分子间磷杂菲与磷腈双基协同阻燃环氧树脂研究

将六苯氧基环三磷腈(HPCP)和9,10–二氢–9–氧杂–10–磷杂菲–10–氧化物(DOPO)复合应用于阻燃环氧树脂(EP),通过极限氧指数和垂直燃烧性能测试、热失重分析、锥形量热分析等研究了其协同阻燃EP的性能,探讨了协同阻燃机理。结果表明,当DOPO在HPCP/DOPO复合阻燃剂中所占比例达到80%时,样品的阻燃级别达到UL94 V–0级,总热释放量降低,优于两种阻燃剂单独使用条件下对EP的阻燃效果,表明磷腈和磷杂菲两种阻燃剂之间存在着协同阻燃效应。     

甲基乙烯基硅橡胶/六苯氧基环三磷腈/三聚氰胺阻燃复合材料的制备与性能

为了提高甲基乙烯基加成硫化型硅橡胶(VMQ)的阻燃性能,向基体中加入了六苯氧基环三磷腈(HPCP)和三聚氰胺(MEL)阻燃剂,研究了VMQ/HPCP/MEL阻燃复合材料的阻燃性能、燃烧行为、热稳定性能和力学性能。结果表明,HPCP和MEL对VMQ具有协同阻燃作用,当HPCP与MEL的质量比为1/2时,VMQ/HPCP/MEL阻燃复合材料的氧指数最高为30.8%,UL-94等级达到V-0级;燃烧时间从520 s缩短到415 s,总热释放量从53.53 MJ/m~2降低到45.80 MJ/m~2,燃烧后得到的残炭致密;材料的热稳定性比单独添加HPCP和MEL时更好,力学性能最好,拉伸强度为1.69 MPa,扯断伸长率为262%。     

六苯氧基环三磷腈的合成及其在丙烯酸树脂中的阻燃应用

以六氯环三磷腈（HCCP）、苯酚、氢化钠为原料,碳酸钾为催化剂,丙酮为溶剂,在氮气保护下合成了六苯氧基环三磷腈（HPCP）。采用红外光谱、核磁氢谱、碳谱、磷谱、差示扫描量热分析、热重分析技术对产物进行了表征。将HPCP作为阻燃剂添加到丙烯酸树脂中,测试了HPCP不同添加量的丙烯酸树脂的阻燃性和热稳定性。结果表明,当HPCP的添加量为20 wt %时,丙烯酸树脂的垂直燃烧可达UL-94 V-0级,极限氧指数从17.5 %增加到32.2 %,空气中700 ℃时残留质量提高至18.95 %,平均热释放速率（Mean HRR）和总热释放量（THR）分别降低至43 kW/m2和37 MJ/m2。     

六苯氧基环三磷腈阻燃PC及其热解过程的研究

将六苯氧基环三磷睛（HPGP）作为阻燃剂添加到聚碳酸醋（PC)中。极限氧指数测试和垂直燃烧测试结果显示,添加20份(质量份,下同)HPCP后,PC极限氧指数可从23. 5%增加至30.5%,垂直燃烧到达V-0级。通过热重（TG)以及热重一质谱CTG MSS联用仪分析了HPCP的阻燃机理,加人HPCP可以抑制PC在热解时因重排而生成羧基的数量。力学性能测试表明HPCP对PC的拉伸强度影响不大,但是添加20份H PCP后,冲击强度降低为纯PC的53. 84%。     

磷腈/三嗪双基分子复配阻燃聚乳酸

将磷腈/三嗪双基分子阻燃剂（HTTCP）分别与六苯氧基环三磷腈（HPCTP）和季戊四醇磷酸酯（PEPA）按不同配比复配,采用熔融共混法制备了阻燃聚乳酸（PLA）的复合材料。采用热失重分析仪、极限氧指数仪、垂直燃烧试验箱和锥形量热仪研究了2种复配阻燃体系及其配比对PLA阻燃复合材料热稳定性和阻燃性能的影响,并采用扫描电子显微镜对材料的残炭形貌进行了分析,探究了其阻燃机理。结果表明,PEPA/HTTCP复配阻燃剂的阻燃效果优于HPCTP/HTTCP复配阻燃剂。当PEPA/HTTCP的质量比为3/1,总添加量为20 %时,阻燃PLA的极限氧指数最高,为27.2 %,热释放速率峰值、平均热释放速率以及热释放总量达到最小值,且能够达到UL 94 V-0级。     

UV固化磷腈阻燃单体的合成与表征

用六氯环三磷腈作为阻燃剂，丙烯酸-2-羟丙酯作为UV固化活性单体，合成UV固化磷腈阻燃单体。当六氯环三磷腈与丙烯酸-2-羟丙酯的物质的量之比为1：6时，产物的产率为80．3％。经FT-IR光谱与^31 PNMR分析，表明六氯环三磷腈和丙烯酸-2-羟丙酯发生了反应。含磷腈阻燃单体的固化物的氧指数为27，不含磷腈阻燃单体的固化物的氧指数为23，说明合成的磷腈阻燃单体具有一定的阻燃效果。     

六苯氧基环三磷腈的合成及对IC封装用EMC的无卤阻燃

采用滴加工艺,制备了六苯氧基环三磷腈,探索出了较佳的合成工艺,并对其进行了FT-IR表征和分析。采用自制的六苯氧基环三磷腈作为阻燃剂,制备了无卤阻燃的大规模集成电路封装用环氧树脂模塑料（EMC）。结果表明,六苯氧基环三磷腈对环氧树脂具有较好的阻燃作用,所制备的EMC可达到UL-94 V0级阻燃性能,其氧指数达到33.1%,阻燃性能大大优于传统含溴阻燃体系,可用于制备大规模集成电路封装用EMC。     

六苯氧基环三磷腈对PA6阻燃性能的影响

将六苯氧基环三磷腈(HPCP)作为阻燃剂,添加到聚酰胺6(PA6)中,并对其力学性能、热性能、阻燃性能进行表征分析。结果表明:HPCP对PA6有良好的阻燃效果,随着HPCP添加量的增加,极限氧指数(LOI)呈上升趋势,添加量为20%时,从纯PA6的26%提升到31%,垂直燃烧测试(UL 94)也达到V-0级,并有效地抑制了PA6的滴落。相比于纯PA6,峰值热释放速率值(PHRR)明显降低。热失重(TG)和残余物的扫描电镜(SEM)分析结果表明,HPCP促使PA6成炭,抑制其燃烧,达到阻燃效果。     

阻燃剂六(4-酰腙基-2-甲氧基苯氧基)环三磷腈的合成及对ABS树脂的阻燃研究

以六氯环三磷腈为原料,与香兰醛发生亲核取代制得六(4-甲酰基-2-甲氧基苯氧基)环三聚磷腈（I）,I再与取代酰肼反应得到相应的六(4-酰腙基-2-甲氧基苯氧基)环三磷腈类化合物（IIa-IIg）,利用IR、1HNMR、13CNMR、ESI-MS和元素分析对化合物的结构进行了表征;并用该化合物（IIa-IIg）对ABS树脂进行阻燃处理,测试了其限氧指数和UL 94垂直燃烧性能。结果表明,所合成的化合物（IIa-IIg）对ABS树脂均具有显著地阻燃效果,化合物IIe、IIf阻燃效果最好。     

苯氧基磷腈的组成对其阻燃PC/ABS的影响

通过极限氧指数测定、垂直燃烧实验和锥形量热分析研究了苯氧基磷腈的组成对其阻燃PC/ABS的影响,并通过锥形量热实验的残炭分析研究了其作用机理。结果表明,苯氧基磷腈的组成对其阻燃PC/ABS有较大影响。随苯氧基磷腈中六苯氧基环三磷腈(HPTCP)含量的降低,其阻燃作用明显降低。残炭分析结果表明,苯氧基磷腈在燃烧过程中分解成磷酸、聚磷酸和偏磷酸等磷酸化合物,这些物质可有效地促进PC/ABS成炭,并形成膨胀性炭层,因而产生阻燃作用。苯氧基磷腈中x(HPTCP)降低,燃烧时形成的磷酸化合物较少,因而降低了其成炭和阻燃作用。     

用于环氧树脂磷-氮阻燃固化剂的合成及应用

以1,2-环己二胺(DACH)和苯基膦酰二氯(PPDC)为原料合成了一种新型环氧树脂(EP)阻燃固化剂苯基膦酰-1,2-环己二胺(PPDAC),并用傅里叶变换红外光谱(FTIR)、氢核磁共振(~1HNMR)和热重分析仪(TGA)对其进行了表征,制备了系列PPDAC/EP,采用TGA、极限氧指数(LOI)、垂直燃烧试验和扫描电镜(SEM)研究了其热稳定性、阻燃性和炭层形貌。结果表明:PPDAC的填充可以提高EP树脂的阻燃性能,添加PPDAC的EP残炭率和阻燃性均得到提高,但其初始分解温度和力学性能下降。添加PPDAC的EP残炭表面发泡膨胀明显,阻燃效果优异。     

纳米Al_2O_3对含磷环氧树脂体系的性能影响

研究了以纳米Al_2O_3作为协同阻燃剂,对EP/DOPO和EP/HPCTP树脂固化物阻燃性能的影响。通过热重分析测试(TGA)、动态热机械分析测试(DMA)、氧指数测定(LOI)及垂直燃烧测试(UL-94)重点探讨了树脂固化物的耐热及阻燃性能。测试结果表明,含磷阻燃剂有助于提高环氧树脂固化物的阻燃性能,但会降低其玻璃化转变温度(Tg)。随着纳米Al_2O_3的加入,残炭率(800℃)、极限氧指数(LOI)得到进一步的提高,并且能够在一定程度上提升树脂固化物的玻璃化转变温度(Tg)和初始热裂解温度(T5%)。     

卡拉胶包覆APP/MnO2增强水性环氧树脂阻燃抑烟性能

用反相乳液法，以卡拉胶（KC）为壳材，聚磷酸铵（APP）和二氧化锰（MnO2）为芯材，制备了KC包覆APP/MnO2阻燃剂（KC-FR）。通过FTIR、 XRD、 SEM和 EDS对KC-FR进行了表征。结果表明：卡拉胶已成功包覆APP和MnO2，合成的样品具有微胶囊结构。将KC-FR应用于水性环氧树脂（EP）中，考察KC、APP、MnO2 三者质量比对EP阻燃、抑烟性能的影响。用极限氧指数（LOI）、垂直燃烧（UL-94）和锥形量热（CCT）测试了涂层的阻燃、抑烟性能。结果发现，当KC/APP/MnO2的质量比为2∶1∶1，并且在EP中添加量为20%时，制备的阻燃涂层EP2的LOI达到29.1%，UL-94达到V-0级，表现出较好的阻燃性能。EP2相比于其它涂层热释放峰值（pHRR）、热释放总量（THR）和烟释放总量（TSP）最低，相比于EP0分别下降了42%、37%和46%，表现出较好的抑烟性能。另外，热重分析（TGA）测试结果显示EP2在800℃残炭量（W800）为33%，表明KC-FR具有促进EP成炭的功能。通过SEM对残炭表面分析发现，EP2表面炭层更加致密，这表明KC-FR对促进形成稳定并且致密的炭层起到至关重要的作用。     

阻燃环氧树脂/有机蒙脱土纳米复合材料制备及阻燃性能

研究制备了环氧树脂(EP)/有机蒙脱土(OMMT)、N,N-二(2-羟乙基)氨甲基膦酸二乙酯(BHAPE)阻燃剂阻燃的EP和EP/OMMT等复合材料。XRD证明分散在复合材料中的OMMT为剥离型的,且BHAPE的加入不影响材料中OMMT剥离后的层间距。研究证明,单独使用BHAPE很难使EP通过UL 94 V-0阻燃级,仅添加OMMT的EP固化物,其氧指数和UL94阻燃性能几乎与纯EP固化物的一样。但是同时添加BHAPE和OMMT的EP固化物,当BHAPE和OMMT的添加量分别为25%和5%时,不仅BHAPE/EP/OMMT复合物的CONE阻燃参数都明显降低,而且能通过UL94V-0级。可能是BHAPE和OMMT在凝聚相同时发挥作用,即BHAPE和OMMT协同阻燃作用提高了复合材料的综合阻燃性能。     

Preparation and investigation of flame‐retardant epoxy resin modified with a novel halogen‐free flame retardant containing phosphaphenanthrene,triazine‐trione,and organoboron units

In this article, a novel flame retardant (coded as BNP) was successfully synthesized through the addition reaction between triglycidyl isocyanurate, 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and phenylboronic acid. BNP was blended with diglycidyl ether of bisphenol‐A to prepare flame‐retardant epoxy resin (EP). Thermal properties, flame retardancy, and combustion behavior of the cured EP were studied by thermogravimetric analysis, limited oxygen index (LOI) measurement, UL94 vertical burning test, and cone calorimeter test. The results indicated that the flame retardancy and smoke suppressing properties of EP/BNP thermosets were significantly enhanced. The LOI value of EP/BNP‐3 thermoset was increased to 32.5% and the sample achieved UL94 V‐0 rating. Compared with the neat EP sample, the peak of heat release rate, average of heat release rate, total heat release, and total smoke production of EP/BNP thermosets were decreased by 58.2%–66.9%, 27.1%–37.9%, 25.8%–41.8%, and 21.3%–41.7%, respectively. The char yields of EP/BNP thermosets were increased by 46.8%–88.4%. The BNP decomposed to produce free radicals with quenching effect and enhanced the charring ability of EP matrix. The multifunctional groups of BNP with flame retardant effects in both gaseous and condensed phases were responsible for the excellent flame retardancy of the EP/BNP thermosets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45291.     

甲基丁基次膦酸铝/环氧树脂阻燃复合材料性能研究

以甲基丁基次膦酸铝[Al(MBP)]作为环氧树脂(EP)的阻燃剂,着重研究了[Al(MBP)/EP]阻燃复合材料的阻燃性能、机械性能、热分解性能及玻璃化转变温度Tg。结果表明,Al(MBP)是EP的高效阻燃剂,15%用量就可以使Al(MBP)/EP复合材料的氧指数值(LOI)达到29.6%,垂直燃烧通过UL94 V-0级标准。Al(MBP)能够明显抑制EP的分解,降低EP的分解速率,提高其成炭能力。此外,Al(MBP)与EP的相容性较好,对复合材料的机械性能影响不大;复合材料的玻璃化转变温度(Tg)明显提高,15%和20%的Al(MBP)/EP复合材料的Tg分别为161.2和172.5℃,远高于纯EP(150.6℃)。     

Synthesis and characterization of a DOPO-substitued organophosphorus oligomer and its application in flame retardant epoxy resins

Advanced flame retardant epoxy resins with different contents of poly(DOPO substituted phenyl dimethanol pentaerythritol diphosphonate) (PFR) were prepared. PFR was synthesized from the polycondensation of DOPO-disubstituted benzenedimethanol (TDCA-DOPO) with pentaerythritol diphosphonate dichloride (SPDPC). The flame retardancy and thermal stability of the EP/PFR hybrids were investigated by limiting oxygen index (LOI), UL-94 test and thermogravimetric analysis (TGA) in air. LOI values increased from 21.5 for pure EP to 36.0 for phosphorus-containing resins, and UL-94 V-0 materials were obtained with the 15 wt% PFR. The TGA results indicated that incorporation of PFR significantly enhanced the char yield and the thermal stability of char layer at higher temperature. Differential scanning calorimetry revealed that the EP/PFR composites possessed higher glass transition temperatures than phosphorus-free EP, which was consistent with dynamic mechanical analysis results. The thermal degradation behaviors of the EP/PFR composites were investigated by real time Fourier transform infrared spectra (RTFTIR), thermogravimetric analysis/infrared spectrometry (TG–IR) and direct pyrolysis/mass (DP–MS) analysis. The results suggested that the addition of PFR can reduce the release of combustible gas, trap the H and OH radicals by releasing the PO radical and induce the formation of char layer, thus retard the polymer degradation and combustion process.     

Property of intrinsic flame retardant epoxy resin cured by functional magnesium organic composite salt and diethylenetriamine

An efficient intrinsic flame retardants composite was prepared by curing epoxy resin with a functional magnesium organic composite salt (FMOCS, 0.685 ± 0.3 nm) and diethylenetriamine (DETA). Curing behavior, thermal and flame‐retardant properties of the cured epoxy resins were systematically investigated by infrared spectrum (FTIR), thermogravimetric analysis (TGA), vertical burning test (UL‐94) and limited oxygen index (LOI) measurement. It was found that flame retardancy and mechanical properties of the cured composite are significantly enhanced compared with DETA/EP. The LOI of the EP reached to 33%, which is much higher than the DETA/EP (19%) or its IFR composite (31%) in the optimal addition of ammonium polyphosphate (APP, 18.69 wt %), pentaerythritol (PER, 6.21 wt %) and FMOCS (3.50 wt %). Furthermore, the mechanical properties of the composite material measurement results to imply that it can enhance tensile strength (150%) and bending strength (88%) rather than DETA/EP, which were tested by impact testing machine and microcomputer control electron universal testing machines. Copyright © 2016 John Wiley & Sons, Ltd.