聚苯乙烯/蒙脱土纳米复合材料的制备及结构研究

以可与苯乙烯发生共聚的阳离子表面活性剂乙烯苄基二甲基十八烷基氯化铵(VOAC)为插层处理剂改性蒙脱土(VC18-MMT),有机蒙脱土在超声波强剪切作用以及乳化剂作用下预分散在乳化剂溶液中,然后引入苯乙烯单体进行原位乳液聚合制备聚苯乙烯/蒙脱土纳米复合材料.采用XRD和TEM对纳米复合材料的结构进行了表征.结果表明,绝大多数的蒙脱土被剥离成单个片层均匀的分散在聚合物基体中;动态力学分析表明,纳米复合材料的储能模量和玻璃化温度均有所增加,而动态损耗有所降低;接枝在蒙脱土片层上的聚合物通过与锂离子进行阳离子交换反应提取下来,采用GPC和NMR对接枝聚合物的结构进行了表征,结果表明,接枝聚合物是较基体分子量低且分布很宽的苯乙烯和乙烯苄基二甲基十八烷基氯化铵的共聚物,计算表明每一个共聚物分子链上平均含有大约25个乙烯苄基二甲基十八烷基氯化铵分子.     

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.     

插层聚合制备聚丙烯/蒙脱土纳米复合材料及其结构性能表征

将插层聚合的概念引入烯烃聚合,制备了聚丙烯／蒙脱土（PP／MMT）纳米复合材料。X射线衍射和TEM分析结果表明,蒙脱土在聚丙烯基体中达到了纳米级的分散,动态力学性能研究结果表明,在高于Tg的温度区域内PP／MMT纳米复合材料的储能模量（E′）成倍增加,加入8％的蒙脱土（MMT）,PP／MMT的E′提高近3倍。PP／MMT的玻璃化转变温度Tg有一定程度的提高,随蒙脱土含量的增加,PP／MMT的热分解温度和热变形温度（HDT）都有大幅度提高。     

Fe3O4/聚苯乙烯纳米复合材料的结构与性能

采用油酸(OA)表面改性的粒径均一的Fe3O4纳米粒子(OA-Fe3O4)与工业化聚苯乙烯(PS)通过溶液共混挥发干燥方法得到了具有超顺磁性的OA-Fe3O4/PS纳米复合材料.透射电子显微镜表征结果表明,在OA-Fe3O4质量分数为1%~10%时,OA-Fe3O4纳米粒子均匀分散在PS聚合物基体中.示差扫描量热分析表明,随着纳米粒子加入量的增加,纳米复合材料的玻璃化转变温度逐渐降低.热失重分析表明,OA-Fe3O4的存在显著提高了PS在空气条件下的热稳定性.流变分析表明,随着纳米粒子加入量的增加(0~10%),复合材料黏度逐渐降低.进一步研究了分子量双峰分布的PS与OA-Fe3O4纳米复合体系的流变行为,结果表明,当PS基体的平均分子量大于临界缠结分子量,且填充的纳米粒子的半径小于双峰分布PS的均方旋转半径时,加入纳米粒子仍然导致体系的复合黏度降低.     

β-羟基丁酸与β-羟基戊酸共聚物 (PHBV)/蒙脱土纳米复合材料的结构与性能

用溶液复合法成功地制备了插层型PHBV／蒙脱土纳米复合材料。采用X射线衍射（XRD）和透射电子显微镜（TEM）研究了复合材料的结构，硅酸盐片层间距从1.8nm升至2.4nm左右。同时研究了复合材料的结晶，熔融，动态力学行为和力学性能，发现有机蒙脱土的加入，可以加快PHBV的结晶,降低熔融温度，使基体的玻璃化转变温度升高，提高了材料的力学性能，有机蒙脱土含量在3％时，其综合性能最佳。     

乳液聚合法制备聚苯乙烯/Mg-Al层状双氢氧化物纳米复合材料

采用乳液聚合法制备阻燃性聚苯乙烯MgAl层状双氢氧化物(LDHs)纳米复合材料.通过对不同合成条件下复合材料的XRD谱,讨论了纳米复合材料的形成过程;经SEM图证实了LDHs是以剥离的纳米级层片分散在基体中的;TG和DSC谱图揭示了LDHs纳米层板可有效提高PS的热稳定性,并可使PS的玻璃化转化温度明显提高;当层状双氢氧化物在插层复合材料中含量为14.92%时,纳米复合材料的氧指数可达23.5%,其用量比在PS中直接添加纳米LDHs时要少约一倍.文中还分析了纳米复合材料的形成过程.     

辐照法制备的醋酸乙烯酯/蒙脱土纳米复合材料与HDPE和PA6共混物的研究

利用γ射线辐射引发醋酸乙烯酯(VAc)在蒙脱土(MMT)中的原位插层聚合,X射线衍射测试与透射电子显微镜观察结果表明,PVAc/MMT复合材料为纳米复合材料.其与HDPE和PA6的共混物的扫描电镜测试结果表明,PVAc-MMT纳米复合物以微胶囊的形式存在于PVAc-MMT/HDPE/PA6共混物中,均匀分散的PVAc-MMT纳米复合物改变了复合材料的相结构.热失重测试结果显示,PVAc-MMT/HDPE/PA6的起始分解温度明显高于PVAc/HDPE/PA6,热失重过程差异较大,MMT纳米粒子的存在改变了材料的结构,使材料热性能得到了改善.在PVAc-MMT/HDPE/PA6共混物中,PVAc-MMT具有增强与增韧作用.     

原位聚合制备聚乙烯/蒙脱土(MMT)纳米复合材料的研究

利用MgCl₂在醇中溶解和蒙脱土(MMT)在醇中层间膨胀的特性,制备了MgCl₂/TiC_l4负载于MMT层间的MMT/MgCl₂/TiC_l4催化剂,并通过原位聚合合成了聚乙烯/蒙脱土纳米复合材料.经广角X射线衍射(WAXD)和透射电子显微镜(TEM)分析表明,蒙脱土片层在乙烯聚合过程中发生了层间剥离,以单片层或几片层共存的形式无规地分散于聚乙烯基质中.与分子量相近的纯聚乙烯相比,极低的蒙脱土含量(质量分数<1%)能使复合材料的屈服强度、拉伸强度和拉伸模量有很大提高.复合材料中蒙脱土片层以纳米尺寸在聚乙烯基质中的良好分布和对聚乙烯分子链运动的限制作用是力学性能提高的主要因素.     

利用静电界面制备高性能蒙脱石/氢化丁腈橡胶

将甲基丙烯酸(MA)和烷基胺改性蒙脱石(MMT)混合成浆料后, 加入到氢化丁腈(HNBR)橡胶中, 通过热硫化工艺, 制备了MMT/HNBR橡胶复合材料. 采用扫描电子显微镜、 透射电子显微镜、 小角X射线衍射仪、 傅里叶变换红外光谱仪和转矩流变仪研究了MA改性的MMT与橡胶间的界面及分散性, 并对复合材料的各种性能进行分析. 结果表明, 在热硫化过程中, 不仅形成了橡胶的交联网络, 而且也促使MA在橡胶中发生原位聚合. 生成的聚甲基丙烯酸与MMT表面的烷基胺形成离子对, 从而在橡胶和MMT间构筑了强的静电界面. 同时MA在MMT层间发生聚合反应, 提高了MMT在橡胶中的分散性. 动态机械性能和200%应变的应力松弛实验表明, 良好分散的MMT和静电界面有效约束了橡胶分子链在力学拉伸过程中的运动. 与纯橡胶相比, MMT/HNBR橡胶复合材料具有更大的拉伸强度和韧性. 此外, 橡胶复合材料还具有良好的N₂气阻隔性能. 因此, 配制MA/MMT浆料是一种简单方便的MMT改性方法, 制备的MMT/HNBR橡胶复合材料可用于制造具有高强韧性和气体阻隔性要求的橡胶产品.     

几种高性能热塑性树脂与蒙脱土插层复合的研究

研究了PEK C ,PES ,PEI和PSU 4种刚性分子链高性能热塑性树脂与蒙脱土插层复合的行为 ,结果表明通过溶液混合PEK C和PES很容易插入到粘土层间并使粘土剥离 ,得到剥离型纳米复合材料 ,而PEI和PSU不能插入到粘土层间 ,分析认为插层能力的差异是由于它们与粘土间的作用力不同导致的 .PEK C和PES与粘土形成纳米复合材料后 ,玻璃化温度大幅度下降 ,但热分解温度有很大提高 ,认为是由于体积很大而且刚硬的聚合物分子与粘土片层混合后形成了较大的自由体积 ,使玻璃化温度下降 ,但聚合物端基与粘土间很强的作用力使它的热解温度提高 .PEI和PSU与粘土复合后热性能没有明显变化 ,说明如果粘土与聚合物间不能形成纳米复合 ,不会对聚合物性能产生显著影响     

Preparation of polystyrene/montmorillonite nanocomposites using a new radical initiator-montmorillonite hybrid via in situ intercalative polymerization

Polystyrene/montmorillonite (PS/MMT) nanocomposites were prepared by in situ free radical intercalative polymerization, using 1, 3 and 5 wt% of a new cationic radical initiator-MMT hybrid. The corresponding nanocomposites were designated as PS/MMT-1, PS/MMT-3 and PS/MMT-5, respectively. The silicate layers were well exfoliated and randomly dispersed in the PS/MMT-1 and PS/MMT-3, but were less exfoliated in the PS/MMT-5, due to the predominant extra-gallery polymerization over the intra-gallery polymerization. The unique properties of nanocomposites resulted from the strong interactions between the nano-sized silicate layer surfaces and the polymer chains. The onset temperature of thermal degradation, and the glass transition temperature, increased with increasing hybrid content, up to 3 wt%. The molecular weights of the PS in the PS/MMT-1 and PS/MMT-3 were less than those calculated theoretically, due to the predominant intra-gallery polymerization.     

Gas barrier of polystyrene montmorillonite clay nanocomposites: Effect of mineral layer aggregation

Three polystyrene (PS)/clay hybrid systems have been prepared via in situ polymerization of styrene in the presence of unmodified sodium montmorillonite (Na‐MMT) clay, MMT modified with zwitterionic cationic surfactant octadecyldimethyl betaine (C18DMB) and MMT modified with polymerizable cationic surfactant vinylbenzyldimethyldodecylammonium chloride (VDAC). X‐ray diffraction and TEM were used to probe mineral layer organization and to expose the morphology of these systems. The PS/Na‐MMT composite was found to exhibit a conventional composite structure consisting of unintercalated micro and nanoclay particles homogeneously dispersed in the PS matrix. The PS/C18DMB‐MMT system exhibited an intercalated layered silicate nanocomposite structure consisting of intercalated tactoids dispersed in the PS matrix. Finally, the PS/VDAC‐MMT system exhibited features of both intercalated and exfoliated nanocomposites. Systematic statistical analysis of aggregate orientation, characteristic width, length, aspect ratio, and number of layers using multiple TEM micrographs enabled the development of representative morphological models for each of the nanocomposite structures. Oxygen barrier properties of all three PS/clay hybrid systems were measured as a function of mineral composition and analyzed in terms of traditional Nielsen and Cussler approaches. A modification of the Nielsen model has been proposed, which considers the effect of layer aggregation (layer stacking) on gas barrier. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1733–1753, 2007     

Kinetic study of the thermal degradation of PS/MMT nanocomposites preparedwith imidazolium surfactants

Styrene and montmorillonite organically modified with imidazolium surfactants (MMT) at various alkyl chain lengths (C₁₂, C₁₆ and C₁₈) were used to prepare the corresponding PS/MMT/C₁₂, PS/MMT/C₁₆ and PS/MMT/C₁₈ nanocomposites by in situ polymerization. XRD and TEM analyses evidenced the formation of both intercalated and exfoliated structures. The glass transition temperatures (T _g) of nanocomposites, as well as that of neat PS, were obtained by DSC measurements. The thermal degradations were carried out in the scanning mode, in both inert and oxidative environments, and the initial temperatures of decomposition (T _i) and the apparent activation energies of degradation (E _a) were determined. Due to an oxidative degradation mechanism, the T _i and E _a values in air atmosphere were lower than those under nitrogen. The results indicated that nanocomposites are more thermally stable than polystyrene, and suggested an increasing degree of exfoliation as a function of alkyl chain length of surfactant, associated with enhancing thermal stability.     

Synthesis of poly(methyl methacrylate) nanocomposites via emulsion polymerization using a zwitterionic surfactant

The synthesis of nanocomposites via emulsion polymerization was investigated using methyl methacrylate (MMA) monomer, 10 wt % montmorillonite (MMT) clay, and a zwitterionic surfactant octadecyl dimethyl betaine (C18DMB). The particle size of the diluted polymer emulsion was about 550 nm, as determined by light scattering, while the sample without clay had a diameter of about 350 nm. The increase in the droplet size suggests that clay was present in the emulsion droplets. X-ray diffraction indicated no peak in the nanocomposites. Transmission electron microscopy showed that emulsion polymerization of MMA in the presence of C18DMB and MMT formed partially exfoliated nanocomposites. Differential scanning calorimetry showed an increase of 18 degrees C in the glass transition temperature (Tg) of the nanocomposites. A dynamic mechanical thermal analyzer also verified a similar Tg increase, 16 degrees C, for the partially exfoliated nanocomposites over poly(methyl methacrylate) (PMMA). Thermogravimetric analysis indicated a 37 degrees C increase in the decomposition temperature for a 20 wt % loss. A PMMA nanocomposite with 10 wt % C18DMB-MMT was also synthesized via in situ polymerization. This nanocomposite was intercalated and had a Tg 10 degrees lower than the emulsion nanocomposite. The storage modulus of the partially exfoliated emulsion nanocomposite was superior to the intercalated structure at higher temperatures and to the pure polymer. The rubbery plateau modulus was over 30 times higher for the emulsion product versus pure PMMA. The emulsion technique produced nanocomposites of the highest molecular weight with a bimodal distribution. This reinstates that exfoliated structures have enhanced thermal and mechanical properties over intercalated hybrids.     

SYNTHESIS AND CHARACTERIZATION OF POLYPROPYLENE/MONTMORILLONITE NANOCOMPOSITES VIA AN in-situ POLYMERIZATION APPROACH

Polypropylene/montmorillonite (PP/MMT)nanocomposites were prepared by in-situ polymerization using aMMT/MgCl_2/TiCl_4-EB Ziegler-Natta catalyst activated by triethylaluminum(TEA). The enlarged layer spacing of MMT wasconfirmed by X-ray wide angle diffraction (WAXD), demonstrating that MMT were intercalated by the catalyst components.X-ray photoelectron spectrometry (XPS) analysis proved that TiCl_4 was mainly supported on MgCl_2 instead of on the surfaceof MMT The exfoliated structure of MMT layers in the PP matrix of PP/MMT composites was demonstrated by WAXDpatterns and transmission electron microscopy (TEM) observation. The higher glass transition temperature and higher storage modulus of the PP/MMT composites in comparison with pure PP were revealed by dynamic mechanical analysis (DMA).     

Preparation and characterization of exfoliated polystyrene/clay nanocomposites using a cationic radical initiator-MMT hybrid

The exfoliated polystyrene (PS)/clay nanocomposites were prepared via in situ polymerization using a cationic radical initiator-intercalated montmorillonite hybrid. The exfoliated structure resulted from the predominant intra-gallery polymerization over the extra-gallery polymerization owing to the anchored radical initiator inside the clay galleries. Several critical properties of the nanocomposites such as the initial thermal degradation temperature, glass transition temperature, storage modulus, Young’s modulus, and tensile strength were estimated and compared with earlier reported literature values. The improvements in such properties were either comparable or much greater than the reported literature values, mainly due to the efficient exfoliation and dispersion of the clay in the PS matrix.     

原位聚合聚乙烯/蒙脱土纳米复合材料的结晶行为

用DSC研究了HDPE与MMT负载的催化剂熔融共混和原位聚合得到的两种纳米复合材料的熔融、 结晶行为和等温结晶动力学.  结果表明, HDPE与熔融共混样品的结晶度、 平衡熔点、 球晶生长速率和结晶能力大体相同; 原位聚合得到的HDPE/MMT纳米复合材料的结晶度和平衡熔点高于纯HDPE; 在相同过冷度条件下熔融结晶速率和结晶能力低于纯HDPE, 而在相同结晶温度Tc下, 熔融结晶速率和结晶能力则高于纯HDPE.  纯HDPE的晶体生长侧向单位面积表面自由能最小, 其次是熔融共混样品, 原位聚合样品最大, 且随ＭＭＴ含量的增加逐渐升高.     

SYNTHESIS AND PROPERTIES OF POLYSTYRENE／LAPONITE NANOCOMPOSITES

Exfoliated polystyrene (PS)/laponite nanocomposites were prepared successfully. The characteristic doo1 diffraction peak of organo-laponite disappeared in the XRD patterns of nanocomposites, indicating that the laponite layers were exfoliated and the ordered crystal structure of laponite was destroyed because of the styrene polymerization. TEM observations showed that the exfoliated laponite primary particles were dispersed randomly in the PS matrix with lateral dimensions from 1 nm to 10 rim. SEM results showed that the PS/laponite nanocomposite particles were almost monodispersed spheres with the size of about 120 rim. Because of the interaction between PS and laponite nanolayers, the nanocomposites exhibited higher thermal stability and glass transition temperature when compared to pure PS.