Poly(butylene terephthalate)–clay nanocomposites prepared by melt intercalation: morphology and thermomechanical properties

Nanocomposites based on poly(butylene terephthalate) (PBT) and an organoclay (Cloisite 30B) were prepared by melt blending using a twin‐screw extruder. Two kinds of PBTs, ie PBT‐A and PBT‐B, with different inherent viscosities (η_inh), were used for this study (η_inh of PBT‐A and PBT‐B were 0.74 and 1.48, respectively). Dispersion of the clay layers in the PBT nanocomposites was characterized by using X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Tensile and dynamic mechanical properties and non‐isothermal crystallization temperatures of the nanocomposites were also examined. Nanocomposites based on the higher‐viscosity PBT (PBT‐B) showed a higher degree of exfoliation of the clay and a higher reinforcing effect when compared to the composites based on the lower‐viscosity PBT (PBT‐A). The clay nanolayers dispersed in PBT matrices lead to increases in the non‐isothermal crystallization temperatures of the PBTs, with such increases being more significant for the PBT‐B nanocomposites than for the PBT‐A nanoocomposites. Copyright © 2004 Society of Chemical Industry     

Facile modifications of polyimide via chloromethylation: II. Synthesis and characterization of thermocurable transparent polyimide having methylene acrylate side groups

From chloromethylated polyimide, a useful starting material for modification of aromatic polyimides, a thermocurable transparent polyimide having acrylate side groups was prepared. In the presence of 1,8‐diazabicyclo[5,4,0]undec‐7‐ene, chloromethylated polyimide was esterified with acrylic acid to synthesize poly(imide methylene acrylate). The polymer was soluble in organic solvent, which makes it possible to prepare a planar film by spin coating. The polymer film became insoluble after thermal treatment at 230 °C for 30 min. Optical transparency of the film at 400 nm (for 1 µm thickness) was higher than 98 % and not affected by further heating at 230 °C for 250 min. Adhesion properties measured by the ASTM D3359‐B method ranged from 4B to 5B. Preliminary results of planarization testing showed a high degree of planarization (DOP) value (>0.53). These properties demonstrate that poly(imide methylene acrylate) could be utilized as a thermocurable transparent material in fabricating display devices such as TFT‐LCD. Copyright © 2004 Society of Chemical Industry     

Holographic polymer‐dispersed liquid crystal fabrication under electric field

The transmission mode of holographic polymer‐dispersed liquid crystals (HPDLCs) was developed an under electric field. It is reported that orientation of LC molecules under an electric field induces orientation of oligomer molecules giving rise to low off‐state diffraction and small grating shrinkage. Copyright © 2005 Society of Chemical Industry     

Properties of poly(ethylene terephthalate)–poly(ethylene naphthalene 2,6‐dicarboxylate) blends with montmorillonite clay

The production and properties of blends of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalene 2,6‐dicarboxylate) (PEN) with three modified clays are reported. Octadecylammonium chloride and maleic anhydride (MAH) are used to modify the surface of the montmorillonite–Na⁺ clay particles (clay–Na⁺) to produce clay–C18 and clay–MAH, respectively, before they are mixed with the PET/PEN system. The transesterification degree, hydrophobicity and the effect of the clays on the mechanical, rheological and thermal properties are analysed. The PET–PEN/clay–C18 system does not show any improvements in the mechanical properties, which is attributed to poor exfoliation. On the other hand, in the PET–PEN/clay–MAH blends, the modified clay restricts crystallization of the matrix, as evidenced in the low value of the crystallization enthalpy. The process‐induced PET–PEN transesterification reaction is affected by the clay particles. Clay–C18 induces the largest proportion of naphthalate–ethylene–terephthalate (NET) blocks, as opposed to clay–Na⁺ which renders the lowest proportion. The clay readily incorporates in the bulk polymer, but receding contact‐angle measurements reveal a small influence of the particles on the surface properties of the sample. The clay–Na⁺ blend shows a predominant solid‐like behaviour, as evidenced by the magnitude of the storage modulus in the low‐frequency range, which reflects a high entanglement density and a substantial degree of polymer–particle interactions. Copyright © 2005 Society of Chemical Industry     

Morphology and properties of poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene]/silica nanoparticle hybrid films

Poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene] (MEH‐PPV)/silica nanoparticle hybrid films were prepared and characterised. Three kinds of materials were compared: parent MEH‐PPV, MEH‐PPV/silica (hybrid A films), and MEH‐PPV/coupling agent MSMA/silica (hybrid B films), in which MSMA is 3‐(trimethoxysilyl) propyl methacrylate. It was found that the hybrid B films could significantly prevent macrophase separation, as evidenced by scanning electron and fluorescence microscopy. Furthermore, the thermal characteristics of the hybrid films were largely improved in comparison with the parent MEH‐PPV. The UV‐visible absorption spectra suggested that the incorporation of MSMA‐modified silica into MEH‐PPV could confine the polymer chain between nanoparticles and thus increase the conjugation length. The photoluminescence (PL) studies also indicated enhancement of the PL intensity and quantum efficiency by incorporating just 2 wt% of MSMA‐modified silica into MEH‐PPV. However, hybrid A films did not show such enhancement of optoelectronic properties as the hybrid B films. The present study suggests the importance of the interface between the luminescent organic polymers and the inorganic silica on morphology and optoelectronic properties. Copyright © 2004 Society of Chemical Industry     

Properties of nanoporous organosilicate hybrid thin films with a bimodal pore size distribution

Low dielectric poly[methylsilsesquioxane‐ran‐trifluoropropylsilsesquioxane‐ran‐(2,4,6,8‐tetramethyl‐2,4,6,8‐tetraethylenecyclotetrasiloxane)silsesquioxane]s {P[M‐ran‐TFP‐ran‐(TCS)]SSQs} having various compositions were synthesized using trifluoropropyl trimethoxysilane, methyl trimethoxysilane and 2,4,6,8‐tetramethyl‐2,4,6,8‐tetra(trimethoxysilylethyl)cyclotetrasiloxane. The chemical composition of the polymers and the content of SiOH end‐groups were controlled by adjusting the reaction conditions, and they were characterized by ¹H‐NMR. The thermally decomposable trifluoropropyl groups on the P[M‐ran‐TFP‐ran‐(TCS)]SSQ backbone and heptakis(2,3,6‐tri‐O‐methyl)‐β‐cyclodextrin (CD) were employed as pore generators. The dielectric constants of the porous CD/P[M‐ran‐TFP‐ran‐(TCS)]SSQ films were in the range 2.0–2.7 (at 100 kHz) depending on the concentration of the porogens, and showed no change over 4 days under aqueous conditions. The pore size of the films showed a bimodal distribution, with diameters of ca 0.5–1.0 nm for those originating from the trifluoropropyl groups and 1.7 nm from the CD. The elastic modulus and hardness of the 30 vol% CD‐blended film with a dielectric constant of 2.26 were 2.40 and 0.38 GPa, respectively, as determined by a nanoindenter. Copyright © 2005 Society of Chemical Industry     

Slow eroding biodegradable multiblock poloxamer copolymers

Biodegradable multiblock poloxamers (BMPs) with gel duration of 8 h to several weeks were prepared by varying their molecular weights from 4000 to 40 000 g mol^?1. The molecular weight of the BMP was controlled by changing the poloxamer to coupling agent ratio. Assuming a micelle packing model of the BMP gel, as in the case of a poloxamer gel, the micelle properties and critical gel concentration of BMPs were investigated on the basis of the scaling concept. The findings suggest that the control of molecular weight by hydrolyzable groups can be a facile approach to optimize the gel properties for biomedical applications. Copyright © 2005 Society of Chemical Industry     

Application of a multi-channel system for continuous monitoring and an early warning system.

A multi-channel continuous toxicity monitoring system developed in our laboratory, based on two-stage mini-bioreactors, was successfully implemented in the form of computer-based data acquisition. The multi-channel system consists of a series of a two-stage minibioreactor systems connected by a fiber optic probe to a luminometer, and uses genetically engineered bioluminescent bacteria for the detection of the potential toxicity from the soluble chemicals. This system can be stably and continuously operated due to the separation of the culture reactor from the test reactor and accomplish easy and long-term monitoring without system shut down by abrupt inflows of severe polluting chemicals. Four different recombinant bioluminescent bacteria were used in different channels so that the modes of the samples toxicities can be reasonably identified and evaluated based upon the response signature of each channel. The bioluminescent signatures were delivered from four channels by switching one at once, while the data is automatically logged to an IBM compatible computer. We also achieved the enhancement of the system through the manipulation of the dilution rate and the use of thermo-lux fusion strains. Finally, this system is now being implemented to a drinking water reservoir and river for remote sensing as an early warning system.