Influence of Phosphorus-containing Polyol OP550 on the Thermal, Mechanical, and Flame-retardant Performance of Poly(tetramethylene ether glycol)-based Thermoplastic Polyurethane

WANG Yu-bao; MA Guo-sheng; SHI Shao-feng; WEI Meng-meng; WANG Xiao-lei; CHENG Li; DENG Kang-qing; CAO Lan

doi:10.14028/j.cnki.1003-3726.2026.26.107

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Influence of Phosphorus-containing Polyol OP550 on the Thermal, Mechanical, and Flame-retardant Performance of Poly(tetramethylene ether glycol)-based Thermoplastic Polyurethane

更新时间：2026-07-27

- Influence of Phosphorus-containing Polyol OP550 on the Thermal, Mechanical, and Flame-retardant Performance of Poly(tetramethylene ether glycol)-based Thermoplastic Polyurethane
- Polymer Bulletin Vol. 39, Issue 8, Pages: 1464-1474(2026)
- 作者机构：
  
  青岛科技大学高分子科学与工程学院　青岛 266042
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2026.26.107
  CLC：
- Received：01 March 2026，
  
  Accepted：28 April 2026，
  
  Online First：13 July 2026，
  
  Published：20 August 2026
- 稿件说明：
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王玉豹, 马国晟, 石绍凤, 魏萌萌, 王小蕾, 程莉, 邓康清, 曹兰. 含磷多元醇OP550对‌聚四氢呋喃‌基热塑性聚氨酯热稳定、力学及阻燃性能的影响. 高分子通报, 2026, 39(8), 1464–1474.

Wang, Y. B.; Ma, G. S.; Shi, S. F.; Wei, M. M.; Wang, X. L.; Cheng, L.; Deng, K. Q.; Cao, L. Influence of phosphorus-containing polyol OP550 on the thermal, mechanical, and flame-retardant performance of poly(tetramethylene ether glycol)-based thermoplastic polyurethane. Polym. Bull. (in Chinese), 2026, 39(8), 1464–1474.
王玉豹, 马国晟, 石绍凤, 魏萌萌, 王小蕾, 程莉, 邓康清, 曹兰. 含磷多元醇OP550对‌聚四氢呋喃‌基热塑性聚氨酯热稳定、力学及阻燃性能的影响. 高分子通报, 2026, 39(8), 1464–1474. DOI： 10.14028/j.cnki.1003-3726.2026.26.107.

Wang, Y. B.; Ma, G. S.; Shi, S. F.; Wei, M. M.; Wang, X. L.; Cheng, L.; Deng, K. Q.; Cao, L. Influence of phosphorus-containing polyol OP550 on the thermal, mechanical, and flame-retardant performance of poly(tetramethylene ether glycol)-based thermoplastic polyurethane. Polym. Bull. (in Chinese), 2026, 39(8), 1464–1474. DOI： 10.14028/j.cnki.1003-3726.2026.26.107.

摘要

热塑性聚氨酯(TPU)作为性能优异的高分子材料，其阻燃改性对拓展应用领域至关重要。本研究将含磷多元醇OP550作为反应型阻燃剂，通过两步本体聚合法制备了一系列PTMG基TPU材料，系统探究了OP550含量对TPU微观结构、力学性能、热稳定性、表面性质及阻燃性能的影响。傅里叶变换红外光谱(FTIR)与示差扫描量热法(DSC)分析表明，OP550中的强极性P＝O基团与硬段N－H形成竞争性氢键，破坏了硬段间的有序堆积与微相分离结构，导致氢键化指数从1.99降至1.73，软段玻璃化转变温度(

)由−16.1 ℃升高至−4.1 ℃。锥形量热与垂直燃烧测试结果显示，OP550的添加使热释放速率峰值(PHRR)显著降低，燃烧进程延缓，残炭率明显提高，UL-94测试中熔滴现象得到有效抑制。扫描电子显微镜(SEM)观察表明，OP550促使燃烧残炭由疏松多孔的“海绵状”结构转变为连续致密的块状炭层，体现出典型的凝聚相阻燃机制。接触角测试显示材料表面由疏水向亲水转变，这反映了引入强极性磷氧基团后TPU本体极性的提升。热重分析法(TGA)结果表明，OP550虽使初始热分解温度略有前移，但显著提高了高温残炭率。体系中复配的磷酸三聚氰胺与OP550产生了显著的氮磷协同效应。MP不仅在气相释放不可燃气体氮气，还在凝聚相与OP550共同促进了致密膨胀炭层的形成，从而有效阻断了热释放与熔滴。本研究揭示了OP550在TPU中的阻燃机理及其对材料综合性能的调控规律，为开发兼具良好阻燃性与力学性能的高性能TPU材料提供了理论依据与实验参考。

Abstract

Thermoplastic polyurethane (TPU)

a high-performance polymer material

requires flame-retardant modification to expand its application fields. In this study

a phosphorus-containing polyol

OP550

was employed as a reactive flame retardant

and a series of poly(tetramethylene ether glycol) (PTMG)-based TPU materials were successfully synthesized

via

a two-step bulk polymerization method. The effects of varying OP550 contents on the microstructure

mechanical properties

thermal stability

surface characteristics

and flame retardancy of TPU were sy

stematically investigated. Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) analyses revealed that the strongly polar P＝O groups in OP550 formed competitive hydrogen bonds with the N－H groups in the hard segments

disrupting the ordered packing and microphase separation of the hard segments. Consequently

the hydrogen bonding index decreased from 1.99 to 1.73

and the glass transition temperature (

) of the soft segments increased from −16.1 ℃ to −4.1 ℃. Cone calorimeter and vertical burning tests demonstrated that the addition of OP550 significantly reduced the peak heat release rate (PHRR)

delayed the combustion process

increased the char residue

and effectively suppressed melt-dripping in UL-94 tests. Scanning electron microscopy (SEM) observations showed that OP550 transformed the combustion residue from a loose

porous “sponge-like” structure into a continuous and dense blocky char layer

indicating a typical condensed-phase flame-retardant mechanism of action. Contact angle measurements revealed a transition from hydrophobic to hydrophilic surface behavior

reflecting the increased polarity of the TPU matrix upon the introduction of polar phosphorus–oxygen groups. Thermogravimetric analysis (TGA) results indicated that although OP550 slightly shifted the initial thermal decomposition temperature to a lower value

it markedly enhanced the char yield at high temperatures. The combination of melamine phosphate (MP) and OP550 produced a significant nitrogen–phosphorus synergistic effect. MP not only released non-flammable nitrogen gas in the gas phase but also promoted

together with OP550 in the condensed phase

the formation of a dense intumescent char layer

effectively suppressing heat release and melt dripping. This study systematically elucidates the flame-retardant mechanism of OP550 in TPU and its regulation of overall material performance

providing a theoretical basis and experimental reference for developing high-performance TP

U materials with desirable flame retardancy and processability.

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