Electrochemical study of PW12O403- in poly(ethylene glycol) electrolyte

The electrochemical properties Of PW12O403- (abbreviated as PW12) anion in poly(ethylene glycol) (PEG) have been studied by cyclic voltammetry, complex impedance and FT-IR spectroscopy. The PW12 anion in PEG-LiClO4 electrolyte shows reasonable facile electrochemistry, and the diffusion coefficients Of PW12 were measured with microelectrode. It is shown that ionic conductivity of polymer electrolytes based on low molecular weight PEG can be improved by the addition of PW12. The increase of conductivity is coupled with decrease of transient cross-links density of polymer chains which is evidenced by the downshift of C-O-C stretching mode. The phenomena are explained in view of ion-ion and ion-polymer interactions.

Ring-opening polymerization and block copolymerization of L-lactide with divalent samarocene complex

Divalent samarocene complex [(C5H9C5H4)(2)Sm(tetrahydrofuran)(2)] was prepared and characterized and used to catalyze the ring-opening polymerization of L-lactide (L-LA) and copolymerization of L-LA with caprolactone (CL). Several factors affecting monomer conversion and molecular weight of polymer, such as polymerization time, temperature, monomer/catalyst ratio, and solvent, were examined. The results indicated that polymerization was rapid, with monomer conversions reaching 100% within 1 h, and the conformation of L-LA was retained. The structure of the block copolymer of CL/L-LA was characterized by NMR and differential scanning calorimetry. The morphological changes during crystallization of poly(caprolactone) (PCL)-b-P(L-LA) copolymer were monitored with real-time hot-stage atomic force microscopy (AFM). The effect of temperature on the morphological change and crystallization behavior of PCL-b-P(L-LA) copolymer was demonstrated through AFM observation.

Syntheses of biphenyl polyimides via nickel-catalyzed coupling polymerization of bis(chlorophthalimide)s

A facile method for the synthesis of biphenyl polyimides, which involves the nickel-catalyzed coupling of aromatic dichlorides containing imide structure in the presence of zinc and triphenylphosphine, has been developed. The polymerizations proceeded smoothly under mild conditions and produced biphenyl polyimides with inherent viscosities of 0.13-0.98 dL/g. The polymerizations of bis(4-chlorophthalimide)s with bulky side substituents gave high molecular weight polymers. Low molecular weight polymers from bis(4-chlorophthalimide)s containing rigid diamine moieties and bis(3-chlorophthalimide)s were obtained because of the formations of polymer precipitate and cyclic oligoimides, respectively. The effects of various factors, such as amount of catalyst, solvent volume, ligand, reaction temperature, and time, on the polymerization were studied. The random copolymerization of two bis(chlorophthalimide)s in varying proportions produced medium molecular weight material. The TgS of prepared polyimides were observed at 245-311 degreesC, and the thermogravimetry of polymers showed 10% weight loss in nitrogen at 470-530 degreesC.

Reactive compatibilization of polyamide 6 with isocyanate functionalized ethylene-propylene copolymer

Reactive compatibilization of ethylene-propylene copolymer functionalized with allyl (3-isocyanato-4-tolyl) carbamate (TAI) isocyanate (EPM-g-TAI) and polyamide 6 (PA6) was investigated in this paper, FTIR analysis revealed the evidence of a chemical reaction between the end groups of PA6 and EPM-g-TAI. Thermal, rheological, morphological, and mechanical properties of the resultant system were examined, DSC analysis indicated that the crystallization of PA6 in Pa6/EPM-g-TAI blends was inhibited, due to the chemical reaction that occurs at the interface of PA6 and EPM-g-TAI. Rheological measurement showed that complex viscosity and storage modulus of PA6/EPM-g-TAI were both dramatically enhanced compared to those of PA6/EPM at the same blending composition. After examining the morphology of both blending systems, smaller particile sizes, more homogeneous distribution of domains and improved interfacial adhesion between matrix and domains were observed in the compatibilized system. Mechanical properties such as tensile strength. Young's modulus, flexural strength and modulus, as well as notched and un-notched impact strength of PA6/EPM-g-TAI blends were also found to improve gradually with increasing the content of grafted TAI.

Preparation and properties of polyethylene/montmorillonite nanocomposites by in situ polymerization

Polyethylene (PE)/montmorillonite (MMT) nanocomposites were prepared by in situ coordination polymerization using a MMT/MgCl2/TiCl4 catalyst activated by AI(Et),. The catalyst was prepared by first diffusing MgCl2 into the swollen MMT layers, followed by loading TiCl4 on the inner/outer layer surfaces of MMT where MgCl2 was already deposited. The intercalation of MMT layers by MgCl2 and TiCl, was demonstrated by the enlarged interlayer spacing determined by WAXD. The nanoscale dispersion of MMT layers in the polyethylene matrix was characterized by WAXD and TEM. As a consequence, the crystallinity of the nanocomposite decreased sharply, whereas the tensile strength was significantly improved compared to that of virgin polyethylene of comparable molecular weight. The confinement of the nanodispersed MMT layers to molecular chain and the strong interaction between the nanoscale MMT layers and the resin matrix were thought to account for the decrease of crystallinity and the remarkable enhancement of strength.

Functionalization of an ethylene-propylene copolymer with allyl (3-isocyanate-4-tolyl) carbamate

An ethylene-propylene copolymer (EPM) was functionalized with an iso cyanate-bearing unsaturated monomer, allyl(3-isocyanate-4-tolyl) carbamate (TAI), with dicumyl peroxide as an initiator in a xylene solution. Fourier transform infrared (FTIR) was used to confirm the formation of EPM-g-TAI. The peak at 2273 cm(-1), characteristic of -NCO groups in EPM-g-TAI, revealed evidence of grafting. The grafting degree was determined with both chemical titration and FTIR. The grafting degree could be adjusted, and the maximum was over 6 wt % without any gelation. The molar mass distribution of EPM-g-TAI was narrower than that of EPM. The rheological behavior of both EPM-g-TAI and EPM was investigated with a rotational rheometer. The apparent viscosity of EPM-g-TAI was higher than that of EPM and increased with an increasing grafting degree of TAI. Surface analysis by contact-angle measurements showed that contact angles of EPM-g-TAI samples to a given polar liquid decreased with an increasing grafting degree of TAI. We also obtained the dispersion component of the surface free energy (gamma(S)(d)), the polar component of the surface free energy (gamma(S)(d)), and the total surface free energy (gamma(S) = gamma(S)(d) + gamma(S)(p)) of the grafted EPM. These parameters increased with the enhancement of the grafting degree, which gave us a quantitative estimation of the polar contribution of the grafted TAI to the total surface free energy of EPM-g-TAI.

Copolymerization of CO2 and propylene oxide under rare earth ternary catalyst: design of ligand in yttrium complex

Copolymerization of carbon dioxide and propylene oxide was carried out employing (RC6H4COO)(3)Y/glycerin/ZnEt2 (R = -H, -CH3, NO2, -OH) ternary catalyst systems. The feature of yttrium carboxylates (ligand, substituent and its position on the aromatic ring) is of great importance in the final copolymerization. Appropriate design of substituent and position of the ligand in benzoate-based yttrium complex can adjust the microstructure of aliphatic polycarbonate in a moderate degree, where the head-to-tail linkage in the copolymer is adjustable from 68.4 to 75.4%. The steric factor of the ligand in the yttrium complex is crucial for the molecular weight distribution of the copolymer, probably due to the fact that the substituent at 2 and 4-position would disturb the coordination or insertion of the monomer, lead the copolymer with broad molecular distribution. Based on the study of ultraviolet-visible spectra of the ternary catalyst in various solvents, it seems that the absorption band at 240-255 nm be closely related to the active species of the rare earth ternary catalysts.

Synthesis and characterization of PCL/PEG/PCL triblock copolymers by using calcium catalyst

Triblock copolymer PCL-PEG-PCL was prepared by ring-opening polymerization of epsilon-caprolactone (CL) in the presence of poly(ethylene glycol) catalyzed by calcium ammoniate at 60 degreesC in xylene solution. The copolymer composition and triblock structure were confirmed by H-1 NMR and C-13 WR measurements. The differential scanning calorimetry and wide-angle X-ray diffraction analyses revealed the micro-domain structure in the copolymer. The melting temperature T-c and crystallization temperature T-c of the PEG domain were influenced by the relative length of the PCL blocks. This was caused by the strong covalent interconnection between the two domains. Aqueous micelles were prepared from the triblock copolymer. The critical micelle concentration was determined to be 0.4-1.2 mg/l by fluorescence technique using pyrene as probe, depending on the length of PCL blocks, and lower than that of corresponding PCL-PEG diblock copolymers. The H-1 NMR spectrum of the micelles in D2O demonstrated only the -CH2CH2O- signal and thus confirmed. the PCL-core/PEG-shell structure of the micelles.