Synthesis of stereoregular poly-O-methyl-[m,n]-polyurethanes derived from D-mannitol

KOLENDER, ADRIANA A.; FIDALGO, DANIELA M.; VARELA, OSCAR

Simposio; 26th International Carbohydrate Symposium; 2012

The design of new polymers with enhanced hydrophilicity and biodegradability starting from carbohydrate-derived monomers has attracted considerable attention. Carbohydrates are massive renewable resources able to provide monomers suitable for the synthesis of polycondensates. The inclusion of hydrophilic monomers into the polymer chain facilitates water attack, increasing the hydrolytic degradation of the material. Polyurethanes are useful materials with wide industrial and biomedical applications. To increase the biodegradability of these polymers, selectively protected derivatives of carbohydrates have been employed as starting materials. Thus, linear [m,n]-polyurethanes were synthesized by reaction of diisocianates with benzyl derivatives of alditols.1 In addition, to avoid the use of toxic diisocyanates, the polycondensation of alkyl diamines with 1,6-bis-Ophenoxycarbonyl derivatives of galactitol (meso form) was employed to afford polyurethanes with pendant hydroxy groups.2 Recently, we have developed a polymerization method to yield [n]-polyurethanes, in the absence of metal catalysts, which involves -amino--phenylcarbonate derivatives of alkanes or alditols as monomers.3 We report here the polycondensation of 2,3,4,5- tetra-O-methyl-1,6-di-O-phenyloxycarbonyl-D-mannitol (2) with several ,-diamines (3, 5-7) of different chain lengths, including the per-O-methyl derivative of 1,6-diamino-1,6-dideoxy-Dmannitol (3). The reaction afforded successfully the linear and stereoregular [m,n]-polyurethanes 4, 8-10. In particular, the stereoregularity of polymer 4 relies on the C2 symmetry of the chiral sugar-based comonomers 2 and 3.