Enhancing the liquid oxygen compatibility of epoxy resin by introducing a novel phosphorus / sulfur-containing flame retardant

IF 7.4 2区 化学 Q1 POLYMER SCIENCE Polymer Degradation and Stability Pub Date : 2025-06-01 Epub Date: 2025-02-27 DOI:10.1016/j.polymdegradstab.2025.111296
Rui Yin , Yuhang Liu , Yi Luo , Jia Yan , Jialiang Li , Duo Chen , Tao Sun , Shichao Li , Zhanjun Wu
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Abstract

The compatibility between epoxy resin with liquid oxygen (LOX) plays the critical role in the application of resin-based composite to LOX tanks of launch vehicles. A novel phosphorus/sulfur-containing flame retardant (DPAMT) was synthesized via a facile one-pot method with DOPO, p-hydroxybenzaldehyde and 2-Amino-5-mercapto-1,3,4-thiadiazole and used to enhance the LOX compatibility of epoxy resin. The chemical structure of DPAMT was confirmed by FTIR spectra, 1H NMR and 31P NMR spectra. The impact reaction sensitivity (IRS) index of modified epoxy resin decreased with increasing DPAMT content and reached zero (means being compatible with LOX) when the DPAMT content was up to 6 wt.%. TGA, LOI values, UL-94 test, Cone calorimeter test (CCT), XPS of residues after LOX impact and pyrolysis behavior of DPAMT were investigated to explore the mechanism of DPAMT affecting the LOX compatibility of epoxy resin. The results showed that DPAMT endowed epoxy resin with enhanced thermal stability and excellent flame retardancy. When the modified epoxy resin suffered impacts, the S·, PO· and PO2· radicals as well as SO2 exserting quenching effect by reacting with the active H·, OH· and O· radicals were released. Meanwhile, the P-containing acids and S-containing acids generated promoted the dehydration and carbonization of the epoxy resin to form protective charring layer. It was considered that the synthesized DPAMT was an effective addictive of epoxy resin to enhance the compatibility with LOX.
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引入新型含磷/含硫阻燃剂,提高环氧树脂的液氧相容性
环氧树脂与液氧的相容性是树脂基复合材料应用于运载火箭液氧储罐的关键。以DOPO、对羟基苯甲醛和2-氨基-5-巯基-1,3,4-噻二唑为原料,采用简易一锅法合成了一种新型含磷/含硫阻燃剂(DPAMT),并用于提高环氧树脂的LOX相容性。DPAMT的化学结构通过FTIR、1H NMR和31P NMR进行了确证。改性环氧树脂的冲击反应灵敏度(IRS)指数随着DPAMT含量的增加而降低,当DPAMT含量达到6 wt.%时达到零(即与LOX相容)。通过对DPAMT的TGA、LOI值、UL-94测试、Cone量热测试(CCT)、冲击后残留物的XPS和热解行为进行研究,探讨DPAMT影响环氧树脂与LOX相容性的机理。结果表明,DPAMT赋予环氧树脂增强的热稳定性和优异的阻燃性。改性后的环氧树脂受到冲击时,S·、PO·、PO2·自由基和SO2通过与活性H·、OH·、O·自由基反应释放出淬灭作用。同时产生的含p酸和含s酸促进了环氧树脂的脱水和碳化,形成保护炭层。认为合成的DPAMT是一种有效的环氧树脂添加剂,可以增强环氧树脂与LOX的相容性。
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来源期刊
Polymer Degradation and Stability
Polymer Degradation and Stability 化学-高分子科学
CiteScore
10.10
自引率
10.20%
发文量
325
审稿时长
23 days
期刊介绍: Polymer Degradation and Stability deals with the degradation reactions and their control which are a major preoccupation of practitioners of the many and diverse aspects of modern polymer technology. Deteriorative reactions occur during processing, when polymers are subjected to heat, oxygen and mechanical stress, and during the useful life of the materials when oxygen and sunlight are the most important degradative agencies. In more specialised applications, degradation may be induced by high energy radiation, ozone, atmospheric pollutants, mechanical stress, biological action, hydrolysis and many other influences. The mechanisms of these reactions and stabilisation processes must be understood if the technology and application of polymers are to continue to advance. The reporting of investigations of this kind is therefore a major function of this journal. However there are also new developments in polymer technology in which degradation processes find positive applications. For example, photodegradable plastics are now available, the recycling of polymeric products will become increasingly important, degradation and combustion studies are involved in the definition of the fire hazards which are associated with polymeric materials and the microelectronics industry is vitally dependent upon polymer degradation in the manufacture of its circuitry. Polymer properties may also be improved by processes like curing and grafting, the chemistry of which can be closely related to that which causes physical deterioration in other circumstances.
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