Green
chemistry calls for reducing the use of environmentally harmful
materials and petroleum resources. Bio-based nylon materials can help
address this problem. In this study, a new bio-based nylon 524T ternary salt was discovered and constructed by a green mechanochemical
method based on the pharmaceutical cocrystal screening and synthesis
strategy. The effects of adding solvents and grinding times on the
formation of a ternary salt were systematically studied, and the formation
of a nylon 524T ternary salt under solvent-assisted grinding
was found to follow a mechanically driven dissolution–recrystallization
mechanism. Furthermore, the chemical and physical properties of nylon
524T ternary salt were determined and compared with corresponding
nylon 54 binary and 5T binary salts. The results demonstrated that
the constructed ternary salt has better thermodynamic property and
humidity stability. This contribution offers a new well-performed
ternary salt monomer for a potential copolymer PA54/5T with high-temperature
resistance, but also a new potential perspective for the molecular
segment regulation of the copolymer by direct solid-state polymerization
and a green and efficient strategy to construct a copolymer ternary
salt monomer.
The compound 1,5-pentanediamine (PDA) is prepared by biological methods using biomass as raw material. The salt of 1,5-pentanediamine oxalate (PDA-OXA) was used directly as the monomer for the preparation of a new bio-based nylon 52 material. High-performance polymer materials require initial high-quality monomers, and crystallization is an essential approach to preparing such a monomer. In this work, three crystal forms of PDA-OXA, the anhydrate, dihydrate and trihydrate, were found and the single crystals of two hydrates were obtained. Their crystal structures were determined using single-crystal and powder X-ray diffraction. The thermal behaviors were characterized by thermodynamic analysis, and the lattice energy was calculated to further explore the relationship between the thermal stability and crystal structure. Detailed computational calculations, Hirshfeld analyses and lattice energy calculations were performed to quantify both the contribution of intra- and intermolecular interactions to the supramolecular assembly, as well as the influence on the stability of the structure. The structure–property relationship between the PDA-OXA crystal forms was established. Moreover, the phase transformation mechanism between the crystalline forms of PDA-OXA has been established, and the control strategy of specific crystal forms was developed from the water activity–temperature phase diagram and relevant thermodynamic data. Finally, the influence of the polymorphism of the monomer and the polymerization methods on the properties of the polymer was investigated. The nylon 52 product obtained showed good appearance, high hardness and thermal stability, the polymer made using the anhydrate as the monomer has better thermodynamic properties than that prepared from the dihydrate, indicating practical industrial application prospects.
Nylon 5O is one of the new bio-based nylon materials since its raw material 1,5-pentanediamine is prepared by biological methods using biomass as raw material. Original high-quality monomers are the...
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