Proceedings of the Korean Fiber Society Conference (한국섬유공학회:학술대회논문집)
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1990.06b
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A new method for the graft polymerization of acrylonitrile onto starch is presented. Graft polymerization of acrylonitrile onto starch and the subsequent hydrolysis in sodium hydroxide solution to prepare absorbents is well known. This process has been utilized to produce the commercial product, Super Slurper. In a typical batch process, ~5% starch in water mixture is gelatinized at
$95^{\circ}C$ under stirring for 1 hour then cooled to room temperature. The graft polymerization itself is carried out for approximately 2 hours at$25~30^{\circ}C$ on the gelatinized starch by eerie ion initiation. In this study, graft polymerization of acrylonitrile onto starch via a reactive extrusion process which is a continuous, efficient process is described. Initial concentration of starch in water is 35% and the reaction temperatures are between$50~80^{\circ}C$ . However, the most significant difference in the reactive extrusion process is the short time in which the graft polymerization takes place. Preliminary results on the properties of graft polymerization products obtained from the reactive extrusion process are compared to those obtained from the batch process as well as the absorbency of the hydrolyzed samples. Absorbent material has also been prepared by sequential grafting and saponification in the extruder followed by a 2 hour heat treatment of the extrudate in an air circulated oven at$100^{\circ}C$ . -
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In the past, facile dissolution of cellulose has been hampered by the lack of suitable nondegrading solvents. Recently, this problem has been solved in our laboratory by the discovery of an inexpensive, convenient solvent system, that is the mixture of
$NH_3\;and\;NH_4SCN$ , for cellulose. Also, the$cellulose/NH_3/NH_4SCN$ solution system has been found to form the anisotropic, i.e., liquid crystalline phase. It is believed that both the cholesterio and the nematic phase occur. This finding has prompted extensive on-going researoh on the formation of the liquid crystalline phase from an inexpensive natural source such as cellulose since the nematic phase is envisioned as an excellent precursor sources for products with desirable properties, for example, high modulus and high strength. This interest naturally leads to a desire to understand the theological properties of the nematic phase so that the transformation of the nematic phase to the solid state with desirable properties can be efficiently accomplished, ;From this point of view, the theological behavior of the$cellulose/NH3_/NH_4SCN$ system has been studied as a function of shear rate and shear stress over a wide range of solvent compositions, cellulose concentration, centrifugation and urea contents, Results indicate that the viscosity decreases with increasing shear rate. A marked shear thinning behavior and a quasi-Newtonian behavior were observed in the low shear rate region and in the high shear rate region, respectively for all solvent compositions. The$cellulose/NH_3/NH_4SCN$ solution system only exhibited the viscosity increase with increasing cellulose concentration and failed to show the viscosity drop generally observed at the point of incipience of liquid crystal formation, This may be due to the gel-like nature of the solution by the association of the rodlike molecules into bundles which may serve as crosslinking points giving the cellulose solution a network structure. Also, simply hydrogen bonding may be so restrictive of molecular mobility that a viscosity drop is blocked. In addition to the above results, yield stress and thixotropy were also observed in the$cellulose/NH_3/NB_4SCN$ solution system which are characteristics of liquid crystal and gel, The results of the effect of centrifugation on viscosity show that viscosity decreases by the application of centrifugation. This may be explained by the change of the piled polydomain structure to the dispersed polydomain structure due to the pressure gradient generated during centrifugation.ation. -
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Three non-ionic and two anioinic spin probes, differing in size and substituent, were synthesized. Their mobility in dried nylon 6 film was investicated by the spin probe technique using electron spin resonance spectrometer. When the size of a spin probe was large and the interaction between the probe molecules and polymer chains existed, the mobility of spin probes decreased. From Arrhenius plots of rotational correlation time, one discontinuity point (
$T_d$ ) was determined. The activation energies for rotation below and above$T_d$ were discussed in terms of the mode of probe rotation. Three spin probes could be viewed as azo dyes having a built-in nitroxide radical. Photolysis of them in dimethylformamide and in nylon 6 film was performed by exposure to 254 nm UV light in the presence of air. It was found that dyes having a built-in nitroxide radical showed better photostability than dyes derived from${\bata}-naphthol$ .. -