Tailorable Thermal Properties Through Reactive Blending Using Orthogonal Chemistries and Layer-by-Layer Deposition of Poly(1,3,5-hexahydro-1,3,5-triazine) Networks

Abstract

The ability to tune both the thermal and mechanical properties of poly(1,3,5-hexahydro-1,3,5-triazine)s (PHTs) is critical to meet the increasingly stringent demands of structural materials. To this end, PHTs are modified during the process of vitrification using a reactive blending technique. Two strategies are employed: (i) the incorporation of a monomer or oligomer that contains amino end groups that are integrated into the network via hemiaminal chemistry and (ii) the incorporation of functional monomers bearing reactive end groups capable of self-polymerization, as well as insertion by copolymerization with the PHT-forming reagents to form mixed networks. Both strategies produce homogeneous materials, mitigating any adverse thermal properties of the parent PHT material. Here, a deposition method bringing the PHT technology platform to more diverse, economical and large-scale applications is also introduced. A unique layer-by-layer spray-coating approach of solutions containing 4,4′-oxydianiline (ODA) and multifunctional amines obtained by conjugate addition to acrylates is developed, allowing for the preparation of large-scale PHT-polymer blend films. The ODA–PHT enables high strength and modulus of the final material, while incorporation of acrylates provide an economical approach to polymer blends with tremendous functional group diversity and will allow for recyclability under mild conditions.