无卤阻燃含磷环氧树脂的研究进展

无卤阻燃含磷环氧树脂中的磷成分具有气相和凝聚相的双重阻燃作用,且材料本身降解产物不产生可持续性环境污染物,因而作为环境友好型阻燃材料而被广泛研究。本文综述了近年来关于含9,10-二氢-9-氧杂-10-磷杂菲10-氧化物(DOPO)环氧树脂体系（包含DOPO环氧树脂、DOPO基固化剂和添加型DOPO改性聚合物）、磷酸酯型环氧树脂体系（包括磷酸酯环氧树脂、环状磷酸酯环氧树脂、磷酸酯型固化剂）、含磷固化剂以及磷腈环氧树脂和磷-硅环氧树脂的研究进展,介绍了每种体系的性能特点。总结了含磷环氧树脂的阻燃性能、热性能、阻燃机理,以及磷-氮协同效应、磷-硅复合二元体系的阻燃机理。     

环氧树脂体系阻燃改性研究进展

介绍了阻燃改性环氧树脂常用方法，讨论了各阻燃体系的阻燃机理，并对环氧树脂阻燃技术作了展望。     

改性三聚氰胺氰尿酸盐阻燃环氧树脂研究

采用分子复合技术合成了改性MCA(M-MCA)阻燃环氧树脂,采用UL94垂直燃烧测试及微型量热分析对其性能进行了研究,同时采用热失重分析方法研究其降解历程和阻燃机理。结果表明,该材料实现了阻燃剂粒子在环氧溶液及基材中超细及均匀分散,解决了常规MCA阻燃剂在环氧树脂胶液中分散困难、易团聚等问题,改性MCA阻燃树脂比传统MCA具有更佳阻燃效果,该体系阻燃机理以气相阻燃为主。     

磷硅阻燃剂协同效应及其应用

介绍了磷系阻燃剂、硅系阻燃剂及其协同阻燃体系的阻燃机理,回顾了磷硅协同阻燃剂在环氧树脂中的应用情况,并对其应用前景进行了展望.     

含磷环氧树脂及其在无卤阻燃覆铜板中的应用研究进展

针对含磷环氧树脂在覆铜板无卤阻燃及其它方面的广阔应用前景,简述了含磷阻燃剂的阻燃机理,详细介绍了反应型含磷阻燃环氧树脂体系的研究状况,并指出含磷环氧树脂的发展方向。     

无卤阻燃含磷环氧树脂体系的研究进展

综述了磷系阻燃环氧树脂体系的研究进展与现状。介绍了含磷阻燃体系的特征与阻燃机理,以及磷系阻燃环氧树脂磷元素引入的方式,包括添加型、反应型以及含磷固化剂。简述了现阶段磷系阻燃环氧树脂所存在的一些问题。     

含磷阻燃环氧树脂体系研究进展

简要介绍了磷系阻燃剂作为一类新型无卤阻燃剂的特点和阻燃机理,重点综述了含磷阻燃环氧树脂体系的含磷固化剂、含磷环氧化合物及含磷环氧半固化物和添加磷型阻燃的进展,并通过热稳定性、成炭率和极限氧指数（LOI）等阻燃性能参数揭示了各类方法的阻燃效果,最后对含磷阻燃环氧树脂体系研究的未来进行了展望。     

氮系阻燃剂的研究及应用概况

氮系阻燃剂高效且本身及其分解产物低毒,成为当今阻燃剂的发展方向。文中概述了氮系阻燃剂及氮-磷复合阻燃剂的特点、分类及其阻燃机理,归纳了该阻燃体系在环氧树脂、不饱和聚酯树脂、酚醛树脂、聚乙烯和聚氨酯等体系中的应用概况,并指出了今后的发展方向。     

阻燃型含硅环氧树脂体系的研究进展

把硅元素引入环氧树脂体系中,硅-磷、硅-氮等协同阻燃效应能使固化物得到优异的阻燃性能。概述了硅系阻燃剂的阻燃机理,介绍了阻燃型含硅环氧树脂体系和含硅固化剂体系的阻燃效果以及硅和磷、氮等元素的协同阻燃效应。     

溴化环氧树脂协同三氧化二锑阻燃PBT热分解动力学研究

利用热重分析法研究了聚对苯二甲酸丁二醇酯(PBT)及溴化环氧树脂(BER)协同三氧化二锑(Sb2O3)阻燃PBT在不同升温速率下的热稳定性及热分解动力学;采用Kissinger及Flynn-Wall-Ozawa方法计算出了PBT和阻燃PBT的热分解活化能;利用Coats-Redfern方法确定了PBT和阻燃PBT的热分解动力学机理及其模型,得出了聚合物主降解阶段的非等温动力学方程。结果表明:BER协同Sb2O3阻燃体系的添加提高了PBT的阻燃性能;通过Kissinger和FWO法的分析可知,阻燃PBT在主分解阶段的活化能明显提高;PBT的热分解机理函数为g(α)=1-(1-α)1/3,阻燃PBT的热分解机理函数为g(α)=2[(1-α)-1/2-1],反应级数n=1.5。     

含磷本质阻燃环氧树脂的研究进展

综述了含磷本质阻燃环氧树脂(包括含磷协同本质阻燃体系)的发展、现状和未来趋势。与添加型阻燃剂阻燃环氧树脂相比,通过含磷环氧化合物和/或含磷固化剂把磷元素嵌入环氧树脂结构中制得的含磷本质阻燃环氧树脂,具有阻燃效率高、阻燃持久、物理力学性能不受影响、燃烧过程中毒性腐蚀性挥发物质的生成量低等优势。利用协同阻燃效应,可以进一步提高阻燃性能。但是,含磷本质阻燃环氧树脂和含磷协同本质阻燃体系存在制备工艺复杂、生产成本较高等不足。     

含磷阻燃型环氧树脂的研究进展

介绍了含磷阻燃型环氧树脂的各种制备方法,并对其阻燃性、热性能和力学性能进行了比较。与普通环氧树脂相比,磷的引入可显著提高其阻燃能力,并具有低毒低烟、对环境友好等优点。此外,还介绍了磷元素与氮、硅、铝在阻燃方面的协同效应,利用协同效应可进一步提高环氧树脂的阻燃性能。     

Preparation of ferric phosphonate/phosphinate and their special action on flame retardancy of epoxy resin

Fe‐ and P‐based compounds have demonstrated promising performance in enhancing flame retardancy of epoxy resins. In this context, this work focuses on the preparation of new Fe/P hybridized nanomaterials and their effect on flame retardancy of epoxy resins. The Fe/P hybrids were facilely prepared via forming ferric phosphinates and phosphonates using hydrothermal reaction. Attractively, ferric phosphinates and phosphonates exhibit the morphology of 1D nanorod and 2D nanosheet, respectively. When incorporating these two fillers in epoxy resin, the limiting oxygen index values of composites were enhanced to above 28 and the composites exhibited self‐extinguishing behavior, thus indicating greatly improved fire resistance. Further investigation revealed that the flame retarding behavior, in particular for ferric phosphonate nanosheets, took place mainly in gas phases via delaying the release of flammable gas. Attractively, it was found that the Fe/P hybrids took part into the pyrolysis reaction of epoxy resins through forming Fe? O and P? O bonds. This finding may provide a new insight to design a series of high performance flame retardants for epoxy resins. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46206.     

Synthesis and properties of flame‐retardant epoxy resins based on DOPO and one of its analog DPPO

Two phosphorus‐containing heterocyclic flame retardants ‐9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) and 2,8‐dimethyl‐phenoxaphosphin‐10‐oxide (DPPO) ‐ and their derivatives were characterized and incorporated in the backbone of epoxy novolac to obtain flame‐retardant epoxy resins. The structures and spectroscopic data including high‐resolution mass spectroscopy of these flame retardants were determined. Flame‐retardant epoxy resins with a phosphorus content of up to 2% based on heterocyclic DOPO and DPPO were cured with 4,4′‐diaminodiphenylmethane (DDM), and their features were examined by UL 94, LOI, and DSC. In this manner, high‐performance polymers with glass transition temperatures around 190°C and the UL 94 rating V0 were obtained. These polymers were compared with epoxy resins incorporating diphenyl phosphite and diphenyl phosphate, which are nonheterocyclic and do not pass the UL 94 test up to 2% phosphorus. DPPO has a similar flame retardancy like the commercially available DOPO. Furthermore, to explain the difference in the efficiency of the tested flame retardants, key experiments for the determination of the active species during the flame‐retarding process were performed and the PO radical was identified. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007.     

阻燃抑烟环氧树脂的合成及其性质

以磷酸、三聚氰胺、尿素为原料制备阻燃抑烟剂聚磷酰氰胺脲,然后将其应用于TDE-85#环氧树脂中,以顺丁烯二酸酐为固化剂制备了阻燃抑烟环氧树脂。研究了阻燃抑烟剂聚磷酰氰胺脲的吸湿性,纯环氧树脂和阻燃抑烟环氧树脂的极限氧指数、UL-94阻燃性、隔热性能、烧蚀速率和透光率等。研究结果表明,聚磷酰氰胺脲对环氧树脂具有非常优异的阻燃、抑烟功效。     

Synthesis of a novel curing agent containing organophosphorus and its application in flame‐retarded epoxy resins

A novel amine‐terminated and organophosphorus‐containing compound m‐aminophenylene phenyl phosphine oxide oligomer (APPPOO) was synthesized and used as curing and flame‐retarding agent for epoxy resins. Its chemical structure was characterized by Fourier transform infrared (FTIR) spectroscopy, ¹H nuclear magnetic resonance (¹H NMR), ¹³C nuclear magnetic resonance, and ³¹P nuclear magnetic resonance. The flame‐retardant properties, combusting performances, and thermal degradation behaviors of the cured epoxy resins were investigated by limiting oxygen index (LOI), vertical burning test (UL‐94), cone calorimeter test, and thermogravimetric analysis. The EPO/APPPOO thermosets passed V‐1 rating with the thickness of 3.0 mm and the LOI value reached 34.8%. The thermosets could pass V‐2 rating when the thickness of the samples was 1.6 mm. The cone calorimeter test demonstrated that the parameters of EPO/APPPOO thermosets including heat release rate and total heat release significantly decreased compared with EPO/PDA thermosets. Scanning electron microscopy revealed that the incorporation of APPPOO into epoxy resins obviously accelerated the formation of the compact and stronger char layer to improve flame‐retardant properties of the cured epoxy resins during combustion. The mechanical properties and water resistance of the cured epoxy resins were also measured. After the water‐resistance test, EPO/APPPOO thermosets still remained excellent flame retardant and the water uptake was only 0.4%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41159.     

无卤阻燃型环氧树脂的研究进展

从两大类无卤阻燃型环氧树脂,即添加型阻燃环氧树脂和反应型阻燃环氧树脂的应用研究出发,综述了其阻燃效果和阻燃机理。无卤阻燃型环氧树脂因具有优异的特性成为研究热点,但依旧存在耐热、耐烧蚀、阻燃性能差的缺陷,不能适用于对性能要求更高的工作环境。基于相关模拟和实验研究,从阻燃环氧树脂特性出发深入探究了其在阻燃材料领域的发展前景。