低聚物型溴／氮阻燃剂在环氧树脂中的应用

以α，α’，2，3，5，6-六溴对二甲苯与乙二胺的线形低聚物（BNFR）为阻燃剂，采用热分析、红外光谱、有限氧指数和UL94V燃烧实验分析了BNFR对环氧树脂热性能和阻燃性能的影响。结果表明：BNFR能够参与树脂的固化反应，通过化学键成为树脂立体固化网络的组成部分。加入BNFR后，体系热降解5％和10％时的热降解温度均升高了15℃。在常规环氧树脂中添加6％BNFR（间苯二胺为固化剂）或者11％BNFR（邻苯二甲酸酐或JAq改性胺为固化剂）即能赋予基材UL94V-0的阻燃级别，有限氧指数大于26。使阻燃体系交联密度增加的固化剂及固化条件能进一步提升该体系的阻燃性能和热性能。阻燃体系中，n（Br）：n（Sb）最佳配比为3：1。     

无溶剂缠绕成型用含磷阻燃环氧树脂的研究

通过有机磷化合物9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）与双酚A型环氧树脂反应合成了一种含磷环氧树脂。通过跟踪测定环氧当量研究了开环反应过程,并用傅里叶红外光谱仪对产物结构进行了表征;采用差示扫描量热法和平板凝胶法表征了树脂体系的固化特性;依据UL94垂直燃烧法研究了磷含量与树脂体系阻燃性能的关系,采用热重分析（TGA）研究了不同含磷量环氧树脂的残炭率及裂解性能;采用差示扫描量热仪和电子万能拉伸试验机研究了阻燃环氧树脂固化物的耐热性和力学性能。结果表明,DOPO与双酚A型环氧树脂在170 ℃下6 h可完成开环加成反应;含磷环氧树脂的固化温度较双酚A型环氧树脂提高;磷含量为2.0 %（质量分数,下同）时,含磷环氧树脂固化物阻燃性能达UL94 V-0级,残炭率为23 %;其固化物的耐热性和力学性能较双酚A型环氧树脂无明显下降。     

包覆态和共混态磷酸酯/无机体系阻燃性能研究

研究了氢氧化镁、氢氧化铝或二氧化硅包覆笼状磷酸酯微胶囊以及上述3种无机阻燃剂和笼状磷酸酯复配共混用于阻燃环氧树脂的性能。采用极限氧指数,垂直燃烧（UL94）以及热分析（TG/DTG）对比了各阻燃体系的阻燃协效性能和热行为。结果表明,3种无机物在复配共混体系中都和笼状磷酸酯有较好的协同阻燃作用,而在包覆体系中阻燃性能都较差。添加量都为20 %（17 %笼状磷酸酯和3 %无机阻燃剂）,复配共混体系阻燃环氧树脂的极限氧指数可达32 %,且都可以达到UL94 V0级;而相应包覆微胶囊体系阻燃环氧树脂的极限氧指数约为24 %,阻燃级别仅达UL94 V2级。     

溴化环氧树脂阻燃剂的热性能及其应用

考察了三种溴化环氧树脂阻燃剂 (自制 ,相对分子质量分别为 2 .5× 10 4、4.3× 10 4和 6.1× 10 4)的热性能。其热分解温度均在 3 10℃以上 ,热分解温度随着相对分子质量的增加略有下降。同时也研究了三者阻燃ABS树脂的阻燃性能及物理力学性能。其阻燃性能与十溴二苯醚相当 (UL94V 0级 ) ,对ABS树脂的冲击强度影响较大 (十溴二苯醚也有同样的影响 ) ,但ABS的其他物理力学性能受影响较小。高相对分子质量溴化环氧树脂阻燃剂可以作为十溴二苯醚较理想的替代品。     

阻燃PBT/ABS合金的研制及应用

研究了溴化环氧树脂、十溴二苯乙烷、溴化聚苯乙烯3种阻燃剂对聚对苯二甲酸丁二酯/丙烯腈-丁二烯-苯乙烯塑料合金熔体流动性能、力学性能及阻燃性能的影响.结果表明,3种阻燃剂的阻燃效果都比较好,合金阻燃性能达到UL94V0级.其中溴化环氧树脂对材料的流动性能和力学性能影响最小.     

阻燃ABS母粒的研制

研究了以ABS、CPE，EVA3种树脂为载体的阻燃母粒体系，得到阻燃母粒中阻燃剂（DBDPO）质量分数为70％，80％，主阻燃剂DBDPO与辅助阻燃剂Sb2O3的配比为3：1，以硬脂酸锌为润滑剂的阻燃体系。通过使用灼热丝试验方法测试材料的阻燃性能，该体系阻燃性能达到美国UL94－V－0标准的要求。     

环氧树脂和ZnO对微胶囊红磷阻燃HIPS体系影响

研究了环氧树脂和ZnO对微胶囊红磷阻燃高抗冲聚苯乙烯(HIPS)性能的影响。结果表明,当微胶囊红磷用量为8 phr时,随着环氧树脂用量的增加,HIPS的阻燃性能提高;当环氧树脂用量大于20 phr时,阻燃HIPS 的垂直燃烧达到UL 94 V-0级,极限氧指数(LOI)为28．8％。在微胶囊红磷-环氧树脂复合阻燃HIPS体系中添加 ZnO具有阻燃协同作用,仅需加入2 phr。的ZnO就能使微胶囊红磷／环氧树脂质量比为8:15的阻燃HIPS体系垂直燃烧达到UL 94 V-O级,LOI也可达到29．2％。     

无卤阻燃热塑性聚氨酯的制备与性能研究

首先自制了无卤阻燃剂,再与TPU挤出共混,通过热失重分析(TGA)和水平垂直燃烧(UL94)测试对阻燃效果及阻燃机理进行了分析,选择了最佳配方的阻燃剂;随后制备了不同阻燃剂含量的无卤阻燃TPU复合材料,并对复合材料的阻燃性能、力学性能及环保性能等进行了测试。结果表明,自制无卤阻燃剂可以使TPU达到理想的阻燃效果,随着无卤阻燃剂含量的增加,TPU的阻燃性能越来越高,拉伸强度越来越低,当添加量为18%时,复合材料阻燃性可以达到UL94 V-0级(0.8 mm),无滴落,且拉伸强度在20 MPa以上。     

膨胀阻燃环氧树脂/有机化凹凸棒土复合材料的制备及性能研究

考察了不同膨胀型阻燃剂(IFR)添加量对环氧树脂(EP)阻燃性能的影响,以及有机化凹凸棒土(OAT)对膨胀阻燃环氧树脂复合材料性能的影响,最后对复合材料的增韧机理及阻燃机理进行了简要分析。结果表明,在环氧树脂中加入25%的IFR,可使复合材料的氧指数(LOI)达到30%,并通过UL94 V-0级测试,但拉伸性能有所降低;在膨胀阻燃环氧树脂体系中,适量添加3%的OAT能使复合材料的力学性能有所提高,对氧指数未见协同改善效果,但都通过了UL94垂直燃烧测试。     

新型磷系阻燃剂四苯基(双酚-A)二磷酸酯阻燃PC/ABS的研究

利用自制的四苯基(双酚-A)二磷酸酯(BDP)及其复配体系制备了阻燃PC/ABS,研究了阻燃PC/ABS的力学性能、氧指数(LOI)和垂直燃烧测试性能(UL94)、材料的阻燃性能和烟气释放。结果表明:采用15%的BDP阻燃PC/ABS,材料的冲击强度下降了12.82%,LOI达到30.0%,UL94阻燃性能达到V—0级,平均热释放速率(av-HRR)和最大热释放速率(pk-HRR)分别下降了35.84%和31.17%,点燃时间(TTI)延长18s,火势增长指数(FGI)下降了46.72%,比消光面积(SEA)上升了6.68%;采用BDP/APP复配阻燃PC/ABS,材料的冲击强度最大降幅为33.33%,LOI最大可达30.1%,UL94阻燃性能由V—0级降为V—1级,av-HRR和pk-HRR最大分别下降40.89%和31.2%,TTI最大延长20s,FGI最大降幅为50.37%,SEA最大涨幅为11.14%;采用BDP/纳米SiO2复配阻燃PC/ABS,当纳米SiO2的添加量为7%时,材料的冲击强度上升了5.13%,LOI达到31.1%,UL94阻燃性能达到V—0级,av-HRR和pk-HRR分别下降了43.18%和4069%,TTI延长20s,FGI降幅为59.12%,平均比消光面积(av-SEA)涨幅为8.09%,6min内av-SEA下降6.92%,(6min总发烟指数)TSPI6min下降5.54%,阻燃、抑烟效果最佳,对PC/ABS材料的力学性能影响最小。     

不同POSS对磷⁃硅协同阻燃环氧树脂性能的影响

将两种多面体低聚倍半硅氧烷(POSS)分别与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)基有机磷阻燃剂(D-bp)复配,制备了磷-硅协同阻燃环氧树脂,并对其阻燃、热、力学和动态力学性能等进行分析.结果表明,在磷含量仅为0.25％(质量分数,下同)时,磷-硅协同阻燃环氧树脂就能达到UL 94 V-0级...     

Preparation and properties of halogen-free flame retardant epoxy resins with phosphorus-containing siloxanes

Novel epoxy resin modifiers, DOPO–TMDS and DOPO–DMDP were synthesized by addition reaction of divinylsiloxane with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). Halogen-free flame retardant epoxy resins were obtained through modification of o-cresol novolac epoxy resin cured by phenol novolac resin using DOPO–TMDS and DOPO–DMDP which were characterized by ¹H NMR, ¹³C NMR, ³¹P NMR and FT-IR measurements. Effects of the phosphorus-containing siloxanes on thermal stabilities, mechanical properties and flame retardant properties of the epoxy resins were investigated. The cured epoxy resins exhibited better mechanical properties and greatly improved flame retardant properties due to the presence of phosphorus-containing siloxanes. The cured epoxy resins with phosphorus loading of 2.0 wt% showed LOI values of 32–33 and achieved UL94V-0 ratings.     

Phosphorus‐containing epoxy resin for an electronic application

A phosphorus‐containing epoxy resin, 6‐H‐dibenz[c,e][1,2] oxaphosphorin‐6‐[2,5‐bis(oxiranylmethoxy)phenyl]‐6‐oxide (DOPO epoxy resin), was synthesized and cured with phenolic novolac (Ph Nov), 4,4′‐diaminodiphenylsulfone (DDS), or dicyandiamide (DICY). The reactivity of these three curing agents toward DOPO epoxy resin was found in the order of DICY > DDS > Ph Nov. Thermal stability and the weight loss behavior of the cured polymers were studied by TGA. The phosphorus‐containing epoxy resin showed lower weight loss temperature and higher char yield than that of bisphenol‐A based epoxy resin. The high char yields and limiting oxygen index (LOI) values as well as excellent UL‐94 vertical burn test results of DOPO epoxy resin indicated the flame‐retardant effectiveness of phosphorus‐containing epoxy resins. The DOPO epoxy resin was investigated as a reactive flame‐retardant additive in an electronic encapsulation application. Owing to the rigid structure of DOPO and the pendant P group, the resulting phosphorus‐containing encapsulant exhibited better flame retardancy, higher glass transition temperature, and thermal stability than the regular encapsulant containing a brominated epoxy resin. High LOI value and UL‐94 V‐0 rating could be achieved with a phosphorus content of as low as 1.03% (comparable to bromine content of 7.24%) in the cured epoxy, and no fume and toxic gas emission were observed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 353–361, 1999     

Polyamide‐enhanced flame retardancy of ammonium polyphosphate on epoxy resin

An attractive intumescent flame retardant epoxy system was prepared from epoxy resin (diglycidyl ether of bisphenol A), low molecular weight polyamide (cure agent, LWPA), and ammonium polyphosphate (APP). The cured epoxy resin was served as carbonization agent as well as blowing agent itself in the intumescent flame retardant formulation. Flammability and thermal stability of the cured epoxy resins with different contents of APP and LWPA were investigated by limited oxygen index (LOI), UL‐94 test, and thermogravimetric analysis (TGA). The results of LOI and UL‐94 indicate that APP can improve the flame retardancy of LWPA‐cured epoxy resins. Only 5 wt % of APP can increase the LOI value of epoxy resins from 19.6 to 27.1, and improve the UL‐94 ratings, reaching V‐0 rating from no rating when the mass ratio of epoxy resin to LWPA is 100/40. It is much interesting that LOI values of flame retardant cured epoxy resins (FR‐CEP) increase with decreasing LWPA. The results of TGA, FTIR, and X‐ray photoelectron spectroscopy (XPS) indicate that the process of thermal degradation of FR‐CEP consists of two main stages: the first stage is that a phosphorus rich char is formed on the surface of the material under 500°C, and then a compact char yields over 500°C; the second stage is that the char residue layer can give more effective protection for the materials than the char formed at the first stage do. The flame retardant mechanism also has been discussed according to the results of TGA, FTIR, and XPS for FR‐CEP. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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 %。     

无卤阻燃环氧树脂固化物及其结构与性能

环氧树脂固化物具有一系列性能优势,是重要的电子材料之一,但因其极易燃烧而存在火灾隐患。采用一类扭曲非对称结构的二氮杂萘酮型二胺和二酚型无卤阻燃固化剂,与双酚A型环氧树脂(E51)和含磷环氧树脂固化,所得固化物具有优异的热学和动态力学性能,T可达157℃,热线胀系数低;与含磷树脂固化后所得g材料的阻燃性顺利通过UL94 V-0级测试。     

Synthesis and performance of a novel nitrogen‐containing cyclic phosphate for intumescent flame retardant and its application in epoxy resin

A novel nitrogen‐containing cyclic phosphate (NDP) was synthesized and well characterized by ¹H, ¹³C, ³¹P NMR, mass spectra and elemental analysis. NDP was used as an additive intumescent flame retardant (AIFR) to impart flame retardancy and dripping resistance for diglycidyl ether of bisphenol‐A epoxy resin (DGEBA) curied by 4,4′‐diaminodiphenylsulfone (DDS) with different phosphorus content. The flammability, thermal stability, and mechanical properties of NDP modified DGEBA/DDS thermosets were investigated by UL‐94 vertical burning test, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and Izod impact strength and flexural property tests. The results showed that NDP modified DGEBA/DDS thermosets exhibited excellent flame retardancy, moderate changes in glass transition temperature and thermal stability. When the phosphorus content reached only 1.5 wt %, the NDP modified DGEBA/DDS thermoset could result in satisfied flame retardancy (UL‐94, V‐0). The TGA curves under nitrogen and air atmosphere suggested that NDP had good ability of char formation, and there existed a distinct synergistic effect between phosphorus and nitrogen. The flame retardant mechanism was further realized by studying the structure and morphology of char residues using FT‐IR and scanning electron microscopy (SEM). It indicated that NDP as phosphorus‐nitrogen containing flame retardant worked by both of the condensed phase action and the vapor phase action. Additionally, the addition of NDP decreased slightly the flexural strength of the flame retarded DGEBA epoxy resins, and increased the Izod impact strength of these thermosets. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41859.     

2-甲基-2，5-二氧-1，2-氧磷杂环戊烷阻燃及固化环氧树脂研究

基于2-甲基-2,5-二氧-1,2-氧磷杂环戊烷（OP）既含有磷原子又有酸酐基团的特殊结构,分别研究了OP对环氧树脂/4,4'-二氨基二苯基甲烷（DDM）固化体系的阻燃性能及其对环氧树脂的固化作用。结果表明,OP对环氧树脂/DDM体系的固化有一定的促进作用,得到的含磷环氧树脂的极限氧指数为24.2 %,垂直燃烧测试达到UL94 V-0级别;OP对单纯环氧树脂也具有一定的固化作用,环氧基团和酸酐基团摩尔比为1:1,160 ℃条件下反应6 h已完全固化。     

新型含磷阻燃剂(PPOHQ)的合成及其在环氧树脂中的应用

以磷酰二氯和对苯醌为初始原料,合成一种新型的含磷阻燃剂双(2-对二苯酚基)-苯基氧磷(PPOHQ),并通过红外光谱对该化合物的结构进行了表征。利用该阻燃剂对环氧树脂进行固化,并对固化物进行了极限氧指数(LOI)、垂直燃烧(UL-94)、SEM以及锥形量热仪(CONE)等测试。结果表明,阻燃剂用量达到40%时,阻燃级别能通过UL-94V-0级,LOI的值为30.5。CONE测试结果表明,使用该阻燃剂固化的环氧树脂PHRR和THR等参数与EPO/PDA体系相比都有明显的降低。通过对残炭的SEM和FT-IR分析可知,燃烧后,固化的环氧树脂会产生磷酸类物质,促进形成致密的炭层,从而提高了阻燃性能。