聚酰胺6/蒙脱石纳米复合材料的紫外光老化

聚合物 /层状硅酸盐纳米复合材料的研究十分活跃 [1～ 4 ] .聚酰胺 6/蒙脱石 ( PA6/MMT)纳米复合材料与纯聚酰胺 6( PA6)相比 ,模量和强度明显提高 ,耐热性能提高尤为显著 .光氧化行为材料科学领域的重要研究课题 .Admas等 [5]报道在紫外光照射下 ,聚丙烯 /粘土纳米复合材料的氧化速度要比纯聚丙烯的快 .对于 PA6/MMT纳米复合材料的光老化研究尚未见报道 .本文以傅里叶变换红外光谱定量研究手段 ,对比分析了 PA6/MMT纳米复合材料与 PA6的紫外光氧化性能 .1　实验部分　　采用熔体插层技术 ,将 PA6( Honeywell B1 0 0 MP)和有机蒙…     

聚苯乙烯/蒙脱土纳米复合材料中的剪切诱导有序结构(Ⅰ)——广角X射线衍射与透射电镜研究

聚合物/层状硅酸盐(PLS)纳米复合材料是近10余年来迅速发展起来的的交叉学科.由于其具有常规复合材料所没有的结构、形态以及较常规聚合物基复合材料更优异的性能等而引起人们的广泛关注[1].以往文献主要报道PLS纳米复合材料的制备与性能表征,如尼龙-6/蒙脱土[2]、PET/蒙脱土[3]和硅橡胶/蒙脱土[4]等.对于熔融加工过程中粘土片层及高分子的取向和结构研究很少.Kojima等[5]发现并研究了尼龙-6/蒙脱土纳米复合材料中的熔融剪切诱导取向结构,其X射线衍射与透射电镜(TEM)结果均表明,粘土片层沿熔体流动方向平行取向,但片层间距不等,因此为一平行取向但无序的结构.对于PLS纳米复合材料中的剪切诱导有序结构尚未见报道.     

茂钛催化剂苯乙烯原位间规聚合制备sPS/蒙脱土纳米复合材料

聚合物基纳米复合材料具有常规有机 /无机复合材料所没有的结构和形态 ,其性能较普通的聚合物复合材料更优异 ,因而引起人们的广泛关注 [1～ 4 ] .近年来的研究表明 ,运用插层聚合和熔融插层等方法可使某些具有层状结构的硅酸盐与聚合物产生特殊的界面作用 ,并以纳米尺寸均匀分     

一步法制备EVA/MMT纳米复合材料的研究

高聚物／粘土纳米复合材料是现今高分子材料研究中的一大热点、在高聚物基体中填充少量的纳米级粘土便可显著增强其力学性能及热稳定性^[1-3]。高聚物／粘土纳米复合材料的制备通常采用有机改性法即先用长链烷基铵盐将粘土有机化，使粘土片层间距增大，并由亲水性变为亲油     

聚合物/粘土纳米复合材料中的粘土有机化

回顾了聚合物/粘土纳米复合材料中所用粘土的有机化方法与有机粘土的热稳定性,及其对复合材料性能的影响,指出在聚合物/粘土复合材料中粘土片层间距的变化同样有可能受到层间插层剂构象变化的影响、聚合物/粘土纳米材料的长期热氧稳定性与热失重结果可能不一致。     

原位聚合法制备聚丙烯酸甲酯/ZnAl层状双氢氧化物插层纳米复合材料及其形貌特征

近 2 0年来 ,聚合物 /层状无机物纳米复合材料引起了广泛关注 ,与聚合物材料相比 ,该类纳米复合材料在力学、热稳定性、阻燃、气体阻隔等性能方面都有显著增强 .但所报道的绝大部分无机物均采用蒙脱土为代表的层状硅酸盐[1～ 3] ,而以层状双氢氧化物 (Layered double hydroxide,LDH)为基础制备的聚合物 /层状无机物纳米复合材料的报道极少 .LDH是由水镁石结构中的二价阳离子 (M2 + )被三价阳离子 (M3+ )取代而形成的 ,层上产生的剩余正电荷被吸附在层间的阴离子平衡 .与层状硅酸盐相比 ,L DH层间电荷密度高 ,层与层之间相互作用强 ,导…     

剪切作用下纳米粘土对LDPE熔体粘弹响应的影响

以LDPE/EVA/纳米粘土复合体系为研究模型,考察了剪切作用下,分散良好的纳米粘土对聚合物基体熔体稳态及瞬态粘弹响应的影响.发现剪切作用下,纳米粘土增加了聚合物熔体粘弹特性对剪切速率、剪切应变及剪切作用史的依赖性,改变了相应的依赖关系.稳态剪切时,纳米粘土的加入使体系第一法向应力差(N1)在低剪切速率区变为负值,而在高剪切速率区N1与粘土的含量无关;同时就瞬态剪切应力及N1的应变依赖关系而言,复合体系明显不同于聚合物基体;预剪切对聚合物基体瞬态粘弹响应几乎没有影响,而当纳米粘土的加入量大于3wt%后,与未经预剪切的样品相比较,经预剪切的复合体系的瞬态剪切应力值、应力过冲程度以及稳态剪切应力值均明显下降,且预剪切前后复合体系达到稳态时其瞬态剪切应力差值随纳米粘土含量的增高而线性增加.此外,纳米粘土的添加对聚合物熔体受剪切作用的非线性粘弹响应存在影响.复合体系熔体呈现特异非线性粘弹响应,其缘由被认为是由于纳米粘土在聚合物基体中剥离分散,或聚合物分子链插层于粘土片层间,形成局部有序结构,受剪切作用而排列取向.     

熔体插层聚合物/粘土纳米复合材料

对国内外熔体插层法制备聚合物／粘土纳米复合材料(PCN)的研究进展进行了综述。介绍了影响PCN结构形态的各种因素；对熔体插层法制备PCN的热力学、动力学研究进行了总结；详细讨论了熔体插层的机理研究及理论模型。并对熔体插层法制备PCN提出了展望。     

剥离型硅橡胶/黏土纳米复合材料研究

利用层状硅酸盐制备有机 无机纳米复合材料是当前人们研究的热点[1,2 ] ,这类材料具有较常规聚合物 无机填料复合材料无法比拟的优点 ,可以明显改善高分子材料的物理机械性能、热稳定性、气体阻隔性、阻燃性、导电性、光学性等 .一般来说 ,聚合物 层状硅酸盐 (Ｐｏｌｙｍｅｒｌａｙｅｒｅｄｓｉｌｉｃａｔｅ ,ＰＬＳ)纳米复合材料可分为插层型和剥离型两种类型 .插层型纳米复合材料即聚合物插入到硅酸盐层中 ,硅酸盐在近程仍保持原有的有序晶体结构 ,在远程则是无序的 .对弹性体而言 ,硅酸盐含量在插层型杂化材料中的含量比较高 ,力学性能…     

聚苯乙烯/蒙脱土纳米复合材料的自组装行为

聚合物／层状硅酸盐（PLS）纳米复合材料由于具有常规复合材料所没有的结构、形态以有较常规聚合物基复合材料更优异的物理力学性能等而引起人们的关注^[1],但以往文献^[1-3]主要报道PLS纳米复合材料的制备与性能表征,对于熔融加工过程中粘土粒子吸高分子的取向和结构研究很少。作者等^[4-6]发现了剥离型聚苯乙烯（PS）／蒙脱土纳米复合材料中的剪切诱导有序结构,并采用广角X射线衍射法（WAXD）、透射电镜法（TEM）和红外二向色性法对其形成机理进行了研究。结果表明,该有序结构的主要来源是分散在PS基体中的蒙脱土初级粒子（Primary particles）内部片层的规整排列以及沿平行于样品表面方面的平面取向,PS的苯环平面平行剪切流动方向取向,而烷项链未见明显取向。本文报道该纳米复合材料的剪切诱导有序结构在升温过程中出现的自组装行为,并用原位升温X射线衍射法和红外二向色性法对蒙脱土初级粒子的规整度以及PS的苯环和烷基链在升温过程中的取向行为进行了研究,在此基础上提出了可能的形成机理。     

聚萘并噁嗪/蒙脱土纳米复合材料的制备与表征

用原位插层反应法地制备了聚萘并嗪 蒙脱土纳米复合材料 .采用X ray衍射 (XRD)及透射电镜(TEM)研究复合材料中蒙脱土硅酸盐片层间距 ,发现硅酸盐片层间距由 1 2 6nm扩增至 5 88nm以上 .同时研究了该复合材料的耐热性 ,并探讨了复合材料的结晶行为     

Preparation and Characteration of UV-cured EA/MMT Nanocomposites Via In-Situ Polymerization

A long-chain surfactant, enzoylbenzyl-N,N-dimethyl-N-octadecylammonium bromide (BDOB) with a benzophenone group, was synthesized to modify the montmorillonites (MMT) for the preparation of nanocomposites via photo-induced polymerization. The BDOB-modified MMT was characterized by the fourier transform infrared spectrometer (FTIR), thermal gravimetric analyzer (TGA) and X-ray diffraction (XRD), and the results of XRD indicated that the intercalated structures of BDOB-modified MMT was obtained. The conversion of the bisphenol A epoxy diacrylate (EA) was quantified by the FTIR, and the results indicated that conversion increased with an increase in the amount of BDOB-modified MMT. The morphologies of the UV-cured EA/MMT nanocomposites prepared from this organically modified MMT were studied by means of XRD and TEM, and the results showed that all the samples contained an intercalated structure with partial exfoliated structure. The results of TGA and mechanical properties also indicated that the thermal and mechanical properties of UV-cured nanocomposites were significantly enhanced due to the presence of the long chain surfactant organically modified MMT.     

原位插层聚合制备聚丁二烯/蒙脱土纳米复合材料及其结构与性能研究

采用负离子引发原位插层聚合法制备了聚丁二烯(PB)/有机蒙脱土(OMMT)纳米复合材料(NC).对OMMT纯化方法、OMMT种类和溶剂等因素对聚合反应的影响进行了研究.不同方法纯化的OMMT消耗的BuLi量相差一倍;采用OMMT-DK1制备的NC具有较宽的分子量分布,而采用OMMT-DK1B和OMMT-DK4制备的NC则具有较窄的分子量分布;OMMT在环己烷中不溶解,在甲苯和二甲苯等溶剂中可形成均匀溶液.采用XRD、TEM和H-NMR等仪器对PB/OMMT NC的插层结构、化学结构和形态进行了分析;采用DSC、TGA和DMA等仪器对PB/OMMT NC的Tg、热学性能和动态力学性能进行了研究,结果表明,采用负离子原位插层聚合可得到剥离型PB/OMMT纳米复合材料;与OMMT插层复合明显改变了PB的微观结构组成,在OMMT含量为6.2wt%时,1,2-结构含量增加了近一倍,Tg和Tdc分别增加了10 K和16 K;E′、E″均明显提高,而tanδ下降.     

The influence of a quaternary ammonium salt and MMT on the in situ intercalative polymerization of PMMA

Poly(methylmetacrylate)/montmorillonite (PMMA)/(MMT) nanocomposites were prepared by a one-step in situ intercalative solution polymerization involving the simultaneous modification of the MMT with a quaternary ammonium salt (cetyl-trimethylammonium bromide (CTMAB)), polymerization and polymer intercalation. Using benzoyl peroxide as an initiator, intercalated nanocomposites were formed and characterized by NMR, DSC, TGA, XRD, TEM and SEC. It was observed that it was not the MMT, but rather the CTMAB, that influences the polymerization reaction, especially the reaction yield, the molar mass averages and the molar mass distribution of the PMMA. The thermal stability of the PMMA was improved by the addition of both the MMT and/or the CTMAB.     

蒙脱土负载型引发剂的制备及在苯乙烯乳液聚合中的应用

通过正离子交换将引发剂AIBA负载在蒙脱土上制得负载型引发剂V50-MMT.进而采用原位乳液聚合方法引发苯乙烯聚合制备PS/MMT纳米复合材料.采用XRD、TGA、DSC、TEM和抽提等方法对负载型引发剂和纳米复合材料进行了表征.结果表明,负载过程中引发剂AIBA进入了MMT的片层之间;聚合过程中介于片层间的引发剂因发生分解一方面产生自由基引发St聚合,另一方面MMT发生了剥离分散;由此法制备的PS/MMT纳米复合材料,MMT片层无规、均匀地分散于PS基体中,片层厚度在几个纳米至十几个纳米之间,长度为几十至几百个纳米不等;大量的PS链段以化学键接枝在MMT的片层上,接枝在MMT片层上的PS的分子量及其分布与游离的PS不同.     

Morphology and thermal properties of polyhedral oligomeric silsesquioxane/polybutadiene nanocomposites prepared by anionic polymerization

The morphology and thermal properties of Allylisobutyl Polyhedral Oligomeric Silsesquioxane (POSS)/Polybutadiene (PB) nanocomposites prepared through anionic polymerization technique were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The results of XRD, SEM and TEM showed that the aggregation of POSS in PB matrix occurred obviously, forming crystalline domains and the size of POSS particles increased with increasing POSS content. The DSC and TGA results indicated that the glass transition temperature (T _g) of the nanocomposites was significantly increased and the maximum degradation temperature (T _dmax) of nanocomposites was slightly increased compared with pure PB, implying an increase in thermal stability.     

Interactions between Nafion resin and protonated dodecylamine modified montmorillonite: a solid state NMR study

A series of nanocomposites have been prepared from perfluorosulfonylfluoride copolymer resin (Nafion) and layered montmorillonite (MMT) modified with protonated dodecylamine by conventional sol-gel intercalation. The structure of these nanocomposite materials have been characterized using FT-IR, elemental analysis, XRD and solid state NMR techniques, including 19F magic-angle spinning (MAS) NMR, 19F NMR relaxation time measurements, 29Si MAS, 1H MAS, 1H-13C cross-polarization magic-angle spinning (CPMAS), and 1H-13C heteronuclear correlation (HETCOR) 2D NMR. The results showed that thermal stability of Nafion was improved moderately by the addition of dodecylamine modified MMT without intercalation. FT-IR and 29Si MAS NMR results indicated that dodecylamine modification did not result in obvious changes in the MMT lattice structure. The XRD results showed that the protonated dodecylamine has been embedded and intercalated into the MMT interlayers, whereas Nafion was not. Elemental analysis results also suggested that some dodecylamine was adsorbed on the surface of MMT. 1H-13C HETCOR 2D NMR experiment clearly indicated that strong electrostatic interactions were present between the NH+3 group of dodecylamine and the fluorine-containing groups (CF3, OCF2, and SCF2) of Nafion resin. Such electrostatic interactions are probably the major contributors for the improved thermal stability of the resultant composite materials.     

Preparation, characterization and application of polymeric diols with comb-branched structure and their nanocomposites containing montmorillonites

The polymeric diols with comb-branched structure (CPD) and their nanocomposites containing montmorillonites (MMT) were prepared through three-step reaction on basis of molecular design. The effect of experimental parameters, such as molar mass of oligomer polyols, catalysts and MMT on conversion of -NCO group during polymerization was investigated by utilizing FTIR to measure content of -NCO group varied as reaction time. In addition, the structure of comb-branched polymeric diols was characterized by FTIR and ¹H NMR. The results show that the comb-branched chains contain reactive CC double bonds in CPD. The nature of dispersion of montmorillonites in CPD was characterized by X-ray diffraction. The results show that Na⁺-MMT is exfoliated and organo-MMT is intercalated in CPD via in-situ polymerization. Finally, the properties of water-borne polyurethane modified with CPD or CPD/2T-MMT nanocomposite were compared with those of common water-borne polyurethane, and the comb-branched chains and 2T-MMT improve the properties of water-borne polyurethane.     

乳液聚合法制备剥离型PS/MMT纳米复合材料

以阳离子表面活性剂十八烷基三甲基氯化铵(OTAC)和烯丙基十八烷基二甲基氯化铵(ATAC)为插层处理剂改性蒙脱土(MMT),原位乳液聚合分别制备了PS/C18MMT和PS/AC18MMT两种纳米复合材料.XRD和TEM分析表明,MMT均被剥离成单个或几个片层无规的分散在PS基体中,TGA分析表明,MMT的加入提高了材料的耐热性能,当PS基体与有机化处理的MMT片层发生一定的化学连接后,PS/AC18MMT纳米复合材料表现出更好的耐热性能.动态力学分析表明,MMT的加入提高了PS的玻璃态储能模量,降低了材料的动态损耗;PS/AC18MMT纳米复合材料的玻璃化温度较PS有所提高,而PS/C18MMT的玻璃化温度与PS相比略有降低.     

Characterization and thermal degradation studies on polyaniline‐intercalated montmorillonite nanocomposites prepared by a solvent‐free mechanochemical route

Polyaniline (PANI)‐montmorillonite (MMT) nanocomposites were prepared by direct intercalation of aniline molecules into MMT galleries, followed by in situ polymerization within the nano‐interlamellar spaces under solvent‐free conditions. The basal spacing of aniline‐intercalated MMT increased gradually up to 1.5 nm with increasing amounts of aniline loaded. This result suggests that aniline molecules were adsorbed by MMT clay and that intercalated aniline likely located perpendicular to the silicate sheets. After polymerization, X‐ray diffraction and Fourier transform infrared analyses confirmed the successful synthesis of PANI chains between the MMT nano‐interlayers. The scanning electron microscopy images indicated that the surface morphologies of PANI–MMTs were strongly different depending on the PANI content. The electrical conductivities of PANI nanocomposite particles in pressed pellets ranged in the order of between 10^?3 and 10^?2 S/cm. UV–vis spectroscopy and doping level measurement were further used to discuss the conductivities of nanocomposites. The thermal stabilities of PANI–MMT nanocomposites were examined by using thermogravimetric‐differential thermal analysis and derivative thermogravimetric analysis, and both analyses consequently demonstrated the improved thermal stabilities of the PANI chains in the nanocomposites as compared to pure PANI. The thermal stabilities of resulting nanocomposites were strongly related to the PANI content, which increased as the PANI content decreased in the nanocomposites. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2705–2714, 2005