复合无机无卤阻燃剂改性聚氨酯泡沫及性能研究

以聚磷酸铵(APP)为主要阻燃剂,复配可膨胀石墨(EG)和膨润土作为阻燃剂和改性剂,制备了完全无机且无卤阻燃剂改性的硬质聚氨酯泡沫(RPUF)。在固定无机阻燃剂及改性剂总量的条件下,研究了膨润土和EG用量及比例对RPUF的热稳定性、阻燃性能、力学性能、泡孔结构等的影响。结果表明,随膨润土或EG含量的增大,泡沫的压缩强度先增大后减小,二者含量分别为10%和5%时压缩强度最大。EG对泡沫阻燃性能的提高有显著影响,但同时也会使泡孔孔径增大;而膨润土作为泡沫成核剂能明显减小孔径。通过热重分析表明膨润土和EG的加入能明显增强泡沫的热稳定性。当APP为泡沫总质量的15%,膨润土为5%,EG为5%时,可以制得阻燃性能、力学性能和泡沫孔径较佳平衡的阻燃泡沫材料。在该条件下,泡沫的压缩强度为0.42 MPa,泡沫平均孔径为434μm,LOI值达到29%。     

反应型含磷多元醇/APP复配阻燃聚氨酯泡沫的制备及性能

以非丁基氧化锡为催化剂,通过甲基膦酸二甲酯(DMMP)与乙二醇(EG)酯交换反应,制备了含磷多元醇(DMMP-EG)。将DMMP-EG与聚磷酸铵(APP)作为复合阻燃剂,制备了阻燃硬质聚氨酯泡沫(RPUF),探讨了复配阻燃剂对RPUF力学性能、阻燃性能、热稳定性的影响。结果表明:DMMP-EG与APP复配阻燃RPUF,在提高阻燃性能的同时,力学性能显著提高;当DMMP-EG添加15份、APP添加30份时,泡沫的力学性能最佳,与纯RPUF相比,压缩强度提高了1.25%,冲击强度提高了101.53%;此时,极限氧指数(LOI)提高至21.7%,烟密度等级为40。热重(TG)分析结果表明:在氮气气氛中,750℃时的残炭率较纯RPUF提高了612.56%。阻燃体系呈现以凝聚相为主的气相-凝聚相双相阻燃特点。     

MG–PF包覆EPS泡沫阻燃及力学性能研究

采用强酸氧化法对石墨进行改性,得到与酚醛树脂(PF)有良好相容性的改性石墨(MG),然后在MG上合成PF,制得可发性聚苯乙烯(EPS)用包覆阻燃剂(MG–PF),将MG–PF涂覆到已预发泡的EPS珠粒上,经二次发泡成型制得MG–PF包覆阻燃EPS材料。研究了石墨的改性效果,以及MG–PF用量与MG–PF中MG含量对材料阻燃性能和力学性能的影响。结果表明,石墨经过改性后,所制得的MG–PF具有较好的稳定性,从而进一步提高了阻燃材料的性能;MG–PF中MG的含量越高,材料的极限氧指数(LOI)随MG–PF用量增加而提高的幅度越大,水平和垂直燃烧等级达到HF-1和V–0级时所需的MG–PF用量越低,但力学性能随MG–PF用量增加而下降的幅度越大。当MG–PF中MG质量分数为30%,EPS与MG–PF质量比为1∶4时,材料的压缩强度为219 kPa,拉伸强度为299 kPa,满足工程应用要求,且LOI达到25.8%、水平和垂直燃烧等级分别为HF-1和V–0级,具有较好的综合性能。     

膨胀型阻燃剂包覆EPS泡沫的阻燃抑烟性能

采用树脂包覆法,用蜜胺树脂和聚磷酸铵/季戊四醇/三聚氰胺组成的膨胀型阻燃剂制备无卤阻燃发泡聚苯乙烯(EPS)泡沫,研究膨胀阻燃剂对EPS泡沫的阻燃性能、抑烟性能及力学性能的影响。结果表明,膨胀阻燃剂可以有效提高EPS泡沫的阻燃性能和抑烟性能,极限氧指数最高可提高到30.6%,UL-94达到V-0等级,生烟量下降35%,EPS泡沫的冲击强度也得到提高。     

复合阻燃剂阻燃硬质聚氨酯泡沫塑料的性能研究

制备了复合阻燃剂阻燃硬质聚氨酯(PUR-R)泡沫塑料,研究了复合阻燃剂甲基膦酸二甲酯(DMMP)、三(2-氯异丙基)磷酸酯(TCPP)、可膨胀型石墨(EG)和氢氧化铝(ATH)对PUR-R泡沫塑料阻燃性能的影响,采用正交试验确定了复合阻燃剂的最佳配比。用极限氧指数(LOI)测定仪、烟密度测定仪和万能试验机测定了阻燃PUR-R泡沫塑料的LOI、烟密度等级和压缩强度,结果表明,当DMMP,TCPP,EG,ATH的质量比为2∶2∶3∶3时,在25份聚醚多元醇中添加12份复合阻燃剂,制备的阻燃PUR-R泡沫塑料的LOI达26.3%,烟密度等级为77.63,压缩强度为0.18 MPa,阻燃PUR-R泡沫塑料具有良好的综合性能。     

APP/EG对PIR-PU泡沫材料阻燃性能的影响

以聚磷酸铵/膨胀石墨(APP/EG)为阻燃剂,制备了高阻燃的聚异氰酸酯-聚氨酯(PIR-PU)泡沫材料。采用极限氧指数(LOI)测试、红外光谱分析(IR)、热重分析(TGA)等方法对所制备PIR-PU泡沫材料的燃烧及热降解行为进行了研究。结果表明:APP与EG存在着良好的协同阻燃作用,APP/EG的添加可有效提高PIR-PU泡沫材料的LOI值,其中当APP/EG用量为25份、其配比为3/7时,PIR-PU泡沫材料具有最佳阻燃性能,材料的LOI值可达35.4%。APP与EG的复配使用,使PIR-PU泡沫材料的炭层较单独使用APP或EG时更为致密,有效提高了材料的热分解温度,降低了热降解速率,进而改善了材料的阻燃性能。     

TPP/EG在软质聚氨酯泡沫中协同阻燃作用的研究

采用磷酸三苯酯(TPP)和可膨胀石墨(EG)进行复配,通过一步法发泡工艺制备了具有阻燃性能的软质聚氨酯泡沫(FPUF)。通过极限氧指数(LOI)、垂直燃烧和烟密度测试对FPUF的阻燃性能进行研究,探索了TPP与EG之间的协同阻燃作用。结果表明:TPP与EG之间存在一定的协同增强FPUF的阻燃性能。当TPP/EG配比为1/3、复配型阻燃剂用量为30份时,阻燃FPUF的LOI值达到25%。同时,复配型阻燃剂添加到FPUF中还能降低有焰燃烧时间,并起到一定的抑烟作用。     

氧化石墨-酚醛树脂包覆阻燃可发性聚苯乙烯

将石墨进行氧化处理得到氧化石墨(GO),采用GO与酚醛树脂(PF)进行原位插层聚合,得到体系均一稳定含氧化石墨的酚醛树脂(GP)。将GP作为阻燃型包覆剂包覆在预发泡的可发性聚苯乙烯(EPS)表面,得到阻燃性EPS保温板,并对材料的阻燃性能、保温性能及力学性能等进行测试。结果表明,GP能明显提高EPS的阻燃性能,但在GP或GO用量较多时,材料的保温性能和力学性能均有所下降。     

可膨胀石墨/聚磷酸铵协效阻燃PUI泡沫塑料研究

通过添加可膨胀石墨(EG)和聚磷酸铵(APP)单组分阻燃剂及其复配阻燃剂,制备了聚氨酯–酰亚胺(PUI)泡沫塑料阻燃体系,并对其阻燃性能、热性能、表面碳层形貌及力学性能等进行了研究。结果表明,在相同阻燃剂添加量下,复配阻燃体系的极限氧指数(LOI)值高于单一阻燃剂阻燃体系,PUI/EG/APP体系的LOI值由18.6%提高至30.9%。热失重分析表明EG和APP间的相互作用导致了PUI/EG/APP体系在高温阶段的热降解速率下降,残炭率显著上升。扫描电镜分析表明PUI/EG/APP体系在燃烧后能生成更加连续和致密的炭层。在相同阻燃剂添加量的情况下,EG/APP复配使用能够减少EG对PUI压缩性能的损害。     

无卤型阻燃聚氨酯泡沫塑料研究

选用可膨胀石墨(EG)作为阻燃剂制备了阻燃聚氨酯泡沫塑料,考察了EG的用量及其表面处理对材料的阻燃性能及力学性能的影响。结果表明,选择EG作为阻燃剂可以有效提高聚氨酯泡沫塑料的阻燃性能;随着EG用量的增加,材料的阻燃性能提高,当EG用量为30%时,其氧指数(LOI)可达27%,但力学性能明显下降;采用聚乙烯醇或钛酸酯101对EG进行表面处理后,材料的力学性能明显改善,且聚乙烯醇优于钛酸酯。     

PF泡沫塑料对PF/EPS复合泡沫塑料性能的影响

研究出一种具有较好稳定性、保温性能、力学性能和阻燃性能的酚醛树脂(PF)/可发性聚苯乙烯(EPS)复合泡沫塑料。在PF泡沫塑料颗粒基体中加入EPS发泡颗粒,充分混合固化,使PF泡沫塑料颗粒与EPS发泡颗粒紧密结合,EPS发泡颗粒被PF泡沫塑料颗粒包围并相互隔离,再用模具发泡成型得到该复合泡沫塑料。实验结果表明,PF的含量越高,稳定性、力学性能和阻燃性能越好,保温性能呈现先升高后下降的趋势,当PF的含量为80%时,PF/EPS复合泡沫塑料的表观密度为38.4 kg/m3,热导率为0.024 W/(m·K),弯曲强度为0.134 k Pa,压缩强度为323 k Pa,极限氧指数为47.9%,烟密度等级小于15,热释放速率峰值小于250 k W/m2,综合性能最好。     

Effects of expandable graphite and ammonium polyphosphate on the flame‐retardant and mechanical properties of rigid polyurethane foams

In this work, the effect of expandable graphite (EG) and ammonium polyphosphate (APP) on the flame retardancy and mechanical properties of the rigid polyurethane foam (RPUF) was studied. The results indicated that both EG and APP could effectively improve the flame retardancy of RPUF, while the retardancy of EG was better than APP. When the flame‐retardant loading was 15 wt %, the limited oxygen index (LOI) values of APP‐ and EG‐filled RPUF were 24.5 and 32 vol %, respectively. According to the LOI test, the optimal ratio of APP to EG in RPUF composites was 1 : 1 by weight, at which the LOI value of 15 wt % (APP + EG)/RPUF was 30.5 vol %. Thermal degradation test of RPUF composites by thermogravimetric analysis indicated that the addition of APP and EG to RPUF could lead to an increase in the amount of high‐temperature residue. Under the same conditions, the residue amount of EG/RPUF was less than that of APP/RPUF at the same temperature. Compression test and dynamic thermal mechanical analysis indicated that both the compressive strength and modulus decreased at a certain extent with the EG‐ or APP‐filled into RPUF, respectively, but with the mixture of EG and APP added into RPUF, the mechanical properties of these materials increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

阻燃聚苯乙烯板的力学性能

以阻燃涂料对可发性聚苯乙烯板(EPS)进行内部包覆和外部涂刷,制备阻燃EPS板。对涂覆涂料的阻燃EPS板进行抗弯压缩、高低温尺寸稳定性以及吸水率的测试结果表明,在阻燃EPS板极限氧指数达34.7%、垂直燃烧达UL94 V–0级及水平燃烧达HF–1级标准时,其力学性能及其它性能均能达到国家要求的保温材料标准,由此表明,阻燃涂料在改善EPS板的阻燃性能的同时,也能保证阻燃EPS板的力学性能。     

环保型溴—锑阻燃体系在聚苯乙烯中的应用

用十溴二苯乙烷(DBDPE)和三氧化二锑(Sb_2O_3)组成的协效阻燃体系作为聚苯乙烯(PS)的阻燃剂,采用熔融共混制备PS片材,并探究了不同配比下,Br/Sb阻燃剂的阻燃效果。结果表明,DBDPE和Sb_2O_3之间存在很好的协效作用,Br/Sb阻燃剂的加入明显提高了PS的热稳定性及阻燃性能。当PS/(Br+Sb)的质量比为83/17(其中Br/Sb质量比为17/3)时,片材的阻燃性能最佳,其UL94测试达到V–0级别,极限氧指数可达30.1%。在力学性能方面,Br/Sb阻燃剂的加入对PS材料的冲击强度影响较小,其拉伸强度有明显降低。     

八溴二苯乙烷及EG对长玻纤增强PP性能的影响

以八溴二苯乙烷(ODOPE)或十溴二苯乙烷(DBDPE)及三氧化二锑(Sb2O3)为阻燃剂,采用熔体浸渍工艺制备阻燃长玻璃纤维增强PP(LGFPP),研究了这两种溴系阻燃剂对阻燃LGFPP的阻燃性能和物理力学性能的影响,并研究了可膨胀石墨(EG)在ODOPE阻燃LGFPP的中的协效效果。结果表明,ODOPE对于LGFPP的阻燃效率高于相同含量下的DBDPE,添加质量分数为14%的ODOPE的阻燃LGFPP垂直燃烧等级为V–0级,极限氧指数(LOI)为23.6%。扫描电子显微镜分析表明,ODOPE均匀分散于阻燃LGFPP树脂基体中,而DBDPE在基体中团聚明显。ODOPE阻燃LGFPP的熔体流动速率(MFR)、拉伸强度、弯曲强度及悬臂梁缺口冲击强度均高于DBDPE阻燃的LGFPP,且其MFR随着ODOPE含量的增加而提高。EG可以略微提升ODOPE阻燃LGFPP的LOI,含3%EG的ODOPE阻燃LGFPP的LOI最高,为24.7%,垂直燃烧等级为V–0级。EG与ODOPE–Sb2O3体系的协效阻燃效果较低,且降低了LGFPP的MFR和力学性能。     

Flame retardancy of hollow glass microsphere/rigid polyurethane foams in the presence of expandable graphite

Rigid polyurethane foams (RPUF) filled with various loadings of expandable graphite (EG) or/and hollow glass microspheres (HGM) were prepared by cast molding. The flame retardant properties of these composites were investigated by limiting oxygen index (LOI), horizontal and vertical burning tests. The composite with 10 wt % HGM and 20 wt % EG had the best flame retardant properties, and its LOI value reached 30 vol %. The addition of an appropriate loading of HGM improved the compressive strength and modulus of RPUF and EG/RPUF. When the HGM content arrived at 10 wt %, the compressive strength and modulus of the composites reached the maximum value. The dynamical mechanical analysis (DMA) showed that the addition of EG and HGM made the glass transition temperature shift to a higher temperature, and 10 wt % EG and 10 wt % HGM filled RPUF had the highest storage modulus. The scanning electronic microscope (SEM) observation indicates that the additives led to the decrease in the cell size. In addition, the flame retardant mechanism, the thermal properties, the burned surfaces and the interface surfaces were elucidated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Flame‐retardant and mechanical properties of high‐density rigid polyurethane foams filled with decabrominated dipheny ethane and expandable graphite

The article reported the flame‐retardant and the mechanical properties of expandable graphite (EG), an intumescent type, and decabrominated dipheny ethane (DBDPE), a gas‐phase type of flame‐retardant‐containing high‐density rigid polyurethane foams (RPUF) with a constant density of 0.5g/cm³. The results indicated that both EG and DBDPE could effectively interdict the burning of RPUF, besides, the EG exhibited more effective flame retardancy than the DBDPE. When the flame‐retardant loadings were 20 wt %, the LOI value of DBDPE‐filled RPUF increased to 33 vol %, while, surprisingly, the EG‐filled RPUF reached 41 vol %. Unfortunately, when they were both simultaneously added into RPUF, there was not any flame‐retardant synergistic effect. Although EG had outstanding flame retardancy, the compressive strength and modulus of 20 wt % EG‐filled RPUF dropped to only 9.1MPa and 229.7MPa respectively, which were lower than those of DBDPE (12.4 MPa and 246.8 MPa). The phenomena were ascribed to the different flame‐retardant mechanisms of EG and DBDPE, which were verified by scanning electronic microscope (SEM) observation of the burned surfaces. Besides, the dynamical mechanical analysis (DMA) demonstrated that the additions of EG and DBDPE made the glass transition temperature shift to the high temperatures, and the EG‐filled RPUF had the higher storage modulus. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

基于磷杂菲衍生物多组分无卤阻燃天然橡胶的制备及性能

将磷杂菲/三嗪双基协同阻燃剂（TGD）、甲基膦酸二甲酯（DMMP）、可膨胀石墨（EG）及氢氧化铝（ATH）复配添加到天然橡胶（NR）中制备阻燃NR硫化胶,考察了TGD/DMMP/EG/ATH复配阻燃剂对NR硫化胶的阻燃性能、热稳定性及物理机械性能的影响。结果表明,TGD/DMMP/EG/ATH复配阻燃剂可有效提升NR硫化胶的阻燃性能和热稳定性,并降低燃烧过程中的热释放速率。当TGD/DMMP/EG/ATH复配阻燃剂的用量为60份（质量）时,NR硫化胶的极限氧指数可达28.4%,残炭质量分数可达25.61%,热释放速率可降低95%,总热释放量可降低21%。TGD/DMMP/EG/ATH复配阻燃剂对NR硫化胶的物理机械性能影响不大。     

Study on char reinforcing of different inorganic fillers for expandable fire resistance silicone rubber

Sodium silicate monohydrate (NSH), glass frits (GF) and aluminum hydroxide (ATH) were incorporated into room temperature vulcanized (RTV) silicone rubber (SR) as char reinforcing materials to improve the fire resistance of intumescent flame retardant silicone rubber. SR composites containing only intumescent flame retardant such as phosphorus nitrogen composite flame retardant (NH₂-C) and expandable graphite (EG) were used as comparison samples. Limiting oxygen index (LOI) test, vertical burning test (UL-94), flame resistance test, scanning electron microscopy (SEM) and X-ray diffraction spectroscopy tests, as well as volume variation and compression strength of char residues were used to discuss the effects of the above-mentioned fillers on the fire resistance, char residue strength and char integrity of SR composites. The results showed that SR composite filled with only intumescent flame retardants EG and NH₂-C had excellent flame retardancy. After adding ATH, the char residue was relatively dense and had good compressive strength, but its thermal insulation performance was reduced. GF or NSH reduced the flame retardancy of SR composites, but it obviously played a role in binding combustion residues, forming new crystals and improving the stability of char residues.