NE/OMMT纳米复合物与TPPi复配阻燃PP的制备与性能

采用酚醛环氧树脂／有机蒙脱土（NE／OMMT）纳米复合物与亚磷酸三苯酯（TPPi）复配作为阻燃剂,制备了阻燃聚丙烯（PP）;研究了各组分的质量比及用量等对PP的阻燃性能及力学性能的影响;并通过x射线衍射分析（XRD）对材料进行了表征。结果发现,NE／OMMT纳米复合物与TPPi对PP具有很好的协同阻燃作用,当NE、TPPi的质量分数分别为9％、6％,OMMT与NE的质量比为0.06时,PP的氧指数高达36．5％,且力学性能优良。XRD分析结果表明：OMMT经NE插层后,层间距扩大明显,与PP熔融共混后可产生部分剥离。     

PP-g-MAH/OMMT阻燃母料的制备及其在PP中的应用

以聚丙烯接枝马来酸酐(PP-g-MAH)和有机蒙脱土(OMMT)为原料,通过熔融插层制备了PP-g-MAH/OMMT纳米复合阻燃母料,利用X射线衍射(XRD)及热失重分析(TGA)对其进行了表征,并将其与碱式硫酸镁晶须(MOS)复配,制备了阻燃性能及力学性能优良的阻燃PP。结果表明,PP-g-MAH能够插层进入OMMT层间,形成插层型纳米复合物;PP-g-MAH/OMMT中PP-g-MAH的外推起始失重温度由纯PP-g-MAH的269.8℃提高到375.6℃。以PP-g-MAH/OMMT及MOS制备的阻燃PP的热释放速率峰值(PHRR)和平均热释放速率(MHRR)分别为163.7kW/m2和117.9kW/m2,比基体树脂下降了80.3%和70.9%。     

PVAc/OMMT纳米复合物的制备及其在阻燃PP中的应用

通过原位乳液插层法制备了有机蒙脱土(OMMT)含量较高的聚醋酸乙烯酯/有机蒙脱土(PVAc/OMMT)纳米复合物,并将其作为阻燃母料与氢氧化镁(MH)复配,与聚丙烯(PP)熔融共混制备了性能良好的无卤阻燃PP,用X射线衍射(XRD)、锥形量热分析(CONE)等对材料进行了表征。结果表明:当OMMT和MH的用量分别为3%和40%时,阻燃PP的热释放速率峰值(PHRR)相比于基体树脂从929.0kW/m2降低至193.7kW/m2,总释放热(THR)从165.2MJ/m2降低到73.6MJ/m2。     

阻燃环氧树脂/有机蒙脱土纳米复合材料制备及阻燃性能

研究制备了环氧树脂(EP)/有机蒙脱土(OMMT)、N,N-二(2-羟乙基)氨甲基膦酸二乙酯(BHAPE)阻燃剂阻燃的EP和EP/OMMT等复合材料。XRD证明分散在复合材料中的OMMT为剥离型的,且BHAPE的加入不影响材料中OMMT剥离后的层间距。研究证明,单独使用BHAPE很难使EP通过UL 94 V-0阻燃级,仅添加OMMT的EP固化物,其氧指数和UL94阻燃性能几乎与纯EP固化物的一样。但是同时添加BHAPE和OMMT的EP固化物,当BHAPE和OMMT的添加量分别为25%和5%时,不仅BHAPE/EP/OMMT复合物的CONE阻燃参数都明显降低,而且能通过UL94V-0级。可能是BHAPE和OMMT在凝聚相同时发挥作用,即BHAPE和OMMT协同阻燃作用提高了复合材料的综合阻燃性能。     

Synergistic Effect of Montmorillonite and Intumescent Flame Retardant on Flame Retardance Enhancement of ABS

The synergistic effects of organic montmorillonite (OMMT) and intumescent flame retardant (IFR) based on the ammonium polyphosphate (APP) and pentaerythritol (PER) on flame retardant enhancement of acrylonitrile-butadiene-styrene copolymer (ABS) were investigated by using the limiting oxygen index (LOI), the UL-94 (vertical flame) test, thermogravimetric analysis (TGA), x-ray diffractometry (XRD) and scanning electron microscopy (SEM). The LOI data and vertical flame tests show that OMMT has a synergistic flame retardant effect with IFR and the LOI value of ABS/OMMT/IFR (96/4/20) reaches 28.7%. The TGA data demonstrate that the incorporation of OMMT and IFR is very effective in enhancing the thermal stability of ABS/OMMT/IFR system at high temperature (T > 500°C). The results of XRD show that the composite of ABS/OMMT is a kind of intercalated nanocomposite and the gallery height of ABS/OMMT nanocomposite is 3.5 nm. The microstructures observed by SEM demonstrate that a suitable amount of OMMT with IFR can promote formation of compact intumescent charred layers in ABS blends.     

Enhancement of organoclay on thermal and flame retardant properties of polystyrene/magnesium hydroxide composite

Organoclay (organically modified montmorillonite, OMMT) was introduced to the composite of polystyrene/magnesium hydroxide (PS/MH) by melt compounding. The structure of the obtained PS/MH/OMMT composite was characterized by X‐ray diffraction and transmission electron microscopy. Thermal degradation behavior and flame retardancy of the composite were investigated by various means. It is shown that the PS/MH/OMMT composite has an intercalated nanostructure with the PS chains intercalated between the OMMT layers and the MH particles dispersed evenly in the PS matrix. Compared with the PS/MH composite containing identical amount of flame retardant, the introduction of OMMT has increased the thermal degradation temperature and lowered the mass loss rate at high temperatures. The PS/MH/OMMT nanocomposite can produce a more continuous and compact charred residue layer upon degradation both in air and burnt in flame than the PS/MH composite. Because of formation of this highly thermally stable and insulating charred residue layer, the nanocomposite exhibits much improved thermal endurance, flame retardancy, smoke suppression, and dripping resistance. Moreover, the combination of MH and OMMT makes the composite more difficult to ignite and decreases the release of toxic gas. The advantage of the PS/MH/OMMT nanocomposite is more pronounced in the early stage of combustion. POLYM. COMPOS., 37:746–755, 2016. © 2014 Society of Plastics Engineers     

聚丙烯/蒙脱土纳米复合材料的制备与性能研究

采用十八烷基三甲基氯化铵（OTAC）和十二烷基二甲基卞基氯化铵（DDBAC）改性蒙脱土,以聚丙烯接枝马来酸酐（PP-g-MAH）作相容剂,通过熔融插层法制备了聚丙烯/蒙脱土纳米复合材料（PP/OMMT）.结果表明,PP-g-MAH能有效地改善PP与OMMT的相容性,当OTAC改性的蒙脱土（OMMT-O）用量为5wt%、PP-g-MAH用量为10wt%时,PP/PP-g-MAH/OMMT-O纳米复合材料的冲击强度为5.4 KJ/m^2,比纯PP提高了80%,极限氧指数（LOI）由PP的18提高到23.X射线衍射（XRD）测试表明,PP已经插层进入到蒙脱土片层中,部分蒙脱土产生了剥离.     

Influences of catalysis and dispersion of organically modified montmorillonite on flame retardancy of polypropylene nanocomposites

The degradation and flame retardancy of polypropylene/organically modified montmorillonite (PP/OMMT) nanocomposite were studied by means of gas chromatography‐mass spectrometry and cone calorimeter. The catalysis of hydrogen proton containing montmorillonite (H‐MMT) derived from thermal decomposition of (alkyl) ammonium in the OMMT on degradation of PP strongly influence carbonization behavior of PP and then flame retardancy. Brønsted acid sites on the H‐MMT could catalyze degradation reaction of PP via cationic mechanism, which leads to the formation of char during combustion of PP via hydride transfer reaction. A continuous carbonaceous MMT‐rich char on the surface of the burned residues, which work as a protective barrier to heat and mass transfer, results from the homogeneous dispersion of OMMT in the PP matrix and appropriate char produced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of clay modification on the morphological,mechanical, and thermal properties of polyamide 6/polypropylene/montmorillonite nanocomposites

Polyamide 6/polypropylene (PA6/PP = 70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic montmorillonite (OMMT) were prepared by melt compounding. The sodium montmorillonite (Na‐MMT) was modified using three different types of alkyl ammonium salts, namely dodecylamine, 12‐aminolauric acid, and stearylamine. The effect of clay modification on the morphological and mechanical properties of PA6/PP nanocomposites was investigated using x‐ray diffraction (XRD), transmission electron microscopy (TEM), tensile, flexural, and impact tests. The thermal properties of PA6/PP nanocomposites were characterized using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and heat distortion temperature (HDT). XRD and TEM results indicated the formation of exfoliated structure for the PA6/PP nanocomposites prepared using stearylamine modified montmorillonite. On the other hand, a mixture of intercalated and exfoliated structures was found for the PA6/PP nanocomposites prepared using 12‐aminolauric acid and dodecylamine modified montmorillonite. Incorporation of OMMT increased the stiffness but decreased the ductility and toughness of PA6/PP blend. The PA6/PP nanocomposite containing stearylamine modified montmorillonite showed the highest tensile, flexural, and thermal properties among all nanocomposites. This could be attributed to better exfoliated structure in the PA6/PP nanocomposite containing stearylamine modified montmorillonite. The storage modulus and HDT of PA6/PP blend were increased significantly with the incorporation of both Na‐MMT and OMMT. The highest value in both storage modulus and HDT was found in the PA6/PP nanocomposite containing stearylamine modified montmorillonite due to its better exfoliated structure. POLYM. COMPOS., 31:1156–1167, 2010. © 2009 Society of Plastics Engineers     

A novel intumescent flame‐retardant system for flame‐retarded LLDPE/EVA composites

A new intumescent flame retardant (IFR) system consisting of ammonium polyphosphate (APP) and charing‐foaming agent (CFA) and a little organic montmorillonite (OMMT) was used in low‐density polyethylene (LLDPE)/ethylene‐vinyl acetate (EVA) composite. According to limiting oxygen index (LOI) value and UL‐94 rating obtained from this work, the reasonable mass ratio of APP to CFA was 3 : 1, and OMMT could obviously enhance the flame retardancy of the composites. Cone calorimeter (CONE) and thermogravimetric analysis (TGA) were applied to evaluate the burning behavior and thermal stability of IFR‐LLDPE/EVA (LLDPE/EVA) composites. The results of cone calorimeter showed that heat release rate peak (HRR‐peak) and smoke production rate peak (SPR‐peak) and time to ignition (TTI) of IFR‐LLDPE/EVA composites decreased clearly compared with the pure blend. TGA data showed that IFR could enhance the thermal stability of the composites at high temperature and effectively increase the char residue. The morphological structures of the composites observed by scanning electron microscopy (SEM) and X‐ray diffraction (XRD) demonstrated that OMMT could well disperse in the composites without exfoliation, and obviously improve the compatibility of components of IFR in LLDPE/EVA blend. The morphological structures of char layer obtained from Cone indicated that OMMT make the char layer structure be more homogenous and more stable. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal Properties and Flammability of Ethylene-Vinyl Acetate Copolymer/Montmorillonite/Polyethylene Nanocomposites with Flame Retardants

Ethylene-vinyl acetate copolymer (EVA)/montmorillonite (MMT) composite was blended with a linear low density polyethylene (LLDPE). X-ray diffraction and transmission electron microscopy (TEM) image of the EVA/MMT composite are in support of an intercalated with partially delaminated nanocomposite. The tensile strength of the nanocomposite is about 20% higher than that without layered silicates, MMT. Furthermore, the incorporation of MMT into polymer blend delays the main thermo-oxidative degradation. Cone calorimeter test points out that the addition of layered silicates into the pristine EVA/LLDPE blend or the blend with a low smoke non-halogen (LSNH) fire retardants, aluminum trihydroxide, and antimony trioxide, can reduce the maximum heat release rate by 30–40%. The smoke suppressing effect of layered silicates is only observed in the nanocomposite containing flame retardants. According to the limiting oxygen index (LOI) data and cone calorimeter test, the addition of the nanodispersed layered silicate and LSNH flame retardants to the EVA/LLDPE exhibits a synergistic effect on the flame retardancy and smoke suppression.     

Synergistic Effect of Epoxy/Organophilic Montorillonite Nanocomposites and Triphenyl Phosphate on Flame Retardance Enhancement of Polypropylene

Epoxy/organophilic montorillonite (Epoxy/OMMT) nanocomposites were prepared by epoxy intercalated into the interlayer of OMMT, and flame retardant polypropylene (PP) was obtained with Epoxy/OMMT nanocomposites and triphenyl phosphate (TPP) mixture as flame retardant agent. The effect of epoxy sorts, mass ratio of OMMT and Epoxy, and the contents of Epoxy/OMMT and TPP on properties of PP were studied. It was found that there is a remarkable synergistic flame retardant effect of novolac epoxy/organophilic montorillonite (NE/OMMT) and TPP on PP. Flame retardant PP with oxygen index (OI) value of 36.5%, peak heat release rate (PHRR) of 654 kW/m², notched Izod impact strength of 6.93 kJ/m² and tensile strength of 30.56 MPa was obtained when the mass ratio of OMMT and NE is 5:100, the content of NE/OMMT and TPP is 13.33 and 6.67 wt.%, respectively. The materials were characterized via X-Ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectrum (FT-IR), and thermogravimetry (TG). The XRD results and TEM photograph indicate OMMT is exfoliated in PP matrix when the mass ratio of OMMT and NE is lower than 10:100. The TG results show the evaporation of TPP is greatly hampered by NE/OMMT nanocomposite. PP with NE/OMMT-TPP has an onset weight loss temperature 31.7°C higher than PP with NE-TPP because of the shielding effect of OMMT layers. The FT-IR spectra indicate phosphoric acid is generated from TPP and carboxylic acid and phenyl ether are generated from NE under thermal degradation, which further results in the formation of thermally stable char. This charring process is also affirmed by the wide thermally stable zone at 380–550°C in TG curves of PP with NE/OMMT-TPP or NE-TPP.     

Synthesis and characterization of polyvinyl acetate/montmorillonite nanocomposite by in situ emulsion polymerization technique

Exfoliated polyvinyl acetate/montmorillonite nanocomposite (PVAc/MMT) was prepared via in situ emulsion polymerization. The resulting PVAc with various organophilic MMT contents was investigated. In the nanocomposite latex preparation, sodium lauryl sulfate (SLS), ammonium persulfate (APS), and poly (vinyl alcohol) (PVA) are used as anionic emulsifier, conventional anionic initiator, and stabilizer, respectively. The samples were characterized using elemental analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM). The XRD and AFM results demonstrate that the MMT well dispersed at molecular level in the PVAc matrix. Thermal properties of the nanocomposite were studied by using differential scanning calorimetric analysis (DSC). The exfoliated PVAc/MMT nanocomposite showed a higher glass transition temperature and a better thermal stability compared to the pure PVAc.     

NE/OMMT纳米复合物与RDP复配阻燃ABS的制备与性能

采用酚醛环氧树脂/有机蒙脱土(NE/OMMT)纳米复合物与间苯二酚双(二苯磷酸酯)(RDP)复配作为阻燃剂,制备了阻燃ABS;研究了OMMT用量对ABS阻燃性能及力学性能的影响;并通过TGA、XRD、TEM对材料进行了表征。结果表明:NE/OMMT纳米复合物与RDP对ABS具有很好的协同阻燃作用,当OMMT、NE和RDP用量分别为0.5%、6.0%和9.0%时,阻燃ABS氧指数高达39.0%,且力学性能优良;OMMT的添加提高了阻燃ABS的热稳定性;OMMT经NE插层后,层间距明显增大,与ABS熔融共混后可产生部分剥离。     

阴离子开环聚合制备尼龙6/蒙脱土复合材料及其性能研究

以十六烷基三甲基溴化铵为有机插层剂对无机蒙脱土进行处理制得有机蒙脱土（OMMT），然后采用阴离子开环聚合，制备了尼龙6／蒙脱土复合材料。用FT-IR、TG和XRD对有机蒙脱土的插层情况进行了表征。结果表明，插层剂已插入蒙脱土片层中；当OMMT用量为2％时，复合材料的熔点最高，结晶度最大，力学性能最好。     

阻燃协效聚乙烯-醋酸乙烯酯/碱式硫酸镁晶须复合材料的研究

通过极限氧指数(LOI)和UL-94垂直燃烧试验研究了微胶囊化红磷(MRP)和有机改性蒙脱土(OMT)对聚乙烯-醋酸乙烯酯/碱式硫酸镁晶须(EVA/MHSH)复合材料阻燃性能的影响.结果表明:MRP或OMT与MHSH联合使用具有阻燃协同效应.     

Synergistic effect of nickel formate on the thermal and flame‐retardant properties of polypropylene

Nickel formate was used as a catalyst to improve the flame‐retardancy of intumescent systems based on ammonium polyphosphate (APP) and pentaerythritol (petol) in polypropylene (PP). Limited oxygen index (LOI), X‐ray diffraction (XRD) and thermogravimetric analysis (TGA) were used to characterize the fire‐retardancy and thermal stability of the PP system and the microstructure of the burned residue. The catalytic effect was shown in an increase in LOI, and a change in the residue microstructure and the thermal stability of the PP system. LOI increased with the concentration of the catalyst in the range 0.1–5 wt% of the composition until a maximum was reached. At higher concentration of the catalyst a decrease in the LOI was observed. Copyright © 2005 Society of Chemical Industry     

聚丙烯/蒙脱土纳米复合材料的制备与性能研究

以马来酸酐接枝低分子量聚丙烯为相容剂,采用双螺杆挤出机熔融挤出法,制备插层型聚丙烯/有机钠基蒙脱土、聚丙烯/酸化有机化钠基蒙脱土、聚丙烯/钠基蒙脱土3种纳米复合材料,发现有机钠基蒙脱土、酸化有机化钠基蒙脱土和钠基蒙脱土对PP力学性能和燃烧性能均有一定程度的提高。经X射线衍射(XRD)和扫描电子显微镜(SEM)观察,发现有机钠基蒙脱土片层间距增幅最大,复合材料的燃烧性能也有很大提高。     

Improving the flame retardancy of polypropylene by nano metal–organic frameworks and bioethanol coproduct

In this work, a novel flame retardant system based on nano zeolitic imidazolate framework‐8 (ZIF‐8) and the distiller's dried grains with solubles (DDGS) without traditional flame retardants has been designed and blended with polypropylene (PP) to prepare the green flame retarded composites. The influences of nano ZIF‐8 and DDGS on mechanical properties and flame retardancy of PP are studied. The results indicate that combination of nano ZIF‐8 and DDGS improves the mechanical properties of PP, and the tensile strength of the composites containing 29 wt% of DDGS and 1 wt% of nano ZIF‐8 reaches 34.0 MPa compared with 24.7 MPa of pure PP. The limiting oxygen index (LOI) of the composites containing 27 wt% DDGS and 3 wt% of nano ZIF‐8 is about 25.0% compared with 17.5% of pure PP. Besides, its horizontal burning velocity also decreases significantly. The char residues after burning of the PP composites are analyzed, and the mechanism is discussed in detail.     

新型无卤阻燃聚丙烯的制备与性能研究

采用碱式硫酸镁晶须(MOS)与有机蒙脱土(OMMT)作为阻燃剂制备了阻燃聚丙烯(PP),研究了MOS和OMMT用量对阻燃PP力学性能和阻燃性能的影响,并通过热失重分析(TGA)和锥形量热仪(CONE)对材料进行了表征。结果表明:MOS对PP有良好的增强阻燃作用,少量OMMT的加入可以进一步提高阻燃PP的阻燃性能。当MOS与OMMT用量分别为40.0%和3.0%时,阻燃PP的OI为28.5%,其热释放速率峰值(pHRR)和平均热释放速率(mHRR)分别为156.5kW/m2和112.9kW/m2,比基体树脂分别下降了83.3%和72.1%,同时其抑烟性能也大为改善。