A bisphenol-A-based resin system that cures via triazole ring formation for marine composite applications

Irene Elizabeth Gorman


Large composite panels, such as those utilized in marine applications, cannot be economically cured in an autoclave. For these structures the elevated temperatures necessary to achieve high crosslink density must come from the curing reaction itself. We are developing a resin system that cures via triazole ring formation (cycloaddition reaction of azides with terminal alkynes) instead of the traditional oxirane/amine reaction. The high exothermicity of the azido/alkyne reaction is expected to yield higher extents of reaction under ambient-cure conditions, making the resin system potentially suitable for "out-of-autoclave" curing processes. This work was conducted through a multi-tiered approach involving synthesis, kinetic studies, thermal characterization, and mechanical analysis. The difunctional azide-terminated resin, di(3-azido-2 hydroxypropyl) ether of bisphenol-A (DAHP-BPA), was selected as the baseline diazide. A number of alkyne crosslinkers were synthesized and characterized, including propiolate esters of di- and trifunctional alcohols, propargyl esters of di- and trifunctional carboxylic acids, propargyl ethers of di- and trifunctional alcohols, and N,N,N',N' -tetrapropargyl derivatives of primary diamines. Commercially available tripropargylamine (TPA) was also studied. Curing energetics as a function of alkyne type and catalyst loading, investigated through a dynamic differential scanning calorimetry approach, displayed two distinct kinetic profiles when considering propiolate and propargyl type crosslinkers. Those systems employing a propiolate-based alkyne were found to be much more reactive towards the Huisgen 1,3-dipolar cycloaddition than the propargyl species. Additionally, the mechanical and thermal properties of resin systems, both un-catalyzed and catalyzed, composed of DAHP-BPA and tripropargyl amine were investigated by compression and rheological studies, differential scanning calorimetry, and thermogravametric analysis. The moduli of both DAHP-BPA/TPA systems were found to be approximately 3500 MPa, comparable to the modulus of EPON-825/4,4'-DDS resin. Ultimately, the utility of the DAHP-BPA/polyalkyne resin system lies not only in its capability for low-temperature curing, but also in the ability to customize the reactivity, thermal properties, and mechanical properties of the system through the use of catalyst and choice of alkyne crosslinker.