Effects of NCO/OH Ratios on Bio-Based Polyurethane Film Properties Made from Acacia mangium Liquefied Wood.

The compatibility between isocyanate and polyol plays an important role in determining a polyurethane product's performance. This study aims to evaluate the effect of varying the ratios between polymeric methylene diphenyl diisocyanate (pMDI) and Acacia mangium liquefied wood polyol on the polyurethane film properties. A. mangium wood sawdust was liquefied in polyethylene glycol/glycerol co-solvent with H2SO4 as a catalyst at 150 °C for 150 min. The A. mangium liquefied wood was mixed with pMDI with difference NCO/OH ratios to produce film through the casting method. The effects of the NCO/OH ratios on the molecular structure of the PU film were examined. The formation of urethane, which was located at 1730 cm-1, was confirmed via FTIR spectroscopy. The TGA and DMA results indicated that high NCO/OH ratios increased the degradation temperature and glass transition from 275 °C to 286 °C and 50 °C to 84 °C, respectively. The prolonged heat appeared to boost the crosslinking density of the A. mangium polyurethane films, which finally resulted in a low sol fraction. From the 2D-COS analysis, the hydrogen-bonded carbonyl (1710 cm-1) had the most significant intensity changes with the increasing NCO/OH ratios. The occurrence of the peak after 1730 cm-1 revealed that there was substantial formation of urethane hydrogen bonding between the hard (PMDI) and soft (polyol) segments as the NCO/OH ratios increased, which gave higher rigidity to the film.

Thermal responsive poly(N-isopropylacrylamide) grafted chicken feather keratin prepared via surface initiated aqueous Cu(0)-mediated RDRP: Synthesis and properties.

Poultry chicken feather keratin was extracted and then modified for the fabrication of keratin-graft-PNIPAM copolymers. The keratin was well extracted from feather fiber and powdered. Subsequently, it underwent the surficial functionalization process with initiator groups. After the study conducted full disproportionation of Cu(I)Br/Me6Tren into Cu(0) and Cu(II)Br2 in the solvent, surface initiated aqueous Cu(0)-mediated reversible-deactivation radical polymerization (RDRP) of N-isopropylacrylamide (NIPAM) was performed in a methanol/water mixture solvent. The reaction was performed rapidly and efficiently, during which over 100% graft rate was achieved at 60 min. After 6 h reaction, 200% graft rate could be achieved. High graft rate (up to 287%) was achieved, and graft rate could be regulated by controlling the reaction time and the addition of monomer. The fabricated keratin-g-PNIPAM exhibited a rough surface. As revealed from the results of thermal analysis, the thermal stability of keratin-g-PNIPAM was enhanced noticeably compared with the original keratin. Besides, grafted PNIPAM chains exhibited a higher glass transition temperature. The grafted keratin particles displayed enhanced hydrophilicity. Keratin-g-PNIPAMs exhibit a lower LCST comparing to homopolymer and the flocculation in hot water behavior could be controlled by regulating graft rate.

Synthesis and characterization of regioselectively substituted curdlan hetero esters via an unexpected acyl migration.

Regioselectively substituted curdlan esters were synthesized by protecting the C6 primary hydroxyl group with a triphenylmethyl group followed by the acylation of the secondary hydroxyl groups at C2 and C4. The subsequent detritylation of C6 trityl group under acidic conditions revealed an unexpected acyl migration from C4 to C6. This unique acyl migration in curdlan was first observed, which haven't been reported in other polysaccharides such as cellulose. The rate of this migration was found to be dependent on the length of the acyl group, leading to the proposal of a new mechanism for this transformation. Based on these results, we synthesized 2,6-di-O-acetyl-4-O-propionyl-curdlan, which was fully characterized by 1H NMR, 13C NMR, COSY, HSQC and HMBC analyses. Thermogravimetric analysis and differential scanning calorimetry measurements revealed that the regioselective esterification to curdlan promoted its crystallization compared with randomly mixed ester derivatives.

Curdlan ester derivatives: synthesis, structure, and properties.

A series of ester derivatives of curdlan, which is a ß-(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 Young's 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.

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.

Atomic Force Microscopy Observation of Polylactide Stereocomplex Edge-On Crystals in Thin Films: Effects of Molecular Weight on Lamellar Curvature.

The shapes of the edge-on lamellar crystals of equiweight poly(l-lactide) (PLLA)/poly(d-lactide) (PDLA) stereocomplexes with various combinations of molecular weights were investigated by using atomic force microscopy. In the cases of the PLLA/PDLA blends with equivalent molecular weights, the straight-shaped edge-on lamellae were observed. On the other hand, the curved edge-on crystals were able to be seen for the PLLA/PDLA stereocomplexes with nonequivalent molecular weights. It was revealed that the direction of lamellar curvature in the polylactide (PLA) stereocomplexes with nonequivalent molecular weights is the same as that of PLA having lower molecular weight. In addition to the PLLA/PDLA blending ratio, the incidence of chain folding, which is strongly influenced by molecular weight, was considered to have a crucial effect on the lamellar curvature in the edge-on crystals of PLA stereocomplexes.

Acetylation and characterization of xylan from hardwood kraft pulp.

Alkaline treatment of eucalyptus hardwood kraft pulp with 10% NaOH yielded 6-8% xylan. The acetylation of the extracted xylan was carried in DMAC/LiCl/pyridine system to obtain a series of xylan acetates with different degrees of substitution (DS). Structure elucidation of xylan and xylan acetate was obtained by 1H and 13C NMR spectroscopy and other homonuclear and heteronuclear 2D-NMR techniques. Inverse-gated 13C NMR was employed to determine the DS of xylan acetate. Furthermore, results also revealed equal reactivities at the C-2 and C-3 positions of xylan towards acetylation. Thermal stability, solubility behavior and nanofiber formation of xylan acetate were influenced by its DS values. The mechanical properties of xylan acetate propionate were also investigated.

Characterization of liquefied product from cellulose with phenol in the presence of sulfuric acid.

The average molecular weight, the amount of bound phenol of liquefied cellulose and the substitution pattern of bound phenol as well as newly formed residue in the late stage of liquefaction were examined in various liquefaction conditions. The linkage fashion of bound phenol was governed by the liquefaction condition. Phenol extended molecular weight by the reaction with decomposed fragments from cellulose and formed new residue when insufficient amount was charged. On the other hand, phenol played a role of an end-cap reagent when sufficient amount was charged. Bound phenol with o-substitution increased with increasing liquefaction temperature.

Characterization of uniaxially aligned chitin film by 2D FT-IR spectroscopy.

Two-dimensional FT-IR spectroscopy (2D FT-IR) was applied to the investigations of crystalline chitin structure. From this study, new information about spectral bands which are not observed in conventional 1D FT-IR was obtained. In 2D spectra, three specific bands were differentiated at 3482, 3421, and 3380 cm(-1) in the OH region. They could be assigned as C(6)OH groups which are hydrogen-bonded to the next C(6)OH; C(3)OH groups hydrogen-bonded to O(5); and C(6)OH groups bifurcated hydrogen-bonded to C(6)OH as well as C=O, respectively. Two pairs of bands appeared in the amide region, indicating the two types of hydrogen-bonded states of C=O groups. This is in good agreement with the results in the OH region; half of the C(6)OH groups are hydrogen-bonded to C=O as well as the next C(6)OH. The results accurately confirmed the Blackwell model which was established by an X-ray diffraction study. The temperature-dependency of hydrogen-bonds was also revealed by 2D FT-IR. Interchain hydrogen-bonds [C(6)OH...O(6)] first respond to a temperature followed by intrachain [C(6)OH...O=C] and [C(3)OH...O(5)] with increasing temperature. Interchain hydrogen-bonds [NH...O=C] are relatively stable in the temperature range of 40-180 degrees C.