title: Synthesis and characterization of poly-O-methyl-[n]-polyurethane from a d-glucamine-based monomer.
abstract: Aminoalditol 1-amino-1-deoxy-D-sorbitol (1) was readily converted into 2,3,4,5-tetra-O-methyl derivative 5, a key precursor of a sugar-based [n]-polyurethane. For the polymerization, the free amino or primary hydroxyl groups of 5 were selectively activated and employed as starting monomers in two alternative procedures. Thus, the amino function of 5 was converted into the isocyanate derivative by treatment with di-tert-butyltricarbonate, and polymerized in situ in the presence of Zr(IV) acetylacetonate. The resulting poly(1-amino-1-deoxy-2,3,4,5-tetra-O-methyl-D-sorbitol)urethane (8) had a moderate molecular weight and showed the presence of urea units. The alternative synthesis of 8 involved the activation of the free hydroxyl group of 5 as the corresponding phenylcarbonate. The polymerization of this α-amino-ω-phenylcarbonate alditol monomer does not require a metal catalyst. The resulting material exhibited an improved molecular weight and higher purity than that obtained via the isocyanate. [n]-polyurethane 8 was highly soluble in water as well as in common organic solvents (chloroform, acetone, ethyl acetate, etc) and was obtained as an amorphous material which was characterized thermally and spectroscopically.
authors.affiliation: CIHIDECAR-CONICET, Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 2, Ciudad Universitaria, 1428 Buenos Aires, Argentina.
authors.forename: Adriana A
authors.initials: AA
authors.lastname: Kolender
authors.forename: Silvina M
authors.initials: SM
authors.lastname: Arce
authors.forename: Oscar
authors.initials: O
authors.lastname: Varela
mesh_terms: D000588:Amines / Q000737:chemistry; D001673:Biodegradation, Environmental; D002254:Carbonates / Q000737:chemistry; D002625:Chemistry, Organic / Q000379:methods*; D002850:Chromatography, Gel; D017953:Isocyanates / Q000737:chemistry; D058105:Polymerization; D011140:Polyurethanes / Q000138:chemical synthesis*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D013237:Stereoisomerism; D013402:Sugar Alcohols / Q000737:chemistry; D013818:Thermogravimetry
chemical_list: D000588:Amines; D002254:Carbonates; D017953:Isocyanates; D011140:Polyurethanes; D013402:Sugar Alcohols