Akio Takemura

Preparation of low-molecular weight alginic acid by acid hydrolysis

Abstract Three kinds of low-molecular weight alginic acid fractions, Alg.A, B, and C, were prepared from a commercial alginic acid by acid hydrolysis using phosphoric acid. Alg.A was obtained as an insoluble fraction by the filtration of mixture. Alg.B was obtained as a precipitate by pouring the filtered solution into water. Alg.C was obtained as a precipitate by pouring the filtrate into methanol. Measurements with 13 C NMR, GPC and WAXS were performed on the prepared fractions for characterization. Alg.A was composed of rich M and G blocks, and had DP n and DP w /DP n values of 79 and 3.11, respectively. Alg.B was mainly composed of M block, and had DP n and DP w /DP n values of 38 and 2.57, respectively. Alg.C had a random structure including many alternating sequences, and had DP n and DP w /DP n values of 35 and 2.11, respectively. Alginic acid oligomers prepared in this study, Alg.B and C, were improved regarding in solubility in water and the viscosity of their aqueous solution.

Effects of miscibility and viscoelasticity on shear creep resistance of natural-rubber-based pressure-sensitive adhesives

Natural rubber (NR) was blended in various ratios with 29 kinds of tackifier resins. Miscibilities of all the blend systems were illustrated as phase diagrams. From these blend systems, we selected 8 systems having typical phase diagrams (completely miscible, immiscible, lower critical solution temperature [LCST] types) and carried out measurements of shear creep resistance (holding power). Holding time was recorded as required time for the pressure-sensitive adhesive (PSA) tape under shear load to completely slip away from the adherend. Holding time of miscible PSA systems tended to decrease as the tackifier content increased. This is attributable to a decrease in plateau modulus of the PSA with increasing tackifier content. There was rather large difference in holding time by tackifier among the miscible PSA systems; the reason for this is also considered to be a difference in plateau modulus. Holding time of an immiscible PSA system scarcely changed by tackifier content. But in another immiscible system, holding time tended to increase with increasing tackifier content. In fact, in the case of immiscible PSAs, the effect of tackifier content on holding time was different from tackifier to tackifier. This may be caused by difference in extent of phase separation.

Effects of miscibility on peel strength of natural-rubber-based pressure-sensitive adhesives

Natural rubber (NR) was blended in various ratios with 29 kinds of tackifier resins, which were prepared from rosin, terpenes, and petroleum. Miscibilities of all the blend systems were illustrated as phase diagrams. From these blend systems, we selected 7 systems having typical phase diagrams [completely miscible, completely immiscible, and lower critical solution temperature (LCST) types] and carried out measurements of peel strength. Peel strength was measured at the angle of 180° at 20°C over the wide range of pulling rates. In the case of pressure-sensitive adhesives (PSAs), which showed phase diagrams of the completely miscible or LCST type, the peak positions in the pulling rate–peel strength curves shifted to the lower velocity as the tackifier content increased. On the contrary, completely immiscible PSAs had a smaller peel strength than miscible ones and did not give manifest shift of peaks. In most of the adhesives, the fracture mode changed from cohesive failure to interfacial failure (between adhesive and adherend), slip-stick failure, and glassy failure (between the tape and adhesive) as the pulling rate increased.

Curdlan ester derivatives: synthesis, structure, and properties.

A series of ester derivatives of curdlan, which is a β-(1 → 3)-D-glucan extracellularly produced by microorganism, with varying alkyl chain lengths (C2-C12) were synthesized by the heterogeneous reaction using trifluoroacetic anhydride. As a result, high-molecular-weight (Mw ≥ 6 × 10(5)) and fully-acylated curdlan was obtained with relatively high yield (>70%). Thermal stability of curdlan was greatly improved by esterification. Crystallization was observed for curdlan esters with C2-C6 side chains. Both Tg (170 → 50 °C) and Tm (290 → 170 °C) of curdlan esters decreased with increasing the side-chain length. By the increase in the side-chain carbon number, curdlan esters showed lower Youngs modulus and tensile strength, and larger elongation at break. Thus, material properties of curdlan esters can be controlled by changing the side-chain length. It was found that the increase of the side-chain length resulted in the decrease of crystallinity and the change of crystal structures.

Thermal Degradation of Natural Fiber-reinforced Polypropylene Composites:

The objective of the present article was to study the thermal degradation behavior of natural fiber polypropylene composites. Composite materials composed of 50% various natural fibers (wood flour, rice hulls, newsprint, and kenaf fibers) and polypropylene were studied using thermogravimetric analysis (TGA), differential thermal analysis (DTA), and differential scanning calorimetry (DSC). The effect of compatibilzer on the thermal stability of the composites was also evaluated. Contributions of components of one composite formulation to thermal degradation were also evaluated. It was found that among natural fibers, rice hulls were the least thermally stable ones in a polypropylene matrix. The compatibilizer slightly reduced thermal stability while enhancing fiber—matrix interaction and fractional crystallinity. The overall thermal degradation profile of the composite materials was found to be a more or less arithmetic average of those of the components.

Miscibility between natural rubber and tackifiers. I. Phase diagrams of the blends of natural rubber with rosin and terpene resins

Natural rubber (NR) was blended in various ratios with 17 kinds of tackifiers, which were prepared from rosin and terpenes. The blends were heated to various temperatures (20–120°C) in order to investigate their miscibility. The blends were visually observed for transparency or opacity at each temperature and further observed under an optical microscope for any existence of phase-separated structure. Miscibility of the blends is illustrated as phase diagrams in this article. Phase diagrams of all blends investigated in this study were classified into four types: completely miscible, lower critical solution temperature, upper critical solution temperature, and completely immiscible. The miscible range of a blend system tends to become smaller as the molecular weight of a tackifier increases. The data also indicate that the esters of hydrogenated rosin and of disproportionated rosin show comparatively good miscibility with NR whereas polymerized rosin and its esters have poor compatibility with NR in most cases.

Syntheses of glucomannan esters and their thermal and mechanical properties

Fully substituted glucomannan (GM) acylates with acyl carbon numbers (n) of 2, 3, 4, 5, 6, 8, 10, and 12 were prepared from konjac GM (KGM) in carboxylic acid/trifluoroacetic anhydride (TFAA). GM acetate acylates (n=3, 4, 5, 8, 12, 16, and 18) were prepared from KGM in acetic acid/carboxylic acid/TFAA. Differential scanning calorimetry (DSC) and X-ray diffraction revealed that the GM esters did not exhibit melting peaks and reflections derived from crystal, indicating they were amorphous. The glass-transition temperatures (Tgs) of the GM esters tended to decrease with increasing acyl carbon number, ranging from 174°C for GM acetate (GMAc) to 64°C for GM laurate (GMLa). Colorless and transparent GM ester films were obtained by solvent casting and thermo-pressing. The mechanical properties of the GM ester films were controlled by the acyl group structure.

Effect of the ethylene/vinyl acetate ratio of ethylene-vinyl acetate emulsion on the curing behavior of an emulsion polymer isocyanate adhesive for wood

We investigated the curing behavior of an emulsion polymer isocyanate adhesive for wood with different ethylene-vinyl acetate (EVA) emulsions, because it was found that the ethylene/vinyl acetate weight composition (E/VA ratio) of EVA could control the volume of gas emitted from the adhesive. EVA with higher VA content reduced the volume of gas emitted at the initial stage, which was caused by the extent of the reaction between the NCO groups and water. The reaction scheme of NCO could not be determined because the broad infrared (IR) absorptions due to CaCO3 and water masked the information of the NCO products in IR spectra. Examination of the degree of swelling suggested that the adhesive films stored for 3 weeks had the same degree of cross-linking structure in spite of the variation of EVA. This result was supported by IR spectroscopy, which showed the same amounts of NCO remained in these films. All the adhesives prepared in this study had satisfactory bond performance. The findings indicate that the E/VA ratio affects the curing behavior of the adhesive in the initial curing stage, whereas the cross-linking structure and the bond performance were independent of the E/VA ratio after storage for 3 weeks.

Miscibility and PSA Performance of Acrylic Copolymer and Tackifier Resin Systems

The influence of miscibility of an acrylic PSA and several tackifier resin systems upon PSA performance was investigated. When the acrylic copolymer and the resins were blended in various proportions, three types of mixing state were found: miscible system, partially miscible system and immiscible system. In the case of miscible systems, PSA performance (tack, peel strength and shear resistance) depended upon the viscoelastic properties of the PSA. In the case of completely immiscible systems, the above PSA performance depended primarily upon the viscoelastic properties of a continuous matrix phase, and the separated resin phase acted as a kind of filler. In the case of partially miscible systems, the PSA performance changed discontinuously at the resin concentration where phase separation occurred. It suggests that the phase structure of a PSA greatly influences the PSAs performance.

Effect of postcure conditions on the dynamic mechanical behavior of water-based polymer-isocyanate adhesive for wood

To study the effect of postcure conditions on the viscoelastic behavior of water-based polymer isocyanate adhesives for wood (API adhesive), dynamic mechanical analysis (DMA) was performed for a simplified model of API adhesives under various postcure conditions. These conditions were achieved by storing the samples at room temperature or by heating them in an oven. Fourier transform infrared (FT-IR) spectroscopy was performed to test for residual isocyanate groups (NCO) and isocyanate derivatives to elucidate the reaction mechanism under the postcure conditions. DMA revealed that the postcure conditions led to wide variations in the viscoelastic behaviors of API films. FT-IR analysis confirmed the decrease of residual isocyanate during postcure treatments. However, the complete consumption of isocyanate could not be achieved under the postcure conditions. A good correlation was found between the DMA result and the chemical changes in the API samples heated above 140°C. However, no correlation was observed in the case of the samples heated at temperatures less than 140°C. This implies that postcure conditions led to a difference in the reaction chemistry of API.