Polyurethane elastomers with low modulus and hardness based on novel copolyether macrodiols

A series of copolyether macrodiols was prepared from either 1,10-decanediol or 1,6-hexanediol, by acid-catalyzed condensation polymerization using several comonomers to investigate the effect of copolymerization on reducing macrodiol crystallinity. The comonomers used to disrupt crystallinity included 2,2-diethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, and 1,7-heptanediol. The product copolyethers were identified as hydroxy terminated copoly(alkylene oxides) by ¹H- and ¹³C-NMR spectroscopy. Based on NMR results, the structures of the copolyethers were established as consisting of blocks of the principal monomer with comonomer 2,2-diethyl-1,3-propanediol incorporated to form only the end structural unit, whereas 1,4-cyclohexanedimethanol incorporated to form the end unit as well as part of the main chain. DSC results confirmed that the copolymerization produced macrodiols with lower crystallinity and lower T_g than those of the corresponding homopolyethers of the principal monomers, with two exceptions. The exceptions were 1,6-hexanediol/1,10-decanediol, and 1,10-decanediol/1,7-heptanediol copolyethers where no reduction in crystallinity was observed. A series of polyurethane elastomers with a constant hard segment percentage (40 wt %) was prepared using 4,4′-methylenediphenyl diisocyanate and 1,4-butanediol as the hard segment. Tensile test results and Shore hardness measurements demonstrated that copolyether macrodiols produced several polyurethanes with lower modulus and hardness than those of polyurethanes based on homopolyethers of the principal monomers. Of the comonomers studied, 2,2-diethyl-1,3-propanediol-based copolyether produced the polyurethane with the lowest hardness and modulus. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1373–1384, 1997