There are many publications on dioxolane's use as a monomer or co-monomer in the formation of polyacetals. We can only describe the basic chemistry here.
Most polymerizations involving dioxolane, either with itself or with aldehydes and ethers, proceed via a cationic mechanism, using strong Lewis acids such as BF3-etherate, SbF5, HCIO4, CF3SO3H, AsF5, etc.
For homopolymerization:
HO-(CH2-CH2-O-CH2-O-)nH
Used as a comonomer with formaldehyde to produce stable POMs – Polyoxymethylene:
CH2O-HO-CH2-O-CH2-CH2-(O-CH2-)nOH
It is also used as a co-monomer with formaldehyde homologs such as tetraoxane, 1,3,5 trioxane and trioxepane. Dioxolane can copolymerize with THF. To prepare polyacetals with improved lubricating properties, dioxolane can be oligomerized with stearaldehyde, then mixed with a high MW trioxane-dioxolane copolymer. Cationically active polydioxolane when mixed with polystyrene will form grafts with no gel.