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。     

DOPO型含磷本质阻燃环氧树脂的研究进展

9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）及其衍生物可以用于合成含磷环氧树脂及环氧固化剂,制备反应型的本质阻燃树脂;此类阻燃树脂阻燃效果持久、阻燃效率高,已成为当今阻燃剂研究开发领域的主攻方向。本文就结构型DOPO基含磷本质阻燃环氧树脂的合成及应用研究进行了综述。     

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。     

反应型阻燃环氧树脂研究进展

本文简述了近年来环氧树脂阻燃改性方法的种类,详述了反应型阻燃法中添加卤素、添加磷元素、添加硅元素这四种方法研究进展,并对其发展方向做出展望。     

新型含磷环氧树脂固化剂

新型含磷环氧树脂固化剂系2-（6-氧杂-6H-二苯-1，2-氧磷-6-烷基）-酚甲醛线性酚醛树脂（OD—PN），是由苯酚-甲醛线性酚醛树脂与2-（6-氧撑-6H-二苯-1，2-氧撑-6烷基）氯化物（ODC）反应制得。而且ODC是以邻苯基酚和三氯氧磷反应制备。由OD—PN得到的含磷环氧树脂固化物比不含环磷固化剂或含溴阻燃环氧树脂具有更优异的阻燃性，较高的玻璃化温度和热稳定性。固化物磷的质量分数可低至1．21％，     

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。     

新型含磷环氧树脂的研究进展

有机和无机磷化物是新一代无卤、环保和绿色新型阻燃改性单体,可合成具有优异热稳定性、阻燃特性和物理机械性能的新型含磷环氧树脂。综述了DOPO的结构性能和化学反应性,以及以DOPO和氧氯化磷为原料合成新型含磷中间体和环氧树脂的结构、合成方法及性能等。     

自制高效无卤含磷阻燃剂阻燃环氧树脂研究

采用自制的阻燃剂双｛4-［4-（4-氨基苄基）苯氨基］ ［（6-氧二苯并［c,e］［1,2］氧磷菲?6?基）甲基］苯基｝苯基膦酸酯（DOP-DDM）,以及DOP?DDM与金属氧化物复合,分别用于制备高效阻燃环氧树脂（EPM）。通过极限氧指数（LOI）、垂直燃烧（UL 94）和锥形量热燃烧试验评价了阻燃性能,利用热失重分析和动态热机械分析研究了热性能,热失重与红外光谱仪联用、扫描电子显微和拉曼光谱分析了阻燃机理。结果表明,DOP-DDM的引入会降低阻燃EPM的起始降解温度,但不会影响其玻璃化转变温度,提高了残炭率、储能模量、损耗模量和阻燃性能;DOP?DDM添加量为4.7 %（质量分数,下同）,磷含量仅0.37 %,阻燃EPM的LOI 值为33.5 %,UL 94达V-0 级,热释放速率峰值、总热释放量和总烟释放量分别降低了23.2 %、17.8 %和12.4 %;3.7 %的DOP-DDM与1.0 %的Al₂O₃复合,阻燃EPM达UL 94 V-0级,不仅热释放速率峰值和总烟释放量进一步降低,而且CO和CO₂毒气分别降低了7.7 %和17.2 %。     

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。     

反应型含磷阻燃剂的应用研究进展

含磷阻燃剂具有低烟无毒、阻燃效果好的特点,是典型的无卤阻燃剂。本文阐述了含磷阻燃剂的阻燃机理,综述了将反应型含磷阻燃剂引入聚氨酯、环氧树脂和丙烯酸树脂等体系中所采用的不同改性方法,这些反应型阻燃聚合物均是主链或侧链含磷。本文还对近几年来国内外关于含磷阻燃剂在这些体系中的应用研究进展进行了概述,提出未来应加深对阻燃剂协同机理及含磷阻燃剂水性化和光固化的研究。     

Synthesis and properties of phosphorus and nitrogen containing intumescent flame-retardant curing agent for epoxy resin

A kind of intumescent ?ame-retardant curing agent (PCDSPB) was synthesised by using pentaerythritol, phosphorus oxycholoride, cyclohexane-1,3-diyldimethanamine (1,3- BAC) as raw materials and the structure was characterised by FTIR and MS. The composite materials were investigated by using TG, TG-FTIR, LOI, UL-94, SEM, and CCT. The results show that the ?lling of PCDSPB can improve the ?ame resistance of EP composites. When the phosphorus content of the composite system was 1.74 wt-%, the initial weight loss temperature was 299°C and the char yield was 26.3% at 600°C. Tensile strength was 35.4 MPa, impact strength was4.3 kJ m?2, LOI was 27.9, and the UL94 passed V-0 level. In the CCT, the peak heat release rate reduced to 276.0 kW m?2(EP-2) from 622.8 kW m?2 (EP-0), the total heat release decreased from 121.8 MJ m?2 (EP-0) to 89.5 MJ m?2 (EP-2). Therefore, the PCDSPB is a good intumescent ?ame-retardant curing agent for EP.     

新型磷／氮协同阻燃环氧树脂的合成与性能

以双酚A环氧树脂E－51与DOPO（9,10-dihydrooxa-20－phosph henanthrene－10-oxide）合成含磷环氧树脂（ED）,以三聚氰胺与苯酚反应制备含氮的酚醛固化剂MFP。采用红外光谱对产物进行分析表征,采用热失重分析和UL94V垂直燃烧测试考查树脂的热性能和阻燃性能,同时探讨了阻燃环氧树脂的力学性能。结果表明,随着含磷量的增加,环氧树脂的热稳定性和阻燃性能得到改善,当含磷量为3％时,环氧树脂的初始分解温度高达330℃以上,在700℃下的残炭率达到30％以上,阻燃性能均达到了UL－94 V—0级。而试样的力学性能则随含磷量的增加而降低。     

Synthesis of novel phosphorus-containing epoxy hardeners and thermal stability and flame-retardant properties of cured products

Two novel flame-retardant curing agents for epoxy resins, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-containing 4-[(phenylamino)methyl]phenol (P-Ph) and DOPO-containing Mannich-type bases (P-DDS-Ph), were synthesized by the condensation of 4-hydroxybenzaldehyde with 4-aminophenol and DDS, respectively, followed by the addition of DOPO to the resulting imine linkage. Chemical structures of these materials were characterized with FTIR, ¹H-NMR spectra, ³¹P-NMR spectra, and elemental analysis. The thermal properties and flame retardancy of o-cresol novolac epoxy resin (CNE) cured with different contents of the phosphorus-containing compounds were investigated by nonisothermal differential scanning calorimetry, thermogravimetric analysis, and limiting oxygen index (LOI). The obtained results showed that more char was formed while containing lower contents of the phosphorus-containing compounds in the P-Ph/CNE and P-DDS-Ph/CNE indicating their excellent flame retardancy. Moreover, the P-DDS-Ph/CNE exhibited higher T_g (224°C) and better thermal stability (T_10%, 330°C) than that of P-Ph/CNE. Therefore, the developed P-DDS-Ph/CNE may be potentially used as environmentally preferable products in electronic fields. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

含磷羧酸类环氧树脂固化剂的合成及固化性能研究

以邻苯基苯酚和三氯氧磷为原料,无水三氯化铝为催化剂,首先合成9,10-二氢-9-氧杂菲-10-膦酰氯(ODC)。再以乙酸为溶剂,通过ODC与酒石酸(TA)的反应,合成了新型含磷羧酸类环氧树脂固化剂2,3-二9,110-二氢-9-氧杂菲-10-膦氧基)丁二酸(ODC-TA)。通过红外光谱、H核磁共振谱对ODC和ODC-TA的结构进行了表征,并通过DSC和TGA对ODC-TA/CYD-128型环氧树脂固化体系的固化性能及阻燃性能进行了研究。     

高耐热透明阻燃环氧树脂固化体系研究

在以双酚A/四溴双酚A混合环氧树脂(EP)与甲基六氢邻苯二甲酸酐(MeHHPA)构成的胶料基础上,通过加入氯桥酸酐,制备出了具有良好耐热性和阻燃性的透明EP固化物。结果表明:与未加入氯桥酸酐体系相比,当w(氯桥酸酐)=20%(相对于固化剂质量而言)时,EP固化物的总燃烧时间由21 s降至2 s,而氧指数由31%增至37%,玻璃化转变温度(Tg)从123℃提高到148℃,负荷热变形温度(HDT)从108℃增加到129℃。     

Synthesis and characterization of a new phosphorus‐containing furan‐based epoxy curing agent as a flame retardant

In this study, 5‐hydroxymethyl‐2‐furfural (HMF) was used as a renewable resource for preparing an epoxy curing agent (furan‐based flame retardant, FBF), and a phosphorus‐containing functional group was also incorporated to enhance the flame retardancy of FBF. FBF was easily synthesized, and the total yield was 83%. 2‐Methyl imidazole was chosen as an accelerant to reduce the activation energy for the reaction of FBF with diglycidyl ether of bisphenol A (DGEBA). The DGEBA cured with FBF showed a low glass transition temperature and cross‐linking density compared with those of DGEBA cured with isophorondiamine (IPDA) and 4,4′‐diaminodiphenylmethane (DDM). However, the FBF‐cured DGEBA exhibited a comparable tensile strength with that of the DGEBA‐IPDA and DGEBA‐DDM systems (81.96 MPa) and a significantly higher tensile modulus (1721 MPa) owing to the H‐bonding via oxygens of the phosphorus group of FBF in the network structure. The DGEBA cured with FBF showed a high char yield and a high limitation of oxygen index value (29.7%) compared with those of the IPDA‐ and DDM‐cured ones. The cone calorimeter measurement also showed that the DGEBA‐FBF system had a low heat release rate, total heat release, and smoke production rate, indicating the improved flame retardancy mediated by FBF.     

活性阻燃技术在环氧树脂上的应用

综述了近年来国内外活性阻燃技术在环氧树脂上研究应用的热点,主要包括溴、磷、氮、硅系阻燃剂的研究与应用。