新型P-Br阻燃剂对环氧树脂阻燃和力学性能的影响

研究了一种新型P-Br阻燃剂-1,3,5－三（5,5－二溴甲基－1,3－二氧杂己内磷酰氧基）苯(FR)的含量对环氧树脂(EP)的阻燃性能和力学性能的影响。结果表明,当阻燃剂FR的含量为15 %（质量分数,下同）时,与纯EP相比,阻燃EP的极限氧指数从25.0 %提高到29.3 %,垂直燃烧通过UL 94 V-0级,火势增长指数从3.63 kW/(m2·s1)下降到0.77 kW/(m2·s1),放热指数从1.89 MJ/m2下降到1.34 MJ/m2,600 ℃残炭率从18.54 %升至29.02 %,呈现良好的阻燃效果,但力学性能有所下降,拉伸强度从62.04 MPa下降到39.81 MPa,冲击强度从13.46 kJ/m2 降到10.13 kJ/m2。     

PP/APP/磷系阻燃剂FR复合材料的燃烧性能研究

将新型磷系阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂环己内磷酸基)苯(FR)、无规聚丙烯(APP)加入聚丙烯(PP)中制备了 PP/APP/FR 复合材料,采用极限氧指数测定、垂直燃烧实验(UL94)、锥形量热分析对复合材料燃烧性能进行了研究。结果表明,APP/FR 提高了 PP 复合材料的氧指数和垂直燃烧性能级别,延长了点燃时间,降低了热释放速率和燃烧烟气中的 CO、CO_2浓度,阻燃效果显著。当15%(质量分数,下同)FR 和10%APP 复配阻燃 PP 时,复合材料的氧指数达29.6%,UL94 V-0级。     

型阻燃环氧树脂复合材料的阻燃及燃烧特性

合成新型树状单分子磷-溴阻燃剂1,3,5-三(5,5-二溴甲基-1,3-二氧杂已内磷酰氧基)苯(FR),制备阻燃环氧树脂(EP)复合材料,利用极限氧指数(LOI)、垂直燃烧(UL-94)、锥形量热(CONE)等方法研究FR对环氧树脂的阻燃性能及燃烧特性的影响.结果表明:当FR添加量为30%时,阻燃EP的LOI达到29.4%,垂直燃烧通过V-O级,其av-HRR,av-EHC,av-SEA及av-MLR较未阻燃EP分别降低87.5%、92.8%、90.8%和58.5%,呈现出良好地阻燃效果和抑烟性能;扫描电子显微镜(SEM)观测发现:阻燃EP燃烧后形成了均匀闭孔炭层.     

磷/溴单分子阻燃硬质聚氨酯泡沫复合材料制备及阻燃性能

将磷/溴单分子阻燃剂1,3,5-三(5,5-二溴甲基-1,3-二氧杂己内磷酰氧基)苯(FR)作用于硬质聚氨酯泡沫,制备出阻燃复合材料(FR/RPUF),利用极限氧指数、水平燃烧、锥形量热研究FR对硬质聚氨酯泡沫的阻燃性能及火灾燃烧性能的影响。结果发现:当FR添加量为15%时,阻燃聚氨酯泡沫的LOI达到24.1%,水平燃烧达到HF-1级,热释放速率平均值、热释放速率峰值、有效燃烧热及一氧化碳平均释放量分别降低78.7%、78.4%、57.1%和32.2%,硬质聚氨酯泡沫材料火灾危险性大幅度降低。     

新型无卤阻燃聚丙烯的制备及性能研究

采用新型磷系阻燃剂1,2,3-三(5,5-二甲基-1,3-二氧杂己内磷酸酯基)苯(FR)制备了无卤阻燃PP材料。通过氧指数、热失重、锥形量热和电镜扫描等考察了阻燃剂对PP阻燃性能及力学性能的影响。结果表明:PP中添加25%阻燃剂可以获得良好的阻燃效果,氧指数达到25.5%,平均热释放速率下降了22.5%,有效燃烧热平均值下降了61.0%。扫描电镜观测发现,阻燃PP燃烧后形成了无数封闭孔洞的焦化炭层。     

膨胀石墨(EG)协同新型磷系膨胀阻燃环氧树脂的制备及阻燃性能研究

经六(4-DOPO羟甲基苯氧基)环三磷腈(DOPOMPC)和聚磷酸铵(APP)处理环氧树脂(EP)的基础上加入可膨胀石墨(EG),制备新型膨胀阻燃环氧树脂复合材料(DOPOMPC/APP/EG/EP)。通过极限氧指数(LOI)、水平垂直燃烧(UL-94)、锥形量热(CONE)、扫描电镜(SEM)等方法,研究了协效剂EG加入对复合材料阻燃性能和力学性能的影响。结果表明,适量EG与DOPOMPC/APP体系有良好的协同阻燃作用,并提高了环氧树脂复合材料力学性能。当DOPOMPC/APP/EG总添加量为22%(DOPOMPC/APP/EG的比例为5/5/1),复合材料LOI值高达38.4%;热释放速率峰值(pk-HRR)、比消光面积(av-SEA)、有效燃烧热平均值(av-EHC)和一氧化碳释放率平均值(av-CO)较纯EP(EP0)分别降低了81.8%,35.5%、29.0%和33.3%;其拉伸强度、弯曲强度和冲击强度比EP1(10%DOPOMPC/10%APP/EP)体系分别提高了70.5%、1.5倍和2.6倍。     

用季戊四醇基化学成炭剂-三氧化二锑-十溴二苯乙烷协同阻燃天然橡胶

用垂直燃烧仪、氧指数仪、马弗炉和锥形量热仪等考察了季戊四醇基化学成炭剂（FR 600）-三氧化二锑-十溴二苯乙烷协同阻燃天然橡胶的阻燃性能。结果表明,FR 600-三氧化二锑-十溴二苯乙烷有明显的协同阻燃效应。与三氧化二锑-十溴二苯乙烷阻燃的天然橡胶相比,FR 600的加入不仅可以降低三氧化二锑的用量,而且所阻燃天然橡胶的极限氧指数和垂直燃烧等级进一步提高;在阻燃剂总用量为40份（质量）、FR 600/三氧化二锑/十溴二苯乙烷（质量比）为4/5/31时,天然橡胶的极限氧指数达27%,垂直燃烧等级为V-0级。与三氧化二锑-十溴二苯乙烷阻燃的天然橡胶相比,FR 600-三氧化二锑-十溴二苯乙烷协同阻燃天然橡胶的成炭率较高,平均热释放速率、峰值热释放速率和发烟总量较低,点燃时间及火灾性能指数较大。     

膨胀型无卤阻燃环氧树脂的制备及性能

采用新型磷系阻燃剂(FR)与聚磷酸铵组成的膨胀型阻燃剂(IFR)制备了膨胀型无卤阻燃环氧树脂(EP)材料.通过氧指数、热失重和扫描电镜等研究IFR对环氧树脂的阻燃性能、热降解行为及微观结构的影响.结果表明:加入IFR使材料的阻燃性能明显提高,IFR/EP的氧指数达到37.6%.600℃时IFR/EP的残炭量较纯EP从21.24%增至43.08%.扫描电镜观察发现.经IFR阻燃的EP在燃烧时形成了由封闭孔洞构成的均匀闭孔结构炭层,表明IFR对EP材料具有良好的膨胀阻燃效果.     

耐水阻燃透明型环氧树脂的制备及其应用研究

以二苯基次磷酰氯和哌嗪为原料,成功合成了疏水性阻燃剂哌嗪-1,4-二烷基双（二苯基氧化膦）（PPDO）,并将其添加到环氧树脂（EP）中,制备了阻燃EP复合材料。通过垂直燃烧、氧指数、热失重分析、锥形量热分析和力学性能测试对EP复合材料的阻燃性能、热分解行为、燃烧行为和力学性能进行了详细研究。结果表明,阻燃剂含量为17 %（质量分数,下同）时,EP/17 % PPDO复合材料通过了UL 94 V-0级测试,极限氧指数达28.9 %,耐水测试后,EP/PPDO复合材料仍保持着优异的阻燃效率;与此同时,PPDO与EP基体间出色的相容性,使复合材料具有良好的透明性和力学性能。此外,PPDO明显促进了EP基体提前降解成炭,使其在燃烧过程中,形成了致密且坚硬的膨胀炭层,有效降低了总热释放量,从而使EP/PPDO复合材料获得了良好的阻燃性能。     

环氧树脂包覆MPP阻燃EVA的研究

通过原位聚合法制备了以环氧树脂(EP)为壁材,三聚氰胺聚磷酸盐(MPP)为芯材的环氧包覆三聚氰胺聚磷酸盐(EPMPP),将其与二乙基次磷酸铝(ADP)复配后制备了阻燃乙烯-醋酸乙烯酯共聚物(EVA)复合材料,并对阻燃材料材料进行了极限氧指数、UL 94垂直燃烧测试以及热失重分析表征。结果表明,当ADP与EPMPP质量比为2:1、添加量为40%(质量分数,下同)时,阻燃复合材料的极限氧指数达到最高值31%,UL 94垂直燃烧测试达V-0级;EVA/ADP/EPMPP阻燃复合材料的初始分解温度为303℃,850℃时残炭量为18%,较EVA/ADP/MPP阻燃复合材料有较大幅度的提高。     

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     

A novel intumescent flame‐retardant epoxy resins system

Pentaerythritol diphosphonate melamine–dicyandiamide–formaldehyde resin salt, a novel macromolecular intumescent flame retardants (IFR), was synthesized, and its structure was a caged bicyclic macromolecule containing phosphorus characterized by IR, NMR and element analysis. The flame retardancy and thermal behavior of a new IFR system for epoxy resin were investigated by LOI, UL‐94 test, TG, and IR. Activation energy for the decomposition of samples was obtained using Kissinger equation. 25% of weight of IFR were doped into epoxy resin to get 27.5 of LOI and UL 94 V‐0. The TG curves and IR spectra show that IFR decreases the initial decomposition temperature and the maximum weight loss rate of epoxy resin, and enhances the thermal stability of epoxy resin at high temperatures and char yield. The activation energy for epoxy resin containing IFR was decreased by 44.8 kJ/mol, which shows that IFR can catalyze decomposition of epoxy resin. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

磷系阻燃剂FR/APP协效阻燃PP

采用氧指数测定仪、热重分析仪和锥形量热仪研究了磷系阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂环己内磷酸基)苯(FR)和聚磷酸铵(APP)复配体系对聚丙烯(PP)材料阻燃性能的影响.结果表明,FR/APP提高了PP的极限氧指数(LOI)、热稳定性和残炭率,降低了热释放速率.当w(FR)为15%和w(APP)为10%复配阻燃PP时,复合材料的LOI为29.6%.阻燃级别达到UL 94 V-0级.     

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     

磷/硅复配体系阻燃环氧树脂的协同效应

通过原位溶胶-凝胶法制备了磷/硅协同阻燃环氧树脂,测试了其阻燃和热稳定性能,并通过傅立叶红外光谱表征了协同体系中主要的官能团。当复配体系中的磷、硅元素达到一定配比时,环氧树脂的极限氧指数(LOI)从19.8%提高到26.5%,达到UL94V-0级,表明硅和磷两种元素在环氧树脂中具有良好的协同阻燃效应。     

大分子溴系复合阻燃剂对PS和发泡PS的阻燃改性

将大分子溴系阻燃剂(FR–122P)与溴化环氧树脂(2200HM)组成的复合阻燃剂应用于聚苯乙烯(PS)复合材料和发泡PS中,研究了复合阻燃剂的配比和含量对PS复合材料阻燃性能以及复合阻燃剂含量对发泡PS泡孔结构和阻燃性能的影响,采用热重分析、扫描电子显微镜观察、极限氧指数(LOI)测试、垂直燃烧(UL–94)和水平燃烧试验等手段进行了表征。结果表明,当FR–122P与2200HM质量比为4∶1、总添加量为25%时,PS复合材料的LOI可达25.8%,并可通过UL–94 V–0等级;当复合阻燃剂的添加量为40%时,可得到泡孔尺寸较小、泡孔密度较大、膨胀倍率较高的发泡PS复合材料,且其可通过泡沫水平燃烧的HF–2等级。大分子溴系阻燃剂与溴化环氧树脂的复合阻燃剂对PS和发泡PS复合材料具有较好的阻燃效果。     

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。     

Comparative study on flame retardancy and thermal degradation of phosphorus- and silicon-containing epoxy resin composites

Epoxy composites containing phosphorus and/or silicon were prepared using polyphenylmethoxysilicone (PPMS) and microencapsulated ammonium polyphosphate (MFAPP) as modifiers. Siliconized epoxy copolymer (EPMS) was obtained via the polycondensation of PPMS and diglycidyl ethers of bisphenol A (DGEBA) type epoxy resin. Then MFAPP was added into EPMS or DGEBA based hybrids respectively to improve their flame retardancy further. Thermal and flame retardant properties of EPMS/MFAPP and DGEBA/MFAPP composites were evaluated by Limited Oxygen index (LOI), UL-94 test and thermogravimetric analysis (TGA). The higher LOI value and UL-94 rating confirmed that MFAPP was an effective flame retardant in DGEBA compared with EPMS. A remarkable synergistic effect of phosphorus and silicon on flame retardation of EPMS/MFAPP was not observed. The reason was that the flame retardancy of epoxy composites containing phosphorus was based on solid phase. FTIR spectra of the char residue showed that when MFAPP was added, without sufficient O-H groups in EPMS/MFAPP, an effective insulative layer which protects underlying materials can’t form during combustion.