RESUMO
This work reveals the influence of pendant hydrogen bonding strength and distribution on self-assembly and the resulting thermomechanical properties of A-AB-A triblock copolymers. Reversible addition-fragmentation chain transfer polymerization afforded a library of A-AB-A acrylic triblock copolymers, wherein the A unit contained cytosine acrylate (CyA) or post-functionalized ureido cytosine acrylate (UCyA) and the B unit consisted of n-butyl acrylate (nBA). Differential scanning calorimetry revealed two glass transition temperatures, suggesting microphase-separation in the A-AB-A triblock copolymers. Thermomechanical and morphological analysis revealed the effects of hydrogen bonding distribution and strength on the self-assembly and microphase-separated morphology. Dynamic mechanical analysis showed multiple tan delta (δ) transitions that correlated to chain relaxation and hydrogen bonding dissociation, further confirming the microphase-separated structure. In addition, UCyA triblock copolymers possessed an extended modulus plateau versus temperature compared to the CyA analogs due to the stronger association of quadruple hydrogen bonding. CyA triblock copolymers exhibited a cylindrical microphase-separated morphology according to small-angle X-ray scattering. In contrast, UCyA triblock copolymers lacked long-range ordering due to hydrogen bonding induced phase mixing. The incorporation of UCyA into the soft central block resulted in improved tensile strength, extensibility, and toughness compared to the AB random copolymer and A-B-A triblock copolymer comparisons. This study provides insight into the structure-property relationships of A-AB-A supramolecular triblock copolymers that result from tunable association strengths.
RESUMO
This manuscript describes the versatility of highly directional, noncovalent interactions, i.e., quadruple hydrogen bonding (QHB), to afford novel polyurea segmented supramolecular polymers for melt extrusion three-dimensional (3D) printing processes. The molecular design of the polyurea elastomers features (1) flexible polyether segments and relatively weak urea hydrogen-bonding sites in the soft segments to provide elasticity and toughness, and (2) strong ureido-cytosine (UCyt) QHB in the hard segments to impart enhanced mechanical integrity. The resulting polyureas were readily compression-molded into mechanically-robust, transparent, and creasable films. Optimization of polyurea composition offered a rare combination of high tensile strength (95 MPa), tensile elongation (788% strain), and toughness (94 MJ/m3), which are superior to a commercially available Ninjaflex elastomer. The incorporation of QHB facilitated melt processability, where hydrogen bonding dissociation provided low viscosities at printing temperatures. During cooling, directional self-assembly of UCyt QHB facilitated the solidification process and contributed to part fidelity with the formation of a robust physical network. The printed objects displayed high layer fidelity, smooth surfaces, minimal warpage, and complex geometries. The presence of highly directional QHB effectively diminished mechanical anisotropy, and the printed samples exhibited comparable Young's moduli along (x-y direction, 0°) and perpendicular to (z-direction, 90°) the layer direction. Remarkably, the printed samples exhibited ultimate tensile strains approaching 500% in the z-direction prior to failure, which was indicative of improved interlayer adhesion. Thus, this design paradigm, which is demonstrated for novel polyurea copolymers, suggests the potential of supramolecular polymers with enhanced mechanical performance, melt processability, recyclability, and improved interlayer adhesion for melt extrusion additive manufacturing processes.
