低热值无卤阻燃剂在环氧树脂中的应用研究进展

Research Progress on Application of Halogen-free Flame Retardants with Low Calorific Value in Epoxy Resins

摘要

环氧树脂（EP）具有优异的力学性能、耐腐蚀性和黏结性，在诸多领域应用广泛，但其易燃性限制其使用范围。文章综述低热值无卤阻燃剂在EP中的应用现状，分析无机、有机、膨胀型及生物基等阻燃剂体系在EP中的应用效果，揭示不同阻燃体系对EP燃烧热值的影响机理。最后，展望低热值无卤阻燃剂在EP领域的优化方向与应用前景。

Abstract

Epoxy resin (EP) exhibits excellent mechanical properties, corrosion resistance, and adhesion, rendering it widely applicable across various fields. Nevertheless, its inherent flammability significantly constrains its practical applications. This paper provides a comprehensive review of the current state of low-calorific-value halogen-free flame retardants in EP, evaluates the performance of inorganic, organic, intumescent, and bio-based flame retardant systems, and elucidates the underlying mechanisms by which these systems influence the combustion calorific value of EP. Furthermore, future optimization strategies and potential applications of low-calorific-value halogen-free flame retardants in EP are prospected.

关键词

低热值无卤阻燃剂 / 无卤阻燃剂体系 / 环氧树脂 / 阻燃改性 / 热稳定性

Key words

Low calorific value halogen-free flame retardant / Halogen-free flame retardant system / EP / Flame retardant modification / Thermal stability

环氧树脂(EP)是一种重要的热固性材料，对金属黏接力强，具有良好的耐化学腐蚀性、电气绝缘性和力学性能，且制造成本较低，广泛应用于集成电路、电子电气和化工涂料等领域^[1-3]。但EP的极限氧指数(LOI)仅为19.8%，属于极易燃材料，应用存在较大局限^[4-6]。因此，提升EP的阻燃性能刻不容缓^[7-9]。低热值无卤阻燃剂作为一类通过化学或物理作用抑制材料燃烧的功能性助剂，其优势在于可通过抑制EP热分解过程中的热量释放，显著降低材料燃烧时的总热释放量(THR)与热释放速率(HRR)^[10-12]。这种低热值特性不仅能延缓火焰蔓延速度，还能同步降低燃烧烟雾的生成量^[13-15]。

本文从低热值无卤阻燃剂在EP中的研究现状、性能影响及应用进展3个维度出发，阐述该类阻燃剂对EP的HRR与THR的影响，综述其对EP阻燃性能的提升作用，展望低热值无卤阻燃剂在EP中的改进方法与应用趋势。

1 低热值无卤无机阻燃剂

近年来，低热值无卤阻燃剂在EP中的应用研究取得显著进展。低热值无机阻燃剂因其环境友好性和高效阻燃性，成为阻燃领域的研究热点^[16-17]。这类阻燃剂与EP复合能够通过吸热降温、催化成炭等机制产生协同作用，不仅可以显著提升材料的LOI与垂直燃烧等级，还能有效降低燃烧过程中的THR，同时增强材料的热稳定性^[18-19]。

1.1 氢氧化铝(ATH)阻燃剂

ATH对EP的阻燃性能、力学性能及热学性能均产生显著影响。在阻燃性能方面，ATH分解产生的水蒸气可稀释可燃气体，使EP的热释放速率峰值(PHRR)降低约30%，显著提升其阻燃性能。在力学性能方面，适量的ATH能增强EP的硬度和刚度，起到填充与增强作用，但因其相容性差，过量添加会导致EP韧性降低，引发应力集中和易断裂问题。在热学性能方面，ATH可提高EP的热稳定性，其在高温下分解产生的物质有助于形成隔热层，减缓热量传递，降低EP材料在高温下的分解速率^[20-22]。

CHAI等^[23]以ATH为阻燃剂，研究ATH/EP体系的抑烟阻燃性能。当ATH添加质量分数为15%时，与EP相比，ATH/EP复合材料的PHRR降低28.49%，THR降低17.65%，CO生成速率(COP)降低30.24%。对残炭率的分析证实了ATH在高温下能吸收大量热量，生成氧化铝(Al₂O₃)膜和水，二者协同作用有效降低了EP的燃烧热值和烟气生成量。LIU等^[24]选用聚磷酸铵(APP)和ATH为阻燃剂，将二者添加EP基体中，制备出具有协同阻燃效应的复合材料。当APP与ATH的总添加质量分数为10%时，EP复合材料的PHRR降低48%，THR下降38%；LOI由19.8%提升至28.9%，达到UL-94 V-0级，具有较高的阻燃水平。图1为ATH和APP的分解过程^[24]。

1.2 碳酸钙(CaCO₃)阻燃剂

CaCO₃用于EP阻燃时，其高温分解生成CaO和CO₂，CO₂气体能够抑制燃烧、降低氧气含量，CaO在材料表面形成炭层，阻止热量传递。但添加量过高可能导致材料变脆，加剧发烟问题^[25]。

REN等^[26]以牡蛎壳粉(OSP) (主要成分为CaCO₃)和APP为原料，采用机械力化学法合成无卤阻燃剂功能化牡蛎壳粉(FOSP)并将其应用于EP复合材料。结果表明：EP复合材料的PHRR、THR、烟生成速率峰值(PSPR)分别从EP的991.9 kW/m²、117.4 MJ/m²、0.254 m²/s下降至492.9 kW/m²、104.6 MJ/m²、0.208 m²/s。CaCO₃在燃烧时可形成更致密的炭层，阻隔热量与O₂的传递，具有高效的阻燃抑烟性能。FOSP对EP复合材料的热释放量具有显著的降低作用。LI等^[27]采用钛酸四丁酯溶胶和氢氧化镍对纳米CaCO₃进行改性，制备新型阻燃剂Ni-TiO₂@CaCO₃并将其引入EP中。锥形量热测试表明：CaCO₃使EP的PHRR和PSPR分别从1 101 kW/m²和0.39 m²/s降至769 kW/m²和0.32 m²/s，Ni-TiO₂@CaCO₃使PHRR和PSPR进一步降至511 kW/m²和0.25 m²/s。热重分析显示，CaCO₃可提高EP的热稳定性，有效减少EP的热量释放。

1.3 APP阻燃剂

APP是一种常见的低热值无卤阻燃剂，在与EP复合时可形成稳定的膨胀炭层，有效提高EP的阻燃效果。然而，阻燃剂添加量过大会使EP的力学性能降低，同时面临发烟量大、热稳定性下降等问题，这极大地限制其在建筑材料领域的广泛应用^[28]。

FAN等^[29]制备新型磷酸酯类阻燃剂聚磷酸-2-10-氢-9-氧杂-10-磷杂菲-10-氧化物基对苯二酚对甲苯酯(POTP)，并加入APP和蒙脱土(MMT)研究其对EP阻燃性能的影响。当MMT与APP的添加质量分数均为0时，EP的LOI仅为19.8%，UL-94无等级；当MMT与APP的添加质量分数分别达到1.00%和5.33%时，EP复合材料的LOI从19.8%升至27.6%，UL-94从无等级升至V-0级。在热稳定性方面，EP复合材料的PHRR、THR、总产烟量(TSP)分别从EP的993.1 kW/m²、88.4 MJ/m²、105.3 m²降至496.2 kW/m²、64.2 MJ/m²、75.4 m²，表明POTP/MMT/APP的加入能有效降低EP的热释放及烟气生成。GENG等^[30]以ZIF-67为桥联剂，制备高效阻燃剂聚磷酸铵负载改性层状双氢氧化物(APP@M-LDH)，同时对其微观结构、化学组成和热稳定性进行表征。结果表明：EP/4APP@M-LDH的PHRR、THR和TSP较EP分别降低34.0%、35.3%和40.3%，表明APP@M-LDH能有效降低EP的热量释放和烟气生成。CHENG等^[31]采用生物基氨基酸L-赖氨酸(Lys)作为APP的表面改性剂，通过阳离子交换反应制备了Lys改性聚磷酸铵(L-APP)，用于EP阻燃。结果表明：与EP相比，经Lys改性后的阻燃复合材料PHRR和PSPR分别降低77.6%和61.6%，体现了L-APP良好的阻燃抑烟性能；当L-APP添加质量分数为15%时，复合材料的LOI高达31.7%，并通过UL-94 V-0级，表明Lys可有效改善APP的阻燃性，并显著降低EP的热量释放。图2为Lys改性APP的阻燃机理^[31]。

1.4 氢氧化镁(MDH)阻燃剂

MDH阻燃剂因其无毒、无烟、无害等优点，被广泛应用于各类复合材料中。此外，MDH还具有优异的热稳定性，已成为重要的无卤阻燃剂^[32]。然而，MDH在EP中难以均匀分散，阻燃性能较差，限制其在阻燃EP中的应用^[33]。

ZHAO等^[34]以马来酸、MDH和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)为原料，合成一种新型有机-无机杂化阻燃剂10-(1,4-二羧酸镁盐)-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DMMH)，将其用于提升EP的阻燃性能。结果表明：添加DMMH质量分数为1.7%的EP复合材料，其PHRR、PSPR、THR、TSP分别从EP的1 615.82 kW/m²、0.456 m²/s、91.11 MJ/m²、26.95 m²降至734.78 kW/m²、0.257 m²/s、59.13 MJ/m²、16.68 m²。研究表明，DMMH可形成连续致密的膨胀炭层，有效降低EP复合材料的热释放和烟气生成。BI等^[35]采用仿生负载铁聚多巴胺(Fe-PDA)对MDH进行表面功能化，制备功能化阻燃剂MDH@Fe-PDA并将其引入EP中。随着MDH@Fe-PDA含量的增加，EP复合材料的LOI从20.5%提高至29.3%，PHRR、TSP、PSPR分别显著降低57%、21%和67%。这表明MDH@Fe-PDA能够显著提高EP的阻燃性能，有效降低其热释放。

2 低热值无卤有机阻燃剂

除无机阻燃剂外，有机阻燃剂在EP中的应用也备受关注。有机阻燃剂不仅能提高EP的阻燃性能、降低烟毒释放量，还能提升其热稳定性。例如，磷系阻燃剂、氮系阻燃剂及磷-氮协同阻燃剂等，在高温下能促使EP形成稳定的炭化层，不仅有助于阻燃，还能有效阻挡热量传递，从而提高EP的热稳定性^[36-38]。

2.1 有机磷系阻燃剂

SHI等^[39]设计一种新型含磷无卤离子液体([Dmim]Tos)并将其用于EP阻燃。当EP中加入质量分数为7.5%的[Dmim]Tos时，EP/[Dmim]Tos复合材料的LOI达到33.9%，通过UL-94 V-0级。锥形量热数据显示，其平均有效燃烧热(av-EHC)、THR和PHRR分别从EP的22.8 MJ/kg、66.2 MJ/m²、1 125.8 kW/m²降至20.1 MJ/kg、56.2 MJ/m²、767.0 kW/m²，表明[Dmim]Tos对EP的热释放具有显著的抑制作用。GAO等^[40]合成了磷酸改性的三嗪类共价有机骨架(PCOF)，用以提高EP的阻燃性能。12% PCOF/EP复合材料的LOI由24.8%提高至28.6%，UL-94达V-0级。热稳定性方面，其PHRR、THR、TSP分别从EP的921 kW/m²、84 MJ/m²、18.20 m²降至641 kW/m²、115 MJ/m²、16.75 m²，表明PCOF可显著提高EP的阻燃性能和热稳定性，并有效降低其燃烧热释放。LÜ等^[41]合成新型沸石咪唑骨架(ZIF-8)纳米粒子@聚磷腙(PZN)核壳结构并将其与APP协同应用于EP阻燃研究。阻燃性能方面，EP/3% ZIF-8@PZN/18% APP复合材料的LOI从19.3%升至31.0%，UL-94从无等级提升至V-0级。热稳定性方面，其PHRR、THR、PSPR分别从EP的1 631.24 kW/m²、88.85 MJ/m²、0.347 m²/s降至312.60 kW/m²、30.37 MJ/m²、0.095 m²/s，表明ZIF-8、PZN与APP三者的协同作用可有效提高EP的阻燃性和热稳定性。图3为ZIF-8@PZN在EP复合材料中的阻燃机理^[41]。

WANG等^[42]合成了含磷苯并三唑阻燃剂(PDI)并用于EP阻燃。在阻燃性能方面，添加质量分数为11% PDI的EP/PDI复合材料其LOI达32%，UL-94达V-0级；与EP相比，其TSP、PHRR、THR分别降低64.1%、46.9%和20.6%，表明PDI具有显著的阻燃抑烟效果。在力学性能方面，添加5% PDI时，EP/PDI复合材料的拉伸强度、断裂伸长率和冲击强度较EP分别提升27.2%、53.3%和91.4%，表明PDI可有效降低EP的HRR，同时增强EP的韧性和强度。

2.2 有机氮系阻燃剂

为改善EP的阻燃性和抑烟性，QIN等^[43]合成一种新型二维超分子三偏磷酸三聚氰胺阻燃剂(MAP)。添加4% MAP的EP复合材料其LOI高达30%，且UL-94达V-0级。热稳定性方面，其PHRR、THR、PSPR、TSP分别从EP的1 076 kW/m²、88.6 MJ/m²、0.44 m²/s、36.9 m²降至370 kW/m²、72.9 MJ/m²、0.16 m²/s、20.1 m²，表明MAP能有效降低EP的热释放量。CHENG等^[44]制备聚多巴胺/三聚氰胺复合微胶囊红磷(RP@PDA/MA)并将其应用于EP阻燃。EP/7% RP@PDA/MA复合材料的LOI从EP的19.4%提高至30.9%，UL-94提升至V-0级。在热稳定性方面，其PHRR、THR、PSPR、TSP分别从EP的1 183.7 kW/m²、101.0 MJ/m²、0.31 m²/s、29.5 m²降至412.6 kW/m²、53.1 MJ/m²、0.26 m²/s、35.7 m²。RP@PDA/MA大幅提高了EP的阻燃和抑烟性能，有效降低EP的HRR。图4为RP@PDA/MA的阻燃机理^[44]。

为同时提高EP的阻燃性和抑烟性，ZHU等^[45]通过一步法合成三聚氰胺苯次膦酸酯(MABP)并将其用于改性EP。在阻燃性能方面，添加10% MABP的EP复合材料其LOI从25%升至33%，UL-94从无等级提升至V-0级。在热稳定性方面，其PHRR、THR、TSP分别从EP的1 085 kW/m²、76.0 MJ/m²、71.4 m²降至487 kW/m²、55.4 MJ/m²、28.6 m²。MABP的加入不仅显著提高了EP的阻燃性，还降低了其HRR。

2.3 有机磷-氮协同阻燃剂

为提高EP的阻燃性和热稳定性，DAI等^[46]以2-苯并噻唑胺和2-羟基-1-萘甲醛为原料合成一种新型磷氮系阻燃剂HBD。结果表明：添加8% HBD的EP复合材料其LOI高达33.5%，UL-94达V-0级；其PHRR、THR、PSPR、TSP分别从EP的1 063.1 kW/m²、76.1 MJ/m²、0.55 m²/s和71.4 m²降至528.5 kW/m²、35.9 MJ/m²、0.24 m²/s和35.18 m²。HBD的加入使EP复合材料兼具高效的抑烟效果以及优异的阻燃性和热稳定性。HUANG等^[47]通过金属有机框架(MOF)与含磷氮离子液体的协同作用，设计一种新型复合阻燃剂[IL@NH₂-MIL-101(Al)]并将其应用于EP。向EP基体中添加3% IL@NH₂-MIL-101(Al)后，复合材料的LOI从25.7%升至29.2%；其PHRR、THR和TSP分别从EP的1 201.31 kW/m²、119.05 MJ/m²和37.86 m²降至585.72 kW/m²、101.92 MJ/m²和32.91 m²。研究表明，IL@NH₂-MIL-101(Al)可有效降低EP的HRR，并赋予EP优异的抑烟性和热稳定性。图5为IL@NH₂-MIL-101(Al)的合成及对EP的阻燃效果^[47]。

WANG等^[48]合成一种新型氮、磷、硅多元阻燃剂(HNTPC)，并将其作为EP的添加型阻燃剂。在阻燃性能方面，添加10% HNTPC的EP复合材料其LOI从26.4%提高至32.6%，UL-94达V-1级；在热稳定性方面，其PHRR、THR和TSP分别从EP的953.53 kW/m²、50.53 MJ/m²和36.43 m²降至571.82 kW/m²、39.65 MJ/m²和29.24 m²，表明HNTPC能够有效提高EP的阻燃性和热稳定性。

3 生物基阻燃剂

EP具有优良的化学和物理性能，在生活和工程中应用广泛，但其低阻燃性阻碍了更广泛的应用^[49]。生物基阻燃剂毒性较低，对人体和生态系统危害较小，常见的生物基阻燃剂有壳聚糖(CS)、木质素、藻酸盐、甲壳素等，具有潜在的阻燃应用价值^[50]。

WANG等^[51]合成了生物质阻燃剂(PAPDOPO)，用于EP阻燃。当添加PAPDOPO质量分数为2%时，EP/PAPD-2的LOI达到31.9% (EP为23.9%)，通过UL-94 V-1级；当添加PAPDOPO质量分数为4%时，EP-PAPD-4的LOI高达35.3%；进一步添加质量分数为6%~8%的DMPY时，EP/PAPD-6和EP/PAPD-8的LOI均高于36%，通过UL-94 V-0级。这表明PAPDOPO能够有效降低EP的HRR，表现出良好的阻燃性能。LIANG等^[52]制备一种可再生环保型木质素基阻燃剂并将其应用于EP。添加质量分数为20%的该阻燃剂后，EP复合材料的残炭率提高了15.3%，LOI高达36.1%，TSP从42.0 m²降至9.9 m²，THR从108.9 MJ/m²降至53.1 MJ/m²，表明木质素基阻燃剂能有效降低EP的热值。

4 新型无卤阻燃剂

近年来，新型无卤阻燃剂在EP中的应用取得一定的性能突破。LIU等^[53]合成经济型阻燃剂焦磷酸二蜜胺(DMPY)并将其用于EP阻燃。当添加DMPY质量分数为9%时，EP/DMPY复合材料通过UL-94 V-0级，LOI达28.7%，THR从123.2 MJ/m²降至75.4 MJ/m²，PHRR从1 345 kW/m²降至608 kW/m²，表明DMPY是有效的EP阻燃剂。DMPY在燃烧过程中分解，促进EP基体的降解和炭化，从而实现有效阻燃。WANG等^[54]合成一种新型成炭剂聚哌嗪苯胺基磷酰胺(PPTA)，并将其与APP共混制备阻燃EP样品。当APP添加质量分数为10%时，EP复合材料的LOI达30.2%，但UL-94无明显改善；当添加7.5% APP与2.5% PPTA时，EP复合材料通过UL-94 V-0级，LOI高达33.0%，PHRR从1 074 kW/m²降至600 kW/m²，表明PPTA与APP复配可有效提高EP的阻燃性能。添加PPTA和APP后，EP复合材料在燃烧过程中形成了更稳定、更致密的炭层，能更好地阻隔热量的传递。图6为PPTA的合成路线^[54]。

5 结论

通过对磷系、氮系及金属无机氢氧化物等典型无卤阻燃剂的研究发现，低热值无卤阻燃剂在赋予EP阻燃性能的同时，能够有效降低材料燃烧时的HRR与THR，并减少有毒烟雾的产生，符合消防安全需求。尽管EP阻燃应用研究已取得一定成果，但仍处于持续发展阶段，存在若干关键问题亟待解决，如阻燃剂添加量较高导致加工性能下降、复杂工艺带来的成本增加等。

未来对低热值无卤阻燃剂的研究可从以下方向展开：一是开发新型多功能协同阻燃体系，通过精准分子设计与复合改性，深度融合凝聚相炭层构建机制与气相自由基捕获，在提升阻燃性能的同时有效降低阻燃剂添加量；二是探索绿色合成路径与规模化制备技术，利用可再生原料与温和反应条件实现阻燃剂的低碳生产；三是深入研究无机阻燃剂与有机磷系阻燃剂等的协同增效机制，通过多组分复合优化EP材料的阻燃性能、力学性能与环境友好性。

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基金资助

绿色化工新材料科研创新团队(兰石化大学校发［2025］201号)