Characterization and preparation of new multiwall carbon nanotube/conducting polymer composites by in situ polymerization

Composites based on poly(diphenyl amine) (PDPA) and multiwall carbon nanotubes (MWNTs) were prepared by chemical oxidative polymerization through two different approaches: in situ polymerization and intimate mixing. In in situ polymerization, DPA was polymerized in the presence of dispersed MWNTs in sulfuric acid medium for different molar composition ratios of MWNT and DPA. Intimate mixing of synthesized PDPA with MWNT was also used for the preparation of PDPA/MWNT composites. Transmission electron microscopy revealed that the diameter of the tubular structure for the composite was 10–20 nm higher than the diameter of pure MWNT. Scanning electron microscopy provided evidence for the differences in the morphology between the MWNTs and the composites. Raman and Fourier transform IR (FTIR) spectroscopy, thermogravimetric analysis, X‐ray diffraction, and UV–visible spectroscopy were used to characterize the composites and reveal the differences in the molecular level interactions between the components in the composites. The Raman and FTIR spectral results revealed doping‐type molecular interactions and coordinate covalent‐type interactions between MWNT and PDPA in the composite prepared by in situ polymerization and intimate mixing, respectively. The backbone structure of PDPA in the composite decomposed at a higher temperature (>340°C) than the pristine PDPA (～300°C). This behavior also favored the molecular level interactions between MWNT and PDPA in the composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3721–3729, 2006     

PROBING HIDDEN POLYMERIC INTERFACES USINGIR-VISIBLE SUM-FREQUENCY GENERATION SPECTROSCOPY

Understanding the molecular-level processes underlying interfacial phenomena is important in the area of adhesion. We briefly introduce IR-visible sum-frequency generation spectroscopy (SFG) using a total-internal-reflection geometry for the study of polymer-air, polymer-solid, and polymer-polymer interfaces. The following examples, predominantly of work done in our lab, illustrating differences in molecular structure and dynamic properties at interfaces are presented: the air- and solid-interface structure of an amorphous polystyrene (PS) and a semicrystalline polymer with side-chain crystallinity, poly(octadecyl acrylate) (PA-18); structure of a polymer-polymer interface between thin films of a semicrystalline polymer with side-chain crystallinity, poly(vinyl-N-octadecylcarbamate- co-vinyl acetate), and an amorphous PS; thermal order-to-disorder transitions of the air and solid interface of PA-18, and the interface of this polymer with PS; and dynamic surface-relaxation studies of a rubbed PS film.     

Preparation of rechargeable lithium batteries with poly(methyl methacrylate) based gel polymer electrolyte by <Emphasis Type="Italic">in situ</Emphasis>γ-ray irradiation-induced polymerization

An admixture of commercial liquid electrolyte (LB302, 1 M solution of LiPF₆ in 1:1 EC/DEC) and methyl methacrylate (MMA) was enclosed in CR2032 cells. The assembled cells were then -ray-irradiated using configurations of half cells and full cells. Through this in situ irradiation polymerization process, we obtained rechargeable lithium ion cells with poly(methyl methacrylate) (PMMA) based gel polymer electrolytes (GPE). Galvanostatic cycling, AC impedance spectroscopy, and cyclic voltammetry were employed to investigate the electrochemical properties of the cells and the gel polymer electrolyte. This PMMA-based gel polymer electrolyte was found to exhibit a high ionic conductivity (at least 10^–3 S cm^–1) at room temperature. Due to a significant increase in the charge transfer resistance between the GPE and the cathode, the cell impedance of a PMMA-based lithium ion cell is greater than that of a liquid-electrolyte-based cell. The discharge capacity of a LiNi_0.8Co_0.2O₂/GPE/graphite is approximately 145 mAh g^–1 for the first cycle and decreases to123 mAh g^–1 after 20 cycles. In addition, a large initial cell impedance (LICI) was observed in the irradiated positive half cell. In this paper, we propose a possible mechanism related to the detachment of the PMMA layer from the lithium electrode. This detachment of the PMMA layer from the lithium electrode has not been explicitly discussed previously.     

Rheological,mechanical, and morphological studies of epoxy/poly(methyl methacrylate) semi‐interpenetrating polymer networks

Semi‐interpenetrating polymer networks (semi‐IPNs) of epoxy resin and poly(methyl methacrylate) (PMMA) were synthesized. Methyl methacrylate (MMA) was polymerized by free radical mechanism with azo‐bis‐isobutyronitrile in the presence of oligomeric epoxy resin (DGEBA), and hexahydrophthalic anhydride as crosslinking agent. The gelation and vitrification transitions during cure/polymerization processes have been examined using parallel‐plates rheological technique. From differential scanning calorimetry and rheological techniques, it was suggested that both curing and polymerization processes occur simultaneously. However, the gelation time was longer for the semi‐IPN than those observed for the cure of pure DGEBA or polymerization of MMA. The gelation time increased significantly when 5% of MMA was employed, suggesting a diluent effect of the monomer. Higher amount of MMA resulted in a decrease of gel time, probably because of the simultaneous polymerization of MMA during the curing process. Structural examination of the semi‐IPNs, using scanning electron microscopy, revealed phase separation in nanoscale size for semi‐IPNs containing PMMA at concentrations up to 15%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of nano‐silica filler on the rheological and morphological properties of polypropylene/liquid‐crystalline polymer blends

A fumed hydrophilic nano‐silica‐filled polypropylene (PP) composite was blended with a liquid‐crystalline polymer (LCP; Rodrun LC5000). The preblended polymer blend was extruded through a capillary die; this was followed by a series of rheological and morphological characterizations. The viscosity of the PP matrix increased with the addition of the hydrophilic nano‐silica. At shear rates between 50 and 200 s^?1, the composite displays marked shear‐thinning characteristics. However, the incorporation of LC5000 in the PP composite eliminated the shear‐thinning characteristic, which suggests that LC5000 destroyed the agglomerated nano‐silica network in the PP matrix. Although the viscosity ratio of LCP/PP was reduced after the addition of nano‐silica fillers, the LCP phases existed as droplets and ellipsoids. The nano‐silicas were concentrated in the LC5000 phase, which hindered the formation of LCP fibers when processed at high shear deformation. We carried out surface modification of the hydrophilic nano‐silica to investigate the effect of modified nano‐silica (M‐silica) on the morphology of the PP/LC5000 blend system. Ethanol was successfully grafted onto the nano‐silica surface with a controlled grafting ratio. The viscosity was reduced for PP filled with ethanol‐M‐silica when compared to the system filled with untreated hydrophilic nano‐silica. The LC5000 in the (PP/M‐silica)/LC5000 blend existed mainly in the form of fibrils. At high shear rates (e.g., 3000 s^?1), the LC5000 fibril network was formed at the skin region of the extrudates. The exclusion of nano‐silica in the LC5000 phase and the increased viscosity of the matrix were responsible for the morphological changes of the LCP phase. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1484–1492, 2003     

Phase separation in polymer blends comprising copolymers: 6. Effect of molecular architecture of block copolymers

To study the effect of the molecular architecture of a copolymer on its miscibility with corresponding homopolymers a series of block copolymers of styrene and isoprene with diblock, triblock and four-arm star architectures have been prepared and the morphologies of the blends of the copolymers and polyisoprene with different molecular weights have been examined by electron microscopy. The results show that miscibility varies in the sequence diblock>triblock>four-arm star copolymers. This sequence is in the opposite direction to the variation of the architectural complexity of the block copolymers, i.e. the more complex is molecular architecture, the greater is conformation restriction in microdomain formation and the less is solubility of homopolymer in corresponding domains.     

Capture of gypsy moth,Lymantria dispar (L.), andLymantria mathura (L.) males in traps baited with disparlure enantiomers and olefin precursor in the People's Republic of China

Pheromone traps baited with (+)-disparlure,cis-7,8-epoxy-2methyocta-decane, captured males ofLymantria dispar, L. monacha, andL. mathura in northeastern People's Republic of China.L. dispar responded to the addition of olefin to (+)-disparlure-baited traps in a negative doseresponse manner. Observations on site and seasonal capture ofL. dispar andL. mathura are discussed.Lepidoptera: Lymantriidae.     

(Z)-4-氯-2-羟亚胺基乙酰乙酸乙酯的合成

采用4-氯乙酰乙酸乙酯为原料,对(Z)-4-氯-2-羟亚胺基乙酰乙酸乙酯的合成条件进行了研究,确定了优化条件:反应温度5℃、反应时间4h、亚硝酸乙酯气体与4-氯乙酰乙酯的摩尔比n(ONOC2H5)∶n(ClCH2COCH2CO2C2H5)=1.4∶1。优化条件下产物收率约96%。     

纳米稀土复合固体超强酸催化合成乙酸苄酯

采用共沉淀法制备了纳米稀土复合固体超强酸SO4^2-／ZrO2-2％Nd2O3催化剂，电镜分析表明，催化剂颗粒直径在25nm左右，比表面积测定：71．03m^2／g。酸强度-12．70〈Ho〈-11．99。并对合成乙酸苄酯的最佳反应条件进行了研究。研究表明：当苯甲醇与乙酸的物质的量比为1：2，反应时间为5h，反应温度为120℃，催化剂用量为6％苯甲醇的质量时，酯化率可达92．04％。研究发现，该催化剂可重复使用并可活化再生。     

用玻璃球负载纳米级SO4^2-／TiO2固体超强酸催化合成乙酸正丁酯

用玻璃球负载纳米级SO42-/TiO2固体超强酸催化合成乙酸正丁酯,对催化剂的制备条件和乙酸正丁酯的合成条件进行了研究。在最佳反应条件下,乙酸的转化率为99.3%,催化剂重复使用8次后乙酸的转化率仍高达92.3%。该催化剂选择性好,未发现有副产物生成,看来具有较好的应用前景。