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. 2024 Feb 8;16(4):480.
doi: 10.3390/polym16040480.

Long-Chain Bio-Based Nylon 514 Salt: Crystal Structure, Phase Transformation, and Polymerization

Zihan Li  1 , Lei Zhang  2 , Xiaohan Zhang  1 , Tianpeng Chen  1 , Pengpeng Yang  1 , Yong Chen  1 , Huajie Lin  3 , Wei Zhuang  1 , Jinglan Wu  1 , Hanjie Ying  1
Affiliations

Long-Chain Bio-Based Nylon 514 Salt: Crystal Structure, Phase Transformation, and Polymerization

Zihan Li et al. Polymers (Basel). .

Abstract

Nylon 514 is one of the new long-chain bio-based nylon materials; its raw material, 1,5-pentanediamine (PDA), is prepared by biological techniques, using biomass as the raw material. The high-performance monomer of nylon 514, 1,5-pentanediamine-tetradecanedioate (PDA-TDA) salt, was obtained through efficient crystallization methods. Here, two crystal forms of PDA-TDA, anhydrous and dihydrate, were identified and studied in this paper. From the characterization data, their crystal structures and thermal behaviors were investigated. Lattice energy was calculated to gain further insight into the relationship between thermal stability and crystal structures. The contribution of hydrogen bonds and other intermolecular interactions to the crystal structure stability have been quantified according to detailed Hirshfeld and IRI analyses. Additionally, the transformation mechanism of the anhydrate and dihydrate was established through a series of well-designed stability experiments, in which the temperature and water activity play a significant role in the structural stability of crystalline forms. Eventually, we obtained nylon 514 products with good thermal stability and low absorption using stable dihydrate powders as monomers. The properties of nylon 514 products prepared by different polymerization methods were also compared.

Keywords: 1,5-pentanediamine-tetradecanedioate; crystal structure; long-chain bio-based nylon 514 monomer; nylon polymerization; phase transformation.

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Conflict of interest statement

Author Lei Zhang was employed by Nanjing Biotogether Co. Ltd. and author Huajie Lin was employed by SINOPEC Ningbo Research Institute of New Materials. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflicts of interest.

Figures

Figure 1
Figure 1
Molecular structure of PDA–TDA and bio-based nylon 514.
Figure 2
Figure 2
PXRD patterns of PDA–TDA (left) and images of the crystalline products of PDA–TDA (right): (a) anhydrate; (b) dihydrate. Both views are obtained at 16 × 4 magnification.
Figure 3
Figure 3
FTIR spectroscopy patterns of PDA–TDA salts; the black line is anhydrate, while the red line is dihydrate.
Figure 4
Figure 4
(a) The smallest asymmetric unit cell with the selected atom labeling scheme of anhydrate. The ellipsoids are shown at a 50% probability. (b) The structure of double layer unit of the anhydrate. (c) A view of the packing motifs of anhydrate, with hydrogen supramolecular synthons between PDA-TDA. (d) The 3D supramolecular framework of the anhydrate, with an open 1D channel along the c axis.
Figure 5
Figure 5
(a) The smallest asymmetric unit cell with the selected atom labeling scheme of dihydrate. The ellipsoids are shown at a 50% probability. (b) The structure of double layer unit of dihydrate. (c) A view of the stacking structure of dihydrate, with supramolecular hydrogen synthons between the interactions of water and PDA-TDA. (d) The 3D supramolecular framework of the dihydrate, with an open 1D channel along the c axis.
Figure 6
Figure 6
The 2D Fingerprint plots showing the close contacts in the anhydrate (a) and dihydrate forms (A). (b,B) The fan chart elucidates the percentage contributions to the calculated Hirshfeld surfaces of the two forms. The HS surface mapped over dnorm is in the color range of −0.6204 to 1.6275 a.u./−0.6979 to 1.2588 a.u., respectively.
Figure 7
Figure 7
IRI plot isosurface of the (a) anhydrate and (b) dihydrate structures of PDA-TDA.
Figure 8
Figure 8
TGA and DSC curves of the anhydrate (a) and dihydrate (b) of PDA–TDA.
Figure 9
Figure 9
Results of SST and slurry experiments of the anhydrate (a–c) and dihydrate (b–d) under different temperature and solvent conditions, respectively.
Scheme 1
Scheme 1
Interconversion pathways of the anhydrate and dihydrate forms of PDA-TDA.
Figure 10
Figure 10
(a) Morphology and the corresponding PXRD patterns of the PA514 products. (b) Thermodynamic analysis of the PA514 products using MP and DSSP methods, respectively.
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