Ring‐opening polymerization of carbohydrate‐derived dialkoxyoxolanes. Approaches to functionalized poly(oxytetramethylene)s

A series of various cis‐3,4‐diacyloxy‐ and dialkyloxy‐oxolanes (4 to 14) as well as the oxolanes 16 and 17 were prepared. Ring‐opening polymerizations of the dialkyloxy derivatives 4, 6, and 11 using the super‐acids FSO3H and CF3SO3H led to novel functionalized poly[oxy(2,3‐dialkyloxy‐tetramethylene)]s. The reaction parameters were thoroughly studied, and optimum conditions lead to a DPn up to 35. All polyethers were fully assigned by polymer analytical procedures such as GPC, osmometry, 1H NMR spectroscopy and end group determination. In the case of the mixed benzyloxy methyloxy polymer 22, by subsequent hydrogenolysis a component with hydroxy functions was obtained. This procedure features a novel change of functionality in selectively derivatized polyethers originally derived from regrowing carbohydrate material.