Structural evolution in microbial polyesters

The crystallization behavior of microbially synthesized poly(3-hydroxybutyrate) (PHB) and its copolymers [P(HB-co-HHx)] containing 2.5, 3.4, and 12 mol % 3-hydroxyhexanoate (HHx) comonomer and the melting of the resultant crystals were studied in detail using time-resolved small-angle X-ray scattering and differential scanning calorimetry. The polyesters were found to undergo primary crystallization as well as secondary crystallization. In the primary crystallization, the thicknesses of the lamellar crystals were sensitive to the crystallization temperature, but no thickening was observed throughout the entire crystallization at a given temperature. The thickness of the lamellar crystals in the PHB homopolymer was always larger than that of the amorphous layers. In the copolymers, by contrast, the randomly distributed HHx comonomer units were found to be excluded from the lamellar crystals into the amorphous regions during the isothermal crystallization process. This interrupted the crystallization of the copolymer chains, resulting in the formation of lamellar crystals with thicknesses smaller than those of the amorphous layers. The lamellar crystals in the copolymers had lower electron densities compared to those formed in the PHB homopolymer. On the other hand, secondary crystallization favorably occurred during the later stage of isothermal crystallization in competition with the continuous primary crystallization, forming secondary crystals in amorphous regions, in particular in the amorphous layers between the primarily formed lamellar crystal stacks. Compared to the primarily formed lamellar crystals, the secondary crystals had short-range-ordered structures of smaller size, a broader size distribution, and a lower electron density.     

Vinyl-Tris-(methoxydiethoxy)silane as an effective and ecofriendly flame retardant for electrolytes in lithium ion batteries

In this paper, we report a new flame retardant, vinyl-Tris-(methoxydiethoxy)silane (VTMS), for use in electrolytes of lithium ion batteries. Burning tests showed that the addition of VTMS at 5–15 vol.% into the currently used electrolyte could effectively reduce the flammability. As long as the added amount was below 10%, electrochemical performance such as reversible capacity and cycling showed little change. In addition, differential scanning calorimetry (DSC) in combination with X-ray photoelectron spectroscopy (XPS) disclosed that VTMS participated in the formation of the surface film on the cathode, which played a pivotal role in markedly improving the thermal stability of the LiCoO₂ cathode. This kind of ecofriendly compound provides a new promising direction for the development of organic additives to improve the safety of lithium ion batteries.     

Synthesis and characterization of conducting poly(aniline‐co‐o‐aminophenethyl alcohol)s

Poly(o‐aminophenethyl alcohol) and its copolymers containing the aniline unit were synthesized in aqueous hydrochloric acid medium by chemical oxidative polymerization. The chemical composition of these novel polymers was determined spectroscopically, and their viscosities were measured. These polymers exhibit good solubility in organic solvents that is attributed mainly to the polar hydroxyethyl side groups. Their structures (chain conformation and morphological structure) and properties (conductivity, electrochemical characteristics, glass transition, and degradation behavior) were characterized and then interpreted on the basis of the chemical composition along with the electronic and steric hindrance effects associated with the hydroxyethyl side group. Overall, the side group has a significant effect on the polymerization and influences the structure, chain conformation, and properties of the resultant polymer. The poly(aniline‐co‐o‐aminophenethyl alcohol)s containing 20–40 mol % o‐aminophenethyl alcohol units are potential conducting materials for microelectronic and electromagnetic shielding applications because they are easier to process than polyaniline but retain its beneficial properties. These polymers can also be used as a functional conducting polymer intermediate owing to the reactivity of the side group. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 983–994, 2002     

Collision-induced dissociation of transition metal-oxide ions: dynamics of VO+ collision with Xe

The collision-induced dissociation of VO(+) by Xe has been studied by the use of classical dynamics procedures on London-Eyring-Polanyi-Sato potential-energy surfaces in the collision energy range of 5.0-30 eV. The dissociation threshold behavior and the dependence of reaction cross sections on the collision energy closely follow the observed data with the threshold energy of 6.00 eV. The principal reaction pathway is VO(+) + Xe --> V(+)+ O + Xe and the minor pathway is VO(+) + Xe--> VXe(+) + O. At higher collision energies (E > 8.0 eV), the former reaction preferentially occurs near the O-V(+)...Xe collinear and perpendicular alignments, but the latter only occurs near the perpendicular alignment. At lower energies close to the threshold, the reactions are found to occur near the collinear configuration. No reaction occurs in the collinear alignment V(+)-O...Xe. The high and low energy-transfer efficiencies of the collinear alignments O-V(+)...Xe and V(+)-O...Xe are attributed to the effects of mass distribution. The activation of the VO(+) bond toward the dissociation threshold occurs through a translation-to-vibration energy transfer in a strong collision on a time scale of about 50 fs.     

Emulsions Stabilized with poly(Hydroxyethyl Acrylate-co-Coumaryl Acrylate-co-2-Ethylhexyl acrylate)

Thermo- and photo-responsive emulsions were prepared using mineral oil as an oil phase and a thermo- and-photo-sensitive polymer as an emulsifier. Hydroxyethyl acrylate (HEA) was copolymerized with Coumaryl acrylate (CA) and 2-Ethylhexyl acrylate (EHA) by a free radical reaction with the content of CA in the reaction mixture being varied (0, 0.5, 1, 2, 3 mol%) and the content of EHA being kept constant (2 mol%). CA was used as a photo-responsive comonomer and EHA was used as a hydrophobic comonomer to endow the copolymer with amphiphilicity. The copolymers prepared using the HEA/CA/EHA mixture where CA content was 1, 2, 3 mol% exhibited a phase transition in the range of 20°C– 45°C, and the phase transition temperature decreased with increasing the content. The CA of the copolymers was readily dimerized under the irradiation of UV (365 nm. 400 W) and the dimerization degree was 27%–47% in 60 min. The droplet size of emulsions significantly increased with increasing the temperature from 27°C- 50°C, possibly due to the thermal contraction of the copolymers. Also, the size markedly increased by 60 min-irradiation of the UV light, possibly because of the photo collapse of the copolymers.     

A new copolymerization process leading to poly(propylene carbonate) with a highly enhanced yield from carbon dioxide and propylene oxide

Using excessively loaded propylene oxide (PO) as a solvent, the copolymerization of carbon dioxide (CO₂) and PO was carried out with zinc glutarate catalyst, consequently producing poly(propylene carbonate) of high molecular weight in a high yield (64–70 g polymer per gram of catalyst) never achieved before. Both the PO used as solvent and the excessively loaded CO₂ were fully recoverable, respectively, and reusable for their copolymerization, indicating that this is a clean, green polymerization process to convert CO₂ to its polycarbonate. The polymer yield was further improved by scaling up the copolymerization process. Among zinc glutarate catalysts prepared through several synthetic routes, one from zinc oxide delivered the highest yield in the copolymerization. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1863–1876, 1999     

Molecular dimensions of polypeptides in helicogenic solvents

The dependence of the molecular dimension of polypeptides in helicogenic solvents on molecular weight was calculated by using the Zimm-Bragg-Nagai theory in collaboration with the broken-rod model, in which the excluded volume effect was taken into account by setting the equivalent chain to be a nonintersecting chain. Our calculated results for PBLG in helicogenic solvents were compared with experiment with good agreement. The flexibility of the helices of PCBL and PELG as broken rods corresponded to that of PBLG without excluded volume effect (i.e., the broken rod of a self-intersecting chain) in a comparison of their experimental data with our calculated results for PBLG of self-intersecting and nonintersecting chains. Over a wide range of molecular weights M our theory explains the dependence of the length per monomeric residue h on M, even for short chains in which h > 1.5 Å.