Intramolecularly crosslinked polystyrene as model of a supercrosslinked network

Globular soluble intramolecularly crosslinked polystyrene (PS) was prepared both by reaction of individual PS coils with monochlorodimethylether in the presence of tin chloride, and by reaction of chloromethyl groups in previously chloromethylated coils with the phenyl rings of the same macromolecule. The concentration of the initial polymer solution subjected to intramolecular crosslinking was 0.1–0.5%. By viscometric, electron microscopic and GPC methods it was established that the globules represent individual PS macromolecules strengthened by a large number of intramolecular crosslinks. The globules of intramolecularly crosslinked PS exhibit the same properties as supercrosslinked PS networks: their internal specific surface reaches 800–1000 m²/g and they can swell in methanol. The equivalence of these unusual properties directly proves that they result from the specific features of supercrosslinked structures at molecular level.