Synthesis and applications of heterobifunctional poly(ethylene oxide) oligomers

Poly(ethylene oxide) (PEO) oligomers are employed extensively in pharmaceutical and biomedical arenas mainly due to their excellent physical and biological properties, including solubility in water and organic solvents, lack of toxicity, and absence of immunogenicity. PEO can be chemically modified and reacted with, or adsorbed onto, other molecules and surfaces. Sophisticated applications for PEO have increased the demand for PEO oligomers with tailored functionalities, and heterobifunctional PEOs are often needed. This review discusses the synthesis and applications of heterobifunctional PEO oligomers possessing amine, carboxylate, thiol, and maleimide functional groups.     

Scaling laws and internal structure for characterizing electrospun poly[(R)-3-hydroxybutyrate] fibers

Using chloroform/dimethylformamide (CF/DMF) co-solvent, electrospinning of poly[(R)-3-hydroxybutyrate] (PHB) solutions was carried out at ambient temperature. The effects of the applied voltage (V), flow-rate (Q), and solution viscoelastic properties on the Taylor cone, electrified jet, and fiber morphology were investigated. In addition, the electric field developed by the needle-plate electrode configuration was calculated using a finite element analysis to reveal the tip-to-collector (H) effect. Among the processing parameters (V, Q and H), it was found that Q played a key role in determining the jet diameter (d_j) and electrospun fiber diameter (d_f), and scaling laws existed between them, i.e., d_j-Q^0.61 and d_f-Q^0.33. The diameter reduction ratios of D_o/d_j (D_o is the needle diameter) and d_j/d_f were measured as 50-120 and 5-10, respectively; it suggested that major jet stretching took place in the straight electrified jet region, and further chain orientation could be gained by the subsequent process of jet whipping. By changing PHB concentrations from 5 to 15 wt%, the solution viscosity (η_o) was increased from 100 to 4900 cP, whereas the surface tension and solution conductivity remained unchanged; it provided a good model solution to exclusively reveal the η_o effect on the electrospinning process. Our results showed that the η_o-dependence of d_j and d_f also followed simple scaling laws: d_j-η_o^0.06, and d_f-η_o^0.39, with a prefactor depending on the processing variables, mainly the flow-rate. Regardless of the PHB concentrations used, the obtained PHB fibers showed a similar crystallinity fraction of ca. 0.63 and possession of major α-crystals together with a small amount of β-crystals with zigzag chain conformation.     

The effect of ionic interaction on the miscibility and crystallization behaviors of poly(ethylene glycol)/poly(L‐lactic acid) blends

The effect of end groups (2NH₂) of poly(ethylene glycol) (PEG) on the miscibility and crystallization behaviors of binary crystalline blends of PEG/poly(L ‐lactic acid) (PLLA) were investigated. The results of conductivity meter and dielectric analyzer (DEA) implied the existence of ions, which could be explained by the amine groups of PEG gaining the protons from the carboxylic acid groups of PLLA. The miscibility of PEG(2NH₂)/PLLA blends was the best because of the ionic interaction as compared with PEG(2OH, 1OH‐1CH₃, and 2CH₃)/PLLA blends. Since the ionic interaction formed only at the chain ends of PEG(2NH₂) and PLLA, unlike hydrogen bonds forming at various sites along the chains in the other PEG/PLLA blend systems, the folding of PLLA blended with PEG(2NH₂) was affected in a different manner. Thus the fold surface free energy played an important role on the crystallization rate of PLLA for the PEG(2NH₂)/PLLA blend system. PLLA had the least fold surface free energy and the fast crystallization rate in the PEG(2NH₂)/PLLA blend system, among all the PEG/PLLA systems studied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects and properties of poly(arylene ether benzonitrile)s of various molecular weights blended with sulfonated poly(ether ether ketone)

Poly(arylene ether benzonitrile) (PAEBN) was synthesized with 2,6‐dichlorobenzonitrile and biphenol. PAEBNs with various molecular weights (MWs), 1,640,000 and 185,000 g/mol, were synthesized by control of the stoichiometry of the monomers and were blended with sulfonated poly(ether ether ketone) (SPEEK). The effects of MW on the water uptake, swelling, methanol permeability, and proton conductivity of the SPEEK/PAEBN blend membranes were investigated. The molecular mobility of the SPEEK/PAEBN blends was also examined in this study. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Plasma power can make better powders

It may be a truism to say that round powders pack better, but spheroidisation of powder particles is one of the successful commercial applications of induction plasma technology and can play a key role in substantial improvement of powder quality and fluidity…     

Parametric circles and spheres

Formulations for parametric circles and spheres in terms of rational Gaussian (RaG) curves and surfaces are introduced. With the proposed formulations, a full circle is generated by interpolating a closed RaG curve to the vertices of an equilateral triangle, and a full sphere is generated by interpolating a closed RaG surface to the vertices of an octahedron with equilateral triangular faces. Generation of circles and spheres in this manner is very intuitive and easy to remember as the weights are all 1 and the nodes are all unique and uniformly spaced.     

海洋钻井液有机物添加剂生物降解性评价

随着海洋石油的勘探开发，钻井液有机添加剂不可避免地进入海洋．因此在海洋勘探开发过程中应选择环保性能好，即生物降解性能好的有机物添加剂。用累计耗氧量法测定了海洋钻井液有机添加剂的生物降解性，研究评价了有机添加剂的生物降解规律和机理，探讨了有机物生物降解性同其化学结构的内在联系，为海洋勘探开发过程中选择环保性能好的有机物添加剂提供理论依据。总结实验结果发现：淀粉类(如DFD-140和FI-E1等)最容易生物降解；其次是纤维素类(如MV-CMC等)和烯类单体聚合物(如PAM和PHP)；而沥青类、两性离子类则难以生物降解，有的甚至对生物降解起抑制作用。     

Solution-chemistry analysis of ammonium bicarbonate consumption in rare-earth-element precipitation

A solution-chemistry analysis is applied to estimating the consumption of ammonium bicarbonate in the recovery of rare-earth (RE) elements from leachates of weathered clays. The theoretical analysis shows that a two-step process is needed for recovering RE from the leachates of the weathered clays by precipitation using ammonium bicarbonate. The first step is a precipitation at solution pH 5 to remove impurities such as Fe and Al. The second step is to precipitate RE by adjusting the solution pH above 8. The consumption of ammonium bicarbonate was found to depend on the concentration of RE elements and impurities in the leachates. The total amount of ammonium bicarbonate consumption for the entire process was determined experimentally, and the results showed an excellent agreement with that calculated based on solution-chemistry analysis. The decomposition of H₂CO₃ was identified as one of the main causes of ammonium bicarbonate overdose, accounting for up to 41 pct in comparison to 20 pct consumption for the removal of impurities. The amount of ammonium bicarbonate required in terms of the NH₄HCO₃: RE₂O₃ (RE oxides) molar ratio was found to be 4:1 for maximal RE recovery. An overall RE recovery around 90 pct was achieved with a product purity being about 90 pct.