Acrylonitrile-modified aliphatic amine adducts are often used as curing agents for room-temperature epoxy formulations (coatings, adhesives, sealants, castings, etc.), yet the curing reaction and properties of resultant epoxy systems still remain less fundamentally understood. Herein we systematically investigate our newly-developed acrylonitrile-modified multifunctional polyamine curing agent for bisphenol A epoxy resin (DGEBA): an acrylonitrile-capped poly(propyleneimine) dendrimer (PAN4). The impact of the molecular structure of PAN4 and a controlled poly(propyleneimine) dendrimer (1.0GPPI) on the curing reactivity, reaction mechanisms, thermal stability, viscoelastic response and mechanical properties of the epoxy systems are highlighted. Differential scanning calorimetry (DSC) confirms DGEBA/PAN4 shows markedly lower reactivity and reaction exotherm than DGEBA/1.0GPPI, and the model-free isoconversional kinetic analysis reveals that DGEBA/PAN4 has the generally lower reaction activation energy. To be quantitative, the progress of the isothermal cure is predicted from the dynamic cure by using the Vyazovkin equation. The isothermal kinetic prediction shows that DGEBA/PAN4 requires about 10 times longer time to achieve the same conversion than DGEBA/1.0GPPI, which agrees with the experimentally observed much longer gel time of DGEBA/PAN4. Subsequently, dynamic mechanical analysis shows that PAN4 results in the cured epoxy network with the lower β- and glass-relaxation temperatures, crosslink density, relaxation activation energy, enthalpy, entropy, but the higher damping near room temperature than 1.0GPPI. Finally, thermogravimetric analysis (TGA) demonstrates cured DGEBA/PAN4 is thermally stable up to 200 °C, and mechanical property tests substantiate that PAN4 endows the cured epoxy with much higher impact and adhesion strengths than 1.0GPPI. Our data can provide a deeper insight into acrylonitrile-modified aliphatic amine curing agents from the two good model compounds (PAN4 and 1.0GPPI).Highlights► We compare the isoconversional curing kinetics of DGEBA/1.0GPPI and DGEBA/PAN4. ► Acrylonitrile-capped PAN4 is much lower reactive than controlled 1.0GPPI. ► TG analysis shows the two cured epoxy systems are thermally stable up to 200 °C. ► DMA results reveal the viscoelastic response of the two cured networks differs greatly. ► PAN4 greatly improves the shear, impact strengths and processability of the epoxy.

Star-branched polymers have being captured much research interest, yet impacts of the star-chain branching on the crystallization still need further elucidating. We originally report a comparative study of the isothermal crystallization kinetics of a star-branched DPA-11 and a linear nylon-11 (PA-11). Differential scanning calorimetry (DSC) confirms DPA-11 crystallizes at a much slower rate than PA-11. The kinetic analysis demonstrates the Avrami equation can generally well predict relative crystallinity X, and DPA-11 exhibits the higher Avrami exponents. The Hoffman–Lauritzen spherulitic growth analysis demonstrates DPA-11 has the decreased G0 and Kg values, accounting for the appreciably lowered spherulitic growth rate. More interestingly, the advanced isoconversional (Vyazovkin) method reveals DPA-11 always manifests the higher activation energy than PA-11, and once X exceeding 0.85 the activation energy of DPA-11 rises sharply, whereas that of PA-11 tends to decrease.Graphical abstractHighlights► Isothermal crystallization of a star-branched DPA-11 and a linear PA-11 are compared. ► DPA-11 exhibits the much lower crystallization rate than PA-11. ► The Vyazovkin method shows that DPA-11 always has the higher activation energy EX. ► The star branching of DPA-11 causes the sharp rise in EX during a high crystallinity range. ► The secondary crystallization of DPA-11 seems suppressed by the star-chain branching.