Thermal polymerizations of alkali 4-(1-bromoethyl)benzoates

Thermal reactions of alkali salts of 4-(1-bromoethyl)benzoic acid in bulk were investigated. These reactions were found to produce unexpectedly the graft copolymer, poly(4-vinylbenzoate)-graft-oligo(oxycarbonyl-1,4-phenylenethylidene) ( 1 ). The relative reactivity of the oligocondensation as well as the vinyl polymerization of the salts decreased in the following order: K > Na > Li. The reaction polymerization rate proceeded rapidly during the initial 15 min, and then slowed down.     

Designing polymer topology by electrostatic self‐assembly and covalent fixation

A novel methodology (electrostatic self‐assembly and covalent fixation) has been proposed for designing unusual polymer topologies such as star polymers, polymacromonomers, dumbbell‐shaped polymers as well as model network polymers. Thus new telechelic polymers having moderately strained cyclic onium salt group as single or both end groups were prepared and subjected to an ion‐exchange reaction to introduce multifunctional carboxylate anions as a counter‐anion. The electrostatically self‐assembled products were then subjected, either directly or after subsequent manipulation, to heat treatment to convert the ionic interaction into the covalent linkage by the ring‐opening reaction to produce a variety of topologically unique polymer architectures in high yields.