嵌入法制备聚合物/层状硅酸盐纳米复合材料的研究进展

本文介绍和对比了嵌入法制备聚合物／层状硅酸盐纳米复合材料的三种类型,与溶液嵌入法（包括单体嵌入聚合法和聚合物溶液嵌入法）相比,熔融嵌入法具有更广泛的适用性。并从热力学和动力学角度出发,分析了影响嵌入过程的各种因素。     

Polymer/layered silicate nanocomposites by combined intercalative polymerization and melt intercalation: a masterbatch process

Poly(ε-caprolactone) (PCL) and poly(vinyl chloride) (PVC) layered silicate nanocomposites were prepared by combination of intercalative polymerization and melt intercalation. In a first step, high clay content PCL nanocomposites were prepared by in situ polymerization of ε-caprolactone intercalated between selected organo-modified silicate layers. The polymerization was catalyzed with dibutyltin dimethoxide in the presence of montmorillonites, the surface of which were previously exchanged with (functionalized) long alkyl chains ammonium cations. Then, these highly filled PCL nanocomposites were added as masterbatches in commercial PCL and PVC by melt blending. The intercalation of PCL chains within the silicate layers by in situ polymerization proved to be very efficient, leading to the formation of intercalated and/or exfoliated structures depending on the organo-clay. These masterbatches were readily dispersed into the molten PCL and PVC matrices yielding intercalated/exfoliated layered silicate nanocomposites which could not be obtained by melt blending the matrix directly with the same organo-modified clays. The formation of nanocomposites was assessed both by X-ray diffraction and transmission electronic microscopy. Interestingly, this so-called ‘masterbatch’ two-step process allowed for preparing PCL nanocomposites even with non-modified natural clay, i.e. sodium montmorillonite, which showed a material stiffness much higher than the corresponding microcomposites recovered by direct melt intercalation. The thermal stability of PCL nanocomposites as a function of clay content was investigated by thermogravimetry (TGA).     

Nanostructure of EVA/organoclay nanocomposites: Effects of kinds of organoclays and grafting of maleic anhydride onto EVA

Nanostructure of poly(ethylene‐co‐vinyl acetate)/organically modified montmorillonite (MMT; EVA/organoclay) nanocomposites prepared by melt intercalation process was investigated using X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Three kinds of organoclays were used to see their influences on the nanostructure of the EVA hybrids. The effects of the polar interactions between the polymer and the silicate layers of organoclays were also investigated by grafting maleic anhydride onto EVA. It was found that the strong polar interactions between the polymer and the silicate layers of organoclays are critical to the formation of polymer‐layered silicate nanocomposites. The results also showed that increasing the mixing temperature was unfavorable to improve the dispersion of organoclays in the EVA matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1901–1909, 2003     

Biodegradable polyester layered silicate nanocomposites based on poly(ϵ‐caprolactone)

Nanocomposites based on biodegradable poly(?‐caprolactone) (PCL) and layered silicates (montmorillonite, MMT) were prepared either by melt interaction with PCL or by in situ ring‐opening polymerization of ?‐caprolactone as promoted by the so‐called coordination‐insertion mechanism. Both non‐modified clays (Na⁺ ‐MMT) and silicates modified by various alkylammonium cations were studied. Mechanical and thermal properties were examined by tensile testing and thermogravimetric analysis. Even at a filler content as low as 3 wt% of inorganic layered silicate, the PCL‐layered silicate nanocomposites exhibited improved mechanical properties (higher Young's modulus) and increased thermal stability as well as enhanced flame retardant characteristics as a result of a charring effect. It was shown that the formation of PCL‐based nanocomposites depended not only on the nature of the ammonium cation and related functionality but also on the selected synthetic route, melt intercalation vs. in situ intercalative polymerization. Interestingly enough, when the intercalative polymerization of ?‐caprolactone was carried out in the presence of MMT organo‐modified with ammonium cations bearing hydroxyl functions, nanocomposites with much improved mechanical properties were recovered. Those hybrid polyester layered silicate nanocomposites were characterized by a covalent bonding between the polyester chains and the clay organo‐surface as a result of the polymerization mechanism, which was actually initiated from the surface hydroxyl functions adequately activated by selected tin (II) or tin (IV) catalysts.     

生物可降解聚乳酸/层状硅酸盐纳米复合材料的研究进展

生物可降解聚乳酸是一种具有广泛应用前景的环境友好型的生物高分子材料,但是其力学性能、热稳定性能不稳定.利用层状硅酸盐的特殊结构,以各种有机改性的层状硅酸盐为添加物,通过原位插层聚合、溶液插层、熔融插层和剥离.吸附等方法制备生物可降解聚乳酸/层状硅酸盐纳米复合材料,其力学性能、热稳定性、生物降解性等均有显著提高,其展现出极其广阔的应用前景.本文概述了近年来生物可降解聚乳酸/层状硅酸盐纳米复合材料的制备、结构、性能和应用等方面的研究进展,并且对各种制备方法进行了分析比较.     

The characterization of organic modified clay and clay‐filled PMMA nanocomposite

Recently, polymer–clay hybrid materials have received considerable attention from both a fundamental research and application point of view. 1 - 3 This organic–inorganic hybrid, which contains a nanoscale dispersion of the layered silicates, is a material with greatly improved physical and mechanical characteristics. These nanocomposites are synthesized through in situ polymerization or direct intercalation of the organically modified layered silicate (OLS) into the polymer matrix. Thus, understanding the relationship between the molecular structure and the thermal stability (decomposition temperature, rate, and the degradation products) of the OLS is critical. In this study, modern thermal analysis techniques combined with infrared spectroscopy and mass spectrometry (TGA‐FTIR‐MS) were used to obtain information on the thermal stability and degradation products of organic modified clay. Furthermore, the thermal and mechanical properties of clay‐filled PMMA nanocomposites were determined by using TGA and DSC. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1702–1710, 2002     

Microstructure, tensile properties, and biodegradability of aliphatic polyester/clay nanocomposites

Novel biodegradable aliphatic polyester (APES)/organoclay nanocomposites were prepared through melt intercalation method. Two kinds of organoclays, Cloisite 30B and Cloisite 10A with different ammonium cations located in the silicate gallery, were chosen for the nanocomposites preparation. The dispersion of the silicate layers in the APES hybrids was characterized by using X-ray diffraction (XRD) and transmission electron microscopy (TEM). Tensile properties and the biodegradability of the APES/organoclay nanocomposites were also studied. APES/Cloisite 30B hybrids showed higher degree of intercalation than APES/Cloisite 10A hybrids due to the strong hydrogen bonding interaction between APES and hydroxyl group in the gallery of Cloisite 30B silicate layers. This leads to higher tensile properties and lower biodegradability for APES/Cloisite 30B hybrids than for the APES/Cloisite 10A hybrids.     

Synthesis and intercalation chemistry of hybrid organo-inorganic nanocomposites

The synthesis and structure of organo-inorganic nanocomposites prepared by intercalation of monomers or polymers into the interlayer galleries of layered matrices are analyzed. General features and the mechanism of the intercalation process, as well as materials used for this purpose, mostly often naturally occurring materials (clays, silicates, layered phosphates, chalcogenides, and other moieties hosts), are discussed. Mechanisms governing the intercalation of monomers or polymer repeating units into the interlayer galleries as guests are compared. One of the most widespread and commercially important intracrystalline chemical reactions is the incorporation of monomer molecules into pores or layered lattices of the host substances with subsequent post-intercalation transformations into polymer, oligomer, or hybrid-sandwich products. This strategy is used for the design of organo-inorganic self-assembling nanocomposites as multilayers (P/M)_n, where M and P are nanosized oppositely charged layers of an inorganic component and a polymer. Particular emphasis is placed on nanocomposites based on polyconjugated conducting polymers (polyaniline, polypyrrole, etc.) and various mineral matrices, as well as on semiconductor polymer-metal chalcogenide inclusion nanocomposites. Basic application areas of hybrid nanomaterials are considered.     

Nanocomposites of poly(methyl methacrylate) and organically modified layered silicates by melt intercalation

Polymer‐layered silicate nanocomposites of poly(methyl methacrylate) (PMMA) and an organically modified silicate [tetraallkyl ditallow ammonium bentonite (B34)] system prepared via melt intercalation were studied. The saturation ratio of PMMA to B34 was 25:75 (w/w), as determined by dynamic mechanical thermal analysis, differential scanning calorimetry, and X‐ray diffraction. The interaction between PMMA and B34 was detected by Fourier transform infrared spectrometry, which showed two new absorption bands of PMMA/B34 hybrids in comparison with unannealed physical mixtures of PMMA and B34. The degradation temperature of the PMMA/B34 hybrids was 26°C higher than that of neat PMMA according to thermogravimetric analysis, the thermal stability of the hybrids having been enhanced. The glass‐transition temperature of excess PMMA remaining outside the clay galleries was about 12–19°C higher than that of neat PMMA. A structural model of the hybrid was also presented. It involves some PMMA chains diffusing into the gallery of B34 and expanding it by 6.8 Å and some penetrating and interacting with the organic chains of the modified cations. Some of the PMMA chains partly contained inside the clay layers were entangled with those remaining outside when PMMA in excess of the saturation ratio was used. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2101–2115, 2004     

Influence of supercritical CO2 on the interactions between maleated polypropylene and alkyl‐ammonium organoclay

Supercritical carbon dioxide (scCO₂) has been proposed as an effective exfoliating agent for the preparation of polymer‐layered silicate nanocomposites, though there is limited fundamental understanding of this mechanism. This study looks at the interactions of this unique green solvent with three maleated polypropylenes of varying anhydride content and molecular size with an alkyl‐ammonium organoclay. Mixtures of compatibilizers and organoclay were melt‐annealed in a high pressure batch vessel at 200°C and subjected to either a blanket of nitrogen or scCO₂ at a pressure of 9.7 MPa. The structures and properties of these melt‐annealed mixtures were characterized by X‐ray diffraction, transmission electron microscopy, Fourier Transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and contact angle measurement. The results indicate that the plasticizing influence of scCO₂ aided intercalation and exfoliation for intercalants of moderate molecular size and anhydride content which would otherwise have limited diffusion into the clay galleries. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Microstructure and rheological behavior of block copolymer/clay nanocomposites

Organic/Inorganic hybrid nanocomposites based on poly(styrene-butadiene-styrene) copolymer (SBS) and clay are fabricated by melt intercalation. The degree of intercalation is dependent on the surface properties of clay and SBS. The epoxized block in epoxized SBS acts as a strong attractive site with the clay surface, which yields the increased interlayer space in the layered silicates. It is also shown that the thermal stability of clay as well as the surface properties is very important in fabricating the polymer/clay nanocomposites. The rheological behavior of the SBS/clay nanocomposites is quite different from that of SBS itself. Both storage moduli and complex viscosity of the SBS/layered silicate nanocomposites increase and show non-terminal flow behavior.     

Investigation on the Mechanical and Thermal Properties of Intercalated Epoxy/Layered Silicate Nanocomposites

Epoxy resin/layered silicate nanocomposites with various clay contents were prepared. The structural studies showed the intercalation of epoxy polymer chains into the clay galleries. The adhesion analysis of nanocomposite coating films on metallic substrates showed the excellent adhesion of epoxy-based nanocomposite coatings on iron plates, especially in lower clay loadings. According to the hardness test results, the organoclay minerals caused the increasing of the hardness of epoxy nanocomposites. The thermal properties of nanocomposites were evaluated by means of DSC and TGA analysis. The tensile and compression strengths of cured epoxy/clay systems were also investigated.     

层状硅酸盐 /聚合物纳米复合材料的研究现状与前景

基于1996年以后的40余篇文献和作者的研究成果，综述了层状硅酸盐／聚合物纳米复合材料在制备技术、新品种、新性能、相关理论及应用等方面的最新研究进展，并总结出了以下观点：（1）粘土的有机化是制备纳米复合材料的第一关键要素，单体、预聚体、聚合物熔体与有机土的相容性是制备纳米复合材料的必要条件，外界剪切力可提供帮助；（2）剥离型结构最能体现层状硅酸盐／聚合物纳米复合材料的性能优势，是层状硅酸盐／聚合物纳米复合材料的制备方向；（3）聚合物熔体插层法为简单，是重要的发展方向，要形成剥离型结构，需要同时考虑热力学和动力学因素，基体或相容剂与层间环境的相容性要适中；（4）聚合物乳液共混共凝法有利于传统的制备方法，适合于具有乳液形成的聚合物；（5）在聚合物中原位生成硅酸盐片层的方法具有新意；（6）层状硅酸盐／聚合物纳米复合材料的主要特点是高刚性、高强度、高耐热性、高阻隔性、较好的阻燃性、质轻，目前，该的制备研究正向所有的聚合物品种扩展。汽车部件、包装材料将是层状硅酸盐／聚合物纳米复合材料先应用的两大领域；（7）层状硅酸盐／聚合物纳米复合材料的理论研究进展延慢。界面区状态以及结构－性能间的关系是理论研究的两个主题。     

Effect of nanofillers as reinforcement agents for lignin composite fibers

Biobased nanocomposites and composite fibers were prepared from organosolv lignin/organoclay mixtures by mechanical mixing and subsequent melt intercalation. Two organically‐modified montmorillonite (MMT) clays with different ammonium cations were used. The effect of organoclay varying from 1 to 10 wt % on the mechanical and thermal properties of the nanocomposites was studied. Thermal analysis revealed an increased in T_g for the nanocomposites as compared with the original organosolv lignin. For both organoclays, lignin intercalation into the silicate layers was observed using X‐ray diffraction (XRD). The intercalated hybrids exhibited a substantial increase in tensile strength and melt processability. In the case of organoclay Cloisite 30B, X‐ray analysis indicates the possibility of complete exfoliation at 1 wt % organoclay loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(ethylene 2,6-naphthalate)/layered silicate nanocomposites: fabrication, crystallization behavior and properties

In this study, poly(ethylene 2,6-naphthalate) (PEN)/layered silicate nanocomposites (PLSNs) were successfully prepared by the intercalation of PEN polymer into organically-modified layered montmorillonite through the melt blending process. Both X-ray diffraction data and transmission electron microscopy images of PEN/layered silicate nanocomposites indicate most of the swellable silicate layers were exfoliated and randomly dispersed into the PEN matrix. Mechanical and barrier properties of the fabricated nanocomposites performed by dynamic mechanical analysis and permeability analysis show significant improvements in the storage modulus and water permeability when compared to neat PEN. Differential scanning calorimeter (DSC) was used to investigate the isothermal crystallization behavior and melting behavior of PLSNs. DSC isothermal results revealed that the crystal growth process of PEN and PLSNs are a three-dimensional spherulitic growth. The activation energy of PEN increases with increasing content of layered silicates. The result indicates that the addition of layered silicate into PEN reduces the transportation ability of polymer chains during crystallization processes.     

Intercalation of epoxy resin in organically modified montmorillonite

Various methods of preparation of epoxy resin/clay mixtures, before the addition of the crosslinking agent and curing to form epoxy‐based polymer layered silicate (PLS) nanocomposites, have been investigated to determine their effect on the nanostructure. Organically modified montmorillonite clay was used, and the mixtures were prepared by both simple mixing and solvent‐based methods. X‐ray diffraction shows that intercalation of the resin into the clay galleries occurs for all clay loadings up to 25 wt % and for both preparation methods, but the dispersion of the clay in the resin, observed by optical microscopy, is significantly better for the solvent preparation method. Differential scanning calorimetry (DSC) shows that the intercalated resin has the same molecular mobility as the extra‐gallery resin, but suggests that the intercalated resin does not penetrate completely into the galleries. Prolonged storage of the resin/clay mixtures at room temperature leads to changes in the DSC response, as well as in the response to thermogravimetry, which are interpreted as resulting from homopolymerization of the epoxy resin, catalyzed by the onium ion in the modified clay. This confirms and explains the earlier observation of Benson Tolle and Anderson (J Appl Polym Sci 2004, 91, 89) that “conditioning” of the resin/clay mixtures at ambient temperature has a significant effect when the crosslinking agent is subsequently added, and indicates that the preparation method has important consequences for the nanostructure development in the PLS nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:3751–3763, 2006     

Fabrication and characterization of biodegradable poly(lactic acid)/layered silicate nanocomposites

In this study biocompatible/biodegradable poly(lactic acid) (PLA)/layered silicate nanocomposites (PLSNs) were successfully prepared by the intercalation of PLA polymer into organically modified layered silicate through the solution mixing process. Both X‐ray diffraction data and transmission electron microscopy images of PLSNs indicate most of the swellable silicate layers were disorderedly intercalated into the PLA matrix. Mechanical properties of the 0.1 wt% silicate‐containing fabricated nanocomposites performed by dynamic mechanical analysis have significant improvements in the storage modulus when compared to that of neat PLA matrix. Adding more layered silicates into PLA matrix induced a decrease in the mechanical properties of PLSNs, probably due to the presence of a large dimension of porosity in the fabricated nanocomposites. POLYM. ENG. SCI., 45:1615–1621, 2005. © 2005 Society of Plastics Engineers     

聚合物／层状硅酸盐纳米复合材料制备原理

围绕着分散相尺寸和两相界面粘接这两个关键问题,简单回顾了复合材料从熔融共混,聚合复合到纳米复合的发展历程。通过对具有重要理论意义和应用价值的聚合物／层状硅酸盐（PLS）纳米复合材料制备过程热力学驱动力的考察以及制备原理的分析,我们首次从理想状态下推导出了能在一定范围内预测聚合物相对分子质量与层状硅酸盐含量,层状硅酸盐片层间距与层状硅酸盐含量以及层状硅酸盐片层间距与聚合物相对分子质量关系的理论公式,并用文献中的实验数据进行了验证。结果表明这些理论关系与文献中的实验数据精确吻合。     

熔融插层法制备聚合物/黏土纳米复合材料研究进展

对国内外熔融插层法制备聚合物／黏土纳米复合材料(PCN)的研究进展进行了介绍。介绍了影响PCN结构形态的几种因素;对熔融插层法制备PCN的热力学、动力学的研究进行了总结;介绍了熔融插层的机理和几种理论模型。并对聚合物／黏土纳米复合材料的开发及应用前景作出了展望。     

Continuous process for melt intercalation of PP–clay nanocomposites with aid of power ultrasound

A continuous ultrasound‐assisted process using a single screw extruder with an ultrasonic attachment was developed to prepare PP/clay nanocomposites of varying clay concentrations. The feed rate that controlled the residence time of the polymer in the ultrasonic treatment zone was varied. Die pressure and power consumption were measured. Rheological properties, morphology, and mechanical properties of the untreated and ultrasonically treated nanocomposites were studied. An intercalation of polymer molecules into clay galleries and a partial exfoliation, which occur at short residence times (of the order of seconds), were observed as evident from measurements by X‐ray diffraction and transmission electron microscopy. The obtained results indicate a possibility of the rapid intercalation and partial exfoliation of PP/clay nanocomposites without the matrix being chemically modified. J. VINYL. ADDIT. TECHNOL. 12:78–82, 2006. © 2006 Society of Plastics Engineers.