熔融插层法制备累托石/聚碳酸亚丙酯纳米复合材料的研究

采用熔融插层法制备了有机化累托石/聚碳酸亚丙酯纳米复合材料,通过X射线衍射、原子力显微镜、热重分析法测试了复合材料的结构与热性能。结果表明:聚碳酸亚丙酯能插层于累托石片层中,累托石/聚碳酸亚丙酯纳米复合材料的耐热性有了很大程度的提高。     

PVC/黏土纳米复合材料研究进展

文章简要概述了黏土的有机改性机理,聚氯乙烯/黏土纳米复合材料的特性及其制备方法、结构与表征方面的研究进展。对熔融插层共混法、溶液插层共混法、原位聚合法和插层聚合法进行了介绍和比较,对聚氯乙烯/黏土纳米复合材料的重点研究领域和发展趋势提出了具有前瞻性的预测。     

Poly(propylene)/Clay Nanocomposites Prepared by Reactive Compounding with an Epoxy Based Masterbatch

Summary: Poly(propylene) (PP)/clay nanocomposites have been prepared via a novel reactive compounding approach, in which an epoxy based masterbatch consisting of 20 wt.‐% clay was introduced to poly(propylene) with the aid of a maleic anhydride grafted PP (MAPP). The masterbatch was prepared using a recently developed “slurry compounding” technique. After melt compounding, most clay particles have been exfoliated and dispersed into small stacks with several clay layers. WAXD data shows that the dispersion of clay is better at low clay content or high MAPP content. Due to the novelty of the preparation process and complication of the system, the tensile properties of nanocomposites exhibit some unique tendencies with varying the content of MAPP or masterbatch. It is believed that the yield strength and Young's modulus can be dramatically improved after minimizing the excess of unreacted epoxy and optimizing the dispersion of clay.

TEM micrograph of PP/clay nanocomposites prepared with epoxy based masterbatch.     

Preparation and Characterization of Polycarbonate/Poly(propylene)/Attapulgite Ternary Nanocomposites with the Morphology of Encapsulation

Summary: Ternary nanocomposites based on polycarbonate (PC), poly(propylene) (PP), and attapulgite (AT) were prepared via the method of two‐step melt blending, by which the AT was blended with PP prior to compound with PC. Structure and properties of the ternary PC/PP/AT nanocomposites were investigated. The degradation of PC triggered by AT during direct blending process can be inhibited effectively by using two‐step melt blending. It was found that the morphology of encapsulation structure like sandbag was formed in PC matrix, where PP encapsulated AT fibrillar single crystals. DSC experiments showed that in PC/PP/AT ternary nanocomposites, AT had a strong heterophase nucleation effect on PP, resulting in the enhancement of crystallization degree and the crystallization temperature of PP. DMA and mechanical property results showed that the ternary nanocomposites exhibited good balanced toughness and stiffness.

TEM photograph of PC/PP/AT ternary nanocomposite.     

聚甲基乙撑碳酸酯/乙烯-乙烯醇共聚物/黏土复合材料的流变性能与阻透性能

采用熔融共混的方法制备了聚甲基乙撑碳酸酯(PPC)/黏土和PPC/乙烯-乙烯醇共聚物(EVOH)/黏土纳米复合材料,测试了复合材料的流变性能和阻氧性能,并对其微观形态进行了分析。结果表明,当基材PPC相对分子质量较高时,PPC/黏土复合材料的复数黏度、储能模量和耗能模量也较高;随着黏土和相容剂马来酸酐接枝聚乙烯（PE-g-MAH）的添加, PPC/EVOH复合材料的复数黏度和模量明显增加,PE-g-MAH的加入使PPC、EVOH和黏土之间的界面作用力增强,改善了PPC与EVOH的相容性,同时提高了PPC/EVOH复合材料的阻氧性能。     

Physical Properties of Isotactic Poly(propylene)/Silver Nanocomposites: Dynamic Crystallization Behavior and Resultant Morphology

Summary: The presence of silver nanoparticles (0.01–5 wt.‐%) increased the crystallization temperature of isotactic poly(propylene) (iPP) (e.g., a 5 wt.‐% content increases the temperature by ca. 7 °C) and produced a sharper crystalline peak. It had little effect on the melt rheology of the nanocomposites. The shear‐induced crystallization behavior of iPP was accelerated with increasing Ag content and imposed frequency. In addition, the promoting effect of Ag nanoparticles on the overall crystallization behavior was more notable at 140 °C than at 130 °C. The wide‐angle X‐ray diffraction scans of iPP nanocomposites with 5 wt.‐% Ag crystallized at 130 °C clearly presented another peak at a 2θ value of 15.8°, which corresponded to a β‐form crystal. The nanocomposites with 5 wt.‐% Ag crystallized at 130 °C gave double melting peaks at 154 and 166 °C. On the other hand, the samples crystallized at 140 °C produced two melting peaks at 166 and 172 °C. The introduction of as much as 0.1 wt.‐% of Ag nanoparticles increased both the tensile strength and elongation at break, but subsequent further addition caused a decrease. In addition, iPP nanocomposites with more than 1 wt.‐% Ag exhibited a higher modulus than pure iPP.

Time dependence of G′ of iPP and iPP/Ag nanocomposites at 130 °C at ω = 1 rad · s^?1.     

碳酸钙改性聚碳酸亚丙酯研究

利用双螺杆挤出机研究了分别填充不同表面改性的碳酸钙后对聚碳酸亚丙酯片材专用料(PPC101)性能的影响。结果表明:随着碳酸钙(CaCO3)用量的增加,试样的维卡软化温度皆呈上升趋势,未进行表面处理的碳酸钙填料对PPC101维卡软化温度的提高更明显;填料是否进行表面处理对PPC101材料的拉伸性能影响不大,随着填料用量的增加,未进行表面处理和硬脂酸处理的碳酸钙填充PPC101材料的拉伸强度均呈先上升后基本稳定的趋势,而使用铝酸酯的碳酸钙填充PPC101材料的拉伸强度几乎不变;随着填料用量的增加,无论填料是否进行表面改性,试样的冲击强度和熔体质量流动速率均呈下降趋势;而且密度均呈线性上升趋势。     

Investigation on the microstructure and the electric property of poly(propylene)/chlorinated poly(propylene)/poly(aniline) composites

The article presents results of studies on composites made from poly(propylene) (PP) modified with poly(aniline) (PANI) doped with dodecylbenzene sulfonic acid (DBSA) and chlorinated poly(propylene) (CPP). The volume resistivity of PP/CPP/PANI composites was detected, and the results show that the volume resistivity decreases with increasing CPP content, and there exists a minimum volume resistivity. Effects of CPP on the microstructure and crystalline structure of the PP/CPP/PANI composites and the relationship between the effects and the electric property were carefully analyzed by scanning electron microscope (SEM) and wide angle X‐ray diffraction (WAXD). The method that the specimens of SEM are polished is appropriate to investigate the morphology of conducting polymer composites. The obtained results illuminate that the area of conducting parts and insulating parts obtained from the digital analysis of the SEM image is obviously influenced by the CPP content, the parameters of the lamellar‐like structure are immediately related to CPP content and denote the dispersion of PANI‐DBSA, and the percent crystallinity and mean crystal size of PP are directly correlated with the CPP content. The increasing area of conducting parts, the increasement of layer distance, the decreasement of size and layer number of the lamellar‐like structure of PANI‐DBSA, and the increasement of the percent crystallinity and mean crystal size of PP are beneficial to the improvement of the conductive property of PP/CPP/PANI composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Factors Effecting the Performance of Montmorillonite/Magnesium Hydroxide/Poly(propylene) Ternary Composites, 1

A two‐level factorial experimental design was used to examine the combined effects of o‐MMT gallery polarity, surface modification of MDH, MA‐g‐PP and antioxidant addition, together with processing variables, on the burning behaviour and thermal stability of ternary composites based on PP, MDH and o‐MMT. Regression equations highlighted the detrimental effect of o‐MMT intercalants and possible improvement in the dispersion of o‐MMT at higher MDH levels. A polar gallery environment (providing quat OH groups) led to increased char formation, and MA‐g‐PP combined with o‐MMT led to a higher oxidation onset temperature. Addition of o‐MMT to PP/MDH composites can lead to a reduction in the level of MDH required for effective flame retardation.

     

Non‐Ionic,Poly(ethylene oxide)‐Based Surfactants as Intercalants/Dispersants/Exfoliants for Poly(propylene)‐Clay Nanocomposites

Summary: Poly(propylene) (PP)‐clay nanocomposites were prepared from unmodified montmorillonite clays (NaMMT), with poly(ethylene oxide)‐based nonionic surfactants as dispersants/intercalants/exfoliants. The primary objective of this research was to find dispersants that (a) allow PP nanocomposites to be formed by direct melt mixing; (b) are effective with unmodified clays and (c) comprise of only a minor component with respect to both the clay and the overall composition. Linear, branched, gemini and sugar‐based surfactants and structures containing poly(dimethyl siloxane) and poly(methyl methacrylate) blocks were examined. These additives were found to be effective in breaking down the clay agglomerates to tactoids, giving some expansion of the clay structure and partial exfoliation and providing substantially improved clay dispersion. The properties of the derived nanocomposites depend on the level of additive and its structure. Tensile and impact properties show significant improvement over the precursor PP. Also notable are the significantly better thermal and thermo‐oxidative stabilities, as compared to both PP and “clay alone” composites. For optimal properties, it is both necessary and desirable that the surfactant should only be a minor constituent (20–50%) of the composition, with respect to the clay. A preferred surfactant is linear PE‐block‐PEO, with a short PEO block and an alkyl chain with approximately 30 carbon atoms (C₃₀).

     

改性碳酸钙用于聚氯乙烯的研究

研究了一种改性碳酸钙的性质及其在聚氯乙烯中的应用情况。研究结果表明,这种改性碳酸钙与普通碳酸钙相比,具有吸油值低、堆积密度大、分散性好、热稳定性高等特点。填充于聚氯乙烯中,不仅能改善物料的加工性能及制品的物理力学性能,而且还具有较高的热稳定性能。     

蒙脱石有机化对PVA/蒙脱石复合薄膜的性能影响

以精制钠基蒙脱石(Na-MMT)、有机化蒙脱石(OMMT)和聚乙烯醇(PVA)为原料,通过水溶液插层-流延成膜法制备纳米复合薄膜。通过X射线衍射(XRD)、扫描电子显微镜(SEM)和热重分析(TGA)对复合材料的结构和性能进行表征,重点探讨蒙脱石有机化对PVA/MMT复合薄膜性能的影响。结果表明Na-MMT和OMMT纳米颗粒在PVA基体中均得到了良好分散;有机改性剂的存在促使PVA/MMT复合薄膜的MMT片层间距扩撑更大,但由于其与PVA相容性较差,导致有效插入MMT片层间的PVA分子较少,PVA/MMT复合薄膜的热稳定性改善效果不明显。     

Thermal Behavior of Isotactic Poly(propylene)/Maleated Poly(propylene) Blends

This paper analyzes the thermal and thermo‐oxidative degradation behavior, phase separation, melting, and crystallization of blends consisting of isotactic poly(propylene) (IPP) and poly(propylene) grafted with maleic anhydride (PP‐g‐MA). It has been established that, depending on the blend composition and crystallization/preparation procedure, the blends of IPP and PP‐g‐MA can either co‐crystallize or evidence phase separation. This conclusion has been attained by comparing the DSC results of crystallization under dynamic and isothermal conditions with X‐ray diffraction results. On the basis of the obtained results, the optimum mixing ratios have been established as 95–85 wt.‐% IPP/5–15 wt.‐% PP‐g‐MA. Thermo‐oxidative behavior has been studied by thermogravimetry and differential thermal analysis.

     

Isotactic Poly(propylene) Nanocomposites Based upon Boehmite Nanofillers

The influence of boehmite crystallite sizes, varied between 10 and 60 nm, was studied with respect to the morphology development, crystallization behavior and mechanical properties of the boehmite‐based iPP nanocomposites. The nanometer‐scaled boehmites were formed during twin‐screw melt extrusion of iPP at 200 °C. Even in the absence of polymer compatibilizers, the boehmites, obtained from Sasol's process, enabled very effective deagglomeration and in‐situ dispersion of nanoboehmites. With increase in boehmite crystallite size it was possible to improve simultaneously stiffness and impact strength of iPP. As evidenced by means of DSC, POM and WAXS measurements, the deagglomerated nanoboehmites nucleated crystallization of poly(propylene)'s α‐modification.

     

Electrical,Thermal, and Mechanical Characterization of Poly(propylene)/Carbon Nanotube/Clay Hybrid Composite Materials

A set of hybrid composite materials based on a PP matrix with multiwalled CNTs and clay particles is prepared and characterized. The incorporation of clay particles into a percolated composite with 3 wt% CNT disrupts the percolation, decreasing dramatically the electrical conductivity. As expected for layered fillers, PP/CNT/clay hybrid composite materials and PP/clay composites display increases as high as 100 °C in the temperature for the maximum rate of weight loss. Surprisingly, these temperatures are just slightly higher than those of PP/CNT composites. PP/CNT composites display viscosities that are considerably lower than those of PP/clay composites. A synergistic effect of both fillers is observed in the viscoelastic response of PP/CNT/clay materials.

     

Poly(propylene)/Carbon Nanofiber Nanocomposites: Ex Situ Solvent‐Assisted Preparation and Analysis of Electrical and Electronic Properties

CNF‐reinforced PP nanocomposites were fabricated from CNFs dispersed in a boiling PP/xylene solution. Their thermal properties were characterized by TGA and DSC and shown to exhibit improved thermal stability and higher crystallinity. They were further processed into thin films by compression molding. The electrical conductivity and dielectric property of the PP/CNF nanocomposite thin films were studied. Both electric conductivity and real permittivity increased with increasing fiber loading. Electrical conductivity percolation is observed between 3.0 and 5.0 wt.‐% fiber loading. The rheological behavior of the nanocomposite melts were also investigated. It was found that a small fiber concentration affects the modulus and viscosity of PP melt significantly.

     

Synthesis and characterization of poly(propylene)/montmorillonite nanocomposites by simultaneous grafting‐intercalation

A novel process for the preparation of poly(propylene)/montmorillonite (PP/MMT) nanocomposites was developed via simultaneous solution grafting‐intercalation in the presence of a reactive ammonium cation that can be grafted onto poly(propylene). Partially introducing this reactive cation into long alkyl ammonium modified MMT interlayers can transfer a conventional microcomposite into intercalated/exfoliated nanocomposites, which was evidenced by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The PP chains were tethered onto the clay surface through the bridge of the reactive ammonium cations, which can be characterized by FTIR. The bridged chemical bonding also results in a good interface adhesion between PP and MMT, as confirmed by SEM investigation. The enhanced thermal properties of PP/MMT nanocomposites were characterized by thermogravimetric analysis. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1018–1023, 2004     

The Effect of γ‐Irradiation on the Structure and Properties of Poly(propylene)/Clay Nanocomposites

The oxidative degradation of PP/OMMT nanocomposites under γ‐irradiation was studied. Changes in structure and properties resulting from γ‐exposure in the range 0–100 kGy were investigated. The results were analyzed by comparing the influence of PP‐g‐MA and pristine OMMT on the oxidation kinetics of neat PP. γ‐Irradiation in the presence of air strongly degraded the properties of PP materials, particularly for radiation doses above 20 kGy. The rate of oxidative degradation of PP/OMMT/PP‐g‐MA nanocomposites was much faster than that of neat PP. This suggests that PP‐g‐MA and pristine OMMT components behave as oxidation catalysts, leading to the formation of free radicals in the polymer matrix.

     

聚乳酸/乙烯-醋酸乙烯酯共聚物/碳酸钙复合材料的性能研究

采用熔融共混法制备了聚乳酸/乙烯-醋酸乙烯酯共聚物/碳酸钙（PLA/EVA/CaCO3）复合材料,利用差示扫描量热仪、X射线衍射仪、偏光显微镜、扫描电子显微镜、力学性能测试和热变形温度测试等手段,研究了EVA和CaCO3对复合材料的结晶性能、断面形貌、力学性能和耐热性能的影响。结果表明,EVA 具有增韧作用,但降低了复合材料的强度和耐热性;而CaCO3可以提高复合材料的强度、韧性、结晶性能和耐热性能;CaCO3与EVA的加入对PLA有协同增韧作用,且不改变PLA的晶型;当PLA/EVA=90/10,加入10 %（质量分数,下同）的CaCO3时,复合材料有最佳的综合性能。     

Impact,Thermal, and Morphological Properties of Poly(Lactic Acid)/Poly(Methyl Methacrylate)/Halloysite Nanotube Nanocomposites

Poly(lactic acid)/poly(methyl methacrylate) blends containing halloysite nanotube (2 and 5 phr) and epoxidized natural rubber (5–15 phr) were prepared by melt mixing. The impact strength of poly(lactic acid)/poly(methyl methacrylate) blend was slightly improved by the addition of halloysite nanotube. Adding epoxidized natural rubber further increased the impact strength of poly(lactic acid)/poly(methyl methacrylate)/halloysite nanotube nanocomposite. Single T_g of poly(lactic acid)/poly(methyl methacrylate) is observed and this indicates that poly(lactic acid)/poly(methyl methacrylate) blend is miscible. The addition of halloysite nanotube into poly(lactic acid)/poly(methyl methacrylate) slightly increased the T_g of the blends. The epoxidized natural rubber could encapsulate some of the halloysite nanotube and prevent the halloysite nanotube from breaking into shorter length tube during the melt shearing process.