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Peer-reviewedCC BY 4.0Polymers

A Phosphorus-Containing Polyamide Oligomer as a Synergist for Flame-Retardant PA66/GF Composites: Concurrent Improvements in Flame Retardancy and Electrical Safety

  1. 1College of Materials Engineering, North China Institute of Aerospace Engineering, Langfang 065000, China
  2. 2National Engineering Research Center of Engineering and Ecological Plastics, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Abstract

As electronics become smaller and more power-dense, glass-fiber-reinforced polyamide 66 (PA66/GF) must combine halogen-free flame retardancy with electrical safety, including a glow-wire ignition temperature (GWIT) ≥ 775 °C and a comparative tracking index (CTI) ≥ 600 V. Conventional low-molecular-weight flame retardants often require loadings above 15 parts by mass, impairing mechanical and electrical properties. Here, a phosphorus-containing polyamide oligomer (DOPO–MA–oligomerPA6) was synthesized via a DOPO–MAH intermediate from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and maleic anhydride (MAH), followed by polymerization with ε-caprolactam, then melt-blended with aluminum diethylphosphinate (ADP) and melamine polyphosphate (MPP) in PA66/GF. Its oligo-PA6 backbone provides good compatibility with PA66, while its low molecular weight (Mn = 10,984 g mol−1; PDI = 2.569) favors dispersion. The phosphorus groups enhance the efficiency of the ADP/MPP system. With 4 parts oligomer and a total flame-retardant loading of 14 parts by mass per 100 parts PA66/GF, the composite achieved UL-94 V-0 rating, a limiting oxygen index (LOI) of 36.1%, a GWIT of 800 °C, and a CTI of 600 V. Its heat deflection temperature, tensile strength, notched impact strength, and flexural modulus were 178.8 °C, 95.0 MPa, 8.7 kJ m−2, and 8984 MPa, respectively. Compared with the conventional 20-part system, total additive loading decreased by 30%, with simultaneous improvements in flame retardancy, electrical safety, and mechanical properties. This offers a scalable route to high-performance PA66/GF composites.

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BibTeX
@article{zhang2026phosphoruscontaining,
  title = {{A Phosphorus-Containing Polyamide Oligomer as a Synergist for Flame-Retardant PA66/GF Composites: Concurrent Improvements in Flame Retardancy and Electrical Safety}},
  author = {Xing Zhang and Lirong Xie and Zhongliang Zhang and Guanghao Guo and Zhichao Zhen and Xuran Liu and Dan Huang},
  journal = {Polymers},
  year = {2026},
  month = nov,
  doi = {10.3390/polym18212706},
  url = {https://www.mdpi.com/2073-4360/18/21/2706},
  note = {CC BY 4.0},
}
RIS
TY  - JOUR
TI  - A Phosphorus-Containing Polyamide Oligomer as a Synergist for Flame-Retardant PA66/GF Composites: Concurrent Improvements in Flame Retardancy and Electrical Safety
AU  - Xing Zhang
AU  - Lirong Xie
AU  - Zhongliang Zhang
AU  - Guanghao Guo
AU  - Zhichao Zhen
AU  - Xuran Liu
AU  - Dan Huang
PY  - 2026
DA  - 2026/11/01
JO  - Polymers
DO  - 10.3390/polym18212706
UR  - https://www.mdpi.com/2073-4360/18/21/2706
AB  - As electronics become smaller and more power-dense, glass-fiber-reinforced polyamide 66 (PA66/GF) must combine halogen-free flame retardancy with electrical safety, including a glow-wire ignition temperature (GWIT) ≥ 775 °C and a comparative tracking index (CTI) ≥ 600 V. Conventional low-molecular-weight flame retardants often require loadings above 15 parts by mass, impairing mechanical and electrical properties. Here, a phosphorus-containing polyamide oligomer (DOPO–MA–oligomerPA6) was synthesized via a DOPO–MAH intermediate from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and maleic anhydride (MAH), followed by polymerization with ε-caprolactam, then melt-blended with aluminum diethylphosphinate (ADP) and melamine polyphosphate (MPP) in PA66/GF. Its oligo-PA6 backbone provides good compatibility with PA66, while its low molecular weight (Mn = 10,984 g mol−1; PDI = 2.569) favors dispersion. The phosphorus groups enhance the efficiency of the ADP/MPP system. With 4 parts oligomer and a total flame-retardant loading of 14 parts by mass per 100 parts PA66/GF, the composite achieved UL-94 V-0 rating, a limiting oxygen index (LOI) of 36.1%, a GWIT of 800 °C, and a CTI of 600 V. Its heat deflection temperature, tensile strength, notched impact strength, and flexural modulus were 178.8 °C, 95.0 MPa, 8.7 kJ m−2, and 8984 MPa, respectively. Compared with the conventional 20-part system, total additive loading decreased by 30%, with simultaneous improvements in flame retardancy, electrical safety, and mechanical properties. This offers a scalable route to high-performance PA66/GF composites.
SN  - 2073-4360
ER  -