Mechanical properties of poly(beta-hydroxybutyrate)/poly(ethylene oxide) blends

Tensile properties of poly (P-hydroxybutyrate)/poly (ethylene oxide) (PHB/PEO) blends were reported in this paper. It was found that the blends of PHB with different molecular-weight PEO exhibited different mechanical properties. The mechanical properties of the blends of PHB and PEO3 (M-w=0.3x10(6)) were very poor. However, the blends of PHB and PEO5 (M-w=5x10(6)) showed compatible in mechanical properties. Excellent synergism was observed not only in tensile stress and tensile elongation but also in modulus. Moreover, the ductility of the blends could be improved further under proper heat-treatment.

Nonisothermal crystallization kinetics: poly(ethylene terephthalate)-poly(ethylene oxide) segmented copolymer and poly(ethylene oxide) homopolymer

The nonisothermal crystallization behavior of polyethylene oxide (PEO) in poly(ethylene terephthalate)poly(ethylene oxide) (PETPEO) segmented copolymer and PEO homopolymer has been studied by means of differential scanning calorimetry, as well as transmission electron microscope. The kinetics of PEO in copolymer and PEO homopolymer under nonisothermal crystallization condition has been analyzed by Ozawa equation. The results show that Ozawa equation only describes the crystallization behavior of PEO-6000 homopolymer successfully, but fails to describe the whole crystallization process of PEO in copolymer because the secondary crystallization in the later stage could not be neglected. Due to the constraint of PET segments imposed on the PEO segments, a distinct two stage of crystallization of PEO in copolymer has been investigated by using Avrami equation modified by Jeziorny to deal with the nonisothermal crystallization data. In the case of PEO-6000 homopolymer, good linear relation for the whole crystallization process is obtained owing to the secondary crystallization does not occur under our experimental condition. (C) 2001 Elsevier Science Ltd. All rights reserved.

Nonisothermal crystallization kinetics of PEO in ethylene terephthalate-ethylene oxide segmented copolymers

The nonisothermal crystallization behavior of Ethylene Terephthalate-Ethylene Oxide (ET-EO) segmented copolymers has been studied with the use of differential scanning calorimetry (DSC). The kinetics of PEO in ET-EO segmented copolymer under nonisothermal crystallization conditions has been analyzed with the Ozawa equation. The results show that there is no agreement with Ozawa's theoretical predictions in the whole crystallization process owing to the constraint of ET segments imposed on the EO segments. A distinct two-crystallization process has been investigated by using the Avrami equation modified by Jeziorny to deal with the nonisothermal crystallization data. The value of the Avrami exponent n is independent of the length of soft segments. However, the crystallization rate is sensitive to the length of soft segments. The longer the soft segments, the faster the crystallization will be.

Spectrometric investigation on the thermooxidative degradation of ethylene oxide and tetra-hydrofuran co-polyether

The thermooxidative degradtion of ethylene oxide and tetra-hydrofuran (EO-THF) co-polyether has been studied by electron spin resonance (ESR), Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy. The initial degradation site was found to be at the a-carbon of the ether bond. Two free radicals which derived from dehydrogenation and oxygen addition were successfully detected by spin-trapping technique which used alpha -phenyl-N-tert-butyl nitrone(PBN) as spin trap. Both FT-IR and NMR have been used to follow structural changes of the copolyether during degradation. Nearly 20 product fragments including formate, carbonate, methyl, alcohol, methylene-dioxy, hydroperoxide and semiformal have been characterized by D-1 and D-2 NMR. The thermooxidtion of co-polyether preferred to occur on the THF units especially at the alternating linkage of EO and THF. Antioxidant (BHT) not only retarded the thermooxidation but also modified the degradation products with less ester and methylene-dioxy groups hut more hydroxyl and methyl groups.

Novel macrocyclic aryl thioether ester oligomers: structure characterization and free-radical ring opening polymerization

Novel macrocyclic aryl thioether ester oligomers have been synthesized in high yield from phthaloyl dichloride and 4,4'-thiodiphenol under pseudo high dilution conditions. The cyclic nature was unambiguously confirmed by a combination of MALDI-TOF MS, gel permeation chromatography and NMR analyses. Single-crystal X-ray diffraction of cyclic ester dimer reveals no severe strain on the cyclic structure. The free-radical ring opening polymerization (ROP) of the macrocyclic oligomers was achieved to give high molecular weight polymers via a transthioetherification reaction. The molecular weight of the polymer resulting from ROP decreases as the conversion of cyclic oligomers increases after a polymerization period of 30 min.

Miscibility and crystallization behavior of poly(beta-hydroxybutyrate)/poly(ethylene oxide) blends

The miscibility and crystallization behavior of poly(beta-hydroxybutyrate) (PHB)/poly(ethylene oxide) (PEO) blends were studied by differential scanning calorimetry(DSC) and polarizing microscopy (POM). It is found that the miscibility is related to the composition of the blends. When the PEO content is over 20 percent, the miscible blends turn into partially miscible and the phase separation can be observed with POM. The addition of the PEO influences not only the morphology of PHB crystals and the radial growth rate of spherulites, but also the cold crystallization temperature.

Binuclear lanthanide complexes as catalysts for the hydrolysis of double-stranded DNA

The efficient cleavage of plasmid DNA ( pCAT) by binuclear lanthanide complexes was investigated. At 37 degrees C and neutral pH, both Ho23+L and Er23+L promoted 100% conversion of supercoiled plasmid to the nicked circular form and linear form in 1 h. The corresponding saturation kinetics curve of cleavage of pCAT plasmid by binuclear lanthanide complexes showed the expected increase with catalyst concentration. (C) 1999 Elsevier Science S.A. All rights reserved.

In-situ microscopic FTIR spectroelectrochemistry of ascorbic acid in poly(ethylene glycol)/LiClO4 electrolyte paste and in the presence of dispersed cobalt hexacyanoferrate microcrystalline powder

In-situ microscopic FTIR spectroelectrochemical technique(MFTIRs) was applied to studying the electrochemical oxidation of ascorbic acid(AA) in poly(ethylene glycol)(PEG) paste at a 100 mu m diameter Pt disk electrode. Using this technique, the catalytic ability of cobalt hexacyanoferrate(CoHCF) microcrystalline toward AA oxidation was also studied, it was found that the dispersed CoHCF powder in the PEG paste can generate well-shaped thin-layer cyclic voltammetric waves with the peak height proportional to the scan rate, corresponding to the Fe centered redox reactions. This oxidation step catalyzed the AA oxidation. Also, this pasted CoHCF powder generated well-resolved in-situ MFTIRs spectra, by which a chemical interaction between C = C bond of AA ring and CoHCF lattice was revealed. A corresponding surface docking mechanism for the catalytic reaction has been proposed.

Water soluble polyaniline and its blend films prepared by aqueous solution casting

Polyaniline (PAn) was doped with phosphonic acid containing hydrophilic tails. The solubility of the doped PAn in water was controlled by changing the length of hydrophilic chain in the dopant. When poly(ethylene glycol) monomethyl ether (PEGME) with molecular weight M-w = 550 was used as the hydrophilic chain of the dopant, the doped PAn was entirely soluble in water. The film cast from aqueous solution showed good electrochemical redox reversibility, Aqueous solution blending of PAn with poly(ethylene glycol) (PEG, M-w = 20 000) and poly(N-vinyl pyrrolidone) (PVP, M-w = 360 000) was achieved. Percolation threshold of the composite film was lower than 3 wt.%. Electrical conductivity of the composite film was in the range of 10(-1)-10(-5) S cm(-1), depending on molecular weight of the acid and the content of PAn in the composite. (C) 1999 Elsevier Science Ltd. All rights reserved.

Mechanism-transformation synthesis and characterization of poly(styrene-b-2-ethyl-2-oxazoline) diblock copolymer

By mechanism-transformation (anionic --> cationic) poly(styrene-6-2-ethyl-2-oxazoline) diblock copolymer, PS-b-PEOx, was synthesized in two steps. The first step is the polymerization of styrene block capped with ethylene oxide and its tosylation; the second step is the cationic ring-opening polymerization of 2-ethyl-2-oxazoline. The products were thoroughly characterized by various methods, such as H-1-NMR, IR, DMA, TEM and SAXS. The results show that the copolymer obtained possesses high molecular weight and narrow molecular weight distribution.

Characterization and ionic conductivity of an amorphous comblike polymer - II: Based on ethylene maleic anhydride copolymer backbone with monoethyl ether of poly(ethylene glycol) of M-W=550 as side chain

Using a graft modification method, a comblike polymer host (CBPE550) was synthesized by reacting monomethyl ether of poly(ethylene glycol) (PEGMA) with ethylene-maleic anhydride copolymer (EMAC) and endcapping the residual carboxylic acid with methanol. The product was characterized by IR and elementary analysis. Result showed that the product was amorphous and semi-ester product is accord with reaction equation. There were two peaks in the plot of the ionic conductivity against Li salt concentration. The plot of log a against 1/(T - T-0) shows a dual VTF behavior when using the glass transition temperature of PEO of side chain as T beta. The comblike polymer is a white rubbery solid. It can be well-dissolved in acetone. (C) 1999 Elsevier Science Ltd. All rights reserved.

The effect of preparation conditions on the catalyst Nd(P-507)(3)/H2O/Al(i-Bu)(3) for the polymerization of styrene

The catalyst system neodymium phosphonate Nd(P-507)(3)/H2O/Al(i-Bu)(3) for the polymerization of styrene was examined. Effects of the addition order of the catalyst components, catalyst aging time and aging temperature on the catalyst activity and the polymer characteristics were investigated. The catalyst activity for isospecific polymerization of styrene increases with aging time and reaches the maximum with a catalyst aged for 45 min at 70 degrees C. The aging time that the catalyst needs to reach the highest activity for isospecific polymerization decreases with increasing aging temperature. The preformed catalyst and the in situ catalyst were compared with respect to the kinetic behavior of the styrene polymerization and the polymer characteristics.

Catalytic oxidization polymerization of aniline in an H2O2-Fe2+ system

Polyaniline is prepared by chemical polymerization of aniline in an acidic solution using H2O2 as an oxidant and ferrous chloride as a catalyst. A wide variety of synthesis parameters are studied, such as the amount of the catalyst, reaction temperature, reaction time, initial molar ratio of oxidant, monomer and catalyst, and aniline and HCl concentrations. The polymerization of aniline can be initiated by a very small amount of catalyst. The yield and the conductivity of product depend on the initial molar ratio of the oxidant and monomer. The polyaniline with a conductivity of about 10 degrees S/cm and a yield of 60% is prepared under optimum conditions. The process of polymerization was studied by in situ ultraviolet-visible spectroscopy and open-circuit potential technology. Compared to the polymerization process in a (NH4)(2)S2O8 system, the features of the H2O2-Fe2+ system are pointed out, and the chain growth mechanism is proposed. (C) 1999 John Wiley & Sons, Inc.

A study of dimethylferrocene diffusion and electrode kinetics using microelectrode voltammetry in poly(ethylene glycol) solvent

The heterogeneous electron transfer rate constant (k(s)) of dimethylferrocene (DMFc) was estimated using cyclic voltammetric peak potential separations taken typically in a mixed diffusion geometry regime in a polyelectrolyte, and the diffusion coefficient (D) of DMFc was obtained using a steady-state voltammogram. The heterogeneous electron transfer rate constant and diffusion coefficient are both smaller by about 100-fold in the polymeric solvent than in the monomeric solvent. The results are in agreement with the difference of longitudinal dielectric relaxation time (tau(L)) in the two kinds of solvents, poly(ethylene glycol) (PEG) and CH3CN, indicating that k(s) varies inversely with tau(L); k(s), is proportional to D of DMFc. Both D and k(s) of DMFc in PEG containing different supporting electrolytes and at different temperatures have been estimated. These results show that D and k(s) of DMFc increase with increasing temperature in the polyelectrolyte, whereas they vary only slightly with changing the supporting electrolyte.

Studies on blends of LLDPE and ethylene-methacrylic acid random copolymer

Blends of linear low-density polyethylene (LLDPE) and poly(ethylene-co-methacrylic acid) (EMA) random copolymer were studied by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and excimer fluorescence. In binary blends, crystallization of EMA was studied, and no modification of crystal structure was detected. In excimer fluorescence measurements, emission intensities of blends of EMA and naphthalene-labeled LLDPE were measured. The ratio of the excimer emission intensity (I-D) to the emission intensity of the isolated "monomer" (I-M) decreases upon addition of EMA, indicating that PE segments of EMA interpenetrate into the amorphous phase of LLDPE. (C) 1998 Published by Elsevier Science Ltd,. All rights reserved.