Nucleophilic displacements upon poly(vinylbenzyl chloride)

High molecular weight poly(vinylbenzyl chloride) fails to undergo many classical organic reactions, but may be reacted essentially quantitatively with a variety of tert‐amines to yield the corresponding quaternary polymers. With dimethyl‐n‐alkylamines, polymers of the type are formed; these are water‐soluble through R = n‐decyl and methanol‐soluble through R = n‐hexadecyl. A number of polyridines and dialkyl sulfides react similarly to yield the corresponding polycationics. These reactions are controlled by several factors not operative in small‐molecule reactions: nucleophile partitioning in the initially heterogeneous systems, swelling power of the medium for the reactant polymer, and a sharp steric limitation imposed by the configuration of the high polymer. This steric effect may be exploited by using certain hindered primary and secondary amines to prepare substituted poly‐(vinylbenzylamines) which are soluble and noncrosslinked.