聚丙烯/蒙脱土纳米复合材料的制备与性能

合成了TiCl4/MgCl2/MMT插层催化剂,通过原位聚合制备了聚丙烯/蒙脱土纳米复合材料。X射线衍射结果表明:蒙脱土在聚丙烯基质中达到了纳米级分散。与纯聚丙烯(PP5004)相比,聚丙烯/蒙脱土纳米复合材料的力学性能、维卡软化点、热变形温度以及热分解温度都有所提高。     

聚丙烯/蒙脱土纳米复合材料的制备与表征

利用固相剪切法使蒙脱土片层完全剥离,制备聚丙烯/蒙脱土(PP/MMT)纳米复合材料,通过X射线衍射、扫描电镜、力学性能的实验得出：用水做为膨胀剂可使蒙脱土的层间距胀大,有利于PP分子的插层和蒙脱土的剥离;固相剪切法和熔融过程使蒙脱土完全地层状剥离,均匀纳米级分散在聚丙烯基体中,沿流动方向取向; PP与用水处理过的有机改性蒙脱土复合材料的冲击强度由5.68 kJ/m2提高到了8.2 kJ/m2,大量提升了材料的冲击性。     

聚丙烯/蒙脱土纳米复合材料的研究进展

对聚丙烯(PP)／蒙脱土(MMT)纳米复合材料的国内外研究进展进行综述,介绍了PP/MMT纳米复合材料的制备原理和制备方法。包括原位插层聚合法、聚合物溶液插层法、聚合物熔融插层法、溶胶一凝胶法,重点介绍了聚合物熔融插层法的研究进展。聚合物熔融插层法具有操作简单、无需处理过多溶剂的优点,避免了环境和能源问题,更易于工业化。最后对PP／MMT纳米复合材料的未来发展进行了展望。     

聚丙烯/蒙脱土纳米复合材料的流变性能研究

制备了MMT/MgCl2/TiCl4插层催化剂,并通过原位聚合的方法制得聚丙烯/蒙脱土纳米复合材料。测试了聚丙烯/蒙脱土复合材料在不同温度及不同蒙脱土含量下的流变性能。结果表明:不同蒙脱土含量的聚丙烯复合材料,其表观黏度随剪切速率的增大而减小,剪切应力随剪切速率的增大而增大。符合流体切变稀释的性质,该性质有利于复合材料的成型加工。     

聚丙烯/BA原位聚合改性MMT纳米复合材料的微观结构

通过原位聚合制备了聚丙烯酸丁酯（PBA）改性蒙脱土（MMT），再与PP熔融复合，制成PP／MMT复合材料，利用X射线衍射（XRD）、扫描电子显微镜（SEM）和电子探直表征了复合材料的微观结构。结果表明：PP／MMT复合材料为纳米复合材料，MMT的加入诱导了β－晶型PP的形成。     

两步法制备剥离型聚丙烯/蒙脱土纳米复合材料(Ⅰ)制备、表征及力学性能

采用两步法制备了剥离型聚丙烯/蒙脱土纳米复合材料 (PMN).两步法即：在使用高活性极性单体丙烯酰胺 (AM)原位聚合插层有机蒙脱土 (O-MMT)的同时,使部分丙烯酰胺接枝到聚丙烯 (PP)大分子链上,从而得到黏土片层已剥离且与PP又具有良好相容性的材料,以此为母料再与PP熔融共混即制备出剥离型聚丙烯/蒙脱土纳米复合材料.XRD表明,复合材料中蒙脱土片层已剥离;扫描电镜观测不到明显的有机-无机相畴,表明蒙脱土片层分散均匀,分散个体尺寸基本达到纳米级;力学测试表明,该复合材料的拉伸强度达42.4MPa,较基体增加了26%,缺口冲击强度达10.5kJ•m^-2,较基体增加了155%.研究结果表明复合材料达到了预期强韧化效果.     

两步法制备聚丙烯/蒙脱土纳米复合材料及其性能研究

采用两步法制备聚丙烯/蒙脱土纳米复合材料PP/MMT,考察了工艺配方和制备条件对材料力学性能的影响。结果表明,两步法制备工艺对PP/MMT的力学性能有明显提高,最佳工艺配方:蒙脱土含量为2%,相容剂含量为15%,最佳制备条件:加工温度200℃,螺杆转速50 r/min。在此条件下制备的PP/MMT复合材料中蒙脱土达到纳米级分散。     

聚丙烯/BA原位聚合改性MMT纳米复合材料的DSC分析与力学性能

通过原位聚合制备了聚丙烯酸丁酯 (PBA )改性蒙脱土 (MMT ) ,与聚丙烯 (PP)熔融复合制成PP/MMT纳米复合材料 ,系统地研究了复合材料的熔融、结晶行为和力学性能。结果表明 :随着处理MMT的BA用量的增加 ,PP/MMT纳米复合材料中PP相的结晶度、熔点和结晶温度明显提高 ,结晶速度加快 ;复合材料的拉伸强度变化不大 ,但拉伸模量和冲击强度有显著提高。当BA/OMMT质量比为 1/ 12左右时 ,复合材料的韧性趋于平衡值 ,而拉伸模量出现最大值     

聚甲基丙烯酸/蒙脱土纳米复合材料的制备及性能

用甲基丙烯酸(methacrylic acid,MAA)在钠基蒙脱土(montmorillonite,MMT)层间直接原位插层聚合制备了聚甲基丙烯酸/蒙脱土(polymethacrylic acid/montmorillonite,PMAA/MMT)纳米复合材料.以蒙脱土的层间距、插层进入蒙脱土层间的聚合物含量及应用于皮革鞣制的实验结果为考察指标,对制备过程中的引发剂用量及蒙脱土用量进行了单因素实验研究.结果表明:所制备的PMAA/MMT纳米复合材料属于剥离型纳米复合材料,应用于皮革鞣制所得坯革的增厚率及湿热稳定性均有较大提高.     

含氮相容剂对聚丙烯/蒙脱土复合材料阻燃性能的影响

以N-羟甲基丙烯酰胺接枝聚丙烯(PP-g-NHA)为相容剂,采用熔融插层法,制备聚丙烯(PP)/蒙脱土(MMT)纳米复合材料;采用X射线衍射仪(XRD)、偏光显微镜(POM)、差式扫描量热仪(DSC)和氧指数仪(LOI)等对复合材料的微观结构和性能进行了研究。结果表明PP-g-NHA能有效地改善PP与MMT的相容性,当蒙脱土用量为5%、PP-g-NHA用量为15%时,PP/PP-g-NHA/MMT纳米复合材料的极限氧指数(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,当蒙脱土用量为5%、PP-g-NHA用量为5%时插层效果最好,DSC分析结果表明,复合材料的熔融温度和分解温度都有所上升。     

Crystallization behaviors of polypropylene/montmorillonite nanocomposites

The isothermal crystallization kinetics of polypropylene/montmorillonite (PP/MMT) nanocomposites synthesized via intercalation polymerization were investigated by using differential scanning calorimeter and polarizing optical microscope (POM). The crystallinity of the nanocomposites decreased with the increase of the montmorillonite content, indicating that the MMT layers dispersed in the PP matrices confined the PP chains and hindered the crystallization of the PP chains. The POM photographs showed that the spherulites of the PP/MMT nanocomposites were greatly decreased in size as MMT was introduced. On the other hand, the crystallization rate increased dramatically with the increasing of MMT content. The interfacial free‐energy per unit area perpendicular to PP chains in PP/MMT nanocomposites decreased with increasing MMT content, suggesting that the MMT layers acted as heterogeneous nuclei in the nucleation of crystallization. The nucleus density increased with the increasing of MMT content, leading to a positive effect on the crystallization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1978–1985, 2002     

Preparation of exfoliated high‐impact polystyrene/MMT nanocomposites via in situ polymerization under controlling viscosity of the reaction medium

Exfoliated high‐impact polystyrene (HIPS)/montmorillonite (MMT) nanocomposites were prepared via in situ polymerization of styrene in the presence of polybutadiene, using an intercalated cationic radical initiator‐MMT hybrid (organoclay). In the solution polymerization in toluene, the silicate layers of the clay were well exfoliated, due to the low extra‐gallery viscosity that can facilitate the diffusion of styrene monomers into the clay layers during the polymerization. The exfoliated HIPS/MMT nanocomposites were also successfully prepared by controlling the viscosity of the reaction medium with prolong swelling of the organoclay in styrene, prior to bulk polymerization. The HIPS/MMT nanocomposites, obtained from bulk polymerization, exhibited a significant improvement in thermal stability, compared to those obtained from solution polymerization as well as the pure polymer counterparts. POLYM. COMPOS., 2008. © 2007 Society of Plastics Engineers     

Polypropylene/organically modified Sabah montmorillonite nanocomposites: Surface modification and nanocomposites characterization

The aim of the work is to extract, purify, and organically modify montmorillonite (MMT) of Lahad Datu, Sabah bentonite. The octadecylamine treated Sabah MMT (S‐OMMT) (2–8 wt%) was then melt blended with polypropylene (PP) and maleated polypropylene (PPgMAH) (10 wt%) via single screw nanomixer extruder followed by injection molding into test samples to examine the mechanical, thermal, and morphological properties of PP/S‐OMMT nanocomposites. Unmodified Sabah MMT (S‐MMT) and commercial grade MMT (Nanomer 1.30P) filled PP nanocomposites were also characterized for comparison purpose. X‐ray diffraction results showed that the interlayer spacing of S‐MMT increased after organic modification as Fourier transform infra‐red and elemental analysis evidenced the presence of octadecylamine. PP/S‐OMMT nanocomposites showed a better dispersion and strength compared to PP/Nanomer 1.30P nanocomposites due to its smaller MMT platelet size. differential scanning calorimetry and Thermogravimetry analysis revealed that the thermal stability and crystallinity of neat PP improved with the addition of all types of MMT. Dynamic mechanical analyzer showed that PP nanocomposites have higher storage modulus (E′) values than the neat PP over the whole temperature range. The new PP/S‐OMMT nanocomposites showed a comparable performance with PP/Nanomer 1.30P nanocomposites exhibiting promising future applications of S‐MMT in polymer/MMT nanocomposites. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Polyimide/montmorillonite nanocomposites based on thermally stable, rigid-rod aromatic amine modifiers

The preparation and processing of most of polymer/clay nanocomposites need high temperature. This limited the application of commonly used organic modifiers of long carbon-chain alkyl ammonium salts because of their low thermal stability. In this study, we synthesized two novel thermally stable, rigid-rod aromatic amines. Montmorillonite (MMT) treated by these amines exhibited larger layer-to-layer spacing, higher thermal stability than that treated by commonly used 1-hexadecylamine and also high ion-exchange ratio (>95%). They were applied to prepare nanocomposites with polyimide (PI) by in situ polymerization. XRD, TEM were used to obtain the information on morphological structure of PI/MMT nanocomposites. DMA, TGA, DSC, universal tester were applied to characterize the mechanical and thermal properties of the nanocomposites. When the MMT content was below 3 wt%, the PI/MMT nanocomposites were strengthened and toughened at the same time. The introduction of a small amount of MMT also led to improvement in thermal stability, slight increase in glass transition temperature, marked decrease in coefficient of thermal expansion and decrease in solvent uptake. MMT treated by these aromatic amines exhibited better dispersibility and (probably) interfacial interaction with PI matrix than that treated by 1-hexadecylamine. The nanocomposites based on these MMT resultantly exhibited better mechanical, thermal and solvent resistance properties than those based on 1-hexadecylamine treated MMT.     

复合载体法制备聚丙烯-蒙脱土复合材料

将传统Z-N催化剂TiCl4负载于蒙脱土．乙醇镁复合载体上,进行丙烯常压原位聚合,制备聚丙烯-蒙脱土纳米复合材料,克服了单-蒙脱土作载体时聚合活性低、产物分子量小的缺点。对比不同制备过程的催化剂,发现TiCl4的后处理可以大幅提高催化活性。引入苯乙烯可有效降低Mg—MMT／Mg(OEt)2/TiCl4/EB体系制备的Cat5催化聚合时所需的Al／Cat比。由Mg—MMT／Mg(OEt)2/Ti(OBu)4/TiCl4/EB体系制备的Cat6具有活性高,所需Al／Cat低的优点,为合适的制备聚丙烯-蒙脱土纳米复合材料的催化剂。WAXS和TEM表明复合材料中蒙脱土主要呈剥离杰分散干聚丙烯基体中。产物的熔点和商用聚丙烯的熔点接近。     

PET/MMT纳米复合材料的制备

采用烷基季铵盐对蒙脱土(MMT)进行有机化处理,采用插层聚合法制备PET/MMT纳米复合材料。探讨了不同的MMT来源、添加量及聚合条件对PET/MMT纳米复合材料耐热性能的影响。结果表明: MMT的添加质量分数为2.5%,缩聚反应终温250℃时,PET/MMT纳米复合材料具有较好的综合性能。     

The Effect of Spray-Freeze Drying of Montmorillonite on the Morphology,Dispersion, and Crystallization in Polypropylene Nanocomposites

The spray-freeze drying (SFD) technique was applied to sonicated aqueous suspensions of spray-dried montmorillonite clay (MMT) to produce highly porous agglomerates (SFD-MMT). Both MMT (used as a reference) and SFD-MMT were subsequently incorporated in polypropylene (PP) via melt compounding to produce 2 wt % nanocomposites with and without maleic anhydride grafted polypropylene (PP-g-MA). Polypropylene nanocomposites containing SFD-MMT exhibited thinner silicate flake layers compared to large agglomerates in PP/MMT nanocomposites. SFD-MMT particles became even more finer in the presence of PP-g-MA (i.e., in PP/PP-g-MA /SFD-MMT) where it hindered PP crystallization instead of serving as nucleation sites for the PP crystallization during rapid cooling. SFD-MMT improved the thermal stability of PP/PP-g-MA by 30°C compared to only 5–8°C for MMT/nanocomposites. MMT acts as a heterogeneous nucleating agent in the nucleation-controlled PP nanocomposites, but the hindrance effect was observed for the PP/PP-g-MA with SFD-MMT. PP/PP-g-MA/SFD-MMT exhibited twice the edge surface energy as compared to PP/PP-g-MA/MMT. The incorporation of both types of MMT raised the tensile moduli of PP and PP/PP-g-MA, with no improvement in their tensile strength and a decrease in the elongation at break. The PP/PP-g-MA/SFD-MMT showed brittle failure. POLYM. ENG. SCI., 60:168–179, 2020. © 2019 Society of Plastics Engineers     

聚丙烯／蒙脱土纳米复合材料的制备与性能

用烷基季铵盐对钠基蒙脱土进行有机化处理,使其成为有机蒙脱土。X射线衍射（XRD）表明有机阳离子已同钠离子发生离子交换作用,导致层间距扩大。用熔融插层法制备聚丙烯／蒙脱土纳米复合材料,测试了力学性能。通过XRD、DSC等手段研究了其结构与结晶行为,并与聚丙烯进行了对比。实验表明,通过熔融插层可使聚丙烯插层于蒙脱土片层之中,且所得聚合物的冲击强度有所提高。     

悬浮聚合聚甲基丙烯酸甲酯／蒙脱土纳米复合材料的制备及表征

采用悬浮聚合法制备了聚甲基丙烯酸甲酯／蒙脱土（PMMA/MMT）纳米复合材料，利用X射线衍射仪、透射电子显微镜和傅里叶变换红外光谱等手段表征了复合材料的结构，研究了不同改性剂对复合材料结构的影响。通过热重分析考察了复合材料的热性能。结果表明，通过悬浮聚合可以成功制备剥离型纳米复合材料，PMMA基体与MMT可以产生较强的相互作用。MMT的加入可以显著提高复合材料的热稳定性。当MMT含量为10％（质量分数，下同）时，PMMA的最大分解温度提高了15℃。