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。     

ADP协效APP/PER阻燃PP的制备及性能

以二乙基次膦酸铝(ADP)为协效剂,与聚磷酸铵(APP)/季戊四醇(PER)传统膨胀型阻燃体系复配,通过熔融共混制备了膨胀阻燃聚丙烯(PP)。采用极限氧指数(LOI)、垂直燃烧测试、锥形量热仪、扫描电子显微镜和热重分析研究了阻燃PP的性能及相关作用机制。结果表明,ADP和APP/PER具有很好的协同阻燃作用,它不但可以同时提高阻燃体系的残炭量和炭层质量,有效抑制熔滴,还可以降低燃烧过程中的生烟量,是更加绿色的阻燃体系。当阻燃体系的总添加量为24%,APP/PER和ADP的质量比为6∶1时,阻燃PP的LOI可达到29.8%,垂直燃烧等级为V–0级,且生烟性比不添加ADP的体系下降了76.9%。阻燃机理研究表明,该体系是以凝聚相为主的凝聚相和气相协同阻燃机制。     

MPOP/APP复合阻燃剂对PP燃烧行为的影响

通过熔融共混法制备了聚丙烯/三聚氰胺聚磷酸盐(PP/MPOP)和聚丙烯/三聚氰胺聚磷酸盐/聚磷酸铵(PP/MPOP/APP)阻燃复合材料,探讨了阻燃剂MPOP的添加量以及MPOP、APP的配比对复合材料燃烧行为的影响。结果表明:PP/MPOP复合材料的热稳定性和阻燃性能随MPOP添加量的增加而提高,且均在MPOP添加量为30份时达到最大值。同PP/MPOP(100/30)相比,当复合阻燃剂MPOP/APP的添加量为30份、且配比为15/15时,复合材料PP/MPOP/APP的热稳定性下降。但在所有试样中,该阻燃PP复合材料具有最低的最大分解速率以及最高的成炭率;其极限氧指数(LOI)为23.6%,较PP/MPOP(100/30)和纯PP分别提高了22.3%和32.6%;并且PP/MPOP/APP(100/15/15)的平均热释放速率、总释热量、有效燃烧热均达到最低值,因此该复合材料具有最佳的阻燃性能。     

PP膨胀阻燃协效剂研究进展

综述了近年来PP膨胀阻燃体系协效阻燃改性的研究进展并指出了今后的发展方向。     

协效剂在ABS/APP/PETA体系中的阻燃协效性

为了提高苯乙烯一丁二烯一丙烯睛(ABS）/聚磷酸铵(APP)/聚对苯二甲酞乙二胺(PETA)膨胀阻燃体系的阻燃性能,将硼酸锌(ZB）、红磷(RP）添加到ABS/ APP/ PETA膨胀阻燃体系中。采用极限氧指数法、垂直燃烧法、热失重、扫描电镜探讨了不同含量协效剂ZB,RP对不同比例ABS/APP/PETA阻燃体系的协效阻燃效应。结果表明,加人协效剂使ABS/APP/PETA体系的阻燃性能得到显著提高;将2.5份(质量份,下同)ZB和4份RP加人到ABS/APP/PETA( 70/22. 5/7. 5)体系,体系的极限氧指数由未加协效剂的30%提高到41%,UL-94测试也达到V-0级;ZB提高了ABS/APP/PETA体系热稳定性和成炭率,RP能极大地促进成炭;加人ZB和RP ,阻燃体系燃烧表面能够形成更多膨胀、致密的炭层。     

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。     

含磷硅高分子阻燃剂与聚磷酸铵对EVA的协效阻燃作用

研究了聚酯型磷-硅无卤阻燃剂(EMPZR)与聚磷酸铵(APP)对乙烯-醋酸乙烯酯共聚物(EVA)阻燃及力学性能的影响。结果表明,添加为40 %（质量分数,下同）的由EMPZR和APP所组成的复合阻燃剂得到的阻燃EVA材料,其极限氧指数达到28.6 %,垂直燃烧测试达到V-0级,拉伸强度为6.4 MPa,断裂伸长率达592 %。热失重分析测试表明,阻燃EVA材料的热失重速率较纯EVA有明显下降;成炭率显著提高,阻燃EVA在800 ℃时残炭量为15 % ,纯EVA仅为0.2 %。通过扫描电子显微镜对残炭形貌进行表征,以及对氧指数测试前后的阻燃EVA材料的红外图谱分析,表明EMPZR与APP在EVA中具有协效阻燃作用。     

ALPi/MPP/FeCo-MOF协效阻燃PBT/PP复合材料的研究

制备了一种双金属协效阻燃剂(FeCo-MOF),研究了二乙基次膦酸铝(ALPi)/三聚氰胺聚磷酸盐(MPP)/FeCo-MOF协效阻燃聚对苯二甲酸丁二醇酯/聚丙烯(PBT/PP)复合材料的性能。结果表明：当ALPi/MPP/FeCo-MOF的质量比为13.00∶6.50∶0.60时,阻燃PBT/PP复合材料的极限氧指数为32%,UL-94垂直燃烧阻燃等级为V-0级,800℃时残炭率达8.97%。     

磷硅阻燃剂协效氢氧化镁无卤阻燃EVA的研究

研究了磷-硅阻燃剂(EMPZR)与氢氧化镁[Mg(OH)2]对乙烯-醋酸乙烯酯共聚物(EVA)阻燃性能的影响。结果表明,复合阻燃剂的添加量为50%(质量分数,下同)时[EMPZR与Mg(OH)2质量比为1∶4],所制得的阻燃EVA材料的极限氧指数可达36.0%,并且复合材料的热失重速率较纯EVA有明显下降,成炭率显著提高,600℃时残炭量为32.2%;通过对极限氧指数测试前后阻燃EVA材料红外光谱的分析,证实了Mg(OH)2与EMPZR在EVA中具有良好的协效阻燃作用。     

High-efficiency ammonium polyphosphate intumescent encapsulated polypropylene flame retardant

The flame retardant polypropylene containing the micro-envelope core-shell structure flame retardant, which encapsulated ammonium polyphosphate into melamine-formaldehyde resin and sodium silicate through in situ polymerization was prepared with polyamide 6, added as a carbon-forming agent. The composition of ammonium polyphosphate, encapsulated ammonium polyphosphate with melamine-formaldehyde resin and the micro-envelope core-shell structure flame retardant were characterized. The fire safety and thermal stability were investigated and showed an improvement including limiting oxygen index, thermogravimetric analysis, vertical burning tests, and microscale combustion calorimeter. The burned compounds were also studied to confirm the burning mechanism. The results showed the flame retardant performance had been greatly improved, while polyamide 6 had better char-forming effect. Besides, the water solubility of flame retardants and their influence on the mechanical properties of polypropylene were also investigated. The results on the effects of additives demonstrated a high efficiency flame retardant to polypropylene. A core-shell flame retardant that sodium silicate and melamine-formaldehyde resin-coated ammonium polyphosphate had been constructed. The effect of the built flame retardant system on the combustion performance of polypropylene was studied from the mechanism and performance. The LOI of the most flame retardant polypropylene reached 28.6%, and UL-94 reached the V-0 level.     

笼状磷酸酯微胶囊/聚磷酸铵阻燃聚丙烯

将笼状磷酸酯微胶囊(ET)与聚磷酸铵(APP)复配用于阻燃聚丙烯(PP)。采用氧指数和UL 94评价了阻燃PP的阻燃性能,采用热重分析、扫描电子显微镜照片、傅里叶变换红外光谱及X射线电子能谱研究了阻燃剂的协同效应和阻燃机理。结果表明:ET与APP有较好的复配协同效应,ET/APP的阻燃性能随m(ET)/m(APP)的不同而变化。当m(ET)/m(APP)为1∶2时,阻燃效果最好。w(ET/APP)为30%时,氧指数达29.7%,且达到UL 94 V-0级。     

三聚氰胺-甲醛树脂微胶囊包覆聚磷酸铵阻燃PP的性能

通过原位聚合法制备三聚氰胺-甲醛树脂(MF)微胶囊包覆聚磷酸铵(APP)粒子,研究了APP粒径对微胶囊化APP(MCAPP)结构与性能的影响。将两种MCAPP(APP平均粒径分别为5,15μm)添加至聚丙烯(PP)基体中,研究了PP/MCAPP阻燃材料的性能。结果表明:不同粒径的APP均能成功被MF包覆,且包覆后的APP粒子的水溶性均大幅下降。PP/MCAPP阻燃材料的耐渗析性和极限氧指数均得到一定程度的提高。粒径小的APP有利于MF的包覆,包覆结构层更完整。MF和APP有很好的协同作用,在APP包覆不完全的情况下,能更有效地发挥两者的相互作用,提高PP复合材料的阻燃性。     

氧化铋协同膨胀阻燃聚丙烯的热降解机理

以Bi2O3为阻燃协同剂,采用聚磷酸铵(APP)和双季戊四醇复配阻燃体系,制备了具有良好阻燃性能的膨胀阻燃聚丙烯(PP)。Bi2O3的用量为0.10 phr时,膨胀阻燃PP的极限氧指数达25.2%,拉伸强度达28.2 MPa。Bi2O3使APP的热失重速率明显降低,高温质量保持率显著提高;高温时,Bi2O3与APP分解产生的多聚磷酸发生反应,形成Bi—O—P,提高了多聚磷酸的热稳定性。研究表明:燃烧过程中Bi2O3与APP相互作用,生成Bi的磷酸盐,抑制了多聚磷酸分解产生P2O5,使更多的多聚磷酸参与酯化反应,促进体系燃烧成炭,从而形成更加致密的膨胀炭层,提高PP阻燃性能。     

聚磷酸铵的合成及其在聚丙烯阻燃中的应用

聚丙烯具有易燃性,限制其进一步应用。以磷酸二氢铵、五氧化二磷、尿素为原料合成聚磷酸铵,然后将其应用于聚丙烯中考察其阻燃性。在氨气压力为0.5 MPa、温度295℃下反应1.5 h,停止加热,降温至150℃,得到聚磷酸铵。红外光谱和X-衍射线表明合成聚磷酸铵是I型和II型混合型。当聚丙烯复合材料中膨胀型阻燃剂质量分数为30%,极限氧指数达30.8%,通过UL-94测试。结果表明,应用聚磷酸铵为原料的阻燃剂具有较好的阻燃性能。     

Synergistic effect of ammonium polyphosphate and expandable graphite on flame‐retardant properties of acrylonitrile‐butadiene‐styrene

A new intumescent flame‐retardant (IFR) system consisting of expandable graphite (EG) and ammonium polyphosphate (APP) was applied in acrylonitrile–butadiene–styrene (ABS) resin. A synergistic effect between EG and APP on the flame retardancy of ABS was observed. Fixing the total loading of flame retardant at 15 wt %, the limited oxygen index (LOI) could reach 31 vol % at a weight ratio of 3 : 1 for EG and APP. While LOI values of EG‐ and APP‐filled ABS were only 26.0 and 21.5 vol % at the same loading, respectively. The UL‐94 vertical burning test suggested that samples with different ratios of EG and APP could all pass V‐0 rating while the samples containing EG and APP alone only passed V‐1 rating. Thermogravimetric analysis indicated that the addition of EG and APP (3 : 1 by weight) to ABS led to an increase in the amount of high‐temperature residue by 11.8 wt %, and a decrease of mass loss rate by 0.7%/°C compared with pure ABS. Scanning electronic microscopy revealed a homogeneous compact intumescent char layer of ABS/EG/APP samples. Based on our experiment and combined with others' previous studies, the synergistic mechanism is inferred. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

新型磷氮溴复合阻燃剂的制备及其阻燃聚丙烯的研究

以氢溴酸三聚氰胺盐（MHB）、聚磷酸铵（APP）、阻燃增效协同剂2、3-二甲基-2、3-二苯基丁烷( DMDPB )3种物质为原料复配成一种新型磷溴氮复合阻燃剂,将不同复配比例的复合阻燃剂添加到聚丙烯（PP）中,对阻燃PP材料的阻燃性能、力学性能及熔体流动速率进行测试,探讨3种物质的最佳复配比;并研究了该复合阻燃剂的添加量对材料阻燃性能的影响。结果表明,当MHB：APP：DMDPB的配比为10:10:1时,为最佳复配比;当磷氮溴复合阻燃剂的添加量为2.0 %（质量分数,下同）时,其极限氧指数值为30.8 %,燃烧等级为UL 94 V-1。     

Enhanced flame retardancy of unsaturated polyester resin composites containing ammonium polyphosphate and metal oxides

Three metal oxides (MOs) (Fe₂O₃, Sb₂O₃, Al₂O₃) were incorporated into blends of unsaturated polyester resin (UPR)/ammonium polyphosphate (APP) composites with the aim of studying and comparing their synergistic effect on flame retardancy with APP. The UPR-APP/MOs composites were prepared, then the thermal stability and flame-retardant properties of the UPR composites were evaluated by thermogravimetric analysis (TGA), limiting oxygen index (LOI), vertical burning test (UL-94), and cone calorimetry test (CCT). Besides, residues after CCT were characterized by scanning electron microscopy and laser Raman spectroscopy. The LOI values of the UPR composites with 0.5 wt% MOs increased to around 40%. However, the CCT results indicated that the incorporation of Sb₂O₃ brought an increase in the total heat release. Moreover, these three MOs had different effects on the process of thermal degradation of UPR composites from the TGA results. Based on the above results, Al₂O₃ provided a best promotion on flame retardancy among three MOs.     

高效阻燃剂聚磷酸铵的合成工艺研究

以磷酸和尿素为原料合成了高聚合度的聚磷酸铵。通过单因素实验对制备工艺进行了优化,考察了原料配比、升温速率、预聚合温度、固化温度和固化时间等对产品质量的影响,采用核磁共振法（NMR）测定了聚磷酸铵的平均聚合度,并用X射线衍射(XRD )和红外(IR)相结合的方法对产品的晶体结构进行了表征,同时测定了聚磷酸铵的溶解度和总磷含量。结果表明,最佳制备工艺条件为：n（磷酸)∶n（尿素）=1∶1.9,预聚合阶段升温速率为2～3 ℃/min,预聚合温度为130 ℃,固化温度为230 ℃,固化时间为90 min。此条件下合成的聚磷酸铵平均聚合度为114,水中溶解度为0.492 g,总磷质量分数为31.75%,XRD表征结果表明,所得产品为Ⅰ型聚磷酸铵。