Synthesis of a Biomass Tyramine-derived Hydroxyl-amide Nucleating Agent and Its Effect on Crystallization and Properties of Polyamide 6

Jia-Le Wu; Wen-Hao Xiao; Jing-Bo Wu; Jiang-Hua Lin; Rui-Jie Xu; Cai-Hong Lei

doi:10.1007/s10118-025-3497-1

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Synthesis of a Biomass Tyramine-derived Hydroxyl-amide Nucleating Agent and Its Effect on Crystallization and Properties of Polyamide 6

RESEARCH ARTICLE | Updated：2026-01-30

- Synthesis of a Biomass Tyramine-derived Hydroxyl-amide Nucleating Agent and Its Effect on Crystallization and Properties of Polyamide 6
- Chinese Journal of Polymer Science Vol. 44, Issue 2, Pages: 576-589(2026)
- Affiliations：
  
  Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China
- Author bio：
  
  xu565786@163.com (R.J.X.)
  lch528@gdut.edu.cn (C.H.L.)
- Funds：
- DOI：10.1007/s10118-025-3497-1
  CLC：
- Received：19 September 2025，
  
  Accepted：08 November 2025，
  
  Online First：15 January 2026，
  
  Published：05 February 2026
- Accepted：
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Wu, J. L.; Xiao, W. H.; Wu, J. B.; Lin, J. H.; Xu, R. J.; Lei, C. H. Synthesis of a biomass tyramine-derived hydroxyl-amide nucleating agent and its effect on crystallization and properties of polyamide 6. Chinese J. Polym. Sci. 2026, 44, 576–589

Jia-Le Wu, Wen-Hao Xiao, Jing-Bo Wu, et al. Synthesis of a Biomass Tyramine-derived Hydroxyl-amide Nucleating Agent and Its Effect on Crystallization and Properties of Polyamide 6[J]. Chinese Journal of Polymer Science, 2026, 44(2): 576-589.
Wu, J. L.; Xiao, W. H.; Wu, J. B.; Lin, J. H.; Xu, R. J.; Lei, C. H. Synthesis of a biomass tyramine-derived hydroxyl-amide nucleating agent and its effect on crystallization and properties of polyamide 6. Chinese J. Polym. Sci. 2026, 44, 576–589 DOI： 10.1007/s10118-025-3497-1.

Jia-Le Wu, Wen-Hao Xiao, Jing-Bo Wu, et al. Synthesis of a Biomass Tyramine-derived Hydroxyl-amide Nucleating Agent and Its Effect on Crystallization and Properties of Polyamide 6[J]. Chinese Journal of Polymer Science, 2026, 44(2): 576-589. DOI： 10.1007/s10118-025-3497-1.

摘要

A hydroxyl-containing amide nucleating agent BHT

synthesized from tyramine-based biomass

blends with polyamide 6 (PA6). BHT enhances hydrogen bonding to drive PA6 segment adjustment

strengthening its crystallization and synergistically optimizing thermal

mechanical and optical properties for high-performance PA6 modification.

Abstract

The chemical structure of polyamide 6 (PA6) dictates that only 50% of hydrogen bonds participate in crystallization during the crystallization process

resulting in the properties of its products being significantly dependent on the molding process. Therefore

the design and development of nucleating agents suitable for PA6 holds great practical significance for high-performance PA6 materials. Amide-based nucleating agents can effectively improve the crystallization rate by increasing intermolecular hydrogen bond density. Further introduction of hydroxyl groups can enhance the hydrogen bonding interactions between the nucleating agent and PA6. In this study

a hydroxyl-containing

amide-based nucleating agent

BHT

was designed and synthesized using a tyramine-based biomass as the raw material. These results demonstrated that BHT exhibited good structural compatibility with PA6. After adding 1 wt% BHT

the crystallization temperature of PA6 increased from 170.9 °C to 193.3 °C

the crystallinity increased 16.6%

the heat distortion temperature and Vicat softening temperature rose to 89.5 and 187.8 °C

respectively

the haze decreased to 46%

achieving the synergistic optimization of mechanical

thermal

and optical properties. The

in situ

time-resolved FTIR results indicated that the addition of BHT increased the enthalpy of hydrogen bond formation during the nucleation stage

facilitated the segmental conformation adjustment of PA6

and enhanced the molar concentration of trans-conformations

ultimately leading to an improvement in the crystallization rate.

关键词

Keywords

references

Aslanzadeh, S.; Saghlatoon, H.; Honari, M. M.; Mirzavand, R.; Montemagno, C.; Mousavi, P. Investigation on electrical and mechanical properties of 3D printed nylon 6 for RF/Microwave electronics applications. Addit. Manuf. 2018 , 21 , 69−75..

Guo, X.; Liu, L.; Feng, H.; Li, D.; Xia, Z.; Yang, R. Flame retardancy of nylon 6 fibers: a review. Polymers 2023 , 15 , 2161..

Zaldua, N.; Maiz, J.; De La Calle, A.; García-Arrieta, S.; Elizetxea, C.; Harismendy, I.; Tercjak, A.; Müller, A. J. Nucleation and crystallization of PA6 composites prepared by T-RTM: effects of carbon and glass fiber loading. Polymers 2019 , 11 , 1680..

Liu, L.; Yang, R.; Xia, Z.; Li, D. Interfacial bonding flame retarded coating of nylon 6: anti-Dropping, self-extinguishment and water-proof. Prog. Org. Coat. 2022 , 170 , 106913..

Zhang, W.; Tang, R.-C. Adsorption and flame retardant properties of potassium diphenyl sulfonate on nylon 6 fabri c. React. Funct. Polym. 2018 , 126 , 36−43..

Annandarajah, C.; Langhorst, A.; Kiziltas, A.; Grewell, D.; Mielewski, D.; Montazami, R. Hybrid cellulose-glass fiber composites for automotive applications. Materials 2019 , 12 , 3189..

Salahuddin, B.; Mutlu, R.; Baigh, T. A.; Alghamdi, M. N.; Aziz, S. Self-reinforced nylon 6 composite for smart vibration damping. Polymers 2021 , 13 , 1235..

Murray, J. J.; Allen, T.; Bickerton, S.; Bajpai, A.; Gleich, K.; McCarthy, E. D.; Ó Brádaigh, C. M. Thermoplastic RTM: impact properties of anionically polymerised polyamide 6 composites for structural automotive parts. Energies 2021 , 14 , 5790..

Du, S.; Wei, Y.; Ahmed, S.; Zhou, F.; Tan, Y.; Li, Y.; Wang, M.; Chen, X.; Zhou, W. Enhanced thermal stability and UV resistance of polyamide 6 filament fabric via in-situ grafting with methyl methacrylate. Colloids Surf., A 2022 , 651 , 129371..

Yuan, L.; Zhu, P.; Wang, Y.; Dong, X.; Wang, D. The preparation of permanent antistatic additive based on poly(ether -b-amide) copolymers and its modification effect on polyamide 6. Pure Appl. Chem. 2024 , 96 , 185−200..

Tjong, S. C.; Bao, S. P. Preparation and nonisothermal crystallization behavior of polyamide 6/montmorillonite nanocomposites. J. Polym. Sci., Part B: Polym. Phys. 2004 , 42 , 2878−2891..

Guo, Z.; Peng, X.; Sang, L. Enhancement of mechanical properties of PA6 blending with talcum for fused deposition modeling. Macromol. Mater. Eng. 2020 , 305 , 2000355..

[Kazemi, S.; Mojtahedi, M. R. M.; Takarada, W.; Kikutani, T. Morphology and crystallization behavior of nylon 6-clay/neat nylon 6 bicomponent nanocomposite fibers. J. Appl. Polym. Sci . 2014 , 131 ..

Faghihi, M.; Shojaei, A.; Bagheri, R. Characterization of polyamide 6/carbon nanotube composites prepared by melt mixing-effect of matrix molecular weight and structure. Compos. Part B 2015 , 78 , 50−64..

Sabatini, V.; Taroni, T.; Rampazzo, R.; Bompieri, M.; Maggioni, D.; Meroni, D.; Or tenzi, M. A.; Ardizzone, S. PA6 and halloysite nanotubes composites with improved hydrothermal ageing resistance: role of filler physicochemical properties, functionalization and dispersion technique. Polymers 2020 , 12 , 211..

Li, J.; Yang, C.; Liu, N.; He, S.; Sun, T.; Zhang, J. A ternary hybrid nucleating agent for isotropic polypropylene: preparation, characterization, and application. e-Polym. 2022 , 22 , 627−640..

Zhou, Y.; He, L.; Gong, W. Effect of organic cage nucleating agent structure on nucleating efficiency and the structure-property relationship. Polymers 2020 , 12 , 1975..

Yan, Z.; Huang, Y.; Zhao, W.; Wu, B.; Liu, C.; Yan, X.; Pan, H.; Zhao, Y.; Zhang, H. Effect of a self-assembled nucleating agent on the crystallization behavior and spherulitic morphology of poly(lactic acid). ACS Omega 2023 , 8 , 44093−44105..

Xia, G.; He, L.; Zhao, Q.; Chen, W.; Song, R.; Ma, Z. In-site observation of the crystallization of nylon-6 mediated by the interfacial hydrogen bonds. Colloid Polym. Sci. 2012 , 290 , 1943−1947..

García-López, D.; Fernández, J. F.; Merino, J. C.; Pastor, J. M. Influence of organic modifier characteristic on the mechanical properties of polyamide 6/organosepiolite nanocomposites. Composites, Part B 2013 , 45 , 459−465..

Karami, P.; Shojaei, A. Improvement of dry sliding tribological properties of polyamide 6 using diamond nanoparticles. Tribol. Int. 2017 , 115 , 370−377..

Mudra, I.; Balázs, G. Comparative study of efficiency of nucleating agents in PA-6. J. Therm. Anal. Calorim. 1998 , 52 , 355−361..

Yin, X.; Zhao, X.; Ye, L. In situ-induced epiphytic crystallization of MC PA6 by self-assembled nucleator and reinforcing effect. Polym. Int. 2023 , 72 , 629−639..

Aitha, S.; Vasanthan, N. Effect of cellulose nanocrystals on crystallization, morphology and phase transition of polyamide 6. Compos. Interfaces 2020 , 27 , 371−384..

Huang, Z.; Yin, Q.; Wang, Q.; Wang, P.; Liu, T.; Qian, L. Mechanical properties and crystallization behavior of three kinds of straws/nylon 6 composites. Int. J. Biol. Macromol. 2017 , 103 , 663−668..

Shi, K.; Liu, G.; Sun, H.; Yang, B.; Weng, Y. Effect of biomass as nucleating agents on crystallization behavior of polylactic acid. Polymers 2022 , 14 , 4305..

Ng, C.; Chow, W. Multifunctional halloysite nanotube–reinforced polypropylene/polyamide binary nanocomposites. Polym. Polym. Compos. 2020 , 28 , 623−630..

Zheng, X.; Li, Y.; Tang, J.; Yu, G. Structure and properties of PVDF/PA6 blends compatibilized by ionic liquid-grafted PA6. ACS Omega 2022 , 7 , 12772−12778..

Illers, K.-H. Polymorphie, kristallinität und schmelzwärme von poly(ε-caprolactam), 2. kalorimetrische untersuchungen. Makromol. Chem. 1978 , 179 , 497−507..

He, Y.; Fan, Z.; Hu, Y.; Wu, T.; Wei, J.; Li, S. DSC analysis of isothermal melt-crystallization, glass transition and melting behavior of poly(l-lactide) with different molecular weights. Eur. Polym. J. 2007 , 43 , 4431−4439..

Ohtani, Y.; Okumura, K.; Kawaguchi, A. Crystallization behavior of amorphous poly(l-lactide). J. Macromol. Sci., Part B: Phys. 2003 , 42 , 875−888..

Lu, W.; Lu, C.; Hu, J.; Wu, J.; Zhou, Q. Effects of the blending time on the properties and non-isothermal crystallization behavior of PA6/EVOH blends. Polym. Eng. Sci. 2021 , 61 , 1719−1731..

Li, J.; Fang, Z.; Zhu, Y.; Tong, L.; Gu, A.; Liu, F. Isothermal crystallization kinetics and melting behavior of multiwalled carbon nanotubes/polyamide-6 composites. J. Appl. Polym. Sci. 2007 , 105 , 3531−3542..

Avrami, M. Kinetics of phase change. I general theory. J. Chem. Phys. 1939 , 7 , 1103−1112..

Chen, E. C.; Wu, T. M. Isothermal and nonisothermal crystallization kinetics of nylon 6/functionalized multi-walled carbon nanotube composites. J. Polym. Sci., Part B: Polym. Phys. 2008 , 46 , 158−169..

Rwei, S. P.; Ranganathan, P.; Lee, Y. H. Isothermal crystallization kinetics study of fully aliphatic PA6 copolyamides: effect of novel long-chain polyamide salt as a comonomer. Polymers 2019 , 11 , 472..

Wang, H. L.; Shi, T. J.; Yang, S. Z.; Hang, G. P. Crystallization behavior of PA6/SiO 2 organic–inorganic hybrid material PA6/SiO 2 . Mater. Res. Bull. 2006 , 41 , 298−306..

Zhang, Y. F.; Zhou, P. Z.; Guo, L. H.; Hou, H. H. The relationship between crystal structure and nucleation effect of 1,3,5-benzenetricarboxylic acid tris(phenylamide) in isotactic polypropylene. Colloid Polym. Sci. 2017 , 295 , 619−626..

Sun, H.; Jiang, F.; Lei, F.; Chen, L.; Zhang, H.; Leng, J.; Sun, D. Graphite fluoride reinforced PA6 composites: crystallization and mechanical properties. Mater. Today Commun. 2018 , 16 , 217−225..

Liu, Y.; Jiang, S.; Yan, W.; Qin, J.; He, M.; Qin, S.; Yu, J. Enhanced mechanical and thermal properties of polyamide 6/P (N-(4-F-phenylmaleimide)–alt-styrene) composites based on interfacial complexation inducing crystal transformation. Polymer 2021 , 214 , 123 237..

Xiao, W.; Wu, J.; Liu, X.; Xie, J.; Xu, R.; Lei, C. Developing an efficient biobased nucleating agent with antimicrobial properties by controlling the conformation of poly(lactic acid) based on intermolecular forces. Macromolecules 2024 , 57 , 7398−7408..

[Wu, J.; Xiao, W.; Xu, R.; Lei, C. The influence of nucleating agent positional isomer structure on the nucleation efficiency of poly(lactic acid): interaction-induced conformational transitions under high lattice matching. Macromolecules 2025 , 58 , 9315−9327..

Krikorian, V.; Pochan, D. J. Crystallization behavior of poly(l-lactic acid) nanocomposites: nucleation and growth probed by infrared spectroscopy. Macromolecules 2005 , 38 , 6520−6527..

Cakir, S.; Jasinska-Walc, L.; Villani, M.; Hansen, M. R.; Koning, C. E. Morphology and local chain structure of polyamide 6 modified in the solid state with a semi-aromatic nylon salt. Mater. Today Commun. 2015 , 2 , e62−e69..

Atkins, E. D. T.; Hill, M. J.; Jones, N. A.; Sikor ski, P. Chain-folding and structures in nylon 6 oligoamide lamellar crystals. J. Mater. Sci. 2000 , 35 , 5179−5186..

Seguela, R. Overview and critical survey of polyamide 6 structural habits: misconceptions and controversies. J. Polym. Sci. 2020 , 58 , 2971−3003..

Li, L.; Yang, G. Variable-temperature FTIR studies on thermal stability of hydrogen bonding in nylon 6/mesoporous silica nanocomposite. Polym. Int. 2009 , 58 , 503−510..

Li, L.; Yang, G. Synthesis and properties of hydroxyapatite nanorod-reinforced polyamide 6 nanocomposites. Polym. Int. 2009 , 58 , 380−387..

Ma, Y.; Zhou, T.; Su, G.; Li, Y.; Zhang, A. Understanding the crystallization behavior of polyamide 6/polyamide 66 alloys from the perspective of hydrogen bonds: projection moving-window 2D correlation FTIR spectroscopy and the enthalpy. RSC Adv. 2016 , 6 , 87405−87415..

Vasanthkumar, P.; Balasundaram, R.; Senthilkumar, N.; Palanikumar, K.; Lenin, K.; Deepanraj, B. Thermal and thermo-mechanical studies on seashell incorporated nylon-6 polymer composites. J. Mater. Res. Technol. 2022 , 21 , 3154−3168..

[García-Carrillo, M.; González-Granados, I.; Hernández-López, A. A.; Espinoza-Martínez, A. B. Exploring the effects of montmorillonite and halloysite nanotubes on mechanical, optical and barrier properties of poly(butylene adipate-co-terephthalate) blown films: implications for sustainable packaging and food storage. J. Appl. Polym. Sci . 2024 , 141 ..

Niu, D.; Shen, T.; Xu, P.; Yu, M.; Liu, T.; Yang, W.; Wang, Z.; Ma, P. Enhanced crystallization, heat resistance and transparency of poly(lactic acid) with self-assembling bis-amide nucleator. Int. J. Biol. Macromol. 2023 , 234 , 123584..

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