Structure and adhesion properties of waterborne poly(urethane urea)s containing small amounts of different graphene derivatives

Waterborne poly(urethane urea)s (PUDs) containing graphene derivatives with different morphologies and surface polarities were synthesized via in situ polymerization by using the acetone method. Small amounts (0.04–0.30 wt.%) of graphene oxide (GO), graphite nanoplatelets (GP) or milled graphite (MG) were mixed with polyadipate of 1,4-butanediol polyol and added during synthesis of the PUDs. The addition of graphene derivatives changed differently the degree of micro-phase separation of the poly(urethane urea)s (PUs) depending on the balance between the extent of covalent interactions between the surface functional groups on the graphene sheets and the isocyanate groups, and the number of stacked graphene sheets. Whereas MG mainly intercalated between the soft segments showing a typical behavior of nanofiller, GP and, particularly, GO showed different degrees of micro-phase separation due to more net covalent interactions with the poly(urethane urea) chains which caused higher crystallinity. The addition of graphene derivative decreased the glass transition temperature of the hard segments and increased the percentages of associated by hydrogen bond urethane and urea groups, more noticeably by adding GP and MG. Lower temperatures of decomposition and higher amounts of urethane and urea hard domains, and soft domains were found in PU + GO and PU + MG, and they showed an additional structural relaxation at 11–16 °C. PU and PU + GP had higher thermal stabilities than PU + GO and PU + MG and the addition of GP and, more markedly, GO imparted toughening to the poly(urethane urea). The T-peel strength values were higher in the joints made with PUD + GO due to the more net covalent interactions between the surface functional groups on the GO sheets and the poly(urethane urea) chains. On the other hand, the lap-shear strength of the joints made with PUD + MG and, in less extent, with PUD + GP noticeably increased.