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Triethoxysilyl-terminated poly(d-lactide)s (eSi-PDLA) were successfully prepared by hydrosilylation of allyl-terminated PDLAs (A-PDLA-ac) which were readily prepared by ring-opening polymerization of d-lactide and the following terminal protection by acetylation. Their acid-catalyzed hydrolysis produced hyper-conjugated PDLAs with terminal silanol coupling. Blend PLLA films containing eSi-PDLA (Mn = 2.1 kDa) in 5-25 wt.% were successfully prepared by the solution casting method. The blend films were found to take a nano-porous or micro-phase separation structure, being different from that of the blend PLLA films containing trimethoxysilyl-terminated poly(d-lactide) (mSi-PDLA) which exhibited particle distribution structure. This difference was reasonably attributed to the different rate of hydrolytic polycondensation of the trimethoxy- and triethoxy-silyl terminals. These results revealed that the competing sterecomplexation/ hyper-conjugation/phase separation can afford specific morphologies, allowing fine control of properties.

A new electrospinning set-up is described for continuous aligning of poly(L-lactide) yarn. It comprises a slowly rotating grounded `funnel' target and a winder placed right up to the funnel. A charged polymer jet is ejected from a nozzle. The electrospun fibers are first accumulated on the mouth plane of the funnel to form a web. The web is then pulled upward and guided to a winder on which twisted fibers are continuously wound as a bundle. Each filament of the bundle is slanted at about 45 relative to the collecting direction, and its average diameter is 6.0+/-1.9 mu m. The drawn fiber shows improved tensile properties as a result of the increased molecular orientation. The morphologies of the twisted fibers before and after drawing are compared.

A new target collector was designed for taking up aligned nanofibers by electrospinning. The collector consists of a rotor around which several fins were attached for winding electrospun filaments continuously in large amounts. The alignment of the nanofibers wound on the collector was affected by the electrospinning conditions, such as the needle-to-collector distance and the applied voltage, but not by the rotation speed of the collector. At a voltage of 0.5 kV · cm -1 , about 60% of the fibers were found to be aligned within an angle of ± 5° relative to the rotational direction of the collector. The fiber alignment was improved to 90% by drawing the fiber bundle 2-3 times at 110°C. The drawing was also effective for crystal orientation of the fibers as revealed by WAXD. The drawn fibers show improved mechanical properties.

The effect of polyethylene glycol (PEG) on the mechanical and thermal properties of poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) blends was examined. Overall, it was found that PEG acted as an effective plasticizer for the PLA phase in these microphase-separated blends, increasing the elongation at break in all blends and decreasing the Tg of the PLA phase. Significant effects on other properties were also observed. The tensile strength and Young's modulus both decreased with increasing PEG content in the blends. In contrast, the elongation at break increased with the addition of PEG, suggesting that PEG acted as a plasticizer in the polymer blends. Scanning electron microscope images showed that the fracture mode of PLA changed from brittle to ductile with the addition of PEG in the polymer blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43044.

The higher order structure of stereocomplex-type poly(lactic acid) melt-spun fibers of an equimolar blend of poly(L-lactic acid) and poly(D-lactic acid) was analyzed with wide-angle X-ray diffraction (WAXD) and birefringence measurements. Two different crystalline structures were observed in the fibers: α-form homocrystals and stereocomplex crystals. The weight fractions of the two crystals were estimated with the WAXD integrated intensity data. The crystalline orientation factors were obtained from the WAXD measurements. Well-oriented homocrystals formed during a drawing process at the crystallization temperature of the homocrystal. Drawing above this temperature caused the stereocomplex crystal to be formed. The crystalline orientation tended to be lower with increasing drawing temperatures. Through the combination of the intrinsic birefringence and the fractions of the α-form homocrystals and stereocomplex crystals, the birefringence of the amorphous phase was evaluated. The amorphous birefringence stayed positive and decreased with increasing drawing temperature.

Poly(lactic acid) (PLA) is a biobased polymer made from biomass having high mechanical properties for engineering materials applications. However, PLA has certain limited properties such as its brittleness and low heat distortion temperature. Thus, the aim of this study is to improve toughness of PLA by blending with poly(butylene succinate-co-adipate) (PBSA), the biodegradable polymer having high toughness. Polymer blends of PLA and PBSA were prepared using a twin screw extruder. The melt rheology and the thermal property of the blends were examined. Further the blends were fabricated into compression molded parts and melt-spun fiber and were subjected to tensile and impact tests. When the PBSA content was low, PBSA phase was finely dispersed in the PLA matrix. On the other hand, when the PBSA content was high, this minor phase dispersed as a large droplet. Mechanical properties of the compression molded parts were affected by the dispersion state of PBSA minor component in PLA matrix. Impact strength of the compression molded parts was also improved by the addition of soft PBSA. The improvement was pronounced when the PBSA phase was finely dispersed in PLA matrix. However, the mechanical property of the blend fibers was affected by the postdrawing condition as well as the PBSA content. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41856.

Solution-grown lamellar crystals of poly(p-dioxanone) (PPDX) have been crystallized isothermally from butane-1,4-diol at 100°C. The crystal structure of PPDX has been determined by interpretation of X-ray fiber diagrams of PPDX fibers and electron diffraction diagrams of lozenge-shaped chain-folder lamellar crystals. The unit cell of PPDX is orthorbombic with space group P2 1 2 1 2 1 and parameters: a=0.970 nm, b=0.74 mm, and c (chain axis) = 0.682 nm. There are two chains per unit cell, which exist in an anti parallel arrangement.

Biodegradable poly[(R)-3-hydroxybutyrate| (P(3HB)) fibers with high tensile strength of 1.32 GPa were processed from ultra-high-molecular-weight P(3HB) by a method combining cold-drawing and two-step-drawing procedures at room temperature. The distribution of molecular structures in a mono-filament was analyzed by micro-beam X-ray diffraction with synchrotron radiation. It was revealed that the P(3HB) fiber has a new core-sheath structure consistent with two types of molecular conformations: a 2 1 helix conformation in the sheath region and a planar zigzag conformation in the core region.

The phase behaviors for the blends of poly(3-hydroxypropionate) (PHP), poly(L-lactide) (PLLA), poly(D-lactide) (PDLA), and poly(D,L-lactide) (PDLLA) with catechin were investigated by differential scanning calorimetry. In PLLA/catechin, PDLA/catechin, and PDLLA/catechin blends, two glass transitions were detected when the catechin content was ≥40 wt %, whereas in PHP/catechin blends only one glass transition was observed over the whole range of blend compositions. The former and the latter results should reflect the inhomogeneous and the homogeneous nature of the blends, respectively, in the amorphous phase. These different phase behaviors should arise from the differences in the chemical structures between PHP and PLLA/PDLA/PDLLA, which dominates the strength and the number of intermolecular hydrogen-bonding interactions between the ester carbonyl groups of polyesters and the phenol groups of catechin. As detected by FTIR spectroscopy, in comparison with PHP, the steric hindrance of side-chain methyl groups of PLLA, PDLA, and PDLLA might restrain the formation of hydrogen bonds between their ester carbonyl groups and the phenol hydroxyl groups of catechin, even weakening the strength of such hydrogen bonds. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3565–3573, 2004

The mono-filaments (> 10 m in length) of chitosan and the blends of chitosan-collagen, chitin-collagen and chitin-silk fibroin were wet-spun. The mono-filaments were chemically N-modified with each of n-fatty acid anhydrides, intra-molecular carboxylic anhydrides, fragrant aldehydes and transition metal ions. The mono-filament was aligned on a straight line with the mono-filament of silk fibroin or poly(ethylene terephthalate) (PET), and a bundle of one to three mono-filaments was coated with a medium of sericin (Se), chitosan or N-acylchitosan to give rise to novel silk-mimic filament composites. The filaments coated with a medium of sericin exhibited 26-27 denier for the titer, 2.46-3.36 gf.denier -1 for the tenacity and 11.8-25.0% for the elongation. The apparent density (denier.μm -1 in the filament diameter) of the filament composites was about 3-4 times higher than that of the mono-filaments. Portion of fragrant aldehydes in Schiff's base was slowly hydrolyzed at room temperature by contacting with atmospheric moisture in the open air, and released from the fragrant filaments and composites. The filament composites coated with a chitosan medium were thrombogenic, and those coated with N-acylchitosans were antithrombogenic.

The effect of the mixing condition in a mill-type mixer on the thermal property and the crystal formation of the poly(l-lactide)/poly(d-lactide) blends is investigated. The blends melt-mixed at 200 and 210 °C under application of a high shear flow tend to show a single melting peak of the stereocomplex crystal (SC) in the differential scanning calorimetry first and second heating processes without indicating the trace of the melting of homo-chiral crystal. The mixing at an elevated temperature causes a serious thermal degradation. Further kneading of the blends at an elevated temperature higher than Tm of SC causes the transesterification between the same enatiomeric chains forming block copolymers of l- and d-chains. This block copolymer acts as a nucleating agent of SC and the compatibilizing agent between poly(l-lactide) and poly(d-lactide) and promotes the formation of SC. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45489.

The relationship between birefringence and polymer structure was studied both by theoretical and experimental analyses of a series of non-crystalline polyurethanes (PU) with different side groups. The most probable steric structures of PUs were estimated by molecular mechanical calculation (MM2) of their oligomeric model compounds, and their birefringence was theoretically calculated on the structural data obtained. In addition, some of the PUs were practically synthesized and melt-spun into thin fibers, which were drawn to a maximum draw ratio to measure the values of birefringence. The comparison of the measured and estimated values revealed that the present estimation method is effective for simulating the chain conformations and the birefringence of fully or partially extended polymer chains, which ought to be formed by drawing and melt-flow of glassy materials. Of particular interest was that phenyl-substituted PUs exhibit an unexpectedly larger birefringence than methyl-substituted PUs. This fact was reasonably explained by the angular rotation of the highly polarizable phenyl group, which is energetically easily allowed and influences strongly the value of birefringence.

The alumina–carbon composite fibers were obtained from poly[(acyloxy)aloxane] (PAA) with 3-ethoxypropanoic (EPA) and m-anisic acids (m-AA) legands. This preceramic polymer can be dissolved in p-xylene-methanol-EPA mixed solvent, and the concentrated solution exhibited an excellent spinnability. During the pyrolysis and sintering processes, aliphatic carboxylate in the side groups was easily decomposed and eliminated. The aromatic carboxylate, however, seems to be converted and migrated to a carbon domain in the alumina matrix into which aloxane repetition was converted. The fibers pyrolyzed up to 800 and 1000°C have electrical conductivities that monotonically increase with increasing temperature. The fiber pyrolyzed up to 1200°C showed the electrical conductivity in a rather complicated manner.

Alumina fibers were obtained from the poly[((3-ethoxypropanoyl)oxy)aloxane] (P-3EPA) by using a polymeric precursor technology. The rheological properties of the concentrated solution of P-3EPA related to the extrusion and spinning processes have been investigated to determine the processability into fine filaments. Thirty weight percent P-3EPA dissolved into toluene showed an excellent spinnability and fine filaments of 20–30 μm in diameter were easily obtained. The phase changes during the sintering of the fiber were studied with wide-angle X-ray diffraction and were shown to be strongly related to the mechanical properties of the fiber. Further the addition of the ethyl silicate (ES) as a sintering agent which prevent the crystal growth of Al2O3 was found to be effective to improve the mechanical properties of the alumina fiber.

A basic study of the influence of thermal degradation of polypropylene on its extrudate swell and melt spinning characteristics is reported. The degradation reduces swell, changes the shape of the spinline diameter/velocity profile (i.e., the spinline apparent elongational viscosity function), and stabilizes the melt spinning process. The importance of molecular weight distribution narrowing during the degradation process is noted in these studies.