新型PA6/EP/SiO2纳米复合材料的制备

PA6;SiO2;环氧树脂;原位聚合;纳米复合材料     

SMA/蒙脱石纳米复合材料增容PA6/ABS共混体系

采用原位插层法制备苯乙烯-马来酸酐交替共聚物/蒙脱石(SMA/MMT)纳米复合材料增容PA6/ABS共混体系,并与SMA及MMT的增容效果进行比较,运用TEM、SEM、DSC及XRD研究了增容剂SMA/MMT及MMT的增容机理.结果表明,采用SMA做增容剂,体系机械性能下降;MMT可使体系拉伸强度提高,但冲击强度下降;采用SMA/MMT纳米复合材料做为增容剂,可提高共混体系的强度及韧性.TEM、XRD、DSC及SEM研究结果表明,PA6/ABS/(SMA-MMT)体系中MMT主要分布于两相界面处,ABS及PA6分子链可进入MMT层间,形成类似于共聚物结构,起到增容剂的作用,从而降低分散相粒径,增加两相界面作用力,有利于体系力学性能的提高.PA6/ABS/MMT体系中MMT主要分布于连续相PA6中,虽然对分散相粒径影响较小,但增强了PA6相强度,使得体系力学性能提高.     

PP/EVA/OMMT纳米复合材料及其阻燃材料的动态燃烧行为

利用锥形量热仪(CONE)在35kW/m2热辐照条件下,并结合极限氧指数(LOI)和UL-94垂直燃烧测试方法对聚丙烯(PP)/乙烯-醋酸乙烯酯共聚物(EVA)/有机蒙脱土(OMMT)纳米复合材料和加入无卤复配阻燃剂制备的PP/EVA/OMMT/氢氧化铝(ATH)/三氧化二锑(AO)纳米复合阻燃材料的热释放速率、烟释放及材料在燃烧时的质量损失行为进行了研究。结果表明,添加5%(质量分数)OMMT可以提高PP/EVA复合材料的阻燃性能,燃烧时的热释放速率、质量损失率以及烟释放量减少,且OMMT与无卤复配阻燃剂之间可产生阻燃协同作用,使纳米复合阻燃材料的阻燃性能、热稳定性和抑烟性进一步增强。     

HIPS/OMMT纳米复合材料的燃烧性能与其残余物炭层结构特征研究

采用SEM、XRD、TGA等分析方法对高抗冲聚苯乙烯/有机蒙脱土(HIPS/OMMT)纳米复合材料在燃烧过程中形成的炭渣残余物结构特征进行了研究,包括炭层断面形态,片层结构及炭渣热稳定性等.结果表明复合材料在热释放速率峰值之后,形成了具有阻燃作用的炭层结构,其特征是在炭层表面形成了一层比较薄但密实的皮层,皮层之下是较厚的一层蜂窝层,这种"皮-窝"结构赋予炭层良好的阻隔热的作用,减缓了热分解过程.XRD分析还表明原有插层结构经过燃烧已破坏,在皮-窝炭层中都已消失,结合SEM观察结果,蒙脱土片层多以剥离的单片层无规分布,皮层和窝层中聚合物已基本烧蚀,只剩下片状的蒙脱土聚集在一起形成了一种纳米尺寸的网状结构并包含了一定量的分解温度很高的碳质物质,不仅形成了稳定的保护层,而且碳质物质的生成也降低了材料分解挥发速率.窝层含有大量尺寸较大的空穴结构,隔气效果不如皮层,但显著地增大了炭层的体积,整体上能起到较大的隔热作用.二者共同构筑的皮-窝炭层结构在复合材料的燃烧过程中起到了阻燃的作用.     

高密度聚乙烯/蒙脱土纳米复合材料膨胀阻燃体系的性能

使用以乙烯/醋酸乙烯共聚物(EVA)为相容剂的高密度聚乙烯/蒙脱土(HDPE/OMT)纳米复合材料作为基体,制备了含不同成炭剂的聚磷酸铵(APP)膨胀阻燃体系,对其阻燃性能进行了比较和研究,并分析了蒙脱土与膨胀阻燃剂协效作用的机理。热重分析(TGA)、垂直燃烧(UL-94)、极限氧指数(LOI)、锥形量热计结果表明:APP/季戊四醇(PER)体系熔融过程较短可形成蒙脱土增强炭层;PER/PA/OMT体系中较高的有机物含量有利于蒙脱土迁移和堆积。     

sPS/PA6/蒙脱土纳米复合材料的制备与性能

讨论了间规聚苯乙烯 (sPS) 尼龙 6(PA6) 磺化间规聚苯乙烯 (SsPS H) 蒙脱土纳米复合材料的制备技术和新材料的结构与性能特征 .蒙脱土经层间改性处理后 (MTN) ,可分别将SsPS H和aPS(无规聚苯乙烯 )插入其纳米层间 ,制备出插层型纳米复合物MTN SsPS和MTN aPS .在sPS/PA6/SsPS H三组分共混体系中加入MTN SsPS或MTN aPS ,进行四组分熔融共混即可制备出sPS/PA6/SsPS H/蒙脱土纳米复合材料 .TEM测定证实了蒙脱土在基体中的层厚分布约为 5 0nm .此外 ,采用DSC、DMA、XRD及力学性能测试仪等现代分析方法对sPS/PA6/SsPS H/蒙脱土纳米复合材料的结构与性能进行了详细研究 .研究结果表明这种纳米复合材料具有优良的综合性能     

尼龙6/石墨纳米导电复合材料的制备与性能

通过原位插层聚合制备了尼龙 6 /石墨纳米导电复合材料 ,其室温导电渗滤阈值为 =0 75vol% ,远远低于常规导电粒子填充的聚合物复合材料 .当石墨体积分数为 2 0vol%时 ,室温电导率可达 10 -4 S/cm .透射电镜研究表明 :由于石墨经高温膨胀后其片层被剥离导致了片状石墨粒子具有巨大的径厚比 ,经原位插层聚合其片层厚度进一步被剥离为几十个纳米 ,同时原位插层聚合使得石墨粒子能够均匀分散在尼龙 6基体中 ,因而导致了该导电复合材料的低渗滤阈值和高导电性能 .     

尼龙6/SiO_2纳米复合材料的制备及其力学性能和热稳定性

以表面含有氨基的可反应性纳米SiO2(RNS-A)和表面含有烷基碳链的可分散性纳米SiO2(DNS-3)作为填料,利用原位聚合法制备了尼龙6/SiO2纳米复合材料(相应的复合材料分别简记为RPA和DP3);采用透射电子显微镜观察了复合材料中纳米SiO2的表面形貌,并利用热失重分析仪测定了复合材料的热稳定性,进而考察了纳米SiO2表面功能基团对尼龙6力学性能和热稳定性的影响.结果显示,纳米SiO2能够很好地分散在尼龙6基体中,并使尼龙6的热分解温度提高10℃左右.与此同时,RPA的最大拉伸强度和冲击强度较纯尼龙6的分别提高34.5%和12.5%,DP3的最大拉伸强度和冲击强度分别提高18.2%和45.7%.这表明两种纳米SiO2均可以有效地提高尼龙6的力学性能和热稳定性;可以推测,纳米SiO2的增强效应与其在尼龙6基体材料中的分散和界面作用有关.     

精细化工实验课程教学改革与实践:可陶瓷化阻燃EVA复合材料的制备与性能研究*

结合科研课题及实验教学经验,设计了题为“可陶瓷化阻燃EVA复合材料的制备与性能研究”的精细化工实验课教学项目。该实验以乙烯-醋酸乙烯酯共聚物(EVA)为基材,以叶腊石粉(PL)和磷酸盐玻璃粉(GD)为陶瓷化填料(CF),以有机蒙脱土(OMMT)为抗熔滴剂,以三聚氰胺氰尿酸盐(MCA)为阻燃剂,制备可陶瓷化阻燃EVA复合材料。实验优化了影响阻燃效果、陶瓷强度和复合材料力学性能的因素,确定了合适的配方组成等内容。本精细化工实验课结合了科研内容,能激发学生主动参与实验设计并自主探索科学的兴趣,有利于培养学生的创新能力和解决实际问题的能力。     

Comparison of alumina and boehmite in (APP/MPP/metal oxide) ternary systems on the thermal and fire behavior of PMMA

A comparison of alumina (Al₂O₃) and boehmite (AlOOH) in (ammonium polyphosphate/melamine polyphosphate/metal oxide) ternary system was performed in poly(methyl methacrylate) on thermal and fire‐resistance properties. A Design of Experiments (DoE) was then done for highlighting the best formulation out of both ternary systems. Laser flash analysis and scanning electron microscopy helped to explain some of the observations made by DoE. Mechanisms in both ternary systems during degradation also were investigated and modes of action could be presented based on pyrolysis‐combustion flow calorimetry, Raman spectroscopy and X‐ray diffraction. Copyright © 2011 John Wiley & Sons, Ltd.     

耐高温杂化阻燃剂/改性红磷阻燃半芳香尼龙的研究

将自制的耐高温勃姆石@苯基次膦酸铝杂化阻燃剂(BM@Al-PPi)与市售改性红磷(MRP)复配制得一种可用于半芳香尼龙PA6T/DT(HTN)的耐高温高效阻燃体系.保持阻燃剂15 wt%的总添加量不变时,MRP的添加量仅为5 wt%即可赋予HTN垂直燃烧V-0级别,极限氧指数为29.8%.锥形量热测试及其燃烧残余物研究表明,MRP阻燃HTN材料以气相阻燃作用为主,抑制热释放效果不佳且烟释放明显增加;而BM@Al-PPi的凝聚相交联成炭作用可同时抑制热释放与烟释放.结合裂解气相色谱质谱联用(Py-GC-MS)分析,给出了HTN/BM@Al-PPi/MRP体系的阻燃机理.BM@Al-PPi与MRP结合使得残炭质量显著提高,同时兼具气相作用,达到了较好的阻燃效果.     

Preparation of high-efficient flame retardant PA6 via DOPO-ITA initiated ring-opening polymerization of caprolactam

It has been a long-term challenge to synthesize intrinsically flame retardant polyamide 6 (FRPA6) with high-molecular weight. In this work, through the ring-opening polymerization of caprolactam initiated by 9,10-dihydro-10-[2,3-di(hydroxycarbonyl)propyl]-10 phosphaphenanthrene-10-oxide (DOPO-ITA), intrinsically flame retardant PA6 with high-molecular weight was successfully prepared. Its chemical structure, thermal stability, mechanical and combustion properties, as well as the retarding mechanism were thoroughly characterized in detail. The FRPA6 containing 3.0% retardant could achieve a V-0 rating with an LOI value of 31.2%. An interesting phenomenon was observed during V-0 tests. The melt drip slowly extended downward to form a long strip after moving fire, which was in favor of its heat release in a short time, thereby effectively prevented it from igniting the cotton. That is, a facile method to prepare intrinsically high-efficiency fire retardant polymer via ring opening and polycondensation was proposed.     

壳聚糖/蒙脱土纳米复合材料的结构与性能研究

以壳聚糖和蒙脱土为原料,将插层复合技术引入天然高分子材料进行改性,制备了壳聚糖/蒙脱土纳米复合材料.红外光谱和X射线衍射分析结果表明,壳聚糖分子已插入蒙脱土层间,形成了插层甚至部分剥离的结构.热重分析、扫描电镜和物理性能测试表明,蒙脱土的引入,大幅度地降低了壳聚糖的热分解速率,明显地提高了壳聚糖的热稳定性和力学性能,有效地抑制了壳聚糖的溶胀.     

Enhancement of a hyperbranched charring and foaming agent on flame retardancy of polyamide 6

A hyperbranched polyamine was prepared using an A₂ + B₃ approach. It acted as a hyperbranched charring and foaming agent (HCFA) in combination with ammonium polyphosphate (APP) to form a new intumescent flame retardant (IFR) system for polyamide 6 (PA6). Effect of HCFA on flame retardant and thermal degradation properties of IFR‐PA6 was investigated by limiting oxygen index (LOI), UL‐94 vertical burning, cone calorimeter, and thermogravimetric analysis (TGA) tests. The IFR system presented the most effective flame retardancy in PA6 when the weight ratio of APP to HCFA was 2:1. The LOI value of IFR‐PA6 could reach 36.5 with V‐0 rating when the IFR loading was 30 wt%. Even if the loading decreased to 25 wt%, IFR‐PA6 could still maintain V‐0 rating with an LOI value of 31. TGA curves indicated that APP would interact with both PA6 and HCFA in PA6/APP/HCFA composite under heating. The interaction between APP and HCFA improved the char formation ability of IFR system and then much more char was formed for PA6/APP/HCFA composite than for PA6/APP. Therefore, better flame retardancy was achieved. Moreover, the structure and morphology of char residue were studied by Fourier transform infrared (FTIR), X‐ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The results indicated that compact and foaming char layer containing P‐O‐C structure was formed for PA6/APP/HCFA system during combustion. Copyright © 2010 John Wiley & Sons, Ltd.     

Simultaneously improving the flame retardancy and mechanical properties for polyamide 6/aluminum diethylphosphinate composites by incorporating of 1,3,5‐triglycidyl isocyanurate

The effect of 1,3,5‐triglycidyl isocyanurate (TGIC) as a synergistic agent on the fire retardancy, thermal, and mechanical properties for polyamide 6/aluminium diethylphosphinate (PA6/AlPi) composites were investigated in detail by limiting oxygen index; vertical burning (UL‐94); cone calorimeter; thermal gravimetric analysis; rheological measurements; and the tests of tensile, flexural, and Izod impact strength. The morphologies and chemical compositions of the char residue were investigated by scanning electron microscopy, X‐ray photoelectron spectroscopy, and Fourier transform infrared spectra. The results demonstrated that AlPi and TGIC exerted an evident synergistic effect for flame retardant PA6 matrix, and the PA6/AlPi/TGIC composites with the thickness of 1.6 mm successfully passed UL‐94 V‐0 rating with the limiting oxygen index value of 30.8% when the total loading amount of AlPi/TGIC with the mass fraction of 97:3 was 11 wt%. However, the samples failed to pass the UL‐94 vertical burning tests when AlPi alone is used to flame retardant PA6 matrix with the same loading amount. The thermal gravimetric analysis data revealed that the introduction of TGIC promoted the char residue formation at high temperature. The rheological measurement demonstrated that the incorporation of TGIC improved the storage modulus, loss modulus, and complex viscosity of PA6/AlPi/TGIC composites comparing with that of neat PA6 and PA6/AlPi composites due to the coupling reaction between TGIC and the terminal groups of PA6 matrix. The morphological structures of char residues demonstrated that TGIC benefited to the formation of more homogenous and integrated char layer with no defects and holes on the surface comparing with that of PA6/AlPi composites during combustion. The higher melt viscosity of composites and the integrated and sealed char layer effectively inhibited the volatilization of flammable gas into the combustion zone and then led to the reduction of the heat release. The results of mechanical properties revealed that the incorporation of TGIC enhanced the mechanical properties for PA6/AlPi/TGIC composites comparing with that of PA6/AlPi composites with the same loading amount of flame retardant caused by the chain extension effect of TGIC. As a result, the flame retardancy and mechanical properties of PA6/AlPi composites simultaneously enhanced due to the introduction of TGIC.     

聚丙烯/聚(丙烯-g-马来酸酐)/蒙脱土纳米复合材料结晶动力学研究

非等温结晶动力学;聚丙烯/聚(丙烯-g-马来酸酐)/蒙脱土纳米复合材料结晶动力学研究     

The effect of hBN on the flame retardancy and thermal stability of P-N flame retardant PA6

A novel thermally conductive Polyamide 6 (PA6) with good fire resistance was prepared by introducing a phosphorous-nitrogen flame retardant (FR) and platelet-shaped hexagonal boron nitride (hBN) into the matrix. With high thermal conductivity and good flame retardancy, the material is suitable for applications in electronic and electrical devices. The limiting oxygen index (LOI) changes for various loadings content of FR. However this formulation still does not show an ideal fire resistance, due to the appearance of melt dripping behavior during the UL 94 test. With the extra introduction of 3 vol% and 5 vol% hBN, the melt dripping behavior during the burning process completely disappeared. The hBN also increased the thermal conductivity. Furthermore PA6 compounded with FR and hBN showed a better thermal stability than neat PA6. The morphology of the char residues was investigated by scanning electron microscopy (SEM). The flaky hBN acted as the framework in the char structure and the rigid hBN could effectively break the bubble-shaped char on the surface of the residues which resulted in the enhancement of the strength and compactness of the char.     

Structure/Property Relationships for Polyamide 6 / Organoclay Nanocomposites in the Melt and in the Solid State

Commercial nanocomposites of polyamide 6 prepared by melt compounding with organoclays were characterized by complex viscosities and relaxation time spectra derived from storage and loss shear moduli measured in the melt state at 230°C, and by wide- and small-angle X-ray scattering, differential scanning calorimetry and stretching calorimetry in the solid state. In the melt state, the decrease of ∼ 25 % (compared to the pristine sample) in Newtonian viscosity at the lowest clay loading (2.5 %) suggested a lower equilibrium elasticity modulus of an entangled melt, as the small amounts of organoclay nanoparticles acted as specific “diluents” for the initial entanglement network. However, by increasing the clay loading this effect disappeared due to the importance of strong interactions at the nanoparticle/melt interface, leading to the formation of a fairly thick boundary interphase (BI) around the nanoparticles and ending up in the build-up of an “infinite cluster” of clay nanoparticles coated with BI at the highest (albeit still unusually low) clay loading (7.5 %). In the solid state, organoclay nanoparticles proved to induce the crystallographic α → γ transformation of PA6 , while the matrix crystallinity in nanocomposites remained essentially unchanged. In the range of elastic (reversible) behavior below the apparent yield strains ϵ* , the highest Young's moduli E and the lowest linear thermal expansion coefficients α_L were observed for dried nanocomposites, while the lowest E and the highest α_L corresponded to the moisturized, pristine PA6. The endothermal process of shape distortion of the lamellar crystals was assumed to precede the onset of the exothermal process of lamellar fragmentation in the range of inelastic (irreversible) behaviour of PA6 above ϵ* . The energy balance of the inelastic behaviour of nanocomposites was dominated by the endothermal process of lamellar shape distortion.     

热塑性弹性体/蒙脱土纳米复合材料的制备及性能

热塑性弹性体;蒙脱土;纳米复合材料;动态硫化