Synthesis of Thermostable, Anti-dripping DOPO-based Phosphorus-nitrogen Synergistic Flame Retardant and Its Application in Flame-retardant PA66 Blends

Chen-long Su; Yu-ting Ren; Ping Zhu; Yong Zhou; Xian-bo Huang; Du-jin Wang; Xia Dong

doi:10.11777/j.issn1000-3304.2026.26086

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Synthesis of Thermostable, Anti-dripping DOPO-based Phosphorus-nitrogen Synergistic Flame Retardant and Its Application in Flame-retardant PA66 Blends

Research Article | 更新时间：2026-10-15

- Synthesis of Thermostable, Anti-dripping DOPO-based Phosphorus-nitrogen Synergistic Flame Retardant and Its Application in Flame-retardant PA66 Blends
- Acta Polymerica Sinica Pages: 1-16(2026)
- 作者机构：
  
  1.中国科学院化学研究所北京分子科学国家研究中心工程塑料院重点实验室北京 100190
  2.中国科学院大学北京 100049
  3.金发科技股份有限公司广州 510663
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26086
  CLC：
- CSTR：32057.14.GFZXB.2026.7638.
- Received：25 April 2026，
  
  Accepted：28 June 2026，
  
  Online First：15 October 2026，
- 稿件说明：
移动端阅览
苏晨龙, 任宇婷, 朱平, 周勇, 黄险波, 王笃金, 董侠. 耐高温、抗熔滴的DOPO基磷氮协同阻燃剂的合成及其在聚酰胺66共混阻燃中的应用. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26086.

Su, C. L.; Ren, Y. T.; Zhu, P.; Zhou, Y.; Huang, X. B.; Wang, D. J.; Dong, X. Synthesis of thermostable, anti-dripping DOPO-based phosphorus-nitrogen synergistic flame retardant and its application in flame-retardant PA66 blends. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26086.
苏晨龙, 任宇婷, 朱平, 周勇, 黄险波, 王笃金, 董侠. 耐高温、抗熔滴的DOPO基磷氮协同阻燃剂的合成及其在聚酰胺66共混阻燃中的应用. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26086. DOI： CSTR： 32057.14.GFZXB.2026.7638..

Su, C. L.; Ren, Y. T.; Zhu, P.; Zhou, Y.; Huang, X. B.; Wang, D. J.; Dong, X. Synthesis of thermostable, anti-dripping DOPO-based phosphorus-nitrogen synergistic flame retardant and its application in flame-retardant PA66 blends. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26086. DOI： CSTR： 32057.14.GFZXB.2026.7638..

摘要

为提升聚酰胺66 (PA66)的阻燃性能并改善其熔滴问题，设计合成了一种新型9

10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)基磷氮协同阻燃剂4

4′-((1

4-亚苯基双(亚胺基))双((6-氧代二苯并[

]

氧磷杂环己烯-6-基)亚甲基))二苯甲腈(PCDO)，将其单独或与二乙基次磷酸铝(ADP)、三聚氰胺聚磷酸盐(MPP)复配后，通过熔融共混法制备了阻燃改性PA66共混料. 系统表征了PCDO的化学结构，研究了共混料的热性能、加工性能、阻燃性能及阻燃机理. 结果表明，PCDO的初始热分解温度达302 ℃，可满足PA66熔融加工要求，且氰基可通过交联作用提高熔体强度、抑制熔滴. 阻燃性能测试显示，采用PCDO和ADP改性的PA66-P-A综合性能最佳，其极限氧指数(LOI)提升至29.0%，通过垂直燃烧测试(UL-94) V-0评级且无熔滴，峰值热释放速率和总热释放量较纯PA66分别下降29.5%和34.9%. 阻燃机理研究表明，PCDO及其复配体系通过气相与凝聚相的协同作用发挥阻燃效果. 本工作开发的PCDO基磷氮阻燃体系环境友好、阻燃性能优异，为PA66在高端阻燃需求领域的应用提供了新方案，也为PA66阻燃改性研究提供了新思路与理论支撑.

Abstract

To improve the flame retardancy and alleviate the melt-dripping problem of polyamide 66 (PA66)

a novel DOPO-based phosphorus-nitrogen synergistic flame retardant

4′-((1

4-phenylenebis(azanediyl))bis((6-oxidodibenzo[

]

oxaphosphinin-6-yl)methyl

ene))dibenzonitrile (PCDO)

was designed and synthesized in this study. Flame-retardant modified PA66 blends were prepared

via

melt blending by incorporating PCDO individually or in combination with aluminum diethylphosphinate (ADP) and melamine polyphosphate (MPP). The chemical structure of PCDO was characterized using nuclear magnetic resonance (NMR)

Fourier transform infrared (FTIR) spectroscopy

and other techniques. The thermal properties

processability

flame retardancy

and flame-retardant mechanism of the composites were systematically investigated using DSC

TGA

Underwriters Laboratories (UL) 94 vertical burning test

limiting oxygen index (LOI)

cone calorimeter test (CCT)

TG-FTIR

scanning electron microscopy (SEM)

and rheological measurements. The results showed that the initial thermal decomposition temperature of PCDO reached 302 ℃

which meets the melt-processing requirements of PA66. Meanwhile

the cyano groups could enhance the melt strength and suppress melt dripping through crosslinking. Flame retardancy tests demonstrated that PA66-P-A (PA66 blended with PCDO and ADP) exhibited the best comprehensive performance

with an LOI of 29.0%

passing the UL-94 V-0 rating without melt dripping. Compared with neat PA66

the peak heat release rate and total heat release were reduced by 29.5% and 34.9%

respectively. The flame-retardant mechanism study revealed that PCDO and its composite systems exert flame-retardant effects through the synergistic action of gas-phase and condensed-phase mechanisms. The environmentally friendly PCDO-based phosphorus-nitrogen flame-retardant system developed in this study demonstrates excellent flame retardancy

providing a novel strategy for the application of PA66 in high-end flame-retardant fields

as well as new ideas and theoretical support for the flame-retardant modification of PA66.

关键词

Keywords

references

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