Structural transformations during chloromethylation of flexible polystyrene networks

Strong morphologic variations were noted in the chloromethylation of styrene copolymers incorporating TAT or DVB as crosslinking agents. In the first case control over the chloromethylation conditoins (solvent, temperature, time) can be applied in order to mold the final porous structure of the chloromethylated polymer. In the case of XE‐305 containing higher concentration of crosslinking agent, the chloromethylation conditions have a less, but still significant, effect on the structure and functional group distribution of the product. Under conditions of low ratios of chloromethylating agent (CME) or catalyst (SnCl₄), the chlorine incorporation figures are medium, but chlorine distribution through the cross section of the bead is more or less homogeneous. Increase in the above ratios results in increased chlorine concentrations, but also in higher degree of secondary crosslinking and uneven chlorine distribution profiles. Preselection of the experimental conditions enables calculated introduction of functional groups. In the case of TAT–styrene copolymers, controlled experimental conditions are used to form a porous structure with low and high chlorine distribution. Such a porous polymer can then be functionalized by other reactions. Under certain chloromethylation conditions, the chloromethylated TAT–styrene copolymer is aminated to produce anion exchange resins, without further morphological changes.