화학공학소재연구정보센터
Journal of Industrial and Engineering Chemistry, Vol.19, No.1, 113-119, January, 2013
Effect of the hydrogen bonding on the inelasticity of thermoplastic polyurethane elastomers
E-mail:
The effect of hydrogen bonding on the cycling tensile responses of thermoplastic polyurethane elastomers (TPUs) was followed. Hydrogen substitution was carried out by replacing the usual fully hydrogenated forms of the diol chain extender diethylene glycol (DEGh) or of the macrodiol polytetrahydrofurane (PTHFh) with their fully deuterated analogues DEGd and PTHFd. The TPUs segmental orientation was followed by means of infrared dichroic measurements. The hard segment (crystallizing or not) was varied by inclusion of a conventional rigid diisocyanate, 4,40-diphenyl methane diisocyanate (MDI) and of an isocyanate with a large conformational mobility 4,40-dibenzyl diisocyanate (DBDI). Inelastic effects were most pronounced when the hard segment crystallized. Irrespective of the isotopic forms of the chain extender and macrodiol used in the material synthesis, the residual strain and hysteresis energy dissipation were highest for hard segments of DBDI than of MDI. While the TPUs derived from DEGd were more resilient than the similar polymers obtained with the DEGh, there were no significant differences between the resilience of the TPUs achieved with the PTHFh and PTHFd. A quantitative correlation was found between the magnitude of the Mullins effect and the fractional energy dissipation by hysteresis under cyclic straining, giving a common relation that was approached by all the materials studied. The results provide new perspectives into the physical origin of inelastic effects in reinforced elastomers.
  1. Petrovic´ ZS, in: Kricheldorf HR, Nuyken O, Swift G (Eds.), Handbook of Polymer Synthesis, second ed., Marcel Dekker, Inc., New York, 512 (2005)
  2. Yu XH, Nagarajan MR, Grasel TG, Gibson PE, Cooper SL, Journal of Polymer Science Part B: Polymer Physics., 23, 2319 (1985)
  3. Brunette CM, Hsu SL, MacKnight WJ, Macromolecules., 15, 71 (1982)
  4. Petrovic´ ZS, Ferguson J, Progress in Polymer Science., 16, 695 (1991)
  5. Oertel G, Polyurethane Handbook, Hanser Publishers, Munich (1985)
  6. Prisacariu C, Scortanu E, J. Appl. Polym. Sci., 122(6), 3544 (2011)
  7. Buckley CP, Prisacariu C, Martin C, Polymer, 51(14), 3213 (2010)
  8. Prisacariu C, Scortanu E, Encyclopedia of Analytical Chemistry, John Wiley & Sons, Ltd., 1 (2006)
  9. Prisacariu C, Olley RH, Caraculacu AA, Bassett DC, Martin C, Polymer, 44(18), 5407 (2003)
  10. Prisacariu C, Buckley CP, Caraculacu AA, Polymer, 46(11), 3884 (2005)
  11. Buckley CP, Prisacariu C, Caraculacu A, Polymer, 48(5), 1388 (2007)
  12. Dziembowska T, Polish Journal of Chemistry., 68, 1455 (1994)
  13. Benigno AJ, Ahmed E, Berg M, J. Chem. Phys., 104(19), 7382 (1996)
  14. Prisacariu C, Scortanu E, Buckley CP, International Journal of Polymer Analysis and Characterization., 14(13), 527 (2009)
  15. Prisacariu C, Agherghinei I, Journal of Macromolecular Science, Part A: Pure and Applied Chemistry., 37(7), 785 (2000)
  16. Prisacariu C, Scortanu E, High Performance Polymers., 20(2), 117 (2008)
  17. Estes GM, Seymour RW, Cooper SL, Macromolecules., 4(4), 452 (1971)
  18. Seymour RW, Allegrezza AE, Cooper SL, Macromolecules., 6, 896 (1973)
  19. Hammond P, Nallicheri R, Rubner M, Materials Science and Engineering A., 126(1-2), 281 (1990)
  20. Buckley CP, Prisacariu C, Caraculacu AA, Martin CS, in: Proceedings of the 4th European Conference for Constitutive Models For Rubber ECCMR 2005, Taylor and Francis, London, 465 (2005)
  21. Ogden RW, Oxburgh DG, Proceedings of the Royal Society of London A., 455, 2861 (1999)