Synthesis and applications of unsaturated polyester resins based on PET waste

Three types of unsaturated polyester resins were synthesized from the glycolysis of polyethylene terephthalate (PET) plastic waste, considering environment, cost and properties for their applications. These synthesized unsaturated polyester resins could be used for various construction processes and materials such as no dig pipelining (NDR-1), pultrusion (PLR-1) and polymer concrete (PCR-1). PET was taken from common soft-drink bottles, and ethylene glycol (EG), diethylene glycol (DEG) and MPdiol glycol mixtures were used for the depolymerization at molar ratios. The glycolyzed PET 1 ^st products (oligomers) were reacted with maleic anhydride, phthalic anhydride and dicyclopentadiene (DCPD) (especially for polymer concrete) to form unsaturated polyester resins with mixed styrene. The lab scale (1–5 kg) and pilot plant scale-up tests (200 kg) were experimented to evaluate the processing characteristics, viscosity, acid number and curing behaviors. The main properties such as hardness, flexural strength, tensile strength, heat distortion temperature, elongation, and chemical resistance were determined based on the various uses of the three resins. Furthermore, the applicability and the properties of these developed resins were verified through many real application tests.     

Continuous polymerization of lactam–lactone block copolymers in a twin‐screw extruder

Continuous copolymerizations of ?‐caprolactone with ?‐caprolactam and ω‐lauryl lactam were carried out in a modular intermeshing corotating twin‐screw extruder. Sodium hydride (initiator) and N‐acetyl caprolactam (coinitiator) were used to synthesize lactam–lactone copolymers in a twin‐screw extruder. We consider the variables of feeding order and feed rate of comonomers on the reactive extrusion of lactam–lactone copolymers. It was observed that simultaneous feeding of both monomers with initiator and coinitiator in the first hopper produced a mixture of homopolymers. When we fed the lactam into the first hopper and caprolactone sequentially into the second hopper, we obtained the lactam–caprolactone block copolymers. However, when we fed caprolactone first into the first hopper and the lactam into the second hopper, the extruded product was a mixture of poly(?‐caprolactone) and lactam monomer. We synthesized high molecular weight copolymers of poly(caprolactam‐b‐caprolactone) and poly(lauryl lactam‐b‐caprolactone) with different block lengths by sequential feeding of monomers. The block length of the block copolymer could be adjusted by controlling the feed rate of each monomer during reactive extrusion. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1429–1437, 2003     

Continuous ethanol production from wood hydrolysate by chemostat and total cell retention culture

Chemostat and total cell retention cultures with internal filter system ofSaecharomyc.es cerevisiae H1-7 were carried out to produce ethanol from wood hydrolysate. Maximum ethanol productivity obtained in a chemostat with the aeration rate of 1 vvm was 3.79 g/(L·h). This was 20% higher than that in a chemostat without aeration. However, the substrate was not completely consumed at the dilution rate with the maximum productivity. The realistic productivity, which has higher than 99% conversion rate of substrate, was. 2.95 g/(L·h). The maximum productivity in the total cell retention culture was 6.65 g/(L·h) at the dilution rate of 0.19 h¹ and the residual glucose concentration was negligible.     

Cure kinetics and mechanical properties of the blend system of epoxy/diaminodiphenyl sulfone and amine terminated polyetherimide-carboxyl terminated poly(butadiene-co-acrylonitrile) block copolymer

The cure kinetics of blends of epoxy resin (4,4’-tetraglycidyl diaminodiphenyl methane; TGDDM)/curing agent (diaminodiphenyl sulfone; DDS) with ATPEI (amine terminated poly-etherimide) -CTBN (carboxyl terminated poly (butadiene-co-acrylonitrile)) block copolymer (AB type) were studied using differential scanning calorimetry under isothermal conditions to determine the reaction kinetic parameters such as activation energy and reaction constants. Final cure conversion decreased with increasing amount of AB in the blends. A diffusion controlled reaction was observed as the cure conversion increased, and the curing reaction was successfully analyzed by incorporating the diffusion control term in the rate equation for the epoxy/DDS/AB blends. The fracture toughness was improved to about 350% compared to that of the unmodified resin at 30% of AB block copolymer. This is attributed to the formation of co-continuous morphology between the epoxy phase and AB block copolymer phase. By increasing the amount of AB, the modulus of the cured blends decreased, which was due to the presence of CTBN rubbery phases.     

The effect of various anti-setting systems in wool dyeing. Part 3; Sodium thiocyanate based systems

Wool fabrics undergo setting during dyeing. The degree of set can be controlled by careful selection of dyebath conditions and also by the addition to the dyebath of chemicals termed anti-setting agents. The anti-setting effect of sodium thiocyanate has been evaluated according to its concentration in the dyebath and the dyebath pH. The fabric crease-angle method was adopted to estimate the degree of anti-setting. In the case of wool fabric boiled in the presence of sodium thiocyanate, good anti-setting effects resulted from the pH 3 and pH 5 treatment baths. Chemical changes in the wool were detected using FTIR analysis.     

Modeling and economic analysis of CO<Subscript>2</Subscript> separation process with hollow fiber membrane modules

The main purpose of the study was to develop a model using ASPEN and Excel simulation method to establish optimum CO₂ separation process utilizing hollow fiber membrane modules to treat exhaust gas from LNG combustion. During the simulation, optimum conditions of each CO₂ separation scenario were determined while operating parameters of CO₂ separation process were varied. The characteristics of hollow fibers membrane were assigned as 60 GPU of permeability and 25 of selectivity for the simulation. The simulation results illustrated that 4 stage connection of membrane module is required in order to achieve over 99% of CO₂ purity and 90% of recovery rate. The resulted optimum design and operation parameters throughout the simulation were also correlated with the experimental data from the actual CO₂ separation facility which has a capacity of 1,000 Nm³/day located in the Korea Research Institute of Chemical Technology. Throughout the simulation, the operating parameters of minimum energy consumption were evaluated. Economic analysis of pilot scale of CO₂ separation plant was done with the comparison of energy cost of CO₂ recovery and equipment cost of the plant based on the simulation model. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Physical and electroresponsive characteristics of the intercalated styrene‐acrylonitrile copolymer/clay nanocomposite under applied electric fields

Styrene‐acrylonitrile copolymer (SAN)/clay nanocomposites were synthesized through an emulsion copolymerization of styrene and acrylonitrile in the presence of sodium montmorillonite, and their physical properties and electroresponsiveness under an applied electric field were characterized. Thermogravimetric analysis (TGA) showed that the thermal stability of the synthesized polymer was sustained. X‐ray diffraction (XRD) analysis confirmed the insertion of SAN into the interlayers of clay, whose separation consequently increased, as compared to those of the pristine clay. Transmission electron microscopy (TEM) was used to observe the suspended state of clay. Dry‐base electrorheological (ER) fluids were prepared by mixing intercalated SAN nanocomposite particles into silicone oil. Typical ER behavior, i.e., enhancement of shear and yield stresses in the presence of an applied electric field, was observed using a rotational rheometer equipped with a high‐voltage generator. A universal yield stress scaling equation was also found to fit our experimental data well. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 821–827, 2003     

Oxidation Behavior and Flexural Strength of Aluminum Nitride Exposed to Air at Elevated Temperatures

The oxidation behavior of a sintered aluminum nitride containing 3 wt% Y₂O₃ as a sintering aid was investigated. Samples were exposed to air at elevated temperatures for times up to 100 h. The weights of the samples were continuously monitored during exposure at various temperatures and humidity levels. The effects of oxidation on room-temperature flexural strength were also determined, and correlated to the observed weight changes of the samples. At temperatures 1200°C, linear weight gains were observed. However, at temperatures above 1200°C, the weight gains became parabolic with respect to exposure time. The oxidation rates were significantly increased by water vapor in the air. The oxidation products were found by X-ray analysis to be a mixture of Al₂O₃ and 5A1₂O₃·3Y₂O₃. The oxide layer formed on the surface was severely cracked because of the thermal expansion mismatch between the oxide layer and the substrate. The cracks initiated in the oxide layer and propagated into the substrate, resulting in severe reduction in the room-temperature flexural strength of the material. When exposed to ambient air for more than 50 h at temperatures greater than 1100°C, the strengths of the samples decreased to less than half that of the as-received material.     

Interfacial adhesion reaction of polyethylene and starch blends using maleated polyethylene reactive compatibilizer

The interfacial reaction of the polyethylene (PE)/starch blend system containing the reactive compatibilizer maleated polyethylene (m‐PE) was directly characterized by Fourier transform infrared (FTIR) spectroscopy. A significant amount of anhydride groups on m‐PE existed as hydrolyzed forms, resulting in a large amount of carboxyl groups. Using a vacuum‐heating‐cell designed in the laboratory, the carboxyl groups were successfully transformed into the dehydrolyzed state (i.e., anhydride group). This result enabled the direct spectroscopic observation of chemical reaction occurring at the interface. For the PE/starch blend system containing m‐PE, the chemical reaction at the interface was verified by the evolution of ester and carboxyl groups in the FTIR spectra. The effect of the reactive compatibilizer on the interfacial morphology was also examined by scanning electron micrography (SEM). Enhanced interfacial adhesion was clearly observed for the blend system containing reactive compatibilizer. Tensile strengths of blend systems containing m‐PE also increased noticeably compared with the corresponding system without compatibilizer. A similar observation was made for the breaking elongation data. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 767–776, 2002     

Theoretical assessment of the catalytic (Pt/TiO2) oxidation of formaldehyde at ambient temperature

A recent article [C. Zhang, H. He, K. Tanaka, Catal. Commun. 6 (2005) 211] investigates the use of a Pt/TiO₂ catalyst for the oxidation of formaldehyde. The findings demonstrate nearly complete oxidation at ambient temperature (25 °C) for values of the surface velocity in the range 5–10 × 10⁴ h⁻¹ and a 45% destruction when using a surface velocity of 20 × 10⁴ h⁻¹.In the present communication, this oxidation was assessed by theoretical considerations of the reaction kinetics. The destruction efficiency was predicted using a first-order reaction rate expression, combined with different theoretical or semi-empirical equations for the intrinsic reaction rate constant. Predicted and experimental data are in fair agreement, thus validating the theoretical approach and confirming the experimental results.