were applied. All copolymers prepared by solution polymerization could be successfully characterized. Copolymers obtained by emulsion techniques using nonionic or anionic surfactants containing oxyethylene groups, or in the absence of chain length modifier behaved anomalously and appeared to have spurious CCD's. Also the average composition calculated from these CCD's did not agree with the average composition determined by 1H-NMR. This anomalous behaviour disappeared when using sodium lauryl sulfate as surfactant or when applying a chain length modifier (n-dodecyl mercaptan) during the preparation of the polymer. Several possibilities have been proposed in order to explain these phenomena. The most probable explanation seems to be reaction of a growing polymer chain with surfactant molecules resulting in a quasi-terpolymer. This polymer containing highly polar oxyethylene groups, remains strongly adsorbed on the silica surface during elution, thus disturbing the separation process

Anomalous copolymerization behavior of styrene and ethyl methacrylate at high conversion

Styrene and ethylmethacrylate were copolymerized in bulk at 62°C and several monomer feed ratios. At moderately high conversion, anomalous copolymerization behaviour occurred. Although the onset of the departures from expected copolymerization behaviour seems to be related to the onset of the gel-effect, this relation did not hold when mimicking higher conversion by adding an amount of homopolymer. Obviously the propagation reactions are not only affected by changes in diffusion characteristics but also by changes in other medium characteristics e.g. interactions between monomeric and copolymeric species. This investigation was supported by The Netherlands Foundation for Chemical Research (SON) with financial aid from The Netherlands Organization for advancement of Pure Research (ZWO)

Anomalous copolymerization behavior of styrene and ethyl methacrylate at high conversion

Styrene and ethylmethacrylate were copolymerized in bulk at 62°C and several monomer feed ratios. At moderately high conversion, anomalous copolymerization behaviour occurred. Although the onset of the departures from expected copolymerization behaviour seems to be related to the onset of the gel-effect, this relation did not hold when mimicking higher conversion by adding an amount of homopolymer. Obviously the propagation reactions are not only affected by changes in diffusion characteristics but also by changes in other medium characteristics e.g. interactions between monomeric and copolymeric species. This investigation was supported by The Netherlands Foundation for Chemical Research (SON) with financial aid from The Netherlands Organization for advancement of Pure Research (ZWO)