新型磷系阻燃剂阻燃环氧树脂的应用研究

以新戊二醇、三氯氧磷、1,2,3-三羟基苯为原料合成新型磷系阻燃剂1,2,3－三(5,5－二甲基－1,3－二氧杂己内磷酰氧基)苯(FR),将FR与环氧树脂(EP)熔融混合制备阻燃EP/FR复合材料。采用极限氧指数测试、垂直燃烧实验、热重分析、锥形量热分析、扫描电镜研究了FR对EP的阻燃性能和阻燃机理。结果表明,添加20 % FR的EP/FR复合材料的极限氧指数达到27.8 %,垂直燃烧通过UL94 V-0级,热释放速率平均值和生烟量平均值比未阻燃EP分别降低了77.0 %和82.8 %,扫描电镜分析表明, EP/FR体系燃烧后能形成连续、致密、封闭的焦化炭层。     

无卤阻燃ABS复合材料的研究

以磷/硅阻燃剂(SPDV)和有机蒙脱土(OMMT)为阻燃剂,通过熔融共混制备无卤阻燃丙烯腈-丁二烯-苯乙烯共聚物(ABS)复合材料。通过锥形量热仪、极限氧指数和UL94垂直燃烧仪测试复合材料的阻燃性能。结果表明:随着SPDV添加量的增加,ABS复合材料的阻燃性能逐渐改善,OMMT的加入降低了材料燃烧的生烟速率;当SPDV与OMMT并用时,复合材料阻燃效率更高,表现出阻燃协同作用。     

含磷阻燃剂阻燃硬质聚氨酯泡沫塑料的性能研究

研究了无卤、含磷添加型阻燃剂红磷、包覆红磷、聚磷酸铵、包覆聚磷酸铵、含磷膨胀型阻燃剂PNP、三聚氰胺焦磷酸盐等6种阻燃剂对硬质聚氨酯泡沫塑料阻燃及力学性能的影响。结果表明,随着阻燃剂添加量的增加,阻燃硬质聚氨酯泡沫塑料的极限氧指数(LOI)总体上呈升高趋势,拉伸强度呈先上升后下降趋势,而冲击强度呈逐渐下降趋势。包覆红磷和包覆聚磷酸铵阻燃材料的阻燃性能和力学性能均明显好于普通红磷和聚磷酸铵阻燃剂,PNP阻燃材料具有最佳的阻燃性能和力学性能,当PNP添加量为25%时,阻燃材料的LOI为29.5%,拉伸强度和冲击强度分别为5.3 MPa和8.7 kJ/m2。     

无机阻燃剂对PVC/木粉复合材料性能的影响

分别采用A1(OH)3、ZB以及Sb2O3等无机阻燃剂对PVC/木粉复合材料改性,研究不同的阻燃剂配方及阻燃剂含量对PVC/木粉复合材料阻燃性能和力学性能的影响。结果表明:随着A1(OH)3,ZB以及Sb2O3添加量的增加,PVC/木粉复合材料的氧指数(LOI)呈逐渐增大的趋势。Sb2O3阻燃效率最高,当添加量为9份时,氧指数达到35.2%;无机阻燃剂的加入普遍降低了PVC/木粉复合材料的冲击韧性,但对拉伸强度起到了一定的增强作用。     

MPOP/TPP/PER复合阻燃剂对PP燃烧行为的影响

采用熔融共混法制备了聚丙烯/三聚氰胺聚磷酸盐/磷酸三苯酯(PP/MPOP/TPP)和聚丙烯/三聚氰胺聚磷酸盐/磷酸三苯酯/季戊四醇(PP/MPOP/TPP/PER)复合材料,研究了不同阻燃组分配比对PP燃烧行为的影响。结果表明:当MPOP/TPP复合阻燃剂的添加量为30份、MPOP与TPP的质量比为20/10时,PP/MPOP/TPP复合材料的热稳定性下降,但其阻燃性能有一定程度的提高。在该体系中添加7.5份PER,当复合阻燃剂FR(MPOP/TPP=20/10)与PER的配比为22.5/7.5时,材料的热稳定性下降,但成炭效果增加,极限氧指数(LOI)达到22.6%,较纯PP提高了26.97%;同时材料的热释放速率、总释热量、有效燃烧热和有害气体的产率均明显减小,PP/MPOP/TPP/PER阻燃复合材料的阻燃性能显著提高。     

三羟甲基氧化磷对苎麻毡/酚醛复合材料性能影响

采用三羟甲基氧化磷(THPO)作阻燃剂,苎麻纤维复合毡作增强材料制备了酚醛树脂基复合材料,对材料的力学性能进行了测试,采用锥形量热仪和极限氧指数测试对复合材料的阻燃性能进行了表征。结果表明,与未添加阻燃剂相比,添加质量分数5%的THPO的复合材料的弯曲强度和内结合强度均得到了明显提高,但随着用量增加,其力学性能逐渐降低。THPO添加质量分数为30%时,复合材料的氧指数达到了26.5,阻燃效果良好。     

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。     

大分子溴系复合阻燃剂对PS和发泡PS的阻燃改性

将大分子溴系阻燃剂(FR–122P)与溴化环氧树脂(2200HM)组成的复合阻燃剂应用于聚苯乙烯(PS)复合材料和发泡PS中,研究了复合阻燃剂的配比和含量对PS复合材料阻燃性能以及复合阻燃剂含量对发泡PS泡孔结构和阻燃性能的影响,采用热重分析、扫描电子显微镜观察、极限氧指数(LOI)测试、垂直燃烧(UL–94)和水平燃烧试验等手段进行了表征。结果表明,当FR–122P与2200HM质量比为4∶1、总添加量为25%时,PS复合材料的LOI可达25.8%,并可通过UL–94 V–0等级;当复合阻燃剂的添加量为40%时,可得到泡孔尺寸较小、泡孔密度较大、膨胀倍率较高的发泡PS复合材料,且其可通过泡沫水平燃烧的HF–2等级。大分子溴系阻燃剂与溴化环氧树脂的复合阻燃剂对PS和发泡PS复合材料具有较好的阻燃效果。     

含磷阻燃剂对碳纤维增强环氧树脂阻燃性能的影响

以DOPO为阻燃剂,短切碳纤维为增强体,环氧树脂为基体,制备了不同DOPO含量的DOPO/碳纤维/环氧树脂复合材料。采用极限氧指数测定法、锥形量热法和UL-94垂直水平燃烧测试法,分析了复合材料的燃烧特性以及DOPO添加量对复合材料阻燃性能的影响。研究结果表明:DOPO可以提高碳纤维环氧复合材料的阻燃性能;添加磷(P)含量为3%时,与未添加样品相比,极限氧指数提高了9%,达到21.8,热释放速率峰值降低了31.2%;当P含量大于2%时,样品的水平分级达到了FH-1级别;火焰增长指数计算表明,含有1%和3%P的复合材料火灾危险性较小,DOPO对复合材料的阻燃作用主要属于气相阻燃机理。     

PP-g-MAH增容膨胀阻燃聚丙烯体系的研究

利用熔融共混制备了聚丙烯/膨胀型阻燃剂/马来酸酐接枝聚丙烯(PP/IFR/PP-g-MAH)阻燃复合材料。通过极限氧指数、热重分析、扫描电子显微镜及力学性能测试研究了PP-g-MAH对阻燃复合材料的阻燃性、热稳定性、微观形貌及力学性能的影响。结果表明,PP-g-MAH作为相容剂,当添加5 %的PP-g-MAH时,复合材料的极限氧指数达到30 %, 垂直燃烧达到UL 94 V-0级;随着PP-g-MAH含量的增加,阻燃剂和基体PP之间的界面作用力提高,体系的拉伸强度和弯曲强度均有提升,冲击强度减小幅度不大;与未加PP-g-MAH的复合材料相比,添加相容剂的复合材料成炭率明显提高。     

Pentaerythritol derived phosphorous based bicyclic compounds as promising flame retardants for thermoplastic polyurethane films

Imparting flame retardancy without melt dripping in thermoplastic polyurethane (TPU) is a challenging task. In the current work, a series of pentaerythritol derived phosphorous based flame retardants (FRs labeled FR1, FR2, FR3, and FR4) were synthesized, and their suitability for TPU thin films (<100 micron) was explored. Vertical flammability tests revealed that a blend of FR2 and TPU at 2% phosphorous content exhibited excellent flame suppression and complete stoppage of melt dripping whereas samples prepared from FR1 showed reduced melt drips. In comparison to FR1 and FR2, FR3 and FR4 manifested excessive nonflamed melt drips, which helps in removal of heat from the combustion cycle and self-extinguishment. The limiting oxygen index value of flame retardant (FRTPU) blends reached up to 33.5% compared to 19% for pure TPU. Thermogravimetric analysis and scanning electron microscopy studies suggest that blends of TPU with FR1 and FR2 display high char residue and condensed phase mechanism, whereas FR3 and FR4 blends show low char residue, working in the gas phase and by the removal of polymer from flame zone through melt dripping phenomena.     

阻燃剂DOPO-FR的合成及阻燃聚氨酯的性能研究

以苯胺、苯甲醛、9,10二氢9氧杂10磷杂菲10氧化物（DOPO）为原料合成了一种新型阻燃剂9,10二氢9氧杂10磷杂菲10氧化物4\[(苯胺)甲基\]苯（DOPO FR）,并与磷酸三乙酯(TEP)、膨胀石墨(EG)复配制备了阻燃聚氨酯泡沫材料。采用红外光谱分析仪、核磁共振分析仪对DOPO FR的化学结构进行表征,并利用极限氧指数、热重分析仪等对阻燃聚氨酯泡沫材料进行性能分析。结果表明,DOPO FR质量为多元醇的20 %,聚氨酯泡沫材料的极限氧指数就可达24.7 %;DOPO FR的加入提高了聚氨酯泡沫的力学性能和热稳定性;EG、TEP、DOPO FR三者协同阻燃可使聚氨酯泡沫的极限氧指数达到32 %。     

Enhanced flame retardancy,smoke suppression,and acid resistance of polypropylene/magnesium hydroxide composite by expandable graphite and microencapsulated red phosphorus

Low flame retardant efficiency and poor acid resistance of filled polymer composites are two main drawbacks of magnesium hydroxide (MH) as a flame retardant (FR). To solve these problems, expandable graphite (EG) and microencapsulated red phosphorus (MRP) were introduced into polypropylene/magnesium hydroxide (PP/MH) composite by melt compounding. The obtained PP/MH/EG/MRP quadruple composite was studied regarding its fire behavior as well as acid resistance. Obvious flame retardant synergism among MH, EG, and MRP is found in PP, which diminishes the loading of FR from 63.0 to 37.5 wt% to obtain V-0 rating in UL-94 test and low smoke release. Compact intumescent char with high thermo-oxidative stability was generated on composite surface, which plays a vital role in flame retardancy. The removal of MH by acid erosion on PP/MH/EG/MRP composite surface does not affect production of intumescent char and fire behavior of this composite. The composite displays good fire retardancy, smoke inhibition, and acid resistivity concurrently. This article renders an easy and cheap route to overcome the main faults of MH.     

壳聚糖/聚磷酸铵膨胀阻燃PP的阻燃及抑烟性能

为了提高聚丙烯(PP)的阻燃和抑烟性能,将壳聚糖(CS)作为膨胀型阻燃剂的碳源、聚磷酸铵(APP)作为膨胀型阻燃剂的酸源和气源,在此基础上通过熔融共混的方法制备了PP/CS/APP复合材料。采用极限氧指数仪、锥形量热仪等仪器研究了PP/CS/APP复合材料的的抑烟性及阻燃性。研究结果表明:CS/APP添加量为30%时,复合材料的极限氧指数值最大可达28.1%;且复合材料在烟气释放总量、CO和CO_2排放上明显降低,抑烟性得到了提升;热释放速率峰值、平均热释放速率值、平均有效燃烧热值、总热释放量值降低,成炭率升高,PP/CS/APP复合材料更难点燃;火灾性能指数明显提高,阻燃性能得到了大幅度提升,火灾蔓延指数显著减小,同时火灾危险性也相应降低。     

磷/溴单分子阻燃硬质聚氨酯泡沫复合材料制备及阻燃性能

将磷/溴单分子阻燃剂1,3,5-三(5,5-二溴甲基-1,3-二氧杂己内磷酰氧基)苯(FR)作用于硬质聚氨酯泡沫,制备出阻燃复合材料(FR/RPUF),利用极限氧指数、水平燃烧、锥形量热研究FR对硬质聚氨酯泡沫的阻燃性能及火灾燃烧性能的影响。结果发现:当FR添加量为15%时,阻燃聚氨酯泡沫的LOI达到24.1%,水平燃烧达到HF-1级,热释放速率平均值、热释放速率峰值、有效燃烧热及一氧化碳平均释放量分别降低78.7%、78.4%、57.1%和32.2%,硬质聚氨酯泡沫材料火灾危险性大幅度降低。     

无卤协效膨胀阻燃聚甲醛体系的性能和阻燃机理

针对聚甲醛(POM)难以阻燃的难题,采用酚醛树脂协效无卤膨胀阻燃剂复合阻燃POM,研究了酚醛树脂含量对POM阻燃性能和力学性能的影响以及相关的成炭阻燃机理.结果表明,酚醛树脂的含量对无卤膨胀阻燃POM体系的阻燃性能有重要影响,当体系中酚醛树脂的质量分数为0.5%～2.0%时,相应阻燃POM体系可达UL941.6 mm ...     

A flame‐retardant composite foam: foaming polyurethane in melamine formaldehyde foam skeleton

A composite foam, polyurethane–melamine formaldehyde (PU/MF) foam, was prepared through foaming PU resins in the three‐dimensional netlike skeleton of MF foam. The chemical structure, morphology, cell size and distribution, flame retardancy, thermal properties and mechanical properties of such composite foam were systematically investigated. It was found that the PU/MF foam possessed better fire retardancy than pristine PU foam and achieved self‐extinguishment. Moreover, no melt dripping occurred due to the contribution of the carbonized MF skeleton network. In order to further improve the flame retardancy of the composite foam, a small amount of a phosphorus flame retardant (ammonium polyphosphate) and a char‐forming agent (pentaerythritol) were incorporated into the foam, together with the nitrogen‐rich MF, thus constituting an intumescent flame‐retardant (IFR) system. Owing to the IFR system, the flame‐retardant PU/MF foam can generate a large bulk of expanded char acting as an efficient shielding layer to hold back the diffusion of heat and oxygen. As a result, the flame‐retardant PU/MF foam achieved a higher limiting oxygen index of 31.2% and exhibited immediate self‐extinguishment. It exhibited significantly reduced peak heat release rate and total heat release, as well as higher char residual ratio compared to PU foam. Furthermore, the composite foam also showed obviously improved mechanical performance in comparison with PU foam. Overall, the present investigation provided a new approach for fabricating a polymer composite foam with satisfactory flame retardancy and good comprehensive properties. © 2018 Society of Chemical Industry     

碱式碳酸镁基复合阻燃剂的制备及其阻燃性能研究

采用硅烷表面处理的碱式碳酸镁纳米片和氢氧化镁以及氢氧化铝为复合阻燃剂,通过密炼模压法制备了一系列复配阻燃剂协效阻燃EVA的复合材料。利用拉伸性能测试仪、熔融指数仪、垂直燃烧测试仪和锥形量热仪分别测试了复合材料的力学性能、加工流动性能和阻燃性能,利用热重分析仪测试了复配阻燃剂的热分解行为。结果表明,复配阻燃剂以适当比例协效阻燃EVA在更宽的燃烧温度范围内发生分解,能够起到更好的阻燃效果。并且复配阻燃剂/EVA复合材料的热释放速率和烟释放率大幅度降低,分别为181.06 kW/m²和0.032 m²/s。另外,复配阻燃剂/EVA复合材料的拉伸强度达到9.73 MPa,断裂伸长率为155.07%,每10 min熔融指数为1.00 g,符合电线电缆行业标准。     

Flame‐retardant and thermal degradation mechanism of low‐density polyethylene modified with aluminum hypophosphite and microencapsulated red phosphorus

Aluminum hypophosphite (AHP), a novel flame retardant, was used to improve the flame retardancy of low‐density polyethylene (LDPE) with microencapsulated red phosphorus (MRP). The synergistic effect between MRP and AHP was investigated by the limiting oxygen index (LOI), vertical burning test (UL‐94), and thermogravimetric analysis. When the contents of MRP and AHP were 10 and 30 phr, the LOI of LDPE/10MRP/30AHP composite was 25.5%, and it passed the UL‐94 V‐0 rating (the number before “MRP” and “AHP” is the loading of MRP and AHP, In LDPE/10MRP/30AHP, the content of the LDPE, MRP and AHP is 100phr, 10phr and 30phr, where phr refers to parts per hundreds of resin). The results of cone calorimetry testing show that the heat release rate of the composites was significantly reduced, and the strength of the char layer improved when the loading of AHP increased. The thermal stability of the LDPE/10MRP/30AHP composite was enhanced. The structure of the char was investigated by Fourier transform infrared spectrometry and scanning electron microscopy/energy‐dispersive spectrometry. The results indicate that AHP promoted the formation of stable char. This research provided a good way to prepare flame‐retardant materials with a halogen‐free flame retardant and contributed to environmental protection. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43225.     

Synergist flame retarding effect of ultrafine zinc borate on LDPE/IFR system

The flame retardancy of low‐density polyethylene (LDPE) treated with complex flame retardant composed of ultrafine zinc borate (UZB) and intumescent flame retardant (IFR) have been investigated by limited oxygen index (LOI), UL‐94 test, thermogravimetric analysis (TGA), cone calorimeter test, scanning electron micrograph (SEM), energy‐dispersive spectrometer (EDS), and X‐ray diffraction (XRD). The results of LOI and UL‐94 test indicate the desired flame retardancy of LDPE is obtained when the mass ratio of UZB to IFR is 4.2 : 25.8 and the complex flame retardant mass content is 30% (based on LDPE). The results of cone calorimeter show that heat release rate (HRR) peak, total heat release (THR), and mass loss of LDPE/IFR/UZB decrease substantially when compared with those of LDPE/IFR. TGA results show that the residue of LDPE/IFR/UZB increases obviously than that of LDPE/IFR when the temperature is above 600°C. SEM indicates the quality of char forming of LDPE/IFR/UZB is superior to that of LDPE/IFR. The results of EDS and XRD indicate that boron orthophosphate (BPO₄) and zinc‐contained compounds are formed in the residual char and these substances may play an important role in stabilizing the intumescent char structure and decrease the degradation speed substantially when subjected to high temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3667–3674, 2007