纳米SiO2对PP/MPP/PEPA膨胀阻燃体系的协同作用

以纳米SiO,为阻燃协效剂,采用多聚磷酸蜜胺(MPP)和茏状季戊四醇磷酸酯(PEPA)复配阻燃剂,制备具有良好阻燃性能的无卤阻燃聚丙烯(PP).研究纳米SiO2用量对PP阻燃性能和协效作用的影响.结果表明:添加少量的纳米SiO2可提高PP的阻燃性能;当纳米SiO2添加量为1%时,阻燃PP的氧指数达28.5%.TGA和FTIR分析及SEM和体式显微镜观测结果表明:添加少量的纳米SiO2可促进体系成炭,稳定炭层,从而提高材料的阻燃性能.     

TiO2对MPP／PEPA阻燃PP性能的影响

采用多聚磷酸蜜胺(MPP)和笼状季戊四醇磷酸酯(PEPA)复配阻燃剂,制备了无卤阻燃聚丙烯(PP).研究了MPP/PEPA质量比和TiO2添加量对PP阻燃性能的影响.结果表明:MPP/PEPA质量比为3∶2时,复配效果好;添加少量的TiO2可以显著提高PP的阻燃性能.当MPP/PEPA/TiO2添加质量分数分别为12%,8%和1%时,阻燃PP的氧指数高达31.5%.热失重分析结果表明:添加TiO2可以起催化MPP/PEPA酯化,促进成炭的作用.扫描电镜形貌观察表明,TiO2可以起到稳定炭层,增加炭层厚度作用.     

ZnO对MPP/PEPA阻燃PP性能的影响

采用多聚磷酸蜜胺(MPP)和笼状季戊四醇磷酸酯(PEPA)复配阻燃剂,制备具有良好阻燃性能的无卤阻燃PP.研究MPP/PEPA质量比和ZnO添加量对PP阻燃性能的影响.结果表明:MPP/PEPA质量比为3:2时,复配效果最好;添加少量的ZnO可以显著提高材料的阻燃性能;当MPP/PEPA/znO添加量分别为12%、8%和1%时,阻燃PP的极限氧指数达29.5%.TGA结果表明:添加ZnO可以起催化MPP/PEPA酯化,促进成炭的作用.SEM分析表明:ZnO可以起到稳定炭层.增加炭层厚度的作用.     

MnO2对MPP/PEPA阻燃PP性能的影响

采用多聚磷酸蜜胺(MPP)和笼状季戊四醇磷酸酯(PEPA)复配阻燃剂以及MnO2为阻燃增效剂,制备了具有良好阻燃性能的无卤阻燃聚丙烯(PP),研究了MnO2用量对PP阻燃和力学性能的影响.结果表明,添加少量的MnO2即可显著提高材料的阻燃性能;当MPP,PEPA,MnO2添加质量分数分别为12%,8%和2%时,材料的氧指数(LOI)高达32.0%,并具有较好的力学性能.Kissinger动力学分析结果表明,添加MnO2可以催化MPP/PEPA问的酯化反应,改变材料的热降解途径.扫描电子显微镜(SEM)和热重分析(TGA)表明,MnO2可以起到稳定炭层,促进成炭、增加炭层厚度作用.     

新型膨胀阻燃聚丙烯结构与性能研究

采用多聚磷酸蜜胺(MPP)和笼状季戊四醇磷酸酯(PEPA)复配阻燃剂,制备了具有良好阻燃性能的膨胀阻燃聚丙烯(PP).研究了MPP/PEPA质量比和Cr2O3用量对PP阻燃和力学性能的影响.结果表明,MPP/PEPA质量比为3:2时,复配效果最好;添加少量的Cr2O3即可显著提高材料的阻燃性能.当MPP,PEPA,Cr2O3添加质量分数分别为12%,8%和2%时,阻燃PP的氧指数高达31.5%,且具有较好的力学性能.热失重(TGA)、扫描电镜(SEM)和Kissinger动力学分析表明添加Cr2O3可催化MPP/PEPA间的酯化反应,促进材料成炭,减缓材料的热降解速率,提高材料隔热、隔氧能力.     

ZnO对PP/MPP/PEPA膨胀阻燃体系的协同作用

以ZnO为阻燃协效剂,采用多聚磷酸蜜胺(MPP)和笼状季戊四醇磷酸酯(PEPA)复配阻燃剂,制备了具有良好阻燃性能的无卤阻燃PP。研究了ZnO用量对PP阻燃性能和协效作用的影响。结果表明:添加少量的ZnO即可显著提高PP的阻燃性能。当MPP、PEPA和ZnO添加量分别为12%、8%和1%时,阻燃PP的氧指数高达29.5%。TGA、FTIR分析和体式显微镜观测结果表明:添加ZnO可以催化MPP/PEPA间的酯化反应,促进体系成炭,形成更致密的炭层,从而提高材料的阻燃性能。     

Cr2O3增效阻燃PP的制备及其热降解性能的研究

以Cr2O3为阻燃协效剂,采用多聚磷酸蜜胺(MPP)和笼状季戊四醇磷酸酯(PEPA)复配阻燃剂,制备了具有良好阻燃性能的无卤阻燃PP.研究了Cr2O3添加量对PP阻燃性能和协效作用的影响.结果表明:添加少量的Cr2O3可显著提高PP的阻燃性能.当MPP/PEPA/Cr2O3添加量分别为12%、8%和2%时,阻燃PP的氧指数高达31.5%.TGA、FTIR和Flynn-Wall法热降解活化能分析结果表明:添加Cr2O3可以起催化MPP/PEPA酯化,促进成炭的作用,使PP的活化能提高.     

PP/MPP/PEPA的制备及其热降解性能研究

采用多聚磷酸蜜胺(MPP)和笼状季戊四醇磷酸酯(PEPA)复配阻燃剂,制备了具有良好阻燃性能的膨胀阻燃聚丙烯(PP),研究了各组分质量比对PP阻燃性和热降解性能的影响.结果表明:MPP与PEPA质量比为3:2时,阻燃复配效果最好;且添加阻燃剂质量分数为20%时,极限氧指数达到27%,UL达到Ⅴ-0级;热失重分析结果表明,MPP/PEPA可以延缓PP的分解;利用Kissinger法求取了材料的活化能,发现添加阻燃剂后,材料的活化能提高;残留物的红外光谱分析结果表明,MPP复配PEPA后,保留了更多的PP特征峰;体视显微镜和扫描电镜分析表明,添加阻燃剂后,材料形成了膨胀炭层,提高了 PP阻燃性能.     

MPP/PEPA阻燃PP的制备及其性能研究

采用多聚磷酸蜜胺(MPP)和笼状季戊四醇磷酸酯(PEPA)复配阻燃剂,制备了具有良好阻燃性能的无卤阻燃PP.研究了各组分质量比及用量对PP阻燃性能的影响.结果表明:MPP/PEPA质量比为3∶2.且总量为20%时,可以制备氧指数为27%的阻燃PP,垂直燃烧等级为V-O.TGA结果表明:MPP/PEPA的复配可以延缓PP的分解,且提高成炭率.     

KH550改性PEPA对PP/IFR体系阻燃、耐水和力学性能的影响

利用硅烷偶联剂KH550对季戊四醇磷酸酯(PEPA)进行表面改性,得到Si-PEPA,将其与三聚氰胺聚磷酸盐(MPP)复配成膨胀型阻燃剂(IFR)对聚丙烯(PP)进行阻燃改性。研究了KH550改性PEPA对PP/IFR体系阻燃、耐水和力学性能的影响。利用极限氧指数(LOI)仪、垂直燃烧(UL94)仪、锥形量热(CONE)仪对阻燃PP的燃烧性能进行测试,结果表明,当IFR的添加量为20%时,PP/MPP/Si-PEPA体系可以达到UL94 V-0级,氧指数达到32.5%,最大热释放速率(PHRR)和总热释放量(THR)都较PP/MPP/PEPA体系有明显降低。热重分析(TGA)显示,经KH550处理后,PP/IFR材料的热稳定性显著提高。经70℃热水浸泡72 h后,PP/MPP/Si-PEPA材料仍然可以通过UL94 V-1级。同时,KH550对PEPA的表面处理也提高了PP/IFR材料的力学强度。     

Flammability and thermal degradation of intumescent flame‐retardant polypropylene composites

The flammability of polypropylene (PP) composites containing intumescent flame‐retardant additives, i.e., melamine pyrophosphate (MPP) and 1‐oxo‐4‐hydroxymethyl‐2,6,7‐trioxa‐1‐phosphabicyclo[2.2.2]octane (PEPA) was characterized by limiting oxygen index (LOI), UL 94 test, and cone calorimeter. In addition, the thermal degradation of the composites was studied using thermogravimetric analysis (TG) and real‐time Fourier transform infrared (RTFTIR). It has been found that the PP composite only containing MPP (or PEPA) does not show good flame retardancy even at 30% additive level. Compared with the PP/MPP binary composite, the LOI values of the PP/MPP/PEPA ternary composites at the same additive loading are all increased, and UL 94 rating of the ternary composite (PP3) studied is raised to V‐0 rating from no rating (PP/MPP). The cone calorimeter results show that the heat release rate of some ternary composites decreases in comparison with the binary composite. It is noted from the TG data that initial decomposition temperatures of ternary composites are lower than that of the binary composites. The RTFTIR study indicates that the PP/MPP/PEPA composites have higher thermal oxidative stability than the pure PP. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Synthesis of a novel char-forming agent (PEIC): Improvement in flame retardancy,thermal stability,and smoke suppression for intumescent flame-retardant polypropylene composites

A novel char-forming agent named PEIC was designed and synthesized combining pentaerythritol octahydrogen tetraphosphate (PEPA) and tris(2-hydroxyethyl) isocyanurate. PEIC was combined with the silica-gel-microencapsulated ammonium polyphosphate (OS-MCAPP), preparing intumescent flame-retardant polypropylene (PP) composites. The results of the limiting oxygen index (LOI) show that the composite containing 30 wt % IFR with OS-MCAPP:PEIC = 2:1 presents the optimal LOI of 32.7%. Meanwhile, the cone calorimeter tests show that its peak heat release rate is 432 kW m⁻², which decreases by 62.1% compared with that of pure PP, showing a high-efficient flame retardancy. The exhibited UL-94 V-0 rating for all the composites indicates that the IFR composed of PEIC and OS-MCAPP has high-efficient flame retardancy in PP. The analysis of residue char reveals that PEIC could improve the quality of char in compactness, intumescentia, and the degree of graphitization. Further, the effect of IFR on the mechanical properties of PP composites was also evaluated and discussed. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48296.     

新型含氮阻燃剂/PEPA协同阻燃PP的性能

以三聚氯氰、对羟基苯甲酸甲酯、水合肼为原料经两步反应合成了一种新型含氮阻燃剂4,4′,4″–(1,3,5–三嗪–2,4,6–三取代)三氧三苯甲酰肼(TNTN),并通过核磁共振等对其进行表征。将合成的含氮阻燃剂TNTN与1–氧–4–羟甲基–2,6,7–三氧杂–1–磷杂双环[2.2.2]辛烷(PEPA)以不同配比制备膨胀型阻燃聚丙烯(PP)材料(IFR–PP)。通过极限氧指数(LOI)、垂直燃烧(UL–94)、热重(TG)分析、锥形量热(CCT)法以及扫描电子显微镜(SEM)对阻燃PP燃烧及热稳定性能进行表征。结果表明,IFR–PP同时具有良好的阻燃性及抗熔滴能力,当PEPA∶TNTN=2∶1时,UL–94达到V–0级,LOI值达到了33.7%,表现出良好的阻燃性能。TG测试表明:阻燃剂的加入使IFR–PP材料提前降解,同时提高了材料的成炭性能,当PEPA∶TNTN=5∶1时,600℃时IFR–PP材料的残炭量由空白样的0.07%提高到了20.6%。CCT测试表明:相对于纯PP,经阻燃剂改性后的PP热释放率和总热释放量均显著减少。SEM测试表明:不同配比阻燃剂的加入使PP在燃烧过程中形成膨胀、致密的炭层,很好地保护了下层材料,提高了PP材料的阻燃性能。     

不同膨胀型阻燃剂改性聚丙烯/聚乳酸复合材料

用两种不同的膨胀型氮磷阻燃剂(IFR1和IFR2)阻燃改性聚丙烯(PP)/聚乳酸(PLA)复合材料。结果表明:两种阻燃剂在PP/PLA基体中都具有良好的分散性和界面粘合性。阻燃剂的加入降低了材料的力学性能,而含有25%阻燃剂的PP/PLA复合材料就能到达垂直燃烧试验(UL-94)的V0等级。燃烧过程中阻燃剂通过在材料表面形成致密的炭层来提高材料的阻燃性,其中IFR1对PP/PLA体系的阻燃改性效果更好。从力学性能和阻燃效果的双重考虑,质量含量25%的阻燃剂适合于PP/PLA材料的阻燃改性。     

润滑剂对PP/IFR复合材料性能的影响

以聚丙烯(PP)为基体树脂、FR–1420为无卤膨胀型阻燃剂,分别加入乙撑双硬脂酰胺(EBS)、聚乙烯(PE)蜡、硬脂酸锌(硬锌)、硅酮及聚偏氟乙烯(PVDF)等五种润滑剂来制备阻燃PP复合材料(PP/IFR),考察了润滑剂及其含量对PP/IFR的阻燃性能和力学性能的影响,并对材料的热分解行为及炭层结构进行了表征和分析。结果表明,FR–1420含量为21%,五种润滑剂含量在0.5%~2%范围内变化时,对PP/IFR复合材料的力学性能影响不大,而对阻燃性能产生了明显影响;EBS与阻燃剂产生对抗作用,不论添加量多少,都显著降低PP/IFR的阻燃性,垂直燃烧等级由V–0级降低至无级;PE蜡、硬锌、硅酮及PVDF的添加量都存在一个最大值,当低于最大值时,不会影响PP/IFR的阻燃性,垂直燃烧等级均为V–0级,而高于最大值时,则会降低PP/IFR的阻燃性;PE蜡、硬锌、硅酮及PVDF均会不同程度延后PP/IFR的起始分解温度,略微降低其成炭率。     

改性聚磷酸铵对三嗪类膨胀阻燃聚丙烯性能的影响

由改性聚磷酸铵(APP)、自制的三嗪类成炭发泡剂(CFA)等复配制成膨胀型阻燃剂(IFR),以二氧化硅、二氧化钛等为协效剂阻燃聚丙烯(PP)。研究了不同组分的IFR及协效剂对阻燃PP复合材料阻燃性能、力学性能和耐水性能的影响。结果表明:改性APP的亲水性下降;由改性APP/CFA(4/1)、二氧化硅协效剂复配的PP复合材料阻燃性能、力学性能优良,助剂在PP基体中分散性好,热水浸泡后氧指数为32.5%,仍能达到UL94V—1级,失重率为2.92%。     

Synergistic effects of hydroxy silicone oil on intumescent flame retardant polypropylene system

The effects of hydroxy silicone oil as a synergistic agent on the flame retardancy of intumescent flame retardant polypropylene composites (IFR-PP) were studied, and the IFR system mainly consisted of the ammonium polyphosphate (APP), melamine (MEL) and pentaerythritol (PER). The UL 94 rating, thermogravimetric analysis (TGA), cone calorimeter (CONE) and digital photograph were used to evaluate the synergistic effects of hydroxy silicone oil (HSO). It has been found that the PP composite containing only APP, MEL and PER does not show good flame retardancy at 30% additive level. The cone calorimeter results show that the heat release rate, mass loss rate, mass, total heat release, carbon monoxide and carbon dioxide of PP/APP/MEL/PER/HSO composites decrease in comparison with the PP/APP/MEL/PER composite. The digital photographs demonstrated that HSO could promote to form the homogenous and compact intumescent char layer. Thus, a suitable amount of HSO plays a synergistic effect in the flame retardancy.     

Flame retardation and thermal degradation of flame‐retarded polypropylene composites containing melamine phosphate and pentaerythritol phosphate

The flame retardation of polypropylene (PP) composites containing melamine phosphate (MP) and pentaerythritol phosphate (PEPA) was characterized by limiting oxygen index (LOI) and UL 94. The morphology of the char obtained from the combustion of the composites was studied by scanning electron microscopy (SEM). The thermal degradation of the composites was investigated using thermogravimetric (TG) analysis and real‐time Fourier transform infrared (RTFTIR) spectroscopy. It has been found that the PP composites containing only MP do not show good flame retardancy even at 40% additive level. Compared with the PP/MP binary composites, all the LOI values of the PP/MP/PEPA ternary composites at the same additive loading increase, and UL 94 ratings of the ternary composites at suitable MP/PEPA ratios are raised to V‐0 from no rating (PP/MP). The TG and RTFTIR studies indicate that the interaction occurs among MP, PEPA and PP. Copyright © 2008 John Wiley & Sons, Ltd.