Variable temperature asymmetric flow field-flow fractionation for the topology separation of poly(methyl methacrylate)

Size exclusion chromatography is the method of choice for the molar mass analysis of polymers, however, it is not selective towards polymer microstructure. Counterintuitively, asymmetric flow field-flow fractionation (AF4), a channel-based molar mass analysis technique, has been shown to be able to fractionate poly(methyl methacrylate (PMMA) according to tacticity. This was revealed by investigating the solution behaviour of syndiotactic- (s-PMMA), atactic- (a-PMMA) and isotactic (i-PMMA) poly(methyl methacrylate) of similar molecular masses in solvents with different thermodynamic properties. In addition to developing a selective fractionation method, the effects of solvent quality and channel temperature on the fractionation were investigated. It was concluded that the thermodynamic quality of the carrier liquid has a significant influence on the retention behaviour of polymers in AF4. It was shown that the separation of s-PMMA and i-PMMA can be improved by using a theta solvent (acetonitrile) as the carrier liquid instead of thermodynamically good solvents such as tetrahydrofuran and chloroform. In addition, it was found that by using a non-stereocomplexing solvent for PMMA, such as chloroform, blends of s-PMMA and i-PMMA can be separated. Lastly, it was established that the AF4 channel temperature has an influence on the retention behaviour of the PMMA samples. For THF as carrier liquid it was found that the maximum difference in retention between s-PMMA and i-PMMA can be achieved at a channel temperature of 35 °C. In the case of ACN being the carrier liquid, it was observed that the retention behaviour of i-PMMA was significantly more influenced by a change in temperature as compared to s-PMMA and a-PMMA.