Waterborne Polyurethane Modified with Cyanide and Phosphaphenanthrene Synergistic Macromolecular Flame Retardant

Jia-hui Zhou; Yu-jie Wang; Wen-zhi Huang; Dong-mei Bao; Jin-xin Zou; Ya-dian Xie; Guo-yong Zhou

doi:10.11777/j.issn1000-3304.2026.26168

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Waterborne Polyurethane Modified with Cyanide and Phosphaphenanthrene Synergistic Macromolecular Flame Retardant

更新时间：2026-10-15

- Waterborne Polyurethane Modified with Cyanide and Phosphaphenanthrene Synergistic Macromolecular Flame Retardant
- Acta Polymerica Sinica Pages: 1-13(2026)
- 作者机构：
  
  1.贵州民族大学化学工程学院贵阳 550025
  2.贵州民族大学北京大学-贵州民族大学-贵州磷化集团“富矿精开”联合创新实验室贵阳 550025
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26168
  CLC：
- CSTR：32057.14.GFZXB.2026.7707
- Received：03 June 2026，
  
  Accepted：30 July 2026，
  
  Online First：15 October 2026，
- 稿件说明：
移动端阅览
周佳卉, 王钰杰, 黄文治, 宝冬梅, 邹金鑫, 谢雅典, 周国永. 氰基和磷杂菲协同型大分子阻燃剂修饰水性聚氨酯. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26168.

Zhou, J. H.; Wang, Y. J.; Huang, W. Z.; Bao, D. M.; Zou, J. X.; Xie, Y. D.; Zhou, G. Y. Waterborne polyurethane modified with cyanide and phosphaphenanthrene synergistic macromolecular flame retardant. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26168.
周佳卉, 王钰杰, 黄文治, 宝冬梅, 邹金鑫, 谢雅典, 周国永. 氰基和磷杂菲协同型大分子阻燃剂修饰水性聚氨酯. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26168. DOI： CSTR： 32057.14.GFZXB.2026.7707.

Zhou, J. H.; Wang, Y. J.; Huang, W. Z.; Bao, D. M.; Zou, J. X.; Xie, Y. D.; Zhou, G. Y. Waterborne polyurethane modified with cyanide and phosphaphenanthrene synergistic macromolecular flame retardant. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26168. DOI： CSTR： 32057.14.GFZXB.2026.7707.

摘要

水性聚氨酯(WPU)存在易燃性强、释热量大、烟气量多等问题. 含氰基或磷杂菲基团单一型阻燃剂，未能协同发挥凝聚相和气相双相阻燃性能，致使阻燃相关性能弱化. 针对此问题，本研究以2

2'-二烯丙基双酚和2

6-二氟苯甲腈为主要原料，设计合成了一种含氰基和磷杂菲协同型的大分子阻燃剂(DAN). 通过傅里叶变换红外光谱(FTIR)和核磁共振波谱(NMR)表征了其化学组成和结构，并将其用于制备阻燃水性聚氨酯(DANWPU). 借用极限氧指数(LOI)、垂直燃烧(UL-94)和锥形量热法等研究了DANWP胶膜的阻燃特性；采用热重法(TG)和示差扫描量热(DSC)等研究了其热稳定性，选用水接触角、表面能、吸水率及力学性能测试仪分析了该胶膜的耐水性能及力学性能等. 当DAN质量分数为9 wt%时，与纯WPU胶膜相比，该胶膜的极限氧指数(LOI)值由22.0%提升至30.6%，残炭率由0.9%提高至9.

6%，阻燃等级至V-0级. 该胶膜的热释放速率(HRR)、总释放热(THR)、总生烟量(TSP)和烟释放速率(SPR)分别降低了49.0%、47.0%，70.0%和83.0%. 该胶膜CO释放速率(COP)最大为0.009 g·s

-1

，其玻璃化转变温度(

)为37 ℃，与纯WPU胶膜

相比，提高了36 ℃. 该研究结果表明：氰基的凝聚相和磷杂菲的气相具有双基双相协同阻燃作用. 该研究为协同型阻燃剂及其应用于高分子材料研究提供了一定的参考.

Abstract

In this work

waterborne polyurethane (WPU) was inherently susceptibled to combustion

accompanied by substantial heat release and abundant flue gas emission during burning. Flame retardants solely functionalized with cyano or phosphaphenanthrene groups are incapable of exerting synergistic condensed- and gas-phase flame-retardant effects

yielding inferior flame retardancy. In response to this problem

a macromolecular flame retardant (DAN) containing the cyano and phosphaphenanthrene moieties was designed and synthesized using 2

2'-diallylbisphenol (DDBA) and 2

6-difluorobenzonitrile as the main raw materials. The chemical composition and molecular structure of DAN were elucidated by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. Subsequently

DAN was employed for the chemical modification of

waterborne polyurethane (WPU)

and the flame-retardant modified WPU (DANWPU) was thereby fabricated. Limiting oxygen index (LOI)

vertical burning test and cone calorimetry were used to assess the flame retardancy of DANWP films

while thermogravimetry (TG) and differential scanning calorimetry (DSC) were employed to characterize their thermal stability. The water resistance and mechanical properties of the films were further analyzed by water contact angle

surface energy

water absorption and mechanical property tests. When the mass fraction of DAN is 9 wt%

compared with the neat WPU

the LOI value of the DANWPU film achieved a notable rise from 22.0% to 30.6%

and the char residue yield a notable increase from 0.9% to 9.6%

achieving a UL-94 V-0 rating in the vertical burning test. The heat release rate (HRR) and total heat release (THR) of the DANWPU film achieved a decrease of 49.0% and 47.0%

respectively; in addition

the total smoke production (TSP) and smoke production rate (SPR) were dropped by 70.0% and 83.0%

respectively. The maximum CO production rate (COP) of DANWPU was 0.009 g⸱s

-1

. The glass transition temperature (

) of DANWPU was 310.0 ℃

a marked increase of 36.0 ℃ higher than that of the neat WPU film. It can be concluded that cyano and phosphaphenanthrene moieties dominate the condensed and gas phases in the field of flame retardant materials

respectively

and deliver prominent dual-group two-phase synergistic flame retardancy. This work offers valuable insights for developing the synergistic flame retardants and promoting their practical applications in polymeric materials.

关键词

Keywords

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