热塑性酚醛树脂／磷酸三苯酯对PC阻燃性能的研究

分别合成了三种不同摩尔质量的热塑性酚醛树脂(PF),并将其分别与磷酸三苯酯(TPP)复配作为阻燃剂,制备了一系列的PF/TPP/PC阻燃体系,通过极限氧指数(LOI)、热失重(TGA)测试,研究了酚醛树脂摩尔质量、阻燃体系各组分配比、阻燃剂用量对聚碳酸酯(PC)阻燃性能的影响.结果表明:PF与仰对PC有良好的协同阻燃作用.当TPP/PF质量比为1:1,总添加量为20%时,PC的极限氧指数可达46%～52%.TGA曲线显示,在降解过程中酚醛树脂的加入能有效地抑制TPP的挥发,提高了PC在降解过程中的热稳定性并促使了更多炭层的形成.     

磷系阻燃剂对PC/ABS共混物燃烧性能的影响

通过磷系阻燃剂(FR)阻燃聚碳酸酯/丙烯腈-丁二烯-苯乙烯(PC/ABS)共混物,制备阻燃材料,研究磷系阻燃剂对PC/ABS阻燃复合材料的燃烧行为和热稳定性的影响。通过UL94垂直燃烧测试、极限氧指数(LOI)测试、马弗炉测试等表征方法,对PC/ABS阻燃复合材料的燃烧行为进了系统的研究。结果表明,磷系阻燃添加量为15%时,PC/ABS阻燃复合材料能够达到UL94 V-2级,LOI的值为29.3%,高温时的残炭量由11.2%提高到20.8%。其中FR阻燃剂在高温下可以产生磷酸酯类黏稠难燃物质,能够有效地起到凝聚相阻燃作用,提高了PC/ABS共混物材料的阻燃性能,表现出良好的阻燃效果。     

磷-氮改性酚醛树脂的制备及其固化环氧树脂阻燃性能的研究

制备的双氰胺酚醛树脂(DICY-NR)与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)发生加成反应制备磷-氮改性酚醛树脂(DOPO-DICY-NR),将制备的DOPO-DICY-NR用于固化邻甲酚醛环氧树脂(CNE),并研究固化树脂体系的阻燃性能与机理。通过超高效聚合物色谱(APC)对DOPO-DICY-NR反应过程进行表征,采用热重分析(TGA)研究固化树脂体系的热分解行为,利用锥形量热仪(CONE)、UL-94阻燃性能以及极限氧指数(LOI)测试固化树脂体系的阻燃性能,通过扫描电镜(SEM)观察固化树脂体系的残炭微观形貌。实验结果表明:固化树脂体系中的磷与氮能够产生协效阻燃作用,从而大大提高固化树脂体系的阻燃性能,并降低热释放速率,且随着磷、氮元素含量的增加,固化后树脂体系的阻燃性能愈加优良,当固化树脂体系的磷和氮含量分别达到1.5%(wt)和2.8%(wt)时,固化树脂体系的阻燃性能可以通过UL-94 V-0阻燃等级,LOI达到29%。     

磷系阻燃剂FR/APP协效阻燃PP

采用氧指数测定仪、热重分析仪和锥形量热仪研究了磷系阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂环己内磷酸基)苯(FR)和聚磷酸铵(APP)复配体系对聚丙烯(PP)材料阻燃性能的影响.结果表明,FR/APP提高了PP的极限氧指数(LOI)、热稳定性和残炭率,降低了热释放速率.当w(FR)为15%和w(APP)为10%复配阻燃PP时,复合材料的LOI为29.6%.阻燃级别达到UL 94 V-0级.     

型阻燃环氧树脂复合材料的阻燃及燃烧特性

合成新型树状单分子磷-溴阻燃剂1,3,5-三(5,5-二溴甲基-1,3-二氧杂已内磷酰氧基)苯(FR),制备阻燃环氧树脂(EP)复合材料,利用极限氧指数(LOI)、垂直燃烧(UL-94)、锥形量热(CONE)等方法研究FR对环氧树脂的阻燃性能及燃烧特性的影响.结果表明:当FR添加量为30%时,阻燃EP的LOI达到29.4%,垂直燃烧通过V-O级,其av-HRR,av-EHC,av-SEA及av-MLR较未阻燃EP分别降低87.5%、92.8%、90.8%和58.5%,呈现出良好地阻燃效果和抑烟性能;扫描电子显微镜(SEM)观测发现:阻燃EP燃烧后形成了均匀闭孔炭层.     

阻燃-阳离子染料易染涤纶短纤维的研制

采用磷系阻燃剂、SIPM与DMT、EG共聚方式合成了阻燃 阳离子染料易染聚酯 (FR CDP) ,并进行了热性能研究。通过对纺丝工艺的探索 ,成功地研制出了FR CDP短纤维 ,其常规物理指标合格 ,并具有优良的染色性能和阻燃性能 ,在 10 0℃下 ,经 90min ,上染率达 89 3 % ,极限氧指数LOI为 3 0 0 %。     

一种磷硅阻燃剂的制备及对聚碳酸酯阻燃性能的研究

采用逐步升温的本体聚合方法,合成了含磷、硅的阻燃剂二苯基硅氧烷-二氧苯基乙酮-苯基磷酸酯共聚物(BHPD),并用傅立叶变换红外光谱(FT-IR)和核磁共振氢谱(1H NMR)对其结构进行了表征。通过热重分析(TGA)对BHPD及其阻燃改性PC的热稳定性进行了研究。采用极限氧指数(LOI)、垂直燃烧(UL94)、微型量热仪(MCC)和扫描电镜(SEM)对BHPD的阻燃性能进行了研究,结果表明BHPD对PC阻燃性能明显提升,BHPD添加量为15%时,极限氧指数从纯PC的26%升高到了48%,UL94阻燃级别从V-2提高到了V-0级。     

豆油基磷–氯协同阻燃增塑剂的合成,表征和应用

使用可再生资源环氧豆油与三氯氧磷合成了豆油基磷–氯协同阻燃增塑剂。使用傅里叶变换红外光谱和核磁共振氢谱对合成产品的结构进行了分析和表征,结果表明得到了预期的产品。将该产品与聚氯乙烯(PVC)热塑共混成型制备了阻燃增塑PVC共混体系,使用热重分析仪、马弗炉、极限氧指数(LOI)仪和万能拉力试验机对阻燃增塑PVC共混体系的热稳定性能、阻燃性能及力学性能进行了表征。结果表明,合成的大豆油基磷–氯协同阻燃增塑剂对PVC具有高效的阻燃和增塑作用,当其用量从0份增加到30份时,阻燃增塑PVC共混体系的LOI从24.1%增加到33.2%,断裂伸长率从170.14%增加到260.32%,热稳定性也得到提高;合成的阻燃增塑剂的阻燃机理主要是通过促进PVC共混体系表面形成致密的炭层来阻止共混体系进一步热降解。     

聚苯基膦酸二苯芴酯的合成与应用

以双酚芴和苯基膦酰二氯为原料,采用溶液聚合法合成了聚苯基膦酸二苯芴酯(PFPPP)。采用FTIR、1H-NMR和31P-NMR对PFPPP的结构、组成进行了表征,GPC和TGA分别对PFPPP的相对分子量、热稳定性能进行了表征,结果表明:成功合成了聚苯基膦酸二苯芴酯,其数均分子量可达11万,分子量分布为1.26,分布较窄;聚苯基膦酸二苯芴酯的初始分解温度为286℃,分解温度分布较宽,于845℃时PFPPP的成炭率高达45%。此外,对PFPPP在PC、PC/ABS体系的阻燃性能进行了测试,研究发现PFPPP在PC体系中的添加量(ω)为3%、PC/ABS体系中ω为5%时,两者阻燃级别均达到V-0级;当ω为10%时,PC的氧指数由25%提高到31%,可见PFPPP的添加提高了PC、PC/ABS的阻燃性能。     

无卤阻燃聚乙烯的阻燃性能及热裂解分析

通过极限氧指数(LOI)和锥形量热法(Cone),考察了添加质量分数30%磷系阻燃剂1,2,3-三(5,5-二甲基-1,3-二氧杂己内磷酰氧基)苯(FR)的PE(阻燃PE)的阻燃性能。借助裂解-气相色谱质谱(PY-GC/MS)联用技术研究了纯PE及阻燃PE的热裂解产物结构以探讨其阻燃机理。结果表明:阻燃PE的LOI达到25.8%,平均热释放速率相对纯PE降低55.4%,呈现出良好的阻燃性能;PY-GC/MS分析表明,FR的加入没有改变PE热分解反应的机理,但FR的添加对PE的热裂解及燃烧反应具有较强的抑制作用。     

Preparation,characterization and its flame retardance performance of microencapsulated ammonium polyphosphate/ bridged polysesquisiloxane polyurethane composites

A core shell material consisting of ammonium polyphosphate as core and 4,4-oxydianiline-formaldehyde resin as shell was prepared through a situ microencapsulation technology. The monomer of the polyurethane (PU) was modified to form bridged polysesquisiloxane. The purpose of modification is to improve the thermal stability of polyurethane matrix through the formation of networks. The degree of the networks was evaluated by solid state ²⁹Si-nuclear magnetic resonance. The structure and hydrophobic property of microencapsulated flame retardant were characterized using X-ray photoelectron spectroscopy and water solubility. The results indicated that the microencapsulation of APP with 4,4′-oxydianiline-formaldehyde resin (OF resin) resulted in improved hydrophobicity. The thermal properties of final flame retardant were systematically analyzed through thermogravimetric analysis. Limiting oxygen index and UL-94 test were used to classfied the flame retardant properties of varying the composition of APP and OFAPP in silanol-terminated polyurethane composites. Pure PU exhibited an LOI of 17 % and failed the UL-94 test. The LOI values of the 40 % OFAPP-added composites can reach 41 % and pass V-0 level. The results revealed that the microcapsulation of commercial flame retardant can improve the flame retardance of the composites.     

Synergistic effect on flame retardancy and thermal behavior of polycarbonate filled with α‐zirconium phosphate@gel‐silica

A new kind of flame retardant (ZS) with layered α‐zirconium phosphate disks (α‐ZrP) as the core and inorganic flame retardant (gel‐silica, GS) to shield solid acid sites on the surface of α‐ZrP as the shell, was synthesized via a facile method. The incorporation effects of ZS with silicone resin on the thermal properties and flame retardance of PC composites were investigated. The presence of ZS could improve the thermal stability of PC matrix. With the addition of ZS contents increased to 3 wt %, the limiting oxygen index (LOI) of the composite was 32.3% and the vertical burning (UL‐94) test reached a V‐0 rating. However, with more contents of ZS, the LOI value decreased, and without the GS layer, the LOI value was decreased significantly as well. The synergism between the α‐ZrP core and gel‐silica shell, also with the silicone resin were found. Based on these results, the flame‐retardant mechanism was proposed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44829.     

Synthesis of a phenylene phenyl phosphine oligomer and its flame retardancy for polycarbonate

A novel flame retardant, phenylene phenyl phosphine oligomer (PPPO) was synthesized and its chemical structure was characterized using Fourier transform infrared spectroscopy, ¹H, ¹³C, ³¹P nuclear magnetic resonance spectroscopy and mass spectrometer. PPPO was used to impart flame retardancy to polycarbonate (PC). Combustion behaviors and thermal degradation properties of PC/PPPO system were assayed by limiting oxygen index (LOI), vertical burning test (UL‐94), cone calorimeter test, and thermogravimetric analysis. PC/6 wt % PPPO passed UL‐94 V‐0 rating with 3.0 mm samples and the LOI value was 34.1%, and PC/8 wt % PPPO also passed UL‐94 V‐0 rating with 1.6 mm samples and the LOI value was 36.3%. Scanning electron microscopy reveals that the char properties had crucial effects on the flame retardancy of PC. Mechanical properties and water resistance of PC/PPPO system were also measured. After water resistance test, PC/6 wt % PPPO with 3.0 mm samples and PC/8 wt % PPPO with 1.6 mm samples kept V‐0 rating and mass loss was only 0.2%. The results revealed that PPPO was an efficient flame retardant for PC. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Application of cyclophosphazene derivatives as flame retardants for ABS

Cyclotriphosphazene derivatives were synthesized for use as a non-halogen flame retardant for ABS. Hexachlorocyclotriphosphazene was reacted with phenol, catechol, or 2,3-dihydroxynaphthalene, respectively, and the fire retardant ability of each product in ABS resin was characterized by UL 94 and LOI tests. The mechanical properties of ABS compounds containing one of these flame retardants were also examined. The derivative (HNCP) synthesized from 2,3-dihydroxynaphthalene showed the best flame retardance among these derivatives studied. Synergistic effects with novolac were observed in the cases using the derivative (PNCP) obtained from phenol, but little synergistic effects were observed in cases using HNCP.     

磷酸三苯酯/热塑性酚醛树脂在PC中协效阻燃作用的研究

采用磷酸三苯酯(TPP)和热塑性酚醛树脂(PF-T)复配阻燃聚碳酸酯(PC),探讨了TPP/PF-T不同配比以及阻燃剂添加总量变化对整个体系的阻燃性能及力学性能的影响。结果表明,当PC/TPP/PF-T质量比为80/10/10时,体系的氧指数达到46%,阻燃级别达到UL94V-0级;TPP/PF-T的协效作用机理为热解过程中PF-T与TPP发生酯交换反应而形成稳定的网状结构,抑制了TPP的挥发,提高了体系的热稳定性及阻燃性能。     

新型阻燃剂BPP的应用研究

研究了阻燃剂磷酸三（2,4-二溴苯基）酯（BPP）的性能及其在30％玻纤增强PBT、PC中的应用。结果表明：BPP毒性低,热稳定性高（开始分解温度达310℃以上）,阻燃性好,能显著改善树脂的加工性能和力学性能。用于30％玻纤增强PBT中,BPP分子中溴,磷的协同效应使其阻燃性能优于阻燃剂PBO。用于透明PC中,由于BPP分子中溴／磷的协同效应大于PBO和Sb2O3的溴,锑协同效应,含BPP的PC氧指数大于含PBO的PC。BPP对PC的透光率无影响,并显著改善了PC和PBO的加工性能和力学性能。     

阻燃PC/ABS合金的研制及其在电器上的应用

通过对3种增容剂增容PC／ABS合金性能的测试对比,选用了1种效果最佳的增容剂制备PC／ABS合金．用十溴联苯醚和三氧化二锑作为阻燃体系,对阻燃PC／ABS合金的力学性能、热性能、阻燃性能进行了检测。结果表明,当PC：ABS：增容剂：阻燃体系为70：30：8：15时,阻燃PC／ABS合金的综合力学性能最好,阻燃性能达到UL 94V-0级．该合金已用于生产防火电器开关、插座面板系列产品。     

Flame‐retardant ABS resins from novel phenyl isocyanate blocked novolac phenols and triphenyl phosphate

In an effort to prepare a novel novolac phenol (NP) based char former with good solubility, the hydroxyl functionalities of NP were blocked with phenyl isocyanate (PI) via a simple urethane‐forming reaction. The chemical structure and properties of the obtained novolac phenol–phenyl isocyanate adduct (NP–PI) were characterized with gel permeation chromatography, Fourier transform infrared spectroscopy, ¹H‐NMR, and differential scanning calorimetry. Adducts of two kinds of NPs (molecular weights = 450 and 800) with PI were used as potential char formers for this study. Thus, a two‐component system using NP–PI as a char former and triphenyl phosphate (TPP) as a phosphorous‐based flame retardant was blended with ABS, and the thermal degradation behavior and flame retardance were examined as a function of the molar mass of NP–PI and the TPP/NP–PI ratio with thermogravimetric analysis and limiting oxygen index (LOI) testing. ABS compositions with no NP–PI were also prepared for comparison. The mixtures showed a synergistic effect between TPP and NP–PI on the flame‐retardance enhancement of ABS. Those containing the higher molar mass NP–PI adduct were the most flame retardant, and a LOI value as high as 41 was obtained. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 721–728, 2006     

氧化亚镍在RTB-IFR膨胀阻燃体系中的协效作用

将氧化亚镍(NiO)与膨胀阻燃剂(RTB-IFR,未添加协效剂成分)复配,应用在聚丙烯(PP)复合材料中以研究NiO的阻燃协效作用。探讨了NiO对膨胀阻燃PP复合材料的阻燃性能、力学性能及热降解行为的影响。结果表明,在PP中单独添加20%RTB-IFR阻燃剂,PP复合材料具有较好的阻燃性能,氧指数为31.8%,3.2 mm样条能通过UL94 V-0级。当RTB-IFR阻燃剂中加入5%NiO时,PP复合材料的阻燃性能明显得到提高,氧指数达到33.6%,1.6 mm样条即能通过UL94 V-0级。同时,NiO对PP复合材料的力学性能影响较小。NiO的引入改变了RTB-IFR及RTB-IFR/PP体系的热降解过程,降低了PP复合材料的热分解速率,提高了复合材料高温时的残炭量和热稳定性。