Influence of ethyl methacrylate content on the volume‐phase transition of temperature‐sensitive poly[(N‐isopropylacrylamide)‐co‐(ethyl methacrylate)] microgels

A novel series of temperature‐sensitive poly[(N‐isopropylacrylamide)‐co‐(ethyl methacrylate)] (p(NIPAM‐co‐EMA)) microgels was prepared by the surfactant‐free radical polymerization of N‐isopropylacrylamide (NIPAM) with ethyl methacrylate (EMA). The shape, size dispersity and volume‐phase transition behavior of the microgels were investigated by transmission electron microscopy (TEM), ultraviolet–visible (UV–Vis) spectroscopy, dynamic light scattering (DLS) and differential scanning calorimetry (DSC). The transmission electron micrographs and DLS results showed that microgels with narrow distributions were prepared. It was shown from UV–Vis, DLS and DSC measurements that the volume‐phase transition temperature (VPTT) of the p(NIPAM‐co‐EMA) microgels decreased with increasing incorporation of EMA, but the temperature‐sensitivity was impaired when more EMA was incorporated, causing the volume‐phase transition of the microgels to become more continuous. It is noteworthy that incorporation of moderate amounts of EMA could not only lower the VPTT but also enhance the temperature‐sensitivity of the microgels. The reason for this phenomenon could be attributed to changes in the complicated interactions between the various molecules. 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     

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     

High performance biofilm process for treating wastewater discharged from coal refining plants containing nitrogen, cyanide and thiocyanate.

Wastewater discharge from coal refining plants contains a number of biologically toxic compounds; 2000-2500 mg/l of COD of which 40% is composed of phenol, 100-400 mg/l of thiocyanate, 10-40 mg/l of cyanide, 100-250 mg/l of NH4+-N and 150-300 mg/l of total nitrogen. In order to treat this kind of high strength wastewater, we have developed a high performance biofilm process using fluidizing bio-carriers of the tube chip type. The fluidizing biofilm carriers are made of a composite of polyethylene and several inorganic materials, whose density is controlled at 0.97-0.98 g/ml. The fluidizing biofilm carriers show sound fluidization characteristics inside bioreactors. The wastewater is treated using three consecutive series reactors in oxic-anoxic-oxic arrangement. Each reactor is charged with the fluidizing biofilm carriers of 50 vol%. Furthermore, newly cultured active microorganisms for the thiocyanate biodegradation are added in the biofilm process. At total hydraulic retention time of 2.2 days, this process can achieve steady state removal efficiencies: COD, 99%; thiocyanate, 99%; NH4+-N, 99% and total nitrogen, 90%.     

改性生物质作为型煤黏结剂的研究

探讨了用NaOH改性生物质秸秆作为型煤黏结剂的可行性,考察了NaOH溶液浓度对生物质改性的影响以及生物质添加量、无机物(MgO和MgCl2)添加量对型煤机械强度、防水性能和着火温度的影响。研究结果表明,NaOH改性液的质量分数为1.0%~2.0%时,制得的生物质型煤有较高的机械强度;生物质添加量在2%~20%时,随生物质添加量的增加,机械强度增加,着火温度降低,但防水性较差;而在生物质型煤中加入适量无机黏结剂后,型煤有很高的浸水强度,表现出优越的防水性能。     

Peracetic acid pretreatment of sugarcane bagasse for enzymatic hydrolysis: a continued work

Previous work has shown that the enzymatic hydrolysis of sugarcane bagasse could be greatly enhanced by peracetic acid (PAA) pretreatment. There are several factors affecting the enzymatic digestibility of the biomass, including lignin and hemicelluloses content, cellulose crystallinity, acetyl group content, accessible surface area and so on. The objective of this work is to analyze the mechanism of the enhancement of enzymatic digestibility caused by PAA pretreatment. Delignification resulted in an increase of the surface area and reduction of the irreversible absorption of cellulase, which helped to increase the enzymatic digestibility. The Fourier transform infrared (FTIR) spectrum showed that the absorption peaks of aromatic skeletal vibrations were weakened or disappeared after PAA pretreatment. However, the infrared crystallization index (N.O'KI) was increased. X‐ray diffraction (XRD) analysis indicated that the crystallinity of PAA‐treated samples was increased owing to the partial removal of amorphous lignin and hemicelluloses and probable physical change of cellulose. The effect of acetyl group content on enzymatic digestibility is negligible compared with the degree of delignification and crystallinity. The results indicate that enhancement of enzymatic digestibility of sugarcane bagasse by PAA pretreatment is achieved mainly by delignification and an increase in the surface area and exposure of cellulose fibers. Copyright © 2008 Society of Chemical Industry