不同囊材聚磷酸铵微胶囊在环氧树脂中的阻燃研究

采用原位聚合法合成制备了以蜜胺树脂(MF)、环氧树脂(EP)以及EP和MF为囊材的微胶囊阻燃剂MFAPP、EPAPP、EMFAPP,用红外光谱(FT-IR)和扫描电镜(SEM)表征微胶囊阻燃剂的核壳结构。采用极限氧指数(LOI)和垂直燃烧等级测试(UL94)对MFAPP、EPAPP、EMFAPP在环氧树脂中的阻燃特性进行了研究。当添加量大于7%时,阻燃复合材料均能通过UL 94 V-0级测试,极限氧指数大于27.0%,表明MFAPP、EPAPP、EMFAPP均为EP的高效阻燃剂,这些阻燃剂在EP阻燃过程中均形成了膨胀炭层,属于膨胀阻燃机理。另外在耐水性实验中发现,添加EPAPP、EMFAPP的EP复合材料具有更好的耐水性,经75℃水浸泡6天后,阻燃性能得到了较好的保持。     

核壳型纳米粒子填充PP-EVA及阻燃材料的动态燃烧行为

利用锥形量热仪(CONE)和热重分析(TGA),并结合极限氧指数(LOI)和UL-94垂直燃烧测试方法对核(PSt/OMMT)-壳(PBA)结构纳米复合粒子(CSN)填充聚丙烯(PP)-乙烯-醋酸乙烯酯共聚物(EVA)复合材料及加入无卤复配阻燃剂制备的PP-EVA/CSN/聚磷酸铵(APP)/层状氢氧化镁铝(LDH)复合阻燃材料的阻燃性能及热降解行为进行了研究。结果表明,添加10%(wt)CSN可以提高PP-EVA复合材料的阻燃性能,且PP-EVA复合体系燃烧时的热释放速率、有效燃烧热减少,热稳定性增强。CSN与APP/LDH产生阻燃协同作用,使复合阻燃材料的阻燃性能、热稳定性能进一步提高。     

碳材料表面特性及形貌对阻燃环氧树脂燃烧和热解行为的影响

将制备的4种植物基多孔碳,甘蔗渣炭(SBC)、竹叶炭(BLC)、稻壳炭(RHC)及竹茎炭(BSC),以及购置的椰壳炭(CSC)、果壳炭(NSC)、碳纳米管(CNTs)及可膨胀石墨(EG)分别与聚磷酸铵(APP)复合用于阻燃环氧树脂(EP),研究了碳材料比表面积、表面活性及微观形貌对APP阻燃EP燃烧和热解行为的影响.物理吸附仪、X射线光电子能谱仪(XPS)、扫描电镜研究指出,颗粒状竹茎多孔碳(BSC)的比表面积(2063m2/g)及表面活性基团C—O—、C≡O及COO—的比例显著大于其他碳材料;各种碳材料均以微米级尺度分布于阻燃EP基体.氧指数(LOI)、UL 94垂直燃烧及锥形量热仪研究表明,0.8 wt%BSC或CNTs与3.1 wt%APP协同阻燃EP的LOI分别由EP的24.6%提高到27.3%和27.6%,UL 94均为V-1级,峰值热释放速率分别比EP/APP降低了27%和28%.碳材料的协同阻燃效果主要取决于微观形貌;对于颗粒状多孔碳,其比表面积、O/C比及表面活性基团比例越大,协同阻燃效果越好.热失重分析、共聚焦拉曼光谱及XPS研究证实,碳材料提高了EP/APP复合材料的初始分解温度和残炭量;大的比表面及表面活性,以及管状形貌能够提高环氧树脂复合材料高温残炭量、促进残炭类石墨化转变、改善残炭耐高温氧化性能.     

聚磷酸铵-苯并噁嗪微胶囊的制备及其对环氧树脂燃烧性能影响

以多聚甲醛、丙烯胺、苯酚为原料,通过Mannich反应合成烯丙基型苯并噁嗪单体(Bala),并通过核磁共振氢谱(~1H-NMR)确定了其化学结构.将Bala在聚磷酸铵(APP)原位开环聚合后,制备APP微胶囊(BMAPP).傅里叶变换红外(FTIR)和静态接触角测试表明,Bala在APP表面成功聚合,并有效提高APP的疏水性,与纯APP相比,BMAPP的接触角从10.8°提高到了71.3°.将BMAPP添加到环氧树脂(EP)中,制备EP/BMAPP复合材料.通过热重分析仪(TGA)、垂直燃烧(UL-94)、极限氧指数(LOI)、锥型量热仪(CONE)和动态热机械分析仪(DMA)对EP和EP/BMAPP的热性能以及燃烧性能进行对比分析.结果显示,10%的BMAPP的成炭效果最佳,有良好的阻燃性能,可使EP的LOI值从22.6%提高到33.6%,并通过UL-94 V-0级,600°C下残炭率达26.3%.同时,BMAPP可大幅度降低EP燃烧过程中烟密度和热释放速率,提高EP的玻璃化转变温度(T_g).BMAPP/EP-10%中,PBala和APP协同后使EP热释放速率峰值(PHRR)由1247 kW·m~(-2)降低到434 kW·m~(-2),生烟速率(SPR)降低67%左右,T_g从169°C提高到了173°C.     

卡拉胶包覆APP微球阻燃水性环氧树脂

以氯化钡提纯k-卡拉胶, 经过氧化氢降解, 通过反相乳液聚合的方式制备了一系列卡拉胶包覆聚磷酸铵(APP)阻燃微球(k-CM/APP); 将其加入到水性环氧树脂(EP)中, 制备了3种钢结构防火涂层EP2, EP3和EP4. 利用红外光谱(IR)、 扫描电子显微镜(SEM)及元素分析(EDS)对k-CM/APP的结构及形貌进行了表征. 利用极限氧指数(LOI)、 垂直燃烧(UL-94)、 背温测试法、 热重分析(TG)、 锥形量热(CONE)、 附着力测试、 IR和SEM等方法分析了涂层的阻燃、 隔热及力学性能. 结果表明, k-CM/APP(3/1)球形结构完整, 800 ℃时的残炭量高达59.5%. 与其它阻燃涂层体系相比, 添加了k-CM/APP(3/1)的EP3防火涂层的极限氧指数达到28.5%, UL-94达到了V-0级, 60 min防火涂层耐火温度为253 ℃. 相比于纯EP涂层, EP3涂层的热释放速率峰值降低了58.26%, 总热释放量降低了20.84%, 附着力达到8.74 MPa.     

聚磷酸酯阻燃剂复配聚磷酸铵对环氧树脂阻燃性能的影响

合成了一种9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)的衍生物——聚苯氧基磷酸-2-10-氢-9-氧杂-磷杂菲基对苯二酚酯(POPP), 以间苯二胺(m-PDA)为固化剂, 环氧树脂(EP)为基料, POPP为阻燃剂, 复配聚磷酸铵(APP), 制备了不同磷含量的阻燃环氧树脂. 利用极限氧指数(LOI)和垂直燃烧(UL94)实验表征了环氧树脂的阻燃性能; 以热重分析、 锥型量热和扫描电镜分析了阻燃环氧树脂的热性能和表面形态. 研究结果表明, 阻燃剂总加入量(质量分数)为5%时即可达到UL94 V-0级, 同时LOI值为27.7%; 当总加入量为15%, 即w_POPP=5%, w_APP=10 %时, 其LOI值可达到33.8%. 随着磷含量的增加, 阻燃环氧树脂的初始降解温度略有降低, 但高温下的残炭率明显增加. POPP/APP的加入在很大程度上降低了环氧树脂的热释放速率、 有效燃烧热、 烟释放量和有毒气体释放量. 阻燃环氧树脂在高温下形成比较稳定的致密膨胀炭层, 为底层的环氧树脂主体隔绝了分解产物及热量和氧气交换, 增强了高温下的热稳定性.     

聚苯氧基磷酸联苯二酚酯/聚磷酸铵膨胀阻燃剂对环氧树脂阻燃性能影响研究

以聚苯氧基磷酸联苯二酚酯(PBPP)与聚磷酸铵(APP)组成复合阻燃剂,对环氧树脂(EP)进行阻燃改性.通过氧指数(LOI)、垂直燃烧(UL-94)、热失重(TGA)、锥形量热(CONE)和扫描电镜(SEM)等方法研究改性环氧树脂的阻燃性能和阻燃机理.结果表明,PBPP/APP体系对EP具有较好的阻燃性能,阻燃剂添加量为10%时能使环氧树脂的氧指数提高到29.6%,垂直燃烧等级达到UL94 V-0级,残炭量大大增加;平均热释放速率下降45.7%,热释放速率峰值下降51.0%,有效燃烧热平均值下降21.1%;TGA、CONE、SEM等综合分析显示了PBPP/APP改性后的环氧树脂比纯环氧树脂具有更高的热稳定性,燃烧后能够形成连续、致密、封闭、坚硬的焦化炭层,在聚合物表面产生有效覆盖、隔绝了氧气,改善了环氧树脂的燃烧性能.     

竹基多孔碳材料的制备及其协同阻燃环氧树脂研究

以KOH为致孔剂,制备了竹基微孔多孔碳材料(PCM);将PCM与聚磷酸铵(APP)添加于环氧树脂(EP),研究了PCM协同APP阻燃EP复合材料的作用及机理.BET吸附、扫描电子显微镜(SEM)及X射线光电子能谱(XPS)分析显示,PCM6的比表面积、孔容、孔径分别为2063 m2/g、0.9 cm2/g、1.8 nm;粒径为1~5μm;表面存在C—C,C—O—,C O及COO—等活性基团.极限氧指数(LOI)、UL 94垂直燃烧及锥形量热仪(Cone)研究表明,0.8 wt%的PCM6与3.1 wt%的APP复合可使EP复合材料的LOI由24.6%提高到27.3%,热释放速率峰值降低45.4%,PCM6表现出良好的协同阻燃作用.热失重分析及XPS研究表明,PCM6提高了阻燃EP复合材料的热稳定性,催化APP释放NH3、H2O,加快了交联成炭的速度及热解产物焦磷酸(酯)的形成,由此揭示了PCM协同APP阻燃EP的作用机理.     

磷杂菲类阻燃剂的合成及其与聚磷酸铵复合膨胀体系对环氧树脂的阻燃性能研究

以9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、五硫化二磷(P2S5)为原料合成9,10-二氢-9-氧杂-10-磷杂菲-10-硫化物(DOPS),并将DOPS与聚磷酸铵(APP)组成复合阻燃剂,用于环氧树脂(EP)的阻燃改性.通过氧指数(LOI)、垂直燃烧(UL-94)、热失重(TGA)、锥形量热(CONE)和扫描电镜(SEM)等方法对改性后的环氧树脂的阻燃性能和阻燃机理进行了测试和分析.实验结果表明,DOPS/APP阻燃体系对EP具有很好的阻燃性能,且复配阻燃剂的阻燃效果比单一的阻燃剂阻燃效果好;其中,当阻燃剂的总添加量达到30%时即W_(DOPS)=10%、W_(APP)=20%时,阻燃EP复合材料的LOI值可达到29.2%,垂直燃烧等级达到UL-94 V-0级,残炭量可达49.3%.     

星型绿色磷腈阻燃剂的制备及阻燃环氧树脂性能

从分子结构设计出发,以六氯环三磷腈、对羟基苯甲醛、三氯氧磷及新戊二醇等为原料,制备了一种新型阻燃剂六[4-(5,5-二甲基-1,3,2-二氧杂己内磷酰基)苯氧基]环三磷腈(HDDCPPCP),并将其与聚磷酸铵(APP)和多壁碳纳米管(MWCNT)复配,应用于环氧树脂(EP)中,制备了HDDCPPCP/APP/MWCNT/EP阻燃复合材料.利用极限氧指数(LOI)、水平燃烧(UL-94)、锥形量热(CONE)、拉伸、弯曲和冲击等方法研究该阻燃复合材料的燃烧性能、热性能及力学性能.实验结果表明,保持阻燃体系总质量分数为30%,当MWCNT质量分数为2%时,EP2(HDDCPPCP/APP/MWCNT/EP)的各项燃烧参数综合表现较好,其LOI值达到42. 8%,热释放速率峰值(pk-HRR)、热释放速率平均值(av-HRR)、有效燃烧热平均值(av-EHC)及一氧化碳释放率平均值(av-CO)相对EP0分别降低92. 5%,93. 0%,65. 2%和66. 6%,呈现出良好的阻燃、抑烟和抑毒性能; EP2的拉伸强度、断裂伸长率、弯曲强度和弯曲模量较好,分别为110. 46 MPa,6. 24%,1259. 99 MPa,377. 72 MPa.     

Flame retardant properties and mechanism of an efficient intumescent flame retardant PLA composites

The charring agent (CNCA‐DA) containing triazine and benzene rings was combined with ammonium polyphosphate (APP) to form intumescent flame retardant (IFR), and it was occupied to modify polylactide (PLA). The flame retardant properties and mechanism of flame retardant PLA composites were investigated by the limited oxygen index (LOI), vertical burning test (UL‐94), thermogravimetric analysis, microscale combustion calorimetry, scanning electron microscopy, laser Raman spectroscopy analysis and X‐ray photoelectron spectroscopy. The analysis from LOI and UL‐94 presented that the IFR was very effective in flame retardancy of PLA. When the weight ratio of APP to CNCA‐DA was 3:1, and the IFR loading was 30%, the IFR showed the best effect, and the LOI value reached 45.6%. It was found that when 20 wt% IFR was loaded, the flame retardancy of PLA/IFR still passed UL‐94 V‐0 rating, and its LOI value reached 32.8%. The microscale combustion calorimetry results showed that PLA/IFR had lower heat release rate, total heat release, and heat release capacity than other composites, and there was an obvious synergistic effect between APP and CNCA‐DA for PLA. IFR containing APP/CNCA‐DA had good thermal stability and char‐forming ability with the char residue 29.3% at 800°C under N₂ atmosphere. Scanning electron microscopy observation further indicated that IFR could promote forming continuous and compact intumescent char layer. The laser Raman spectroscopy analysis and X‐ray photoelectron spectroscopy analysis results indicated that an appropriate graphitization degree of the residue char was formed, and more O and N were remained to form more cross‐linking structure. Copyright © 2016 John Wiley & Sons, Ltd.     

The investigation of intumescent flame-retarded polypropylene using poly(hexamethylene terephthalamide) as carbonization agent

A novel intumescent flame retardant, containing ammonium polyphosphate (APP), and poly(hexamethylene terephthalamide) (PA6T), was prepared for flame retarding polypropylene (PP). The flame retardation of the PP composites was characterized by limiting oxygen index (LOI). The thermal degradation of the composites was investigated by means of thermogravimetric analysis (TG) and TG coupled with Fourier transform infrared spectroscopy (TG-FTIR). The morphology of the char obtained after combustion of the composites was studied by scanning electron microscopy. It has been found the intumescent flame retardant showed good flame retardancy, with the LOI value of the PA6T/APP/PP (5/25/70) system increasing from 17.5 to 32. Meanwhile, the TG and TG-FTIR work indicated that PA6T could be effective as a carbonization agent and there was a synergistic reaction between PA6T and APP, which effectively promoted the char formation of the PP composites. Moreover, it was revealed that uniform and compact intumescent char layer was formed after combustion of the intumescent flame retarded PP composites.     

A novel intumescent flame retardant imparts high flame retardancy to epoxy resin

Intumescent flame retardant (IFR) has received the considerable attention ascribed to the inherent advantages including non‐halogen, low toxicity, low smoke release and environmentally friendly. In this work, a novel charring agent poly (piperazine phenylaminophosphamide) named as PPTA was successfully synthesized and characterized by Fourier transform infrared spectra (FTIR) and X‐ray photoelectron spectroscopy (XPS). Then, a series of flame‐retardant EP samples were prepared by blending with ammonium polyphosphate (APP) and PPTA. Combustion tests include oxygen Index (LOI), vertical Burning Test (UL‐94) and cone calorimeter testing,these test results showed that PPTA greatly enhances the flame retardancy of EP/APP. According to detailed results, EP containing 10 wt% APP had a LOI value of 30.2%,but had no enhancement on UL‐94 rating. However, after both 7.5 wt% APP and 2.5 wt% PPTA were added, EP‐7 passed UL‐94 V‐0 rating with a LOI value of 33.0%. Moreover, the peak heat release rate (PHRR) and peak of smoke product rate (PSPR) of EP‐7 were greatly decreased. Meanwhile, the flame‐retardant mechanism of EP‐7 was investigated by scanning electron microscopy (SEM), thermogravimetric analysis/infrared spectrometry (TG‐IR) and X‐ray photoelectron spectroscopy (XPS). The corresponding results presented PPTA significantly increased the density of char layer, resulting in the good flame retardancy.     

Effect of a triazine ring‐containing charring agent on fire retardancy and thermal degradation of intumescent flame retardant epoxy resins

A triazine ring‐containing charring agent (PEPATA) was synthesized via the reaction between 2,6,7‐trioxa‐l‐phosphabicyclo‐[2.2.2]octane‐4‐methanol (PEPA) and cyanuric chloride. It was applied into intumescent flame retardant epoxy resins (IFR‐EP) as a charring agent. The effect of PEPATA on fire retardancy and thermal degradation behavior of IFR‐EP system was investigated by limited oxygen index (LOI), UL‐94 test, microscale combustion calorimetry (MCC), thermogravimetric analysis (TGA) and thermogravimetric analysis/infrared spectrometry (TG‐IR). The glass transition temperatures (T_g) of IFR‐EP systems were studied by dynamic mechanical analysis (DMA). The LOI values increased from 21.5 for neat epoxy resins (EPs) to 34.0 for IFR‐EP, demonstrating improved flame retardancy. The TGA curves showed that the amount of residue of IFR‐EP system was largely increased compared to that of neat EP at 700 °C. The new IFR‐EP system could apparently reduce the amount of decomposing products at higher temperatures and promotes the formation of carbonaceous charred layers that slowed down the degradation. Copyright © 2010 John Wiley & Sons, Ltd.     

Synergistic effect of boron containing substances on flame retardancy and thermal stability of clay containing intumescent polypropylene nanoclay composites

The functions of nanoclay and three different boron containing substances, zinc borate (ZnB), borophosphate (BPO₄), and boron silicon containing preceramic oligomer (BSi), were studied to improve the flame retardancy of polypropylene (PP)‐nanoclay‐intumescent system composed of ammonium polyphosphate (APP) and pentaerythritol (PER). The flame retardancy of PP composites was investigated using limiting oxygen index (LOI), UL‐94 standard, thermogravimetric analysis (TGA), and cone calorimeter. According to the results obtained, the addition of 20 wt% intumescent flame retardant (IFR) improved the flame retardancy by increasing the char formation. Addition of clay slightly increases the LOI value and reduces the maximum heat release rate (HRR). Addition of clay also increases the barrier effect due to intumescent char, especially in thin samples. Boron compounds show their highest synergistic effect at about 3 wt% loading. According to UL‐94 test and LOI test, 3 wt% ZnB containing composite shows the highest rating (V0) and BPO₄ containing sample shows the highest LOI value (26.5). Copyright © 2010 John Wiley & Sons, Ltd.     

Enhancement of a hyperbranched charring and foaming agent on flame retardancy of polyamide 6

A hyperbranched polyamine was prepared using an A₂ + B₃ approach. It acted as a hyperbranched charring and foaming agent (HCFA) in combination with ammonium polyphosphate (APP) to form a new intumescent flame retardant (IFR) system for polyamide 6 (PA6). Effect of HCFA on flame retardant and thermal degradation properties of IFR‐PA6 was investigated by limiting oxygen index (LOI), UL‐94 vertical burning, cone calorimeter, and thermogravimetric analysis (TGA) tests. The IFR system presented the most effective flame retardancy in PA6 when the weight ratio of APP to HCFA was 2:1. The LOI value of IFR‐PA6 could reach 36.5 with V‐0 rating when the IFR loading was 30 wt%. Even if the loading decreased to 25 wt%, IFR‐PA6 could still maintain V‐0 rating with an LOI value of 31. TGA curves indicated that APP would interact with both PA6 and HCFA in PA6/APP/HCFA composite under heating. The interaction between APP and HCFA improved the char formation ability of IFR system and then much more char was formed for PA6/APP/HCFA composite than for PA6/APP. Therefore, better flame retardancy was achieved. Moreover, the structure and morphology of char residue were studied by Fourier transform infrared (FTIR), X‐ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The results indicated that compact and foaming char layer containing P‐O‐C structure was formed for PA6/APP/HCFA system during combustion. Copyright © 2010 John Wiley & Sons, Ltd.