Mikio Kajiyama

Analysis on residue formation during wood liquefaction with polyhydric alcohol

Liquefactions of cellulose powder, steamed lignin, alkali lignin, and their mixtures were carried out to analyze the reaction process of wood using polyhydric alcohol. The liquefaction of wood proceeded immediately and wood components were converted to N,N-dimethylformamide (DMF)-soluble components. After that, the condensation reaction occurred with increasing reaction time. However, none of cellulose powder, steamed lignin, and alkali lignin condensed by themselves during their liquefaction. The mixture of cellulose and lignin was also liquefied, and condensed after a long reaction time. The results of analysis showed that the behavior of the mixture resembled that of wood with respect to molecular weight distribution and the main functional groups. Lignin was converted to DMF-soluble compounds in the initial stage of wood liquefaction, followed by cellulose gradually being converted into soluble compounds. After that, condensation reactions took place among some parts of depolymerized and degraded compounds from cellulose and lignin, and were converted into DMF-insoluble compounds. It was concluded that the rate-determining step of wood liquefaction was the depolymerization of cellulose. Furthermore, it was suggested that the condensation reaction was due to the mutual reaction among depolymerized cellulose and degraded aromatic derivatives from lignin or due to the nucleophilic displacement reaction of cellulose by phenoxide ion.

Miscibility and pressure-sensitive adhesive performances of acrylic copolymer and hydrogenated rosin systems

Relationship between the miscibility of pressure-sensitive adhesives (PSAs) acrylic copolymer/hydrogenated rosin systems and their performance (180° peel strength, probe tack, and holding power), which was measured over a wide range of time and temperature, were investigated. The miscible range of the blend system tended to become smaller as the molecular weight of the tackifier increased. In the case of miscible blend systems, the viscoelastic properties (such as the storage modulus and the loss modulus) shifted toward higher temperature or toward lower frequency and, at the same time, the pressure-sensitive adhesive performance shifted toward the lower rate side as the Tg of the blend increased. In the case of acrylic copolymer/hydrogenated rosin acid systems, a somewhat unusual trend was observed in the relationship among the phase diagram, Tg, and the pressure-sensitive adhesive performance. Tg of the blend was higher than that expected from Tgs of the pure components. This trend can be due to the presence of free carboxyl group in the tackifier resin. However, the phase diagram depended on the molecular weight of the tackifier. The pressure-sensitive adhesive performance depended on the viscoelastic properties of the bulk phase. A few systems where a single Tg could be measured, despite the fact that two phases were observed microscopically, were found. The curve of the probe tack of this system shifted toward a lower rate side as the Tg increases. However, both the curve of the peel strength and the holding power of such system did not shift along the rate axis.

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.

Syntheses and properties of liquefied products of ozone treated wood/epoxy resins having high wood contents

Abstract Liquefied products with high wood content were prepared by pretreating wood with ozone before liquefaction. As a result, the ratio of wood to polyhydric alcohol (W/P ratio) used as solvent could be increased to 2:1. Resin blends were prepared by mixing liquefied products with ethylene glycol diglycidyl ether (EGDGE, water-soluble) and diglycidyl ether of bisphenol A (DGEBA, oily consistency). The wood content of the resin blend could be increased to 53%. The resins were cured by citric acid or triethylene tetramine (TETA), and their mechanical properties were evaluated. Dynamic mechanical measurements revealed that the former had higher glass transition temperatures than the latter. It was found that the resin with DGEBA cured by citric acid had almost the same level of tensile strength as commercial plastics.

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.

Effect of ozone treatment of wood on its liquefaction

The effects of ozone treatment were investigated to improve the process of liquefaction of wood with polyhydric alcohol solvents. The liquefied wood having a high wood to polyhydric alcohol ratio (W/P ratio) could be prepared by using the wood treated with ozone in the liquid phase. The liquefied wood with a W/P ratio of 2 : 1 had enough fluidity to act as a raw material for chemical products. To get some information about the effects of ozone treatment toward the wood components, cellulose powder and steamed lignin were treated with ozone and liquefied. In particular, ozone treatment in the liquid phase was found to be effective for wood and cellulose powder. On the other hand, steamed lignin self-condensed during liquefaction after treatment with ozone in the liquid phase. Thus, ozone treatment provided lignin with reactive functional groups, and caused the subsequent condensation reaction. Although lignin was converted to a more condensable structure by ozone treatment, the condensation reaction was found to be suppressed for wood during its liquefaction. The wood liquefied products displayed good solubilities in N,N-dimethyl formamide (DMF) even after treatments of long duration. It was suggested that one of the main effects of ozone treatment toward wood was the decomposition of cellulose.

Rheological study on the adhesion properties of the blends of ethylene vinyl acetate/terpene phenol adhesives

Measurements of the shear, tensile, peel, and creep strength of ethylene vinyl acetate (EVA)/CaCO3/terpene phenol adhesive system at three different ratios [100/60/0 (EVA-O), 80/48/20 (EVA-20), and 60/36/40 (EVA-40) by weight, using wood and aluminum as adherends] were conducted. Over a wide range of temperatures and rates of deformation, adhesion shear, tensile, and peel strength results, as well as the creep response over a broad range of temperature and stresses, were found to yield a single master curve by means of the reduced-variable technique. It was observed that the peak of E′ representing Tg, shifted toward higher temperatures as the amount of terpene phenol in the blend was increased. The most obvious effect of increasing the tackifier resin was the shifting of the adhesion strength master curves to the direction of lower rates. The shift was associated with the rise in Tg as the blend ratio was increased. The influence of the tackifier resin in modifying the viscoelastic properties of the adhesive was further described in a comparison of the adhesion strength master curves with corresponding dynamic viscoelastic curves of the adhesive films. The master curves for the creep response of the adhesives showed that the stress-breaking time relationship shifts toward longer time for EVA-40 with high Tg. Thus, it was found that the strength of adhesion is due mainly to dynamic effects in the adhesive of a viscous nature in the same way to the cohesive strength of the viscoelastic materials.

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.

Synthesis and characterization of aromatic polymers derived from 5‐perfluoroalkylisophthalic acid

A series of polyisophthalamides and polyisophthalates having perfluorinated side chains were prepared from 5-perfluoroalkylisophthaloyl dichlorides. The aromatic polyamides and polyarylates synthesized by conventional low temperature solution polycondensation and interfacial polycondensation, respectively, had inherent viscosities of 0.19 to 1.28 dL g -1 in yields of 65 to 100%. Solubilies of the resulting polymers were improved by incorporating nonafluorobutyl groups but not improved by incorporating heptadecafluorooctyl groups. Although the effect on the glass transition temperature (T g ) of incorporating perfluoroalkyl groups into the aromatic polyamides or polyarylate backbone is great, the incorporation maintained the thermal stability of the polymers. In spite of the rigid nature of perfluoroalkyl groups, T g s were decreased by incorporating perfluoroalkyl groups. The value of the contact angle of water on the aromatic polyamides films gradually increased with incorporation of the perfluoroalkyl groups. On the other hand, the value of the contact angle remarkably increased when perfluoroalkyl groups were incorporated into polyarylates. The Owens γs were also calculated for some aromatic polyamides by measuring contact angles of diiodomethane on the polymer films. The γs were estimated at 23-37 mN m -1 and about 10% of them were contributed by hydrogen bonding.

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.