Novel phosphorous-containing epoxy thermosets with improved anti-flammability, smoke suppression, and dielectric properties

IF 6.3 2区化学 Q1 POLYMER SCIENCE Polymer Degradation and Stability Pub Date : 2024-08-14 DOI:10.1016/j.polymdegradstab.2024.110954

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Abstract

As one of the most commonly used thermosetting resins, the flammability of epoxy resins (EPs) has become a key factor limiting the expansion of their application range. Herein, a novel phosphorous-containing epoxy monomer (EDPPO) was synthesized using diallyl amine and diphenyl phosphoryl chloride as the starting materials. Subsequently, EDPPO was thermally cured with two diamine hardeners, 4, 4′-diaminodiphenyl sulfone (DDS) and 4,4′-dithiodianiline (DTDA). Additionally, commercial diglycidyl ether of bisphenol A (DGEBA)-type epoxy pre-polymers were cured with DDS and DTDA as comparative samples. The cured EDPPO-based thermosets showed excellent flame-retardant properties coupled with smoke suppression. Specifically, the limiting oxygen index (LOI) for the EDPPO/DDS (P content 6.4 wt.%) reached 32.0 %, and the UL-94 vertical burning test reached a V-0 rating. In addition, the PHRR, THR, and TSP values of EDPPO/DDS were 61.6 %, 49.1 %, and 58.5 % lower than those of DGEBA/DDS, respectively. The flame retardant mechanism analysis indicated that the excellent flame retardancy for cured EDPPO-based thermosets was attributed to the combined modes of action in condensed (promoting the charring capacity) and gaseous phases (quenching the active radicals). More importantly, EDPPO/DDS and EDPPO/DTDA exhibited lower dielectric constant and dielectric loss than DGEBA/DDS and DGEBA/DTDA. This work provided novel phosphorous-containing epoxy thermosets with improved anti-flammability, smoke suppression, and dielectric properties.

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新型含磷环氧热固性塑料具有更好的抗燃性、抑烟性和介电性能

作为最常用的热固性树脂之一，环氧树脂（EPs）的可燃性已成为限制其应用范围扩大的关键因素。本文以二烯丙基胺和二苯基磷酰氯为起始原料，合成了一种新型含磷环氧单体（EDPPO）。随后，用 4，4′-二氨基二苯砜（DDS）和 4，4′-二硫代二苯胺（DTDA）这两种二胺固化剂对 EDPPO 进行热固化。此外，还使用 DDS 和 DTDA 固化了商用双酚 A 二缩水甘油醚（DGEBA）型环氧预聚物作为对比样品。固化后的 EDPPO 基热固性塑料具有优异的阻燃性能和抑烟性能。具体来说，EDPPO/DDS（P 含量为 6.4 wt.%）的极限氧指数（LOI）达到了 32.0%，UL-94 垂直燃烧测试达到了 V-0 级。此外，EDPPO/DDS 的 PHRR、THR 和 TSP 值分别比 DGEBA/DDS 低 61.6%、49.1% 和 58.5%。阻燃机理分析表明，固化后的 EDPPO 基热固性塑料之所以具有优异的阻燃性，是由于其在凝聚相（促进炭化能力）和气相（淬灭活性自由基）中的综合作用模式。更重要的是，与 DGEBA/DDS 和 DGEBA/DTDA 相比，EDPPO/DDS 和 EDPPO/DTDA 的介电常数和介电损耗更低。这项工作提供了新型含磷环氧热固性材料，其抗燃性、烟雾抑制和介电特性都得到了改善。

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来源期刊

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.