Chemical transformations of polymers. XIII. Effect of supermolecular structure on the transformation of polyethylene with chlorosulphonic acid

The degree of transformation of polyethylene with chlorosulphonic acid depends on the number of branches. It is increased not only by using better swelling agents, but also—and prevailingly—by an increase in the amorphous portion of the starting polymer. Chlorosulphonation takes place in amorphous regions, because they are accessible to low‐molecular‐weight components and contain reactive parts of the polymer chains with tertiary carbon atoms. As the transformation proceeds, crystallinity falls down and dimensions of crystallites run low by oxidation splitting of chains.