Effect of the Dianhydride/Branched Diamine Ratio on the Architecture and Room Temperature Healing Behavior of Polyetherimides.

Traditional polyetherimides (PEIs) are commonly synthesized from an aromatic diamine and an aromatic dianhydride (e.g., 3,4'-oxidianiline (ODA) and 4,4'-oxidiphtalic anhydride (ODPA)) leading to the imide linkage and outstanding chemical, thermal and mechanical properties yet lacking any self-healing functionality. In this work, we have replaced the traditional aromatic diamine by a branched aliphatic fatty dimer diamine (DD1). This led to a whole family of self-healing polymers not containing reversible chemical bonds, capable of healing at (near) room temperature yet maintaining very high elastomeric-like mechanical properties (up to 6 MPa stress and 570% strain at break). In this work, we present the effect of the DD1/ODPA ratio on the general performance and healing behavior of a room temperature healing polyetherimide. A dedicated analysis suggests that healing proceeds in three steps: (i) an initial adhesive step leading to the formation of a relatively weak interface; (ii) a second step at long healing times leading to the formation of an interphase with different properties than the bulk material and (iii) disappearance of the damaged zone leading to full healing. We argue that the fast interfacial adhesive step is due to van der Waals interactions of long dangling alkyl chains followed by an interphase formation due to polymer chain interdiffusion. An increase in DD1/ODPA ratio leads to an increase in the healing kinetics and displacement shift of the first healing step toward lower temperatures. An excess of DD1 leads to the cross-linking of the polymer thereby restricting the necessary mobility for the interphase formation and limiting the self-healing behavior. The results here presented offer a new route for the development of room temperature self-healing thermoplastic elastomers with improved mechanical properties using fatty dimer diamines.