高速气流冲击式粉体表面改性装置——HYBRIDIZATION系统及应用

利用高速气流冲击法进行粉体/粉体系表面改性技术,是迄今为止各种粉体材料开发中最为引人注目的技术之一。HYBRIDIZATION(下称HYB)系统是利用高速气流冲击法对微粉体进行干式/机械化处理,是使材料复合化的最实用的装置,可对各类有机物、无机物、金属等进行广泛组合,通用性很强,适用于许多行业领域。从本文所述的系统构成、型式,有关的典型球形化处理的运转特性,利用复合化高温粉体测定被处理粉体表面温度,利用颜料改变色调等的处理特点及该系统的适用性等(一部分是从已发表的学术论文及专利上摘录的),可以说明HYB系统的概况。     

Synthesis of well-defined poly(styrene)-b-poly(p-tert-butoxystyrene) multiblock copolymer from poly(alkoxyamine) macroinitiator

The stepwise insertion reaction of styrene (St) and p-tert-butoxystyrene (BOSt) into poly(alkoxyamine) macroinitiator was carried out to provide well-defined poly(St)-b-poly(BOSt) multiblock copolymers. Structural confirmation of the multiblock copolymers was accomplished by NMR and IR measurements. The model reaction also supported that the monomer insertion into the macroinitiator proceeded in accordance with a living fashion.     

Preparation of poly(p-phenylene terephthalamide)/poly(vinyl chloride) molecular composite and its thermal and mechanical properties

Poly(p-phenylene terephthalamide) (PPTA) was blended with poly(vinyl chloride) (PVC) by solution-blending method. PPTA was metalated for dissolving in dimethyl sulfoxide. Dimethyl sulfoxide was used as a common solvent. In PPTA/PVC composite, PPTA accelerated the thermal degradation of PVC. PPTA molecules are aggregated as microfibrillar form in PVC matrix. Such microfibrils are dispersed homogeneously in PVC matrix, according to polarizing microscopic observation. The average diameter of the microfibrils becomes smaller in the composite with lower content of PPTA. In the surface region of PPTA microfibrils the intermolecular hydrogen bonds between C? Cl of PVC and N? H of PPTA are formed. Young's modulus and the yield stress at room temperature were higher in the composites than those in PVC. The modulus of the composites was higher, especially at the high temperatures above their glass transition temperatures, than that in PVC. The temperature dependence of modulus can be calculated by using the mechanical model equivalent to the quasi-3-dimensional microfibrillar model which will be approximately applied to the composite structure. It becomes apparent that the modulus of the PPTA microfibrils evaluated by using the mechanical model is higher in the higher molecular weight PPTA.     

Physical properties of silk fibers treated with ethylene glycol diglycidyl ether by the pad/batch method

This paper deals with the epoxide treatment of silk fabrics by the pad/batch method. The optimum reaction conditions, i.e., NaOH concentration, and reaction temperature were 2.5 g/L and 30°C, respectively. A weight gain of 8.5% was attained at a reaction time of 6 h. This value slightly increased to 10% after 24 h. The reactivity of tyrosine and basic amino acid residues was dependent on the reaction time and did not significantly differ from the results of epoxide-treated silk fiber by the conventional method in tetrachloroethylene. The moisture regain slightly decreased at 4% weight gain and then increased with the epoxide content, exceeding the value of the untreated control. The crease recovery of the epoxide-treated silk fabrics measured in the wet state was significantly improved, whereas that in the dry state was almost unchanged. The rate of photoyellowing of the epoxide-treated silk fabrics by the pad/batch method was reduced significantly compared with that of the untreated control. Among the mechanical properties, elongation at break and tensile modulus remained unchanged, whereas the tensile strength slightly increased following the epoxide reaction. The thermal properties were evaluated by DSC and TGA and on the basis of the dynamic viscoelastic measurements. The DSC curve of the epoxide-treated sample showed a slight increase of the decomposition temperature of silk fibroin. The rate of weight loss determined by TGA remained unchanged regardless of the chemical modification, whereas the peak of loss modulus became broader and shifted to lower temperature. The X-ray diffractograms showed that the crystalline structure of silk fibers was not affected by the reaction with epoxides. © 1993 John Wiley & Sons, Inc.     

Chemical modification of silk with aromatic acid anhydrides

Bombyx mori silk fibers were chemically modified by acylation with aromatic acid anhydrides, such as phthalic and o-sulfobenzoic anhydrides. We examined the reactivity of these modifying agents toward silk fibers, the physical and thermal properties, and the dyeing behavior with acid and cationic dyes. The o-sulfobenzoic anhydride was more reactive toward silk fibroin than phthalic anhydride. The amount of both basic and acidic amino acid residues decreased after modification with aromatic acid anhydrides. The moisture regain of silk treated with phthalic anhydride remained almost unchanged, while that of the samples modified with o-sulfobenzoic anhydride increased linearly as the weight gain increased. Chemically modified silk fabrics showed improved crease recovery behavior, even though phthalic anhydride seemed more effective at comparatively low weight gain. The modification of silk with o-sulfobenzoic anhydride caused a drastic a reduction of acid dye uptake and enhanced the affinity of silk for cationic dye. Silk fibers did not show any significant change in thermal behavior, regardless of the modification with o-sulfobenzoic anhydride. Silk fibers modified with phthalic anhydride showed on differential scanning calorimetry (DSC) curves a minor and broad endothermic peak at around 210°C, attributed probably to the breaking of the crosslinks formed between adjacent fibroin molecules.     

The reaction of polypropylene with maleic anhydride

An addition reaction of maleic anhydride with polypropylene takes place in the presence of radical reagents or sunlight. The initial rate of the reaction was proportional to the concentration of polypropylene and maleic anhydride, and one-half power of the concentration of the radical reagents. The increase in the temperature from 80 to 120°C increased the rate of the reaction and di-cumyl peroxide was effective as a radical reagent for this reaction. Ionic crosslinked rubber-like polymers were obtained from the reaction of maleic polypropylene with some alkali metal compounds. They showed the characteristic absorption band due to ? COO^? in their infrared spectra.     

New type of tin support for hydroprocessing catalyst

TiN supported molybdenum sulfide catalysts showed much higher activity for cleavage of C-C bonds than oxide supported molybdenum sulfide catalysts, indicating the possibility of a new generation of supports for hydroprocessing catalysts.     

Critical temperature for production of MAG by esterification of different FA with glycerol using <Emphasis Type="Italic">Penicillium camembertii</Emphasis> lipase

Production of MAG by a lipase-catalyzed reaction is known to be effective at low temperature. This phenomenon can be explained by assuming that synthesized MAG are excluded from the reaction system because MAG, which have low m.p., are solidified at low temperatures. Consequently, MAG are efficiently accumulated and do not serve as the precursor of DAG. If this hypothesis is correct, the critical temperature for MAG production, defined as the highest temperature at which DAG synthesis is repressed, should depend on the m.p. of the MAG. Esterification of FFA with glycerol using Candida rugosa, Rhizopus oryzae, and Penicillium camembertii lipases produced MAG efficiently at low temperatures. However, Candida lipase showed very low esterification activity at high temperatures (>20°C), and Rhizopus lipase produced not only MAG but also DAG even at low temperatures. Meanwhile, P. camembertii lipase catalyzed synthesis of MAG only from FFA and glycerol at low temperatures, although the enzyme catalyzed synthesis of DAG from MAG in addition to synthesis of MAG at high temperatures. We thus studied the effect of temperature on esterification of C₁₀−C₁₈ FFA with glycerol using Penicillium lipase as a catalyst and determined the critical temperatures for production of MAG. The critical temperature for production of each MAG showed a linear correlation with m.p. of the MAG, which supported the hypothesis. In addition, because the m.p. of MAG are estimated from that of the constituent FA, the optimal temperature for production of MAG can be predicted from the m.p. of the FFA used as a substrate.     

Electrochemical formation of AlN in molten LiCl-KCl-Li3N systems

Electrochemical formation of aluminum nitride was investigated in molten LiCl-KCl-Li₃N systems at 723 K. When Al was anodically polarized at 1.0 V (versus Li⁺/Li), oxidation of nitride ions proceeded to form adsorbed nitrogen atoms, which reacted with the surface to form AlN film. The obtained nitrided film had a thickness of sub-micron order. The obtained nitrided layer consisted of two regions; the outer layer involving AlN and aluminum oxynitride and the inner layer involving metallic Al and AlN. When Al electrode was anodically polarized at 2.0 V, anodic dissolution of Al electrode occurred to give aluminum ions, which reacted with nitride ions in the melt to produce AlN particles (1-5 μm of diameter) of wurtzite structure.     

Mechanisms of CO2 separation by microporous crystals estimated by computational chemistry

The diffusion and adsorption of CO₂ inside the pores of Li, Na, and K ion-exchanged X-type zeolites were simulated by molecular dynamics and Monte Carlo calculations. Carbon dioxide diffused inside the zeolites pores while it was colliding with pore walls. Then it stayed in a super cage of zeolites. Inside the pore of Li ⁺ ion-exchanged X-type zeolite (Li-X), the electrostatic potential term was −570 kcal/mol, this value was considerably smaller than those of CO₂ inside the pores of Na-X and K-X. On the other hand, from Monte Carlo calculations, CO₂ was found to strongly absorb near the 3B site for Li ⁺ ions. When CO₂ passed through the pores of alkali ion-exchanged X-type zeolites, the interaction between the CO₂ molecule and the 3B site for Li cation was fairly large.