Graphite oxide/poly(methyl methacrylate) nanocomposites prepared by a novel method utilizing macroazoinitiator

Graphite oxide (GO)/poly(methyl methacrylate) (PMMA) nanocomposites were prepared by a novel method utilizing macroazoinitiator (MAI). The MAI, which has a poly(ethylene oxide) (PEO) segment, was intercalated between the lamellae of GO to induce the inter-gallery polymerization of methyl methacrylate (MMA) and exfoliate the GO. The morphological, conductivity, thermal, mechanical and rheological properties of these nanocomposites were examined and compared with those of intercalated nanocomposites prepared by polymerization with the normal radical initiator, 2,2′-azobisisobutyronitrile. The improvement in conductivity by GO was more evident in exfoliated nanocomposites compared to that of intercalated nanocomposites. For example, a conductivity of 1.78 × 10⁻⁷ S/cm was attained in the exfoliated nanocomposite prepared with 2.5 parts GO per 100 parts MMA, which was about 50-fold higher than that of the intercalated nanocomposite. The thermal, mechanical and rheological properties also indicate that thin GO with a high aspect ratio is finely dispersed and effectively reinforced the PMMA matrix in both exfoliated and intercalated nanocomposites.     

Novel polyacrylonitrile/Na-MMT/silica nanocomposite: Co-incorporation of two different form nano materials into polymer matrix

Polyacrylonitrile (PAN)/Na-montmorillonite (Na-MMT)/SiO₂ nanocomposites were synthesized via in-situ emulsion polymerization. The X-ray diffraction (XRD) measurements and transmission electron microscopy (TEM) observations show that the Na-MMT layers were exfoliated in polymerization and the nano materials are well dispersed in the polymer matrix. The thermogravimetric analysis (TGA) suggests that co-incorporating Na-MMT and SiO₂ into the polymer matrix significantly enhances the thermal stability of the polymer. At same nano material loading, the PAN/Na-MMT/SiO₂ nanocomposites show superior thermal stability with respect to the PAN/Na-MMT and PAN/SiO₂ nanocomposites. The mechanical properties of the nanocomposites were also examined. It was found that the PAN/Na-MMT/SiO₂ nanocomposites exhibit considerably enhanced moduli compared with the PAN/Na-MMT and PAN/SiO₂ nanocomposites due to the synergistic reinforcing effect.     

钠基与钙基蒙脱石插层牛血清白蛋白的比较研究

蒙脱石负载蛋白质的研究为纳米复合材料开发、药物的负载与缓释等方面研究奠定基础.为了进一步分析蒙脱石不同结构对蛋白质插层蒙脱石的影响,作者根据离子交换的原理,研究了在不同pH值条件下,牛血清白蛋白(BSA)插层钠、钙基蒙脱石的插层效果.研究发现,在pH值低于等电点时,钙基蒙脱石(Ca-MMT)与钠基蒙脱石(Na-MMT)插层效果差异明显;相同pH值下,Na-MMT插入的蛋白质比例高.FT-IR和UV-vis分析都显示蒙脱石颗粒的存在改变了蛋白质的结构;UV-vis分析显示,由于蒙脱石表面助色基作用,共轭效应加强,上清液中的蛋白质214nm吸收峰,产生了明显的红移;氢键等的破坏则导致蛋白质部分螺旋结构消失而使蒙脱石层间缓释出来的蛋白质吸收峰发生明显的蓝移.Ca-MMT与Na-MMT对牛血清白蛋白结构变化的作用程度存在差别.     

An in vitro investigation of the PEMA/THFMA system using chondrocyte culture

Adult articular cartilage has a limited capacity for self-repair and a biomaterial to aid the process would be ideal. The polymer system, poly(ethyl methacrylate)/tetrahydrofurfuryl methacrylate (PEMA/THFMA) has shown potential in a rabbit model for such a role. The ability of the polymer system to support chondrocytes in vitro was investigated by light microscopy, transmission electron microscopy and biochemical assays. The PEMA/THFMA system maintained chondrocytes in agarose in a viable state with more glycosaminoglycan (GAG) produced per unit DNA after 14 days in culture compared to the tissue culture plastic control. Chondrocytes remained rounded on the polymer system surface as opposed to well spread on the Thermanox. The PEMA/THFMA system has been shown to be biocompatible for bovine chondrocytes maintaining them in a differentiated state with enhanced GAG production.     

Characterization of fatigue resistance in photochromic composite materials for 3D rewritable optical memory applications

Fatigue resistance of the photochromic diarylethene molecules 1,2-bis[2-methylbenzo[b]thyophen-3-yl]-3,3,4,4,5,5-hexafluoro-1-cyclopentene embedded in three different acrylic polymers is studied upon multiple coloration–decoloration cycles. The resistance to photofatigue is found to be different in the three polymeric materials when one-photon excitation was used for the reversible photoconversion experiment. In particular, the photochromic molecules lose their photoisomerization ability faster if they are embedded in poly(methyl methacrylate) (PMMA) with respect to poly(ethyl methacrylate-co-methyl acrylate) (PEMMA) and poly(ethyl methacrylate) (PEMA). We propose several explanations based on the physico-chemical properties of the matrix and of the photochromic molecules. In the case of two-photon excitation, which is necessary for 3D optical writing, the fatigue resistance is found to be poorer than in the one-photon case. The accelerated photodegradation can be assigned to the non-linear nature of interaction between the polymeric composite material and light.     

四臂双亲性PEMA-b-PMAA嵌段共聚物的合成

由2-溴异丁酰溴和季戊四醇反应合成了四臂引发剂,以CuCl为催化剂,N,N,N′,N″,N″-五甲基二亚乙基三胺（PMDETA）为配体,在N,N-二甲基甲酰胺（DMF）中分步引发甲基丙烯酸乙酯（EMA）和甲基丙烯酸叔丁酯（tBMA）进行原子转移自由基聚合（ATRP）,得到了四臂型嵌段共聚物PEMA-b-PtBMA。改变...     

PEMA/PEA自交联乳胶IPN阻尼材料的研究

利用种子乳液聚合和双丙酮丙烯酰胺与己二酰肼的交联反应合成了PEM A/PEA乳胶IPN。DM S结果表明,组成比对L IPN的相容性和阻尼性能有显著的影响;组成比为35/65的L IPN具有较优异的阻尼性能;界面自交联能改善组分相容性,但使材料的阻尼性能有所下降。拉伸实验结果表明,增加硬组分和交联剂的含量,拉伸强度显著增加。     

In vitro drug release study of methacrylate polymer blend system: effect of polymer blend composition,drug loading and solubilizing surfactants on drug release

The application of polymers as the drug delivery systems for treating oral infections is a relatively new area of research. The present study was to test the release of the antibacterial drug chlorhexidine diacetate (CHDA), the antifungal drug Nystatin (NYS) and the antiviral drug acyclovir (ACY) from polymer blends of poly(ethyl methacrylate) and poly(n-hexyl methacrylate) of different compositions. The effects of polymer blend composition, drug loading and solubilizing surfactants on the release of the drugs have been studied. Measurements of the in vitro rate of drug release showed a sustained release of drug over extended periods of time. Drug release rates decreased with increasing PEMA content in polymer blends. CHDA release rates increased steadily with increasing drug load. The drug release rates increased with the addition of surfactants. This study demonstrates that the three therapeutic agents show a sustained rate of drug release from polymer blends of PEMA and PHMA over extended periods of time. By varying polymer blend compositions as well as the drug concentration (loading), it is possible to control the drug release rates to a desired value. The drug release rate is enhanced by addition of surfactants that solubilize drugs in the polymer blends.     

Morphology,thermal and mechanical properties of PVC/MMT nanocomposites prepared by solution blending and solution blending + melt compounding

Two types of montmorillonite (MMT), natural sodium montmorillonite (Na-MMT) and organically modified montmorillonite (OMMT), in different amounts of 1, 2, 5, 10 and 25 phr (parts per hundred resin), were dispersed in rigid poly (vinyl chloride) by two different methods: solution blending and solution blending + melt compounding. The effects on morphology, thermal and mechanical properties of the PVC/MMT nanocomposites were studied by varying the amount of Na-MMT and OMMT in both methods. SEM and XRD analysis revealed that possible intercalated and exfoliated structures were obtained in all of the PVC/MMT nanocomposites. Thermogravimetric analysis revealed that PVC/Na-MMT nanocomposites have better thermal stability than PVC/OMMT nanocomposites and PVC. In general, PVC/MMT nanocomposites prepared by solution blending + melt compounding revealed improved thermal properties compared to PVC/MMT nanocomposites prepared by solution blending. Vicat tests revealed a significant decrease in Vicat softening temperature of PVC/MMT nanocomposites prepared by solution blending + melt compounding compared to unfilled PVC.     

Temperature gradient interaction chromatography and MALDI-TOF mass spectrometry analysis of stereoregular poly(ethyl methacrylate)s

Temperature gradient interaction chromatography (TGIC) was applied for the separation of stereoregular poly(ethyl methacrylate) (PEMA) according to the tacticity. The three PEMA samples with differing tacticity (rr triad content 0, 53, and 91%) prepared by anionic polymerization were used. C18 bonded silica and a mixture of CH2Cl2 and CH3CN (30/70, v/v) were used as stationary and mobile phase, respectively. TGIC was able to separate the PEMA samples, showing the increasing retention in the order of decreasing rr triad contents; however TGIC elution peaks of the three PEMAs were not fully resolved but, rather, were partially overlapped. To isolate the tacticity effect from the molecular weight effect on the TGIC retention, the PEMA samples were fractionated by TGIC, and the accurate molecular weight of the fractions was determined by MALDI-TOF mass spectrometry. The fractions showed a much narrower molecular weight distribution than the mother PEMAs. The TGIC fractions of similar molecular weight but with different tacticity were fully resolved by TGIC, but mother PEMAs were not. These results indicate that the retention in TGIC is affected by both tacticity and molecular weight.     

Effect of the molecular weight of poly(ethylene glycol) on the plasticization of green sheets composed of ultrafine BaTiO3 particles and poly(vinyl butyral)

The effect of the molecular weight (MW) of poly(ethylene glycol) (PEG) on the plasticization of poly(vinyl butyral) (PVB) binder in green BaTiO₃ sheets prepared with PEG with MW values of 400 and 1530 was investigated. The MW of PEG had a profound effect on the rheological properties of the suspension as well as the physical properties of the green sheet. The suspension viscosity decreased with decreasing MW of PEG for shear rates above 4 s⁻¹. PEG 400 gave rise to a higher degree of plasticization of the green sheet than PEG 1530. This was due to the reduction in hydrogen bonding between the vinyl alcohol units in the PVB binder in the green BaTiO₃ sheet, as identified by FT-IR spectroscopy. As the MW of the PEG decreased, the green BaTiO₃ sheets exhibited a lower glass transition temperature, and a noticeably more ductile behavior. These results indicate that the green sheets became more flexible due to a higher plasticizing effect. However, laminated green BaTiO₃ sheets prepared with PEG 1530 showed delamination defects that were observed at a cut surface, which arose because of the low plasticization. This suggests that PEG 1530 has limited utilization as a plasticizer for the BaTiO₃/PVB binder system.     

Poly(ethylene naphthalate)/clay nanocomposites based on thermally stable trialkylimidazolium-treated montmorillonite: thermal and dynamic mechanical properties

Thermally stable organically modified clays based on 1,3-didecyl-2-methylimidazolium (IM2C10) and 1-hexadecyl-2,3-dimethyl-imidazolium (IMC16) were used to prepare poly(ethylene naphthalate) (PEN)/montmorillonite (MMT) nanocomposites via a melt intercalation process. Examination by X-ray diffraction and transmission electron microscopy indicates that an intercalated nanocomposite was formed with IMC16-MMT, while unmodified MMT (Na-MMT) and IM2C10-MMT are generally incompatible with PEN. Thermogravimetric analysis reveals that the peak derivative weight loss temperature of the intercalated PEN/IMC16-MMT was more than 10 "C higher compared to neat PEN, PEN/Na-MMT, or PEN/IM2C10-MMT. Dynamic mechanical analysis also showed that a more significant improvement of the storage modulus was achieved in the better dispersed PEN/IMC16-MMT. The effect of annealing on the dynamic storage modulus of the hybrids is also investigated.     

UP/Na-MMT纳米复合材料的制备与性能

研究了UP／Na-MMT纳米复合材料的制备与性能，并考察了插层剂种类、有机蒙脱土加入量及离子交换量对复合材料性能的影响。结果表明，UP／Na-MMT纳米复合材料的XRD曲线中蒙脱土晶体结构的布拉格衍射峰已经消失，说明其晶层已被树脂撑开，达到纳米级分散；复合材料的耐热性能得到明显改善，其冲击强度和拉伸强度均有较大提高。     

Analysis of poly(ethyl methacrylate)s by on-line hyphenation of liquid chromatography at the critical adsorption point and nuclear magnetic resonance spectroscopy

Liquid chromatography at the critical adsorption point (LC CAP) with on-line NMR detection (on-line LC CAP NMR) was utilized for analysis of tacticity distribution of stereo-regular poly(ethyl methacrylate)s (PEMAs). The separation of a model PEMA sample composed of four constituents with similar molar masses (Mw = (14-16) x 10(3) g mol-1) differing in their tacticity (rr triad content = 0, 33, 68, and 89%) was achieved by LC CAP with a mixed eluent composed of acetone, acetone-d6, and cyclohexane. The tacticity composition within each peak eluted from the LC CAP column was directly determined by a 750-MHz 1H NMR spectrometer that was used as a real-time detector in the continuous-flow mode. Tacticity distribution in a particular PEMA sample with mm/mr/rr = 2/45/53 and narrow molar mass distribution of Mw/Mn = 1.05 has been revealed by the LC CAP NMR technique.     

Preparation and properties of nitrile rubber/montmorillonite nanocomposites via latex blending

The nitrile rubber (NBR)/unmodified montmorillonite (Na-MMT) clay nanocomposites were prepared by latex blending method followed by melt mixing of compounding ingredients by using two-roll mill. The X-ray diffraction (XRD) studies showed an increase in the basal spacing and broadening of peak corresponding to crystal structure of Na-MMT indicating the formation of intercalated/exfoliated clay layers in the NBR matrix. Increase in clay content of nanocomposite increased the XRD peak height due to the formation of many of clay tactoids at higher loading. The transmission electron microscopy (TEM) strengthened the XRD finding by showing the presence of intercalated/exfoliated morphology of clay platelets having good dispersion. The modulus and tensile properties of the nanocomposites were improved with addition of Na-MMT which is proportional to clay concentration. The retention of tensile properties of aged nanocomposites, with all clay concentration, was superior to either pure NBR and carbon black filled NBR composite. The dynamic mechanical analysis showed proportional increase in storage modulus analogous to Na-MMT loading at all the temperature ranges due to the confinement of polymer chains between the clay layers. Nanocomposites with different proportions of clay showed a decrease in tan δ_max peak height with a shift towards higher temperature indicating the reduction in the segmental mobility of polymer chain. A linear model was proposed to correlate the influence of Na-MMT content on storage modulus of nanocomposites. Differential scanning calorimetry indicated a linear increase in glass transition of nanocomposites which is proportional to clay loading. Thermogravimetric analysis revealed a small improvement in the thermal stability of nitrile rubber/clay nanocomposites.     

Effects of modified Clay on the morphology and thermal stability of PMMA/clay nanocomposites

The potential to improve the mechanical, thermal, and optical properties of poly(methyl methacrylate) (PMMA)/clay nanocomposites prepared with clay containing an organic modifier was investigated. Pristine sodium montmorillonite clay was modified using cocoamphodipropionate, which absorbs UVB in the 280–320 nm range, via ion exchange to enhance the compatibility between the clay platelets and the methyl methacrylate polymer matrix. PMMA/clay nanocomposites were synthesized via in situ free-radical polymerization. Three types of clay with various cation-exchange capacities (CEC) were used as inorganic layered materials in these organic–inorganic hybrid nanocomposites: CL42, CL120, and CL88 with CEC values of 116, 168, and 200 meq/100 g of clay, respectively. We characterized the effects of the organoclay dispersion on UV resistance, effectiveness as an O₂ gas barrier, thermal stability, and mechanical properties of PMMA/clay nanocomposites. Gas permeability analysis demonstrated the excellent gas barrier properties of the nanocomposites, consistent with the intercalated or exfoliated morphologies observed. The optical properties were assessed using UV–Visible spectroscopy, which revealed that these materials have good optical clarity, UV resistance, and scratch resistance. The effect of the dispersion capability of organoclay on the thermal properties of PMMA/clay nanocomposites was investigated by thermogravimetric analysis and differential scanning calorimetry; these analyses revealed excellent thermal stability of some of the modified clay nanocomposites.     

Physical aging behavior of the normal force and torque in polymer glasses

In prior work we reported results from torsion in stress relaxation experiments in which we measured simultaneously, torque and normal force for two types of amorphous polymers. In one set the materials, poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA), have large sub-vitreous β relaxations, while in the second set, polycarbonate (PC) and polysulfone (PSF), have weak β relaxations. It was found that the prominent β process influences the magnitude of the normal force modulus of PMMA and PEMA while the shear modulus is primarily affected by the α process. In the present work we have extended our study on the effect of the β and α relaxations on the normal force and torque in amorphous polymers by examining the aging behavior of both torque and normal forces of PMMA, PEMA and PC measured at various temperatures between the β and α transitions and at a given deformation (γ=0.04). It is found that for the PMMA the normal force shows aging behavior that is different from the torque response for the PMMA but ages in the same fashion as the torque for both the PEMA and the PC. These results are only partially consistent with the hypothesis that the β process is the cause of the differing behaviors.     

Characterization of organo-montmorillonite (OMMT) modified wood flour and properties of its composites with poly(lactic acid)

In this research, sodium-montmorillonite (Na-MMT) at four different concentrations (0.5%, 1.0%, 2.0% and 4.0%) and didecyl dimethyl ammonium chloride (DDAC) were used to modify wood flour (WF) in a two-step process to form organo-montmorillonite (OMMT) inside the WF. Then the WFs with three sizes were mixed with poly(lactic acid) (PLA) to produce WF/PLA composites. The treated WF was characterized and some physical and mechanical properties of the composites were tested. The results showed that: (1) Na-MMT was successfully transformed to OMMT and uniformly distributed inside WF; (2) at 0.5% MMT concentration, water repellency, flexural and tensile properties of the composites were improved significantly. However, after introducing more OMMT, the enhancements diminished because of poor interfacial adhesion caused by OMMT agglomeration; (3) the composites with the maximum size of WF showed the most significant improvements among all, suggesting bigger WF was more suitable for this modification process.     

Effect of montmorillonite on carboxylated styrene butadiene rubber/hindered phenol damping material with improved extraction resistance

Three methods of blending, including direct blending, melt blending and latex blending, were introduced to disperse sodium based montmorillonite (Na-MMT) and N,N′-hexane-1,6-diylbis{3-(5-di-tert-butyl-4-hydroxyphenyl-propionamide)} (HP1098) into the carboxylated styrene butadiene (XSBR) matrix. Small angle X-ray Diffraction testing indicated that melting Na-MMT with HP1098 enlarged the d-spacing of Na-MMT, which was further enlarged by mechanical blending with XSBR, and this led to homogeneous dispersion of Na-MMT and HP1098, which was indicated by Transmission Electronic Microscopy; latex blending was found most advantageous in dispersing HP1098 which was essential for improved damping performance. Dynamic Mechanical Analysis was utilized to characterize damping properties, and enhanced static mechanical properties were presumably originated from molecule chains being intercalated into the enlarged galleries of Na-MMT by mechanical blending. Formation of hydrogen bonds was observed by Fourier Transformation Infrared Spectrum and was supposed to be responsible for exceptional damping performance at elevated temperature. Extraction measurement of XSBR/Na-MMT/HP1098 composite indicated that XSBR and Na-MMT showed synergic effect in protecting HP1098 molecules from being extracted, which is a promising method in preparing rubber/hindered phenol damping materials with improved extraction resistance, whereby increasing the performance stability and lifespan of the composite materials. Additional advantage of this type of materials is better processability and shortened vulcanization process.     

Morphological,thermal and dynamic mechanical properties of Cathay poplar/organoclay composites prepared by in situ process

In order to improve the thermal stability and dynamic mechanical properties of Cathay poplar (Populus cathayana Rehd.) wood, a kind of organoclay, that is, organo-montmorillonite (OMMT), was introduced into its structure via an in situ process by sequentially impregnating poplar wood with sodium-montmorillonite (Na-MMT, in concentrations of 1.0%, 2.0%, and 4.0%) and didecyldimethylammonium chloride (DDAC, in a concentration of 2.0%). Consequently, the wood/organoclay composites were prepared. The X-ray diffraction (XRD), scanning electron microscopy coupled with energy dispersed X-ray analysis (SEM-EDXA) and Fourier transform infrared spectroscopy (FTIR) were used to characterize the morphological and chemical alterations of the composites. Also the effects of clay type and concentrations on the thermal stability and dynamic mechanical properties of the composites were studied. The results showed that didecyldimethylammonium ions were intercalated into the galleries of Na-MMT through cation exchange, partially separating the silicate layers. Thereafter, the inorganic Na-MMT transformed to OMMT during the in situ synthesis process, and the latter was successfully intercalated into the wood cell wall. The thermal degradation was alleviated in the wood/clay composites, among which the wood/OMMT composites exhibited the best thermal stability. According to dynamic mechanical analysis (DMA) results, the wood/OMMT composites showed an enhancement in energy storage and a diminution in energy dissipation compared to other groups. The improvements in the thermal stability and dynamic mechanical properties of the composites became more significant with the increasing clay content.