Crystal structure and variation in unit cell parameters with crystallization temperatures of poly (ether ketone ether ketone ketone)s containing meta-phenyl links (PEKEKmK)

The X-ray diffraction patterns of the crystalline aromatic ketone polymer PEKEKmK (aryl ether ketone ether ketone ketone polymer containing meta-phenyl links) have been investigated (for the chemical structure, see Formula). An orthorhombic unit cell is proposed to contain two chains with a = 0.772 nm, b = 0.604 nm and c = 2.572 nm. According to the orthorhombic system, the 11 reflections of this polymer were indexed. Meanwhile, variation in unit cell parameters with crystallization temperatures of PEKEKmK was also investigated. [GRAPHICS]

Observation of inverted phases in poly(styrene-b-butadiene-b-styrene) triblock copolymer by solvent-induced order-disorder phase transition

We report observation of inverted phases consisting of spheres and/or cylinders of the majority fraction block in a poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymer by solvent-induced order-disorder phase transition (ODT). The SBS sample has a molecular weight of 140K Da and a polystyrene (PS) weight fraction of 30%. Tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM) were utilized to study the copolymer microstructure of a set of solution-cast SBS films dried with different solvent evaporation rates, R. The control with different R leads to kinetic frozen-in of microstructures corresponding to a different combination parameter chi (eff)Z of the drying films (where chi (eff) is the effective interaction parameter of the polymer solution in the cast film and Z the number of "blobs" of size equal to the correlation length one block copolymer chain contains), for which faster evaporation rates result in microstructures of smaller chi (eff)Z. As R was decreased from rapid evaporations (similar to0.1 mL/h), the microstructure evolved from a totally disordered one sequentially to inverted phases consisting of spheres and then cylinders of polybutadiene (PB) in a PS matrix and finally reached the equilibrium phase, namely cylinders of PS in a PB matrix. We interpret the formation of inverted phases as due to the increased relative importance of entropy as chi (eff)Z is decreased, which may dominate the energy penalty for having a bigger interfacial area between the immiscible blocks in the inverted phases.

Fabrication and electrochemical behaviors of multilayers composed of heteropholyanions and poly(diallyldimethylammonium chloride) on 4-aminothiophenol modified gold electrodes

Multilayer films composed of heteropolyanions (HPAS, SiMo11 VO405-) and cationic polymer poly(diallyldimethylammonium chloride) on 4-aminothiophenol self-assembled-monolayer were fabricated by electrochemical growth. Growth processes of the composite films were characterized by cyclic voltammetry. The results prove the third redox peak of Mo increases more rapidly, otherwise the other Mo redox peaks increase very slowly when the number of layers of heteropolyanions is greater. The peak potentials of composite films shift linearly to negative position with higher pH, which implies that protons are involved in the redox processes of HPA. The investigation of electrocatalytic behaviors of composite films shows a good catalytic activity for the reductions of HNO2 and BrO3-. Catalytic currents increase with increasing number of layers of heteropolyanions, moreover, the catalytic currents have a good linear relationship with the concentrations of BrO3-.

Isothermal crystallization kinetics of PEO in poly(ethylene terephthalate)-poly(ethylene oxide) segmented copolymers. I. Effect of the sofi-block length

The isothermal crystallization kinetics of poly(ethylene oxide) (PEO) block in two poly(ethylene terephthalate) (PET)-PEO segmented copolymers was studied with differential scanning calorimetry. The Avrami equation failed to describe the overall crystallization process, but a modified Avrami equation, the Q equation, did. The crystallizability of the PET block and the different lengths of the PEO block exerted strong influences on the crystallization process, the crystallinity, and time final morphology of the PEO block. The mechanism of nucleation and the growth dimension of the PEG block were different because of the crystallizability of time PET block and the compositional heterogeneity. The crystallization of the PEO block was physically constrained by the microstructure of time PET crystalline phase, which resulted in a lower crystallization rate. However, this influence became weak with the increase in the soft-block length. (C) 2000 John Wiley & Sons, Inc.

Spatially-confined crystallization of poly(vinylidene fluoride)

Nanometre-sized poly(vinylidene fluoride) (PVDF) particle domains in a confined space were obtained by blending PVDF with excess poly(methyl methacrylate) (PMMA). When these particles were small enough they showed beta -form structure, which was different from the structure of bigger particles or PVDF bulk. However, the beta -form was thermodynamically metastable because it could eventually be transformed to a more stable phase by annealing at a certain temperature. Larger particle domains were of identical phase to the bulk, indicating that small size favours the formation of the beta -form. (C) 2000 Society of Chemical Industry.

Electron self-exchange reaction of viologen and its derivatives in poly(ethylene glycol)

The electron self-exchange rates (k(ex)) of viologen and its derivatives are estimated by using microelectrode voltammetry in poly(ethylene glycol) films. The dependences of supporting electrolyte concentration and sizes of viologen and its derivatives on k(ex) and diffusion coefficients (D) are discussed. Results show that k(ex) increases with the decrease of supporting electrolyte concentration and sizes of reactants. (C) 2000 Elsevier Science S.A. All rights reserved.

Poly(3-dodecylthiophenes) polymerized with different amounts of catalyst

The effect of the amount of the catalyst FeCl3, used during the direct oxidation polymerization, on the structure and properties of the obtained poly(3-dodecylthiophene) (P3DDT) was investigated in this paper. Such measurements as gel permeation chromatography (GPC), nuclear magnetic resonance (NMR) spectroscopy, thermal analysis, X-ray diffraction, infrared spectroscopy (FTIR) and ultraviolet-visible (W-vis) spectroscopy were applied. It is found that a suitable addition of FeCl3 can contribute to generate a P3DDT with greater percentage of head-to-tail head-to-tail (HT-HT) linkages, which are generally favored. The reduction of the other linkage defects helps to lengthen conjugation length, thus leading to more orderly chain packing. (C) 2000 Elsevier Science S.A. All rights reserved.

Synthesis and crystallization of a novel poly(ether ketone ether ketone ketone) containing meta-phenylene linkage: PEKEKK(T/I)

Poly(ether ketone ether ketone ketone) containing meta-phenylene linkage (PEKEKK(T/I)) was synthesized by electrophilic Friedel-Crafts acylation condensation of 1, 4-diphenoxybenzophenone with terephthaloyl chloride (T) and isophthaloyl chloride (I) with a T/I ratio of 1 and characterized by LR,DSC,TGA and WAXD. PEKEKK(T/I) has two different crystal structures: a conventional Farm I structure, the same as that observed in PEEK and PEK, wich is usually developed from melt crystallization, and a new Form II structure which can be developed from cold crystallization or solvent induced crystallization (by exposing the glassy sample to methylene chloride).

A study of the crystallographic equivalence of ether and ketone groups in poly(aryl ether ketone)s

Crystallographic equivalence of ether and ketone in all para-substituted PAEKs crystallized in form I was discussed in this paper. In a word, crystallographic equivalence between ether and ketone groups is tenable when polymer contains only phenyl rings in the repeat unit. If a polymer contains a diphenyl group in the repeat unit, two cases should be distinguished. In the case of PEDEKK and PEEKDK, crystallographic equivalence between ether and ketone linkages is untenable, However, in the case of PEDK and PEDEKDK, crystallographic equivalence between ether and ketone linkages is still tenable.

Aromatic poly(ester imide)s and poly(amide imide)s having 1,1 '-binaphthyl-2,2 '-diyls in the main chain

Full Paper: Two new 1,1'-binaphthyl-2,2'-diyl-based dianhydrides, i.e., 2,2'-bis(3,4-dicarboxybenzamido)-1,1'-binaphthyl dianhydride (BNDADA) and 2,2'-bis(3,4-dicarboxybenzoyloxy)-1,1'-binaphthyl dianhydride (BNDEDA), were synthesized and polymerized with various aromatic diamines to afford polyimides through the traditional two-step method. The polyimides with inherent viscosities ranging from 0.27 to 0.70 dl . g(-1) showed excellent solubilities in polar solvents such as DMAc, DMSO and NMP etc., except of the poly(ester imide) prepared from BNDEDA and benzidine. Poly(ester imide)s based on BNDEDA can also be readily dissolved in weakly polar solvents such as THF, CH2Cl2 and CHCl3. The glass transition temperatures of these polyimides are in the range of 210-310 degrees C; the 5% weight loss temperatures are in the range of 390-465 degrees C in nitrogen and 384-447 degrees c in air. These polymers from light yellow, tough films that were transparent above 365 nm. The effects of different flexible units attached in the 2- and 2'-positions, i.e., amide, ester and ether, on the properties of the polyimides obtained are discussed.

Gas transport properties of novel cardo poly(aryl ether ketone)s with pendant alkyl groups

Gas transport of hydrogen, oxygen, nitrogen, carbon dioxide, and methane in four cardo poly(aryl ether ketone)s containing different alkyl substituents on the phenyl ring has been examined from 30 to 100 degrees C. The permeability, diffusivity, solubility, and their temperature dependency were studied by correlations with gas shape, size, and critical temperature as well as polymeric structural factors including glass transition, secondary transition, cohesive energy density, and free volume. The bulky, stiff cardo and alkyl groups in tetramethyl-substituted TMPEK-C resulted in increased H-2 permeability (by 55%) and H-2/N-2 permselectivity (by 106%) relative to bisphenol A polysulfone (PSF). Moreover, the weak dependence of gas transport on temperature in TMPEK-C made it maintain high permselectivities (alpha(H2/N2) in 68.3 and alpha(O2/N2) in 5.71) up to 100 degrees C, exhibiting potential for high-temperature gas separation applications.

Isothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone)

The isothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone) are investigated by differential scanning calorimetry over two temperature regions. The Avrami equation describes the primary stage of isothermal crystallization kinetics with the exponent n approximate to 2 for both melt and cold crystallization. With the Hoffman-Weeks method, the equilibrium melting point is estimated to be 406 degrees C. From the spherulitic growth equation proposed by Hoffman and Lauritzen, the nucleation parameter (K-g) of the isothermal melt and cold crystallization is estimated. In addition, the K-g value of the isothermal melt crystallization is compared to those of the other poly(aryl ether ketone)s. (C) 2000 John Wiley & Sons, Inc.

Nonisothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone)

Nonisothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone) (PEKEKK) were investigated by differential scanning calorimetry (DSC). The Avrami equation modified by Jeziorny could only describe the primary stage of nonisothermal crystallization kinetics of PEKEKK. Also, the Ozawa equation could not describe its nonisothermal crystallization behavior. A convenient and reasonable kinetic approach was used to describe the nonisothermal crystallization behavior. The crystallization activation energy were estimated to be -264 and 370 KJ/mol for nonisothermal melt and cold crystallization by the Kissinger method. (C) 2000 John Wiley & Sons, Inc.

Novel macrocyclic precursors of poly{aryl ether ketone (sulfone)} containing hexafluoroisopropylidene units: Synthesis, characterization, and polymerization

Cyclic oligomers containing hexafluoroiso-propylidene(HFIP) units were prepared in excellent yields by a nucleophilic aromatic substitution reaction of 4,4(7)- (hexafluoroisopropylidene) diphenol with difluoro-monomers in the presence of anhydrous potassium carbonate under pseudo high dilution conditions. A combination of GPC, MALDI-TOF MS and NMR analysis confirmed the structure of the cyclic oligomers. All macrocyclic oligomers are crystalline and undergo facile melt polymerization to give high molecular weight fluorinated polyethers.