金属氧化物对聚丙烯膨胀阻燃体系阻燃性能的影响

将Bi2O3、Sb2O3、SnO2添加到聚磷酸铵(APP)和双季戊四醇(DPER)膨胀型阻燃聚丙烯(PP)体系中,采用氧指数(OI)、热分析(TGA)、热红联用(TG-FTIR)和扫描电镜(SEM),考察它们对膨胀阻燃体系的催化协效作用,探讨其作用机理.结果表明,3种金属氧化物在适量的添加下都可以提高体系的氧指数.TG结果表明,Bi2O3的加入可以提高膨胀炭层在高温时的热稳定性,增加高温时残余物的量;TG-FTIR结果显示添加Bi2O3后,膨胀阻燃剂在热分解过程中,气体的释放过程发生了改变.膨胀炭层的SEM图表明,Bi2O3可以改善膨胀炭层的形貌,提高炭层的隔热隔质性能.0.1 wt%的Bi2O3和1 wt%的纳米黏土复配用于膨胀阻燃体系中,可以在阻燃剂添加20份下,样品氧指数达到28.3;在阻燃剂添加25时,样品(3.2 mm)通过UL-94 V-0级.0.1 wt%的Bi2O3和1 wt%纳黏粘土的添加,还可以提高体系的力学性能.     

一种无卤阻燃ABS体系的阻燃性能研究

ABS是本世纪40年代发展起来的通用型热塑性材料[1],它有良好的力学性能,耐化学腐蚀、易加工等优点[2-6].     

阻燃剂的复配协效技术及纺织品的阻燃整理

环保型纺织品阻燃剂对人体和环境危害较小,符合绿色发展的理念.传统的阻燃剂如卤素阻燃剂阻燃效率较高,但在使用时会释放大量有毒及腐蚀性气体.氮系、磷系、硼系、硅系等阻燃剂在单独使用时,阻燃效果并不理想,而且成本高,因此需与其它阻燃剂复配协效使用才能达到阻燃效果.复配协效技术避免了使用单一阻燃剂的缺陷,综合了各种阻燃剂的优势...     

磷化淀粉的合成及其与聚磷酸铵协效阻燃聚乳酸的性能研究

利用9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和马来酸酐(MA)对淀粉进行改性得到磷化淀粉(DOPOMASt),通过红外光谱(FTIR)、核磁共振谱(1H-NMR)和X射线光电子能谱(XPS)确定其结构.利用DOPOMASt作为碳源,与聚磷酸铵(APP)复配后通过熔融共混制备了阻燃聚乳酸(PLA)...     

协效剂对膨胀阻燃聚丙烯基木塑复合材料的阻燃增效研究

赋予木塑复合材料(WPC)的阻燃性能成为近年来该领域国内外的研究热点之一。本文通过两轮正交试验,研究8种常见的协效剂对膨胀型阻燃剂(IFRs,m(聚磷酸铵,APP)∶m(季戊四醇,PER)=2∶1)的阻燃增效作用,筛选出具有显著协效作用的协效剂组MgO/EG(可膨胀石墨)/SiO_2,其组成为m(MgO)∶m(EG)∶m(SiO_2)=1∶5∶5,其与IFRs的最佳配比为m(IFRs)∶m(MgO/EG/SiO_2)=1∶0.18,得到性能良好的阻燃型聚丙烯基木塑复合材料。通过热重分析(TGA)和锥形量热分析(CONE)评价IFRs及协效剂组对聚丙烯(PP)基木塑复合材料(WPC)热稳定性能和阻燃性能的影响。结果表明,IFRs及MgO/EG/SiO_2的加入可以有效提高WPC的热稳定性,WPC/IFRs/MgO/EG/SiO_2600℃的残炭率达到22.42%。WPC/IFRs的热释放速率峰(PHRR)、总热释放量(THR)和总烟释放量(TSP)相比于WPC分别降低了21.9%、8.7%和22%。MgO/EG/SiO_2的加入可以进一步提高IFRs的阻燃效率,WPC/IFRs/MgO/EG/SiO_2的PHRR和THR相比于WPC分别降低了33.0%和13.8%。     

含亚胺结构新型磷-氮协效阻燃化合物的合成及对环氧树脂的阻燃作用

采用醛胺缩合反应,以4-(5,5-二甲基-1,3-二氧杂环己内磷酰基)苯甲醛(PCHO)分别与对苯二胺、乙二胺反应合成两种磷酸酯-亚胺双官能化合物阻燃剂(FR:N¹,N⁴-二[4-(5,5-二甲基-1,3-二氧杂环己内磷酰氧基)苯基亚甲基]-1,4-苯二胺(PNB)和N¹,N²-二[4-(5,5-二甲基-1,3-二氧杂环己内磷酰氧基)苯基亚甲基]-1,2-乙二胺(PNE)),研究了FR对4,4'-二氨基二苯砜(DDS)固化双酚A二缩水甘油醚型环氧树脂(DGEBA)体系的阻燃作用及阻燃机理。 研究发现FR的引入显著提高了DGEBA/DDS在700 ℃时的残炭率(R_c),同时提升了材料的阻燃性能,其中以乙二胺合成的PNE阻燃性能显著优于以苯二胺合成的PNB。 当磷添加质量分数为1.5%时,PNE-1.5/DGEBA/DDS在N₂气下的R_c为35.1%,在空气下的R_c为14.4%,极限氧指数(LOI)为33.2%,并可达阻燃等级UL-94最高阻燃级别V-0级。 同时,PNE-1.5/DGEBA/DDS相较于DGEBA/DDS保持了弯曲强度和76%以上的冲击强度,机械性能显著优于PNB-1.5/DGEBA/DDS。 通过阻燃机理分析FR在DGEBA/DDS体系中具有凝聚相、气相及磷-氮协效共同作用的阻燃特点。 磷酸酯-亚胺双官能团化合物FR对环氧树脂体系具有良好的阻燃作用,其中PNE阻燃效率高、机械性能负面影响小,具有潜在应用价值。     

三聚氰胺聚磷酸盐/季戊四醇配比、协效剂组及表面改性对聚丙烯基木塑复合材料的膨胀阻燃影响

通过极限氧指数(LOI)、线性燃烧速率(LBR)、热重分析和锥形量热分析等技术手段研究膨胀型阻燃剂(IFRs)中三聚氰胺聚磷酸盐(MPP)和季戊四醇(PER)的质量比、组成为m(MgO):m(可膨胀石墨,EG):m(SiO₂)=1:5:5的协效剂组(MgO/EG/SiO₂)和硅烷偶联剂(KH550)对聚丙烯基木塑复合材料(WPC)阻燃性能的影响。 结果表明,当IFRs中m(MPP):m(PER)=23:2(IFRs-M1)、质量分数为25%时的阻燃性能最佳,膨胀阻燃复合材料WPC/IFRs-M1的LOI和LBR分别为27.1%和3.89 mm/min,较未添加的WPC分别提高48.1%和下降89.79%,燃烧时的热释放速率、总热释放量、总烟释放量和CO₂释放量分别降低了76.2%、50.1%、6.9%和65.4%,600 ℃时的残炭率提高了498.3%。 协效剂组和KH550表面处理均可进一步改善WPC/IFRs-M1的阻燃性能,均对IFRs-M1具有良好的阻燃增效作用。 相比于WPC/IFRs-M1,同时用这两种阻燃增效手段的WPC/IFRs-M1/MgO/EG/SiO₂/KH550,其LOI提高了3.7%,LBR降低了20.3%;材料的热稳定性明显提高,热失重降低;燃烧时的热释放速率、总热释放量、总烟释放量和CO₂释放量分别降低了36.5%、37.6%、57.5%和33.33%,600 ℃时的残炭率提高了84.02%,显示出二者更好的协同效应。     

聚磷酸铵的疏水改性及聚丙烯阻燃性能

首先以γ-氨丙基三乙氧基硅烷(KH550)对聚磷酸铵(APP)进行表面化学修饰,然后用水解后的正硅酸四乙酯在其表面引发原位聚合,最后用十七氟癸基三乙氧基硅烷(氟硅烷)进行外表面修饰,制备了疏水聚磷酸铵(M-APP).M-APP的静态接触角为134°,表明M-APP具有很好的疏水性.通过傅里叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)对M-APP的结构及表面元素进行分析,结果表明,M-APP即为目标产物.将M-APP与三嗪成炭发泡剂(CFA)以质量比4∶1复配制备改性膨胀型阻燃剂(M-APP/CFA),并添加到聚丙烯(PP)中,制备阻燃PP(PP/M-APP/CFA).通过极限氧指数(LOI)和垂直燃烧(UL-94)研究了其阻燃性能,用热重分析(TGA)研究了材料的热降解行为,通过耐水测试研究了耐水性能,通过拉伸、弯曲和冲击强度研究了材料的力学性能,通过扫描电子显微镜(SEM)研究了改性膨胀型阻燃剂与聚合物的相容性.结果表明,当m IFR的添加量为23%时,PP/M-APP/CFA通过UL-94 V-0级,LOI值达到30.8%,且经过耐水测试后,依然能通过UL-94 V-0级,PP/M-APP/CFA的失重率仅为0.92%.在相同实验条件下,由APP制备的PP/M-APP/CFA材料在耐水测试后UL-94测试无级别,失重率达2.45%,表明APP的表面疏水改性大大提高了PP/M-APP/CFA材料的耐水性能.M-APP/CFA的加入提高了材料的热稳定性及成炭性能,燃烧时形成的膨胀炭层能很好地保护内部材料的降解和燃烧,从而提高了材料的阻燃性能.APP的改性提高了M-APP/CFA与PP的相容性,从而提高了材料的力学性能.     

含磷/氮/硫协效阻燃剂的合成及对环氧树脂的阻燃作用

本文以DOPO(9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物)、苯甲醛和4,4’-二氨基二苯砜(DDS)为原料,一锅法合成了含磷、氮、硫的化合物PNS。以PNS为阻燃剂,双酚A型树脂DGEBA为基材,DDS为环氧固化剂,制备了阻燃环氧固化物PNS/DGEBA/DDS,研究了PNS对DGEBA阻燃性能的影响,并与商业化有机磷阻燃剂DOPO作对比,同时初步探讨了PNS的阻燃机理。研究结果表明,PNS呈现磷/氮/硫协效阻燃作用,具有比DOPO更优异的残炭生产促进作用、抑烟效果和阻燃作用。在体系磷含量为1.5 wt%时,PNS-1.5/DGEBA/DDS的LOI值高达33.2%,并获UL 94最高阻燃级别V-0级,总烟释放量相较于DOPO-1.5/DGEBA/DDS降低15.4%,DGEBA/DDS降低2.86%,呈现良好的抑烟性能。     

Reprocessed High Impact Polypropylene Containing Oil Pollutant Exhibiting Flame Retardant Properties

Summary: In this work, the reaction to fire of reprocessed polypropylene (PP)/Ethylene Propylene Rubber (EPR) materials containing engine oil as pollutant was investigated by mass loss calorimetry. It was compared to the behaviour of the corresponding original high impact PP material. In order to flame retard the polymers, an intumescent system was studied in combination with zinc borate (ZB) as potential synergistic agent. It is shown that 20% of additives are necessary to obtain good FR properties. The use of ZB greatly improves the reaction to fire of original PP/EPR materials due to the formation of borophosphates during the degradation process that permit to reinforce the char structure. In the case of the polluted and reprocessed formulations, ZB has no influence on the fire performance because the minerals included in the engine oil act also as a flame retardant. For the two types of materials, it is demonstrated that the expansion rate at the beginning of the intumescent process plays a crucial role in the formation of an efficient insulating layer at the surface of the substrate. On the contrary, the fire performance is not related to the thickness of the carbonaceous shield.     

可膨胀石墨阻燃体系在聚丙烯中的作用

采用可膨胀石墨(EG)为主阻燃剂,包裹红磷(MRP)为阻燃协效剂制备阻燃聚丙烯(PP)。在mEG∶mMRP≥2时,阻燃效果最佳。阻燃剂(FR)含量达到30%后,阻燃效果大幅度提高,氧指数大于28。采用热失重和流变学方法分析了炭层质量,探讨了在mEG∶mMRP≥2时,阻燃效率最高的原因。相容剂马来酸酐接枝聚丙烯(PP-g-MAH)能够改善阻燃剂和聚丙烯之间的相容性,提高粘结力,改善炭层质量,提高材料的氧指数,PP-g-MAH用量为30%时,材料的氧指数达到31.4。     

Synergistic effect of DOPO immobilized silica nanoparticles in the intumescent flame retarded polypropylene composites

The synergistic effect of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) immobilized silica (SiO₂‐DOPO) nanoparticles with an intumescent flame retardant (IFR) on the flame retardancy of polypropylene (PP) was investigated by UL 94 vertical tests and limiting oxygen index (LOI) measurements. It was found that the PP/IFR composites (25 wt%) achieved the UL94 V0 grade and LOI increased to 32.1 with an incorporation of 1.0 wt% SiO₂‐DOPO nanoparticles. Based on thermogravimetric analysis, scanning electronic microscopy and rheological analysis, it is speculated that three factors are mainly contributed to the improvement of the flame retardancy. First, the thermal stability of PP/IFR composites was improved by incorporating SiO₂‐DOPO nanoparticles. Second, the presence of SiO₂‐DOPO nanoparticles could induce the formation of a continuous char skin layer during combustion. The compact char layer could effectively impede the transport of bubbles and heat. Third, rheological analysis indicated that SiO₂‐DOPO nanoparticles could increase viscosity of the PP/IFR composites, which was also benefited to increase flame retardancy. Copyright © 2013 John Wiley & Sons, Ltd.     

Preparation of Intumescent Flame Retardant Polypropylene composite through Solid State Mechanochemical Method

Polypropylene (PP), with characteristics of good mechanical properties, good resistance to water and low cost, has been widely used in many fields such as building, transport, furniture and electrical industries. However, a fateful drawback of polypropylene is its high flammability,restricting its wider applications. Addition of flame retardants is an effective way to improve its flame retardancy. An effective halogen-free flame retardant system used is the mixture of melamine, ammounium phosphate and pentaerythritol (intumescent flame retardant). But how to enhance the dispersion of this mixture in polypropylene matrix is a big problem. A self-made mechanochemical reactor, pan type milling equipment, can exert strong shear and squeeze forces,and has good mixing function. As a result, a uniform dispersion of flame retardants in the polymer matrix can be expectably obtained by using this equipment.In this paper, flame-retarded Polypropylene (PP) composites with intumescent flame retardant (IFR) were prepared via solid state mechanochemical method (pan-mill) and conventional method (twin-roll masticator) respectively. Particle diameter analysis, melt flow index (MFI), differential scanning calorimetry (DSC) and scanning electronic microscopy (SEM) were used to characterize these composites, and the mechanical properties and flame retardancy were also determined. The experimental results showed that the blend of PP and IFR were effectively pulverized from 3～4 mm to less than 300i m under the strong shear forces of pan-mill. With increasing the milling cycles, the MFI value of IFR/PP blend decreased first and then increased. The mechanical properties and flame retardancy of IFR/PP blends prepared by solid state mechanochemical method were proved to be better than those prepared by conventional method because of the dispersing function of pan-mill.Also it was found that IFRs were the nucleating agent for PP and the crystallinity of PP increased first and then decreased with increasing the milling cycles.     

膨胀型环状类磷酸酯蜜胺盐阻燃剂的合成及阻燃聚丙烯的结构与性能

以双季戊四醇、三季戊四醇、多聚磷酸、五氧化二磷和三聚氰胺为原料,合成了膨胀型环状类磷酸酯蜜胺盐阻燃剂,并与聚丙烯共混制成阻燃聚丙烯.红外分析表明该阻燃剂具有环状结构.通过扫描电镜和X射线衍射对阻燃聚丙烯进行了结构分析和表面纹理的表征.实验结果表明：该阻燃剂阻燃性能良好,但在聚丙烯中的分散性较差;用甲基纤维素对该阻燃剂进行表面化学修饰以后,该阻燃剂在聚丙烯中的分散性及阻燃材料的机械性能得到了明显的改善.     

新型单组分磷-氮膨胀型阻燃剂的合成及其阻燃性能

以氯化螺环磷酸酯(1)和对甲苯胺(2)为原料,经亲核取代反应合成了三源一体的新型单分子磷-氮膨胀型阻燃剂——季戊四醇螺环磷酰对甲苯胺(3),其结构经1H NMR和IR表征。考察了溶剂、原料配比、反应温度、反应时间和缚酸剂对3产率的影响。合成3的最佳反应条件为:乙腈为溶剂,三乙胺为缚酸剂,1 10mmol,n(1)∶n(2)=1∶3,于80℃反应4 h,产率79.3%。阻燃性能研究结果表明,3的初始分解温度为220℃,500℃成炭率达43.3%。     

Flammability and Thermal Oxidative Degradation Kinetics of Magnesium Hydroxide and Expandable Graphite Flame Retarded Polypropylene Composites

The flammability and the thermal oxidative degradation kinetics of expandable graphite (EG) with magnesium hydroxide (MH) in flame‐retardant polypropylene (PP) composites were studied by limiting oxygen index (LOI), UL‐94 test, and thermogravimetric analysis (TGA). The results show that EG is a good synergist for improving the flame retardancy of PP/MH composite and the effect is enhanced with decreasing EG particle size. The Kissinger method and Flynn‐Wall‐Ozawa method were used to determine the apparent activation energy (E) for degradation of PP and flame retarded PP composites. The data obtained from the TGA curve indicate that EG markedly increases the thermal degradation temperature of PP/MH composites and improves the thermal stability of the composites. The kinetic results show that the values of E for degradation of flame retarded PP composites is much higher than that of neat PP, especially PP/MH composites with suitable amount of EG, which indicates that the flame retardants used in this work have a great effect on the mechanisms of pyrolysis and combustion of PP.     

Synergistic effect of boron containing substances on flame retardancy and thermal stability of clay containing intumescent polypropylene nanoclay composites

The functions of nanoclay and three different boron containing substances, zinc borate (ZnB), borophosphate (BPO₄), and boron silicon containing preceramic oligomer (BSi), were studied to improve the flame retardancy of polypropylene (PP)‐nanoclay‐intumescent system composed of ammonium polyphosphate (APP) and pentaerythritol (PER). The flame retardancy of PP composites was investigated using limiting oxygen index (LOI), UL‐94 standard, thermogravimetric analysis (TGA), and cone calorimeter. According to the results obtained, the addition of 20 wt% intumescent flame retardant (IFR) improved the flame retardancy by increasing the char formation. Addition of clay slightly increases the LOI value and reduces the maximum heat release rate (HRR). Addition of clay also increases the barrier effect due to intumescent char, especially in thin samples. Boron compounds show their highest synergistic effect at about 3 wt% loading. According to UL‐94 test and LOI test, 3 wt% ZnB containing composite shows the highest rating (V0) and BPO₄ containing sample shows the highest LOI value (26.5). Copyright © 2010 John Wiley & Sons, Ltd.     

膨胀型类磷酸酯蜜胺盐阻燃剂的合成及应用研究

以双季戊四醇(DPE)、五氧化二磷、水和三聚氰胺为原料,合成了膨胀型环状类磷酸酯蜜胺盐阻燃剂。通过实验提出了合成该阻燃剂的最佳反应条件为：双季戊四醇(DPE)、五氧化二磷、水和三聚氰胺反应物料摩尔配比为1／2．5／2.0／3．45、反应时间4h和反应温度120℃。红外吸收图谱分析表明该阻燃剂具有环状结构,在热重分析和差热分析中该阻燃剂显示出优异的热稳定性和很高的成碳性。以该阻燃剂掺入聚丙烯中,阻燃效果显著,经测试阻燃聚丙烯的极限氧指数(LOI)为33．6,烟密度等级(SDR)为44．25,通过了UL94V-0级。