新型磷-氮膨胀阻燃剂在改性聚丙烯中的应用研究

采用自制干法合成的磷-氮膨胀型阻燃剂(磷酸酯三聚氰胺盐,IFR)复配聚磷酸胺(APP)和聚四氟乙烯(PT-FE)阻燃改性聚丙烯(PP),利用极限氧指数法、垂直燃烧法分析了阻燃PP的燃烧性能,通过热重分析仪、傅里叶变换红外光谱仪、扫描电子显微镜和X射线光电子能谱对阻燃PP的热降解过程、燃烧性能、残炭结构进行了分析,并研究了燃烧过程中复配阻燃体系对PP的阻燃机理。结果发现,IFR、APP和PTFE之间具有明显的阻燃协效作用;当阻燃剂总添加量为24%(APP为6%、IFR为17.5%、PTFE为0.5%)(质量分数)时,阻燃PP的极限氧指数达到30.1%,垂直燃烧测试达UL 94V-0级;加入阻燃剂还能提高PP的热稳定性。     

埃洛石复配阻燃剂对聚丙烯阻燃性能和力学性能的影响

用埃洛石、三聚氰胺作为阻燃剂,制备了无卤阻燃聚丙烯(PP)复合材料。通过氧指数(OI)、垂直燃烧、万能力学仪、扫描电镜分析研究了埃洛石复配阻燃剂对PP阻燃性能、力学性能的影响。结果表明:埃洛石复配阻燃剂可使PP复合材料通过UL94燃烧性能测试,在提高材料OI的同时,保持了其优良的力学性能。     

滑石粉和有机蒙脱土对溴系阻燃聚丙烯材料性能影响的研究

研究了滑石粉及纳米有机蒙脱土（OMMT）对十溴二苯乙烷（DBDPE）阻燃聚丙烯（PP）的阻燃协效作用,评估了滑石粉、溴系阻燃剂、OMMT的添加量对PP材料阻燃性能、燃烧行为及物理性能的影响。结果表明,滑石粉和OMMT对于DBDPE阻燃PP体系具有显著的协效作用,增加滑石粉和DBDPE用量可以有效提高垂直燃烧性能和极限氧指数水平,添加OMMT可进一步提升垂直燃烧性能和氧指数水平,OMMT还可以显著降低燃烧过程的热/烟释放速率及总量;滑石粉、溴系阻燃剂、OMMT会在不同程度导致材料拉伸强度、冲击强度和熔体流动速率的下降。     

膨胀型阻燃剂在聚丙烯中的应用

将膨胀型阻燃剂应用在聚丙烯(PP)中,评价了阻燃体系的阻燃、耐水、绝缘等性能。结果显示:当阻燃剂质量分数为20%时,国产新型磷氮系膨胀型阻燃剂(IFR-A)阻燃PP的极限氧指数比国外高效膨胀型阻燃剂阻燃PP的极限氧指数低,但IFR-A阻燃PP的耐水性能较好;随着阻燃剂含量增加,PP的表面电阻率与体积电阻率都维持在1×1012数量级;当w(IFR-A)为20%时,采用添加阻燃母粒的方式与直接添加IFR-A阻燃PP的燃烧性能和力学性能变化不大。     

PP/纳米SiO2复合材料的阻燃性能研究

将磷系阻燃剂1,3,5-三（5,5-二甲基-1,3-二氧杂环己内磷酸基）苯（FR）、聚磷酸铵（APP）、纳米SiO2复配,制备聚丙烯(PP)纳米复合阻燃材料。采用氧指数测定仪、水平垂直燃烧测定仪、热重分析仪、锥形量热仪对PP纳米复合阻燃材料的阻燃性能进行了研究。结果表明,FR/APP/SiO2提高了PP的氧指数、水平燃烧等级、热稳定性和残炭率,降低了热释放速率。当阻燃剂FR/APP/SiO2的总体含量为25 %,FR/APP/SiO2配比为15/7/3的情况下,PP纳米复合阻燃材料的氧指数为29.4 %,水平燃烧等级为FH-1。     

无卤阻燃聚丙烯材料的研究

用自制的膨胀型阻燃剂(IFR)与成炭剂、无机填料复配和聚丙烯(PP)共混,进行燃烧性能测试,考察了共混体系的燃烧行为;利用锥形量热仪研究了表面处理剂对膨胀阻燃体系的影响;用氧指数(OI)分析了阻燃剂及其他助剂在PP中的阻燃作用。结果表明,该阻燃体系既有较好的阻燃效果,又有抑烟作用。     

新型环保高效膨胀型阻燃剂阻燃聚丙烯

对2个复合体系聚丙烯/膨胀型阻燃剂(PP/IFR)及聚丙烯/聚烯烃弹性体/纳米碳酸钙/膨胀型阻燃剂(PP/POE/nano-CaCO3/IFR)的阻燃性进行研究,通过测试氧指数、水平燃烧速率、烟密度以及燃烧测试后试样的形貌观察,分析了复合体系的阻燃效果及机理。结果表明,PP/IFR复合体系可达到优异的阻燃性能,IFR用量为30份时氧指数达到34.4%,并且可明显改善PP的熔滴现象。而添加POE破坏了阻燃炭层的形成,降低了氧指数,并伴随严重的熔滴,却能明显降低释烟量。     

新型磷-氮系复配阻燃剂在聚丙烯中的应用

采用一种新型磷-氮系阻燃剂与聚磷酸铵(APP)复配成膨胀型阻燃剂,对聚丙烯(PP)进行阻燃改性。研究了阻燃PP的阻燃性能、热分解过程及力学性能。结果表明:当复配阻燃剂添加量为30%时,阻燃改性PP的氧指数和垂直燃烧等级分别达到32.3%和UL94 V-0级,拉伸强度为37.4 MPa,缺口冲击强度为39.5 kJ/m2,并且具有很好的热稳定性。     

无卤阻燃PP材料的火灾危险性分析

利用氧指数、热重分析等测试方法对无卤阻燃聚丙烯(PP)的阻燃性能、热降解行为及火灾危险性进行了系统分析。结果表明:当添加无卤阻燃剂质量分数为20%时,PP垂直燃烧(UL-94)达到V-0级,极限氧指数达到33.2%,同时热降解过程发生滞后现象,热稳定性提高;无卤阻燃PP在燃烧过程中可以有效地降低体系热释放速率、烟释放速率和总烟释放。     

含硅成炭剂的合成及其在阻燃PP中的应用研究

以三聚氰氯、γ-氨丙基三乙氧基硅烷及对苯二胺为主要原料合成了一种含有机硅的三嗪类成炭剂（CA）,将其与多聚磷酸铵(APP)复配成膨胀型阻燃剂(IFR)用于聚丙烯(PP) 阻燃。研究了APP与CA的配比及用量对PP阻燃性能、力学性能和热稳定性能的影响。结果表明,阻燃改性后的PP具有良好的阻燃性能和力学性能;CA具有优良的成炭作用,含硅基团能够促进PP成炭,提高了PP的热稳定性,有效地抑制了PP的进一步燃烧;当APP/CA为3/1、复配阻燃剂添加量为28 %（质量分数,下同）时,阻燃 PP的极限氧指数为32.5 %,垂直燃烧达UL 94 V-0级。     

阻燃LGFPP的阻燃性能研究

将有机蒙脱土(OMMT)和水滑石(LDH)分别与膨胀阻燃剂(IFR)构成阻燃体系,对长玻纤增强聚丙烯(LGFPP)复合材料进行阻燃改性,通过极限氧指数(LOI)和锥形量热仪(CONE)测试,对比研究了两种体系阻燃LGFPP的阻燃性能及阻燃机理。结果表明:当OMMT质量分数为2%时,复合材料的LOI达到最大值24.2%,且垂直燃烧达到了UL-94 V-0级;当LDH质量分数为1%时,LOI达到最大值23.3%,而垂直燃烧等级仍为V-1级。以炭层阻隔的IFR/OMMT体系比以稀释阻燃的IFR/LDH体系更加有效地改善LGFPP的阻燃性能。     

Effect of charring agent THEIC on flame retardant properties of polypropylene

Tris(2‐hydroxyethyl) isocyanurate (THEIC) was used as charring agent and combined with ammonium polyphosphate (APP) to form an intumescent flame retardant (IFR) for polypropylene (PP). The flame retardancy and combustion performance of PP/IFR composite was tested by limiting oxygen index (LOI), UL‐94 vertical burning test and cone calorimeter. The results showed that PP/IFR composite had highest LOI of 34.8 and obtained V‐0 rating when 30 wt % IFR was loaded and mass ratio APP/THEIC was 2 : 1. The peak heat release (PHRR) and total heat release (THR) values of PP composite containing FRs were remarkably reduced compared with that of pure PP. However, water resistant test demonstrated the PP/IFR composite had poor flame retardant durability, both the LOI value and UL‐94 V‐rating decreased when PP/IFR composite was soaked in water at 70°C after 36 h. The degradation process and the char morphology of IFR and PP/IFR composite were investigated by TGA and SEM images. The possible reaction path between APP and THEIC in the swollen process was proposed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41214.     

三邻苯二胺基环三磷腈的合成及在EVA中的阻燃研究

以六氯环三磷腈和邻苯二胺为为起始原料,甲苯为溶剂,三乙胺为缚酸剂,一步法合成三邻苯二胺基环三磷腈(HACTP)。采用HPLC、FT-IR、MS、31P-NMR和1H-NMR对化合物进行了表征。所得HACTP和聚磷酸铵(APP)、阻燃协效剂复配成膨胀型阻燃剂(IFR),添加到EVA材料中进行阻燃研究。通过对不同配方的试验,得到阻燃效果较好的阻燃剂配方:HACTP为32.84%,APP为50.04%,阻燃协效剂为17.12%。用该配方阻燃的EVA,LOI为36.8%,拉伸强度为5.46 MPa,断裂伸长率为594.95%,整体性能优良。     

PP/LGF复合材料的膨胀性阻燃与协效阻燃性能

采用膨胀型阻燃剂(IFR)及协效剂海泡石(SP)对长玻璃纤维增强聚丙烯(PP/LGF)复合材料进行阻燃,通过双螺杆挤出机制备了PP/LGF母粒,IFR母粒和SP母粒,然后将这3种母粒通过注塑机制备了PP/LGF/IFR/SP复合材料,通过极限氧指数(LOI)、垂直燃烧测试、锥形量热仪、热重分析、扫描电子显微镜、力学性能测试等表征PP/LGF各阻燃复合体系的性能。结果表明,当IFR质量分数为22%时,PP/LGF/IFR阻燃复合材料的LOI为28.8%,且垂直燃烧等级达到V–0级;锥形量热仪测试结果表明加入IFR及SP后阻燃复合体系的第一热释放速率峰值降低,而第二热释放速率峰消失;SP质量分数为1%,IFR质量分数为21%的PP/LGF/IFR/SP阻燃复合材料LOI为29.6%,垂直燃烧等级达到V–0级,热释放速率峰值和总热释放量得到有效降低,热稳定性最好,且燃烧时产生致密的炭层覆盖于玻璃纤维表面,同时加入1%SP后复合材料的力学性能下降幅度相对较小。     

不同增韧体系阻燃聚丙烯的制备和性能研究

通过高温预混制备了膨胀型阻燃剂(IFR),以马来酸酐接枝聚丙烯(PP-g-MAH)为增容剂,选用SBS、EVA、CPE、MBS分别对PP进行增韧改性,采用熔融插层法制备了阻燃聚丙烯(FRPP)。用TGA、LOI、SEM和力学性能测试等研究了不同种类的增韧剂对阻燃PP的热稳定性、阻燃性、力学性能的影响。结果表明:SBS的加入使阻燃PP的缺口冲击强度显著提高;IFR的加入,使得体系的极限氧指数普遍升高,其中EVA和CPE的极限氧指数达到32和30;综合材料的性能,选用SBS作为阻燃PP的增韧剂,所制得的阻燃PP的各性能优良。     

Preparation of a chitosan‐based flame‐retardant synergist and its application in flame‐retardant polypropylene

A novel flame‐retardant synergist, chitosan/urea compound based phosphonic acid melamine salt (HUMCS), was synthesized and characterized by Fourier transform infrared spectroscopy and ³¹P‐NMR. Subsequently, HUMCS was added to a fire‐retardant polypropylene (PP) compound containing an intumescent flame‐retardant (IFR) system to improve its flame‐retardant properties. The PP/IFR/HUMCS composites were characterized by limiting oxygen index (LOI) tests, vertical burning tests (UL‐94 tests), microscale combustion calorimetry tests, and thermogravimetric analysis to study the combustion behavior and thermal stability. The addition of 3 wt % HUMCS increased the LOI from 31.4 to 33.0. The addition of HUMCS at a low additive amount reduced the peak heat‐release rate, total heat release, and heat‐release capacity obviously. Furthermore, scanning electron micrographs of char residues revealed that HUMCS could prevent the IFR–PP composites from forming a dense and compact multicell char, which could effectively protect the substrate material from combusting. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40845.     

超声协助蒙脱土分散于聚磷酸铵阻燃聚丙烯的研究

阻燃剂能够增强聚丙烯（PP）的阻燃性能,但也会降低其力学性能,因此对阻燃剂进行改性以改善聚丙烯的力学性能显得至关重要。以传统的膨胀型阻燃剂（IFR）[由聚磷酸铵（APP）、季戊四醇（PER）、三聚氰胺（MA）组成]为PP阻燃。在合成APP过程中引入有机蒙脱土（OMt）。APP围绕OMt形成,剥离OMt使其能够较好地分散在阻燃剂中。为使OMt更好地分散在阻燃剂中,在磷酸氢二铵（DAP）、尿素（UREA）溶液中加入OMt,之后对溶液进行超声处理,蒸干后形成DAP-UREA-OMt与五氧化二磷反应生成APP。在PP中添加改性阻燃剂,有助于PP材料阻燃性能的提升与减缓力学性能的下降。当阻燃剂添加量为30%（阻燃剂添加量占总质量的质量分数）时,PP/IFR_APP/OMt复合材料的氧指数达到29.8%,通过V-0测试,拉伸强度为22.0 MPa,高出传统方法0.7 MPa。     

Effect of modified layered double hydroxide on the flammability of intumescent flame retardant PP nanocomposites

The dodecyl sulfate intercalated CaMgAl-hydrotalcites (layered double hydroxides [LDHs]) were successfully prepared by co-precipitation method, and characterized by X-ray diffraction analysis, infrared spectroscopy (Fourier transform infrared spectra [FT-IR]), thermogravimetry (TG-DTA), scanning electron microscope, and Brunner−Emmet−Teller (BET). The prepared LDHs were added to the intumescent flame retardant (IFR) polypropylene (PP) nanocomposites, and the limiting oxygen index method (LOI), vertical combustion method (UL-94), cone calorimetry (CCT), and other test methods were used to study its thermal stability and combustion performance. The results showed that when the flame retardant was composed of 23 wt% IFR and 2 wt% O-SDS-LDHs, the LOI value of the material was increased to 31.5%, reaching the V-0 level, and the flame retardant performance was significantly improved. The results also showed that there was a significant synergistic effect between IFR and O-SDS-LDHs, which could improve the thermal stability and graphitization degree of PP nanocomposites. In addition, the peak heat release rate, total heat release, and total smoke production of the PP/IFR/O-SDS-LDHs system were 177 kW/m², 101 MJ/m², and 15.4 m², respectively, which were 82.2%, 51.0%, and 23.0% lower than those of pure PP, respectively. These improvements could be attributed to the presence of dense and continuous char layer formed by the synergistic effect.     

改性海泡石与金属氧化物对膨胀阻燃PP燃烧性能的影响

采用极限氧指数、垂直燃烧、TGA、FTIR和SEM等方法研究了改性海泡石(SP)及金属氧化物(ZnO、Ni2O3)对聚丙烯(PP)/马来酸酐接枝三元乙丙橡胶(EPDM-g-MAH)/膨胀阻燃剂(IFR)体系燃烧性能的影响。极限氧指数和垂直燃烧结果表明:SP及金属氧化物均对IFR有一定的协效作用,能提高体系的极限氧指数和阻燃性能。TGA结果表明:SP可以提高燃烧残余炭层的稳定性和残炭率。SEM观察表明:SP与ZnO复配体系的燃烧残余炭层更致密和连续。FTIR测试发现SP、金属氧化物促进了IFR在PP体系中的交联成炭作用,较快生成连续的保护性炭层。