Abdullah M. Alabdulrahman

Recyclable, strong thermosets and organogels via paraformaldehyde condensation with diamines

Recyclable Thermoset Polymers The high mechanical strength and durability of thermoset polymers are exploited in applications such as composite materials, where they form the matrix surrounding carbon fibers. The thermally driven polymerization reaction is usually irreversible, so it is difficult to recycle the constituent monomers and to remove and repair portions of a composite part. García et al. (p. 732; see the Perspective by Long) now describe a family of polymers formed by condensation of paraformaldehyde with bisanilines that could form hard thermoset polymers or, when more oxygenated, produce self-healing gels. Strong acid digestion allowed recovery of the bisaniline monomers. A strong polymer formed by heating can be digested with strong acid to recover and recycle its bisaniline monomers. [Also see Perspective by Long] Nitrogen-based thermoset polymers have many industrial applications (for example, in composites), but are difficult to recycle or rework. We report a simple one-pot, low-temperature polycondensation between paraformaldehyde and 4,4ʹ-oxydianiline (ODA) that forms hemiaminal dynamic covalent networks (HDCNs), which can further cyclize at high temperatures, producing poly(hexahydrotriazine)s (PHTs). Both materials are strong thermosetting polymers, and the PHTs exhibited very high Young’s moduli (up to ~14.0 gigapascals and up to 20 gigapascals when reinforced with surface-treated carbon nanotubes), excellent solvent resistance, and resistance to environmental stress cracking. However, both HDCNs and PHTs could be digested at low pH (<2) to recover the bisaniline monomers. By simply using different diamine monomers, the HDCN- and PHT-forming reactions afford extremely versatile materials platforms. For example, when poly(ethylene glycol) (PEG) diamine monomers were used to form HDCNs, elastic organogels formed that exhibited self-healing properties.

Advanced chemical recycling of poly(ethylene terephthalate) through organocatalytic aminolysis

We report the effective organocatalysis of the aminolytic depolymerization of waste poly(ethylene terephthalate) (PET) using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) producing a broad range of crystalline terephthalamides. This diverse set of monomers possesses great potential as building blocks for high performance materials with desirable thermal and mechanical properties deriving from the terephthalic moiety and amide hydrogen bonding. Further, a computational study established mechanistic insight into self-catalyzed and organocatalyzed aminolysis of terephthalic esters, suggesting that the bifunctionality of TBD particularly concerning activation of the carbonyl group differentiates TBD from other organic bases.

Computational investigations on base-catalyzed diaryl ether formation.

We report investigations with the dispersion-corrected B3LYP density functional method on mechanisms and energetics for reactions of group I metal phenoxides with halobenzenes as models for polyether formation. Calculated barriers for ether formation from para-substituted fluorobenzenes are well correlated with the electron-donating or -withdrawing properties of the substituent at the para position. These trends have also been explained with the distortion/interaction energy theory model which show that the major component of the activation energy is the energy required to distort the arylfluoride reactant into the geometry that it adopts at the transition state. Resonance-stabilized aryl anion intermediates (Meisenheimer complexes) are predicted to be energetically disfavored in reactions involving fluorobenzenes with a single electron-withdrawing group at the para position of the arene, but are formed when the fluorobenzenes are very electron-deficient, or when chelating substituents at the ortho position of the aryl ring are capable of binding with the metal cation, or both. Our results suggest that the presence of the metal cation does not increase the rate of reaction, but plays an important role in these reactions by binding the fluoride or nitrite leaving group and facilitating displacement. We have found that the barrier to reaction decreases as the size of the metal cation increases among a series of group I metal phenoxides due to the fact that the phenoxide becomes less distorted in the transition state as the size of the metal increases.