Polyacrylonitrile/Nylon 6 Blends: Preparation and Characterization

Summary: Polyacrylonitrile (PAN) particles with micro‐size ranges (0.15–2 μm) were prepared by emulsion and dispersion polymerizationa and in supercritical carbon dioxide media. The PAN particles were blended with Nylon 6 (PA6) at 220 °C by using a miniature mixer; it was found that melt‐mixing was possible for PAN‐rich compositions as high as 70 wt.‐%. Blends were characterized by scanning electron microscopy, IR, viscosity measurements, differential scanning calorimetry, and dynamic mechanical thermal analysis (DMTA). The size and shape of original PAN particles were retained in PAN/PA6 blends. The useful range to blend PAN particles size was less than 1 μm in terms of shape retention of the PAN particles in blends. Blends with 40 wt.‐% PAN content were found to be melt‐processable. The elastic modulus was higher for PAN/PA6 blends than pure PA6.

SEM photograph of PAN‐SC/PA6 blend with a 40/60 weight ratio.     

Synthesis of polyoxyethylene derivatives of diesters of sucrose with long-chain fatty acids

Summary Since the long-chain fatty acid sucrose diesters inevitably produced in the synthesis of monoesters are only slightly soluble in water, no important use can be found for them at the present time except as oilsoluble emulsifying agents. In order to exploit new uses we have attempted to improve their solubility in water by introducing oxyethylene radicals into the molecule. The addition reaction of ethylene oxide with the sucrose diesters was carried out in an autoclave in the presence of alkaline catalysts. With the reaction temperature maintained between 100–130° the pressure decreased as the reaction proceeded, and one to two hours were required to consume the ethylene oxide used. The addition products are yellow or orange oily materials soluble in water. Aqueous solutions showed good surface-active properties.     

Studies on miscibility in homopolymer/ random copolymer blends by equation of state theory

The miscibility of poly(methyl methacrylate) (PMMA) and styrene-acrylonitrile random copolymers (SAN) blends was investigated on the basis of the Flory—Orwoll—Vrij equation of state theory. To obtain the equation of state parameters (P*, V*_sp, T*: characteristic parameters), the pressure—volume—temperature (PVT) behaviour was measured for PMMA and a series of SANs with various acrylonitrile contents. The exchange energy parameter X_ij was also calculated by fitting the theory to some phase diagrams of PMMA/SAN blends. The Flory—Huggins interaction parameter χ was separated into two contributions based on the equation of state theory for mixtures: the exchange energy term χ_inter and the free volume term χ_free. Both the temperature and copolymer composition dependences of χ_inter and χ_free were estimated by calculations using the equation of state parameters. There exists a region in which χ_inter is negative, leading to a miscibility window in PMMA/SAN blends. However, the immiscibility at high temperatures in the blends cannot be explained only by χ_inter; it is caused by the free volume contribution, χ_free. The miscibility window behaviour in PMMA/SAN blends may be explained within the framework of the equation of state theory.     

Reactive processing of polymer blends: Analysis of the change in morphological and interfacial parameters with processing

The change in morphology and interface quantities have been analyzed for an immiscible polymer blend during reactive processing. A model polymer/polymer combination, hydroxy-terminated poly(ε-caprolactone)/liquid rubber with α, ω-carboxy groups, was employed. The blend was subjected to light scattering measurements, ellipsometry, and gel permeation chromatography (GPC). Size reduction of the dispersed phase during processing was followed by a systematic decrease in the correlation distance ζ and an increase in the specific interfacial area Ssp, both by the Debye-Bueche plot of light scattering profiles. Also observed was the time variation of the volume fraction of interface V_λ estimated as a product of the Ssp and the interfacial thickness by ellipsometry. The changes in ζ, Ssp, and V_λ with processing were accelerated when a coupling agent,γ-aminopropyltriethoxysilane (APS), was added. The amount of block copolymer formed in-situ in the APS-loaded system was estimated by GPC with RI and UV detectors. For the size reduction kinetics in both APS-loaded and -unloaded systems, Rittinger's law was found to be applicable.     

Antitumor activity of synthetic alkylphospholipids with or without PAF activity

1-O-Octadecyl-2-O-methyl-sn-glycero-3-phosphocholine (ET-18-OMe) has been reported to possess definite antitumor activity in vivo. Twenty-two alkyl lysophospholipid analogs were chemically synthesized, and their antitumor activity against mouse experimental tumors (Sarcoma 180, MM46, P388) was examined. Among them, 1-O-octadecyl-2-O-acetoacetyl-rac-glycerol-3-phosphocholine was found to show antitumor activity similar to ET-18-OMe with less acute toxicity. Intravenous injection of the ET-18-OMe withsn-3 configuration retarded the subcutaneous growth of Sarcoma 180 cells effectively, while the growth inhibition by thesn-1 isomer was much less effective. This stereospecificity was similar to that observed in their activities as platelet-activating factor (PAF) agonists. The acetoacetyl compound, another PAF agonist, showed similar stereospecific antitumor action in vivo. These findings suggest that some alkyl lysophospholipids may activate host cells to a cytostatic stage against tumor cells in vivo through binding to a PAF receptor. Our preliminary results indicated that the responsible cells under these conditions might be primarily immature macrophages present in the bone marrow. No appreciable or even adverse stereospecificity was observed in the different sets of experiments where the activity of ET-18-OMe against MM46 tumor cells in vivo or the direct cytotoxicity against human promyelocytic leukemia HL-60 cells in vitro was examined. Under, some conditions, the antitumor activity of ET-18-OMe in vivo may be revealed through direct cytotoxicity and/or modulation of the host defense system by “nonspecific” mechanisms. Some alkylphospholipids without PAF activity may also show antitumor activity through similar, “nonspecific” mechanisms.     

Ultra-high pressure sterilization of powdery food stuff—a new application of a roller compactor

A new non-heating technique was developed for the sterilization of food stuff. Applying a roller compactor, ultra-high pressure sterilization has experimentally demonstrated its ability to sterilize dry powders, such as corn flour and Chinese herbs, with little quality deterioration. Also, the degree of food sterilization was found correlated well with the linear press forces between the rollers, roller gaps, and number of compaction passes. In comparison to the conventional high pressure sterilization technique, the new dry continuous processing method has the advantage of lower investment cost and is more versatile for sterilizing various food powders.     

Photocatalysts using hexa- and octa-titanates with different tunnel space for water decomposition

Photocatalytic activities for water decomposition were examined for photocatalysts using hexa- and octa-titanates and TiO2(B) with different tunnel space in the structure. Using RuO2 as promoter, M2Ti6O13 (M = Li, Na, K, Rb) showed the stoichiometric production of Hz and O₂ except for Li, whereas H₂Ti₈O₁₇ and TiO₂(B) had very low activity producing only hydrogen as a product. The effects of promoters on Na₂Ti₆O₁₃ showed that the activity increased in the order of RuO₂ > RuO₂ + IrO₂ > IrO₂ > RuO₂ + Pt > MnO₂. These effects along with other related ones are discussed: it emerges that the presence of the tunnels is important for the achievement of high photocatalytic activity.     

Performance of solvothermally prepared Ga2O3-Al2O3 catalysts for SCR of NO with methane

The solvothermal reaction of mixtures of aluminum isopropoxide (AIP) and gallium acetylacetonate (Ga(acac)₃) directly yielded the mixed oxides of γ-Ga₂O₃-Al₂O₃. In the solvothermal synthesis, the crystal structure of mixed oxides was controlled by the initial formation of γ-Ga₂O₃ nuclei. The mixed oxides prepared in diethylenetriamine have extremely high activities for selective catalytic reduction (SCR) of NO with methane as a reducing agent. With increasing crystallite size of the spinel structure, the catalytic activity increased. The ratio of the amount of methane consumed by combustion to total methane conversion was proportional to the density of acid sites on the surface of the mixed oxides. The mixed oxide catalysts prepared in diethylenetriamine had lower densities of acid sites and showed a higher methane-efficiency for CH₄-SCR than those prepared in other solvents. These catalysts maintained their high activity even when the reaction was carried out under the severe conditions (i.e., high space velocity and low NO concentration).     

Thermotropic polyarylates derived from substituted hydroquinones and p-terphenyl-4,4″-dicarboxylic acid

Polyarylates from substituted hydroquinones (HQs) and p-terphenyl-4,4″-dicarboxylic acid (TPDA) that were modified with 1,2-bis(phenoxy)ethane-4,4′-dicarboxylic acid (PEC), 1,2-bis(2-chlorophenoxy)ethane-4,4′-dicarboxylic acid (ClPEC), terephthalic acid (TA) and p-hydroxybenzoic acid (HBA) were prepared and their thermal and mechanical properties were investigated. These polyarylates exhibited liquid crystallinity at about the same temperatures as polyarylates derived from substituted HQs and 4,4′-diphenyldicarboxylic acid (BB). However, as-spun fibers and injection-molded specimens of these polyarylates exhibited lower moduli than those of substituted HQs and BB that were modified with PEC, Cl-PEC and TA.     

Lysozyme requires fluctuation of the active site for the manifestation of activity

Mutations around His15 which lie far away from the active site,stimulated glycol chitin activity of lysozyme at physiologicaltemperature. Del-Argl4Hisl5 lysozyme, a mutant lysozyme whoseArgl4 and Hisl5 were deleted together, and has the highest activityamong these mutant lysozymes, had a similar binding abilityto a trimer of N-acetyl-glucosamine, a substrate analogue, relativeto native lysozyme. This suggests that the increased activitywas due to an increased k_cat in the catalysis reaction. TheH-D exchange rate of the N-1 proton in the Trp63 which is locatedin the active site cleft, was enhanced in the Del-Argl4Hisl5lysozyme, while 2-D proton NMR analysis revealed no conformationalchange around Trp63. We conclude that some sort of fluctuationat the active site might be required for the manifestation ofactivity. This theory is supported by the finding that the Del-Argl4Hisl5lysozyme showed a shift in temperature dependency of activityto lower temperatures compared with that of native lysozyme.