Synthesis of poly(ether ether ketone)s with high content of sodium sulfonate groups as gas dehumidification membrane materials

Sodium sulfonate-functionalized polyether ether ketone)s derived from Bisphenol A with a degree of sulfonation up to 2.0 were synthesized by aromatic nucleophilic polycondensation of various amounts of 5,5-carbonylbis(2-fluorobenzenesulfonate) (1), 4,4'-diflurobenzophenone (2) and Bisphenol A (2). Copolymers showed excellent thermal stability and good mechanical properties. The selectivity of water vapor over nitrogen of membranes prepared from copolymers 3a and 3h was determined to be 3.43 x 10(6) and 1.05 x 10(7), respectively.

Study on a series of main-chain liquid-crystalline ionomers containing sulfonate groups

A series of main-chain Liquid-crystalline ionomers containing sulfonate groups pendant on the polymer backbone were synthesized by an interfacial condensation reaction of 4,4'-dihydroxy-alpha,alpha'-dimethyl benzalazine, a mesogenic monomer, with brilliant yellow (BY), a sulfonate-containing monomer, and a 1/9 mixture of terephthaloyl and sebacoyl dichloride. The structures of the polymers were characterized by LR and UV spectroscopies. DSC and thermogravimetric analysis were used to measure the thermal properties of those polymers, and the mesogenic properties were characterized by a polarized optical microscope, DSC, and wide-angle X-ray diffraction. The ionomers were thermally stable to about 310 degreesC. They were thermotropic liquid-crystalline polymers (LCPs) with high mesomorphic-phase transition temperatures and exhibited broad nematic mesogenic regions of 160-170 degreesC, and they were lyotropic LCPs with willowy leaf-shaped textures in sulfuric acid. However, the thermotropic liquid-crystalline properties were somewhat weakened because the concentration of BY was more than 8%. The inherent viscosity in N-methyl-2-pyrrolidone suggested that intramolecular associations of sulfonate groups occurred at low concentration, and intermolecular associations predominated at higher concentration. (C) 2001 John Wiley & Sons, Inc.

Synthesis and characterization of chiral smectic side-chain liquid crystalline polysiloxanes and ionomers containing sulfonic acid groups

The synthesis of new chiral smectic A (S-A) side-chain liquid crystalline polysiloxanes (LCPs) and ionomers (LCIs) containing 4-allyloxy-benzoyl-4-(S-2-ethylhexanoyl) p-benzenediol his ate (ABB) as mesogenic units and 4-[[4-(2-propenyloxy)phenyl] azo]benzensulfonic acid (AABS) as nonmesogenic units is presented. The chemical structures of the monomers and polymers are confirmed by FTIR spectroscopy or H-1-NMR. Differential scanning calorimetry (DSC), optical polarizing microscopy, and X-ray diffraction measurements reveal that all the polymers P-I-P-IV and ionomers P-V-P-VI exhibit S-A texture. The results seem to demonstrate that the tendency toward the S-A-phase region increases with increasing sulfonic acid concentration, and the thermal stability of the S-A phase is determined by the flexibility of the polymer backbones and the interactions of sulfonic acid groups. (C) 2001 John Wiley & Sons, Inc.

Synthesis, crystal structure and luminescence studies of a lanthanide coordination polymer with a new double betaine ligand

A novel europium(III) coordination polymer with a new double betaine derivative, {[Eu(L')(NO3)(H2O)(3)](NO3)(2). 3.5H(2)O}(n) (L-1 = 1,3-bis(pyridinio-4-carboxylato)-propane) has been synthesized and its structure determined. Its luminescence properties have also been studied. The title metal carboxylate coordination polymer contains centrosymmetric dimeric units in which each pair of metal ions is linked by a pair of syn-anti carboxylato-O,O' groups, and each pair of such dimeric units is bridged by the backbones of L-1 ligands to form infinite double chains in the b direction. These metal carboxylate chains are further cross-linked by hydrogen bonds among both coordinated and discrete nitrate anions, aqua ligands and lattice water molecules to form a three-dimensional network. Luminescent data show that the L-1 ligand is a good energy donor and the complex has a relatively long luminescent lifetime.

K-2[MoO3(C2O4)].H2O

In the title compound, catena-poly[dipotassium [[(oxalato-O,O')dioxomolybdate]-mu-oxo]monohydrate], oxalate acts as a bidentate ligand coordinating to each Mo atom through the two deprotonated carboxylate groups. The coordination polyhedron of molybdenum is distorted octahedral and there are infinite chains in the structure. Principal dimensions are: Mo-O(terminal) 1.560 (3) and 1.739 (3) Angstrom, Mo-O(bridging) 2.046 (4) and 2.410 (4) Angstrom, and Mo-O(carboxylate) 1.949 (3) and 2.113 (3) Angstrom.

Structural characterization and luminescence studies of new lanthanide(III) complexes with nicotinic and isonicotinic acid N-oxides

Four new polymeric lanthanide(III) complexes of nicotinic acid N-oxide and isonicotinic acid N-oxide have been synthesized and structurally determined. In the isomorphous compounds [(Ln(L-1)(3) (H2O)(2))(n)]. 4nH(2)O(HL1 = nicotinic acid N-oxide; Ln = Eu, 1; Ln = Er, 2) the lanthanide(III) ions form infinite double chains along the b direction through the coordination of bridging carboxylate and N-oxide groups. The chains are cross-linked through hydrogen bonds between aqua ligands and uncoordinated N-oxide groups and between aqua ligands and lattice water molecules, to form a three-dimensional network. [(Eu(L-2)(2)-(H2O)(4))(n)](NO3)(n). nH(2)O (HL2 = isonicotinic acid N-oxide, 3) has a polymeric structure in which the europium (III) ions are connected into infinite chains by pairs of syn-syn carboxylate groups. Adjacent chains are interlinked by hydrogen bonds between aqua ligands and N-oxide groups to form a layer parallel to the (100) plane, and such layers are connected by hydrogen bonds between nitrate anions and aqua ligands, and between oxide groups and lattice water molecules, into a three-dimensional network. In [(Er-2(L-2)(4)(H2O)(10))](NO3)(2). H2O, 4, dinuclear units are inter-linked into a three-dimensional network through hydrogen bonding between aqua ligands and N-oxide groups of both bidentate bridging and unidentate L-2 ligands. Factors affecting the formation of coordination chains and dinuclear units are discussed. Luminescence properties of 1 and 3 have also been studied. (C) 1998 Elsevier Science Ltd. All rights reserved.

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.

Synthesis and structural characterization of a novel polymeric praseodymium(III) complex with a new flexible double betaine

A novel polymeric Pr(III) complex with a new double betaine, namely [{Pr(L-1)(1.5)(H2O)(2)}(n)] [ClOli4]3(n). nH(2)O (1) (L-1= 1,4-diazoniobicyclo[2,2,2]octane- 1,4-dipropionate), has been synthesized and characterized by X-ray analysis. In the title complex, the Pr(III) atom is nine-coordinated by seven oxygen atoms from five L-1 ligands and two aqua ligands. Each pair of adjacent praseodymium(III) atoms is linked by a pair of mu(3) chelating and bridging carboxylate groups, thus forming an infinite metal metal chain running parallel to the a direction, and such chains are cross-linked by flexible backbones of L-1 ligands into a three-dimensional network with the perchlorate anions and lattice water molecules accommodated in the interstitial space. The title complex crystallizes in the monoclinic space group P2(1)/n with a = 8.085(2), b = 14.316(3), c = 29.775(6) Angstrom, beta = 103.04(3)degrees and Z = 4.

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.

Crystal structure of a Pr-III complex with a novel macrocyclic ligand

The crystal structure of a novel macrocyclic ligand complex of Pr-III, C112H178O52N8S4Pr2, [Pr2L2(HL)(2)(H2O)(6)]. 22H(2)O is reported. The macrocyclic ligand has pendant acetic acid through which the ligand is coordinated to the Pr-III ion. For the dimeric unit, [Pr2L2(HL)(2)(H2O)(6)], two Pr-III ions are connected by two bridging-chelating carboxyl groups and two bridging carboxyl groups of the ligands, and each Pr-III ion is also bonded to a unidentate carboxyl group of the ligand and three water molecules. The dimeric units are bridged by four ligands through their carboxyl groups to form an infinite one-dimensional chain. The coordination number of the Pr-III ion is nine, with a distorted tricapped trigonal prismatic configuration. (C) 1997 Elsevier Science Ltd.

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.