Rigid and semi rigid polyurethane resins: A structural investigation using DMA, SAXS and Le Bail method

• PU resins were synthesized with pre-polymer/polyol ratios of 1:1 (rigid PU) and 1:1.5 (semi rigid PU).
• Le Bail method allowed the determination of unit cell parameters and crystallite size and shape.
• Kratky plots showed that increasing the mass polyol ratio it were produced less organized systems.

Two different types of polyurethane (PU) resins were synthesized with pre-polymer/polyol (–NCO/–OH) mass proportions of 1:1 (Rigid PU) and 1:1.5 (Semi rigid PU). Based on the results from Dynamic Mechanical Analysis (DMA), rigid PU showed a higher Storage Modulus (E′) which may be related to the macromolecules crosslinking process. In contrast, the greater Loss Modulus (E″) in semi rigid PU was related to the greater ability to dissipate energy, suggesting that the change in polyol/pre-polymer ratio promotes structural changes in PU resins. Le Bail method was performed with a triclinic crystal structure (for rigid PU, a = 4.9117 (2) Å, b = 8.1103 (2) Å, c = 19.7224 (2) Å, α = 116.2831 (2)°, β = 125.4058 (2)° and γ = 83.6960 (2)°). Average crystallite size was found in the range of 26 (1) Å for rigid PU and somewhat smaller around 20 (1) Å for semi rigid PU. The Guinier radii of gyration (Rg) and the maximum particle sizes (Dmax) were calculated based on Small Angle X-ray Scattering (SAXS) curves. Two different values for Radii of gyration (Rg) were calculated, one obtained from Guinier’s plot using the program Microcal Origin 7.5 (RgORIGIN) and other from the pair-distance distribution function (p(r)) calculation, using the GNOM (RgGNOM) program package The possible highest values of (RgORIGIN) were obtained from Guinier’s curves. For rigid and semi rigid PU resins, the (RgORIGIN) values were, respectively, (320 ± 1) and (260 ± 1) Å. The average radii of gyration (RgGNOM) were obtained from the calculated pair-distance distribution function (p(r)). For rigid and semi rigid PU resins, the RgGNOM values were, respectively, (95 ± 1) Å and (86 ± 1) Å. Dmax values were obtained from the p(r) and ranged from (330 ± 3) Å to (260 ± 3) Å for rigid and semi rigid PU, respectively. Kratky curves showed that less organized systems were produced when the polyol amount was increased.