Synthesis and polymerization of some macrocyclic (arylene ether sulfone) containing cardo groups and macrocyclic (arylene ether ketone sulfone) oligomers

Some novel macrocyclic (arylene ether sulfone) containing cardo groups and (arylene ether ketone sulfone) oligomers have been synthesized in high yields by a nucleophilic aromatic substitution reaction of 4,4'-difluorophenylsulfone with bisphenols in the presence of anhydrous potassium carbonate under a pseudo-high-dilution condition. Detailed structural characterization of these oligomers by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS), fast atom bombardment mass spectrometry (f.a.b.-m.s.), nuclear magnetic resonance spectrometry (n.m.r.) and single-crystal X-ray structure analysis confirms their cyclic nature, and the composition of the oligomeric mixtures is provided by g.p.c. analysis. Ring polymerization of cyclic oligomers 3a to a high molecular weight polymer with M-w of 59.1 k was achieved by heating at 290 degrees C for 40 min in the presence of a nucleophilic initiator. (C) 1998 Elsevier Science Ltd. All rights reserved.

Studies on the side chain liquid crystalline copolymer containing nonlinear optical groups

A new side chain liquid crystalline poly[4-(methacryloxy)hexanoloxy-4'-benzyloxy biphenyl] was synthesized. The phase behavior of the monomer and homopolymer was studied. The monomer shows a smectic B phase, while the homopolymer shows a nematic phase. The nonmesogenic nonlinear optical group was introduced to synthesize a series of side chain liquid crystalline copolymers which also show a nematic phase. Owing to the liquid crystallinity of the copolymer has been the orientational stability improved, down the relax of the orientation slowed and the nonlinear optical properties enhanced.

Nonlinear optical properties of (B3O7)(5-) and (B3O6)(3-) groups

From the chemical bond viewpoint, LiB3O5 (LBO) crystal has been studied by using the bond valence theory of complex crystals. Chemical bond parameters and linear and nonlinear optical (NLO) properties of each type of constituent chemical bonds are quantitatively determined. Because of the different crystal structure characteristics of LBO from those of beta-BaB2O4 (BBO), the two anionic groups, (B3O7)(5-) in LBO and (B3O6)(3-) in BBO, play different roles in contributions to their own total NLO tensor coefficients of LBO and BBO, respectively. By comparison, we find that planar (B3O6)(3-) groups are the ideal structure model, leading to little cancellation of contributions of each kind of bond in these groups, and this gives us a useful guide to design new NLO materials in the future.

Novel poly(aryl ether ketone)s containing various pendant groups .2. Gas-transport properties

The gas transport of hydrogen, oxygen, nitrogen, carbon dioxide, and methane gases in a series of poly(aryl ether ketone)s was examined. These polymer membranes have a wide range of permeability coefficients and permselectivity coefficients, showing excellent gas-transport properties. The enhanced interchain interaction in the polymers due to intermolecular hydrogen bonds and ionic bonds results in a considerable increase in permselectivity but a decrease in permeability. On the contrary, the polymers with bulky arkyl substituents show significantly increased permeability. The causes of this trend are interpreted in terms of the free volume, interchain distance, and glass transition temperature together with the respective contribution of gas solubility and diffusivity to the overall permeability. Of interest is the observation that the ionomer IMPEK-K+, which simultaneously contains bulky isopropyl substituents and pendant carboxylate groups, exhibits over twice higher CO2 permeability and 15% higher CO2/CH4 permselectivity than those of bisphenol-A p'olysulfone (PSF). The possibility of using the new synthesized poly(aryl ether ketone)s in gas separation membrane application is also discussed. (C) 1997 John Wiley & Sons, Inc.

Synthesis of a series of chiral copolymers with azo groups and investigations of reversible liquid crystalline alignment induced by the LB films of these materials

A series of liquid crystalline copolymers, poly{2-hydroxyethyl methacrylate}-co-{6-[4-(S-2-methyl-1-butyloxycarbonylphenylazo)phenoxy]hexyl methacrylate} with an azobenzene moiety as photoreactive mesogenic unit, was prepared and investigated by using DSC, polarized optical microscopy and X-ray diffraction. The results show that these polymers exhibit smectic phases. Z-type Langmuir-Blodgett films of these copolymers were successfully deposited onto calcium fluoride and quartz. Reversible homeotropic and planar liquid crystal alignments were induced by using the photochromism of the LB films of one of the copolymers containing 20.6 mol % of the azo unit.

Detection of menadione sodium bisulfite (vitamin K-3) by reversed-phase high performance liquid chromatography with series dual-electrode amperometric detector

A reversed-phase high-performance liquid chromatography with series dual glassy carbon electrodes for the amperometric detection of water-soluble menadione is described. The complex post-column derivatization reaction and the high background currents were avoided. The menadione sodium bisulfite was reduced at -0.3 V vs. SCE at the upstream (generator) electrode and oxidized at +0.2V vs. SCE at the downstream (collector) electrode. The mobile phase was 0.2moll(-1) HAc-NaAc aqueous buffer (pH 5.50) and 40% (v/v) methanol. The linear response was in the range of 35 ng to 15 mu g, with a detection Limit of 15 ng (S/N=3). The correlation coefficient was 0.9997 (n=6). The electrochemical detection with series dual electrodes has a higher selectivity for menadione (vitamin K-3) compound than with UV detection.

Novel polyaryletherketones containing various pendant groups .1. Synthesis and characterization

Novel high glass transition temperature polyaryletherketones, containing pendant amido, alkyl, and carboxyl groups with reduced viscosity above 0.54 dL/g, were synthesized via solution nucleophilic polycondensation reaction of phenolphthalin, 2',2 ''-diisopropyl-5',5 ''-dimethylphenolphthalin, and 3,3'-bis(4-hydroxyphenyl)isobenzopyrrolidone with bis(4-nitrophenyl)ketone in the presence of potassium carbonate. By ion exchange with Na+ and K+, four ionomers were also prepared. A new monomer simultaneously containing carboxyl and algyl substituents was synthesized by reduction reaction of 2',2 ''-diisopropyl-5',5 ''-dimethyl-phenolphthalein. The resulting polymers were soluble in a few polar aprotic solvents; transparent, colorless, and tough films could easily be cast from DMF or DMSO solution. The mechanical properties of the films were excellent; and their tensile strength, elongation at break, and tensile moduli were in the range of 67.1-97.1 MPa, 7.8-165%, and 1.47-2.27 GPa, respectively. The prepared polymers showed fairly good thermal stability and resonably high glass transition temperatures above 210 degrees C. (C) 1997 John Wiley & Sons, Inc.

Syntheses and crystal structures of [(C6H5CH2C5H4)(2)GdCl center dot THF](2) and (C6H5CH2C5H4)(2)ErCl center dot THF

[(C6H5CH2C5H4)(2)GdCl . THF](2) (1) and (C6H5CH2C5H4)(2)ErCl . THF (2) were prepared by the reaction of LnCl(3) (Ln=Gd, Er) with benzylcyclopentadienyl sodium in THF and characterized by elemental analysis, IR, H-1 NMR, C-13 NMR, MS and thermal gravimetry. The crystal structures of both compounds were determined. Complex 1 is dimeric and its structure belongs to the monoclinic, P2(1)/c space group with a=1.1432(2), b=1.2978(2), c=1.7604(3) nm, beta=108.75(2), V=2.4732(9) nm(3), Z=2(four monomers), D-c=1.54 g . cm(-3). R=0.0342 and R(w)=0.0362. Complex 2 is monomer and its structure belongs to the orthorhombic, P2(1)2(1)2(1) space group with a=0.8645(2), b=1.1394(3), c=2.5289(4) nm, V=2.4919(9) nm(3), Z=4, D-c=1.56 g . cm(-3). R=0.0514, R(w)=0.0529. The determination of the crystal structure shows that in complex 1 the benzyl groups on the cyclopentadienyls coordinated to Gd3+ are located in the opposite direction (139 degrees); in complex 2 the benzyl groups on the cyclopentadienyls coordinated to Er3+ are located in the same direction (6.5 degrees).

Synthesis and thermal transitional properties of side-chain liquid crystalline polyacrylates containing para-nitroazobenzene as mesogenic groups

The synthesis and characterization of side-chain liquid crystalline (LC) polyacrylates containing para-nitroazobenzene (Pn) as mesogenic groups were described. Homopolymers with 3 and 4 carbon atoms in the spacers were non-LC polymers; for homopolymers with 6 carbon atoms in the spacer, nematic LC behavior was observed. Copolymers with acrylic acid as one component exhibited an S-Ad phase according to the WAXD results which showed the d/l of 1.4-1.54 for the copolymers with 3, 4, and 6 carbon atoms in the spacers. Considering the molecular structure as well as the WAXD results of the copolymers, the possible molecular arrangement in the smectic Sad phase was proposed, in which the smectic layers were composed of the antiparallel mesogens and the antiparallel arrangement was considered to be enhanced due to the H bond between - COOH and - NO2. The stress-induced orientational phenomena of Pn in the LC states was also discussed. (C) 1996 John Wiley & Sons, Inc.

IN-SITU SCANNING-TUNNELING-MICROSCOPY IMAGE OF A HIGHLY ORIENTED PYROLYTIC-GRAPHITE ELECTRODE MODIFIED WITH POTASSIUM BIS(11-MOLYBDOSILICATO) DYSPROSATE(III) IN SODIUM-SULFATE SOLUTION

The variation in molecule adsorption mode on pretreated highly oriented pyrolytic graphite electrodes, modified with the title complex K10H3[Dy(SiMo11O39)(2)] by cyclic voltammetry in the title complex solution, was observed in situ by electrochemical scanning tunnelling microscopy (ECSTM) with molecular resolution in sodium sulphate solution. According to the ECSTM images and the known molecular structure we conclude that the adsorption mode of the title complex modified electrode changed during potential cycling from ''vertical'' to ''inclined'' and then ''horizontal'' or ''flat'' mode, i.e. the title complex adsorbed on the surface of electrode by one ligand of the complex at first, then began to incline and was finally adsorbed by two ligands of the complex. This result indicates that the adsorption mode on the modified electrode surface changed during potential cycling in the sulphate solution and a much more stable molecular layer was formed. The change in adlattice of adsorbates on the modified electrode surface from hexagonal to rectangular was also observed by ECSTM. A plausible model was given to explain this process.

SYNTHESIS AND CHARACTERIZATION OF POLYACRYLATES CONTAINING CHARGE-TRANSFER GROUPS

Polyacrylates containing para-nitro azobenzene have been synthesized by free radical polymerization. The influence of the length of the spacer of the homopolyacrylates (HPn, n=3,4,6), content of methyl acrylate in the copolyacrylates (CP6) with para-nitro azobenzene groups on the thermal properties, such as liquid crystallinity, Tg and Tm, was studied by DSC, WAXD and polarized optical microscopy. Among the polymers studied, only the homopolyacrylate (HP6)with six carbon atoms in the spacer exhibited a nematic phase. The second-harmonic generation (SHG) signal of the poled HP6 film was detected qualitatively by Maker-fringer method.

THE CHAIN STRUCTURE AND LIGHT-SCATTERING-STUDIES FOR ACRYLAMIDE-SODIUM ACRYLIC-ACID (AM-AA) COPOLYMERS

A set of AM-AA copolymer samples with the same comonomer content and different average molecular weight have been characterized by C-13 NMB and light scattering methods in this paper. The chemical composition (comonomer AA, mole content 16.9 +/- 1.1%) of these samples is uniform. the sequence of AA in the macromolecular chain is of alone and random distribution and the light scattering theory from polyelectrolyte in added-salt solutions is suitable for the AM-AA copolymers-0.12 mol/L NaCl water systems. The actual values of M(w), the second Virial coefficient A(2) and the mean square radius of gyration (R(2)), for the studied samples have been obtained. The relationships between the molecular parameters are as follows: A(2)=0.0619 ($) over bar M(w)(-0.24), < R(2) >(1/2)(t)= 0.0210 ($) over bar M(w)(0.54).

ELECTROCHEMICAL CONTROLLED-RELEASE OF ADENOSINE-TRIPHOSPHATE

Polypyrrole (PPy) film was synthesized by anodic polymerization of pyrrole onto the surface of platinum electrode in the solution of sodium p-toluene sulfonate (NaTsO). When this film was oxidized anodically in an aqueous solution of adenosine triphosphatle (ATP), the ATP anions were incorporated into the film. Release of ATP From the film could be accomplished by reduction of the film in aqueous electrolyte solution. The total amount of ATP released from the film was determined by UV spectroscopic method.

Chemical Bonding between Heteropoly Acid and Oxygen-containing Groups on the Surface of Activated Carbon

In order to define the force of heteropoly acids on absorbed activated carbon surface, IR spectra of 12-silicotungstic acid (SiW12) and 12-tungstophosphoric acid (PW12) absorbed on activated carbon and in oxygen-containing organic compound solutions were studied. Based on the IR spectra and UV characteristics of the heteropoly acids in various chemical conditions, the chemical bonding between heteropoly acid and oxygen-containing gropus on the surface of activated carbon was suggested.