A Method for Characterizing the Chemical Heterogeneity of Comb-Copolymers and Its Dependence on Synthesis Routes

The heterogeneity in chemical structure of polymers is difficult to characterize and consequently remains an often-overlooked factor in mechanistic studies of functional polymers, as well as in their industrial scale optimization. In this study, we present a method to characterize chemical heterogeneity and apply it to illustrate how it can be affected differently in different synthesis routes. The polymers used are comb-copolymer dispersants used in particulate suspensions which are composed of a polycarboxylate backbone onto which PEG side chains are grafted. The largest use of these polymers concerns concrete, where they are referred to as poly(carboxylate ether) (PCE) superplasticizers and produced at a very large industrial scale. Apart from their practical relevance, PCEs provide a good test case for studying the means and benefits of characterizing chemical heterogeneity. Indeed, the simple addition of a UV detector to a traditional SEC setup with RI detection allowed us to monitor variations in the grafting ratio in dependence on the molecular size. We show that the synthesis pathway significantly impacts the chemical heterogeneity. The suggested method is versatile and can be adapted for a wide range of hydrophilic copolymers. Thus, we present a tool to comprehensively analyze the molecular heterogeneity of dispersants and give a deep insight into their chemical dispersity.