环保型无卤阻燃剂在PA6材料中的应用

以聚酰胺(PA) 6为基体材料,添加二乙基次膦酸铝(ADP)、三聚氰胺氰尿酸盐(MCA)为阻燃剂,通过熔融共混制备无卤阻燃PA6复合材料。采用水平垂直燃烧仪、氧指数测定仪、万能材料试验机以及热重分析仪研究了ADP和MCA用量对无卤阻燃PA6阻燃性能、力学性能、热降解行为的影响,并采用扫描电子显微镜观察了燃烧后炭层的形貌,探讨了ADP与MCA间的协效阻燃作用。结果表明,制备的阻燃PA6复合材料均能达到UL94 V–0阻燃级别;当ADP添加量为18%时,极限氧指数(LOI)可达33.3%;当添加14% ADP时,ADP/MCA复配阻燃体系的LOI值保持在31%以上;MCA对ADP产生协效阻燃作用,MCA的加入使得热分解温度降低,加速了PA6在燃烧时的成炭,改善了炭层结构,并使PA6具有较好的力学性能。     

AlPi和PPBBA复配阻燃PET的燃烧性能

采用二乙基次膦酸铝(Al Pi)和聚丙烯酸五溴卞酯(PPBBA)复配,提高聚对苯二甲酸乙二酯(PET)的阻燃性能。测定了阻燃PET的极限氧指数(LOI)、垂直燃烧性能、热失重分析、动态流变性能,并采用扫描电子显微镜(SEM)观测了燃烧炭层的形貌。结果表明,Al Pi∶PPBBA分别以5∶5和10∶5复配,添加量分别为10%和15%时,LOI达到28.0%和33.3%,垂直燃烧测试均达到V–0级。复配阻燃体系的加入促进了PET的提前分解,阻燃剂主要在气相发挥阻燃作用,同时有利于成炭。当添加15%复配阻燃剂时,相比于纯PET,阻燃PET的最大分解速率降低21.2%,残炭率提高97.6%,提高了阻燃PET在高温下的热稳定性。在角频率为1 rad/s条件下,当添加10%和15%复配阻燃剂时,体系的复数黏度由39.4 Pa·s分别提高到296 Pa·s和1 970 Pa·s,具有较高的抗熔滴性能。烧结后的残留物高倍膨胀,炭层致密连续。     

二乙基次膦酸铝和三聚氰胺氰尿酸盐对PA6的协同阻燃作用

通过极限氧指数(LOI)测定、垂直燃烧试验和锥型量热分析研究了二乙基次膦酸铝(ADEP)和三聚氰胺氰尿酸盐(MCA)对聚酰胺6(PA6)的协同阻燃作用。结果表明ADEP和MCA对PA6具有良好的协同阻燃作用;热失重分析结果表明添加ADEP,MCA和ADEP/MCA均降低PA6的热稳定性,但ADEP/MCA的影响较小;残余物分析结果证实ADEP主要是通过气相产生阻燃作用,在燃烧过程中,通过捕获燃烧产生的自由基而抑制燃烧;MCA分解成挥发性CO2和NH3等惰性气体,通过燃料稀释作用而产生阻燃。     

烷基次膦酸盐在PET材料中的阻燃性能

以二乙基次膦酸铝(ADP)和二乙基次膦酸锌(ZDP)复配为阻燃剂制备了PET阻燃材料,通过极限氧指数测试(LOI)和垂直燃烧测试(UL-94)分析了材料的阻燃性能。通过热重分析测试(TGA)探讨了材料的热降解行为及其成炭性能。采用锥形量热测试(CONE)研究了材料的燃烧行为,并对其燃烧后残炭的形貌进行了表征。结果表明:用ADP和ZDP复配制备的PET阻燃材料能显著提高其阻燃性能。当阻燃剂含量为12%,即ADP与ZDP的质量配比为8∶4时,PET阻燃材料的LOI可达37.2%,且能通过UL-94 V-0级,此时材料的燃烧滴落物炭化程度高,燃烧时热释放速率低。     

2–羧乙基苯基次膦酸铝的制备及其对PA6阻燃研究

以2–羧乙基苯基次膦酸(CEPPA)为原料,合成了2–羧乙基苯基次膦酸铝(CEPPA–Al),并通过傅立叶变换红外光谱(FTIR)、电感耦合等离子体发射光谱(ICP)对产物结构进行了表征。热重(TG)研究表明,CEPPA–Al的起始分解温度为281.8℃,700℃的质量保持率为27.5%。将CEPPA–Al应用于尼龙(PA)6,TG分析表明,CEPPA–Al可促进PA6形成稳定的炭层,减少气相产物的生成量。次磷酸盐质量分数为15%时,阻燃PA6的极限氧指数(LOI)达到27.4%,垂直燃烧性能达到UL94 V–1级,锥形量热计分析表明,加入CEPPA–Al可使最大热释放速率和热释放总量分别降低16%和38%。力学性能研究表明,添加质量分数15%的CEPPA–Al可使PA6/CEPPA–A1复合材料的拉伸性能与弯曲性能与PA6接近。     

二丙基次膦酸铝和氢氧化镁对PA6的复合阻燃作用

通过极限氧指数测定、垂直燃烧实验和锥形量热分析研究了二丙基次膦酸铝(ADPP)和氢氧化镁(MH)对尼龙6(PA6)的复合阻燃作用。结果表明:ADPP与MH对PA6无协同阻燃作用,ADPP复配少量的MH(质量分数10%)阻燃PA6的LOI和垂直燃烧级别变化不大,总热释放量(THR)和最高热释放速率(PHRR)略有增加,但热稳定性有明显改善。残余物分析结果表明,复合少量的MH略增加了材料的成炭性,但炭层结构变得比较松散,因而对ADPP阻燃PA6的影响不大。而随着MH用量增加,成炭性明显下降,因而降低了ADPP对PA6的阻燃作用。     

高磷含量聚酯多元醇的制备及其在阻燃PA6中的应用

以苯基膦酰二氯(BPOD)和双羟甲基甲基氧化磷(BMPO)为原料,制备了一种高含磷聚磷酸酯多元醇阻燃剂(PHPOP),并通过红外光谱(FTIR)和热重分析(TGA)表征了产物的结构及热稳定性。采用熔融共混法制备了PHPOP阻燃的聚酰胺6(PA6)材料,通过极限氧指数(LOI)法和垂直燃烧法测试了材料的阻燃性能,并采用热重分析仪考察了阻燃PA6的热分解过程及其成炭性能,随后采用扫描电镜(SEM)对其炭层形貌进行了观察。结果表明:阻燃剂PHPOP对PA6具有良好的阻燃效果。当20%阻燃剂的加入即可使PA6的LOI由21.2%提高至27.5%,并通过UL 94V-0级测试。热降解及炭层形貌分析结果表明,PHPOP的添加对PA6在降解过程中的成炭具有良好的促进作用,使炭层致密性提高,阻碍了热和可燃气体的传递,从而提高了PA6材料的阻燃性能。     

磷-氮改性水性聚氨酯在涤纶织物上的阻燃研究

以N,N-双(2-羟甲基)氨基乙基膦酸二甲酯与甲苯二异氰酸酯反应合成出磷-氮阻燃水性聚氨酯,应用于涤纶织物上,考察了其阻燃性能、耐水洗性能、热失重等性能,并用扫描电镜(SEM)和能谱仪(EDS)对阻燃处理的涤纶织物燃烧后的炭层进行分析.结果表明;与未阻燃整理的涤纶织物相比,阻燃整理的涤纶织物的极限氧指数(LOI)值提高了5.7％,垂直燃烧性能达到GB/T5455-1997 B1级,燃烧后布面干净,并具有良好的耐水洗性能.涤纶织物燃烧后表面形成致密、光滑、无孔洞的炭层,炭层中磷含量远远超过阻燃织物中原始含量,磷富集于炭层表面.阻燃整理织物的热失重曲线上快速热解阶段缩短,最大分解速率减小了32.7％.     

ALPi和MPP协同阻燃PBT的研究

采用二乙基次磷酸铝(ALPi)作为阻燃剂、三聚氰胺聚磷酸盐(MPP)为协效剂、聚对苯二甲酸丁二醇酯(PBT)为基体,通过熔融共混,制得阻燃PBT。通过极限氧指数(LOI)和垂直燃烧(UL-94)研究了阻燃PBT的阻燃性能,通过热重分析(TGA)研究了阻燃PBT的热分解过程,采用扫描电镜(SEM)观察阻燃PBT燃烧炭层的形貌。结果表明,ALPi和MPP质量比为2∶1时,阻燃PBT的阻燃效果最好,LOI达到31%,垂直燃烧达到UL-94V-0级。TGA表明,复配阻燃体系的加入促进了PBT的提前分解,有利于在PBT表面形成保护性炭层,从而提高PBT的阻燃性。阻燃PBT燃烧炭层扫描电镜说明,复配阻燃体系能增加炭层密度,提高阻燃效果。     

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。     

A phosphorus‐containing inorganic compound as an effective flame retardant for glass‐fiber‐reinforced polyamide 6

A novel inorganic compound, aluminum hypophosphite (AP), was synthesized successfully and applied as a flame retardant to glass‐fiber‐reinforced polyamide 6 (GF–PA6). The thermal stability and burning behaviors of the GF–PA6 samples containing AP (flame‐retardant GF–PA6) were investigated by thermogravimetric analysis, vertical burning testing (with a UL‐94 instrument), limiting oxygen index (LOI) testing, and cone calorimeter testing (CCT). The thermogravimetric data indicated that the addition of AP decreased the onset decomposition temperatures, the maximum mass loss rate (MLR), and the maximum‐rate decomposition temperature of GF–PA6 and increased the residue chars of the samples. Compared with the neat GF–PA6, the AP‐containing GF–PA6 samples had obviously improved flame retardancy: the LOI value increased from 22.5 to 30.1, and the UL‐94 rating went from no rating to V‐0 (1.6 mm) when the AP content increased from 0 to 25 wt % in GF–PA6. The results of CCT reveal that the heat release rate, total heat release, and MLR of the AP‐containing GF–PA6 samples were lower than those of GF–PA6. Furthermore, the higher additive amount of AP affected the mechanical properties of GF–PA6, but they remained acceptable. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

酚醛树脂基新戊二醇磷酸酯阻燃剂的合成及其性能研究

通过用新戊二醇磷酰氯对线型酚醛树脂(PF)酚羟基实行磷酰化封端处理,制备了线型PF基新戊二醇磷酸酯(NDMPP)阻燃剂,将其应用于阻燃PA6。采用核磁共振氢谱(1H NMR)、核磁共振磷谱(31P NMR)和傅立叶变换红外光谱(FTIR)表征了NDMPP的结构,采用热重(TG)分析研究其热分解行为,采用极限氧指数(LOI)和UL 94测试其阻燃PA6材料的阻燃性能,采用万能材料试验机和冲击试验机测试阻燃材料的力学性能。1H NMR,31P NMR和FTIR结果表明,线型PF中大约82%的羟基被磷酰化,NDMPP中的磷含量约为11.9%。TG分析结果表明,NDMPP阻燃剂在氮气气氛下起始分解温度超过250℃,600℃的残炭率达到43.5%,显示出良好的热稳定性。当NDMPP质量分数为25%时,其阻燃的PA6达到UL 94 V–0等级,LOI达到33.4%,而拉伸强度、缺口冲击强度、弯曲强度和弯曲弹性模量分别为纯PA6的76%,41%,72%和71%。     

阻燃聚丁二酸丁二醇酯复合材料的制备及其阻燃性能研究

采用熔融共混技术,将次磷酸铝(AHP)和三聚氰胺氰尿酸盐(MC)引入聚丁二酸丁二醇酯(PBS),制备了一系列阻燃PBS复合材料,并采用极限氧指数、垂直燃烧、微型量热测试以及热失重分析研究了复合材料的阻燃性能以及热稳定性。结果表明,AHP可以有效提高PBS复合材料的阻燃性能;AHP与MC复配可以进一步提高复合材料的阻燃性能,两者质量比为2∶1,添加量为20 %（质量分数,下同）即可使复合材料达到UL 94 V 0级别,极限氧指数达到29 %;AHP以及复合阻燃体系可以有效提高复合材料初始分解温度及其高温稳定性。     

Flame-retardant behavior and protective layer effect of phosphazene-triazine bi-group flame retardant on polycarbonate

A series of flame-retardant polycarbonate (PC) composites with different ratios of phosphazene-triazine bi-group flame retardant (A3) were prepared. The flame retardant performance and thermal stability of PC/A3 composites were characterized by LOI, UL 94 vertical burning test, cone calorimetry test and TG. Results show that when the addition of A3 is 13.5%, the PC/A3 composite can pass UL94 V-0 level with a LOI value of 29.3% and reduce the peak heat release rate by 47.5% during the combustion. TG results show that adding 5% A3 can increase the initial decomposition temperature of the PC by 7°C in nitrogen and 9°C in air. Investigation of the morphology and chemical structure of char residue demonstrates that A3 promotes the formation of more complete and compact char residue which acts as physical barriers to inhibit the transfer of heat and oxygen, resulting the good flame retardant properties. The analysis of gaseous pyrolysis product reveals that A3 also exerts a flame-retardant effect in gas phase by releasing PO· free radicals.     

聚磷酸三聚氰胺对玻纤增强PA66的膨胀阻燃作用

采用自制的新型膨胀型阻燃剂——聚磷酸三聚氰胺(MPP)对玻纤增强PA66进行阻燃,以氧指数和垂直燃烧(UL94)评价了其阻燃作用;以热失重测定了材料的热分解性能;以扫描电镜观察了材料残炭的结构;并探讨了MPP阻燃玻纤增强PA66的阻燃机理。试验表明,单一MPP对玻纤增强PA66有良好的阻燃效果,当添加25％时,阻燃材料的氧指数为38,0％,达到UL94V-0级;MPP参与了玻纤增强PA66的降解过程,在材料表面形成了致密的隔热、隔氧的泡沫炭层。     

改性三氧化二锑协效二乙基次磷酸铝阻燃PA6研究

采用硅烷偶联剂（KH560）对三氧化二锑（Sb₂O₃）进行表面改性处理,并将其协效二乙基次磷酸铝（ADP）应用于聚酰胺6（PA6）阻燃研究。采用傅里叶变换红外光谱和热失重分析对改性Sb₂O₃进行表征,运用垂直燃烧、氧指数、锥形量热仪、热分析以及扫描电子显微镜和拉曼光谱等对阻燃PA6进行了阻燃性能及机理分析。结果表明,改性 Sb₂O₃与Sb₂O₃相比,与ADP具有更好的协同阻燃效应,其作用机制主要是在气相发挥阻燃作用;当ADP含量为8 %,改性Sb₂O₃含量为2 %时,阻燃PA6复合材料的UL 94等级达到V?0级,极限氧指数达到33.8 %。     

Influence of polyamide 6 as a charring agent on the flame retardancy,thermal, and mechanical properties of polypropylene composites

In this work, polyamide 6 (PA6) as a charring agent has been used in combination with thermoplastic polyurethane (TPU)‐microencapsulated ammonium polyphosphate (MTAPP) forming intumescent flame retardants (IFRs) which applies in polypropylene (PP). The effects of the IFRs on the flame retardancy, morphology of char layers, water resistance, thermal properties and mechanical properties of flame‐retardant PP composites are investigated by limiting oxygen index (LOI), UL‐94 test, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and mechanical properties test. The results show that the PP/MTAPP/PA6 composites exhibit much better flame‐retardant performances than the PP/MTAPP composites. The higher LOI values and UL‐94 V‐2 of the PP/MTAPP composites with suitable amount of PA6 are obtained, which is attributed to the thick and compact char layer structure evidenced by SEM. The results from TGA and DSC demonstrate that the introduction of PA6 into PP/MTAPP composites has a great effect on the thermal stability and crystallization behaviors of the composites. Furthermore, the mechanical properties of PP/MTAPP/PA6 composites are also improved greatly due to the presence of PA6 as a charring agent. POLYM. ENG. SCI., 55:1355–1360, 2015. © 2015 Society of Plastics Engineers     

新型磷–氮–卤三系阻燃剂的合成及其在PP中的应用

五硫化二磷、对卤苯酚和二乙胺经过两步反应,合成了两种新型磷–氮–卤三系阻燃剂:O,O’–二(4–卤代苯基)二硫代磷酸–N,N–二乙铵(4–XC_6H_4O)_2PS_2NH_2Et_2[X=Br(1),Cl(2)],用元素分析、傅里叶变换红外光谱、核磁共振氢谱、紫外–可见吸收光谱和热重分析测定了两种阻燃剂的结构和热稳定性,并测定了它们在聚丙烯(PP)材料中的阻燃性能。热分析结果表明:两种阻燃剂的热稳定高,热分解温度分别为234.8℃和200.7℃;阻燃剂在PP中的质量分数为30%时,两种阻燃剂的极限氧指数(LOI)分别为28.5%和27.1%,垂直燃烧等级达到UL94 V–0级,表明所合成的两种阻燃剂具有良好的阻燃性能和潜在应用前景。     

环氧树脂和ZnO对微胶囊红磷阻燃HIPS体系影响

研究了环氧树脂和ZnO对微胶囊红磷阻燃高抗冲聚苯乙烯(HIPS)性能的影响。结果表明,当微胶囊红磷用量为8 phr时,随着环氧树脂用量的增加,HIPS的阻燃性能提高;当环氧树脂用量大于20 phr时,阻燃HIPS 的垂直燃烧达到UL 94 V-0级,极限氧指数(LOI)为28．8％。在微胶囊红磷-环氧树脂复合阻燃HIPS体系中添加 ZnO具有阻燃协同作用,仅需加入2 phr。的ZnO就能使微胶囊红磷／环氧树脂质量比为8:15的阻燃HIPS体系垂直燃烧达到UL 94 V-O级,LOI也可达到29．2％。     

Effects of organopalygorskite on intumescent flame‐retarded polypropylene

The effect of organopalygorskite (OPGS) on an intumescent flame retardant (IFR) low‐density polypropylene (PP) has been investigated using the limited oxygen index (LOI), vertical burning test (UL‐94) and thermogravimetric analysis (TGA). The results of the LOI and UL‐94 tests indicate that the addition of OPGS substantially increases the LOI value for PP/IFR at a OPGS to IRF mass ratio of 2/28 with 30 wt% of total flame retardant. In addition, the samples pass the V‐0 rating in the UL‐94 tests. The results indicate that the addition of 2.0 wt% of OPGS simultaneously increases the tensile strength and bending strength of PP/IFR. J. VINYL ADDIT. TECHNOL., 24:281–287, 2018. © 2016 Society of Plastics Engineers